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Petrography and geochemistry of tourmaline breccia in the Longtoushan Au

deposit, South China: Genesis and its exploration significance

Article  in  Geochemistry Exploration Environment Analysis · March 2019

DOI: 10.1144/geochem2018-082

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 Research article Geochemistry: Exploration, Environment, Analysis
Published Online First https://doi.org/10.1144/geochem2018-082

Petrography and geochemistry of tourmaline breccia in the

Longtoushan Au deposit, South China: genesis and
its exploration significance
Mingji Zhang1, Dehui Zhang1*, Bo Zhao2, Mingqian Wu1,3, Bo Bao4, Yingkang Liu5 &
Chong Huang5
1
State Key Laboratory of Geological Processes and Mineral Resources, School of Earth Sciences and Resources, China
University of Geosciences (Beijing), Beijing 100083, China
2
Advanced Algorithm Research Division, Beijing PIESAT Information Technology Company Ltd, Beijing 100195, China
3
Department of Earth and Environmental Sciences, University of Windsor, Windsor, Ontario, N9B 3P4, Canada
4
Wuhan Center, China Geological Survey, Wuhan 430205, China
5
JinDi Mining LLC, China National Gold Group Co., Ltd., Guigang 537100, China
* Correspondence: Zhdehui@cugb.edu.cn

Abstract: The Longtoushan Au deposit, located in the Qin-Hang Metallogenic Belt, South China, is a breccia-hosted epithermal
Au deposit. It is characterized by the distinctive occurrence of magmatic-hydrothermal tourmaline-cemented breccia. Tourmaline-
group minerals have an extensive range of chemical composition that could reflect their host environments, including some of
economic interest. To investigate the potential of tourmaline as a geochemical indicator for ore exploration, chemical and boron
isotope compositions of tourmaline from the Longtoushan Au deposit have been determined. Tourmaline mainly occurs as
orbicular aggregates, clusters and veinlets in rhyolite porphyries, granite porphyries and in spatially associated hydrothermal
breccias (Au-mineralized and Au-barren). Three types of tourmaline (I, II and III) are recognized at Longtoushan, most of which
being alkali-deficient schorl-dravites. The pre-ore Tourmaline I in the rhyolite porphyry is Fe-rich schorl, contrasting with the
dravitic ore-stage Tourmaline II in the mineralized breccia and Tourmaline III in the granite porphyry. Locally, Tourmaline II
shows concentric zoning which correlates with core-rim chemical variations (higher Fe, Al in the rim than in the core).
Tourmalines from Longtoushan are characterized by a dominant MgFe-1 exchange vector and have relatively low Na contents (avg.
0.66 apfu; formula normalized on 15 total cations), indicating they possibly crystallized in reduced fluids of low-salinity. The δ11B
values of tourmalines from this study fall in a narrow range of −14.5 to −10.2‰, indicating dominant magmatic-hydrothermal
fluids of continent crust origin. The results suggest that tourmaline from Longtoushan may originate from boron-rich vapor fluids
unmixed from felsic magmas. Tourmaline breccia was likely formed by hydraulic fracturing, with open spaces infilled by boron-
rich boiling fluids released from the magma. The fluid boiling process during brecciation would be critical for Au-bearing pyrite
precipitation, which could compete with coexisting tourmaline for Fe, leaving tourmaline Fe-depleted. We propose that the
Fe-poor dravitic tourmaline in the hydrothermal breccia could be used as prospecting guide at the Longtoushan Au deposit.
Keywords: Longtoushan; tourmaline; tourmaline breccia; boron isotopes; fluid source; ore exploration
Supplementary material: major element and boron isotope composition analyses of tourmaline are available at https://doi.org/
10.6084/m9.figshare.c.4468808
Received 3 December 2018; revised 6 March 2019; accepted 8 March 2019

Minerals of tourmaline-group (referred to as tourmaline here for
unspecified compositions) are common borosilicates in the Earth’s
crust (van Hinsberg et al. 2011b). They can sensitively adjust their
composition to suit a wide variety of environments, and have a large
P-T stability range (from as low as 150°C, 100 Mpa to between 725
and 950°C depending on pressure and composition; van Hinsberg
et al. 2011b, and references therein). Once formed, tourmaline is
highly resistant to post-depositional alteration and weathering, and
exhibits negligible element diffusion in its structure (van Hinsberg
et al. 2011a). Therefore, tourmaline can record and preserve
geochemical information and has been considered as an excellent
monitor of its host environment (Marschall & Jiang 2011; van
Hinsberg et al. 2011b).
As a major constituent of tourmaline, boron is an incompatible
element that tends to concentrate in fractionated melts (London et al.
1996; Marschall & Jiang 2011). The fluid-mobility of boron allows
it to partition preferentially into low-salinity fluids exsolved from
felsic magmas at shallow depths (Schatz et al. 2004). Thus,
tourmaline can often be found in granitoids, breccias, hydrothermal
veins and stockworks (Sillitoe 1985; London & Manning 1995;
Williamson et al. 2000; Solomovich et al. 2012). Tourmaline
breccias are generally magmatic-hydrothermal breccias cemented
mainly by tourmaline and quartz, with or without sulphide (Sillitoe
& Sawkins 1971; Warnaars et al. 1985; Baker & Andrew 1991;
Williamson et al. 2000). Many studies have been carried out on
tourmaline breccias related to Sn or Sn-W deposits in mineral
exploration (Pollard et al. 1987; Smith & Yardley 1996; Williamson
et al. 2000; Solomovich et al. 2012). Krienitz et al. (2008);
Hazarika et al. (2015) and Lambert-Smith et al. (2016) have
reported the formation of syn-ore tourmaline in orogenic Au
deposits, with emphasis on constraining the source of ore-forming
fluids. However, limited research has been conducted to examine
whether tourmaline breccia is a good proximal indicator for Au
deposits, and the interrelationship between tourmaline breccia and
Au mineralization is relatively poorly understood.
Boron has two stable isotopes – 10B (c. 20%) and 11B (c. 80%) –
which differ significantly in atomic mass and this leads to significant
isotope fractionation during geochemical processes (Palmer &
Swihart 1996). Consequently, the 11B/10B ratios of boron-bearing
environments vary widely among different geological reservoirs,

© 2019 The Author(s). Published by The Geological Society of London for GSL and AAG. All rights reserved. For permissions: http://www.geolsoc.org.uk/
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 M. Zhang et al.
with δ11B values ranging from c. −30 to +59‰ (Barth 1993; Jiang &
Palmer 1998; Marschall & Jiang 2011). Modern seawater has a
constant δ11B value of +39.6‰ (van Hinsberg et al. 2011b), whereas
the mean δ11B value of continental crust is −10 ±3‰, and is in the
range of −10 to +2.5‰ in primary mantle (Chaussidon & Albarède
1992; Chaussidon & Jambon 1994; Marschall & Jiang 2011). This
marked difference in isotopic composition makes boron isotope a
valuable tool for constraining the source of boron and fluids
responsible for boron-rich hydrothermal alteration.
Abundant tourmaline and tourmaline breccia occurrences are
present in the Longtoushan Au deposit, a known breccia-hosted
epithermal Au deposit in South China (Mao et al. 2003, 2013;
Zhong et al. 2017). The Au mineralization at Longtoushan is
associated with tourmaline, pyrite and quartz alteration (Chen 1992;
Xie & Sun 1993; Mao et al. 2003; Zhang & Zeng 2013). In this
study, we present detailed petrography and in situ analyses of
chemical and boron isotope compositions of tourmaline samples in
the rhyolite porphyry, granite porphyry and hydrothermal breccia
from the deposit, in order to better constrain the origin of tourmaline
and the ore-forming fluid, and to investigate the tourmaline
geochemistry as a potential tool in ore exploration. This study
highlights that hydrothermal tourmaline in granite-related Au
deposits is useful for identifying the ore-forming fluid and
determining the ore fluid sources.
Geological setting
Regional geology
The Dayaoshan region is situated in the southwestern part of the
Qin-Hang Metallogenic Belt, South China (Mao et al. 2011; Dang
et al. 2018). It is an important Au-Ag-W-Mo-Cu-Pb-Zn polymet-
allic metallogenic zone (60–100 t Au with grade ranging from 1.5 to
40.0 g/t; Deng 2012) in Guangxi. The Longshan Au orefield is
located in the southwestern part of the Dayaoshan region, where
over 100 Au deposits or Au prospects have been discovered (Liu &
Tang 2007), such as the large-size Fuliuling Carlin-type Au deposit
(22.4 t Au at 7.3 g/t; Cui 2009), the medium-size Longtoushan
breccia-hosted epithermal Au deposit (16 t Au at 2 g/t; Mao et al.
2013) and the medium-size Shanhua epithermal Au deposit (>5 t
Au at 3.2 g/t; Li 2008) (Fig. 1).
The Longshan Au orefield is tectonically a NE-trending anticline,
with a c. 28 km long axis and c. 12 km wide limbs, covering an area
of about 300 km2 (Fig. 1; Liu & Tang 2007). The Longshan
anticline is mainly composed of the Cambrian low-grade
metamorphosed clastic rocks of Huangdongkou Formation in the
core and the Devonian clastic rocks of Lianhuashan Formation in
the limbs (Liu & Tang 2007). Both the metamorphosed rocks and
clastic rocks were intruded in the southeastern part of the anticline
by Cretaceous felsic rocks, including granodiorite and biotite
granite at Pingtianshan, and rhyolite porphyry and granite porphyry
at Longtoushan (Fig. 1; Liu & Tang 2007; Wei & Fu 2013). The
Cambrian Huangdongkou Formation – comprising low-grade
metamorphosed turbiditic sandstone, siltstone, pelite and slate – is
the main ore host in this area (15.6 to 19.5 ppb Au; Chen 1992; Xie
& Sun 1993; Deng 2011; Wei & Fu 2013). Multiphase structural
deformation was developed in this orefield, producing a series of
NW-, NS- and NE-trending faults (Wei & Fu 2013). The ore
formation is mainly controlled by the Mesozoic NW-trending faults
(Xie & Sun 1993).
Geology of the Longtoushan Au deposit
The Longtoushan Au deposit is situated at the southeastern limb of
the Longshan anticline, 14 km NW of Guigang (Fig. 1). The deposit
is hosted in a late Mesozoic residual volcanic neck, which is in
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abrupt contact with wall rocks of the Cambrian Huangdongkou
Formation and the overlying Early Devonian Lianhuashan
Formation (Fig. 2). The latter is subdivided into a lower member
comprising conglomerate and medium- to fine-grained sandstone,
and an upper member comprising fine-grained sandstone, pelitic
siltstone and quartz sandstone (Fig. 2; Xie & Sun 1993). The
volcanic neck is a pipe-like body with an exposed area of c. 800 ×
650 m (Chen 1992). From the core outward, the volcanic neck is
composed of granite porphyry, rhyolite porphyry and ‘cryptoex-
plosive breccia’ (Figs 2 and 3; Chen 1992; Xie & Sun 1993; Zhong
et al. 2017). The term ‘cryptoexplosive breccia’ was used to refer to
hydrothermal breccia formed at shallow (<1 km) levels due to the
rhyolite porphyry emplacement (Chen 1992; Xie & Sun 1993),
which is comparable to the magmatic-hydrothermal breccia in
Sillitoe (1985). We therefore use the expression ‘magmatic-
hydrothermal breccia’ instead in the following text. Generally,
magmatic-hydrothermal breccia forms a transitional contact with
rhyolite porphyry (Fig. 4c) and surrounds the volcanic neck (Chen
1992; Xie & Sun 1993). The breccia contains angular to sub-
rounded clasts ranging in size from 1 to 30 cm, with clast material
represented by rhyolite, sandstone and pelitic siltstone, and was
mainly cemented by tourmaline, quartz and pyrite. The breccia and
rhyolite porphyry constitute the main ore-related sub-volcanic rocks
of the deposit, which were intruded by granite porphyry inside of
the volcanic neck (Figs 3, 4a and b; Chen 1992). Pingtianshan Au-
barren granitic stock is located about 2 km to the NE of
Longtoushan (Fig. 1). The stock consists of granodiorite in the
inner zone and biotite granite in the outer zone. Magmatic-
hydrothermal breccia cemented mainly by tourmaline and quartz
occurs in the roof of the granodiorite. Bulk composition analyses of
the rhyolite porphyry, granite porphyry and granodiorite show that
they are all calcalkaline, peraluminous, LREE-enriched granitic
rocks (Wang 2011), with SHRIMP zircon U–Pb ages of 103.3 ±
2.4 Ma, 100.3 ± 1.4 Ma and 96.5 ± 0.7 Ma, respectively (Chen
et al. 2008; Wang 2011), suggesting that they were formed at
different stages of the Cretaceous from the same magmatic source
(Chen et al. 2008; Wang 2011).
Au mineralization at Longtoushan was divided into two types: (1)
disseminations in rhyolite porphyry, dissemination-veins in mag-
matic-hydrothermal breccia; and (2) veins in the faults or fractures
of the clastic rocks of Lianhuashan Formation (Chen 1992; Xie &
Sun 1993). Over 20 ore bodies were found as steeply dipping veins
and lenses trending NW–NNW, with Au grades of 2.2–10.3 g/t
(avg. 4.8 g/t) in the sub-volcanic rocks and 3.0–20.0 g/t (avg. 5.4 g/t)
in the clastic rocks (Wang 2011). Ore minerals are mainly native
gold, pyrite, and minor marcasite, chalcopyrite, galena and
Fe-oxides/hydroxides such as limonite and hematite (Xie & Sun
1993; Wang 2011). Most of the native gold is visible and occurs as
inclusions (46%), interstitial (33%) and fissure-fillings (21%) in
pyrite (61%), quartz (± tourmaline, 36%) and to a lesser extent in
chalcopyrite (3%) (Huang et al. 1999). Quartz, tourmaline, sericite
and kaolinite constitute major gangue minerals (Chen 1992).
Intense hydrothermal alteration was developed throughout the
deposit: tourmaline, quartz and pyrite alteration in the rhyolite
porphyry and hydrothermal breccia; tourmaline, quartz, pyrite,
sericite and kaolinite alteration in the granite porphyry; and chlorite,
epidote and carbonate alteration in the clastic rocks (Xie & Sun
1993; Zhang & Zeng 2013). Au mineralization is closely related to
the tourmaline + pyrite + silicic alteration (Chen 1992; Xie & Sun
1993; Zhang & Zeng 2013).
Four mineralization stages were recognized at Longtoushan
(Chen 1992): (1) magmatic; (2) magmatic-hydrothermal; (3)
hydrothermal; and (4) supergene stages. And four pyrite generations
were identified: (G1) pre-ore euhedral cubic pyrite in the rhyolite
porphyry; (G2) ore-stage euhedral-subhedral quadrilateral-
pentagonal pyrite (51–72 g/t Au; Chen 1992) in the rhyolite
 Geochemistry of tourmaline: ore exploration

Fig. 1 Simplified regional geological map of the Longshan Au orefield (modified after Liu & Tang 2007; Wang 2011).

porphyry and breccias; (G3) ore-stage anhedral fractured pyrite
(0.01 wt% Au; Chen et al. 1988) in the breccias and veins; and (G4)
post-ore subhedral tetragonal pyrite in the granite porphyry (Zhu &
Zhu 2005). The magmatic stage occurred with rhyolite porphyry
emplacement, forming tourmaline and G1-pyrite in the porphyry
matrix. The magmatic-hydrothermal stage began with brecciation
and Au precipitation, forming disseminated G2-pyrite in the
rhyolite porphyry and massive quartz-tourmaline-G3-pyrite assem-
blages in the breccias. Some G3-pyrite-bearing quartz-sulphide
veins formed at the contact between sub-volcanics and wall rocks.
The hydrothermal stage extended after granite porphyry intrusion.
Early in this stage, tourmaline + quartz developed in the granite
porphyry, and Au-bearing quartz-sulphide veins formed in the distal
wall rocks. Late in this stage, G4-pyrite with sericite developed in
the granite porphyry, and chlorite, epidote and carbonate developed
in the clastic rocks. The supergene stage occurred near surface,
where the primary sulphides were transformed into oxides and
hydroxides through long-term weathering. The weathering and
leaching process was accompanied by secondary gold enrichment,
which formed some high-grade (10–20 g/t) ore-bodies in the
shallow part of the deposit (Chen 1992).

Fig. 2 Geological map of the Longtoushan Au deposit (modified after Xie Fig. 3 Cross-section profile of the Longtoushan deposit (modified after
& Sun 1993; Wang 2011). Xie & Sun 1993; Wang 2011).

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 M. Zhang et al.
Fig. 4 Field photographs showing (a) and (b) the rhyolite porphyry was intruded by the granite porphyry, (c) the transitional contact between the rhyolite
porphyry and the magmatic-hydrothermal breccia.
Sampling and analytical methods
Sampling focused on tourmaline-bearing rocks (sub-volcanics and
magmatic-hydrothermal breccias) in the Longtoushan Au deposit.
A total of thirty samples of rhyolite porphyry, granite porphyry and
Au-mineralized breccia were collected on levels between 380 and
550 m from the Longtoushan, including two samples of granite
porphyry taken from the drill core of 235–285 m in depth (c. on the
levels of 515–465 m). For comparison, four samples of Au-barren
breccia were collected in surface outcrops (on the level of 110 m)
from the Pingtianshan (c. 5 km NE of the Longtoushan deposit).
The sampling sites are shown in Figures 1 and 3. Approximately 40
thin sections made from the representative samples were studied
under the microscope, and 20 samples were selected for major
element and boron isotopic composition analysis of the tourmaline.
Major element analysis
Major element analysis of tourmaline was performed using a JEOL
JXA-8100 Electron Probe Microanalyzer (EPMA) equipped with
four wavelength-dispersive spectrometers (WDS) at the State Key
Laboratory of Geological Processes and Mineral Resources
(GPMR), China University of Geosciences (CUG, Wuhan). Prior
to the analysis, all the polished thin-sections were coated with a
20 nm-thick uniform carbon layer using the method suggested by
Zhang & Yang (2016). The EPMA operating conditions were 15 kV
accelerating voltage, 20 nA beam current and 1–5 µm beam
diameter. Standards used for calibration were: olivine (Si), rutile
(Ti), pyrope garnet (Al), almandine garnet (Fe), rhodonite (Mn),
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diopside (Mg, Ca), jadeite (Na), sanidine (K), fluorite (F) and halite
(Cl). The minimum limits of detection (in ppm) were: 135 (Si), 139
(Ti), 126 (Al), 188 (Fe), 116 (Mn), 104 (Mg), 123 (Ca), 125 (Na),
95 (K), 726 (F), and 60 (Cl). The peak counting times for all
elements except Ti and Mn were 10 s (20 s for Ti and Mn), and the
background counting time was one-half of the peak counting time
on the high- and low-energy background positions. Data were
corrected on-line using the ZAF (atomic number, absorption,
fluorescence) correction procedure.
The general formula of tourmaline is expressed as XY3Z6[T6O18]
[BO3]V3W, where X = Na+, K+, Ca2+, X□ (vacancy); Y = Fe2+,
Mg2+, Mn2+, Al3+, Fe3+, Ti4+, Li+; Z = Al3+, Fe3+, Mg2+, Fe2+; T =
Si4+, Al3+, B3+; B = B3+; V = OH1-, O2-; and W = OH1-, F1-, O2-
(Henry et al. 2011). Concentrations of light elements (e.g. H, Li and
B) and the Fe3+/ΣFe value have not been measured with EPMA.
Tourmaline structural formulae were calculated by normalizing to 15
cations in the tetrahedral and octahedral sites (T + Z + Y) according
to Henry & Dutrow (1996), assuming: (1) 3 B atoms per formula unit
(apfu) and 4 apfu (OH + F + Cl); (2) total Fe (Fetot) is all divalent;
and (3) minimal Li contents at the Y site. The B2O3 and H2O
contents are calculated based on stoichiometry. The full data are
given in the supplementary material and the statistical data are
summarized in Table 1.
Boron isotope analysis
Boron isotope analysis of tourmaline was carried out using a Nu
Plasma II Multi-Collector–Inductively Coupled Plasma–Mass
Spectrometer (MC-ICP-MS) (Nu Instrument, UK) connected to a
 Geochemistry of tourmaline: ore exploration
Resonetics-S155 Laser Ablation (LA) system (Resonetics, USA) at
the GPMR, CUG, Wuhan. Each analysis was performed with a
uniform beam diameter of 50 µm, a 10 Hz repetition rate for 40 s
ablation, and an energy flux of about 11 J/cm2. The aerosol
produced in the ablation cell was transported with high-purity He
(c. 0.7 l/min) as the carrier gas, and then was mixed with Ar and
small amounts of N2 before being carried into the plasma of the
MC-ICP-MS. Data were collected statically and simultaneously in
cycles of 100 with an integration time of 0.131 s. The analytical
procedure is similar to that described by Hou et al. (2010) and Yang
& Jiang (2012). Mass bias of the instrument and the isotopic
fractionation were calibrated by the standard-sample-bracketing
(SSB) method with tourmaline IAEA B4 (δ11B = –8.7‰) as the
external standard (Tonarini et al. 2003). Instrumental mass
fractionation (IMF) and analytical quality were assessed by replicate
analyses of tourmaline laboratory standard IMR RB1. The
determined δ11B value of tourmaline IMR RB1 is −13.10 ±
0.09‰, which is in good agreement with the recommended value
−12.96 ± 0.97‰ reported by Hou et al. (2010). The internal
precision (2σ) for individual analysis was typically around ± 0.5‰.
Boron isotope compositions of the samples are reported in δ11B
notation as: δ11Bsample (‰) = (11B/10Bsample ÷ 11B/10Bstandard−1) ×
1000, where 11B/10Bstandard = 4.043627 for NIST SRM 951
(Catanzaro et al. 1970).
Results
Sample description and tourmaline occurrence
Generally, tourmaline in hand-specimens appears as black aggre-
gates in the matrix of rhyolite porphyry and granite porphyry, and as
black matrix in the magmatic-hydrothermal breccias (Fig. 5a–5f). At
Longtoushan, three types of tourmaline (namely Tourmaline I, II,
and III) are recognized based on their textures and host rocks. The
Tourmaline I-bearing rhyolite porphyry was intruded by the
Tourmaline III-bearing granite porphyry, implying that Tourmaline
III precipitated later than Tourmaline I. Since the tourmaline
II-cemented hydrothermal breccia formation was triggered by the
emplacement of the Tourmaline I-bearing rhyolite porphyry,
Tourmaline II may have precipitated following Tourmaline I
crystallization. Tourmaline cementing the granodiorite clasts of
breccia from Pingtianshan clearly formed after granodiorite
solidification. Combined with the zircon U–Pb ages of the host
rocks mentioned above, the formation sequence of tourmaline is
interpreted to be Tourmaline I-II-III-Pingtianshan tourmaline from
early to late stage.
Tourmaline I occurs as orbicular isolated tourmaline aggregates
in the rhyolite porphyry matrix (Fig. 5a) or as orbicular tourmaline–
pyrite aggregates (Fig. 5c) in the contact between rhyolite porphyry
and magmatic-hydrothermal breccia. In the rhyolite porphyry, the
geometry of the tourmaline aggregate is similar to that of tourmaline
orbicules (or nodules) documented in granitoids worldwide
(Trumbull et al. 2008; Balen & Broska 2011; Drivenes et al.
2015; Hong et al. 2017), although the tourmaline aggregates are
smaller (0.5 to 10 mm in diameter) and rarely have a leucocratic
halo (Fig. 6a and b). Tourmaline in the aggregates commonly forms
very fine (20 to 60 µm in diameter), poorly shaped crystals, showing
dark blue-brown patchy zonings in plane-polarized light (Fig. 6a).
Minor quartz occurs as interstitial grains in the massive aggregates.
Miarolitic cavities are occasionally present inside the aggregates
(Fig. 6b). In the hydrothermal breccias, tourmaline aggregates are
commonly infilled by G2-pyrite in the core (Figs 5c and 7b), with
fine-grained brown tourmaline in the rim (Fig. 7b). Occasionally,
tourmaline proximal to the core formed pale or light-blue prismatic
crystals (50 to 100 µm in diameter) (Fig. 7b). Tourmaline I is
considered to be formed at the pre-ore stage.
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Tourmaline II is present as clusters with quartz and pyrite in the
cement of Au-mineralized magmatic-hydrothermal breccias
(Fig. 5d and f ). In general, the angular to sub-rounded clasts of
the breccia were separated by 5 to 30 vol percent open spaces prior
to the cementation (Fig. 5d and f ). Tourmaline, quartz and pyrite in
the cement form open-space filling textures, providing evidence for
their hydrothermal origin. Clusters that are mainly composed of
tourmaline usually display a roughly concentric zoning, with
brown-coloured rim and pale yellow-coloured core (Fig. 6c).
Tourmaline in the cluster rims was poorly crystallized, while it
formed subhedral acicular (100–500 µm in length) crystals in the
core (Fig. 6c). Subhedral-anhedral pyrites (0.5 to 20 mm in size) are
frequently present with tourmaline and quartz inside the clusters
(Figs 5d and 6d). Some subhedral pentagonal G2-pyrite forms
approximately straight boundaries with tourmaline aggregate
(Fig. 6d), while some anhedral G3-pyrite filled in the spaces of
tourmaline aggregate (Fig. 6d). The close association of tourmalines
and G2-G3 pyrites suggests that these tourmalines likely formed
during the magmatic-hydrothermal Au-mineralization stage not-
withstanding shortly before the peak metallogenic period. This is
consistent with the high Au contents in the tourmaline (0.75 g/t;
Chen et al. 1988) from the hydrothermal breccias.
Tourmaline III occurs as tourmaline patches and veinlets in the
granite porphyry matrix (Figs 5b and 6e). The tourmaline patches
vary in shape from sub-spherical to radial aggregates (Fig. 6f and g).
The sub-spherical tourmaline aggregates are similar in shape to
Tourmaline I in the rhyolite porphyry, but they are commonly
associated with tourmaline veinlets (80–300 µm in width).
Aggregates that are composed almost all of tourmaline show a
clear concentric zonation, with a dark-brown rim and a light-yellow
or light-blue core (Fig. 6f ). Tourmalines in the aggregates occur as
subhedral-anhedral, fine-grained (30–50 µm in length) needle-like
crystals. In the radial patches, tourmalines occur as euhedral-
subhedral prismatic crystals (up to 2 mm long), with pleochroism
ranging from dark brown to dark green in the base and pale yellow in
the tip (Fig. 6g). The tips of the tourmaline crystals were frequently
embedded by G4-pyrite (Figs 6g and 7f ), indicating Tourmaline III
formation occurred prior to post-ore stage.
Tourmaline in the Au-barren breccias from Pingtianshan
(referred to as Pingtianshan tourmaline) occurs in the black
cement of the breccias (Fig. 5e). The breccia is hosted in the
granodiorite, with angular to sub-rounded clasts (5–100 mm in size)
mainly composed of granodiorite. The cement of breccia contains
tourmaline (c. 80%) and quartz (c. 19%), and trace amount of
zircon, monazite and sphene. No Au mineralization occurred in
these breccias. Tourmalines in the cement form two generations of
crystals, with coarse-grained (200–600 µm in diameter) orange
tourmaline clasts (early-generation) embedded within fine-grained
(10–30 µm in size) green tourmaline matrix (late-generation)
(Fig. 6h).
Tourmaline chemical compositions and classification
In general, the major element analyses of representative tourmaline
show significant variations for FeO (21.31–1.44 wt%), MgO (9.79–
0.20 wt%), Al2O3 (35.35–25.35 wt%) and CaO (2.0–below the
detection limit (bdl) wt%), but small variations for SiO2 (38.44–
34.62 wt%), MnO (0.26–bdl wt%), and Na2O (2.78–1.32 wt%).
Most of the TiO2 contents are below 1.10 wt%, except for five
analyses fluctuating up to 2.20 wt% on tourmaline in the breccias
(both Au-mineralized and Au-barren). K2O and Cl values are close
to or below the detection limit. The range of F values is relatively
wide (0.8–bdl wt%), with high values (>0.5 wt%) in tourmaline
from the breccias (both Au-mineralized and Au-barren). According
to the classification scheme of Henry et al. (2011), most of the
tourmaline falls within the alkali group, showing a relatively wide
 Table 1. Statistical data of EPMA analyses on tourmaline from the Longtoushan deposit

Tur I in rhyolite porphyry Tur I in breccia Tur II

n = 13 Core (n = 6) Rim (n = 3) Core (n = 17)

Type
wt.% Mean R Max Min Mean R Max Min Mean R Max Min Mean R Max Min
SiO2 35.06 0.57 35.77 34.29 36.48 0.48 37.54 36.11 36.07 0.08 36.16 35.96 36.72 0.69 38.44 35.83
TiO2 0.56 0.50 1.09 bdl 0.77 0.40 1.37 0.35 0.46 0.19 0.72 0.28 0.39 0.24 0.93 0.10
Al2O3 32.50 1.04 34.34 30.75 30.41 1.93 31.83 26.19 31.13 0.23 31.33 30.81 32.13 1.77 35.26 29.26
FeO 14.75 1.61 18.18 11.68 6.38 1.81 8.76 3.19 10.47 1.63 12.76 9.13 4.85 1.66 7.01 1.97
MnO 0.03 0.06 0.24 bdl 0.08 0.09 0.21 0.00 0.06 0.04 0.12 0.02 0.02 0.02 0.07 bdl
MgO 1.34 0.53 2.29 0.20 8.50 0.50 9.33 7.79 4.83 0.91 5.52 3.56 8.27 0.97 9.85 6.98
CaO 0.17 0.07 0.23 bdl 1.33 0.53 2.00 0.55 0.32 0.15 0.48 0.13 0.94 0.55 2.26 0.21
Na2O 1.90 0.17 2.27 1.64 1.78 0.29 2.35 1.47 2.16 0.13 2.32 2.00 1.98 0.20 2.52 1.59
K2O 0.03 0.01 0.05 0.01 0.02 0.01 0.04 0.00 0.05 0.01 0.06 0.04 0.03 0.01 0.06 0.00
F 0.24 0.22 0.54 bdl 0.33 0.26 0.65 bdl 0.23 0.14 0.41 0.06 0.23 0.23 0.80 bdl

M. Zhang et al.
Cl 0.00 0.00 0.01 bdl 0.01 0.02 0.06 bdl 0.01 0.00 0.01 0.01 0.01 0.01 0.02 bdl
B2O3* 10.21 0.09 10.37 10.08 10.54 0.12 10.67 10.37 10.33 0.02 10.35 10.29 10.58 0.15 10.91 10.31
H2O * 3.11 0.12 3.31 2.97 3.31 0.13 3.50 3.14 3.25 0.08 3.35 3.17 3.31 0.19 3.57 2.73
Total 99.81 0.44 100.60 98.78 99.79 0.99 100.92 98.28 99.26 0.52 99.98 98.76 99.34 0.81 101.30 98.19
Formula normalized on 15 cations (T + Z + Y) (Henry & Dutrow 1996)
B 3.00 0.00 3.00 3.00 3.00 0.00 3.00 3.00 3.00 0.00 3.00 3.00 3.00 0.00 3.00 3.00
Si 5.97 0.06 6.09 5.90 6.02 0.12 6.21 5.88 6.07 0.03 6.11 6.04 6.03 0.08 6.18 5.87
AlT 0.05 0.04 0.10 0.00 0.04 0.04 0.12 0.00 0.00 0.00 0.00 0.00 0.02 0.03 0.13 0.00
AlZ 6.00 0.00 6.00 6.00 5.82 0.29 6.00 5.18 6.00 0.00 6.00 6.00 5.96 0.08 6.00 5.74
AlY 0.47 0.18 0.78 0.22 0.05 0.09 0.25 0.00 0.18 0.03 0.20 0.13 0.24 0.22 0.69 0.00
AlTot 6.52 0.16 6.78 6.22 5.91 0.34 6.25 5.18 6.18 0.03 6.20 6.13 6.22 0.28 6.73 5.74
Fe 2.10 0.24 2.61 1.64 0.88 0.25 1.23 0.44 1.47 0.23 1.80 1.28 0.67 0.23 0.97 0.27
Ti 0.07 0.06 0.14 0.00 0.09 0.05 0.17 0.04 0.06 0.02 0.09 0.04 0.05 0.03 0.12 0.01
Mn 0.00 0.01 0.03 0.00 0.01 0.01 0.03 0.00 0.01 0.01 0.02 0.00 0.00 0.00 0.01 0.00
Mg 0.34 0.13 0.57 0.05 2.09 0.14 2.33 1.93 1.21 0.22 1.38 0.90 2.02 0.23 2.42 1.73
Ca 0.03 0.01 0.04 0.00 0.23 0.09 0.36 0.10 0.06 0.03 0.09 0.02 0.17 0.10 0.40 0.04
Na 0.63 0.06 0.75 0.53 0.57 0.10 0.76 0.47 0.70 0.04 0.76 0.65 0.63 0.07 0.81 0.50
K 0.01 0.00 0.01 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.01 0.01 0.01 0.00 0.01 0.00
X-vacancy 0.34 0.06 0.44 0.24 0.19 0.08 0.31 0.05 0.23 0.03 0.27 0.20 0.20 0.12 0.43 -0.02
F 0.13 0.12 0.29 0.00 0.17 0.14 0.34 0.00 0.12 0.08 0.22 0.03 0.12 0.12 0.40 0.00
Cl 0.00 0.00 0.00 0.00 0.00 0.01 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

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 Type Tur II Tur III Pingtianshan Tur

Rim (n = 12) Core (n = 12) Rim (n = 8) n=9

wt.% Mean R Max Min Mean R Max Min Mean R Max Min Mean R Max Min

SiO2 36.34 0.49 37.10 35.63 37.00 0.62 38.02 35.93 36.69 0.38 37.56 36.25 36.06 0.31 36.73 35.61
TiO2 0.66 0.58 2.20 0.06 0.34 0.17 0.69 0.14 0.41 0.27 0.91 0.13 0.63 0.42 1.61 0.16
Al2O3 30.70 3.26 35.35 24.75 32.68 1.21 34.50 30.83 30.77 1.43 33.03 28.71 29.38 1.66 30.81 25.67
FeO 8.65 1.35 10.73 6.98 4.72 1.60 6.67 1.44 8.89 1.45 10.77 7.06 9.05 1.31 11.72 7.19
MnO 0.04 0.07 0.26 bdl 0.02 0.02 0.07 0.00 0.01 0.01 0.04 bdl 0.03 0.01 0.04 bdl
MgO 6.59 1.73 9.79 3.94 7.98 0.69 9.34 6.90 6.65 0.32 7.01 5.99 7.31 0.66 8.44 6.33

Geochemistry of tourmaline: ore exploration

CaO 0.61 0.57 1.87 0.08 0.63 0.25 1.13 0.16 0.62 0.24 0.89 0.14 0.96 0.39 1.70 0.41
Na2O 1.95 0.35 2.52 1.32 2.37 0.30 2.73 1.48 2.41 0.20 2.70 2.14 2.37 0.27 2.78 1.88
K2O 0.03 0.01 0.05 bdl 0.03 0.01 0.05 0.01 0.03 0.01 0.04 0.01 0.04 0.01 0.06 0.03
F 0.26 0.25 0.73 0.01 0.15 0.08 0.25 bdl 0.12 0.07 0.22 bdl 0.31 0.15 0.59 0.11
Cl 0.01 0.00 0.01 bdl 0.01 0.01 0.02 bdl 0.01 0.01 0.04 bdl 0.01 0.01 0.02 bdl
B2O3* 10.44 0.11 10.64 10.29 10.62 0.11 10.87 10.48 10.50 0.12 10.74 10.37 10.39 0.10 10.57 10.23
H2O * 3.25 0.19 3.54 2.80 3.47 0.08 3.61 3.29 3.35 0.29 3.52 2.59 2.99 0.41 3.49 2.48
Total 99.41 0.68 100.56 98.13 99.94 0.82 101.49 98.36 100.42 0.57 101.28 99.16 99.39 0.69 100.91 98.75
Formula normalized on 15 cations (T + Z + Y) (Henry & Dutrow 1996)
B 3.00 0.00 3.00 3.00 3.00 0.00 3.00 3.00 3.00 0.00 3.00 3.00 3.00 0.00 3.00 3.00
Si 6.05 0.05 6.17 5.98 6.06 0.08 6.16 5.93 6.07 0.03 6.11 6.01 6.03 0.05 6.08 5.92
AlT 0.00 0.01 0.02 0.00 0.01 0.02 0.07 0.00 0.00 0.00 0.00 0.00 0.01 0.02 0.08 0.00
AlZ 5.77 0.39 6.00 4.93 6.00 0.00 6.00 5.99 5.90 0.12 6.00 5.65 5.78 0.30 6.00 5.14
AlY 0.24 0.28 0.81 0.00 0.29 0.18 0.54 0.00 0.10 0.13 0.30 0.00 0.00 0.00 0.00 0.00
AlTot 6.02 0.59 6.81 4.93 6.30 0.18 6.61 5.99 6.00 0.22 6.30 5.65 5.79 0.30 6.02 5.14
Fe 1.20 0.19 1.51 0.95 0.65 0.22 0.92 0.19 1.23 0.21 1.50 0.97 1.27 0.19 1.66 1.00
Ti 0.08 0.07 0.28 0.01 0.04 0.02 0.09 0.02 0.05 0.03 0.11 0.02 0.08 0.05 0.20 0.02
Mn 0.01 0.01 0.04 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.01 0.00
Mg 1.64 0.44 2.46 0.98 1.95 0.16 2.29 1.70 1.64 0.07 1.73 1.50 1.82 0.16 2.07 1.59
Ca 0.11 0.10 0.34 0.01 0.11 0.04 0.20 0.03 0.11 0.04 0.16 0.03 0.17 0.07 0.31 0.07
Na 0.63 0.12 0.82 0.42 0.75 0.10 0.88 0.47 0.77 0.07 0.88 0.68 0.77 0.09 0.91 0.60
K 0.01 0.00 0.01 0.00 0.01 0.00 0.01 0.00 0.01 0.00 0.01 0.00 0.01 0.00 0.01 0.01
X-vacancy 0.25 0.18 0.56 0.00 0.13 0.11 0.43 0.00 0.11 0.09 0.27 -0.02 0.05 0.06 0.16 -0.01
F 0.14 0.13 0.39 0.01 0.08 0.04 0.13 0.00 0.06 0.04 0.12 0.00 0.16 0.08 0.31 0.06
Cl 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00

Tur, tourmaline; R, standard deviation.

B2O3* and H2O * were calculated by stoichiometry of B = 3 apfu and OH + F+Cl = 4 apfu, respectively.
bdl = below detection limit; The minimum limits of detection (in ppm) of Ti, Mn, Ca, K, F, Cl were: 139, 116, 123, 125, 95, 726, 60, respectively.

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 M. Zhang et al.

Fig. 5 Hand specimen and field photographs of tourmaline-rich rocks from Longtoushan and Pingtianshan. (a) Tourmaline I orbicular aggregates in the rholite
porphyry matrix. (b) Tourmaline III patches in the granite porphyry matrix. (c) Tourmaline I-pyrite aggregates in the Au-mineralized breccia. (d) Tourmaline II
cluster in the hydrothermal breccia. (e) Tourmaline in the Au-barren breccia from Pingtianshan. (f) Field photograph illustrating the abrupt contact between the
Tourmaline II-bearing hydrothermal breccia and the sandstone. Tur, tourmaline; G1(2, 3, 4)-Py, pyrite of fist (second, third and fourth) generation.

variation in the X-site vacancies (Fig. 8a). They belong to the
schorl-dravite series, with X□/(X□ + Na + K) and Mg/(Mg + Fe)
values varying from 0 to 0.5 and from 0.02 to 0.92, respectively
(Fig. 9a).
Tourmaline I falls into two chemical groups: those hosted in the
rhyolite porphyry are Fe-enriched and plot in the schorl field with
Fe# (Fe# = FeO wt%/(FeO + MgO) wt%) values above 0.8
(Fig. 9b); while those in the breccia are Fe-depleted and fall in
the dravite field (Fe# <0.78) (Fig. 9b). They all have low to moderate
Na contents (0.47–0.76 apfu; avg. 0.62 apfu) and high Al contents
(6.22–6.78 apfu; avg. 6.3 apfu). Most of the Tourmaline II has
dravitic compositions, with a few exceptions being Mg-rich schorl
in the rim (Fig. 9a). Fe# values of Tourmaline II are all below 0.8 but
show a large variation (0.71–0.17) from the rim to the core (Fig. 9b).
Na contents are similar to that of Tourmaline I, while Al contents are
in a larger range (from 4.93 to 6.81 apfu). Tourmaline III falls into
the dravite field (Fig. 9a) with Fe# values varying from 0.64 to 0.14
(Fig. 9b). They have higher Na contents (0.47–0.88 apfu; avg.
0.73 apfu) with the values higher than 0.8 mostly obtained at the
base of the radial tourmaline grains. Pingtianshan tourmaline can
also be regarded as dravite (Fig. 9a), but it shows a subtle variation
of Fe# values (from 0.59 for the early-formed coarse tourmaline to
0.48 for the late-stage microcrystalline tourmaline) (Fig. 9b), and
has the highest Na contents (0.6–0.91 apfu; avg. 0.77 apfu). In the
ternary Al-Fe-Mg discrimination diagram (Henry & Guidotti 1985)
(Fig. 8b), the schorlitic Tourmaline I plot into Field 2, while most of
the dravitic Tourmalines I, Tourmaline II, III and Pingtianshan
tourmaline plot into Fields 4, 5 and 6 (Field 2 = Li-poor granitoids;
Fields 4-5-6 = metasedimentary rocks). In addition, a close
correlation is found between Fe# value of tourmaline from
Longtoushan and its color zonings observed both on optical
transmitted-light and back-scatter electron (BSE) images: Dark-
coloured rims or bases of tourmaline aggregates and clusters in the
microphotographs (Fig. 7b and f ), or bright-coloured counterparts
in BSE images (Fig. 7a and e) have systematically higher Fe# values
than the light-coloured cores or tips (Fig. 9b) in the microphoto-
graphs (Fig. 7b and f ), and the grey-coloured counterparts in BSE
images (Fig. 7a and e).
The large Fe# variations showed in most of the Longtoushan
tourmaline (Tourmaline I, II, and III) reflect the dominant MgFe-1
exchange vector (Henry & Guidotti 1985) (Fig. 9c). The low Σ(Fe +
Mg + Mn + Ti) values (mostly <3 apfu) of these tourmalines on the
Y-site indicate Al substitution, which is consistent with their high
Al contents (>6 apfu) for the ideal schorl-dravite. Furthermore,
there is an inverse Na v. X-site vacancy correlation, suggesting that
the Al substitution is probably coupled with the alkali-deficient

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 Geochemistry of tourmaline: ore exploration

Fig. 6 Microphotographs of tourmaline from Longtoushan and Pingtianshan. (a) Fine-grained, poorly shaped Tourmaline I aggregates showing patchy
zonings. (b) Miraolitic cavity presents inside of the Tourmaline I aggregate. (c) Tourmaline II cluster showing concentric zoning. (d) Tourmaline II
intergrown with G2-pyrite and was filled by G3-pyrite. (e) Tourmaline III veinlet in granite porphyry. (f ) Sub-spherical Tourmaline III aggregate with
concentric zoning. (g) Radial Tourmaline III patches were embedded by G4-pyrite. (h) Coarse-grained orange Pingtianshan tourmaline clasts
(early-generation) embedded within fine-grained green tourmaline matrix (late-generation). Tur, tourmaline; Fsp, feldspar; Bt, biotite; Qtz, quartz;
G1(2,3,4)-Py, pyrite of fist (second, third and fourth) generation.

exchange vector X□Al(NaR2+)-1 (Henry & Guidotti 1985), where
R = Fe + Mg + Mn (Fig. 9d). A few Tourmaline II have relatively
high Ca contents (0.22–0.34 apfu) possibly involving the uvite
substitution CaMg(NaAl)-1 (Fig. 9c). However, some of the
Pingtianshan tourmaline with Σ(Fe + Mg)>3 do not have high Ca
contents, suggesting the dominant substitution is represented by Fe3
+
Al-1 exchange (Henry & Guidotti 1985) (Fig. 9c).
Boron isotopes of tourmaline
The measured B-isotope data collected for tourmaline in this study
are given in the supplementary material. The total δ11B values in
tourmaline from Longtoushan and Pingtianshan range from −14.5
to −10.2‰ (avg. −12.3‰, ± 0.5‰ 2σ, n = 71; Fig. 10; Table 2) and
overlap largely among different tourmaline types. Tourmaline I has
relatively low δ11B values (−14.5 to −12.0‰; avg. −13.2‰, n =
20), whereas Tourmaline II and III are isotopically heavier and have
nearly similar B-isotope range (−13.8 to −10.8‰; −13.8 to
−10.2‰, respectively). From Tourmaline I to III, the δ11B values
show a slightly increasing trend. In the breccia specimens collected
from Pingtianshan, tourmaline has relatively uniform δ11B values
(−12.7 to −10.8‰; avg. −12.0‰, n = 14), overlapping in the
heavier end of the range of Tourmaline II and III. No significant B-
isotope variations are observed across different color zones of the

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 M. Zhang et al.

Fig. 7 Back-scattered electron (BSE) image of (a) Tourmaline I aggregate infilled by G3-pyrite, (c) Tourmaline II cluster infilled by G3-pyrite and (e)
Tourmaline III radial patches embedded by G4-pyrite. (b), (d) and (f ) microphotographs corresponding to (a), (c) and (e), respectively.

tourmaline aggregates, or between tourmalines in the Au-miner-
alized and Au-barren breccias. The observed variations are within
analytical uncertainties.
Discussion
Boron isotope constraints
Boron isotopes are useful tracers of the source of boron and
hydrothermal fluids based on distinct δ11B values among different
reservoirs (Palmer & Swihart 1996; Jiang & Palmer 1998; Xavier
et al. 2008; Marschall & Jiang 2011; Trumbull et al. 2011).
Previous studies have shown that B-isotope variations are likely
affected by: (1) composition of the boron source; (2) B-isotope
fractionation; (3) water/rock ratios; and (4) regional metamorphism
(Palmer & Swihart 1996; Xiao et al. 1999; Drivenes et al. 2015).
B-isotope fractionation is mainly controlled by the relative
partitioning of the two isotopes of 11B and 10B between coexisting
phases, with 11B concentrated in the trigonal species and 10B
concentrated in the tetrahedral species (Palmer & Swihart 1996, and
references therein). The trigonally coordinated boron dominates in
aqueous fluids at pH of tourmaline stability (Palmer & Swihart
1996). Thus, the heavier isotope 11B is preferentially partitioned
into the fluid phase during melt-fluid and solid-fluid separation
(Palmer & Swihart 1996; Xiao et al. 1999), resulting in higher δ11B
values in hydrothermal tourmaline than that in the magmatic one
(Smith & Yardley 1996; Jiang et al. 2008), and higher δ11B values
of late-formed tourmaline from the evolved hydrothermal fluids
(Drivenes et al. 2015). The B-isotope fractionation between liquid
and vapor is weak (Liebscher et al. 2005), hence the δ11B value of
tourmaline that crystallized from vapour should approximate that of
the hydrothermal tourmaline.
The tourmaline specimens collected from Longtoushan and
Pingtianshan have a narrow range in δ11B values from −14.5 to
−10.2‰, and they fall within the boron isotope range of tourmaline
from granite and granite-related veins worldwide (−30 to −5‰,
mostly −15 to −5‰; Fig. 11c; Jiang & Palmer 1998; Marschall &
Jiang 2011), implying that the tourmaline possibly crystallized
directly from the granitic magma or from exsolved magmatic fluids.
If the tourmaline had formed during the magmatic stage, a
decreasing trend of δ11B value in tourmaline from early to late
stage would be expected due to melt-fluid isotope fractionation
(Smith & Yardley 1996; Jiang et al. 2008). The slightly increasing
δ11B trend and the large degree of overlap in δ11B values among
tourmalines from type I to type III indicate that the tourmaline from
Longtoushan probably crystallized from the exsolved fluids rather
than directly from melts. Tourmaline in the hydrothermal breccias
from Pingtianshan evidently precipitated from hydrothermal fluids.

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 Geochemistry of tourmaline: ore exploration

Fig. 8 (a) Classification based on X-site occupancy distinguishing tourmalines of the calcic group, vacancy group and alkali group (after Henry et al. 2011). (b)
Al-Fe-Mg ternary diagram (after Henry & Guidotti 1985) showing the chemical variation. The labeled fields of (b) represent: (1) Li-rich granitoid pegmatites
and aplites; (2) Li-poor granitoids, pegmatites, and aplites; (3) Fe3+-rich quartz-tourmaline rocks (altered granitoids); (4) metapelites and metapsammites with
an Al-saturated phase; (5) metapelites and metapsammites lacking an Al-saturated phase; (6) Fe3+-rich quartz-tourmaline rocks, calc-silicate rocks, and
metapelites; (7) low-Ca meta-ultramafic rocks and Cr- and V-rich metasediments; and (8) metacarbonates and metapyroxenites. Tur, tourmaline.

Fig. 9 Tourmalines from Longtoushan and Pingtianshan plotting in (a) Classification diagram Mg/(Mg+Fe) vs. X≤/( X≤+Na+K) from Henry et al. 2011.
(b) MgO vs. FeO/(FeO + MgO) (Fe#) diagram. (c) Mg (apfu) vs. Fe (apfu) diagram. (d) Altot (apfu) vs. X-site vacancies diagram. Apfu, atoms per formula
units; Tur, tourmaline. Exchange vectors are indicated by arrows.

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Fig. 10 Histogam of the δ11B values of tourmalines from Longtoushan
and Pingtianshan.
In addition, the δ11B values of tourmaline also fall in the boron
isotope range for clastic metasediments and non-marine evaporates
(Fig. 11b and c; Barth 1993; Jiang & Palmer 1998; Marschall &
Jiang 2011). A non-marine evaporate origin can be precluded,
because no evaporate has been found or reported in this area. It is
possible that boron from clastic metasediments was added into the
exsolved fluids by water-rock reaction or fluid mixing, especially
for the fluids that contributed to the formation of hydrothermal
breccias near the wall rocks, since low-grade metamorphosed clastic
rocks of the Huangdongkou Formation and clastic rocks of the
Lianhuashan Formation constitute the major wall rocks of the
deposit. However, the external boron addition may be insignificant
for tourmaline hosted in the rhyolite porphyry, considering its
isolated occurrence.
Estimation of the origin of tourmaline in magmatic-hydrothermal
systems could be made by following a semi-quantitative approach
with boron isotopes, based on experiments or empirical evaluations
on temperature-dependent fractionation of boron isotopes between
melt, fluid and tourmaline. In this study, the average δ11B value
(–12.3‰) is selected to represent the boron isotope composition of
tourmaline from Longtoushan and Pingtianshan, because the δ11B
variation of different types of tourmaline is quite small. Since the
precise temperature of tourmaline formation is difficult to be
determined directly, we took 500–400°C (based on homogeneous
temperatures of fluid inclusions in quartz co-existing with
tourmaline; Wang 2011) as its approximate equilibrium temperature
range. According to the experimental equation of Δ11Btour-fluid =
−4.2 × [1000/T(K)] + 3.52 proposed by Meyer et al. 2008, the
tourmaline-fluid fractionation factor of Δ11Btour-fluid would be −1.9
to −2.7‰. Thus, the exsolved fluids from which the tourmaline
crystallized could have δ11B values of about −10.4 to −9.6‰,
which are typical of the continental crust (Fig. 11b). Hervig et al.
Table 2. Statistic B-isotope data of tourmaline from the Longtoushan
deposit
Typewe Tur I Tur II Tur III Pingtianshan Tur
No. n = 20 n = 17 n = 20
Mean (‰) –13.19 –11.99 –11.74
R 0.74 0.87 1.02
Min (‰) –14.45 –13.80 –13.80
Max (‰) –12.00 –10.75 –10.16
R, standard deviation.
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by The Lib. East China Geol Inst. user
M. Zhang et al.
(2002) conducted experiments on B-isotope fractionation between
hydrous fluid and silicate melt, but the determined fractionation
factor (Δ11Bmelt-fluid = −10‰ at 500°C) is considered too high
(Trumbull et al. 2013). Here we assume the Δ11Bmelt-fluid is about
−5‰, as suggested by Trumbull et al. (2013). Thus, the tourmaline-
forming fluid could be derived from a granitic magma with δ11B
about −15‰, which falls within the lower range for S-type granites
worldwide (−16 to −5‰; Trumbull & Slack (2018). This is
consistent with the peraluminous bulk composition of the
Longtoushan rhyolite porphyry, granite porphyry and
Pingtianshan granodiorite (Chen 1992; Xie & Sun 1993), as
indicated by their high A/CNK values (>1.38, 1.04, 0.92–1.25,
respectively; Wang 2011). Furthermore, the magmatic zircons in
these rocks have low 176Hf/177Hf values (<0.282772) and negative
εHf(t) values, demonstrating features of crustal origin (Wang 2011).
Therefore, the boron isotope compositions suggest that tourmaline
from Longtoushan and Pingtianshan has dominantly originated
from a common felsic magma with crustal origin. Similar
interpretation is given by Yang & Jiang (2012), who attributed
the B-isotope data (−14 to −11‰) of taken for tourmaline hosted in
the Xiangshan volcanic-intrusive complex, Southeast China to a
common magmatic boron source derived from partial melting of the
Xiangshan crustal basement rocks.
Variation of tourmaline composition and fluid chemistry
Chemical composition of tourmaline is mainly controlled by the
bulk composition of host rocks, fluids and P-T-fO2 conditions of the
environment (Henry & Guidotti 1985; Slack & Trumbull 2011; van
Hinsberg et al. 2011a). In high fluid/rock systems, such as those in
breccia pipes and hydrothermal veins, tourmaline chemistry is
generally buffered by the fluid phase (Slack & Trumbull 2011).
While in low fluid/rock systems, represented by tourmalinites,
tourmaline chemistry is mainly controlled by the bulk composition
of host rocks (Smith & Yardley 1996; Slack & Trumbull 2011).
In this study, the dravitic Tourmaline I, II and Pingtianshan
tourmaline that cemented the magmatic-hydrothermal breccia
evidently precipitated in hydrothermal fluids (i.e. high fluid/rock
systems). Therefore, they would most likely reflect the composition
of the hydrothermal fluids. However, the formation environments of
tourmaline aggregates of Tourmaline I and III would be different
considering their origins. As mentioned above, these orbicular
tourmaline aggregates are similar in occurrence to the tourmaline
orbicules (or nodules). Three main hypotheses have been proposed
for the origin of tourmaline orbicules: (1) post-magmatic meta-
somatism by external boron-rich fluid (Rozendaal & Bruwer 1995);
(2) syn-magmatic crystallization of granite-derived fluids (Trumbull
et al. 2008; Balen & Broska 2011; Drivenes et al. 2015; Hong et al.
2017); (3) direct crystallization from a boron-rich granitic melt via
diffusion-limited aggregation (DLA) (Perugini & Poli 2007;
Longfellow & Swanson 2011). For tourmaline aggregates hosted
in the rhyolite porphyry, the first hypothesis can be precluded by
their isolated occurrence in the porphyry matrix. The presence of
miarolitic cavities inside of the aggregate (Fig. 6b) suggests it is
more likely that these tourmalines formed from boron-rich vapor
bubbles unmixed within the granitic melt (London et al. 1996;
Hong et al. 2017), than that they crystallized directly from the melt.
This immiscible vapor fluid could represent primary magmatic fluid
separated from the silicate melt. Thus, Tourmaline I hosted in the
n = 14 rhyolite porphyry could reflect the compositions of the felsic melt,
which is consistent with their compositions falling into the granitic
–12.0
0.69
rocks (Fig. 8b, Henry & Guidotti 1985). The tourmaline aggregates
–12.76 in the granite porphyry have likely resulted from post-magmatic
–10.67 hydrothermal alteration, as evidenced by their association with
tourmaline veinlets. Therefore, Tourmaline III would mirror the
chemistry of the late-stage hydrothermal fluids.
 Geochemistry of tourmaline: ore exploration
The marked decrease of Fe# values in Tourmaline II from rim to
core indicates that significant Fe depletion occurred in the
associated hydrothermal fluids. The composition of hydrothermal
fluids can be influenced by many factors, such as water–rock
interaction, fluid mixing and competition of equilibrium phases.
Water–rock reaction between the fluids and the clastic rocks may
occur at Longtoushan during fluid migration, but its influence on the
ferromagnesian components of fluid is hard to evaluate, due to the
lack of composition analysis of the clastic rocks. As discussed
above, the addition of boron-rich metamorphic fluid into the
tourmaline-forming fluids is possible, which is consistent with these
tourmaline compositions plotting into the metasedimentary rocks
(Fig. 8b, Henry & Guidotti 1985) and the Mg-rich nature of
tourmaline (Jiang et al. 2002). The widespread occurrence of pyrite
(especially G2-pyrite) associated with tourmaline as well as absence
of other Fe-rich minerals in the cement indicate that Fe depletion in
the hydrothermal fluids was probably related to Fe incorporation
into pyrites. Thus, the Fe# decrease corresponding to the fine-scale
concentric zonation of Tourmaline II is tentatively interpreted to be
mainly caused by fluid mixing and pyrite crystallization.
The presence of the MgFe-1 exchange vector indicates high
proportions of Fe2+ in tourmaline. If tourmaline is enriched in Fe3+,
a compositional trend between ‘oxy-dravite’ and povondraite
(the so-called O-P trend) or the Fe3+Al-1 exchange vector would
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Fig. 11 (a) Compilation of boron isotopes from
other Au deposits. Data from Jiang et al. (2002),
Krienitz et al. (2008), Xavier et al. (2008), Tornos
et al. (2012), Beaudoin et al. (2013), Baksheev
et al. (2015), Lambert-Smith et al. (2016), Molnar
et al. (2016), Su et al. (2016), Jin et al. (2017),
Ranta et al. (2017). (b) Range of boron isotopes
from various boron reservoirs in nature. (c) Range
of boron isotopes in tourmaline from different
geological settings. Data from Barth (1993),
Palmer & Swihart (1996), Jiang & Palmer (1998),
Trumbull et al. (2011) and Trumbull & slack
(2018).
be expected (Henry & Dutrow 2012; Hazarika et al. 2015).
However, neither the O-P trend nor the Fe3+Al-1 exchange is shown
in Longtoushan tourmaline, which implies very low Fe3+/Fe2+ ratio
in it. Negligible Fe3+/Fe2+ ratios in Longtoushan tourmaline reflect
the reducing fluid conditions under which these tourmalines
precipitated (van Hinsberg et al. 2011b; Henry & Dutrow 2012;
Hazarika et al. 2015; Ranta et al. 2017). This is consistent with the
widespread occurrence of pyrite, tourmaline-pyrite assemblages
and the absence of oxidized minerals (e.g. magnetite and anhydrite)
in the porphyries and breccias at Longtoushan. Thus, we suggest
that tourmaline at Longtoushan crystallized from reduced fluids
with low oxygen fugacity (estimated log fO2 < FMQ, where FMQ is
the fayalite-magnetite-quartz oxygen buffer).
The relatively low Na contents (avg. 0.66 apfu) and high average
X-site vacancy of Longtoushan tourmaline with clear X□Al(NaR)-1
exchange (Fig. 9d) indicate that they were formed in low-salinity
fluids (cf. van Hinsberg et al. 2011b; Henry & Dutrow 2012;
Hazarika et al. 2015; Ranta et al. 2017). This inferred low fluid
salinity is supported by results from fluid inclusion studies of quartz
associated with tourmaline (1.6 to 10.9 wt% NaCl equiv; Wang
2011). Such a low-salinity fluid is analogous to the vapour fluid
unmixed with melts, or a metamorphic-hydrothermal fluid (Hazarika
et al. 2015). Experiments conducted by Schatz et al. (2004) show that
boron partitions preferentially into the vapour over the high-salinity
 M. Zhang et al.
brine in hydrous granitic melt at low pressures (1 kbar). Furthermore,
experimental studies by Pichavant (1981); Hervig et al. (2002) and
Schatz et al. (2004) also demonstrate that boron partitions favourably
into the vapour over the felsic melt. The above experimental results
could explain the low fluid salinity inferred from Tourmaline I
composition and further support a boron-rich vapour fluid origin of
the tourmaline aggregate in the rhyolite porphyry. The low fluid
salinity inferred from compositions of Tourmaline II and III is
attributed to dilution of the evolved magmatic hydrothermal fluids by
the addition of metamorphic fluids.
Implications for ore exploration
There is a long-term question whether the occurrence of tourmaline
and tourmaline breccia, or the compositional features in major
elements and boron isotopes of the tourmaline, could indicate the
presence or absence of metal enrichment (e.g. Au, Cu) (Trumbull
et al. 2011). Tourmaline is a common constituent of hydrothermal
breccias in granitoid-related ore systems, including Au ± Cu and Sn
± W deposits, such as the Kidston Au deposit in Australia (Baker &
Andrew 1991), the Los Bronces-Rio Blanco Cu deposit in Chile
(Warnaars et al. 1985) and the Sn-W deposits in SW England
(Smith & Yardley 1996; Williamson et al. 2000). The distribution of
tourmaline in these ore deposits is usually much greater than the
dimension of the orebodies, suggesting that tourmaline has potential
to be a useful indicator for ore exploration. Indeed, tourmaline has
been employed as a pathfinder mineral for Archean lode-Au deposit
in Big Bell and Mount Gibson, Australia (Jiang et al. 2002).
The intrinsic mechanism of tourmaline and tourmaline breccia
occurrence associated with mineralization is generally revealed by
previous experimental efforts (e.g. Pichavant 1981; Hervig et al. 2002;
Schatz et al. 2004). In magmatic-hydrothermal systems, extensive
tourmalinization of host-rocks could reflect the circulation of boron-
rich hydrothermal fluids, and ultimately indicates the presence of
boron-rich magmas (Trumbull et al. 2008; van Hinsberg et al. 2011a).
According to the experiments by Pichavant (1981, 1987), boron could
lower the solidus temperature and significantly promote the solubility
of H2O in granitic melt at low pressures. Further experiment by Schatz
et al. (2004) suggests that boron preferentially partitions into the
aqueous vapour phase relative to the melt (vapour-melt partition
vapor=melt
coefficient of boron: DB ¼ 3:1–6:3; Schatz et al. 2004). These
distinctive effects of boron on silicate melts and its incompatible
behavior would lead to the generation of H2O-saturated magma, and
boron-rich aqueous vapour fluids unmixed from the melt (Pollard
et al. 1987). Importantly, composition analysis of fluid inclusions
formed at 300–700°C and below 1 kbar from magmatic-hydrothermal
deposits showed that Cu and Au are spectacularly enriched in vapour
phases (Heinrich et al. 1999). Further, Pokrovski et al. (2008)
provided experimental evidence for the dramatic increase of Cu, Au
and Pt in sulphur-rich acidic magmatic-hydrothermal vapours. Thus,
the vapour unmixed with melt would have potential to scavenge and
concentrate metals (e.g. Au, Cu) from the melt. During fractional
crystallizaiton, the small vapour would coalesce and migrate upward,
and accumulate in the magma roof, increasing the internal pressures
(Parmigiani et al. 2017). When the hydrostatic pressure exceeds the
lithostatic one, fractures would eventually be generated by hydraulic
fracturing. The succeeding open-space filling of H2O-B-rich fluids
would result in the formation of magmatic-hydrothermal tourmaline
breccia (Sillitoe 1985). For Au-rich fluids, boiling due to rapid
decompression during brecciation is critical for Au mineralization
(Zhang 1997a, b, 2015). Moreover, the enhanced permeability of
brecciated rocks provided by the open spaces would help to elevate ore
grades (Sillitoe & Sawkins 1971). Therefore, the occurrence of
tourmaline breccia in granite-related systems may indicate a H2O-B-
rich environment that is favourable for ore enrichment and ore
deposition. However, we cannot ignore that there are still many
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tourmaline breccias that are barren of economic mineralization
(London & Manning 1995; Slack 1996). The formation of ore
deposits also depends on other various factors, including the metal
abundance of the magma and the dynamic of the magmatic chamber.
Thus, the occurrence of tourmaline and tourmaline breccia observed in
the field alone may be insufficient to accurately evaluate their potential
for ore exploration, and further comprehensive petrographic and
geochemical study of tourmaline is indispensable.
The exploration potential of boron and boron isotopes has been
investigated by many researchers. An early study of the relation
between boron isotopes and distances from mineralization in an
undisclosed area of Russia has been reported by Shergina &
Kaminskaya (1965). They showed that the ratio of 11B/10B
decreases as the ore zone is approached, without giving further
information about the mineralizaton. Trumbull et al. (2011)
observed two distinct groups of δ11B values in tourmaline
between mineralized and barren zone in the Blackbird Co-Cu-Au-
Bi-Y-REE district, America, with tourmalines in the barren
metasedimentary rocks having low δ11B values (−21.7 to −7.6‰)
and tourmalines in the mineralized stratabound and breccias having
δ11B values of −6.9 to +3.2‰. They attributed the B-isotope
distinction of tourmaline to formation from different fluid sources,
yet emphasized that light elements like B and S did not necessarily
indicate the source of metals such as Cu, Au. Similarly, in an
extensive study of tourmaline composition from the Cornubian
granites, England, London & Manning (1995) disproved that B was
necessarily involved in the transport and concentration of Sn. An
increasing number of B-isotope studies of tourmaline have been
conducted for IOCG and orogenic Au deposits (Jiang et al. 2002;
Krienitz et al. 2008; Xavier et al. 2008; Tornos et al. 2012;
Beaudoin et al. 2013; Baksheev et al. 2015; Lambert-Smith et al.
2016; Molnar et al. 2016; Su et al. 2016), which have successfully
distinguished ore-forming fluids of metamorphic, magmatic and
marine fluid sources (Fig. 11a). Results of two B-isotope studies in
magmatic-related Au deposit have exhibited magmatic-hydrother-
mal fluid B-isotope features (–11.2 to 0‰; Fig. 11a; Jin et al. 2017;
Ranta et al. 2017). In this study, B-isotope compositions determined
do not show significant differences in δ11B signatures of tourmaline
between the Au-mineralized (−13.8 to −10.8‰) and Au-barren
breccias (−12.7 to −10.8‰). However, the overall B-isotope data
(−14.5 to −10.2‰) demonstrate dominant magmatic-hydrothermal
fluids of continental crust origin, consistent with the magmatic-
hydrothermal Au mineralization of the deposit. Thus, we suggest
the B-isotope composition of tourmaline could serve as a good
tracer to identify the source of ore-forming fluids at Longtoushan.
Meanwhile, continuing investigations in Pingtianshan area are
recommended.
In terms of major element compositions determined in this study,
distinctive features have been shown in the Fe# values of
tourmaline. The pre-ore Tourmaline I in the rhyolite porphyry is
Fe-rich (Fe# >0.84) and the ore-stage Tourmaline II and III are Mg-
rich (Fe# <0.71), with a few pre-ore Tourmaline I in the breccia also
being Mg-rich (Fe# <0.78). A similar compositional trend of
tourmaline has been found by Jiang et al. (2002) in Big Bell and
Mount Gibson Archean lode-Au deposits, Australia, where Mg-rich
tourmalines with Fe/(Fe + Mg) ratios of 0.11–0.30 are closely
associated with gold and sulphide ores, and Fe-rich tourmalines in
sulphide-poor schists have Fe/(Fe + Mg) ratios of 0.30–0.63.
However, tourmaline in many granite-related Sn deposits shows
an opposite compositional trend. For example, in the San Rafael
granite-related Sn deposit, Southeastern Peru, ore-stage tourmaline
is Fe-rich and pre-ore tourmaline is Mg-rich (Mlynarczyk &
Williams-Jones 2006). Pirajno & Smithies (1992) even proposed
that the systematic increase of Fe# in tourmaline is positively
correlated with the proximity to the source of the mineralizing fluids
in the granite-related Sn-W deposits of South Africa. While
 Geochemistry of tourmaline: ore exploration
Esmaeily et al. (2009) emphasized that the host rock composition
could affect the Fe# value of tourmaline, and disapproved the
qualitative application of this proximity index at Nezamabad, Iran.
The discrepancy of tourmaline Fe# trend between hydrothermal Au
and Sn deposits may be caused by the different ore-forming
conditions between Au and Sn. Thus, we propose that the Fe-poor
dravitic tourmaline would serve as an Au fertility indicator at
Longtoushan. In addition, the significant decline of Fe# that
corresponds to the microscopic-scale concentric zonation of
Tourmaline II does not indicate the distance to the source fluids.
In light of the high fluid/rock ratio and reducing fluid conditions
proposed above, the Fe# decrease of the G2-G3 pyrite-related
tourmaline is possibly due to ore-forming process that are
accompanied by Fe incorporation into pyrites, as well as fluid
mixing with external metamorphic Fe-poor fluids. Further studies
involving in situ analysis of ore element contents (e.g. Au, As, Cu)
of tourmaline, tourmaline chronology and bulk compositions of
wall rocks could provide more evidence to explore the nature and
connection between tourmalinization and Au minerlization at
Longtoushan.
Conclusions
Besides tourmaline in the Au-barren breccia from Pingtianshan,
three types of tourmaline are identified at Longtoushan: (1) pre-ore
Tourmaline I in the rhyolite porphyry and hydrothermal breccia; (2)
ore-stage Tourmaline II in the hydrothermal breccia; and (3) ore-
stage Tourmaline III in the granite porphyry.
Major element compositions of the tourmalines show that they
belong to the alkali-deficient schorl-dravite series. Only Tourmaline
I in the rhyolite is Fe-rich schorl (Fe# >0.84). Other types of
tourmaline are dravite with large Fe# variation (0.78–0.14).
Compared with Pingtianshan tourmaline, tourmalines from
Longtoushan have relatively low Na contents (avg. 0.66 apfu) and
are characterized by a dominant MgFe-1 exchange vector.
The total spectrum of δ11B values in tourmaline from this study
falls into a narrow range between −14.5 and −10.2‰, which
indicates dominant magmatic-hydrothermal fluids of continental
crust origin.
Combining the petrography, major element and B-isotope
composition of tourmaline from this study, we suggest that
tourmaline at Longtoushan may have originated from a boron-rich
vapour fluid unmixed from granitic magmas. Tourmaline breccia
was likely formed by hydraulic fracturing, with open spaces infilled
by boron-rich boiling fluids released from the magma. The boron-
rich vapour fluid may provide a favourable agent for Au
transportation and concentration, and boiling of the Au-bearing
fluids during brecciation would be critical for the precipitation of Au-
bearing pyrites, which could compete with coexisting tourmaline for
Fe, leaving tourmaline Fe-depleted. We propose the Fe-poor dravitic
tourmaline could be used as prospecting guide at Longtoushan Au
deposit. This Fe-poor dravitic tourmaline in hydrothermal breccias is
possibly also useful for Au exploration in other granite-related
mineral systems with similar geological settings.
Acknowledgements We would like to thank Prof. Kuidong Zhao and
Prof. Shuiyuan Yang for their help with LA-MC-ICP-MS and EMPA analyses.
Engineer Qiqiang Wu is thanked for helping with the field work. Constructive
comments and suggestions by Dr Matthieu Harlaux and an anonymous reviewer,
and detailed edits and comments by Chief Editor Prof. Scott Wood significantly
improved the manuscript, and are greatly appreciated. Chief Editor Prof. Scott
Wood and the staff editor are thanked for the editorial handling.
Funding This study was financially supported by two National Natural
Science Foundation of China (NSFC) grants (No. 41373048 and No. 41773030)
to Dehui Zhang.
Correction notice: Figure 1 has been corrected.
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