Applied Clay Science 190 (2020) 105585

Contents lists available at ScienceDirect

Applied Clay Science

journal homepage: www.elsevier.com/locate/clay

Research Paper

Chlorite alteration in porphyry Cu systems: New insights from mineralogy T

and mineral chemistry
⁎
Bing Xiaoa, Huayong Chena, , Pete Hollingsb, Yu Zhangc, Yuzhou Fenga, Xi Chend
a
Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute sof Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China
b
Geology Department, Lakehead University, Thunder Bay, Ontario P7B 5E1, Canada
c
School of Geosciences and Info-Physics, Central South University, Changsha 410083, China
d
School of Geoscience and Technology, Southwest Petroleum University, Chengdu 637001, China

A R T I C LE I N FO A B S T R A C T

Keywords: Chlorite, an important mica-like clay mineral formed in a variety of geological environments, is sensitive to bulk
Chlorite alteration rock composition and physicochemical conditions during formation, and thus an ideal mineral to investigate the
Titanite nature of fluid-rock reactions and mass transfer during hydrothermal fluid interaction. Samples of chlorite from
Precursor minerals alteration systems around three large porphyry Cu deposits, Tuwu (NW China), Atlas (Philippines) and
Mineral chemistry
Xiaokelehe (NE China), were used to investigate element transfer from pyroxene, amphibole, and biotite to
Porphyry deposit
chlorite.
By calculating the chlorite formation temperatures using the chlorite empirical thermometer, the temperature
ranges for biotite, hornblende, and pyroxene chloritization in this study were broadly the same (around 270 °C).
Contacts are gradational between biotite and chlorite grains along biotite cleavage but abrupt between horn-
blende/pyroxene and chlorite. Concentrations of K2O, Na2O, TiO2, and SiO2 decreased gradually from biotite to
chlorite, whereas MgO, FeOT, Al2O3, and MnO concentrations increase. Different forms of hydrothermal titanite
grains occurred commonly in the biotite, hornblende, and pyroxene chloritization processes in the porphyry
systems studied, and titanite formed during chloritization of biotite had higher Al2O3 and F contents compared
to titanite that formed during chloritization of hornblende and pyroxene. Given the high Al2O3 and F contents in
biotite, this suggested the concentrations of these components in titanite may be controlled by the composition
of the precursor minerals. The FeOT and MgO contents of chlorite correlated with the composition of the pre-
cursor mineral, whereas their TiO2 and Al2O3 contents did not, with all chlorite having similar contents. This
suggested that FeOT and MgO contents of chlorite were more likely controlled by the precursor minerals,
whereas TiO2 and Al2O3 were probably controlled by the similar formation temperature of chlorite without
obvious influence of precursor minerals. Thus, TiO2 and Al2O3 contents of chlorite could be more suitable for use
as a mineral geochemical vector for hydrothermal center in porphyry deposits.

1. Introduction (such as biotite, hornblende and pyroxene) as a result of hydrothermal

fluid (Walker, 1993). Recent studies at the Cenozoic Batu Hijau por-
Chlorite, a ubiquitous hydrous phyllosilicate characterized by an phyry deposit (Indonesia) have shown that chlorite compositions in
alternating stack of talc-like and brucite-like sheets (Lauf, 2010), is a porphyry systems can provide lateral and vertical elemental variation
common product of diagenesis, low-grade metamorphism and hydro- trends (Wilkinson et al., 2015). Wilkinson et al. (2015) showed that Ti,
thermal alteration. Chlorite group minerals have a wide range of stoi- V and Al concentrations of chlorite decrease exponentially with in-
chiometric compositions which may be related to the compositions of creasing distance from the orebodies, whereas K, Li, Ca, Sr, Ba, Mn, Co,
precursor minerals, hydrothermal fluids and temperatures during for- Ni, Zn and Pb concentrations increase. These variations can be observed
mation (Kranidiotis and Maclean, 1987). As one of the most widely at least 4.5 km from the porphyry orebodies at Batu Hijau, giving a
developed alteration minerals in porphyry deposits (Seedorff et al., much larger footprint than whole rock geochemical anomalies (gen-
2005; Sillitoe, 2010; Zhong et al., 2012; Dora and Randive, 2015), erally ≤1.5 km; Wilkinson et al., 2015), which could be used to help
chlorite mainly forms through replacement of ferromagnesian minerals focus exploration for porphyry deposits. Based on the relationship

⁎
Corresponding author.
E-mail address: [email protected] (H. Chen).

https://doi.org/10.1016/j.clay.2020.105585
Received 1 December 2019; Received in revised form 7 February 2020; Accepted 23 March 2020
Available online 29 March 2020
0169-1317/ © 2020 Elsevier B.V. All rights reserved.
B. Xiao, et al. Applied Clay Science 190 (2020) 105585

between the trace element concentrations in chlorite and formation 1981). The main lithostratigraphic units in the district are the Cretac-
temperatures of the Paleozoic Tuwu porphyry deposit, Xiao et al. eous Managa Group (Cansi and Pandan Formations) and the Oligocene
(2018) found that elements, such as Sc, V, Ti, Ga, Li, Sr, Mn, and Zn Naga Formation (Philippine Bureau of Mines and Geosciences, 1986).
may be controlled by temperature, whereas B, K, Ca, Co, Ni, Rb, Cs and The dominant igneous rock at Atlas is the Lutopan stock which is a
Ba are probably not only controlled by temperature but also by host mineralization-related quartz diorite porphyry that intruded the Cre-
rock composition. Other elements such as Na, Cr, Cu, Sn and Pb may taceous Cansi Formation (Divis, 1983; Deng et al., 2015). Hydrothermal
not be affected by changes in temperature. The detailed process and alteration and mineralization at the Atlas CueAu deposit have been
mechanism of element transport and enrichment during chlorite al- divided into potassic, propylitic, and phyllic zones (Sillitoe and Gappe,
teration is relatively poorly understood (Hart et al., 2016), and the 1984).
impacts that the compositions of precursor minerals have on chlorite
have not been investigated in detail (Wilkinson et al., 2015; Brzozowski 2.3. Tuwu porphyry Cu deposit
et al., 2018; Xiao et al., 2018).
Previous studies have focused mainly on alteration of biotite to The Paleozoic Tuwu porphyry deposit (metal reserve: 104 Mt. ore @
chlorite in hydrothermally altered granites (Eggleton and Banfield, 0.67 wt% Cu; Xiao et al., 2018) is located in the Dananhu-Tousuquan
1985; Parneix et al., 1985; Yuguchi et al., 2015; Wang et al., 2018), belt of the Chinese Tianshan orogenic belt (Fig. 1), about 1–4 km north
with the chloritization of hornblende and pyroxene receiving relatively of the Kanggur Fault. The main lithostratigraphic unit in the mine
little attention. To address this gap in knowledge, this contribution district is the Carboniferous Qi'eshan Group (Shen et al., 2014), which
combines detailed mineralogical observations with geochemical ana- is mainly composed of basalt, andesite, dacite and tuff, and the baslt is
lyses to characterize how the composition of chlorite in porphyry sys- the main country rock of the Tuwu porphyry deposit. The Qi'eshan
tems is affected by the composition and texture of biotite, hornblende, Group was intruded by diorite, tonalite porphyry, quartz-albite por-
and pyroxene that have been partially replaced. phyry and quartz porphyry in the Carboniferous. Hydrothermal al-
teration and mineralization of the Tuwu deposit can be divided into
2. Geological setting porphyry mineralization (including potassic, propylitic and phyllic
stages) and late overprinting mineralization stages, related to the to-
2.1. Xiaokelehe porphyry Cu deposit nalite porphyry and quartz-albite porphyry, respectively. Hypogene Cu
mineralization formed during both the porphyry and overprinting mi-
The newly discovered Mesozoic Xiaokelehe porphyry CueMo de- neralization events (Xiao et al., 2018).
posit (250 Mt. ore @ 0.2 wt% Cu and @ 0.03–0.8 wt% Mo; Shang,
2017) is situated in the northeastern part of the Great Hingan Range 3. Sampling and analytical procedures
metallogenic belt, NE China (Fig. 1). The main lithostratigraphic units
in the district are the Neoproterozoic Dawangzi and Jixianggou for- Granodiorite porphyry samples from Xiaokelehe, quartz diorite
mations, and the Lower Cretaceous Guanghua Formation, which were porphyry samples from Atlas, and basalt samples from the Tuwu Cu
intruded by granodiorite porphyry, monzonite, diorite porphyry and deposit, were collected. Over 50 polished thin sections were prepared
granite porphyry in the Late Jurassic (Shang, 2017). At Xiaokelehe, and studied using transmitted and reflected light microscopy, and re-
CueMo mineralization dominantly occurs in the granodiorite porphyry presentative samples were then analysed with EMPA to aid mineral
and rarely extends outward into the surrounding volcanic and sedi- identification and determine compositions. Samples containing chlorite
mentary rocks. Four alteration stages have been identified, consisting of were all selected from major alteration zones of the porphyry deposits.
sodic-calcic, potassic, chlorite, and phyllic alteration (Shang, 2017). They include chlorite alteration of; 1) biotite in the Xiaokelehe grano-
diorite; 2) biotite in the Atlas quartz diorite; 3) hornblende in the Altas
2.2. Atlas porphyry CueAu deposit quartz diorite and 4) pyroxene in the Tuwu basalt.
Back-scattered electron (BSE) and major element analyses of
The giant Atlas porphyry CueAu deposit (1420 Mt. ore @ 0.45 wt% chlorite, biotite, hornblende, pyroxene, apatite, magnetite, rutile, il-
Cu and 0.24 g/t Au; Singer et al., 2008, Zhang et al., 2019), Cebu Is- menite and titanite were conducted using a Cameca SX100 electron
land, Philippines (Fig. 1), is the oldest porphyry deposit in the Phi- microprobe at the School of Geoscience and Technology, Southwest
lippines with a whole-rock RbeSr age of 108 ± 1 Ma (Walther et al., Petroleum University with a JEOL JXA-8230 Superprobe. EMPA results
are listed in Electronic Appendix 1. The microprobe was operated at an
accelerating voltage of 15 kV, a beam current of 20 nA, and a beam size
of 5 μm. Natural minerals and synthetic oxides were used as standards.
Matrix corrections were performed using the ZAF correction program
supplied by the instrument manufacturer (Bernard and Van, 1986).

4. Petrography and mineral chemistry

4.1. Sample descriptions and chlorite alteration

4.1.1. Biotite from Xiaokelehe granodiorite porphyry

The Xiaokelehe granodiorite porphyry displays porphyritic-like
textures and is mainly composed of plagioclase (~30 vol%), quartz
(~20 vol%), biotite (~10 vol%), K–feldspar (~10 vol%), with minor
hornblende (Fig. 2a) as phenocrysts. Plagioclase and K–feldspar phe-
nocrysts occur as subhedral to euhedral crystals, that have been re-
placed by illite. Biotite has been partially or wholly altered to chlorite
+ titanite ( ± apatite; Fig. 2b).
The Xiaokelehe biotite contains 36.72–38.63 wt% SiO2,
Fig. 1. Location of the Tuwu, Atlas and Xiaokelehe porphyry Cu deposits in this 0.00–0.28 wt% CaO, 13.18–14.15 wt% MgO, 14.20–17.70 wt% FeOT,
study. 14.12–17.08 wt% Al2O3, 2.95–3.86 wt% TiO2, 0.08–0.22 wt% Na2O,

2
B. Xiao, et al. Applied Clay Science 190 (2020) 105585

Fig. 2. Hand specimen photographs and microphotographs showing representative mineral assemblages, textural features and chloritization of the Xiaokelehe
granodiorite porphyry, Atlas quartz diorite porphyry, and Tuwu basalt. (a) The Xiaokelehe granodiorite porphyry contains plagioclase, quartz, biotite, and K–feldspar
phenocrysts generally < 0.5 cm (51°40′53″N, 124°32′5.3″E, Elevation = −50 m); (b) Plagioclase and biotite phenocrysts of the Xiaokelehe granodiorite porphyry in
a fine-grained groundmass of K–feldspar and quartz. Biotite is partially replaced by chlorite. (c) The Atlas quartz diorite porphyry contains plagioclase, biotite, and
amphibole phenocrysts generally < 0.4 cm (10°20′0.25″N, 123°43′46.58″E, Elevation = 91 m); (d) Plagioclase and biotite phenocrysts of the Atlas quartz diorite
porphyry in a fine-grained groundmass of K–feldspar, quartz, and plagioclase. Biotite and amphibole is replaced by chlorite. (e) The Tuwu basalt contains pyroxene
phenocrysts generally < 0.1 cm (42°6′29″N, 92°36′7″E, Elevation = 749 m); (f) Pyroxene and plagioclase phenocrysts in the Tuwu basalt. Pyroxene have been partly
replaced by chlorite. Mineral abbreviations: Ap, apatite; Bt, biotite; Chl, chlorite; Hbl, hornblende; Kfs, K–feldspar; Ilm, ilmenite; Pl, plagioclase; Pyx, pyroxene; Qz,
quartz; Ttn, titanite.

0.08–0.16 wt% MnO, 7.34–9.47 wt% K2O. Using a Mg-(Fe2+ + Mn)- (~50 vol% plagioclase, ~25 vol% amphibole and minor biotite) in a
(Fe3+ + AlVI + Ti) biotite classification diagram (Foster, 1962), microcrystalline quartz and feldspar groundmass (Fig. 2c). Minor
Xiaokelehe biotite is classified as magnesio-biotite (Fig. 3a). magnetite, zircon and apatite occur as accessory minerals. Plagioclase
and K–feldspar phenocrysts occur as subhedral to euhedral crystals,
replaced by secondary illite. Biotite phenocrysts occur as euhedral
4.1.2. Biotite and hornblende from Atlas quartz diorite porphyry
crystals, and have been partially or wholly altered (Fig. 2d). The
The Atlas quartz diorite porphyry contains ~75 vol% phenocrysts

3
B. Xiao, et al. Applied Clay Science 190 (2020) 105585

Fig. 3. Classification of biotites, hornblendes, and pyroxenes according to the nomenclature of Foster (1962); Leake et al. (1978), and Morimoto (1988), respectively.

assemblages formed by chlorite alteration of biotite include chlorite + along the cleavage (Fig. 4a), and has a composition range of
titanite ( ± magnetite). Hornblende phenocrysts also occur as euhedral 27.96–29.84 wt% SiO2, 0.03–0.14 wt% CaO, 18.40–22.17 wt% MgO,
crystals and have been partially altered to chlorite + titanite ( ± il- 16.32–22.00 wt% FeOT, 18.08–18.73 wt% Al2O3, 0.18–0.25 wt% MnO,
menite ± apatite; Fig. 2d). 0.01–0.15 wt% K2O. The Cr2O3, TiO2, P2O5 and Na2O abundances are
Atlas biotite contains 34.79–37.34 wt% SiO2, 0.05–0.38 wt% CaO, close to, or below, the detection limits. On the chlorite classification
15.51–18.01 wt% MgO, 12.50–15.49 wt% FeOT, 14.10–15.32 wt% diagram, Xiaokelehe chlorite mainly falls in the pycnochlorite field
Al2O3, 3.32–4.81 wt% TiO2, 0.09–0.25 wt% Na2O, 0.26–0.56 wt% (Fig. 4e; Deer et al., 1962). Needle-like titanite grains formed along
MnO, 4.99–7.57 wt% K2O. According to the classification diagram of cleavage of biotite are coeval with chlorite and contain 29.16–31.48 wt
Foster (1962), Atlas biotite is magnesio-biotite, similar to Xiaokelehe % SiO2, 25.17–35.45 wt% TiO2, 24.09–28.38 wt% CaO, 5.10–9.65 wt%
(Fig. 3a). Atlas hornblende contains 47.85–49.91 wt% SiO2, Al2O3, 1.09–1.74 wt% FeOT, 0.00–0.29 wt% MgO, 2.08–5.21 wt% F.
10.28–11.12 wt% CaO, 15.00–16.34 wt% MgO, 10.79–12.22 wt The contents of Cr2O3, Na2O, MnO, P2O5, K2O and Cl are close to, or
% FeOT, 6.80–7.97 wt% Al2O3, 0.85–1.43 wt% TiO2, 1.18–1.64 wt% below, the detection limits in all titanite samples in this study (Elec-
Na2O, 0.32–0.53 wt% MnO, 0.21–0.47 wt% K2O. In the classification tronic Appendix 1).
diagram of Leake (1978), the Atlas hornblendes fall in the magnesium
hornblende field (Fig. 3b).
4.2.2. Atlas chlorite and titanite
Two types of chlorite are recognized at Atlas. Type A chlorite has
4.1.3. Pyroxene from Tuwu basalt partially replaced biotite whereas Type B chlorite has partially replaced
Tuwu basalt samples have medium- to fine-grained porphyritic hornblende (Fig. 4b and c). Atlas Type A chlorite is mainly developed
textures (Fig. 2e), and contain 10 vol% to 20 vol% euhedral to sub- along the biotite cleavage and contains 27.90–30.67 wt% SiO2,
hedral pyroxene and plagioclase phenocrysts in a fine-grained, inter- 0.03–0.36 wt% CaO, 18.77–21.68 wt% MgO, 17.68–20.43 wt% FeOT,
sertal to intergranular groundmass, with accessory apatite and mag- 15.79–19.05 wt% Al2O3, 0.00–0.29 wt% TiO2, 0.00–0.05 wt% Na2O,
netite. Plagioclase occurs as subhedral to euhedral crystals, and has 0.32–0.73 wt% MnO and 0.00–0.10 wt% K2O. Needle-like titanite also
typically been partly replaced by illite. Pyroxene has been partially or occurs along cleavages in biotite and contains 30.81–31.88 wt% SiO2,
wholly altered to chlorite + titanite ( ± epidote; Fig. 2f). 26.19–35.07 wt% TiO2, 24.82–28.13 wt% CaO, 1.88–8.26 wt% Al2O3,
Unaltered Tuwu pyroxene occurs as subhedral to euhedral pheno- 1.17–3.20 wt% FeOT, 0.03–2.32 wt% MgO, and 0.43–4.41 wt% F. Type
crysts (up to 500 μm in length), usually forming aggregates. It contains B chlorite occurs along the margins and interiors of hornblende crystals,
49.58–51.98 wt% SiO2, 19.31–21.53 wt% CaO, 14.43–15.47 wt% MgO, and contains 26.97–28.90 wt% SiO2, 0.02–0.24 wt% CaO,
6.89–9.08 wt% FeOT, 3.00–4.39 wt% Al2O3, 0.68–1.14 wt% TiO2, 18.08–21.17 wt% MgO, 17.06–20.99 wt% FeOT, 18.73–20.16 wt%
0.33–0.42 wt% Na2O, 0.13–0.23 wt% MnO, 0.00–0.02 wt% K2O, in- Al2O3, 0.00–0.25 wt% TiO2, 0.00–0.03 wt% Na2O, 0.40–0.66 wt%
dicating an augitic composition (Wo41–45En43–45Fs12–15; Fig. 3c). MnO, 0.00–0.05 wt% K2O. Atlas Type A chlorite has similar Si contents
to Type B chlorite, and both types are predominantly pycnochlorite
4.2. Chlorite and titanite compositions (Fig. 4e). Titanite grains occur as irregular crystals and contain
30.86–31.28 wt% SiO2, 32.11–36.94 wt% TiO2, 27.45–28.36 wt% CaO,
4.2.1. Xiaokelehe chlorite and titanite 1.35–4.22 wt% Al2O3, 0.80–1.84 wt% FeOT, 0.00–0.26 wt% MgO, and
In the Xiaokelehe samples, chlorite has typically replaced biotite 0.10–1.59 wt% F.

4
B. Xiao, et al. Applied Clay Science 190 (2020) 105585

Fig. 4. BSE images (a, b, c, d) showing chloritization of biotite, hornblende, and pyroxene. (a) the Xiaokelehe granodiorite porphyry and (b) the Atlas quartz diorite
porphyry are partially replaced by chlorite, with needle-like titanite grains formed along cleavage of biotite; (c) hornblende of the Atlas quartz diorite porphyry and
(d) pyroxene of the Tuwu basalt are partially replaced by chlorite, with irregular titanite; (e) chlorite classification diagram according to Deer et al. (1962); (f)
chloritization temperatures according to chlorite thermometer of Cathelineau (1988). Mineral abbreviations: Bt, biotite; Chl, chlorite; Ep, epidote; Hbl, hornblende;
Pyx, pyroxene; Ttn, titanite.

4.2.3. Tuwu chlorite and titanite 5. Discussion

Tuwu chlorite occurs along the cleavage of pyroxene and is asso-
ciated with epidote and titanite (Fig. 4d). It contains 26.98–29.20 wt% 5.1. Chlorite alteration processes in porphyry deposits
SiO2, 0.12–0.34 wt% CaO, 17.42–18.54 wt% MgO, 21.25–22.64 wt
% FeOT, 17.46–18.66 wt% Al2O3, 0.00–0.05 wt% TiO2, 0.00–0.03 wt% Chlorite displays wide compositional variations that are related to
Na2O, 0.28–0.39 wt% MnO, and 0.03–0.11 wt% K2O. Tuwu chlorite the pressure, temperature and redox conditions, as well as bulk-rock
mainly falls in the pycnochlorite field (Fig. 4e). Irregular titanite crys- and fluid composition during its formation (Bailey, 1988; Vidal et al.,
tals contain 30.74–31.34 wt% SiO2, 30.09–32.09 wt% TiO2, 2001). Previous studies suggested that chloritization of biotite occurs
26.76–27.13 wt% CaO, 3.51–3.74 wt% Al2O3, FeOT = 2.31–2.77 wt%, over a wide temperature range below about 400 °C (Yuguchi et al.,
0.26–0.51 wt% MgO, and 0.23–0.40 wt% F. 2015), accompanied by the formation of epidote, muscovite, rutile,

5
B. Xiao, et al. Applied Clay Science 190 (2020) 105585

Fig. 5. Concentration profiles through biotite, hornblende, and pyroxene to chlorite. Mineral abbreviations: Bt, biotite; Chl, chlorite; Hbl, hornblende; Pyx, pyroxene;
Ttn, titanite.

albite, etc. (Dilles and Einaudi, 1992; Seedorff et al., 2005). Two ap- temperatures of 249–278 °C (average of 264 °C) for Xiaokelehe chlorite;
proaches have been proposed for using the chemical composition of 212–282 °C (average of 264 °C) for Atlas Type A chlorite; 265–304 °C
chlorite to determine its formation temperature: (1) the use of empirical (average of 282 °C) for Atlas Type B chlorite; and 254–295 °C (average
calibrations based on the tetrahedral aluminium (AlIV) occupancy as a of 273 °C) for Tuwu chlorite (Fig. 4f). The temperature ranges for all the
function of measured temperature in geothermal systems (e.g. chlorites studied are therefore broadly the same.
Cathelineau, 1988); and (2) thermodynamic calculation of equilibrium Fig. 5 illustrates linear compositional profiles through chlorite that
conditions for chlorites (Walshe, 1986). The second method could not has replaced biotite, hornblende and pyroxene. In the Xiaokelehe and
be used for chlorites in this study as they do not all coexist with quartz. Atlas samples, chlorite has replaced biotite along the cleavage and is
Accordingly, we calculated the chlorite formation temperatures using associated with the formation of abundant titanite grains. In all samples
the chlorite thermometer of Cathelineau (1988) which yielded the K2O, Na2O, TiO2, and SiO2 concentrations decrease, while MgO,

6
B. Xiao, et al. Applied Clay Science 190 (2020) 105585

Fig. 6. Binary plots Al2O3 + FeOT vs. (a) TiO2 and (b) F of titanites, showing the magmatic and hydrothermal fields of titanite from Xie et al. (2018); (c) and (d) F and
Al2O3 contents of titanite formed with chlorite replacement of Xiaokelehe biotite, Atlas biotite and hornblende, and Tuwu pyroxene; (e) and (f) F and Al2O3 contents
of Xiaokelehe biotite, Atlas biotite and hornblende, and Tuwu pyroxene.

FeOT, Al2O3 and MnO concentrations increase from biotite to chlorite means that chlorite is more likely to inherit part of biotite structure
along biotite cleavage, over a gradual transition zone (Fig. 5). Both ti- during alteration which would explain the gradual transition between
tanite and chlorite contain no or limited Na, K and Cl, meaning that Na, biotite and chlorite, compared to the abrupt transition between horn-
K, and Cl must be released into entering the hydrothermal fluid. In the blende/pyroxene and chlorite (Fig. 5).
compositional profiles through hornblende and pyroxene to chlorite,
there are sharp contacts between hornblende or pyroxene and chlorite. 5.2. Genesis of hydrothermal titanite in chlorite alteration
Atlas hornblende contains 1.18–1.64 wt% Na2O and 0.21–0.47 wt%
K2O, and Tuwu pyroxene contain 0.33–0.42 wt% Na2O, whereas Na2O Titanite is a dominant Ti-bearing phase and widespread accessory
and K2O contents of chlorite formed from Atlas hornblende and Tuwu mineral in igneous rocks, metamorphic rocks and hydrothermal mineral
pyroxene are either close to or below the detection limits of EPMA. This deposits, such as porphyry and skarn deposits (Xie et al., 2019). In this
indicates that chloritization releases Na and K from Atlas hornblende, study, titanite coexists with chlorite formed by the alteration of biotite,
and Na from Tuwu pyroxene to enter into the hydrothermal fluid. hornblende and pyroxene in all samples from the three porphyry sys-
Biotite and chlorite are both phyllosilicate minerals, whereas pyroxene tems. In the Xiaokelehe and Atlas samples with biotite chloritization,
is a single-chain silicate and hornblende is a double chain silicate (Deer needle-like titanite grains occur along cleavage of biotite (Figs. 4a, c),
et al., 1962). The similarity between the structure of chlorite and biotite whereas it occurs as irregular crystals associated with Atlas hornblende

7
B. Xiao, et al. Applied Clay Science 190 (2020) 105585

Fig. 7. TiO2, Al2O3, FeOT, and MgO contents of chlorite, biotite, hornblende and pyroxene.

8
B. Xiao, et al. Applied Clay Science 190 (2020) 105585

and Tuwu pyroxene chloritization (Figs. 4b, d). Titanite grains in this mineral exploration in the porphyry ore deposits at Batu Hijau, which
study all exhibit good negative linear relationships between was proved to be efficient, especially for trace element of chlorite. Our
Al2O3 + FeOT and TiO2, and positive relationships between study primarily focused on the influence of precursor minerals on major
Al2O3 + FeOT and F (Fig. 6), indicating that Al and Fe substitute into elements of chlorite, and understanding the influence on trace elements
the Ti octahedral site with an additional Al-involving reaction ((Al, are very meaningful to understand the mechanism of chlorite alteration
Fe)3+ + (F, OH)− ↔ Ti4+ + O2−; Xie et al., 2018). In addition, nearly and for using chlorite elements as geochemical vectoring for mineral
all titanite grains plot within the hydrothermal titanite field (Figs. 6a, exploration of porphyry deposits, which will be the direction of this
b) consistent with their occurrence with hydrothermal chlorite. study in the future.
The occurrence of titanite associated with chlorite alteration re-
quires the transfer of Ca and Ti from the precursor minerals or be 6. Conclusions
supplied by the fluid. The Xiaokelehe biotite, Atlas biotite and horn-
blende, and Tuwu pyroxene have high TiO2 contents (2.95–3.86 wt%, This study focuses on chlorite alteration of biotite, hornblende and
3.32–4.81 wt%, 0.85–1.43 wt% and 0.68–1.14 wt%, respectively). This pyroxene in porphyry deposits, which records the nature of fluid-rock
suggests that the Ti of titanite was likely derived from the precursor reactions and mass transfer during hydrothermal fluid interaction.
minerals. The CaO contents of Xiaokelehe and Atlas biotite are very low Chlorite is more likely to inherit part of biotite structure during al-
(0.00–0.28 wt% and 0.05–0.38 wt%), indicating the Ca of titanite were teration due to similar crystal structure and shows transitional altera-
mainly supplied by the fluid during the chloritization Xiaokelehe and tion process compared to hornblende and pyroxene. Different forms of
Atlas biotite, while Atlas hornblende and Tuwu pyroxene have high hydrothermal titanite grains occur commonly in the chloritization
CaO contents (10.28–11.12 wt% and 19.31–21.53 wt%), indicating the processes in the porphyry systems studied, indicating movement of Ti
precursor minerals could also provide Ca of titanite during chlorite and Ca between fluids and altered minerals. FeOT and MgO contents of
alteration. Our results also suggest that Ti could be commonly trans- chlorite are likely controlled by precursor minerals, whereas TiO2 and
ported into hydrothermal solutions in porphyry Cu deposits, although it Al2O3 are probably controlled by formation temperature of chlorite
is typically considered to be an immobile element in hydrothermal without obvious influence of precursor minerals. Consequently, the
environments (Jiang et al., 2005). Titanite formed during chloritization composition and texture of precursor minerals affect chlorite and tita-
of biotite at Xiaokelehe and Atlas contains higher Al2O3 and F contents nite compositions, and TiO2 and Al2O3 of chlorite may be suitable for
than titanite formed in Atlas hornblende and Tuwu pyroxene (Figs. 6c, use as a mineral geochemical vectoring tool for hydrothermal centers in
d), meanwhile, Xiaokelehe and Atlas biotite has higher Al2O3 and F exploration for porphyry deposits.
contents than Atlas hornblende and Tuwu pyroxene (Figs. 6e, f). These
results suggest that Al2O3 and F contents of titanite may be controlled Credit author statement
by the chemistry of the precursor minerals.
Bing Xiao: Conceptualization, Investigation, Sampling, Software,
5.3. Impacts of precursor mineral on chlorite compositions Writing-original draft preparation, Visualization.
Huayong Chen: Methodology, Supervision, Writing-Reviewing and
The hydrothermal fluids that generated chlorite alteration at Editing, Validation.
Xiaokelehe, Atlas, and Tuwu are all related to porphyry systems and are Pete Hollings: Writing-Reviewing.
here assumed to have been broadly similar, consistent with the similar Yu Zhang and Yuzhou Feng: Sampling.
formation temperatures (Fig. 4f). TiO2 and Al2O3 contents of all the Xi Chen: Data curation.
chlorites studies are generally similar (Figs. 7a, c), regardless of the
variable TiO2 and Al2O3 contents of precursor minerals (Figs. 7b, d). Declaration of Competing Interest
Titanite coexists with chlorite during the alteration of biotite, horn-
blende and pyroxene in all samples from the three porphyry systems, The authors declare that they have no known competing financial
which indicates that Ti was oversaturated during the formation of interests or personal relationships that could have appeared to influ-
chlorite. Al2O3 contents of Atlas hornblende and Tuwu pyroxene are far ence the work reported in this paper.
below that of chlorite from the alteration of Atlas hornblende and Tuwu
pyroxene, indicating the Al of chlorite were supplied by the fluid during Acknowledgements
the chloritization of Atlas hornblende and Tuwu pyroxene. Atlas
hornblende and Tuwu pyroxene chloritization are often accompanied This study was funded by the Chinese National Science Fund for
by feldspar sericitization, during which Al could be released (Parneix Chinese National Science Foundation (41702068 and U1603244),
et al., 1985; Morad et al., 2009) and could be partially introduced into Distinguished Young Scholars (41725009) and Chinese academy of
the chlorite from hornblende and pyroxene alteration. Moreover, sciences strategic pilot science and technology special (XDB18000000).
Wilkinson et al. (2015) found that TiO2 and Al2O3 contents of chlorite
correlate positively with formation temperature of chlorite. This would Appendix A. Supplementary data
suggest that the TiO2 and Al2O3 contents of chlorite may be mainly
controlled by their formation temperatures rather than the concentra- Supplementary data to this article can be found online at https://
tions of Ti and Al in the precursor minerals. The FeOT and MgO contents doi.org/10.1016/j.clay.2020.105585.
of chlorite are, however, influenced by their precursor minerals. For
example, FeOT contents of chlorite increase with its decreasing trend in References
precursor minerals (Fig. 7e, f); MgO contents are variable in precursor
minerals but uniformly high in chlorite altered from biotite (Fig. 7g, h). Bailey, S.W., 1988. Chlorites: structures and crystal chemistry. Rev. Mineral. Geochem.
In summary, FeO and MgO contents of chlorite are clearly affected by 19, 347–403.
precursor minerals compared to Ti2O and Al2O3 which are possibly Bernard, P.C., Van Grieken, R.E., 1986. Classification of estuarine particles using auto-
mated electron microprobe analysis and multivariate techniques. Environ. Sci.
mainly controlled by temperature or other factors, and we can use Al Technol. 20, 467–473.
and Ti contents of chlorite to identify the centers of hydrothermal Brzozowski, M.J., Samson, I.M., Gagnon, J.E., Linnen, R.L., Good, D.J., Ames, D.E.,
systems of porphyry system which is related to individual mineralized Flemming, R., 2018. Controls on the chemistry of minerals in late-stage veins and
implications for exploration vectoring tools for mineral deposits: an example from the
porphyry intrusion. In the study of Wilkinson et al. (2015), the major, Marathon Cu-Pd deposit, Ontario. Canada. J. Geochem. Explor. 190, 109–129.
minor and trace element chemistry of chlorite were used as a tool for

9
B. Xiao, et al. Applied Clay Science 190 (2020) 105585

Cathelineau, M., 1988. Cation site occupancy in chlorites and illites as a function of Shen, P., Pan, H.D., Zhou, T.F., Wang, J.B., 2014. Petrography, geochemistry and geo-
temperature. Clay Miner. 23, 471–485. chronology of the host porphyries and associated alteration at the Tuwu Cu deposit,
Deer, W.A., Howie, R.A., Iussman, J., 1962. Rock-forming minerals: sheet silicates. NW China: a case for increased depositional efficiency by reaction with mafic hos-
Longmans, Green, and Co., Ltd., London. trock? Mineral. Deposita 49, 709–731.
Deng, J.H., Yang, X.Y., Zhang, Z.F., Santosh, M., 2015. Early cretaceous arc volcanic suite Sillitoe, R.H., 2010. Porphyry copper systems. Econ. Geol. 105, 3–41.
in Cebu Island, Central Philippines and its implications on paleo-Pacific plate sub- Sillitoe, R.H., Gappe, I.M., 1984. Philippine porphyry copper deposits: geologic setting
duction: Constraints from geochemistry, zircon U–Pb geochronology and Lu–Hf iso- and characteristics. CCOP-ESCAP Tech. Publicat. 14, 89.
topes. Lithos 230, 166–179. Singer, D.A., Berger, V.I., Moring, B.C., 2008. Porphyry copper deposits of the
Dilles, P.H., Einaudi, M.T., 1992. Wall-RockA lterationa nd HydrothermaFl low Pathsa World—database and grade and tonnage models. In: 2008: U.S. Geological Survey
boutt he Ann-Maso Porphyry Copper Deposit, Nevada–a 6-Kin vertical Open-File Report 2008–1155, accessed June 1, 2011, at. http://pubs.usgs.gov/of/
Reconstruction. Econ. Geol. 87, 1963–2001. 2008/1155/.
Divis, A.F., 1983. The geology and geochemistry of Philippine porphyry copper deposits. Vidal, O., Parra, T., Trotet, F., 2001. A thermodynamic model for Fe-Mg aluminous
In: Hayes, D.E. (Ed.), The Tectonic and Geologic Evolution of Southeast Asian Seas chlorite using data from phase equilibrium experiments and natural pelitic assem-
and Islands—Part 2. American Geophysical Union, Washington D.C.. blages in the 100° to 600 °C, 1 to 25 kb range. Am. J. Sci. 301, 557–592.
Dora, M.L., Randive, K.R., 2015. Chloritisation along the Thanewasna shear zone, Walker, J.R., 1993. Chlorite polytype geothermometry. Clay Clay Miner. 41, 260.
Western Bastar Craton, Central India: Its genetic linkage to Cu–Au mineralisation. Walshe, J.L., 1986. A six-component chlorite solid solution model and the conditions of
Ore Geol. Rev. 70, 151–172. chlorite formation in hydrothermal and geothermal systems. Econ. Geol. 81,
Eggleton, R.A., Banfield, J.F., 1985. The alteration of granitic biotite to chlorite. Am. 681–703.
Mineral. 70, 902–910. Walther, H.W., Forster, H., Harre, W., Kreuzer, H., Lenz, H., Muller, P., Raschka, H., 1981.
Foster, M.D., 1962. Interpretation of the composition and a classification of the chlorites. Early Cretaceous porphyry copper mineralization on Cebu Island, Philippines, dated
In: U.S. Geological Survey Professionsal Papes, pp. 1–31. with K–Ar and Rb–Sr methods. Geologisches Jahrbuch 48, 21–35.
Hart, L., Wilkinson, J., Armstrong, R., Araujo, D., 2016. Element mobility during pro- Wang, Z.Q., Chen, B., Yan, X., Li, S.W., 2018. Characteristics of hydrothermal chlorite
pylitic alteration in porphyry ore systems: a case study of the Oyu Tolgoi deposits, from the Niujuan Ag-Au-Pb-Zn deposit in the north margin of NCC and implications
Mongolia. Appl. Earth Sci. 125, 84. for exploration tools for ore deposits. Ore Geol. Rev. 101, 398–412.
Jiang, S.Y., Wang, R.C., Xu, X.S., Zhao, K.D., 2005. Mobility of high field strength ele- Wilkinson, J.J., Chang, Z.S., Cooke, D.R., Baker, M.J., Wilkinson, C.C., Inglis, S., Chen,
ments (HFSE) in magmatic-, metamorphic-, and submarine-hydrothermal systems. H.Y., Bruce Gemmell, J., 2015. The chlorite proximitor: a new tool for detecting
Phys. Chem. Earth Parts A/B/C 30, 1020–1029. porphyry ore deposits. J. Geochem. Explor. 152, 10–26.
Kranidiotis, P., MacLean, W.H., 1987. Systematics of chlorite alteration at the Phelps Xiao, B., Chen, H.Y., Hollings, P., Wang, Y.F., Yang, J.T., Wang, F.Y., 2018. Element
Dodge massive sulfide deposit, Matagami, Quebec. Econ. Geol. 82, 1898–1911. transport and enrichment during propylitic alteration in Paleozoic porphyry Cu mi-
Lauf, R.J., 2010. Collector's guide to the chlorite group. Rocks Miner. 85, 318–325. neralization systems: Insights from chlorite chemistry. Ore Geol. Rev. 102, 437–448.
Leake, B.E., 1978. Nomenclature of amphiboles. Mineral. Mag. 42, 533–563. Xie, G.Q., Mao, J.W., Bagas, L., Fu, B., Zhang, Z.Y., 2019. Mineralogy and titanite geo-
Morad, S., El-Ghali, M.A.K., Caja, M.A., Al-Ramadan, K., Mansurbeg, H., 2009. chronology of the Caojiaba W deposit, Xiangzhong metallogenic province, southern
Hydrothermal alteration of magmatic titanite: evidence from Proterozoic granitic China: implications for a distal reduced skarn W formation. Mineral. Deposita 54,
rocks, Southeastern Sweden. Can. Mineral. 47, 801–811. 459–472.
Morimoto, N., 1988. Nomenclature of pyroxenes. Mineral. Petrol. 39, 55–76. Yuguchi, T., Sasao, E., Ishibashi, M., Nishiyama, T., 2015. Hydrothermal chloritization
Parneix, J.C., Beaufort, D., Dudoignon, P., Meunier, A., 1985. Biotite chloritization pro- processes from biotite in the Toki granite, Central Japan: Temporal variations of of
cess in hydrothermally altered granites. Chem. Geol. 51, 89–101. the compositions of hydrothermal fluids associated with chloritization. Am. Mineral.
Philippine Bureau of Mines and Geosciences, 1986. Geology and mineral resources of the 100, 1134–1152.
Philippines. Geology 1, 406. Zhang, Y., Tian, J., Hollings, P., Gong, L., Alburo, I., Berador, A.E., Francisco, D.G., Li, J.,
Seedorff, E., Dilles, J.H., Proffett Jr., J.M., Einaudi, M.T., Zurcher, L., Stavast, W.J.A., Chen, H.Y., 2019. Mesozoic porphyry Cu–Au mineralization and associated adakite-
Johnson, D.A., Barton, M.D., 2005. Porphyry deposits: characteristics and origin of like magmatism in the Philippines: insights from the giant Atlas deposit. Mineral.
hypogene features. In: Society of Economic Geologists, Economic Geology 100th Deposita. https://doi.org/10.1007/s00126-019-00907-2.
Anniversary, pp. 251–298. Zhong, R.C., Li, W.B., Chen, Y.J., Huo, H.L., 2012. Ore-forming conditions and genesis of
Shang, Y.G., 2017. Study on the Geological Characteristics and Metallogenic Prognosis of the Huogeqi Cu–Pb–Zn–Fe deposit in the northern margin of the North China Craton:
Xiaokele and 972 Highland Gold Polymetallic Deposit in Daxinganling. Jilin evidence from ore petrologic characteristics. Ore Geol. Rev. 44, 107–120.
University, Jilin, China, Heilongjiang Province Master Degree Thesis.

10