Provenance and tectonic setting of middle-upper Devonian sandstones in the
Qinling Orogen (Shanyang area): New insights from geochemistry, heavy
minerals and tourmaline chemistry
Guanzhong Shi, Hua Wang, Chuanyan Huang, Shuiyuan Yang, Guangzeng
Song
PII:
DOI:
Reference:

S0040-1951(16)30384-5
doi: 10.1016/j.tecto.2016.09.023
TECTO 127255

To appear in:

Tectonophysics

Received date:
Revised date:
Accepted date:

3 November 2015
25 August 2016
15 September 2016

Please cite this article as: Shi, Guanzhong, Wang, Hua, Huang, Chuanyan, Yang,
Shuiyuan, Song, Guangzeng, Provenance and tectonic setting of middle-upper Devonian sandstones in the Qinling Orogen (Shanyang area): New insights from geochemistry, heavy minerals and tourmaline chemistry, Tectonophysics (2016), doi:
10.1016/j.tecto.2016.09.023

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Provenance and Tectonic Setting of Middle-Upper Devonian sandstones in the
Qinling Orogen (Shanyang area): New insights from Geochemistry, Heavy

Minerals and Tourmaline Chemistry

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Guanzhong Shi1, 2, Hua Wang1, 2*, Chuanyan Huang1, 2, Shuiyuan Yang3, Guangzeng

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Song4

1. Key Laboratory of Tectonics and Petroleum Resources, Ministry of Education,

China University of Geosciences, Wuhan 430074, China

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2. Faculty of Earth Resources, China University of Geosciences, Wuhan 430074,

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China

3. State Key Laboratory of Geological Processes and Mineral Resources, China

University of Geosciences, Wuhan 430074, China

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4. School of Earth Resource and Environments, University of Jinan, Jinan 250022,

China

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*corresponding author: huawang@cug.edu.cn

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Abstract: Devonian sandstones in the Shanyang area crop out in the southern part of
the Qinling Orogenic Belt. Geochemical analyses show that the sandstones are
enriched in Zr and have high Th/U and Rb/Sr ratios indicating the sandstones
underwent repeated recycling. Zircon, tourmaline, apatite, rutile and anatase are the
predominant heavy minerals while minor minerals include spinel, pyroxene, ilmenite
and magnetite. The mineral compositions of detrital tourmaline grains indicate that
the alkali compositional subgroup dominates; schorl and dravite are the main
tourmaline species. A tourmaline composition environment discrimination diagram
shows that about 70% grains are consistent with metapelite, metapsammite, and
calc-silicates sources and about 30% of grains are from granitoids and associated

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pegmatites, and aplites. Metamorphic and granitic rocks in the Qinling Complex area
are potential provenance. Overall data from geochemistry, heavy minerals and

tourmaline chemistry suggests the Devonian sandstones were extensively recycled in

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a foreland basin setting rather than at a passive continental margin.

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Key words: heavy mineral analysis, tourmaline chemistry, Devonian sandstones,

provenance analysis, Qinling orogenic belt, Paleozoic orogeny.

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1. Introduction

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The Qinling-Dabie-Sulu Orogens of central China extend WNW-ESE for about

1000 km (Fig. 1a). They were constructed by northward subduction of the Shangdan

Ocean and subsequent collision between the North China Block (NCB) and South

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China Block (SCB) along the Shangdan suture zone (e.g. Mattauer et al., 1985;
engor, 1985; Kroner et al., 1993; Hacker et al., 1998; Zhai et al., 1998; Faure et al.,

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2001, 2003). Their structural framework and division into litho-tectonic units have
been debated for decades (Li et al., 1993; Ames et al., 1996; Zhang et al., 1997, 2001;

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Enkin et al., 1992; Faure et al., 2003, 2008; Dong et al., 2011, Lin et al., 2015).
Devonian sedimentary rocks exposed in the Southern part of the Qinling region have
been variously interpreted as: i) a molasse trough in front of the Qinling belt
(Mattauer et al., 1985), ii) a passive continental margin (Meng, 1994; Zhang et al.,
2001), and iii) a foreland basin (Li et al., 1994; Dong et al., 2011, 2013). The
sandstones record important information about the Qinling Orogens and so
determining their origin and provenance would help us to understand the tectonic
setting and geodynamic evolution.
Geochemical analyses and heavy mineral studies of sedimentary rocks are
frequently used for provenance studies (e.g. Yan et al., 2002; Yang et al., 2007; Long

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et al., 2008; Moosavirad et al., 2011; L et al., 2015). The chemical composition of
clastic sediments is controlled by a complex interplay between several variables such

as source composition, extent of weathering, transportation and diagenesis (e.g.

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Taylor and McLennan, 1985; Bhatia and Crook, 1986; Fedo et al., 1995, 1997a, b).

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Geochemical indicators for bulk-rock geochemistry, such as the major elements

(Fe2O3+MgO), TiO2, Al2O3/SiO2, K2O/Na2O, and trace elements like La, Th, Sc, Zr
and their ratios are frequently used (e.g. Bhatia, 1983; Bhatia and Crook, 1986;

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McLennan et al., 1993; Cullers, 1994, 2000; Kemkin and Kemkina, 2015; Gao et al.,

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2016).

Heavy minerals such as garnet, tourmaline, apatite, spinel and zircon have been

widely used in provenance analysis (e.g., von Eynatten and Gaupp, 1999; Morton et

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al., 2005; Bojar et al., 2010; Olivarius et al., 2014). Chemical analyses of heavy
minerals may permit the determination of source rocks and subsequent sediment

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transport directions (e.g. Pinto et al., 2007; Morton et al., 2011; Tsikouras et al., 2011).
Tourmaline is a mineral frequently found in igneous and metamorphic rocks (e.g.,

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Dutrow and Henry, 2011; van Hinsberg et al., 2011a, b). The environment diagram by
comparing Al-Fe-Mg abundances connects tourmaline composition with parent rock
types (Henry and Guidotti, 1985) and provides valuable information about
provenance (e.g. Burinek et al., 2003; opjakov et al., 2009).
This paper presents new data on Qinling Devonian sandstone geochemistry,
heavy mineral assemblages and tourmaline chemistry to constrain the source rocks
and determine the tectonic setting.

2. Geological Setting
2.1 Geological framework

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The Qinling Orogen is divided into four zones, from north to south: the Southern
North China Block (S-NCB), North Qinling Belt (NQB), South Qinling Belt (SQB)

and Northern South China Block (N-SCB) (Fig. 1a; Mattauer et al., 1985; Zhang et al.,

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1995; Dong et al., 1997, 2011; Xu et al., 2002; Li et al., 2007). Six lithostratigraphic

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units crop out in our study area, from north to south: the Kuanping Unit, Erlangping
Unit, ophiolite unit, Qinling Complex, Devonian sandstone unit and Douling
Complex (Fig. 1b).

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The Kuanping unit contains a group of metamorphic rocks and a group of

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terrestrial clastic rocks (Dong et al., 2011). The metamorphic group is dominated by
greenschists, amphibolites, quartz-rich micaschists and marbles. Protoliths of the

amphibolites are N-MORB and E-MORB tholeiitic basalts of ca. 940 Ma age (Zhang

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and Zhang, 1995; Diwu et al., 2010). The clastic rock group was deposited in the

2011a, b).

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Early Paleozoic and has undergone greenschist facies metamorphism (Dong et al.,

The Erlangping Unit consists predominantly of andesite, basalt, dolerite, and

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sedimentary rocks intruded by gabbro, diorite and granodiorite plutons (Zhao et al.,
2012; Zhang et al., 2012). Zircons from gabbro, tonalite and trondjemite have yielded
Early Paleozoic ages ranging from ca. 510 to ca. 430 Ma (Tian, 2003; Zhao et al.,
2012; Dong et al., 2016 and refs. therein). This unit has been interpreted as a
continental arc (Faure et al., 2008), intra-oceanic arc (e.g., Hacker et al., 2004;
Ratschbacher et al., 2003), and back-arc basin based on its rock associations and
geochemistry (Dong et al., 2011, 2016).
The ophiolite unit contains mafic and ultramafic bodies, tholeiitic pillow basalts,
mafic volcaniclastic rocks and cherts enclosed within a metapelitic matrix. In the
Shangzhou area the rocks are strongly sheared, and overprinted by greenschist to

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lower amphibolite facies metamorphism. Ordovician to Silurian radiolarians have
been found in bedded cherts and constrain the time of formation (Zhang and Tang,

1983).

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The Qinling Complex consists of biotite-plagioclase gneisses, garnet-sillimanite

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gneisses, mica-quartz schists, graphite-bearing marbles and amphibolites, with lenses

of eclogites and migmatites. It underwent at least two episodes of metamorphism
reaching peak eclogite facies metamorphism at ca. 480-500 Ma, followed by

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retrograde metamorphism at 420-460 Ma. Migmatites displaying melanosome and

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leucosome segregation formed by partial melting of orthogneiss, paragneiss, and

amphibolites (Faure et al., 2008; Yu et al., 2016). Lower Paleozoic gabbroic and

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2013; Zhang et al., 2015).

granite plutons intrude this unit (Faure et al., 2008; Wang et al., 2009; Zhang C L.,

The Devonian sandstone unit crops out further south, south of the Shangdan

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Fault. It is of typical old red sandstone facies, and comprised of the Liuling Group and
Jiuliping Group (Fig. 1c). The Liuling Group is up to 10 km thick and characterized

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by thick bedded sandstone, mudstone-sandstone alternations, and intraformational

conglomerates (Hacker et al., 2004; He et al., 2005; Yan et al., 2007). In ascending
order, it includes the Middle Devonian Niuerchuan (D2n), Chigou (D2c) and
Qingshiya (D2q) formations (ca. 393-382 Ma), and also the Late Devonian Tongyusi
Formation (D3ty, ca. 382-359 Ma; Zhang et al., 2001). Ripple marks indicating a
southward paleocurrent direction are observed in the Qingshiya and Niuerchuan
formations (Fig. 2a). Meng, (1994), Mei et al., (1999), and Zhang et al., (2001) provide
detailed stratigraphic sequences and descriptions of sedimentary structures. Several

intraformational conglomerate beds are exposed near the Shangdan Fault Zone, and
contain pebbles of metamorphic, volcano-clastic rocks and limestone intensively

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reworked by the Shangdan Fault (Yu et al., 1995; Dong et al., 2013).
Upper Devonian terrigenous sediments of the Jiuliping Group and metamorphic

rocks of the Neoproterozoic Douling Group crop out to the south of the Shangyang

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Fault (Fig. 1c). The Jiuliping Group is dominated by deep-water turbidite sequences.

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The lower part mainly contains arkose-quartz sandstone with interlayers of siltstone
and mudstone and the upper part is mainly composed of siltstone and mudstone with
subordinate arkose and marl. These sedimentary sequences reflect a southward

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deepening sedimentary environment (Meng, 1994; Mei et al., 1999). The Douling

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Group is composed of micaschist, gneiss and migmatites and considered to be

basement rocks that were originally beneath the Jiuliuping Group (Faure et al., 2008).

The Devonian sandstones suffered intensive folding and faulting after deposition

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(e.g. Li et al., 1994; Meng, 1994; Mei et al., 1999; Zhang et al., 2001) which adds to
the difficulty of interpreting their tectonic setting and sedimentary provenance. We

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thus describe the structural geology first before study sandstone geochemistry and

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heavy mineral analysis.

2.2 Structural Geology of the Devonian Sandstone Unit

The Devonian sandstones strike E-W (Fig. 1c). In the north of the region, the
Shandan Fault comprises a series of sub-vertical faults with subhorizontal slickenlines
indicating sinistral movement. Siltstone and limestone sequences develop a series of
tight upright folds with highly strained limbs and pervasive axial planar cleavage (Fig.
2b). The folds axial planar cleavage changes southward from vertical to gently
inclined to the north (Fig. 2c). Small-scale thrust faults are developed in thick
mudstone and limestone layers. Near the fault are phyllites containing muscovite,
biotite, garnet and andalusite, reflecting fluid circling along faults (Liu et al., 1999;

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Liu et al., 2015). Kinematic indicators such as S-C bands indicate a top to the south
shear sense (Fig. 2d).

In the south, the Shanyang Fault displays sinistral strike-slip fabrics such as

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horizontal striation lineation and mullion structures, but the strata near the fault are

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dominated by a series of imbricated south-vergent asymmetric folds (Fig. 2e). Locally,

recumbent folds are south-vergent in present-day coordinates (Fig. 2f). To the south of
the Shanyang Fault, the Jiuliping Group develops a series of open folds and low-angle

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thrust faults. Fold axial planes and fault surface dip statistically to the NE-NW (Fig.

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1).

There is no convincing age dating at present to prove that southward thrusting

occurred during the Devonian. Devonian fabrics, if there are any, would have been

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reworked by the Carboniferous sinistral strike-slip movement, and Triassic

intracontinental deformation (Hacker, et al., 2004; Lin et al., 2005). We argue here

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that there was Devonian southward thrusting for the following reasons: i) Thick
bedded conglomerates (Dong et al., 2013) that might have resulted from regional fault

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activity crop out to the south of the Shangdan Fault; ii) We have observed several
beds of conglomerate up to 1 m thick to the south of the Shanyang Fault (Fig. 1c) that
might be linked with the Shanyang thrust fault.

3 Sampling and analytic methods

Sandstone samples were collected along a traverse to west of Shanyang City (Fig.
1c). Sample locations, brief descriptions and analytical methods are listed in Table 1.
Framework grains are difficult to identify because the sandstones have suffered
different degrees of diagenetic alteration. Mineral proportions have been estimated
from relative areas of mineral grains under the microscope. Thirteen of the least

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weathered samples were selected for geochemical study at the Laboratories of
ALS-Minerals & ALS-Chemex in Guangzhou City, China. We analyzed different

grain-size fractions of the sandstones, siltstone, and mudstone that we had selected for

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bulk-rock analysis to investigate the influence of grain size on rock composition. We

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duplicated geochemical analyses of 32 samples from He et al. (2005) from the same
study section, and plot them in the diagram below.

Major and selected trace element (i.e., Sc, V, Cr, Co, Ni) contents were

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determined by Inductively Coupled Plasma-Atomic Emission Spectroscopy

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(ICP-AES). The samples are digested with perchloric, nitric, hydrofluoric and
hydrochloric acids. The residue was topped up with dilute hydrochloric acid and the

resulting solution was analyzed. The detection limit for major elements is 0.01%, and

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for the elements Sc, V, Cr, Co, Ni 1 ppm. Si was not measured due to its tending to
volatilize during hydrofluoric and hydrochloric acid digestion. The values of SiO2

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here have been calculated assuming a total sum of 100% and LOI=1.5% from
sandstone geochemical measurements in a nearby area by He et al., (2005). All other

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trace and rare earth elements were determined using Inductively Coupled
Plasma-Mass Spectrometer (ICP-MS). The prepared samples were added to lithium
metaborate/lithium tetraborate flux, mixed well and fused in a furnace at 1025C. The
resulting melt was then cooled and dissolved in an acid mixture containing nitric,
hydrochloric and hydrofluoric acids. This solution was then analyzed by ICP-MS. The
detection limit is 0.01 ppm (Lu, Ho, Tb, Tm ), 0.03 ppm (Er, Eu, Pr, Sm, Yb), 0.05
ppm (Dy, Gd, U), 0.1 ppm (Nd, Sr, Ta), 0.2 ppm (Nb, Hf, Rb), 0.5 ppm (Ba, Ce, La,
Th, Y), and 2 ppm (Zr), respectively. The precision of the ICP-MS analyses was better
than 5%.
Fourteen samples in total were examined for heavy mineral association (tables 1

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and 2). Heavy minerals were separated from the very fine sand fraction (0.10-0.063
mm) using heavy liquid with specific gravity 2.84 g/cm3. At least 300 grains of heavy

mineral concentrate were randomly selected under the microscope to count their

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relative proportions and tourmaline grains were specially selected from three samples

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from the D3ty and the D2n formations, and the D3j Group. The detrital grains were
embedded in epoxy resin, polished and coated with carbon. Mineral compositions
were determined at the State Key Laboratory of Geological Processes and Mineral

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Resources, China University of Geosciences (Wuhan), with a JEOL JXA-8100

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Electron Probe Micro Analyzer equipped with four wavelength-dispersive

spectrometers (WDS). An accelerating voltage of 15 kV and a beam current of 20 nA

and a 1< m focused electron beam were used to analyze the minerals. Element peaks

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and backgrounds were measured for most elements for counting times of 10 s and 5 s
respectively, except that Ti and Mn were counted for 20 s and 10 s, respectively. The

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following standards were used: Jadeite (Si, Na), Rutile (Ti), Pyrope Garnet (Al, Fe),
Rhodonite (Mn), Diopside (Mg,Ca), Sanidine (K), and Fluorite(F).Data were

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corrected on-line using a modified ZAF (atomic number, absorption, fluorescence)

correction procedure.
Tourmaline analyses were recalculated using WinTcac software by Yavuz et al.
(2014): B2O3 concentrations were calculated to 3B per formula unit, H2O contents to
4(H+F) per formula unit, and structural formulae were obtained on the basis of 24.5
oxygen atoms, and Fe3+ was estimated assuming standard tourmaline stoichiometry,
using the formula XY3Z6T6O18(BO3)3V3W, where X=Na, Ca, K, vacancies; Y = Fe,
Mg, Mn, Ti, Al; Z=Al, Mg; T=Si, Al; B=B; V+W=OH+F=4, using a classification
procedure proposed by Henry et al. (2011) to identify tourmaline varieties.

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4. Results
4.1Sample descriptions

Grains of the fine grained samples are sub-rounded to sub-angular, mainly

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composed of quartz (~30-60%), alkali feldspar (~20-30%), and plagioclase (~5-15%).

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Three samples have a relatively high proportion of mudstone matrix (~5-20%) often
altered to tiny muscovite crystals. Quartz grains predominated in all samples,
accompanied by minor polycrystalline quartz grains. Resorbed grain boundaries of

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quartz and feldspar suggest dissolution of SiO2 during diagenesis and/or deformation

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(Fig. 3a). Accessory minerals included zircon, pyroxene, apatite, rutile and opaque
mineral grains. Only six garnet grains were obtained by heavy mineral separation.

They were rounded with serrated grain boundaries. The conglomerate sample SL-136

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included pebbles of carbonate, sandstone and mudstone, sub-rounded to angular in

shape, poorly sorted, ranging from 2 mm -5 cm (Fig. 3b). More detailed descriptions

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for each sample are given in Table 1.

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4.2 Geochemistry

The analytical samples are not evidently influenced by grain-size fractions (Fig.
4). Major elements show a gradually changing trend from the Middle Devonian to the
Upper Devonian (Table 2, Fig. 4). Measured SiO2 contents for the D2c+D2q+D2n, D3j
and D3ty sandstones increase from 66-72%, 65-75%, and 80-87%, respectively. The
TiO2 contents in D2c+D2q+D2n and D3j are about 0.4-0.5%, nearly double that in the
D3ty (~0.2%, Table 2). This might correlate to a relative lower proportion of rutile and
Ti-bearing heavy minerals in D3ty (see section below). The K2O abundances of D3ty
and D3j are similar (0.74-1.45%, mean=1.18 and 0.9-2.59%, mean=1.53%,
respectively), but lower than those of the D2c+D2q+D2n (2.08-3.58%, mean=2.9%).

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The content of Al2O3 in the D3ty is also lower than that in the D2c+D2q+D2n and the
D3j. The variety of K2O and Al2O3 between the Middle Devonian and the Upper

Devonian is consistent with the relative high amount of alkali-feldspar in the Middle

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Devonian sandstones (Table 2). The CaO contents in the D2c+D2q+D2n and the D3j

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are extremely high than that in the D3ty. The alternated carbonate minerals and tiny
calcite veins might greatly contribute the relatively high CaO. The mudstone sample
SL-141 in the D3j shows higher Al2O3 content than the other samples of sandstone.

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We conclude that the Middle Devonian sandstones are relatively rich in K2O, Al2O3,

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TiO2 and CaO than that of the Upper Devonian sandstones, whereas the Upper
Devonian sandstones have higher SiO2 content.

The major elements have significant relative variations when compared to upper

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continental crust (UCC, Fig. 4). All the analyzed samples are depleted in Al2O3, TiO2,
Na2O, K2O and P2O5 relative to UCC (Fig. 4a). The most variable element Na2O

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ranges from 0.13 to 2.41 wt.%, lower than the average value of UCC (3.27wt.%,
Taylor and McLennan, 1985). Depletion of Na2O is consistent with the low

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proportion of feldspar seen in thin sections. K2O/Na2O ratios in all samples except
SL-141 and SL-143 are >1 because of the absence of plagioclase and Na-rich alkali
feldspars. Fe2O3T, MnO and MgO are similar to or slight lower than that of the
average UCC (Fig. 4a).
Trace element analyses show that the Upper Devonian sandstones are enriched in
Zr compared with Middle Devonian sandstones (Table 2, Fig. 4b). Abundances of Zr
range from about 150 to 310 ppm. High Zr abundances are caused by concentration of
zircon grains (Roser, 2000) and higher Zr contents in our samples correlate with high
modal proportions of zircon (see below).
The average abundances of trace elements are generally similar to those in UCC,

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but there are some significant differences; relative enrichment in Zr, Hf and
depletions in Ba and Sr. Alkali feldspar was probably the reservoir for Sr, Ba and Rb

(e.g., Gtze, 1998). The significant Sr and Ba depletion compared with UCC

Devonian

sandstones

irrespective

of

their

lithology

have

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The

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correlates with low proportions of alkali feldspar.

chondrite-normalized REE patterns similar to those of UCC (Fig. 4c) suggesting that
they derived from a similar, uniform source. All the analyzed samples display LREE

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enrichment relative to HREE, with flat to slightly depleted HREE patterns (Fig. 4c).

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LaN/SmN averages for all sandstones (average LaN/SmN=4.1) are generally similar to
UCC (4.15, Taylor and Mclennan, 1985). The samples show variable negative Eu

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Taylor and Mclennan, 1985).

anomalies (Eu/Eu*: 0.48-0.94, mean 0.63) similar to the UCC mean value (0.65;

To sum up, the Middle Devonian sandstones are higher in K2O, Al2O3, TiO2 and

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CaO, but lower in SiO2 than that the Upper Devonian sandstones. High Zr abundances
in the Upper Devonian sandstones correlate with the concentration of zircon grains.

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There are distinct Sr and Ba depletions in all samples caused by the low amount of
feldspar. REE patterns are uniform and LREE is enriched relative to HREE. There are
distinctly negative Eu anomalies.

4.3Heavy mineral proportions

The heavy mineral assemblages include tourmaline, zircon, rutile, apatite,
anatase, leucoxene, ilmenite, spinel, pyroxene, magnetite, and non-counted authigenic
iron hydroxides, oxides and calcite. Tourmaline grains are mainly sub-rounded and
prismatic but occasionally euhedral and are pleochroic, brown, green-brown to
colorless in plane polarized light (Fig. 3c). A few have isostructural authigenic

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overgrowths developed along the +c axis (Fig. 3c). BSE images of tourmaline grains
mostly do not show evidence of chemical zonation, but a few grains preserve relicts

of older prisms or fragments of prisms which are usually dark grey in the BSE image,

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while the outer part is lighter (Fig. 3d). Zircon grains are rounded to sub-rounded,

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purple and colorless in plane polarized light, and have tough irregular surface. Rutile
is generally irregular angular- to sub-angular and prismatic, with red- to yellow-brown
color.

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The modal amount of zircon is highly variable, with an average value of 44%

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(Fig. 5, Table 3). Lower proportions of zircon grains are found in the D2q+D2c
formations (~8%), but they increase in D3ty (17.5-65.7%). In the D3j group of the

southern Shanyang area there are higher modal amount of zircon than in the Middle

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Devonian sandstones. The heavy minerals separated from sample SL-137 were only
zircon and apatite so the modal amount of zircon is extremely high. The conglomerate

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sample SL-136 in D2n shows a relative low amount of zircon because it is dominated
by carbonate minerals. The modal amount of tourmaline varies from 1.3% to 27.3%,

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with average value of 13.5%. No tourmaline grains were found in Sample SL-120.
The third most abundant phases are apatite and rutile, with average modal amounts of
19.5% and 1.7%, respectively. The modal proportion of Ti-bearing minerals except
for rutile, including anatase, leucoxene and ilmenite, is highly variable, but constitutes
on average 21% of the assemblages. Significantly, euhedral spinel grains appear in
heavy mineral spectra of samples from D3ty (e.g. SL-120 and SL-121). Samples from
the D2q Formation contain a significant amount of magnetite (up to 41%) and
pyroxene grains.
The ZTR maturity index (sum of the percentage proportion of zircon, tourmaline
and rutile; Hubert, 1962) ranges from 15% to 91%. Several samples show low ZTR

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values, e.g. 16% in sample SL-127, 15% in sample SL-134 probably reflecting rock
types in the source area, or alternatively different size fractions. Conglomerate sample

SL-136 has a ZTR value of 27%.

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In summary, zircon, tourmaline, apatite rutile and anatase are the principal heavy

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minerals. The Upper Devonian sandstones have higher modal amounts of zircon than
the Middle Devonian. A few unexpected minerals, like spinel, pyroxene, ilmenite and

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magnetite, appear in heavy mineral spectra and may constrain the potential source.

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4.4 Tourmaline chemistry

Our study of tourmaline composition focused on the central parts of crystals and

avoided the authigenic overgrowths formed during diagenesis and deformation. 87

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EPMA analytical spots show that the detrital tourmalines mainly belong to the
alkali-tourmaline compositional group. Na1+predominates (0.44-0.92 apfu) with a

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subordinate amount of K1+ (0.0-0.01). There are three grains are uvite belonging to a
calcic subgroup with Ca2+ at (0.50-0.56 apfu) (Fig. 6a, Table 4 and Appendix I). The

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tourmalines have X-site vacancies ranging from 0.03 to 0.45 apfu and the W-site
occupancy of 75 of 87 grains are hydroxyl-species, 8 grains belong to fluor-species,
and 4 grains represent oxy-species.
Tourmaline grains of the alkali subgroup fall into the fields of both dravite and
schorl (Fig. 6b). In the dravite grains, the Z-site is occupied, mostly by Al3+, and
subordinately by Mg2+ (up to 0.38 apfu). Several grains have Fe3+ in this position. The
Y-site position is dominated by Mg2+ (1.20-2.01 apfu) and Fe 2+ (0.71-1.43 apfu), and
subordinate amounts of Al3+ (up to 0.48), Mn2+ (up to 0.02 apfu) and Ti4+ (0.02-0.12
apfu). The various Mg2+ and Fe2+ contents show Mg/Mg+Fe ratios ranging
of >0.50-0.74. Tourmaline grains display varied chemical compositions, including

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some relatively homogenous dravite-schorl compositions (Fig. 6b). The fluoride ion
content is up to 0.43 apfu.

In the case of the schorl grains, the Z site is mainly occupied by Al3+ ions, with

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subordinate Mg2+ (up to 0.43 apfu) with minor amount of Fe3+ ions in two grains.

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Fe2+(1.22-2.33 apfu), Mg2+(0.27-1.29 apfu), Al3+(up to 0.59 apfu), Ti4+(0.04-0.45 apfu)

and Mn2+(<0.04 apfu) occur in the Y-position. The Mg/Mg+Fe ratios range from 0.11

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to 0.48, indicating Mg-rich schorl to homogenous schorl-dravite (Fig. 6b). The

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fluoride ion content reaches up to 0.76 apfu.

Tourmaline is resistant to both chemical weathering and mechanical abrasion,

and is thus a common accessory mineral in sedimentary rocks (e.g. Henry and Dutrow

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1996). Henry and Guidotti (1985) distinguished tourmaline compositions from

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different rock types by their Al-Fe-Mg contents and demonstrated that they are useful
petrogenetic indicators (e.g., Li et al., 2004; Morton et al., 2005; Dutrow and Henry,

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2011; van Hinsberg et al., 2011b; Kowal-Linka, 2013). Chemical analyses of

tourmaline from our rock samples show that they plot in similar fields (Fig. 7). 52%
of tourmaline grains are derived from metasedimentary rocks such as metapelites and
metapsammites. About 34% of tourmaline grains are from Li-poor granitoids and
associated pegmatites and aplites. A small tourmaline population (~14%) plots in the
field of quartz-tourmaline rocks, calc-silicates and metapelites (Fig. 7).

5. Discussion
5.1 Source rock type
5.1.1 Geochemical constraints

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The high values of K2O/Na2O ratio reflect rocks sandstones derived from
potassium feldspar rich rocks rather than plagioclase-rich rocks although other major

elements (i.e., K2O, Na2O, CaO) are variable. On Roser and Korschs (1988)

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discrimination diagram, clusters display a varying trend from intermediate igneous

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source rocks to a field of quartzose recycled rocks (Fig. 8a).

Immobile elements such as Th, Sc, Zr and La, and their ratios provide a better
constraint on the source rocks due to their low concentrations, high resistance to

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alteration by natural waters and easily transfer from source to sediment (Taylor &

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McLennan 1985). On a Th/ScZr/Sc diagram (McLennan et al. 1993), the Devonian

sediments concentrate in the field of rhyolite (Fig. 8b) and a La/ScTi/Zr plot

confirms this result, with samples plotting near the fields of dacite and rhyolite

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compositions (Fig. 8c). A similar provenance is also indicated by an HfLa/Th plot

(Floyd and Leveridge, 1987) in which most of the sandstones in the Shanyang area

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fall within the felsic source area with some samples spreading into the mixed source
zone but trending towards an increasing component of crystalline basement (Fig. 8d).

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The REE patterns of all the samples are similar, suggesting derivation from a
uniform source region. Ratios such Eu/Eu*, La/Sc, Th/Sc, and Cr/Th are significantly
different between mafic and felsic source rocks. The Eu/Eu*, (La/Lu)N, La/Sc, Th/Sc,
and Cr/Th ratios are similar to those of sediments derived from felsic source rocks
(e.g., La/Sc=2.5-16.3, Th/Sc=0.8-20.5, Cr/Th=4.0-15.0, Eu/Eu*=0.4-0.9). The
significant Eu-anomaly (average Eu/Eu*=0.63) and flat HREE patterns imply a
granodioritic source (Cullers and Podkovyrov, 2000) but do not preclude a minor
accession of mafic rocks (Fedo et al., 1996). Thus, the overall geochemical evidences
suggest a source region of granitic or felsic igneous rocks.

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5.1.2 Heavy mineral constraints
Zircon, tourmaline, apatite, rutile and anatase are the main heavy minerals

although there are a few exceptional minerals, like spinel, pyroxene, ilmenite and

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magnetite. Tourmaline is commonly associated with pegmatites and metamorphic

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rocks. Rutile and anatase appear as accessory minerals in granites, pegmatites, and
metamorphic schists, gneisses and eclogites. Spinel may occur in granitic pegmatites,
metacarbonates, and ultramafic rocks. Ilmenite may be a component of both

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ultramafic/mafic and felsic rocks. Thus, the heavy minerals assemblages indicate that

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granitic rocks, ultramafic/mafic rocks and metamorphosed schists, gneisses could be

potential parent rocks.

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5.1.3 Tourmaline chemistry constraints

Tourmaline Mg/Mg+Fe ratios indicate that the tourmaline grains might derive

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from both metamorphic and igneous rocks. Chemical analyses of tourmaline show
that the compositions of about 70% grains correlate with metapelites, metapsammites,

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and calc-silicates. About 30% of tourmaline grains could derive from granitoids and
associated pegmatites and aplites (Fig. 7). Metamorphic tourmalines rarely form
under granulite-facies conditions (e. g. Thomson, 2006) but typically from rocks of
either low, medium or upper amphibolite facies conditions (van Hinsberg et al., 2011a,
b). Thus, the most probable source lithologies are granitic pegmatites, paragneisses
and politicto felsic schists, possibly containing lenses of amphibolites.
We therefore conclude by synthesizing geochemistry, heavy mineral
assemblages and tourmaline chemistry that the source rocks should include felsic
igneous rocks such as granitoids and their associated pegmatites and aplites, and
metamorphic rocks such as metapelite, metapsammiteand calc-silicates. A small

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amount of mafic or ultramafic rocks is possible.

5.2 Potential provenance

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The most probable source rocks in the study region occur in the Qinling

which

is

predominantly

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Orogenic Belt. We favor the Qinling metamorphic Complex as the most likely source,
biotite-plagioclase

gneisses,

mica-quartz

schists,

graphite-bearing marbles, and amphibolites or garnet amphibolites, with some

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eclogite lenses and migmatitic granites that have suffered eclogite facies and

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retrograde metamorphism. There are pegmatite veins that formed when the
migmatites developed and Lower Paleozoic gabbroic and granitic intrusions also
occur in this unit (Chen et al, 1991; Faure et al., 2008; Wang et al., 2009; Zhang et al.,

source of tourmaline.

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2001; Zhang C L., 2013; Dong et al., 2016; Zhang et al., 2015) that could be the

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Bulk rock geochemistry and tourmaline chemical analyses rule out the Kuanping,
Erlanping, and ophiolite units as significant sources, since as protoliths they are

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mafic/ultramafic bodies, tholeiitic basalts, and mafic volcaniclastic rocks (Dong et al.,
2011, 2016).

South of the Devonian sandstone unit, the Neoproterozoic Douling group is

composed of micaschist, gneiss, migmatite, diorite, quartz-diorite, granodiorites and
rare hornblende gabbro with ages ranging between 680-750 Ma (Li, 2003; Yang et al.,
2011). We rule them out as source rocks because: i) Uniform REE and trace element
patterns among the sandstone samples suggest they derived from a restricted source
area. ii) The available paleocurrent data in the area and elsewhere (Yan et al., 2007)
showa southwardtransport direction. iii) The detrital zircon grains in the Liuling and
Jiuliping groups have three distinct age groups: 400600 Ma, 700850 Ma and

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9001100 Ma (Dong et al., 2013) but not an age population of 680750 Ma of the
Douling Group. The Douling group unit was a Triassic or younger pop-up structure

and so could not supply sediments to the Devonian sandstones (e.g., Lin et al., 2015;

5.3 Source rock weathering and recycling

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Faure et al., 2008).

The extent of chemical weathering can be estimated using the Chemical Index of
(CIA;

Nesbitt

and

Young,

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Alteration

1982),

where

CIA=100

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[Al2O3/(Al2O3+CaO*+Na2O+K2O)] in molecular proportions, and CaO* represents

the value of Ca in the silicate fraction only. CIA values of about 4555 imply minor

weathering (e.g., McLennan, 1993; Fedo et al., 1995; Lan et al., 2016) and values

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around 100 indicate intense weathering with complete removal of alkali and alkaline
earth elements and increasing Al2O3 content. CIA values for the Devonian sandstones

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in the Shanyang area are highly variable (5182), with an average of 65. The low CIA
values may be due to low concentrations of alkali and alkaline earth elements in

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source rocks (Table 3) rather than variable degrees of source area weathering. Even so,
a majority of the samples have CIA values greater than 60 indicating moderate to high
weathering conditions in the source area. Plots in an ACNK system are also useful
for evaluating fresh rock compositions and examining their weathering trend (Nesbitt
and Young, 1984; Nesbitt and Young, 1989; Fedo et al., 1995). All the samples
analyzed in this study plot parallel to weathering trends of granodiorite and adamellite,
supporting the conclusion that the sandstones derived from a felsic source terrain (Fig.
9).
During rock weathering, important U-bearing minerals (e.g. uraninite) are easily
dissolved (e.g. Baker, 2014; Boekhout et al., 2015). U+4 is oxidized to U+6 and forms

ACCEPTED MANUSCRIPT
the highly soluble species [UO2]2- which can be removed from the system, whereas
Th remains relatively insoluble. As a consequence, Th/U ratios increase during

successive cycles of weathering and re-deposition (e.g. McLennan and Taylor, 1980;

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Baker, 2014). Most Th/U ratios of the Devonian sedimentary rocks (2.1610.55,

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Table 2) are higher than the average value for the upper crust (3.8; McLennan and
Taylor, 1980), suggesting a repeated cycling history. Weathering and diagenetic
processes can often lead to significant increases in Rb/Sr ratios (McLennan et al.,

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1993) and the high Rb/Sr ratios of the rock samples in this study (mean=1.7) also

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suggest a recycling history.

5.4 Tectonic implications

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The immobile elements fall into the fields of continental island arc (CIA) and
passive margin (PM) in ThScZr, ThCoZr and LaThSc ternary diagrams

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(Fig. 10; Bhatia and Crook, 1986) and display an evolving trend from CIA to PM.
There is a similar trend in Fig. 8a. But in the major element diagrams such as

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SiO2K2O/Na2O, (Roser and Korsch, 1986) the sandstones plot in the passive margin
field (e.g., He et al., 2005). The immobile minor or trace elements are not consistent
with the plot of major element data which leaves the tectonic setting uncertain (e.g.,
Mattauer et al., 1985; Li et al., 1994;Meng, 1994; Zhang et al., 2001; Dong et al.,
2011, 2013). We interpret this paradox in the Devonian sandstones as a
consequence of recycling in a foreland basin setting.
Recycling of sediments is also proved by high Th/U, Rb/Sr ratio, and different
degree of weathering among the samples. The well-developed south verging folds and
thrust faults in the study area also suggest a foreland basin setting rather than a
passive margin. The Devonian basin probably received materials from the Qinling

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Complex unit. The sediments exhibit inherited geochemical features of the Complex
showing continental island arc affinity. Related tectonic scenarios are shown in Figure

11. The thrusting and folding in foreland setting led to the sediments suffering

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polyphase recycling when some elements were selectively dissolved. There is

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therefore an evolving trend from the Middle Devonian to the Upper Devonian that
explains the significant geochemical discrepancy between major and trace elements.
Our sedimentological and geochemical studies indicate that the Qinling

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metamorphic Complex unit was already exhumed and eroded during Middle

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Devonian times, along with a small area of mafic and ultramafic rocks in an ophiolitic

suture zone.

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6 Conclusions

A combination of geochemistry, heavy mineral assemblages, and tourmaline

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chemical analyses provides new insights to decipher the source rocks of Devonian
sandstones in the southern part of the Qinling Orogenic Belt, supporting the following

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conclusions:

(1) The source rocks of the Devonian sandstones in the Shanyang area were
granitoids and associated pegmatites and aplites, and metapelite, metapsammite
and calc-silicate metamorphic rocks and perhaps a small amount of mafic or
ultramafic rocks. The Qinling Complex unit is a comparable provenance in the
study area.
(2) The sedimentological, structural and geochemical features of sandstones in the
Shanyang area suggest that they were deposited in Devonian times in a foreland
setting to the south of the Qinling Orogenic Belt rather than in a passive
continental margin.

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Acknowledgements

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This study was supported by the National Natural Science Foundation of China

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(No. 41402192) and the China Postdoctoral Science Foundation (No. 2014M562080).
Michel Faure is thanked for beneficial discussion to improve the manuscript. Fuat
Yavuz is thanked for kindly providing the tourmaline calculation software of WinTcac.

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The detailed and constructive comments of Prof. Barbara L. Dutrow and the

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anonymous reviewer are highly appreciated. We also thank Roger Mason who

polished the English of a late draft.

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Figure captions

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Figure 1. (a) Tectonic divisions of the Qinling Orogenic Belt and location of the study
area. (b) Simplified geological map showing the study area in the Qinling Orogenic
Belt (After Dong et al., 2011 and 1: 20, 0000 geological map of Shang County). (c)
Simplified geological map showing sample locations of Devonian sandstones in the
Shanyang area (after He et al., 2005). (Red arrows represent post-Devonian fabrics).

Figure 2. Field images of geological features in the Devonian sandstones. (a) Ripple
marks in siltstone of the Niuerchuan Formation. A curved wave crest indicates a
southward paleocurrent direction. (b) Tight upright fold with an E-W axis, vertical
axial planar foliation in the D3 Tongyusi Formation adjacent to the Shangdan fault. (c)

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Isoclinal fold with axial plane dipping to the North, in the Qingshiya Formation. (d)
Metapelite containing mica, biotite and garnet with an alteration zone caused by

syn-faulting fluid activity. A boudinaged quartz vein and sigmoid shear band indicate

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a top to south shear sense. (e) South-verging asymmetric folds (left) associated with

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southward thrusting of Devonian rocks; vertical foliations to (right) related to

post-Devonian strike-slip movement along the Shanyang Fault. (f) South-verging

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recumbent syncline in the Chigou Formation.

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Figure 3. Microphotographs of sandstone samples and detrital tourmaline grains. (a)

Representative thin section of sandstone sample SL-124 (between crossed polars). (b)

Conglomerate sample SL-136, dark siltstone fragment (right), limestone fragments

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(right) (between crossed polars). (c) Representative tourmalines with diverse shapes,
roundness, color and overgrowths; serrated grain margins represent overgrowths

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(plane polarized light).(d) Back Scattered Electron image showing chemical zonation

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of euhedral tourmaline and a relict inclusion.

Figure 4. UCC normalized (a) major oxides and (b) trace elements of sandstones, (c)
chondrite normalized REE patterns of sandstones from the Shanyang Basin. Data for
UCC and Chondrite from Taylor and Mclennan (1985).Samples from the same
formationsin the same colors but with different ornaments to compare samples from
the Middle Devonian and the Upper Devonian; pink symbols represent samples from
D3ty, purple from D2q, D2c and D2n, and green from the D3j group.

Figure 5. Relative compositions of heavy mineral assemblages obtained from

Devonian sandstones in Shanyang area, south of Qinling orogenic belt.

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Figure 6.Chemical compositions of detrital tourmalines on an X-site ternary

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diagram(vacancyCaNa+K)indicating tourmaline chemical species.

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Figure 7. AlFeMg ternary diagram to indicate detrital tourmaline provenance

(Henry and Guidotti, 1985): (1) Li-rich granitoids, pegmatites and aplites, (2) Li-poor
granitoids, pegmatites and aplites, (3) hydrothermally altered granitic rocks, (4)
and

aluminous

metapsammites,

(5)

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metapelites

metapelites

and

Al-poor

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metapsammites, (6) Fe3+-rich quartz-tourmaline rocks, calc-silicates and metapelites,

(7) low-Ca meta-ultramafics, and (8) metacarbonates and metapyroxenites.

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Figure 8. Provenance discrimination diagram, colored symbols from present study of

Devonian sandstones. Grey circles, data from He et al., (2005). (a) Provenance

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discriminant function diagram using major elements (F1 and F2 are calculated
coefficients (Roser and Korsch, 1988). (b) Plot of Th/Sc versus Zr/Sc for sandstones

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(McLennan et al., 1993). (c) Ti/Zr versus La/Sc for sandstones. Stars BAS, LSA,
AND, DAC, RHY and GR are average basalt, low-silica andesite, dacite, rhyolite and
granite, respectively, from Roser (2000). UCC composition from Rudnick & Gao
(2005). (d) HfLa/Th diagram (Floyd and Leveridge, 1987).

Figure 9. ACNK ternary diagram (after Nesbitt and Young, 1984)of molecular
proportions

of

Al2O3(CaO+Na2O)K2O

for

Lower

Paleozoic

sandstones,

includingaverage upper continental crust (Taylor and McLennan, 1985). Arrows 1-3
represent weathering trends of granodiorite, adamellite and granite, respectively
(Nesbitt and Young, 1984).

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Figure 10. Plot of Shanyang sandstone samples in the tectonic discrimination

diagrams LaScTh, ThScZr/10 and ThCoZr/10 to discriminate tectonic settings

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of sandstones (after Bhatia and Crook, 1986) Grey circle data from He et al. (2005).

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OIA, oceanic island arc; CIA, continental island arc; ACM, active continental margin;
PM, passive margin.

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Figure 11. Tentative models of the tectonic settings of Devonian sandstones in the

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Shanyang area during Middle to Late Devonian times.

Table 1 Sample locations, lithologic descriptions and analytical methods of Devonian

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sandstones.

Table 2 Major element compositions (weight %), trace element and rare earth element

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concentrations (ppm) of Devonian sandstones in the Shanyang area.

Table 3 Proportions (% of counted number of grains) of heavy minerals in 14 samples

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with their ZTR indices.

Table 4 Representative chemical compositions of detrital tourmalines from the

Devonian sandstones in the Shanyang area. See text for details of the recalculation
procedure.

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Table 1
Analytical methods
Location coordinates

3340'27''E

10943'00''E

SL-120

3338'22''E

10943'02''E

SL-121

3337'59''E

10942'59''E

SL-122

3337'37''E

10942'54''E

SL-124

3336'50''E

10942'55''E

SL-127

3334'26''E

10942'32''E

3333'01''E

3331'53''E

10942'44''E

3329'33''E

10944'11''E

3329'24''E

10944'01''E

SL-136

3328'34''E

10944'06''E

SL-137

3328'17''E

10944'16''E

3327'29''E

10943'59''E

SL-132

SL-134

SL-141

D2 c

AC

SL-133

D2 n

D3 j

10942'21''E

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D2 q
SL-131

D3ty

SL-142

3326'37''E

10944'04''E

SL-143

3325'42''E

10945'06''E

Mudstone. Muscovite alteration.

Fine grained sandstone. The grains are
oriented. Elongated quartz (30%), alkali
feldspar (20%), plagioclase (15%). a few
carbonate veins. (Muscovite <5%); it
developed dirty opaque bands along grain
boundaries. Quart margin is recrystalization.
Fine grained sandstone. The grains are
sub-angular, poorly sorted. Quartz (45%),
alkali feldspar (15%), plagioclase (15%).
alternated mineral of muscovite (~10%).

Heavy
minerals

Tourmaline
chemistry

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SL-117

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10942'36''E

Medium grained sandstone. The grains are

sub-rounded to sub-angular, well sorted.
Quartz (~55%), alkali feldspar (~20%),
plagioclase (~15%). minor alterated minerals
of muscovite and carbonate (<5%)
Fine grained sandstone. Quartz (65%),
margin of quartz grain is recrystalization.
Matrix of tiny muscovite (~10%). Opaque
minerals (<5%)
Fine grained sandstone. The grains are
rounded, well sorted. Quartz (~60%), alkali
feldspar (~10%), plagioclase (~5%).
Undetermined minerals (~15%); minor
alterated carbonate minerals.
Fine grained sandstone. The grains are round,
to sub-round, well sorted. Quartz (~60%),
has corrosion margin; plagioclase (~5%).
Undetermined minerals (~25%) with dirty
surface, sericite and carbonate alteration,
slightly choritoid; opaque anhudral minerals
(<5%).
Fine grained sandstone. The grains are
sub-rounded, well sorted. Quartz (~60%),
plagioclase (~10%), alkali feldspar (~5%).
Matrix cements are muscovite (~5%). Heavy
minerals of pyroxene and opaque minerals
are observed.
Fine grained sandstone. The grains are
sub-angular, poorly sorted. Quartz (60%),
alkali feldspar (~20%), plagioclase (~10%).
minor alterated minerals of muscovite and
carbonate (<5%)
Fine grained sandstone with minor mudstone
lamina. The grains are sub-rounded to
sub-angular, well sorted. Quartz (~45%),
alkali feldspar (~25-30%), plagioclase
(~10%). mudstone lamina (~5%). Minor
muscovite (<5%).
Greywacke. Fine grained, angular-, to
sub-angular, poorly sorted. Matrix of
mudstone (25%); quartz (25%), Opaque
anhudral minerals (3%). The matrix is
slightly carbonatization and sericitation
(muscovite).
Siltstone. The grains areoriented. Quartz
(~55%), and calcite (~10%); quartz
elongated and corrosion; opaque minerals
(5%).
Fine grained sandstone. The grains are
sub-rounded, well sorted. Quartz (~50%),
plagioclase (~10%), alkali feldspar (~10%).
Matrix is muscovite materials (~5%).
Fine grained sandstone. The grains are
sub-rounded, well sorted. Quartz (~45%),
alkali feldspar (~30%) plagioclase (~5%),
undetermined minerals (15%), and surface
dirty; apatite was observed.
Conglomerate. Poorly sorted. Pebbles of
Carbonatic fragment (~40%) and
sedimentary fragment (~30%). Matrix of fine
grained sandstone (~20%) and mudstone
(~10%). Pyroxene and opaque minerals are
observed.
Fine grain sandstone. The grains are angular
to sub-angular, well sorted. Quartz (45%),
alkali feldspar (~15%), plagioclase (10%).
Minor carbonate veins and alternated mineral
of muscovite. Quartz margin was corrosion.

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3341'38''E

Sandstone
geochemistry

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SL-114

Lithological Description

Stratigraphic
age and
formation

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Sample
No.

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Table 2
D2 q

D2 c

D2 n

SL-114

SL-120

SL-121

SL-122

SL-124

SL-127

SL-131

SL-133

SL-134

SiO2

87.38

84.31

80.91

81.66

82.90

71.61

66.61

70.94

68.81

Al2O3

5.60

7.07

7.38

6.63

6.13

11.46

11.69

9.81

9.72

TiO2

0.22

0.20

0.22

0.20

0.27

0.58

0.58

Fe2O3

1.57

2.63

4.67

4.35

3.18

4.85

5.37

CaO

1.42

1.27

1.63

2.00

3.68

3.55

6.58

MnO

0.04

0.04

0.10

0.08

0.08

0.09

0.13

MgO

0.66

0.37

1.15

1.66

1.20

2.47

2.99

Na2O

0.32

1.01

1.00

0.55

0.16

1.64

K2O

1.21

1.45

1.24

1.24

0.74

2.08

P2O5

0.07

0.15

0.20

0.14

0.15

0.16

CIA

70

59

61

68

82

Sc

3.00

7.00

8.00

7.00

21.00

55.00

60.00

60.00

Cr

30.00

63.00

87.00

Co

4.00

5.00

13.00

Ni

11.00

19.00

32.00

Ga

5.20

8.30

Rb

65.30

Sr

133.5

SL-141

SL-142

SL-143

72.60

65.89

72.94

74.41

10.10

11.66

6.93

9.97

SC
R
0.47

0.40

0.40

0.38

0.47

5.47

4.38

4.31

4.92

3.35

6.08

7.20

9.27

3.72

8.99

12.14

2.34

0.08

0.10

0.07

0.08

0.04

0.16

0.81

2.83

3.26

2.90

0.45

2.34

1.05

0.08

0.13

2.41

0.92

1.16

1.42

3.33

3.58

2.62

1.50

2.59

0.90

1.13

0.16

0.17

0.16

0.14

0.14

0.20

0.18

60

62

70

75

51

67

59

63

7.00

12.00

12.00

9.00

9.00

9.00

12.00

8.00

9.00

48.00

85.00

83.00

70.00

75.00

63.00

83.00

52.00

66.00

73.00

71.00

77.00

69.00

54.00

52.00

53.00

61.00

51.00

59.00

11.00

17.00

10.00

14.00

7.00

9.00

12.00

12.00

10.00

14.00

28.00

19.00

30.00

41.00

14.00

26.00

34.00

31.00

26.00

33.00

8.20

8.20

7.30

13.90

15.00

11.40

11.20

11.70

15.70

7.70

12.00

71.80

59.50

60.50

38.70

99.80

159.0

176.0

107.5

60.70

114.5

45.60

58.20

37.10

67.50

124.5

297.0

104.0

83.80

15.90

77.80

40.30

242.0

217.0

81.40

MA

TE

CE
P

NU

0.35

AC

SL-137

IP

Sample

D3 j

D3ty

10.30

17.50

28.00

18.90

18.90

23.10

25.10

26.00

23.60

22.10

20.60

17.50

22.30

113

225

436

229

375

196

164

235

160

143

127

122

179

Nb

5.00

8.60

11.20

9.30

8.80

11.40

12.00

11.70

10.80

11.10

11.60

8.30

11.60

Cs

3.67

3.69

3.03

1.99

1.91

6.23

7.80

1.59

3.60

2.18

3.83

2.67

2.83

Ba

357.0

411.0

248.0

218.0

588.0

491.0

348.0

244.0

304.0

175.5

430.0

157.5

226.0

Hf

3.20

6.40

12.20

6.30

10.60

5.40

4.70

6.60

4.60

4.00

3.90

3.40

5.00

Ta

0.40

0.60

0.80

0.70

0.70

0.90

0.90

0.90

0.70

0.70

0.80

0.60

0.90

Th

5.66

9.59

14.55

9.95

10.85

12.65

11.95

11.40

9.72

9.53

11.35

8.58

10.95

0.89

2.29

3.01

1.55

2.08

2.11

2.37

2.40

2.89

1.96

1.61

1.85

1.91

Zr/Sc

37.7

32.1

54.5

32.7

53.6

16.9

13.7

26.1

17.8

15.9

10.6

15.3

19.9

Th/Sc

1.89

1.37

1.82

1.42

1.55

1.05

1.00

1.27

1.08

1.06

0.95

1.07

1.22

La/Sc

5.60

3.67

3.74

3.46

2.79

2.90

2.61

4.08

2.52

6.14

2.60

2.76

3.13

Cr/Th

5.30

6.57

5.98

7.34

6.54

6.09

5.77

4.74

5.35

5.56

5.37

5.94

5.39

Th/U

6.36

4.19

4.83

6.42

5.22

6.00

5.04

4.75

3.36

4.86

7.05

4.64

5.73

Zr

0.49

1.94

0.88

0.49

0.13

0.96

1.90

11.07

1.38

1.51

0.47

0.21

0.71

La

16.80

25.70

29.90

24.20

19.50

34.80

31.30

36.70

22.70

55.30

31.20

22.10

28.20

Ce

32.90

52.30

61.70

50.10

41.40

70.30

62.60

69.40

45.80

109.0

62.00

48.90

55.20

Pr

3.81

6.06

6.95

5.78

4.93

7.76

7.11

8.04

5.45

12.15

7.22

5.31

6.23

Nd

13.60

23.80

26.90

21.60

19.30

31.00

27.10

29.50

20.80

46.50

27.00

21.80

24.70

Sm

2.51

4.37

5.26

4.19

3.88

5.91

5.46

5.29

4.44

8.61

4.92

4.47

4.82

Eu

0.49

0.83

0.99

0.83

0.74

1.21

1.00

1.53

0.84

1.44

0.95

0.67

0.99

Gd

1.89

3.54

5.49

3.51

3.17

5.19

4.71

4.46

4.08

6.22

4.11

3.85

4.39

Tb

0.32

0.57

0.89

0.60

0.53

0.80

0.77

0.72

0.77

0.88

0.59

0.63

0.77

Dy

1.83

3.28

5.52

3.50

3.59

4.88

4.70

4.39

4.09

4.23

3.80

3.42

4.09

Ho

0.38

0.67

1.19

0.75

0.72

0.92

0.92

0.91

0.89

0.86

0.80

0.76

0.90

Er

1.10

1.82

3.24

1.94

2.01

2.44

2.65

2.53

2.24

2.44

2.05

1.96

2.23

Tm

0.16

0.27

0.50

0.33

0.31

0.40

0.39

0.35

0.34

0.33

0.34

0.30

0.36

Yb

1.01

2.00

3.08

2.01

2.09

2.55

2.53

2.42

2.18

2.17

1.98

1.83

2.26

Lu

0.16

0.28

0.53

0.31

0.28

0.36

0.40

0.31

0.34

0.35

0.32

0.29

0.30

REE

76.9

125

152

119

102

168

151

166

115

250

147

116

135

LaN/SmN

4.32

3.80

3.67

3.73

3.24

3.80

3.70

4.48

3.30

4.15

4.09

3.19

3.78

Eu/Eu*

0.66

0.63

0.56

0.64

0.65

0.59

0.94

0.59

0.57

0.63

0.48

0.65

Table 3

SC
R

NU

MA

CE
P

TE

0.63

Rb/Sr

IP

ACCEPTED MANUSCRIPT

D3ty

Zircon

SL-120
(%)

AC

Sample No.

SL-117
(%)

D2 c

D2 n

SL-121
(%)

SL-122
(%)

SL-124
(%)

SL-127
(%)

SL-131
(%)

D2 q
SL-132
(%)

SL-133
(%)

SL-134
(%)

SL-136
(%)

SL-137
(%)

D3 j
SL-142
(%)

SL-143
(%)

21.7

65.7

17.5

43.2

49.5

15.1

19.8

29.4

8.3

8.9

90.8

47.1

48.8

27.3

21.5

23.3

5.8

1.3

27.9

0.6

64

6.3

0.7

1.6

1.9

2.2

1.2

1.5

4.9

1.1

Anatase

5.6

18.9

3.9

12.8

1.4

10.4

2.9

2.6

7.6

Leucoxene

40.6

9.4

6.3

4.9

30.9

27.8

2.3

Ilmenite

7.2

24.3

33.3

42.8

Apatite

2.9

19.1

21.8

22.1

25.5

8.5

11.7

12.8

0.5

84.8

37.2

9.2

12.9

3.4

Spinel

13.6

1.5

Pyroxene

1.5

1.7

40.5

0.1

Magnetite

41.2

41.7

Total

100

100

100

100

100

100

100

100

100

100

100

100

100

100

ZTR index

51

66

41

68

57

16

48

35

72

15

27

91

50

52

Tourmaline
Rutile

ACCEPTED MANUSCRIPT

120-1

120-2

120-3

120-4

120-5

120-6

120-7

120-8

120-9

120-16

134-1

134-4

134-9

SiO2

37.119

36.703

35.076

35.979

36.198

34.482

35.695

35.55

36.042

34.184

35.961

35.748

35.501

TiO2

0.406

0.69

0.312

0.616

0.087

0.644

0.377

0.324

0.436

1.074

0.271

0.741

1.128

Al2O3

32.047

32.958

33.319

33.413

28.998

32.835

31.59

34.411

30.951

29.525

35.18

30.383

28.199

FeO

5.185

7.725

12.506

8.336

7.691

14.682

9.385

10.753

11.927

16.033

7.988

8.029

8.458

MnO

0.03

0.076

0.146

0.136

0.267

0.016

0.065

0.015

0.02

0.081

0.043

0.206

MgO

8.156

5.498

2.645

5.169

8.723

1.22

6.028

3.024

4.457

2.259

3.946

6.607

8.217

CaO

0.3

0.06

0.316

0.72

2.198

0.186

0.792

0.282

0.306

0.73

0.204

0.989

3.123

Na2O

2.44

2.275

2.12

1.907

1.722

2.152

1.992

1.799

2.219

2.431

1.608

1.825

1.166

K2O

0.044

0.057

0.071

0.03

0.053

0.047

0.052

0.092

0.02

0.036

0.058

0.338

0.462

0.522

0.155

0.489

0.565

0.051

1.236

0.052

0.72

0.479

O=F

0.142

0.195

0.22

0.065

0.206

0.238

0.021

0.52

0.022

0.303

0.202

O=Cl

H2O*

3.28

3.076

3.033

3.224

3.287

2.969

3.388

3.161

3.346

2.796

3.074

2.95

3.218

B2O3*

10.691

10.622

10.391

10.599

10.447

10.259

10.461

10.503

10.397

10.085

10.566

10.341

10.397

Total(%)

99.85

99.994

100.223

100.259

99.665

100.077

99.771

99.953

100.097

99.945

98.929

98.11

99.948

Si4+

6.034

6.006

5.867

5.9

6.022

5.841

5.931

5.883

6.025

5.891

5.915

6.008

5.935

Al3+

0.133

0.1

0.159

0.069

0.117

0.109

0.085

0.065

subtotal

6.034

6.006

6.022

6.025

6.008

SC
R

NU

MA

5.686

5.888

5.49

0.314

0.112

0.51

0.356

0.435

0.357

0.397

0.116

0.594

0.098

0.735

0.018

0.05

0.085

0.039

0.076

0.011

0.082

0.047

0.04

0.055

0.139

0.034

0.094

0.142

0.705

1.057

1.749

1.143

1.07

2.08

1.304

1.488

1.667

2.311

1.099

1.128

1.182

0.004

0.011

0.021

0.019

0.038

0.002

0.009

0.002

0.003

0.011

0.006

0.029

1.977

1.341

0.66

1.264

1.849

0.308

1.493

0.746

1.111

0.468

0.968

1.655

1.538

2.875

2.85

2.904

2.859

2.93

2.906

2.963

2.877

2.933

2.921

2.847

2.902

2.891

Ca2+

0.052

0.011

0.057

0.126

0.392

0.034

0.141

0.05

0.055

0.135

0.036

0.178

0.559

0.769

0.722

0.687

0.606

0.555

0.707

0.642

0.577

0.719

0.812

0.513

0.595

0.378

0.009

0.012

0.015

0.006

0.011

0.01

0.011

0.02

0.004

0.008

0.012

X-vacancy

0.179

0.259

0.244

0.252

0.046

0.248

0.207

0.362

0.226

0.033

0.447

0.22

0.05

subtotal

2+

Mg

subtotal

TE

Al3+

CE
P

Z site

T site

IP

Sample No.

Table 4

0
6

Y site

4+

Ti

2+

Fe

2+

Mn

2+

Mg

subtotal

0.14

AC

Al3+

X site

Na
K

V+W site
OHO

3.557

3.358

3.384

3.526

3.648

3.355

3.755

3.489

3.731

3.214

3.373

3.308

3.588

2-

0.269

0.403

0.34

0.394

0.095

0.342

0.245

0.485

0.269

0.112

0.6

0.31

0.159

0.174

0.239

0.276

0.08

0.257

0.303

0.027

0.674

0.027

0.383

0.253

ACCEPTED MANUSCRIPT
subtotal

Antion sum

31

31

31

31

31

31

31

31

31

31

31

31

31

Tourmaline
species

Dravite

Dravite

Schorl

Dravite

Dravite

Schorl

Dravite

Schorl

Schorl

Fluor-schorl

Oxy-schorl

Fluor-dravite

Uvite

3+

AC

CE
P

TE

MA

NU

SC
R

IP

*calculated on the basis of ideal stoichiometry (B=3 apfu; OH+F=4 apfu).

ACCEPTED MANUSCRIPT
Highlights

CE
P

TE

MA

NU

SC
R

IP

The Devonian sandstones in the Shanzhou area are highly recycled.

Detrital tourmalines correlate with protolithes of granitic and metamorphic rocks.
The Qinling Complex is a principal source area of the Devonian sandstones.
The Devonian sandstones are deposited in a foreland tectonic setting.

AC