# Giant Mesozoic gold ores derived from subducted oceanic slab and overlying sediments

Kun-Feng Qiu, Jun Deng, Crystal Laflamme, Zheng-Yu Long, Ruo-Qi Wan, Frédéric Moynier, Hao-Cheng Yu, Jing-Yuan Zhang, Zheng-Jiang Ding, Richard Goldfarb

► To cite this version:

Kun-Feng Qiu, Jun Deng, Crystal Laflamme, Zheng-Yu Long, Ruo-Qi Wan, et al.. Giant Mesozoic gold ores derived from subducted oceanic slab and overlying sediments. Geochimica et Cosmochimica Acta, 2023, 343, pp.133-141. 10.1016/j.gca.2023.01.002. hal-03935990

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1 Giant Mesozoic gold ores derived from subducted oceanic slab

2 and overlying sediments

3

4 Kun-Feng Qiu¹,²,³, Jun Deng¹,²,*, Crystal Laflamme⁴, Zheng-Yu Long¹, Ruo-Qi Wan¹,

5 Frederic Moynier⁵, Hao-Cheng Yu¹, Jing-Yuan Zhang¹, Zheng-Jiang Ding², Richard

6 Goldfarb¹,³

7 ¹State Key Laboratory of Geological Processes and Mineral Resources, School of Earth

8 Sciences and Resources, China University of Geosciences, Beijing 100083, China

9 ²Ministry of Natural Resources Technology Innovation Center for Deep Gold Resources

10 Exploration and Mining, No. 6 Geological Team of Shandong Provincial Bureau of Geology and

11 Mineral Resources, Weihai, Shandong, 264209, China

12 ³Center for Mineral Resources Science, Department of Geology and Geological Engineering,

13 Colorado School of Mines, 1516 Illinois Street, Golden, CO 80401, USA

14 ⁴Département de géologie et de génie géologique, Université Laval, Quebec City QC G1V 0A6,

15 Canada

16 ⁵Université Paris Cité, Institut de physique du globe de Paris, CNRS, F-75005 Paris, France

17

18 *Correspondence to:

19 Prof. Jun Deng (djun@cugb.edu.cn)

20
22 Orogenic gold deposits account for more than 30% of the global gold resources. To
23 understand the genesis of orogenic gold deposits and ultimately target new orogenic gold
24 deposits, it is important to determine the origin of gold. However, there has been a continuing
25 debate surrounding gold source reservoirs. The Jiaodong gold province, comprising ore hosted
26 within Mesozoic granitoids that intruded Archean metamorphic rocks, together with other gold
27 occurrences in the North China block, collectively constitute the only Mesozoic world-class gold
28 resource in a Precambrian basement. This geological setting, with young deposits in ancient
29 rocks, offers a great opportunity to better determine the gold source because it allows us to
30 fingerprint the isotopically distinct reservoirs. Specifically, it is possible to determine whether
31 the mass-independent isotopic fractionation sulfur (MIF-S)-bearing Archean supracrustal rocks
32 that form the lower crust are a permissive source. We present multiple sulfur isotope (δ³⁴S and
33 Δ³³S) measurements of pyrite grains (n = 161) from 18 gold deposits in the six main districts of
34 the Mesozoic Jiaodong gold province. Gold-associated pyrite grains yield non-MIF-S signatures
35 (Δ³³S=0 ‰), indicating that Archean metasedimentary rocks are not a source reservoir of sulfur
36 and gold. The isotopically heavy S (average δ³⁴S = +9.0 ± 3.7 ‰, 2SD) demonstrates a sulfur
37 contribution from a subducted oceanic slab and, in particular, its overlying sediments while
38 excluding mantle and magmatic sources. The subduction-related metamorphism released
39 appreciable gold and sulfur from the top of the downgoing slab into aqueous-carbonic fluids that
40 ascended into the upper plate along crustal structures traversing a tectonically thinned crust.
41 Here, we demonstrate that these giant Mesozoic orogenic gold deposits sourced gold and sulfur
42 during subduction-related devolatilization reactions.

43 **Keywords:** Gold source; Multiple sulfur isotope; Subducted sediments; Orogenic gold deposits;
44 Jiaodong gold province

45

46 **1. INTRODUCTION**

47 Gold is one of the most precious commodities, widely desired for jewelry and finances,
48 as well as being increasingly used in electronics, communications, aerospace, and medical
49 applications. To meet the growing demand for gold in modern society, it is necessary to improve
50 our understanding of where gold deposits form and of the key factors controlling the formation
51 of gold deposits. Orogenic gold deposits account for more than 30% of the global gold resources,
52 thus representing one of the most important types of gold deposits. These deposits generally have
53 formed during accretionary and collisional orogenesis and are preserved near the margins of
54 lithospheric blocks amalgamated during supercontinent cycles (Groves et al., 1998; Goldfarb et
55 al., 2005). The Phanerozoic orogenic gold deposits are described mainly as having formed in
56 orogens due to prograde metamorphism, consistent with a supracrustal devolatilization model
57 (Phillips and Powell, 2010; Tomkins, 2010). In accretionary orogens, crustal rocks added to
58 continental blocks may release auriferous fluid as they are heated through greenschist and
59 amphibolite facies conditions. However, a notable exception is the giant Jiaodong gold province
60 of China, where the gold deposits formed in a reactivated and previously heated Precambrian
61 basement along the Asian continental margin during the latter stages of Jurassic-Cretaceous
62 orogenesis and are, therefore, distinguished from other Phanerozoic orogenic gold deposits
63 (Goldfarb et al., 2021). Approximately 95% of the gold resources in Jiaodong are hosted within
64 Mesozoic granitoids that have intruded Archean and, to a lesser degree, Paleoproterozoic
65 basement rocks (Goldfarb et al., 2019; Qiu et al., 2020). The Jiaodong deposits formed
66 approximately two billion years after the high-grade metamorphism of the Precambrian rocks,
which depleted the restitic crust of the Precambrian basement in volatiles (Goldfarb and Santosh, 2014; Wang et al., 2021), thus negating the typical supracrustal devolatilization model. The case of Jiaodong indicates the genetic model for Phanerozoic orogenic gold deposits requires a variety of scenarios for metal, sulfur, and fluid sources for the ores.

The unique geological setting of the Jiaodong gold province, with young deposits hosted in ancient basement rocks, creates the perfect natural laboratory to evaluate potential source reservoirs for gold. This setting is characterized by a continuing debate regarding whether sulfur and gold were derived from Precambrian metamorphic rocks (Mills et al., 2015; Hu et al., 2022), granitic magmas (Li et al., 2015), lithospheric mantle (Wang et al., 2020), or the top of a subducted oceanic slab (Goldfarb and Santosh, 2014).

The recycling of sulfur among geochemical reservoirs plays a significant role in the formation of ore deposits. In particular, gold is mostly carried by H₂S complexes in the aqueous-carbonic fluids that form orogenic gold deposits, thus implying that sulfur acts as the dominant complexing ligand (e.g., bisulfide complexes) for gold transport and precipitation. Tracing the transfer of sulfur from one reservoir to another thus can potentially fingerprint the gold released from a specific reservoir (LaFlamme et al., 2018b).

The mass-dependent isotopic signature (reported as δ³⁴S, the permil deviation of the sulfur isotopic ratio relative to V-CDT) of sulfides in ore deposits is an ideal proxy to fingerprint reservoirs from which sulfur is sourced. However, there have been limitations when using δ³⁴S in the Jiaodong gold deposits, as the characterization of its value in the source reservoir has remained problematic. First, various sulfur reservoirs have similar δ³⁴S values (Deng et al., 2020b). Second, δ³⁴S is sensitive to changing fluid thermochemistry (i.e., changes in temperature-pH-fO₂) as it transcends the crust and undergoes a variety of fluid-rock reactions
90 (Zhu et al., 2018; Sugiono et al., 2022; Long et al., 2023). Mass-independent fractionation of
91 sulfur (MIF-S; here as Δ³³S) represents the deviation from the mass-dependent fractionation
92 process. The Δ³³S of sulfides can unequivocally monitor the input of Archean sedimentary sulfur
93 that preserves MIF-S signatures (Fig.3; LaFlamme et al. 2018b). The MIF-S was exclusively
94 produced by atmospheric photolysis reactions before the Great Oxidation Event and is thus
95 recorded in Archean sedimentary rocks prior to ca. 2.4 Ga (Farquhar et al., 2001; Whitehill et al.,
96 2015). Once formed, the anomalous MIF-S signal is preserved and transferred between
97 reservoirs during any chemical reaction. The MIF-S signature provides a robust imprint of the
98 Archean supracrustal rock record (Cabral et al., 2013), and fluid-rock interaction and
99 metamorphic devolatilization related to subduction or burial processes are the possible pathways
100 to recycle the MIF-S component to orogenic gold deposits (LaFlamme et al., 2018b). Many
101 Precambrian orogenic gold deposits are characterized by a non-zero Δ³³S signature, which
102 reflects the recycling of sulfur from Archean sedimentary rocks (e.g., LaFlamme et al., 2018a;
103 LaFlamme et al., 2018b; Santiago et al., 2021). Furthermore, the analyses of Δ³³S can provide
104 essential clues for identifying Archean signatures in the continental lithosphere and for revealing
105 the subduction-related recycling of Archean surficial components at mantle depths (Smit et al.,
106 2019).
107 Here, we present a detailed multiple sulfur isotope study of the Jiaodong gold deposits,
108 which includes ore-related pyrite sampled from 18 gold deposits in the six gold-producing
109 districts. Combining δ³⁴S and Δ³³S, we fingerprint the likely source for the voluminous Mesozoic
110 gold accumulation, which offers a new window into revealing the formation process for world-
111 class gold deposits.
112
## 2. GEOLOGICAL BACKGROUND OF THE NORTH CHINA BLOCK

The Jiaodong gold province is tectonically located in the eastern part of the North China block (NCB). The eastern block has been tectonically active and has a complex depositional, magmatic, and orogenic history from the Early Archean to the Mesoproterozoic and later in the Mesozoic (Kusky et al., 2007). Large Archean banded iron formations (BIF) developed in the eastern NCB. These BIF, mainly related to metamorphosed sedimentary and volcanic rocks, are located in the Archean metamorphosed basement. According to field and oxygen isotopic studies, some of these formed in a submarine volcanic setting related to Archean subduction processes (e.g., Zhang et al., 2012). Significant MIF-S signals (Δ³³S values = -0.9 ‰ to +1.2 ‰; Hou et al., 2007) have been identified in syn-sedimentary pyrites from the Archean BIF, indicating that MIF-S was recycled in Archean supracrustal rocks of the NCB. In fact, multiple episodes of subduction from the Archean to Mesozoic have been recorded in the NCB (Kusky and Li, 2003; Zhao et al., 2005). For example, incipient intra-oceanic subduction has been confirmed at ~2.55 Ga, which metasomatized the mantle and generated many island-arc tholeiites, high-Mg andesites, and adakites (Kusky et al., 2016). During the Neoarchean to Early Paleoproterozoic, the western margin of the eastern NCB bordered a major ocean that subducted beneath the eastern NCB and resulted in extensive thrusting and high-pressure metamorphism (Zhao et al., 2005). Northward deep subduction of the Yangtze block below the NCB occurred during the Late Permian to Late Triassic.

More importantly, oblique subduction of the Paleo-Pacific Plate (Izanagi slab) occurred along the eastern margin of the NCB during the Jurassic and Early Cretaceous (Zhou and Li, 2000). In Jiaodong, initial subduction-related magmatism resulted in the emplacement of Linglong granitoids at ca. 160 to 150 Ma, followed by Guojialing granitoids and by slightly
136 younger mafic dikes during slab rollback at ca. 130 to 120 Ma (Deng et al., 2020b). The mafic
137 dikes emplaced at 130 to 120 Ma show a compositional signature indicating that they were
138 sourced from an enriched lithospheric mantle, while younger dikes (ca. 100 to 80 Ma) show
139 chemical affinities with oceanic island basalt and are considered to be derived from the
140 asthenospheric mantle. This geochemical characteristic suggests that lithospheric mantle thinning
141 may have been common during much of the Cretaceous (e.g., Liu et al., 2009; Deng et al., 2017).
142 The ca. 120 Ma age for the gold deposits of the Jiaodong province corresponds to the extensional
143 regime at the end of lithospheric delamination at the base of NCB. It is also correlated with
144 major changes in plate kinematics in the Pacific Basin and the onset of seismicity along the Tan-
145 Lu fault system (Fig. 1A).
146

146

147 3. GEOLOGY OF THE JIAODONG GOLD PROVINCE AND SAMPLING

148 The giant Jiaodong gold province, together with other gold occurrences within the NCB,
149 collectively constitute a Mesozoic world-class gold resource (Fig. 1A) responsible for about 3 to
150 4 percent of the annual global gold production. The Jiaodong gold deposits define the largest
151 gold-producing province in China, with an estimated pre-mining resource of 5,000 tonnes of
152 gold (Qiu et al., 2020). Numerous gold ores are concentrated in the San-Cang, Jiao-Xin, Zhao-
153 Ping, Qi-Peng, Mu-Ru, and northeast Jiaolai Basin gold districts (Fig. 1B). The deposits occur in
154 linear gold belts along NE- to NNE-striking transtensional fault zones. The rocks in Jiaodong are
155 dominated by Neoarchean high-grade basement lithologies but also include some
156 Paleoproterozoic metamorphosed rocks in the Jiaobei Terrane to the west and Triassic UHP
157 metamorphic rocks in the Sulu Terrane to the east (Fig. 1B). Mesozoic granitic intrusions were
158 mainly emplaced into the basement rocks of the Neoarchean Jiaodong Group, consisting of 2.9 to
159
160

2.6 Ga tonalite-trondhjemite-granodiorite (TTG) gneisses, amphibolites, and granulite facies
metavolcanic rocks (Qiu et al., 2020).

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Throughout the Jiaodong gold province, ores mostly occur in the footwall of the faults within the Linglong granitoids. Although there is a spatial association between the gold ores and the Linglong granitoids, the emplacement of these crustal magmas predates the gold event (~120 Ma) by approximately 25 to 40 m.y (Deng et al., 2020a; Zhang et al., 2020). The Guojialing granitoids have temporal overlap with the gold mineralization but lack a spatial association with the ores and their hosting structures. The mineralization styles of the Jiaodong gold deposits are characterized by auriferous quartz-pyrite veins (Fig. 2A) and disseminated sulfide-stockworks (Fig. 2B). The auriferous quartz-sulfide veins occur in small brittle fracture systems and generally contain abundant pyrites (Fig. 2C). In comparison, disseminated-stockwork ore is hosted in regional ductile-shear fracture systems and is characterized by disseminated sulfides in the center of quartz-pyrite-sericite altered rocks surrounded by K-feldspar alteration haloes (Fig. 2D). Orebodies in all districts primarily consist of native gold, electrum, sulfides, and carbonate minerals. The auriferous carbonate vein and breccia orebodies in the Jiaolai Basin are typically hosted by breccia zones between Cretaceous sedimentary and volcanic rocks and late Jurassic granitoids and have intense pyrite-sericite-quartz-calcite alteration. Pyrite is the dominant gold-hosting mineral. Native gold and electrum grains occur as inclusions (Fig. 2E) or fill cracks in pyrite and quartz (Fig. 2F), and, less commonly, invisible gold may be hosted within pyrite in solid solution and/or as nanoparticles (Deng et al., 2020a).

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An H₂O-CO₂-rich fluid composition for the Jiaodong ores is identified in most fluid inclusion studies (e.g., Qiu et al., 2020). An important observation is that the veining can extend down-dip for >3 km, with ore formation estimated at 5.4 to 9 km in the Linglong gold district,
with no significant changes in mineralogy, alteration, and fluid chemistry (Guo et al., 2020; Deng et al., 2020b). The lack of zoning over such great vertical ranges and the unlikely scenario of extensive magmatic fluid release at such depths argue against a magmatic-hydrothermal fluid source (e.g., Goldfarb and Pitcairn, 2022). Features of the Jiaodong gold province resemble those of orogenic gold deposits, including the linear structural distribution of the deposits, fluid chemistry, mineralization styles, and alteration assemblages (Goldfarb and Santosh, 2014; Deng et al., 2020b; Qiu et al., 2020).

The sample set of this study was collected from 18 gold deposits within the six main gold districts in the Jiaodong province (Fig. 1B). Ore samples from four mineralization styles (e.g., auriferous quartz-pyrite vein, disseminated sulfide-stockwork, carbonate-pyrite vein, and breccia) were collected and characterized during field sampling. Based on these lithological and petrographic observations, pyrite grains formed in the same paragenetic event as gold were selected for isotopic analysis to constrain the sulfur, and thus metal, source.

195

## 4. ANALYTICAL METHOD

Multiple sulfur isotopic ratios ($^{33}$S/$^{32}$S and $^{34}$S/$^{32}$S) of pyrite grains were analyzed using a CAMECA IMS1280 large-geometry ion microprobe at the Centre for Microscopy, Characterisation, and Analysis (CMCA), University of Western Australia (UWA). Trimmed mounts (to a 4 mm width) were coated with 30 nm of gold and loaded with a standard block into the sample holder. The 2.5 to 5 nA focused (Gaussian mode) Cs$^{+}$ primary beam interacted with the sample at 20 keV. The analyzed area was pre-sputtered for 30 s using a 25 × 25 µm raster, followed by secondary beam centering and analysis using a 15 × 15 µm rastered beam. The secondary sulfur ions from the target sample were extracted and passed to the mass spectrometer
at 100× magnification with automated centering of the secondary beam in the field/aperture (both x and y; aperture size 4000 µm) and entrance slit (x direction only; slit width 60 µm).

Isotopes ³²S, ³³S, and ³⁴S were simultaneously detected in the mass spectrometer by three Faraday Cups equipped with 10¹⁰ Ω (L'2), 10¹¹ Ω (L1), and 10¹¹ Ω (H1) resistors, respectively.

Specific preparation, analytical procedures, and reference materials are described in LaFlamme et al. (2016). Drift correction, monitoring internal sample repeatability, and calibration of isotope ratios are based on the analyses of Sierra pyrite (δ³⁴S = +2.17 ‰, 1SE = ±0.04 ‰; δ³³S = +1.09 ‰, 1SE = ±0.02 ‰). The long-term reproducibility (2SD) of Sierra is δ³⁴S = ±0.28 ‰ and δ³³S = ±0.15 ‰. The δ³⁴S and Δ³³S data are reported in per mil (‰), expressed as:

$$214 \quad \delta^{3x}S (\text{‰}) = \left[ \frac{\left( \frac{3xS}{32S} \right)_{\text{sample}}}{\left( \frac{3xS}{32S} \right)_{\text{V-CDT}}} - 1 \right] \times 1000 \quad (\text{with } x = 3 \text{ or } 4)$$

$$215 \quad \Delta^{33}S (\text{‰}) = \delta^{33}S_{\text{measured}} - [(1 + \delta^{34}S)^{33\lambda} - 1] \times 1000$$

where ³³λ = 0.515 (Hulston and Thode, 1965). The λ values approximate the relationships for high-temperature equilibrium isotopic fractionations. The measurement uncertainty for the δ³³S and δ³⁴S values of each analysis propagates the internal error on the raw isotopic ratios, the uncertainty on the drift correction where necessary, and the uncertainty on the measured reference material (LaFlamme et al., 2016). Within this run, measurement error (2σ) on the analyses is less than δ³⁴S ±0.4‰ and Δ³³S ±0.16‰.

## 5. RESULTS

The analytical results show that pyrite grains (n = 161) yield Δ³³S values ranging between -0.14 ‰ and +0.09 ‰ with a mean of -0.04 ± 0.09 ‰ (2SD on the mean). The resulting δ³⁴S-Δ³³S trend of Jiaodong pyrites is distinct from the Archean reference array (Fig. 3). In addition, when considering measurement error on each analysis (±0.10 to 0.16 ‰ for Δ³³S; 2σ), each data
point is within the uncertainty of the updated limit extent of MDF-S defined by LaFlamme et al. (2018a) (Fig. 4). Pyrite grains from the Jiaodong gold province yield relatively high δ³⁴S values ranging from +3.2 ‰ to +14.1 ‰ with a mean of +9.0 ± 3.7 ‰ (2SD on the mean).

231

## 6. DISCUSSION

233 **6.1. Archean crustal basement played a limited role in forming the giant Jiaodong gold province**

234 Various genetic models for the origin of the massive gold resource in the Jiaodong gold province have been proposed. Mills et al. (2015) suggested a crustal source in which upwelling asthenosphere, as a response to lithospheric mantle erosion and crustal thinning during slab subduction, triggered the melting of Archean crust to form gold-bearing magmas. Exsolution of auriferous fluids from these Early Cretaceous granitic intrusions was hypothesized to result in gold mineralization (Li et al., 2015). In addition, Wang et al. (2020) argued for an auriferous fluid exsolved from magma derived from the enriched subcontinental lithospheric mantle (SCLM). In contrast to a fluid exsolved from a melt, Goldfarb and Santosh (2014) hypothesized that gold was derived from the devolatilization of Mesozoic subducted sediments from the top of the Izanagi slab. This would be consistent with the above observation that the lack of vertical zoning in the ores and the depth of ore formation are inconsistent with most magmatic-hydrothermal systems. Nevertheless, these arguments are not fully definitive.

246 The Archean basement rocks have been hypothesized to be the source of sulfur in the Jiaodong gold province in some studies (e.g., Mills et al., 2015; Hu et al., 2022). Multiple sulfur isotopes can conclusively evaluate the opposing models and the potential of recycling of the Archean crust as a potential source of sulfur and gold. Given the widely existing Δ³³S record in globally Archean supracrustal rocks (Fig. 3) and likewise in the NCB (Hou et al., 2007), if

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auriferous fluids were sourced from the Archean rocks, then the gold-associated sulfides would exhibit the recycled MIF-S signature as demonstrated in many orogenic gold deposits in Archean terranes (e.g., LaFlamme et al., 2018b; Godefroy-Rodriguez et al., 2020; Santiago et al., 2021; Sugiono et al., 2021). Moreover, LaFlamme et al. (2018b) interpret the largely consistent but diluted MIF-S signature ($\Delta^{33}\text{S}$= +0.1 to +0.5‰) across many orogenic gold deposits of the Yilgarn craton to indicate that the source of Archean sedimentary sulfur is at depth, rather than proximal to the deposits. The MIF-S signature would be preserved if local fluid-rock interaction contributed sulfur to the fluid during its ascent (Sugiono et al., 2021). For the Jiaodong gold province, all measured pyrite grains lack MIF-S across the $\delta^{34}\text{S}$ range (Fig. 4), thereby excluding the contribution of any substantial amount of sulfur from Archean rocks to the ore-forming process via devolatilization or fluid-rock interaction. It also rules out remelting of the Archean crust as a gold source.

## 6.2. Gold and sulfur sourced from sediments subducted beneath a thinned Precambrian upper plate?

The Jiaodong gold deposits show temporal and spatial associations with lamprophyres derived from the SCLM. Given the limited volume of lamprophyres compared to gold deposits, these mafic dikes cannot be the parental magma of ore fluids, but they have been suggested as sharing a common mantle source with the auriferous fluids (Deng et al., 2020b; Wang et al., 2022). The prerequisite for the SCLM as the gold and sulfur source is that the SCLM must have been metasomatized and fertilized by metal- and sulfur-rich melts/fluids derived from the convecting mantle and subducted crustal materials (Griffin et al., 2013). The Early Cretaceous mafic dikes from Jiaodong show large ion lithophile element enrichment, high field strength
element depletion, and crustal Sr-Nd isotopic composition (($^{87}$Sr/$^{86}$Sr)$_{i}$ = ~0.709; ε$_{Nd}$(t) = ~-15; Ma et al., 2014; Deng et al., 2017), indicative of derivation from a metasomatized SCLM.

Moreover, gold-associated pyrites are characterized by consistently positive δ³⁴S (average +9.0 ± 3.7 ‰, 2SD). These high δ³⁴S values are consistent between the different mineralization styles throughout the Jiaodong gold province (Fig. 4). The δ³⁴S values of pyrites thus can reflect the source characteristic. With appropriate consideration of the sulfur isotope fractionation associated with the transport, this still indicates that a sulfur source of relatively high δ³⁴S values is required to form the Jiaodong gold deposits. For mantle-derived sulfur, the δ³⁴S values typically cluster around 0 ± 3 ‰ (Labidi et al., 2013). The high δ³⁴S thus displays a significant crustal contribution rather than mantle sourcing.

Subduction-related metamorphism would release H₂S and gold into the resulting fluid through the breakdown of pyrite to pyrrhotite (Tomkins, 2010; Steadman et al., 2013). Slab-derived fluids metasomatized the overlying mantle and enriched the domain in volatiles, including sulfur, preserving the signal of crustal δ³⁴S. Because of the polyphase subduction history surrounding the NCB, the SCLM beneath the Jiaodong gold province is potentially a residence for sulfur throughout different geological periods, including the Archean, Proterozoic, and Mesozoic. Sulfur can be transported from subducted slab and sediments into the ambient mantle and be long-lived in the SCLM over Earth's history (Delavault et al., 2016; Smit et al., 2019; Hutchison et al., 2021; Magalhaes et al., 2019). Mantle xenoliths hosted within kimberlites and basalts from the NCB, representing the underlying Archean to Paleoproterozoic SCLM, contain high sulfur contents of 140 to 510 ppm (Chu et al., 2009) but low Au contents of 0.06 to 0.50 ppb (Wang et al., 2020) relative to the primitive mantle, which suggests the addition of a portion of crustal sulfur before the Phanerozoic. Numerous studies highlighted the metasomatism
and incorporation of subducted Archean sediments into the enriched mantle beneath the NCB based on geochemical and isotopic signatures (e.g., Wang et al., 2017, Smithies et al., 2019; Gao et al., 2020). Recycling of Archean supracrustal sulfur from a previously metasomatized mantle has been observed through non-zero Δ³³S signatures within Proterozoic (Magalhaes et al., 2019; LaFlamme et al., 2018c) and Cenozoic igneous rocks (Cabral et al., 2013). Given that subducted Archean sedimentary rocks would recycle MIF-S to the SCLM beneath the NCB, melts or fluids derived from or that have interacted with the SCLM may inherit this unique signal (e.g., Smit et al., 2019). Moreover, the δ³⁴S values of sediments have been relatively invariant (−5 to +5 ‰) during the Archean (Canfield and Farquhar, 2009). Therefore, the near-zero Δ³³S and significantly positive δ³⁴S signals of pyrites do not support any Archean subducted materials within the SCLM beneath the Jiaodong gold province as an initial source for sulfur in these gold deposits.

Globally, alkaline igneous rocks (derived from the metasomatized SCLM) record a secular evolution of δ³⁴S values, which reflect the changing composition of the SCLM and are interpreted to be controlled by increasingly fractionated subducted sediments through time (Hutchison et al., 2019). In view of the variable δ³⁴S values of sediments throughout geological history, the Proterozoic sediments, of which δ³⁴S pyrite increases from a mean of 0 ‰ at ~ 1.5 Ga to +20 ‰ at ~ 600 Ma (Canfield and Farquhar 2009), are seemingly a compatible candidate for the isotopically heavy sulfur. If this were the case, then a sulfur endowment in the mantle occurred much earlier, and the Proterozoic isotopically heavy sulfur would be preserved during the long-term residence in the SCLM (Burness et al., 2021; Lee et al., 2018). Processes related to the lithospheric extension and/or asthenosphere upwelling reactivated the pre-existing sulfur that transported gold released from Mesozoic oceanic sediments back to the surface. However, given
the volume of Proterozoic sediments, it is problematic whether the Proterozoic sulfur subducted into the SCLM is extensive enough to cover the entire Jiaodong gold province to the extent that sufficient sulfur could be released at 120 Ma.

A key observation is that the 130 to 120 Ma lamprophyres spatially associated with the Jiaodong gold deposits, which represent small-volume melts of the metasomatic mantle, display elevated Au (mainly 1 to 3 ppb) and S (400 to 3000 ppm) contents, indicating subduction-related metasomatism of the mantle that endowed it with both gold and sulfur in the Mesozoic (Wang et al., 2022). The large-scale gold events in the Jiaodong gold province collectively occurred at 120 Ma (Deng et al., 2020a; Zhang et al., 2020), which is in agreement with Mesozoic gold enrichment during the middle-late Mesozoic oceanic subduction event. For gold deposits formed during the Phanerozoic, increased marine oxygenation promoted gold uptake by biogenic and diagenetic pyrite grains that may become a source of gold (Tomkins, 2013). Thus, a more favorable model here is that the fluid, gold, and a large proportion of sulfur are derived from the devolatilization of the westerly subducting Izanagi slab and overlying sediments during the Mesozoic (Qiu et al., 2020). The gold accumulation in newly formed SCLM temporally associated with the giant gold ores deposited at supracrustal depths could result from Mesozoic subduction. Oceanic slab subduction produces a high flux of gold and other metals (e.g., Ag, As, Sb, and Te), sulfur, and volatile-enriched fluid/melt that fertilize the SCLM (Steadman et al., 2013; Epstein et al., 2021). These volatiles act as transporting agents for the gold and may play a key role in amplifying the gold contents of the melt/fluid released from the SCLM or subducted slab (Wang et al., 2022). The heavy sulfur isotopic compositions in the Jiaodong gold province thus inherited from the sulfur that originated from the sulfate reduction. Although the mean $\delta^{34}$S value of Phanerozoic sediments is significantly negative, a compilation from Canfield and
Farquhar (2009) shows seafloor pyrite can locally be very largely fractionated to both positive and negative values (Δ³⁴S = ~ 40‰) in the Phanerozoic due to the bacterial sulfate reduction and other metabolizing pathways (Farquhar et al., 2010; Leavitt et al. 2013; Tostevin et al., 2014).

This inference is reasonable because the signals of isotopically heavy sulfur recycling into the mantle have also been found in the Phanerozoic alkaline igneous rocks (Hutchison et al., 2019 and reference therein). The SCLM beneath the Jiaodong gold province may represent an abnormally metasomatized domain characterized by near-zero Δ³³S and positive δ³⁴S compositions. Although a small fraction of the Proterozoic sulfur stored in the SCLM is not ruled out, the scenario involving the contribution of Mesozoic subducted oceanic slab appears the most reasonable hypothesis to account for the Jiaodong gold province.

To summarize, by using multiple sulfur isotopes, this study pinpoints a deep reservoir for sulfur and gold and eliminates the alternative scenario of mixing with external sulfur derived from Archean metamorphic rocks through fluid-rock interaction during fluid ascent or at the deposition location. New observations constrain the giant Mesozoic gold source, i.e., the subducted oceanic slab and overlying sediments exclusively acted as the source for the giant Mesozoic gold ores at supracrustal depths, excluding the previously proposed scenario of the mantle and magmatic sources. The subduction-related metamorphism released appreciable H₂O, CO₂, gold, and sulfur from the top of the downgoing slab to form a large fluid volume associated with the formation of giant gold deposits in the crust.

### 6.3. Implications for giant Mesozoic orogenic gold deposits

The genetic model related to fluid and metal sourced from a subducted slab may be most applicable to the formation of orogenic gold deposits in active margins that are non-accretionary.
The giant Jiaodong orogenic gold province is an excellent case of such a tectonic event.

However, it remains unclear whether metamorphism to release the auriferous fluids from the slab would occur during ca. 120 Ma rollback or during ca. 160 to 150 Ma underthrusting. If the latter, fluids, as well as the gold and sulfur, would have been temporarily stored in the overlying SCLM and subsequently released in a transient geodynamic event at 120 Ma (Goldfarb and Santosh, 2014). The instantaneous giant gold event at 120 Ma (Zhang et al., 2020) suggests a specific trigger for fluid re-migration. Much of the originally slab-derived sulfur and gold stored in the metasomatized mantle domain might be heated and released during the extension-induced tectonic conversion and/or asthenosphere upwelling in the Early Cretaceous (e.g., Wu et al., 2019). There may well have been some major changes in the stress regime related to the reorganization of the Paleo-Pacific plate configuration and the onset of seismicity along the Tan-Lu fault system (Goldfarb et al., 2007). Released auriferous fluids would migrate updip along the deep fault and eventually precipitate during intersecting favorable structures in the supracrust.

This study highlights the importance of the subducted slab and overlying sediments as source reservoirs of gold and sulfur, which may be released during subduction, stored in the mantle wedge, and ascend through the crust to form orogenic gold deposits during lithospheric rollback.

## 7. CONCLUSIONS

New multiple sulfur isotope data ($\delta^{34}$S = +9.0 ‰ and $\Delta^{33}$S = ~0 ‰) suggest no derivation of sulfur and gold from the underlying Archean supracrustal rocks to the Jiaodong gold deposits. This finding indicates that Mesozoic gold deposits in Archean cratons do not recycle sulfur from the lower crust, potentially leading new insights into source reservoirs of Phanerozoic orogenic gold deposits worldwide. Analysis of samples throughout the Jiaodong
gold deposits reveals an overall <sup>34</sup>S-enriched signature indicating a significant crustal
contribution rather than mantle origin. This study supports the devolatilization of subducting
sediments as the source of sulfur and gold for orogenic gold deposits. We therefore propose that
the subducted oceanic slab and especially overlying sediments provide gold and sulfur for the
giant Jiaodong gold province, where gold ascends together with the released H<sub>2</sub>S during the
devolatilization of the downgoing oceanic slab during the subduction.

395

396 ACKNOWLEDGMENTS

We gratefully acknowledge the constructive comments of the Executive Editor Jeffrey
Catalano, Associate Editor Adam Simon, and two anonymous journal reviewers, and earlier
suggestions by Shaun Barker, Stephen Kesler and William Hutchison. This study was financially
supported by the National Natural Science Foundation of China (42130801, 42261134535,
42072087, and 41973048), the National Key Research Program (2019YFA0708603), the Beijing
Nova Program (Z201100006820097), the 111 Project of the Ministry of Science and Technology
(BP0719021), and the Shandong Provincial Engineering Laboratory of Application and
Development of Big Data for Deep Gold Exploration (SDK202211, SDK202214).

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600

601 FIGURE CAPTIONS

602 Figure 1. (A) Simplified geologic map of the NCB. Modified after Qiu et al. (2020); (B) Sample
603 locations on a simplified map of the Jiaodong gold province. Modified after Deng et al. (2020b).

604 Figure 2. Field photographs and photomicrographs showing the characteristics of typical
605 alterations and ores of the Jiaodong gold province. (A) Auriferous quartz-sulfide vein with
606 alteration halos cutting K-feldspar altered granitoid. (B) Disseminated-stockwork mineralization
607 in pyrite-sericite-quartz alteration zone. (C) Hand specimen of auriferous quartz-sulfide vein. (D)
608 Hand specimen of disseminated-stockwork ore. (E) Pyrite and native gold (Au) in vein
609 mineralization. (F) Pyrite and native gold in disseminated mineralization.

610 Figure 3. Multiple sulfur isotope composition of the pyrites from the Jiaodong gold province and
611 comparison with the Archean rocks. The full data of Archean sediments are from the available
612 database published by LaFlamme et al. (2018a).

613 Figure 4. Comparison of multiple sulfur isotopes of pyrites from different mineralization style
614 ores. Gray triangle represents the updated limit (<sup>33</sup>λ ranging from 0.508 to 0.519) of mass-
615 dependent isotopic fractionation of sulfur defined by LaFlamme et al. (2018a).
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