Rhenium enrichment in the northwest Pacific arc

Journal Pre-proofs Rhenium enrichment in the northwest Pacific arc Renqiang Liao, Congying Li, He Liu, Qian Chen, Weidong Sun PII: DOI: Reference:

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Please cite this article as: R. Liao, C. Li, H. Liu, Q. Chen, W. Sun, Rhenium enrichment in the northwest Pacific arc, Ore Geology Reviews (2019), doi: https://doi.org/10.1016/j.oregeorev.2019.103176

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Rhenium enrichment in the northwest Pacific arc Renqiang Liao1,3,4, Congying Li1,2,4, He Liu1,2, 4, Qian Chen1,3,4, Weidong Sun1-4* 1Center

of Deep Sea Research, Institute of Oceanology, Chinese Academy of Sciences,

266071 Qingdao, China 2Laboratory

for Marine Mineral Resources, Pilot National Laboratory for Marine

Science and Technology (Qingdao), 266237 Qingdao, China 3University 4Center

of Chinese Academy of Sciences, 100049 Beijing, China

for Ocean Mega-Science, Chinese Academy of Sciences, 266071 Qingdao,

China *Corresponding

author: [email protected]

Abstract Rhenium (Re) is one of the least abundant elements in the silicate Earth. However, independent rhenium sulfide was reported in the Usu and Kudryavy volcanos, namely rheniite (ReS2, 74.5 wt% of Re). This raises questions about the sources of the Kurile–Kamchatka volcanic island arc magmas and geochemical cycling of Re. The oxidation-reduction cycle on the Earth's surface is the major process that concentrates Re in reduced sediments. The northwest part of the Pacific plate mainly consists of Jurassic to Cretaceous oceanic crust, with abundant organic-rich sediments. During plate subduction, Re is remobilized early due to the devolatilization of organic-rich sediments and then the decomposition of sulfide (e.g., pyrite), and is subsequently added to the mantle wedge at shallow depths, which is usually not sampled by arc magmas unless there is a major change in the subduction regime. Ridge subduction in the northwest Pacific was initially characterized by low angle subduction. When slab rollback started, rhenium-enriched components were involved in arc magmas, and further concentrated in volcanic vents because of the volatility of Re, forming rheniite.

Keywords: Rhenium; Black shales; Oceanic anoxic events; Subduction; Dehydration 1

1. Introduction Rhenium (Re) is one of the most important elements for the aviation industry because of its heat resistance and its ability to make super-hard alloys. However, rhenium is also one of the least abundant elements on Earth (McDonough and Sun, 1995; Sun et al., 2003a; Rudnick and Gao, 2014). The rhenium resources are predominantly as a substituting element in molybdenite of porphyry Cu-Mo deposits and sulfides in the sediment-hosted mineralization. Remarkably, pure rhenium sulfide rheniite (ReS2) with 74.5 wt% Re (Znamensky et al., 2005) was reported in Kudryavy volcano, the Kuril-Kamchatka arc, in northwest Pacific. The Re contents of the Kudryavy volcanic rocks hosting the rheniite range from 3.5 to 17.1 ppb, with an average of 7 ppb (Tessalina et al., 2008), which are higher than the 0.65 to 6 ppb Re in melt inclusions from undegassed primary arc volcanics worldwide (Sun et al., 2003a). Such high Re contents in subaerially deposited arc volcanic rocks are unusual. Although the sources of the unique Re enrichment have been discussed in many studies (Taran et al., 1995; Ishikawa and Tera, 1997; Fischer et al., 1998; Botcharnikov et al., 2003), consensus has not yet been achieved. Based on the Re–Os isotope systematics and trace elements in volcanic gases, sulfide precipitates and the hosted volcanic rocks, it has been proposed that the high Re contents can be explained by Re remobilization from the altered oceanic crust and subducted organic-rich sediments of the Pacific plate by Cl-rich water (Tessalina et al., 2008). Given that organic-rich sediments are widely distributed in the Pacific Ocean, a question arises as to why rheniite has only been reported in the Kuril-Kamchatka arc, of the northwest Pacific? Here we propose that subduction of rhenium-enriched sediments followed by slab rollback is the key factor that controlled the extreme Re enrichment.

2

2. Geochemical characteristics and enrichment of rhenium Rhenium is one of the least abundant elements in Earth, with an abundance of 0.28 ppb in the primitive mantle (McDonough and Sun, 1995), while MORB has an estimated Re abundance of 1 ppb (Schiano et al., 1997; Sun et al., 2003b). The Re abundance varies dramatically in crustal sediments and rocks ranging from 0.2 to 0.4 ppb in loess (Peucker-Ehrenbrink and Jahn, 2001), and up to 6 ppb in melt inclusions and submarine volcanic glasses from convergent margins (Sun et al., 2003a). It is highly enriched in black shales, with concentrations ranging from 3-1000 ppb (van der Weijden et al., 2006; Poirier and Hillaire-Marcel, 2011). Therefore, the estimated Re abundance in the continental crust varies significantly (Esser and Turekian, 1993; Peucker-Ehrenbrink and Jahn, 2001; Taylor and McLennan, 1985, 1995; Rudnick and Gao, 2014). Nevertheless, as a moderately incompatible element, Re should be enriched in the continental crust (McDonough and Sun, 1995; Sun et al., 2003b; Rudnick and Gao, 2014) compared to MORB, which is depleted in incompatible elements (Sun and McDonough, 1989). The Re abundance in the continental crust should be higher than the MORB value of 1 ppb and has been estimated to be around 2 ppb (Sun et al., 2003a). High temperature experiments show that Re is incompatible in most rock-forming minerals, such as olivine, pyroxene, plagioclase and spinel, and compatible in garnet and magnetite in the absence of sulfide, and strongly compatible in sulfide liquid (Righter et al., 1995, 1998, 2004; Righter and Hauri, 1998; Waston et al., 1987; Roy-Barman et al., 1994; Table 1). During mantle magmatic processes, Re partitions into sulfide liquid with respect to silicate melt under reducing condition. Since Re is moderately incompatible in most silicate minerals depending on oxygen fugacity, the partition coefficient of Re in magmas is controlled by both sulfur and oxygen fugacity (Mallmann and O’Neill, 2007; Fonseca et al., 2007). Similar to Mo, Re is concentrated through the oxidation-reduction cycle during chemical weathering on the surface of the Earth (Sun et al., 2016). During weathering, Re is readily oxidized to form water-soluble ReO4― in surface environments (Helz 3

and Dolor, 2012; Sun et al., 2015) and during volcanic degassing (Yudovskaya et al., 2006, 2008). Water-soluble ReO4― is transported to oceans and lakes, and then, through reduction in anoxic sediments it precipitates and is retained to form Re sulfides or S-rich complexes. In general, reduced water bodies with large catchment areas are avorable places for the formation of Re-enriched sediments, due to anoxic environments and Re-enriched surface water. Enclosed and semi-enclosed water bodies regularly form reducing environments, which facilitates reduction and absorption of Re and other elements with variable valences (Sun et al., 2016) resulting in their high enrichment in black shales (Morford et al., 2012; Dubin and Peucker-Ehrenbrink, 2015). The Re content in different anoxic sediments varies greatly, ranging from a few to up to several thousand ppb. However, there are positive correlations between Re and total organic carbon (TOC) contents in modern organic-rich sediments of the same locality (Fig. 1). The compositions of sediments from different environments are characterized by trends with different slopes on TOC versus Re plots that may reflect the redox conditions of the water body during the Re deposition, or may be related to the Re/TOC in the source region (Sun et al., 2016).

3. Rhenium-enriched sulfides in the northwest Pacific arc The first Re disulfide was found in Usu volcano, Hokkaido in 1986 (Bernard and Dumortier, 1986). Following this discovery, Korzhinsky et al. (1994) reported rheniite (ReS2) (Znamensky et al., 2005) in a hand specimen from fumaroles on Kudryavy volcano, Iturup Island, in the Kuril Islands. Rhenium-enriched sulfide and other oxide and sulfide minerals precipitate from volcanic gases within the Kudryavy fumarolic fields. Those minerals also have high Re contents, e.g., molybdenite (MoS2), powellite (CaMoO4) and cannizzarite (Pb4Bi6S13) contain 1.5-1.7 wt%, 10 ppm, and 65-252 ppb Re, respectively (Tessalina et al., 2008). It is estimated that the Kudryavy volcano discharges up to 20-60 kg rhenium per year mostly in the form of volatile species in gas emission with subordinate local concentrations in the fumarolic crust (Kremenetsky and Chaplygin, 2010; Tessalina et al., 2008). Although the exact age of 4

the volcano is unknown, the stationary degassing is believed to have been active for the last l40 years (Taran et al., 1995; Tessalina et al., 2008). The open system degassing likely prevents significant metal accumulations, which otherwise could be as high as ~ 8 tons Re. The Re contents of the subaerially-erupted Kudryavy volcanic rocks are much higher than those of Kamchatka (av. 0.5 ppb) and other arc volcanic rocks (Alves et al., 2002), as well as MORB (Escrig et al., 2005). The values are several times higher than the Re abundances in melt inclusions from undegassed primary arc volcanic glasses (0.65 to 6.0 ppb Re) (Sun et al., 2003a) but are lower than those of black shales (Fig. 2), which have the highest Re contents among silicate rocks. Noticeably, although some fumaroles in other volcanoes on the Kamchatka-Kuril Island arc, such as gases, sublimates, condensates, etc., do not form pure Re sulfides, the content of Re in the products is also very high, e.g., Gorely volcano (Chaplygin et al., 2015), Tolbachik volcano (Zelenski et al., 2014; Chaplygin et al., 2016). In particular, Taran et al. (2008) reported exceptionally high Re abundances in fumaroles of Pallas volcano that are three times higher than those in the Kudryavy fumaroles.

4. Oceanic anoxic events and black shales in the Pacific Nine

major

Oceanic

Anoxic

Events

(OAEs)

occurred

during

the

Jurassic-Cretaceous period worldwide, including those of the early Toarcian (~183 Ma), early Aptian (~120 Ma), early Albian (~111 Ma), and Cenomaniane-Turonian (~93 Ma) (Alberdi-Genolet and Tocco, 1999; Jenkyns, 2010; McElwain et al., 2005; Scopelliti et al., 2006; Suan et al., 2010; Turgeon and Brumsack, 2006; Turgeon and Creaser, 2008; Wang et al., 2001; Wilson and Norris, 2001; Zou et al., 2005). The prevailing view suggests that the major forcing conditions behind OAEs were abrupt increases in global temperatures (Suan et al., 2010; Wilson and Norris, 2001), induced by rapid ingrowth of CO2 and/or methane to the atmosphere (Hesselbo et al., 2000; Jenkyns, 2010). OAEs accompany significant changes in marine biota (Erba, 1994; Erba and Tremolada, 2004) and widespread deposition of organic matter-rich 5

sediments (e.g. Sliter, 1989; Bralower et al., 1994; Menegatti et al., 1998; Leckie et al., 2002). Initially, Schlanger and Jenkyns (1976) put forward the term “Oceanic Anoxic Events (OAEs)” to explain the origin of the “black shales” amongst Cretaceous sediments discovered during deep-sea drilling (Leg 32, 33) in the Pacific Ocean. Black shales and organic-rich sediments that formed during OAEs (Jenkyns, 2010) in the Jurassic and the Cretaceous are widely distributed in the Pacific (Robinson et al., 2004; Takashima et al., 2010). Many Deep Sea Drilling Project (DSDP) and Ocean Drilling Program (ODP) expeditions have drilled into thick Re-rich black shales in the central and northwest Pacific Ocean (Fig. 3) (Morford et al., 2012; Fig. 2). During high oxygen periods before the OAEs, Re was intensively oxidized to form water soluble ReO4― , which consequently results in enhanced Re discharge to oceans and lakes (Sun et al., 2016). Given that Re cannot be retained by sediments in oxidized bottom waters (Dubin and Peucker-Ehrenbrink, 2015), the Re concentration in sea waters rose to much higher levels during warm high-oxygen periods than that occurring under lower temperature conditions. Subsequently, accumulated Re precipitated under the reduced conditions associated with the OAEs and results in the Re concentrations in anoxic sediments being up to several hundred times higher than those in the continental crust (Ravizza and Turekian, 1989, 1992; Cohen et al., 1999; Peucker-Ehrenbrink and Hannigan, 2000; Creaser et al., 2002; Brumsack, 2006).

5. Geochemical behavior of rhenium during plate subduction In general, dehydration of the subducting slab and consequent element migration are continuous processes that take place over a range of temperatures and pressures. Considering that concentrations are controlled by different minerals with different stability fields, the composition of fluids and melts derived from the subducting slab also varies with depths (Ishikawa and Nakamura, 1994; Ishikawa and Tera, 1997; Bebout, 2007). Slab fluids and melts are both rich in volatiles, including H2O, H2S and Cl species, and able to transport chalcophile and siderophile metals from the slab 6

to the overriding mantle wedge (Keppler, 2017). Many studies have shown that seafloor sediments on the surface of the down-going slab may deliver significant contributions to the mantle wedge (e.g., Wysoczanski et al., 2006; Plank and Langmuir, 1998; Labanieh et al., 2018). Sea-floor sediments are water-rich and pelitic in composition, and thus are more likely to undergo dehydration and partial melting with respect to the basaltic oceanic crust under subduction zone conditions (Hermann and Spandler, 2008). Among them, organic-rich sediments control the recycling of Re. Rhenium is highly mobile during dehydration of the subducting slab (Sun et al., 2004a), as well as during blueschist metamorphism (Becker, 2000). In black shales and organic-rich sediments, Re is mainly hosted by sulfides and S-rich complexes (Dubin and Peucker-Ehrenbrink, 2015). Compounds bonded to organic matter are released mostly at the early stage of plate subduction, whereas sulfide species are released later. The presence of a sulfide mineral has a significant effect on the behavior of chalcophile metals like Re during metamorphism (Righter, 2005; Li, 2014; Li and Audetat, 2012; Huang and Keppler, 2015). Among many natural sulfides, pyrite is a widespread trace component of many different rock types prior to regional metamorphism and subduction (Craig and Vokes, 1993; Tomkins, 2010). It commonly forms in sedimentary environments through bacterial sulfate reduction (Volker et al., 2001; Large et al., 2014; Cavalazzi et al., 2014) that leads to its common association with organic-rich sediments and black shales. Pyrite is also a typical accessory mineral of igneous and volcaniclastic rocks, including mafic rocks that have undergone sea-floor metasomatism (Li et al., 2004; Laflamme et al., 2016). A major sulfur liberation event occurs at breakdown of pyrite during prograde metamorphism that may scavenge chalcophile elements out of silicate rocks (Tomkins, 2010; Sun et al., 2013). In the continental crust, the pyrite breakdown in mafic rocks occurs mainly at the transition from greenschist to amphibolite facies (Tomkins, 2010) as the conditions force a significant proportion of metamorphic H2O to be liberated from chlorite. This results in the transfer of S2- into the metamorphic fluids, which 7

then migrate upwards. The highest concentrations of S2- in metamorphic fluids have been found within and in the vicinity of pyrite- and graphite-bearing metasediments metamorphosed at moderate to low pressures corresponding to the conditions of terminal breakdown of chlorite (Tomkins, 2010; Li et al., 2015). This process can induce another major release of Re.

6. Mechanism of rhenium enrichment in the northwest Pacific arc One of the common and unique characteristics of arc magmas, compared to MORBs

and

back-arc

basin

basalts,

is

volatile

enrichment

due

to

subducted-slab-released fluids (e.g., Arculus, 1994; Pearce and Peate, 1995; Sun et al., 2003b, c). Consistent with its geotectonic settings, the Kuril-Kamchatka island arc also exhibits these characteristics (Taran et al., 1995; Fischer et al., 1998; Botcharnikov et al., 2003; Ishikawa and Tera, 1997; Yudovskaya et al., 2008; Bindeman and Bailey, 1999; Kersting and Arculus, 1995; Tomascak et al., 2002; Tessalina et al., 2008). However, compared to other subduction systems, one of the most remarkable features of the Kuril-Kamchatka arc is its enrichment in Re. Many efforts have been made to explain the sources of the unique Re enrichment in Kuril-Kamchatka arc. The radiogenic Re-Os isotope signature of volcanic rocks and the elevated Re and Os abundances in fluids of the Kudryavy volcano were used to argue for a significant Re input from subducted seafloor sediments (Tessalina et al., 2008). Meanwhile, peridotite xenoliths, which are regarded as the nearest representatives of a residual mantle of the Kamchatka-Kuril region, have shown similar Re-Os isotope characteristics (Saal et al., 2001; Widom et al., 2003; Saha et al., 2005). These studies showed that the Kamchatka peridotite xenoliths have a more radiogenic Os isotope signature compared to the relatively unradiogenic Horoman peridotites in Hokkaido suggesting that the Kamchatka sub-arc mantle wedge was likely more seriously affected by fluid metasomatism. Remarkably, trace elements and isotopic ratios of volcanic rocks in the Kamchatka-Kuril arc, such as Sm-Nd, Rb-Sr and Pb-Pb isotope systematics, indicate 8

that their geochemical signatures were mostly inherited from a depleted MORB-type source (Yudovskaya et al., 2008) and that the input of sedimentary materials was minor and insignificant (Bindeman and Bailey, 1999; Kersting and Arculus, 1995). Lithium isotope compositions (δ7Li, +2.9‰ – +7.4‰) (Tomascak et al., 2002) and B isotope compositions (δ11B, +4‰ – +4.6‰) (Ishikawa and Tera, 1997) show that the sequestration of slab-derived Li and B in the sub-arc mantle occurred before they reached the zone of melting and volatiles were mainly derived from the altered oceanic crust. Studies of H, He and C isotopic compositions of the fumarolic gases suggest that subducted sediments, the mantle wedge, and altered oceanic crust were all sources of fluids for the Kudryavy volcano (Taran et al., 1995; Fischer et al., 1998; Botcharnikov et al., 2003). The differences in abundance between highly fluid mobile elements and less mobile elements strongly indicate the influences of subduction released fluids. Based on the geochemical features of Re and geological settings of Kuril-Kamchatka arc, we show that Re enrichment is related to the subduction of seafloor black shales widely distributed in Pacific Ocean. As noted in previous studies, anoxic sediments and black shales are the primary sink for Re in the continental crust (Koide et al., 1986; Colodner et al., 1993; Crusius et al., 1996; Hauri and Hart, 1997; Morford et al., 2005; Morford et al., 2012). The high Re/Os ratios and high concentrations of Re in reduced sediments (Fig. 2), as compared to the average continental crust indicate that supergene sedimentary processes are very important in Re enrichment. In the northwest Pacific Ocean, conditions were favorable for Re enrichment. The northwest part of the Pacific plate subducts underneath the Kuril-Kamchatka arc, and mainly consists of Jurassic to Cretaceous oceanic crust, with abundant organic-rich sediments (Fig. 3). As discussed in Section 5, subducted Re-enriched sediments release a large amount of Re into hydrothermal fluids formed from breakdown of organic matter, pyrite and chlorite during prograde metamorphism in the greenschist to blueschist and amphibolite facies (Fig. 4a). Due to the low temperatures, such fluids have low Si and lithophile element contents (Spandler and 9

Pirard, 2013) that results in their buoyant behavior and migration upwards into the overlying mantle wedge. Partial melting of the mantle wedge corresponds to depths where transition from the amphibolite to eclogite facies in the subducting slab occurs (Tatsumi and Eggins, 1995; Xiong et al., 2011) (Fig .4b). Therefore, the Re-enriched part of the mantle wedge is not subjected to partial melting unless there is a major change in the subduction regime. The drift history of the Pacific and the Izanagi plates since the Late Cretaceous suggests that there was a low-angle ridge subduction in this region (Kinoshita, 1995; Sun et al., 2007; Wu et al., 2017). The subduction angle increased from ridge subduction to slab rollback and resulted in partial melting of mantle peridotite metasomatized by Re-enriched fluids. During partial melting, Re behaves as a moderately incompatible element and enters the melts (Hauri and Hart, 1993; Shirey and Walker, 1998; Sun et al., 2003c). Experiments have shown that Re is strongly compatible in sulfide liquid with respect to silicate melts (Roy-Barman et al., 1994; Brenan, 2002, 2008; Li, 2014). In silicate melts, sulfur is mainly presented as sulfide S2- under relatively reduced conditions, e.g. oxygen fugacity lower than Ni-NiO (Pokrovski and Dubrovinsky, 2011; Sun et al., 2013). The partition coefficient of sulfur between fluids and magmas is also very high (519±30) (Huang and Keppler 2015). Therefore, siderophile elements including Re would be scavenged into hydrous fluids in the form of hydrosulfide or sulfide complexes in the absence of coexisting sulfide melts (Carroll and Rutherford, 1988; Sun et al., 2004b; Wilkinson, 2013; Huang and Keppler, 2015). Vapor-transport may also play an important role in the upward migration of Re-rich fluids (Williams-Jones et al., 2002; Mungall et al., 2015). Given that Re is highly volatile, it is further enriched during degassing with discrete Re disulfide mineralization eventually forming in volcanic vents. Noticeably, the Re abundances in fumaroles formed in other geological settings, e.g., continental rift (Zelenski et al., 2013), are also relatively high. The geological settings of the region needs to be taken into account in explaining the elevated Re abundances of the volcanic fumaroles. 10

7. Conclusions Anoxic Re-rich sediments that formed during Oceanic Anoxic Events, especially Early Albian (OAE1a), are widely distributed in the northwest Pacific. During initial low-angle plate subduction, sediments release significant amounts of a volatile Re species in to the fluids formed through metamorphic dehydration, devolatilization of organic matter, as well as through the decomposition of pyrite. This fluid migrates upward and metasomatizes the mantle wedge. As the subduction angle increases, partial melting of the lower temperature portions of the mantle wedge that has been metasomatized by Re-bearing fluids, produces Re-enriched arc magmas. The high volatility of Re promotes its further enrichment to form discrete rhenium sulfide, rheniite. Acknowledgment This work was supported by National Key Resource & Development Program of China (2016YFC0600408) and Chinese Academy of Sciences Strategic Pilot Project (XDB18020000). Thanks to professor Trevor Ireland of Australian National University for proof reading the final version of this contribution. References Alberdi-Genolet, M., Tocco, R., 1999. Trace metals and organic geochemistry of the Machiques

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Figure captions Fig. 1 Rhenium contents versus total organic content (TOC) in black shales. Coupled Re-TOC data for ancient and modern anoxic sealed-basin environments. A well-defined relationship is observed between Re and TOC local concentrations suggesting a specific source Re/TOC for each locality. The different slopes in the different localities may reflect different redox states or source characteristics. Modern anoxic sealed-basin environments: Redcar Mudstone Formation, UK (Porter et al., 2013), Algae Member, Hekkingen Formation, Barents Sea (Georgiev et al., 2017), Lomonosov Ridge, Central Arctic Ocean (Poirier and Hillaire-Marcel, 2011), 24

Mt.McRae Shale, Western Australia (Anbar et al., 2007; Kendall et al., 2015), Fjacka Shale, Sweden (Lu et al., 2017), OAE1a, Maiolica & Marne a Fucoidi Formations, Italy (Tejada et al., 2009; Ancient anoxic sealed-basin environments: Murray Ridge, Arabian Sea (Ravizza et al., 1991), Black Sea (Van der Weijden et al., 2006; Piper and Calvert, 2011).

Fig. 2 Re vs. Re/Os plot for the Kudryavy volcanic rocks (modified from Tessalina et al., 2008). Data on black shales are from Ravizza and Turekian, 1989; Cohen et al., 1999; Peucker-Ehrenbrink and Hannigan, 2000; Creaser et al., 2002; Brumsack, 2006. The compositions of Kamchatka (Widom et al., 2003; Saha et al., 2005) and Japan xenoliths (Senda et al., 2007; Brandon et al., 1996), arc lavas from Java, Lesser Antilles and Kamchatka (Alves et al., 2002), MORB (Roy-Barman and Allegre, 1994), Kuriles (Tessalina et al., 2008), melt inclusions from arc volcanics (Sun et al., 2003c), Hawaii (Hauri and Hart, 1997; Lassiter, 2003), DMM and PUM (Shirey and Walker, 1998) are shown for comparison. Note that the black shales have the highest Re contents.

Fig. 3 The current age distribution of oceanic crust in the Central-Western Pacific Ocean (modified from Muller et al., 2008). Drilling sites that recovered mid-Cretaceous (OAE1a) organic-rich strata are shown numbered according to DSDP and ODP Initial Reports. The inferred were based on the contents of organic carbon, C/N ratios, gamma radiation and resistivity in relative sediments (Jenkyns, 2010), and Initial Reports (http://www.deepseadrilling.org/i_reports.htm). Insert figure shows total thickness of organic-rich sediments distributed in different Sites. Some of the cores with black shales layers have very poor recovery, most lower than 10%, or even as low as 1%, indicating the total thickness of organic-rich sediments may be very thick.

Fig. 4 Cartoons showing the position of rhenium release and the formation of rhenium-enriched sulfide (modified from Sun et al., 2016). a. Devolatility of organic 25

matters and decomposition of pyrite releasing S2- occurred at conditions ranging from the lower greenschist facies to the greenschist–amphibolite facies transition and subsequently remobilizing Re in anoxic sediments and forming rhenium-enriched hydrothermal fluids. b. With the change of subduction angle from flat to steep, the temperature increases, causing partial melting of the mantle wedge metasomatized by rhenium-enriched fluids. See text for detail discussion.

Table captions Table 1: Summary of partition coefficient data (mineral/silicate melt) for Re

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Table 1: Summary of partition coefficient data (mineral/silicate melt) for Re Mineral Phase

Kd(Re)§

log fO2/Buffer#

References

Cr-spinel

0.0012-0.21

-3.39~<-1.5/MHO-None

Righter et al., 2004

(Ru) Plagioclase

0.01

>NNO

Righter et al., 1995

Orthopyroxene

0.013

<-1.5/None (Ru)

Righter et al., 2004

Olivine

0.017-0.073

-6.49~-1.65/NNO-HM

Righter et al., 2004

Augite

0.03-0.05

>NNO

Righter et al., 1995; Waston et al., 1987

Clinopyroxene

0.18-0.21

-6.49~<-1.5/NNO-None

Righter et al., 2004

Magnetite

20-50*

unknow

Righter et al., 1998

Garnet

1.5-3.0

-10.6~-8.4/ΔFMQ

Righter and Hauri, 1998

Sulfide liquid

1200

0.41~3.21/ΔFMOP

Roy-Barman et al., 1994

(Ru)

§

Kd(Re)=CRe(mineral)/CRe(silicate liquid)

* Estimated #

from the Re-SiO2 trend in the Alcedo suit. See detail information from Righter et al., 1998

MHO = magnetite–hematite, NNO = nickel–nickel oxide, HM = hematite–magnetite, FMQ =

fayalite–magnetite–quartz, FMQP = fayalite–magnetite–quartz–pyrrhotite

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Graphical Abstract

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Highlights 

Rhenium enrichment in the Kuril-Kamchatka arc is related to the subduction of Pacific plate.



Subduction of rhenium-enriched sediments followed by slab rollback is the key factor that controlled the extreme Re enrichment.



The high volatility of Re promotes further enrichment of rhenium to form independent rhenium sulfide.

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