Plate subduction, oxygen fugacity, and mineralization

Plate subduction is the largest natural factory that processes elements,which controls recycling and mineralization of a variety of elements.There are three major ore deposit belts in the world:the circumPacific,the centralAsian,and the Tethys belts.All the three belts are closely associated with plate subductions,the mechanism remains obscure.We approached this problem from systematic studies on the behaviours of elements during geologic processes.This contribution summaries the recent progress of our research group.Our results suggest that porphyry Cu deposits form through partial melting of subducted young oceanic crust under oxygen fugacities higher than AFMQ^+1.5,which is promoted after the elevation of atmospheric oxygen at ca.550 Ma.Tin deposits are associated with reducing magmatic rocks formed as a consequence of slab rollback.The Neo-Tethys tectonic regime hosts more than 60%of the world's total Sn reserves.This is due to the reducing environment formed during the subduction of organic rich sediments.For the same reason,porphyry Cu deposits formed in the late stages during the closure of the Neo-Tethys Ocean.Tungsten deposits are also controlled by slab rollback,but is not so sensitive to oxygen fugacity.Subduction related W/Sn deposits are mostly accompanied by abundant accessory fluorites due to the breakdown of phengite and apatite.Decomposition of phengite is also significant for hard rock lithium deposits,whereas orogenic belt resulted from plate subduction promote the formation of Li brine deposits.Cretaceous red bed basins near the Nanling region are favorable for Li brines.Both Mo and Re are enriched in the oxidationreduction cycle during surface processes,and may get further enriched once Mo-,Re-enriched sediments are subducted and involved in magmatism.During plate subduction,Mo and Re fractionate from each other.Molybdenum is mainly hosted in porphyry Mo deposits and to a less extent,porphyry Cu-Mo deposits,whereas Re is predominantly hosted in porphyry Cu-Mo deposits and sedimentary sulfide deposits.

High oxygen fugacity magma:implication for the destruction of the North China Craton

The mechanism of lithospheric removal and destruction of the North China Craton(NCC)has been hotly debated for decades.It is now generally accepted that the subduction of the(Paleo)-Pacific plate played an important role in this process.However,how the plate subduction contributed to the craton destruction remains unclear.Here we report high oxygen fugacity(fO2)characteristics of the Yunmengshan granite,e.g.,hematitemagnetite intergrowth supported by zircon Ce^4+/Ce^3+ratios and apatite Mn oxygen fugacity indicator.High fO2 magmas are widely discovered in Late Mesozoic(160-130 Ma)adakitic rocks in central NCC.The origin of high fO2 magma is likely related to the input of the"oxidized mantle components",which shows a dose connection between plate subduction and destruction of the craton.The research area is^1500 km away from the current Pacific subduction zone.Considering the back-arc extension of Japan Sea since the Cretaceous,this distance may be shortened to^800 km,which is still too far for normal plate subduction.Ridge subduction is the best candidate that was responsible for the large scale magmatism and the destruction of the NCC.Massive slab-derived fluids and/or melts were liberated into an overlying mantle wedge and modified the lithospheric mantle.Rollback of the subducting plate induced the large-scale upwelling of asthenospheric mantle and triggered the formation of extensive high fO2 intraplate magmas.

Study of oxygen fugacity during magma evolution and ore genesis in the Hongge mafic–ultramafic intrusion, the Panxi region, SW China

Economic concentrations of Fe–Ti oxides occurring as massive layers in the middle and upper parts of the Hongge intrusion are different from other layered intrusions(Panzhihua and Baima) in the Emeishan large igneous province, SW China. This paper reports on the new mineral compositions of magnetite and ilmenite for selected cumulate rocks and clinopyroxene and plagioclase for basalts. We use these data to estimate the oxidation state of parental magmas and during ore formation to constrain the factors leading to the abundant accumulation of Fe–Ti oxides involved with the Hongge layered intrusion. The results show that the oxygen fugacities of parental magma are in the range of FMQ-1.56 to FMQ+0.14, and the oxygen fugacities during the ore formation of the Fe–Ti oxides located in the lower olivine clinopyroxenite zone(LOZ) and the middle clinopyroxenite zone(MCZ) of the Hongge intrusion are in the range of FMQ-1.29 to FMQ-0.2 and FMQ-0.49 to FMQ+0.82, respectively.The MELTS model demonstrates that, as the oxygen fugacity increases from the FMQ-1 to FMQ+1, the proportion of crystallization magnetite increases from 11 % to 16 % and the crystallization temperature of the Fe–Ti oxides advances from 1134 to 1164 °C. The moderate oxygen fugacities for the Hongge MCZ indicate that the oxygen fugacity was not the only factor affecting the crystallization of Fe–Ti oxides. We speculated that theinitial anhydrous magma that arrived at the Hongge shallow magma chamber became hydrous by attracting the H_2O of the strata. In combination with increasing oxygen fugacities from the LOZ(FMQ-1.29 to FMQ-0.2) to the MCZ(FMQ-0.49 to FMQ+0.82), these two factors probably account for the large-scale Fe–Ti oxide ore layers in the MCZ of the Hongge intrusion.

The effect of oxygen fugacity on ionic conductivity in olivine

The oxygen fugacity(f_(O2)) may affect the ionic conductivity of olivine under upper mantle conditions because Mg vacancies can be produced in the crystal structure by the oxidization of iron from Fe^(2+) to Fe3+. Here we investigated olivine ionic conductivity at 4 GPa, as a function of temperature, crystallographic orientation, and oxygen fugacity, corresponding to the topmost asthenospheric conditions. The results demonstrate that the ionic conductivity is insensitive to f_(O2) under relatively reduced conditions(f_(O2) below Re-ReO_(2) buffer), whereas it has a clear f_(O2)-dependence under relatively oxidized conditions(f_(O2) around the magnetite-hematite buffer). The ionic conduction in olivine may contribute significantly to the conductivity anomaly in the topmost asthenosphere especially at relatively oxidized conditions.

Oxygen Fugacity and Water Activity during Thermal Peak and Retrogression of Granulites around the Sarvapuram Area, Karimnagar Granulite Terrane, Andhra Pradesh, India

The investigated area around Sarvapuram represents a part of the Karimnagar granulite terrane of the Eastern Dharwar Craton, India. Garnet–bearing gneiss is hosted as enclaves, pods within granite gneiss and charnockite. It is largely made up of garnet, orthopyroxene, cordierite, biotite, plagioclase, K–feldspar, sillimanite and quartz. The peak metamorphic stage is represented by the equilibrium mineral assemblage i.e. garnet, orthopyroxene, cordierite, biotite, plagioclase, sillimanite and quartz. Breakdown of the garnet as well as preservation of the orthopyroxene–cordierite symplectite, formation of cordierite with the consumption of the garnet + sillimanite + quartz represents the decompressional event. The thermobarometric calculations suggest a retrograde P–T path with a substantial decompression of c. 3.0 kbar. The water activity(XH2 O) conditions obtained with the win TWQ program for core and symplectite compositions from garnet–bearing gneiss are 0.07–0.14 and 0.11–0.16 respectively. The quantitative estimation of oxygen fugacity in garnet–bearing gneiss reveal log f O2 values ranging from-11.38 to-14.05. This high oxidation state could be one of the reasons that account for the absence of graphite in these rocks.

Prospects for Future Application of Fugacity Model to Fate Studying of POPs in China

POPs can stay long enough to diffuse and transfer sufficiently in the environment. Researches indicate that it's inadequate to study POPs' fate and environmental behavior, in order to get comprehensive knowledge of the POPs' fate and transfer processes in an area, experiment should be combined with model simulation. Recently multimedia models have become the primary choice in simulating organic pollutant's fate and assessing exposure risk to ecosystem for they can nearly represent the real environment. Among all models, with simple structure, less required parameters, fugacity model has been an efficient tool used widely on simulating the fate and transport of POPs and put into practice in many countries and areas successfully. On the basis of achievements in scientific research, this paper will emphatically take up the following three questions one by one that consist of fugacity model's principle, pivotal questions and application prospects in china.

In-situ control of oxygen fugacity for laboratory measurements of electrical conductivity of minerals and rocks in a multi-anvil press

In this paper, a new of oxygen fugaeity controltechnique that can be widely applied to in-situ measurement of the grain interior electrical conductivities of minerals and rocks is presented for high temperature and high pressure. Inside the sample assembly, a metal and corresponding metal oxide form a solid oxygen buffer. The principle of this technique is to randomly monitor and adjust oxygen fugacity in the large-volume multi-anvil press by changing the types of solid oxygen buffer, metal shielding case and electrodes. At a pressure of up to 5.0 GPa and a temperature of up to 1423 K, the electrical conductivities of the dry peridotite are tested under the conditions of different oxygen fugacities. By virtue of this new technique, more and more reasonable and accurate laboratory electrical property data will be successfully obtained under controlled thermodynamic conditions.

A new technology for controlling in-situ oxygen fugacity in diamond anvil cells and measuring electrical conductivity of anhydrous olivine at high pressures and temperatures

We present a novel technique for controlling oxygen fugacity,which is broadly used to in-situ measure the electrical conductivities in minerals and rocks during diamond anvil cell experiments.The electrical conductivities of olivine are determined under controlled oxygen fugacity conditions(Mo–MoO2)at pressures up to 4.0 GPa and temperatures up to 873 K.The advantages of this new technique enable the measuring of the activation enthalpy,activation energy,and activation bulk volume in the Arrhenius relationship.This provides an improved understanding of the mechanism of conduction in olivine.Electrical conduction in olivine is best explained by small polaron movement,given the oxygen fugacity-dependent variations in conductivity.

Mineral Chemistry, Geobarometry and Oxygen Fugacity of the Granitic Rocks from the Itremo Domain, Central Madagascar

Major and accessory minerals from the Ibity granite, Tsarasaotra monzonitic and granite dykes, and Antsahakely granite of the Itremo domain in the Precambrian basement of Madagascar were characterized by using microscopic observations and chemical analyses with the aim of understanding their chemical characteristics and estimating the crystallization pressure and oxygen fugacity of their host rocks. Plagioclases in these rocks are albite and oligoclase, while alkali feldspars are orthoclase. For the phlogopite-micas, Fe-biotite and Li-phengite are common for the Ibity and Antsahakely granites, Mg-biotite is common for the Ibity granite and the Tsarasaotra monzonitic and granite dykes, and siderophyllite and Zinnwaldite are specific to the Ibity granite. Phlogopite-micas in the studied rocks are mainly primary, accessorily re-equilibrated, and rarely secondary. Calcic amphiboles distributed in the Magnesio-and Ferro-hornblende are identified in the Tsarasaotra monzonitic, whereas amphibole is rare and absent in the other rocks. Igneous titanite is observed in the Ibity granite and in the Tsarasaotra monzonitic rocks, which have similar compositions to some REE oxide-rich titanites. Concerning the Fe-Ti oxide phases, the rhombohedral and spinel/trifer tetroxide phases are found in both the Tsarasaotra monzonitic and the Tsarasaotra granite dyke, the trifer tetroxide and spinel + wüstite phases are found only in the Ibity granite, and the pseudobrookite + rhombohedral phase is found only in the Tsarasaotra granite dyke. The epidote mineral, rarely found in the Antsahakely granite, could be an indicator of metamorphism or hydrothermal activity involved during the emplacement of this rock. Aluminum in hornblende geobarometer gave pressure ranges of around 5 kbar for the Tsarasaotra monzonitic rocks. The Titanite geobarometer gave pressures of 2.5 - 3.2 kbar for the Ibity granite, 2.9 kbar for the Tsarasaotra monzonitic, and 7.1 kbar for the Antsahakely granite. Both amphibole and Fe-Ti oxide-base oxygen fugacity reveal high oxygen fugacity conditions for the Tsarasaotra monzonitic and granite dyke emplacements, which might have a relationship with a porphyritic environment.

Fate of organophosphate esters from the Northwestern Pacific to the Southern Ocean:Occurrence,distribution,and fugacity model simulation

Eleven organophosphate esters(OPEs)in the air and seawater were investigated from the northwestern Pacific Ocean to the Southern Ocean during the 2018 Chinese 34th Antarctic Scientific Expedition.The concentration of total OPEs ranged from 164.82 to 3501.79 pg/m~3in air and from 4.54 to 70.09 ng/L in seawater.Two halogenated OPEs,tri(chloropropyl)phosphate(TCPP)and tri(2-chloroethyl)phosphate(TCEP),were generally more abundant than the non-halogenated OPEs.A levelⅢfugacity model was developed to simulate the transfer and fate of seven OPEs in the air and seawater regions of the central Ross Sea.The model results indicate that OPEs are transferred from the air to the seawater in the central Ross Sea in summer,during which the Ross Sea acts as a final OPE sink.Dry and wet deposition dominated the processes involving OPE transfer to seawater.The OPE degradation process was also found to be more pervasive in the atmosphere than in the seawater region.These findings highlights the importance of long-range transport of OPEs and their air–seawater interface behavior in the Antarctic.

Geology and mineralization of the Dongping supergiant alkalic-hosted Au-Te deposit(>100 t Au)in Northern Hebei Province,China:A review

The Dongping deposit is the largest alkalic-hosted gold deposit in China containing>100 t of Au.This paper presents a new understanding for Dongping ore system,based on the previous studies.The mineralization originally occurred at 400-380 Ma,simultaneous with emplacement of the Shuiquangou alkaline complex,and was overprinted by the hydrothermal activity in the Yanshanian.Isotope compositions of ores indicate metals of the deposit are mainly provided by the Shuiquangou complex.Ore-forming fluids are characterized by increasing oxygen fugacity and decreasing sulfur fugacity,while tellurium fugacity increased in the Stage II-2 and decreased in Stage II-3.These systematic changes are closely related to the processes of mineral precipitation and fluid evolution.Sulfide precipitation from Stage Ⅰ to Stage Ⅱ was triggered by fluid boiling,which leads to the precipitation of Pb-Bi-Te,due to decrement of sulfur fugacity.Condensation of gas phase containing high concentration of H_2Te leads to precipitation of Te-Au-Ag minerals and native tellurium.Based on these hypotheses,this paper present a polyphase metallogenic model as follow.During the Devonian,fluids were released from alkaline magmas,which carried ore-forming materials form the surrounding rocks and precipitate the early ores.During the Jurassic-Cretaceous,fluorine-rich fluids exsolved from highly factionated Shangshuiquan granite,which extracted and concentrated Au from the Shuiquangou complex and the Sanggan Group metamorphic rocks,and finally formed the Dongping gold deposit.

Geochemistry and mineral chemistry of the armoor granitoids,eastern dharwar craton: implications for the redox conditions and tectono-magmatic environment

The mineralogical and geochemical characteristics of the K-rich granites from the Armoor granitic rocks in the northeastern portion of the Eastern Dharwar Craton(EDC) are presented.In order to understand its physicochemical conditions,the petrogenesis of the granitoid was explained from biotite chemistry and geochemical systematics.Studies of mineral chemistry expose that compositionally,K-feldspar and plagioclase in Armoor granite rocks range from An0,Ab_(3-5.9),Or_(94-96.9) and An_(5-29,-Ab71.9-94.9),Or_(0-1.5),respectively.The mineral chemistry of biotite crystals exhibits composition that varies from primary to re-equilibrated primary biotites.Although biotites from the Armoor granites generally exhibit an I-type trend,with calc-alkaline parental magma in a subduction setting.Biotite chemistry of granites displays magnetite(oxidized)series nature,which has oxygen fugacity(fO_(2))=-15.1 to-16.7(log_(10) bar),under high oxidizing conditions.Temperature and pressure estimates for the crystallization of Armoor granites based on biotite composition are T=612-716 ℃ and 1.0-0.4 kbar,respectively.Geochemically,these rocks are metaluminous to slightly peraluminous and magnesian,with calc-alkaline potassiumrich granite.On the chondrite normalized REE diagram,the granites have positive europium anomalies;rich Sr/Y,(Dy/Yb)_(N) ratios and reduced Mg#,Rb/Sr,Rb,Sr indicate that the melting of earlier rocks,crystal accumulation and residual garnet source formed at high pressures.The examined granites show that they are produced from the melting of crustal sources.Thus,the extensive analyses of the described Armoor granite suggest that they were produced by crust sources and developed under oxidizing conditions in subduction setting.

Reduced magma generation and its implications for the Pulang giant porphyry Cu-polymetallic deposit in Northwest Yunnan,China

The Pulang giant porphyry Cu-Mo polymetallic deposit is located in the Zhongdian area in the center of the Sanjiang Tethys tectonic domain,which was formed by the westward subduction of the Garze-Litang oceanic slab beneath the Zhongza massif.Chalcopyrite-pyrrhotite-pyritemolybdenite occurs as disseminations,veins,veinlets,and stockworks distributed in the K-silicate alteration zone in the monzonite porphyry,which is superimposed by propylitization.The chemical compositions of biotite and amphibole analyzed by electron probe microanalysis(EPMA)indicate that the ore-forming magma and exsolved fluids experienced a continuous decrease in the oxygen fugacity(fO_(2)).Primary amphibolite and biotite(type I)crystallized at relatively high temperatures(744-827°C)and low fO_(2)(log fO_(2)=−12.26 to−11.91)during the magmatic stage.Hydrothermal fluids exsolved from the magma have a relatively lower temperature(621-711°C)and fO_(2)(log fO_(2)=−14.36 to−13.32)than the original magma.In addition,the presence of a high abundance of pyrrhotite and an insufficiency of primary magnetite and sulfate in the ore(i.e.,anhydrite and gypsum)indicate that the deposit may be a reduced porphyry deposit.Magma and fluid fO_(2)results,combined with previous research on magmatic fO_(2)at the Pulang deposit,indicate that the magma associated with the reduced Pulang ore assemblages was initially generated as a highly oxidized magma that was subsequently reduced by sedimentary rocks of the Tumugou Formation.

Nontarget screening using passive air and water sampling with a level Ⅱ fugacity model to identify unregulated environmental contaminants

It is thought that there are many unregulated anthropogenic chemicals in the environment.For risk assessment of chemicals, it is essential to estimate the predicted environmental concentrations. As an effort of identifying residual organic contaminants in air and water in Korea, nontarget screening using two-dimensional gas chromatography time-of-flight mass spectrometry（GC × GC-TOFMS） was conducted at 10 sites using polyurethane foam passive air sampler and at 6 sites using polydimethyl siloxane（PDMS） passive water sampler in three different seasons in 2014. More than 600 chemical peaks were identified satisfying the identification criteria in air and water samples, respectively, providing a list for further investigation. Chemical substances with reported national emission rates in2014（n = 149） were also screened for potential existence in the environment using a level Ⅱ fugacity model. Most of chemical substances classified as not detectable were not identified with detection frequency greater than 20% by nontarget screening, indicating that a simple equilibrium model has a strong potential to be used to exclude chemicals that are not likely to remain in the environment after emissions from targeted monitoring.

New technique to control in situ oxygen fugacity in water-free high-pressure system──Using Cu-O as an example

Through inserting a solid oxygen-specific electrolyte (YSZ) inside and exerting an electrical power of direct current outside between the sample and oxygen reservoir (an solid oxygen buffer), oxygen was driven by the power from the cathodic electrode area into the positive electrode area at high temperature and high pressure. In this way, the oxygen fugacity in the sample was in situ controlled independently of temperature and pressure. By using Cu-O system as an example, this technique was proved to be successful.

Unveil the Redox Evolution of Ore-forming Fluids using Sulfur Isotope:A Case Study of the Zhengguang Intermediate Sulfidation Epithermal Au-Zn Deposit,NE China

Oxygen fugacity(fO_(2))is a key intensity variable during the entire magmatic-hydrothermal mineralization courses.The redox state and its variations between different stages of the ore-forming fluids of intermediate sulfidation epithermal deposits are rarely deciphered due to the lack of appropriate approaches to determine fO_(2)of the fluids.Here,we reported theδ^(34)S of the sulfides from three different stages(stageⅠ,Ⅱ,Ⅲ)of Zhengguang,an Early Ordovician Au-rich intermediate sulfidation(IS)epithermal deposit,to decipher the redox evolution of the ore-forming fluids.The increasingδ^(34)S values from stageⅠpyrite(pyl,average-2.6‰)through py2(average-1.9‰)to py3(average-0.2‰)indicates a decrease of the oxygen fugacity of the ore-forming fluids.A compilation ofδ^(34)S values of sulfides from two subtypes of IS deposits(Au-rich and Ag-rich)from NE China shows that theδ^(34)S values of sulfides from Au-rich IS deposits are systematically lighter than those of Ag-rich IS Ag-Pb-Zn deposit,indicating the ore-forming fluids of the former are more oxidized than the latter.We highlight that sulfur isotopic composition of hypogene sulfides is an efficacious proxy to fingerprint the oxygen fugacity fluctuations of epithermal deposits and could potentially be used to distinguish the subtypes of IS deposits.

Formation and Evolution of Chromitites in the Hongshishan Complex,Beishan Orogenic Collage,NW China:Constraints from Mineralogical Compositions,Re-Os Isotopes and Platinum-Group Element Geochemistry

The Hongshishan chromitite deposits are situated to the north of the Beishan orogenic collage,in the southern part of the Central Asian Orogenic Belt.This study describes the mineral chemistry,Re-Os isotopes and platinum-group elements geochemistry of the Hongshishan chromitites for the purpose of constraining the origin,evolution and composition of their parental melts.The restricted ranges of Al_(2)O_(3),Cr_(2)O_(3)and Cr#-Mg#variation of chromite-cores and chromites fall within the field of the mid-ocean ridge and ophiolitic podiform chromite settings.The(^(187)Os/^(188)Os)i ratios of the chromitites are in the range of 0.12449–0.12745(average 0.12637)and theγOs are from-1.92 to-0.06(average-0.83).In the Re-Os isotope diagrams,all the samples fall in the field of chromitites and show a residual peridotitic trend.The range of Os isotopic compositions andγOs values indicate that they overlap the depleted MORB mantle(DMM)as well as being close to global Os isotopic data andγOs of ophiolite chromitites.The characteristics of the PGE contents can be roughly subdivided into two groups:podiform chromitites and Ural-Alaskan type complexes.For the ferritchromite cores,the calculated Al_(2)O_(3)concentrations of the parental melt are higher(average 16.65 wt%)in high-Cr than high-Al chromitite(average 16.17 wt%)and for the chromite,the calculated Al_(2)O_(3)concentrations are even higher(average 16.48 wt%)in the high-Cr than the high-Al examples(average 15.38 wt%).In the(TiO_(2))melt vs.TiO_(2)diagrams,most high-Al melts fall in the MORB,while the high-Cr melts fall in the ARC field.The calculated Fe O/Mg O ratios for the parental melt show the closest resemblance to a MORB magma composition.The inferred parental melt composition for studied chromitites falls in the field of mid-ocean ridge basalt(MORB)magmas and far away from boninite.The calculated degrees of partial melting producing the chromitites are 16%-22%(average 19%),which is around the range of those of the MORB magmas.The chromitites are suggested to have been formed in a MORB setting.The chromites and ferritchromite cores are mostly scattered along the MORB and SSZ harzburgite–dunite fields.Ferritchromite rims and ferritchromites with high YFes formed as a result of alteration during serpentinization..

The formation of porphyry copper deposits

Copper is a moderately incompatible chalcophile element.Its behavior is strongly controlled by sulfides.The speciation of sulfur is controlled by oxygen fugacity.Therefore,porphyry Cu deposits are usually oxidized(with oxygen fugacities > AFMQ +2)(Mungall 2002;Sun et al.2015).The problem is that while most of the magmas at convergent margins are highly oxidized,porphyry Cu deposits are very rare,suggesting that high oxygen fugacity alone is not sufficient.Partial melting of mantle peridotite even at very high oxygen fugacities forms arc magmas with initial Cu contents too low to form porphyry Cu deposits directly(Lee et al.2012;Wilkinson 2013).Here we show that partial melting of subducted young oceanic slabs at high oxygen fugacity(>AFMQ +2) may form magmas with initial Cu contents up to >500 ppm,favorable for porphyry mineralization.Pre-enrichment of Cu through sulfide saturation and accumulation is not necessarily beneficial to porphyry Cu mineralization.In contrast,remelting of porphyritic hydrothermal sulfide associated with iron oxides may have major contributions to porphyry deposits.Thick overriding continental crust reduces the "leakage" of hydrothermal fluids,thereby promoting porphyry mineralization.Nevertheless,it is also more difficult for ore forming fluids to penetrate the thick continental crust to reach the depths of 2—4 km where porphyry deposits form.

Is seawater geochemical composition recorded in marine carbonate? Evidence from iron and manganese contents in Late Devonian carbonate rocks

Iron and manganese are the important redoxsensitive elements in the ocean. Previous studies have established a series of paleo-depositional redox proxies based on the form and content of iron in sedimentary rocks(e.g., degree of pyritization, FeHR/FeT, Fe/Al). These proxies were developed and applied on siliciclastic-rich marine sediments. Although marine carbonate rocks are generally considered to preserve the geochemical signals of ancient seawater, neither Fe nor Mn content in marine carbonate rocks(Fecarb, Mncarb) has been independently used as a proxy to quantify environmental cues in paleo-oceans. Both Fe and Mn are insoluble in oxic conditions(Fe_2O_3, Fe(OH)_3,MnO_2), while their reduced forms(Fe^(2+) and Mn^(2+)) are soluble. Therefore, oxic seawater should have low concentrations of dissolved Fe^(2+)and Mn^(2+), and accordingly carbonate rocks precipitated from oxic seawater should have low Fecarband Mncarb, and vice versa. To evaluate whether Fecarband Mncarbcan be used to quantify oxygen fugacity in seawater, we measured Fecarband Mncarbof Upper Devonian marine carbonate rocks collected from nine sections in South China. Fecarbof intraplatform basin samples wassignificantly higher than that of shelf samples, while shelf and basin samples had comparable Mncarb. The modeling result indicates that the dramatic difference in Fecarbcannot be explained by variation in oxygen fugacity between the shelf and basin seawater. Instead, both Fecarband Mncarb appear to be more sensitive to benthic flux from sediment porewater that is enriched in Fe^(2+)and Mn^(2+). Porewater Fe^(2+)and Mn^(2+)derive from bacterial iron and manganese reduction; flux was controlled by sedimentation rate and the depth of the Fe(Mn) reduction zone in sediments, the latter of which is determined by oxygen fugacity at the water–sediment interface. Thus, high Fecarbof the basin samples might be attributed to low sedimentation rate and/or low oxygen fugacity at the seafloor. However, invariant Mncarbof the shelf and basin samples might be the consequence of complete reduction of Mn in sediments. Our study indicates that marine carbonate rocks may not necessarily record seawater composition, particularly for benthic carbonate rocks. The influence of benthic flux might cause carbonate rocks' geochemical signals to deviate significantly from seawater values. Our study suggests that interpretation of geochemical data from carbonate rocks, including carbonate carbon isotopes, should consider the process of carbonate formation.

Redox evolution of western Tianshan subduction zone and its effect on deep carbon cycle

Knowing the phase relations of carbon-bearing phases at high-pressure(HP) and high-temperature(HT) condition is essential for understanding the deep carbon cycle in the subduction zones.In particular,the phase relation of carbon-bearing phases is also strongly influenced by redox condition of subduction zones,which is poorly explored.Here we summarized the phase relations of carbon-bearing phases(calcite,aragonite,dolomite,magnesite,graphite,hydrocarbon) in HP metamorphic rocks(marble,metapelite,eclogite) from the Western Tianshan subduction zone and high-pressure experiments.During prograde progress of subduction,carbonates in altered oceanic crust change from Ca-carbonate(calcite) to Ca,Mg-carbonate(dolomite),then finally to Mgcarbonate(magnesite) via Mg-Ca cation exchange reaction between silicate and carbonate,while calcite in sedimentary calcareous ooze on oceanic crust directly transfers to high-pressure aragonite in marble or amorphous CaCO3 in subduction zones.Redox evolution also plays a significant effect on the carbon speciation in the Western Tianshan subduction zone.The prograde oxygen fugacity of the Western Tianshan subduction zone was constrained by mineral assemblage of garnet-omphacite from FMQ-1.9 to FMQ-2.5 at its metamorphic peak(maximum P-T) conditions.In comparison with redox conditions of other subduction zones,Western Tianshan has the lowest oxygen fugacity.Graphite and light hydrocarbon inclusions were ubiqutously identified in Western Tianshan HP metamorphic rocks and speculated to be formed from reduction of Fe-carbonate at low redox condition,which is also confirmed by high-pressure experimental simulation.Based on petrological observation and high-pressure simulation,a polarized redox model of reducing slab but oxidizing mantle wedge in subduction zone is proposed,and its effect on deep carbon cycle in subduction zones is further discussed.