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.

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.

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.

Mineral Chemistry Indicates the Petrogenesis of Rhyolite From The Southwestern Okinawa Trough

To reveal the petrogenesis of rhyolite from the southwestern Okinawa Trough, the mineral chemistry of plagioclase, orthopyroxene, amphibole, quartz and Fe-Ti oxide phenocrysts were analyzed using an electron microprobe, and in suit Sr and Ba contents of plagioclase analysed by LA-ICPMS were chosen for fingerprinting plagioclases of different provenances. Results indicate an overall homogeneous composition for each of the mineral phases except for plagioclase phenocrysts which have a wide range of composition(An=39~88). Plagioclase crystals characterized by An contents of >70 are not in equilibrium with their whole-rock compositions, and coarse-sieved plagioclase phenocryst interiors record high An contents(>70) and Sr/Ba ratios(>7), which are similar to the those of plagioclase crystals in basalt. Therefore, these crystals must have been introduced to the rhyolitic magma from a more mafic source. Equilibrium temperatures estimated using orthopyroxene-liquid, iron–titanium oxide, titanium-in-quartz and amphibole geothermometers show consistent values ranging from 792 to 869℃. The equilibrium pressure calculated using amphibole compositions is close to 121 MPa which corresponds to an approximate depth of 4 km. The fO_2 conditions estimated from Fe-Ti oxides and amphiboles plot slightly above the NNO buffer, which indicates that the rock formed under more oxidized conditions. Our results suggests that petrogenesis of the rhyolite due to basaltic magma ascend with the high An and Sr/Ba plaigoclases from deep magma chamber into the shallow chamber where the fractional crystallization and crustal assimilation happened. It also indicates that a two-layer magma chamber structure may occur under the southwestern Okinawa Trough.

Experimental Study on the Electrical Conductivity of Orthopyroxene at High Temperature and High Pressure under Different Oxygen Fugacities

At presure 1.0-4.0 GPa and temperature 1073-1423 K and under oxygen partial pressure conditions, a YJ-3000t multi-anvil solid high-pressure apparatus and Sarltron-1260 Impedance/Gain-Phase analyzer were employed to conduct an in-situ measurement of the electrical conductivity of orthopyroxene. The buffering reagents consist of Ni＋NiO, Fe＋Fe3O4, Fe＋FeO and Mo＋MoO2 in order to control the environmental oxygen fugacity. Experimental results made clear that： （1） within the measuring frequency range from 10-1 to 106 Hz, the complex impedance （R） is of intensive dependence on the frequency; （2） The electrical conductivity （a） tends to increase along to the rise of temperature （T）, and Log a vs. 1/ T fit the Arrenhius linear relations; （3） Under the control of oxygen buffer Fe＋Fe3O4, with the rise of pressure, the activation enthalpy tends to increase whereas the electrical conductivity tends to decrease. The activation energy and activation volume of the main current carders of orthopyroxene have been obtained, which are （1.715±0.035） eV and （0.03±0.01） cm^3/mol, respectively; （4） Under given pressure and temperature, the electrical conductivity tends to increase with increasing oxygen fugacity, while under given pressure the activation enthalpy tends to decrease with increasing oxygen fugacity; and （5） The sample＇s small polarons mechanism has provided a reasonable explanations to the conduction behavior at high temperature and high pressure.

Metallogenic controls on the granite-related W–Sn deposits in the Hunan–Jiangxi region, China: evidence from zircon trace element geochemistry

The Nanling Range in South China is well known for its rich granite-related W–Sn deposits.To elucidate the controls of different granite-related W–Sn metallogenesis in the region,we chose five representative orerelated granites(Yanbei,Mikengshan,Tieshanlong,Qianlishan,and Yaogangxian intrusions)in the Hunan–Jiangxi region,and studied their magmatic zircon ages and trace element geochemistry.Our new zircon data showed the differences in ages,temperatures and oxygen fugacity of the ore-forming magmas.Zircon U–Pb ages of the Yanbei and Mikengshan intrusions are characterized by 142.4±2.4 and 143.0±2.3 Ma,respectively,whereas the Tieshanlong and Qianlishan intrusions are 159.5±2.3and 153.2±3.3 Ma,respectively.The Sn-related intrusions were younger than the W-related intrusions.The Tiin-zircon thermometry showed that there was no systematic difference between the Sn-related Yanbei(680–744℃)and Mikengshan(697–763℃)intrusions and the W-related Tieshanlong(730–800℃),Qianlishan(690–755℃)and Yaogangxian(686–751℃)intrusions.However,the zircon Ce^4+/Ce^3+ratios of the Yanbei(averaged at 18.3)and Mikengshan(averaged at 18.8)intrusions are lower than those of the Tieshanlong(averaged at 36.9),Qianlishan(averaged at 38.4)and Yaogangxian(averaged at 37)intrusions,indicating that the Sn-related granitic magmas might have lower oxygen fugacities than those of the W-related.This can be explained by that,in more reduced magmas,Sn is more soluble than W and thus is more enriched in the residual melt to form Sn mineralization.The difference in source materials between the Sn-related and the W-related granites seems to have contributed to the different redox conditions of the melts.

Contrasting oxidation states of low-Ti and high-Ti magmas control Ni-Cu sulfide and Fe-Ti oxide mineralization in Emeishan Large Igneous Province

Magmatic Ni-Cu-(PGE) sulfide and Fe-Ti oxide deposits in plume-related large igneous provinces(LIPs)are commonly related to low-Ti and high-Ti series magmas, respectively, but the major factors that control such a relationship of metallogenic types and magma compositions are unclear. Magma fOcontrols sulfur status and relative timing of Fe-Ti oxide saturation in mafic magmas, which may help clarify this issue. Taking the Emeishan LIP as a case, we calculated the magma fOof the high-Ti and low-Ti picrites based on the olivine-spinel oxygen barometer, and the partitioning of V in olivine. The obtained fOof the high-Ti series magma(FMQ + 1.1 to FMQ + 2.6) is higher than that of the low-Ti series magma(FMQ-0.5to FMQ + 0.5). The magma fOof the high-Ti and low-Ti picrites containing Fo > 90 olivine reveals that the mantle source of the high-Ti series is likely more oxidized than that of the low-Ti series. The results using the ’lambda REE’ approach show that the high-Ti series may have been derived from relatively oxidized mantle with garnet pyroxenite component. The S contents at sulfide saturation(SCSS) of the two series magmas were calculated based on liquid compositions obtained from the alpha Melts modeling, and the results show that the low-Ti series magma could easily attain the sulfide saturation as it has low fOwith S being dominantly as S. In contrast, the oxidized high-Ti series magma is difficult to attain the sulfide saturation, but could crystallize Fe-Ti oxides at magma MgO content of ~7.0 wt.%. Thus, contrasting magma fOof low-Ti and high-Ti series in plume-related LIPs may play an important role in producing two different styles of metallogeny.

Determination of the subcooled liquid solubilities of PAHs in partitioning batch experiments

Subcooled liquid solubility is the water solubility for a hypothetical state of liquid. It is an important parameter for multicomponent nonaqueous phase liquids （NAPLs） containing polycyclic aromatic hydrocarbons （PAHs）, which can exist as liquids even though most of the solutes are solid in their pure form at ambient temperature. So far, subcooled liquid solubilities were estimated from the solid water solubility and fugacity ratio of the solid and （subcooled） liquid phase, but rarely derived from experi- mental data. In our study, partitioning batch experiments were performed to determine the subcooled liquid solubility of PAHs in NAPL-water system. For selected PAH, a series of batch experiments were carried out at increased mole fractions of the target component in the NAPL and at a constant NAPL/ water volume ratio. The equilibrium aqueous PAH concentrations were measured with HPLC and/or GC- MS. The suhcooled liquid solubility was derived by extrapolation of the experimental equilibrium aqueous concentration to a mole fraction of unity. With the derived subcooled liquid solubility, the fugacity ratio and enthalpy of fusion of the solute were also estimated. Our results show a good agreement between the experimentally determined and published data.