黄铜矿在氨水-氯化铵溶液中的界面反应（英文）

对黄铜矿在氨水-氯化铵溶液中的反应界面进行研究。利用X射线光电子能谱分析(XPS)技术对黄铜矿反应界面进行表征。研究发现,覆盖在黄铜矿基底之上的反应界面钝化层由表层的铁氧化物以及被其覆盖的硫化铜组成。黄铜矿结构中的铁离子存在优先溶解现象,形成钝化层中的硫化铜或CuFe_(1-x)S_2。当表层铁氧化物层逐渐自发剥离后,硫化铜层成为新的钝化层。由硫化铜层表面S^(2-), S_2^(2-), S_n^(2-), S^0和SO_4^(2-)等组分含量推算硫化铜的组成。提出黄铜矿在不同p H和氧化电位条件下的氧化和钝化机理。最后,建立黄铜矿界面三步反应模型,剖析钝化层的形成及转化机理。

Subduction zone geochemistry

Crustal recycling at convergent plate boundaries is essential to mantle heterogeneity.However,crustal signatures in the mantle source of basaltic rocks above subduction zones were primarily incorporated in the form of liquid rather than solid phases.The physicochemical property of liquid phases is determined by the dehydration behavior of crustal rocks at the slab-mantle interface in subduction channels.Because of the significant fractionation in incompatible trace elements but the full inheritance in radiogenic isotopes relative to their crustal sources,the production of liquid phases is crucial to the geochemical transfer from the subducting crust into the mantle.In this process,the stability of specific minerals in subducting crustal rocks exerts a primary control on the enrichment of given trace elements in the liquid phases.For this reason,geochemically enriched oceanic basalts can be categorized into two types in terms of their trace element distribution patterns in the primitive mantle-normalized diagram.One is island arc basalts(IAB),showing enrichment in LILE,Pb and LREE but depletion in HFSE such as Nb and Ta relative to HREE,The other is ocean island basalts(OIB),exhibiting enrichment in LILE and LREE,enrichment or non-depletion in HFSE but depletion in Pb relative to HREE.In either types,these basalts show the enhanced enrichment of LILE and LREE with increasing their incompatibility relative to normal mid-ocean ridge basalts(MORB).The thermal regime of subduction zones can be categorized into two stages in both time and space,The first stage is characterized by compressional tectonism at low thermal gradients.As a consequence,metamorphic dehydration of the subducting crust prevails at forearc to subarc depths due to the breakdown of hydrous minerals such as mica and amphibole in the stability field of garnet and rutile,resulting in the liberation of aqueous solutions with the trace element composition that is considerably enriched in LILE,Pb and LREE but depleted in HFSE and HREE relative to normal MORB.This provides the crustal signature for the mantle sources of IAB.The second stage is indicated by extensional tectonism at high thermal gradients,leading to the partial melting of metamorphically dehydrated crustal rocks at subarc to postarc depths.This involves not only the breakdown of hydrous minerals such as amphibole,phengite and allanite in the stability field of garnet but also the dissolution of rutile into hydrous melts.As such,the hydrous melts can acquire the trace element composition that is significantly enriched in LILE,HFSE and LREE but depleted in Pb and HREE relative to normal MORB,providing the crustal signature for the mantle sources of OIB.In either case,these liquid phases would metasomatize the overlying mantle wedge peridotite at different depths,generating ultramafic metasomatites such as serpentinized and chloritized peridotites,and olivine-poor pyroxenites and hornblendites.As a consequence,the crustal signatures are transferred by the liquid phases from the subducting slab into the mantle.

Generation of andesite through partial melting of basaltic metasomatites in the mantle wedge:Insight from quantitative study of Andean andesites

Continental crust in average exhibits a similar composition in both major and trace elements to andesites along active continental margins.For this reason,andesitic magmatism above oceanic subduction zones is considered to have played a key role in the generation of continental crust along convergent plate boundaries.With respect to the origin of andesites themselves,however,there is still a hot debate on how they have acquired their geochemcial compositions.The debate is mainly centralized on the relative contributions of crustal contamination,magma differentiation and source mixing,which reaches an impasse in the past decades.The essential reason for this kind of debates is that these three mechanisms only can account for some of the geochemical observations for andesites,leading to insufficient discrimination among them.Nevertheless,the geochemical features of andesites are primarily controled from early to late by the composition of their source rocks in addition to partial melting and magma differentiation processes.If source mixing and partial melting processes in the early stage of andesite magmatism can account for the first-order geochemical features of andesites,there is no need to invoke the late processes of magma differentiation and crustal contamination for andesite petrogenesis.This is illustrated by quantitative forward modeling of the geochemical data for Quaternary andesites from the Andean arc in South America based on an integrated interpretation of these data.The modeling has run with four steps from early to late:(1)dehydration of the subducting oceanic crust at forearc depths;(2)partial melting of the subducting terrigenous sediment and altered oceanic basalt at subarc depths to produce hydrous felsic melts;(3)the generation of basaltic metasomatites(e.g.,Si-excess pyroxenite)in the mantle wedge through reaction of the mantle wedge peridotite with large amounts of the hydrous felsic melts;(4)the production of andesitic melts by partial melting of the basaltic metasomatites.The results not only testify the hypothesis that the trace element and radiogenic isotope compositions of andesites can be directly produced by the source mixing and mantle melting but also demonstrate that partial melting of the basaltic metasomatites can reproduce the lithochemical composition of andesites.The compositional variations of Andean andesites within a single volcanic zone and among different volcanic zones can be explained by incorporating different amounts of heterogeneous hydrous felsic melts into their mantle sources,followed by different degree of partial melting under different pressures and temperatures.Therefore,the source mixing and partial melting processes at subarc depths can account for the first-order geochemical features of Andean andesites.In this regard,it may be not necessary for andesite petrogenesis to invoke the significant contributions from the processes of magma differentiation and crustal contamination.

Plate tectonics in the twenty-first century

Plate tectonics was originally established as a kinematic theory of global tectonics,in which the Earth’s rigid outer layer,the lithosphere,consists of different size plates that move relative to each other along divergent,convergent or transform boundaries overlying the ductile asthenosphere.It comprises three elements:rigid lithosphere plates,ductile asthenosphere,and coupled movement systems.It operates through the interlinked processes of continental drift,seafloor spreading and lithospheric subduction,resulting in the generation,modification and demise of lithospheres throughout geological time.The system of lithospheric plates in horizontal and vertical movements forms the spatiotemporal linkages of matter and energy between the surface and interior of Earth,advancing the kinematic theory with a dynamic explanation.While top-down tectonics through lithospheric subduction plays a key role in the operation of plate tectonics,it is balanced for the conservation of both mass and momentum on the spherical Earth by bottom-up tectonics through asthenospheric upwelling to yield seafloor spreading after continental breakup.The gravity-driven subduction of cool lithosphere proceeds through convergence between two plates on one side,and rollback of the subducting slab makes the vacancy for upwelling of the hotter asthenosphere to form active rifting in backarc sites.Plate convergence is coupled with plate divergence between two plates along mid-ocean ridges on the other side,inducing passive rifting for seafloor spreading as a remote effect.Thus,plate tectonics is recognizable in rock records produced by tectonic processes along divergent and convergent plate margins.Although the asthenospheric upwelling along fossil suture zones may result in continental breakup,seafloor spreading is only induced by gravitational pull of the subducting oceanic slab on the remote side.Therefore,the onset and operation of plate tectonics are associated with a series of plate divergent-convergent coupling systems,and they are critically dependent on whether both construction and destruction of plates would have achieved and maintained the conservation of both mass and momentum on the spherical Earth.Plate margins experience different types of deformation,metamorphism and magmatism during their divergence,convergence or strike-slip,leaving various geological records in the interior of continental plates.After plate convergence,the thickened lithosphere along fossil suture zones in intracontinental regions may be thinned by foundering.This causes the asthenospheric upwelling to reactivate the thinned lithosphere,resulting in superimposition and modification of the geological record at previous plate margins.The operation of plate tectonics,likely since the Eoarchean,has led to heat loss at plate margins and secular cooling of the mantle,resulting in the decrease of geothermal gradients and the increase of rheological strength at convergent plate margins.Modern plate tectonics is characterized by the predominance of rigid plate margins for cold subduction,and it has prevailed through the Phanerozoic.In contrast,ancient plate tectonics,that prevailed in the Archean and Proterozoic,is dominated by relatively ductile plate margins for collisional thickening at forearc depths and then warm subduction to subarc depths.In either period,the plate divergence after lithospheric breakup must be coupled with the plate convergence in both time and space,otherwise it is impossible for the operation of plate tectonics.In this context,the creation and maintenance of plate divergent-convergent coupling systems are responsible for the onset and operation of plate tectonics,respectively.Although a global network of mobile belts is common between major plates on modern Earth,it is difficult to find its geological record on early Earth if microplates would prevail at that time.In either case,it is important to identify different types of the geological record on Earth in order to discriminate between the different styles of plate tectonics in different periods of geological history.

Multiple Episodes of Zircon Growth during Anatectic Metamorphism of Metasedimentary Rocks in Collisional Orogens:Constraints from Felsic Granulites in the Bohemian Massif

Zircon is a key accessary mineral for metamorphic geochronology and geochemical tracing,but it has been a challenge to interpret its complex chemical zoning and age record acquired during multiple episodes of anatectic metamorphism in collisional orogens.This is illustrated by a combined study of petrography,phase equilibrium modeling and metamorphic P-T-t determination for granulites from the Bohemian Massif in the Variscan Orogen.These rocks record multiple episodes of zircon growth during anatectic metamorphism.They started from the compressional heating for prograde metamorphism to high-pressure(HP)to ultrahigh-pressure(UHP)eclogite facies with low degrees of partial melting.Afterwards,they underwent a decompressional stage from UHP eclogite facies to HP granulite facies for dehydration melting.These were followed by a further decompressional stage either to kyanite granulite facies or to sillimanite granulite facies at ultrahigh-temperature(UHT)conditions.Episodes of zircon growth are linked to specific metamorphic conditions for peritectic reactions on the basis of zoning patterns,trace element signatures,index mineral inclusions in dated domains and textural relationships to coexisting minerals.The results indicate that relict zircon domains are preserved even at UHT granulite facies conditions.A few zircon domains in the kyanite granulite grew during the prograde to peak UHP metamorphism,possibly corresponding to consumption of biotite and plagioclase but growth of garnet.During the decompressional exhumation to the HP granulite-facies,relict or prograde zircon domains were mostly dissolved into anatectic melts produced by muscovite breakdown.Most zircon grains grew during this transition to the HP granulite-facies in the kyanite granulite and are chemically related to continuous growth of garnet,whereas abundant zircon grains grew subsequently at the UHT granulite facies in the sillimanite granulite and are chemically related to garnet breakdown reactions.Another peak of zircon growth occurred at the final crystallization of anatectic melts in the sillimanite granulite rather than in the kyanite granulite,and these zircon grains mostly show oscillatory zoning,low HREE+Y contents and significantly negative Eu anomalies.In terms of the inference for protolith nature,it appears that zircon in metasedimentary rocks can grow at a short timescale in different stages of anatectic metamorphism,and its dissolution and growth are mainly dictated by anatectic conditions and extent,the property of peritectic reactions,and the stability of Ti-rich minerals.

地球历史上两种范式的板块构造

板块构造在地球上开始出现的时间及其如何随着时间而演化,是地球科学中的最基本问题.尽管重力驱动的俯冲作用已经被看成是地球上板块构造运作的关键条件,但是地球历史上俯冲带动力机制和热状态变化如何影响板块构造范式这个问题依然值得探讨.沿汇聚板块边界分布的区域变质岩记录了地壳岩石在岩石圈深度通过脱水和熔融作用发生的再造.区域变质作用的性质受控于板块边缘热状态,在变质相系全球分布上随时间推移所发生的变化就记录了板块边缘动力体制随时间的演化.现代板块构造开始于新元古代,这时板块边缘具备了足够的刚性得以冷俯冲;远古板块构造则开始于太古代,那时板块边缘因具有足够的韧性而进行暖俯冲.这种差异主要是由于太古代地幔比显生宙地幔具有显著较高的温度,在冷和暖两种状态下的板块俯冲属性主要受控于板块边缘的流变学.因此,本文建立了地球历史上不同时期板块构造范式的功能性整体模型.

An Experimental Study of Partial Melting of Metafelsic Rocks:Constraints on the Feature of Anatectic Melts and the Origin of Garnets in Collisional Orogens

Crustal anatexis in continental subduction zones has great bearing on chemical differentiation of the continental crust at convergent plate boundaries.This was experimentally investigated for ultrahigh-pressure(UHP)metafelsic rocks at 0.5-3.0 GPa and 650-900℃.The results show that partial melting begins at about 750℃ when pressure drops from 3.0 to 2.0 GPa,corresponding to decompressional exhumation of the deeply subducted continental crust.As the pressure further decreases to 1.0 GPa,the partial melting degree reaches the maximum of~25%at 900℃.Partial melts produced in these experiments are rich in silica and alkali,and poor in iron,manganese and magnesium.As the degree of partial melting increases,the composition of partial melts gradually converges toward homogeneous one.In the absence of free water,the partial melting of metafelsic rocks were triggered by the breakdown of hydrous minerals.At low temperatures of~750℃at 1.0-2.0 GPa,phengite dehydration melting occurs at first,giving rise to small amounts of felsic melts and peritectic K-feldspar.As the temperature rises up to 850-900℃,biotite begins to break down and gives rise to large amounts of felsic melts and peritectic minerals such as garnet,K-feldspar and orthopyroxene.It is noted that peritectic garnet is much different from anatectic garnet crystallized from anatectic melts and metamorphic garnet formed through metamorphic dehydration reaction under subsolidus conditions.The peritectic garnet is characterized not only by anhedral shapes with many multiphase crystal inclusions but also by compositions poor in spessartine and grossular but rich in almandine and pyrope.On the other hand,the anatectic garnets are characterized not only by euhedral shapes with few inclusions but also by compositions rich in grossular and spessartine but poor in almandine and pyrope.These observations provide experimental constraints on the origin of garnets in UHP metamorphic rocks,which have great bearing on understanding of anatectic metamorphism in collisional orogens.