The Formation and Evolution of Uvarovite in UHP Serpentinite and Rodingite and its Constraints on Chromium Mobility in the Oceanic Subduction Zone

The uvarovite-andradite and uvarovite-andradite-grossular solid-solution series are rare in nature.The discovery of uvarovite-andradite in serpentinite and rodingite from the ultra-high pressure(UHP)metamorphic belt in southwestern Tianshan provided an opportunity to investigate its behavior in the subduction zone.Uvarovite(defined as chromiumgarnet)from serpentinite is homogeneous in a single grain,covering compositions in the uvarovite-andradite solid solution series of Adr_(58-66)Uv_(33-41),with few grossular components.Uvarovite from rodingites contain various Cr_(2)O_(3) contents(1.7-17.9 wt%)and mineral compositions being in the range of Adr_(21-31)Uv_(41-50)Grs_(22-37),Adr_(52-90)Uv_(5-25)Grs_(0-21) and Adr_(19-67)Uv_(3-63)Grs_(13-42).Discontinuous chemical variation of uvarovite from core to rim indicates that uvarovite formed by consuming andradite and chromite,which could provide Ca,Cr,Al and Fe.Raman signals of water were identified for uvarovite from both serpentinite and rodingite,with high water content in uvarovite from serpentinite.The high pressure mineral assemblage,as well as the association with perovskite,indicated that the studied uvarovite from serpentinite and rodingite was formed through high pressure metamorphism,during the subduction zone serpentinization and rodingitization.High alkaline and highly reduced fluids released from serpentinization or rodingitization in the oceanic subduction zone promote the mobility of chromium and enable its long-distance migration.

OCCURRENCE OF HIGH-PRESSURE RODINGITES IN THE OPHIOLITES OF INDUS SUTURE ZONE, EASTERN LADAKH,THE HIMALAYA:TECTONIC AND METALLOGENIC SIGNIFICANCE

Recently,considerable attention is being paid in studying the high\|pressure (rodingites and eclogites etc)crustal segments for understanding the architecture and evolution of collision orogens.This paper presents the geology,mineralogy and geochemistry of the rodingites,the first reported occurrence in eastern Ladakh,the Himalaya.Nidar ophiolite is one of the well exposed,nearly a complete ophiolite of the Indus Suture Zone present in the eastern Ladakh.Field studies across the Nidar ophiolite in the Nidar—Kyun Tso section unraveled the occurrence of relatively strongly developed rodingites.Rodingites are very hard and dense.They occur as layers and also as boudins within and at the contacts of the serpentinites.The rodingites are fine to medium grained.Grossular is the dominant rodingite mineral and occurs as well developed crystals.At places grossular has coronitic texture.Diopside,clinozosite,rutile and opaques are the other main Ca\|rich minerals present in rodingites.The matrix of the rodingite minerals is highly birefringent.The rodingite mineral assemblage indicates the development of rodingite in the pressure and temperature range of 18～25 kbar and 700 to 800℃,respectively.Rodingites have high abundances (mass fraction) of CaO (10%～12%) and Al\-2O\-3 (12%) contents and generally low in SiO\-2 (46%) and MgO (7%～8%) contents.They have chondrite\|normalized Rare Earth Element (REE) abundances of 25 to 40× on the LREE and 37 to 50× on the MREE and 15 to 24× on the HREE.Overall the REE patterns tend to be concave\|upwards,or relatively light\|REE depleted with almost no Eu\|anomaly.The geologic occurrence,the mineralogy and geochemical (major,trace and REE) data of the rodingites indicate that they were initially gabbros/basalt that have undergone Ca\|metasomatism during serpentinization,followed by high\|pressure recrystallization to rodingites.

Multi-stage rodingitization of ophiolitic bodies from Northern Apennines(Italy): Constraints from petrography, geochemistry and thermodynamic modelling

The investigated mantle bodies from the External Ligurians(Groppo di Gorro and Mt.Rocchetta)show evidences of a complex evolution determined by an early high temperature metasomatism,due to percolating melts of asthenospheric origin,and a later metasomatism at relatively high temperature by hydrothermal fluids,with formation of rodingites.At Groppo di Gorro,the serpentinization and chloritization processes obliterated totally the pyroxenite protolith,whereas at Mt.Rocchetta relics of peridotite and pyroxenite protoliths were preserved from serpentinization.The rodingite parageneses consist of diopside+vesuvianite+garnet+calcite+chlorite at Groppo di Gorro and garnet+diopside+serpentine±vesuvianite±prehnite±chlorite±pumpellyite at Mt.Rocchetta.Fluid inclusion measurements show that rodingitization occurred at relatively high temperatures(264-334℃ at 500 bar and 300-380℃ at 1 kbar).Garnet,the first phase of rodingite to form,consists of abundant hydrogarnet component at Groppo di Gorro,whereas it is mainly composed of grossular and andradite at Mt.Rocchetta.The last stage of rodingitization is characterized by the vesuvianite formation.Hydrogarnet nucleation requires high Ca and low silica fluids,whereas the formation of vesuvianite does not need CO2-poor fluids.The formation of calcite at Groppo di Gorro points to mildly oxidizing conditions compatible with hydrothermal fluids;the presence of andradite associated with serpentine and magnetite at Mt.Rocchetta suggests Fe^3+-bearing fluids with fO2 slightly higher than iron-magnetite buffer.We propose that the formation of the studied rodingite could be related to different pulses of hydrothermal fluids mainly occurring in an oceancontinent transitional setting and,locally,in an accretionary prism associated with intra-oceanic subduction.

Thermodynamic modeling and elemental migration for the early stage of rodingitization:An example from the Xialu massif of the Xigaze ophiolite,southern Tibet

The analysis of early stage rodingite from the ultramafic rocks of the Xialu Massif in the Xigaze Ophiolite,Tibet,in China shows that the rodingitization involved continuous changes in fluid composition during different stages of subduction.The early stage prehnite-bearing rodingite was produced at low pressures and temperatures along extensional fractures.Samples of rodingite were collected along a profile from the center to the margin of a rodingitized intrusive igneous rock(^10 m×30 m),and they record wide variations in bulk composition,mineralogy,and texture.The mineral assemblages,from center to margin,vary from(1)relics of primary clinopyroxene(Cpx_(r))and primary amphibole(Amp_(r))+newly formed late amphibole(Act)+primary plagioclase(Pl_(r))+clinozoisite+prehnite+albite+chlorite+titanite+ilmenite(R1 rodingite),through(2)relics of primary clinopyroxene(Cpx_(r))+newly formed late clinopyroxene(Cpx_(n))+primary and late amphiboles(Amp_(r)+Act)+clinozoisite+prehnite+albite+chlorite+titanite(R2 rodingite),to(3)newly formed late clinopyroxene(Cpx_(n))and amphibole(Act)+clinozoisite+prehnite+albite+chlorite+titanite(R3 rodingite).As a result of the metasomatic process of rodingitization,the content of CaO in the whole rock chemical composition from R1 to R3 increases,SiO_(2) decreases,and Na_(2)O+K_(2)O is almost completely removed.Massbalance diagrams show enrichments in large ion lithophile elements such as Rb,Cs,Ba,and Pb as well as Ni during rodingitization.The central part of the rodingitized intrusion(R1 rodingite)was only slightly affected by metasomatism.On the other hand,the contents of the rare earth elements(REEs),high field strength elements(HFSEs;e.g.Zr,Nb,Ta,Hf,and Y),and some highly compatible elements such as Cr and Sc decreased slightly during rodingitization.Thermodynamic modeling based on equilibrium mineral assemblages indicates that the rodingite of the Xialu Massif formed in an H_(2)O-saturated,CO_(2)-rich environment.The estimated conditions of metamorphism were-281-323℃and 0.4-3.9 kbar,representing the subgreenschist facies.In this environment,REEs and HFSEs were soluble in the fluids and partly removed.Moreover,these prehnite rodingites formed in a progressively reducing and less alkaline environment,as indicated by decreases in f(O_(2))and bulk-rock Fe^(3+)/Fe^(2+) ratios,and the records of fluidΔpH from the center to the margin of the studied rodingitized intrusion.

Record of Early-Stage Rodingitization from the Purang Ophiolite Complex,Western Tibet

Rodingitization,commonly coupled with serpentinization of ultramafic rocks,bears significant information for fluid-rock interactions and element transfer from sea-floor to subduction zone environments.Numerous outcrops of rodingites are exposed along the Yarlung Zangbo suture zone(YZSZ)of southern Tibet,providing us an excellent opportunity to probe the petrogenetic processes,and unravel their implications for regional tectonic evolution.Several studies have been performed on rodingites from the eastern to central portions of the YZSZ,whereas limited work has ever been conducted on rodingitized rocks from the western segment of the YZSZ,precluding a comprehensive understanding of this lithological type.In this paper,we present detailed studies of petrology,mineral,whole-rock geochemistry and phase equilibrium modeling on a suite of newly recognized rodingites within the Purang ophiolite massif in the southwestern part of the YZSZ.The rodingites have a major metasomatic mineral association of chlorite,clinozoisite,amphibole and minor amounts of plagioclase,representing products of an early-stage rodingitization.They generally present compositions of low SiO2(48.89 wt.%–53.57 wt.%),Fe2O3^T(3.77 wt.%–5.56 wt.%),Na2O(1.31 wt.%–1.93 wt.%),Al2O3(4.78 wt.%–8.84 wt.%),moderate CaO(9.69 wt.%–11.23 wt.%),and high MgO(24.11 wt.%–26.08 wt.%)concentrations with extremely high Mg^# values[Mg^#=100×Mg/(Mg+Fe^2+)molar]of 89–92.Bulk-rock recalculation reveals that the rodingites have a protolith of mantle-derived olivine gabbro or gabbronorite.They have low rare earth element compositions(∑REE=2.4 ppm–6.5 ppm)and are characterized by flat LREE and slightly enriched HREE patterns with positive Eu anomalies;they also exhibit positive anomalies in Sr,U and Pb and negative anomalies in high-field strength elements,including Nb,P and Ti,suggesting for a subduction-zone imprinting.Phase equilibrium modeling shows that the rodingitization did take place at P<2 kbar and T=~350–400℃,consistent with low greenschist facies conditions.Taking into account of all these petrological and geochemical features,we propose that the rodingites record evidence of early-stage fluid-rock interactions between olivine gabbroic rocks and Ca-rich fluids,which may have derived from weakly serpentinized ultramafic country rocks.Although this process may initially have occurred in a mid-ocean ridge setting,an obvious overprinting by supra-subduction zone fluids in a fore-arc environment is recognized.