Synthesis of Fe-pumpellyite and its stability relations with epidote

Hydrothermal synthesis of Fe-pum-pellyites was conducted using high pressure cold-seal apparatus and solid oxygen buffering techniques at temperatures between 250°C and 550°C and 2.0–9.1 kbar P_fluid. Fe-pumpellyites were synthesized from partially crystalline gel mixtures of compositions: 4CaO - 2.1Al₂O₃_1.5FeO - 0.3MgO - 6SiO₂ (II) and 3CaO - 1.5 Al₂O₃ - 2.7FeO - 0.3MgO - 6SiO₂ (III) in the presence of excess H₂O at P_fluid of 5–9.1 Kbar, temperatures between 275°C and 325°C, and f_O2 defined by the QFM and HM buffers; for both of these compositions (II and III), the condensed synthetic run products included minor 7Å chlorite ± garnet ± Fe-oxide. The cell dimensions and aggregate refractive index (a= 19.13(2)Å, b= 5.940(4)Å, c= 8.847(5)Å, ±= 97.37(6)±, and n= 1.702(2)) of the pum-pellyite synthesized from the bulk composition II mix are compatible with those of natural pumpellyites containing similar total Fe contents. Attempts at synthesizing Fe-pumpellyites from a Mg-free bulk composition were not successful; these results are consistent with the total absence of natural Mg-free pumpellyites. The higher temperature, higher oxygen fugacity assemblages of the equivalent bulk compositions (II and III) consist of epidote ± minor amounts of chlorite, garnet, quartz, hematite, and magnetite. The results of these synthesis experiments accord with the mineral parageneses observed in low-grade metabasites which imply that Fe-pumpellyites are replaced by epidote with increasing temperature and/or f_O2 and that Fe³⁺ is preferentially partitioned into epidote with respect to coexisting pum-pellyite. In addition, these synthesis experiments indicate that Fe-bearing pumpellyites crystallize at and are stable to lower temperatures than more aluminous pumpellyites—a result also consistent with natural systems.     

Metasomatism of garnet peridotite from Jiangzhuang,southern Sulu UHP belt: constraints on the interactions between crust and mantle rocks during subduction of continental lithosphere

The Jiangzhuang ultrahigh‐pressure (UHP) metamorphic peridotite from south Sulu, eastern China occurs as a layer within gneiss with eclogite blocks, and consists of coarse‐grained garnet porphyroblasts and a fine‐grained matrix assemblage of garnet + forsterite + enstatite + diopside ± phlogopite ± Ti‐clinohumite ± magnesite. Both types of garnet are characterized by high MgO content and depletion of light rare earth element (LREE) and enrichment of heavy rare earth element, but the matrix garnet has lower MgO, TiO₂ and higher Cr₂O₃ and REE contents. Diopside displays LREE enrichment, and has low but variable large‐ion lithophile element (LILE) contents. Phlogopite is a major carrier of LILE. Ti‐clinohumite contains high Nb, Ta, Cr, Ni, V and Co contents. The P–T conditions of 4.5–6.0 GPa and 850–950 °C were estimated for matrix mineral assemblages. Most peridotites are depleted in Al₂O₃, CaO and TiO₂, and enriched in SiO₂, K₂O, REE and LILE. In contrast to phlogopite‐free peridotites, the phlogopite‐bearing peridotites have higher K₂O, Zr, REE and LILE contents. Zircon occurs only in the phlogopite‐bearing peridotites, shows no zoning, with low REE contents and Th/U ratios, and yields tight U–Pb ages of 225–220 Ma, indicating the peridotites experienced consistent Triassic UHP metamorphism with subducted supercrustal rocks. These data demonstrate that the Jiangzhuang peridotites were derived from the depleted mantle wedge of the North China Craton, and experienced various degrees of metasomatism. The phlogopite‐free peridotites may have been subjected to an early cryptic metasomatism at UHP conditions of the mantle wedge, whereas the phlogopite‐bearing peridotites were subjected to a subsequent strong metasomatism, characterized by distinctly enrichment in LILE, LREE, Zr and K as well as the growth of zircon and volatile‐bearing minerals at UHP subduction conditions. The related metasomatism may have resulted from the filtration of fluids sourced mainly from deeply subducted supracrustal rocks.     

Two stages of granulite facies metamorphism in the eastern Himalayan syntaxis,south Tibet: petrology,zircon geochronology and implications for the subduction of Neo‐Tethys and the Indian continent beneath Asia

The eastern Himalayan syntaxis in southeastern Tibet consists of the Lhasa terrane, High Himalayan rocks and Indus‐Tsangpo suture zone. The Lhasa terrane constitutes the hangingwall of a subduction zone, whereas the High Himalayan rocks represent the subducted Indian continent. Our petrological and geochronological data reveal that the Lhasa terrane has undergone two stages of medium‐P metamorphism: an early granulite facies event at c. 90 Ma and a late amphibolite facies event at 36–33 Ma. However, the High Himalayan rocks experienced only a single high‐P granulite facies metamorphic event at 37–32 Ma. It is inferred that the Late Cretaceous (c. 90 Ma) medium‐P metamorphism of the southern Lhasa terrane resulted from a northward subduction of the Neo‐Tethyan ocean, and that the Oligocene (37–32 Ma) high‐P (1.8–1.4 GPa) rocks of the High Himalayan and coeval medium‐P (0.8–1.1 GPa) rocks of the Lhasa terrane represent paired metamorphic belts that resulted from the northward subduction of the Indian continent beneath Asia. Our results provide robust constraints on the Mesozoic and Cenozoic tectonic evolution of south Tibet.     

Source of coesite inclusions within inherited magmatic zircon from Sulu UHP rocks, eastern China, and their bearing for fluid–rock interaction and SHRIMP dating

The 5-km deep Chinese Continental Scientific Drilling Main Hole penetrated a sequence of ultrahigh pressure (UHP)-metamorphic rocks consisting mainly of eclogite, gneiss and garnet-peridotite with minor schist and quartzite. Zircon separates taken from thin layers of schist and gneiss within eclogite were investigated. Cathodoluminescence images of zircon grains show that they have oscillatory zoned magmatic cores and unzoned to patchy zoned metamorphic rims. Zircon rims contain rare coesite and calcite inclusions whereas cores contain inclusions of both low- P minerals (e.g. feldspar, biotite and quartz) and coesite and other eclogite-facies minerals such as phengite and jadeite. The zircon cores give highly variable ²⁰⁶Pb/²³⁸U ages ranging from 760 to 431 Ma for schist and from 698 to 285 Ma for gneiss, and relatively high but variable Th/U ratios (0.16–1.91). We suggest that the coesite and other eclogite facies mineral inclusions in zircon cores were not magmatic but formed through metasomatic processes caused by fluids during UHP metamorphism, and that the fluids contain components of SiO₂, Al₂O₃, K₂O, FeO, MgO, Na₂O and H₂O. Metasomatism of the Sulu UHP rocks during continental subduction to mantle depths has partly altered magmatic zircon cores and reset isotopic systems. This study provides key evidence that mineral inclusions within magmatic zircon domains are not unequivocal indicators of the formation conditions of the respective domain. This finding leads us to conclude that the routine procedure for dating of metamorphic events solely based on the occurrence of mineral inclusions in zoned zircon could be misleading and the data should be treated with caution.     

Raman spectra of polycrystalline microdiamond inclusions in zircons,and ultrahigh-pressure metamorphism of a quartzofeldspathic rock from the Erzgebirge terrane,Germany

ABSTRACT

Polycrystalline microdiamonds are rare in ultrahigh-pressure (UHP) rocks worldwide. Among samples collected at Erzgebirge, Germany, we found abundant polycrystalline microdiamonds as inclusions in zircons from a quartzofeldspathic rock. To illuminate their origin and forming age, we investigated morphologies and Raman spectra of 52 microdiamond inclusions, and dated the zircon host. The zircons have low Th/U values (0.03–0.07) and a concordia U/Pb age of 335.8 ± 1.9 Ma. Polycrystalline diamond (10–40 µm) consists of many fine-grained crystals (1.5–3 µm) with different orientations; discrete single diamonds (2–20 µm) are rare. All measured Raman spectra show an intense diamond band at 1332–1328 cm^?1 and have a negative correlation with full width at half maximum (FWHM) of 5.8–11.3 cm^?1. These data combined with previously reported diamond band data (1331–1337 cm^?1) are compatible with those of diamond inclusions in various host minerals from other UHP terranes, but are different from those of ureilite diamonds. The Erzgebirge microdiamonds in zircon do not display visible disordered sp³-carbon, but show downshifting of the Raman band from the ideal value (1332 cm^?1), and have a broader diamond band (FWHM >3 cm^?1) than those of well-ordered diamonds. These features may reflect imperfect ordering due to rapid nucleation/crystallization during UHP metamorphism and rapid exhumation of the UHP terrane. Graphite inclusions in zircon show a typical G-band at 1587 cm^?1. Our study together with previously reported C-isotopic compositions (δ¹³C, ?17 to ?27‰) of diamond and occurrences of fluid/melt inclusions in diamond and garnet indicates that Erzgebirge microdiamonds are metamorphic, have an organic carbon source, and crystallized from aqueous fluids. Limited long-range ordering suggested by the Raman spectra is a function of the P–T time of crystallization and subsequent thermal annealing on decompression. Combined with regional geology, our work further constrains the tectonic evolution of the Erzgebirge terrane.     

Zircon U–Pb ages,REE concentrations and Hf isotope compositions of granitic leucosome and pegmatite from the north Sulu UHP terrane in China: Constraints on the timing and nature of partial melting

Granitic leucosome and pegmatite are widely distributed within biotite-bearing orthogneiss in the northern part of the Sulu ultrahigh-pressure (UHP) metamorphic terrane, eastern China. A combined study of mineral inclusions, cathodoluminescence (CL) images, U–Pb SHRIMP dates, and in situ trace element and Lu–Hf isotope analyses of zircons provided insight into the nature and timing of partial melting in these rocks. Zircon grains separated from biotite-bearing orthogneiss typically have three distinct domains: (1) pre-metamorphic (magmatic) cores with Qtz + Kfs + Pl + Ap inclusions, which record a Neoproterozoic protolith age of ～ 790 Ma, (2) mantles with Coe + Phe + Ap inclusions that record Triassic UHP age at 227 ± 3 Ma, and (3) narrow rims with quartz inclusions that record HP granulite-facies retrograde metamorphism at ～ 210 ± 3 Ma. In contrast, zircons separated from granitic leucosome have only two distinct domains: (1) the central UHP areas with Coe + Phe + Ap inclusions record Triassic UHP age of 227 ± 3 Ma, and (2) outer magmatic areas with Qtz + Kfs + Ab + Ap inclusions that record partial melting time of 212 ± 2 Ma. Zircons separated from pegmatite contain mineral inclusions of Qtz + Kfs + Ap and show regular magmatic zoning from centre to edge. The centres record partial melting time of 212 ± 2 Ma in line with the outer domains of granitic leucosome, whereas the edges give a younger age of 201 ± 2 Ma related to Pb loss and partial recrystallization during late Triassic regional amphibolite-facies retrogression. These data indicate that partial melting in the north Sulu UHP gneissic rocks took place during post-UHP, retrograde HP granulite-facies metamorphism.Pre-metamorphic (magmatic) zircon cores from biotite-bearing orthogneiss give uniform ¹⁷⁶Hf/¹⁷⁷Hf of 0.28187 ± 0.00003 (2 SD; standard deviation) corresponding to εHf₍₇₉₀₎ and Hf model ages (T_DM2) of about ? 16.3 and 2.41 Ga, respectively. This is consistent with the generation of its protolith by reworking of Paleoproterozoic to late Archean crust. In contrast, UHP zircon domains from biotite-bearing orthogneiss and granitic leucosome are characterized by distinct trace element composition with low Lu/Hf (< 0.006), low Th/U (< 0.1) and considerably higher, ¹⁷⁶Hf/¹⁷⁷Hf (0.28233 ± 0.00002; 2 SD) than the pre-metamorphic cores. The uniform but significantly different Hf isotope composition between the UHP (εHf₍₂₂₇₎ = ? 14.6 ± 0.8; 2 SD) and pre-metamorphic (εHf₍₂₂₇₎ = ? 27.7) domains indicates equilibration of the Lu–Hf isotope system only within the UHP metamorphic mineral assemblage. The disequilibrium between whole rock and UHP zircon suggests that about two thirds of the whole rock Hf retained in the pre-metamorphic zircon domains. Zircon domains crystallized during partial melting at 212 Ma in granitic leucosome and pegmatites have a Hf isotope composition indistinguishable from that of the UHP zircon domains. This suggests that only Hf (and Zr) equilibrated during UHP metamorphism was remobilized during partial melting while pre-metamorphic zircon remained stable or was not accessible. In contrast, the magmatic zircon edges from pegmatite have somewhat lower ¹⁷⁶Hf/¹⁷⁷Hf (～ 0.28216) and εHf(t) (? 17.6 ± 1.2; 2 SD) indicating some release of less radiogenic Hf for instance by dissolution of pre-metamorphic zircon during late regional amphibolite-facies retrogression.     

Four-stream Radiative Transfer Parameterization Scheme in a Land Surface Process Model

Accurate estimates of albedos are required in climate modeling. Accurate and simple schemes for radiative transfer within canopy are required for these estimates, but severe limitations exist. This paper developed a four-stream solar radiative transfer model and coupled it with a land surface process model. The radiative model uses a four-stream approximation method as in the atmosphere to obtain analytic solutions of the basic equation of canopy radiative transfer. As an analytical model, the four-stream radiative transfer model can be easily applied efficiently to improve the parameterization of land surface radiation in climate models. Our four-stream solar radiative transfer model is based on a two-stream short wave radiative transfer model. It can simulate short wave solar radiative transfer within canopy according to the relevant theory in the atmosphere. Each parameter of the basic radiative transfer equation of canopy has special geometry and optical characters of leaves or canopy. The upward or downward radiative fluxes are related to the diffuse phase function, the G-function, leaf reflectivity and transmission, leaf area index, and the solar angle of the incident beam. The four-stream simulation is compared with that of the two-stream model. The four-stream model is proved successful through its consistent modeling of canopy albedo at any solar incident angle. In order to compare and find differences between the results predicted by the four- and two-stream models, a number of numerical experiments are performed through examining the effects of different leaf area indices, leaf angle distributions, optical properties of leaves, and ground surface conditions on the canopy albedo. Parallel experiments show that the canopy albedos predicted by the two models differ significantly when the leaf angle distribution is spherical and vertical. The results also show that the difference is particularly great for different incident solar beams. One additional experiment is carried out to evaluate the simulations of the BATS land surface model coupled with the two- and four-stream radiative transfer models. Station observations in 1998 are used for comparison. The results indicate that the simulation of BATS coupled with the four-stream model is the best because the surface absorbed solar radiation from the four-stream model is the closest to the observation.     

Mineral evolution of a garnet-pyroxenite nodule within eclogite, eastern Sulu ultrahigh-pressure metamorphic terrane, East China

Detailed microtextural observations and bulk chemical analysis were undertaken on a garnet‐pyroxenite nodule within retrograde eclogites from the NE Sulu ultrahigh‐pressure metamorphic (UHPM) terrane. The results suggest that the protolith was a cumulate from a gabbroic body. The nodule consists primarily of coarse clinopyroxene grains with a very high content of the Ca‐Tschermakite molecule. Microscopic observations and back‐scattered electron images (BSE) demonstrate a complicated intergrowth of clinopyroxene, garnet and ilmenite, which represents the peak metamorphic assemblage. The primary clinopyroxene grains are armoured with a thin garnet corona up to 0.5 mm wide that forms an interconnected network. Within the clinopyroxene grains, four sets of garnet lamellae are distributed along crystallographic planes; locally, a vermicular intergrowth of garnet and diopside is developed. Besides the garnet, parallel arrays of ilmenite blebs are common within the clinopyroxene. Hydrous minerals such as amphibole, zoisite and titanite formed at later stages, and replaced diopside, garnet and ilmenite respectively. The P–T conditions determined for the formation of the garnet lamellae indicate that the garnet pyroxenite experienced UHP metamorphism at the same peak P–T condition as its host eclogite. The very high Ca‐Tschermakite content (31–34 mol.%) of the primary clinopyroxene indicates crystallization at about 9–17 kbar and 1250–1450 °C, and together with the microtextural observations, suggests that the protolith of the garnet pyroxenite was a cumulate from a former gabbroic body, in which case, the host eclogite might represent the gabbroic body.     

Petrochemistry, oxygen isotopes and U-Pb SHRIMP geochronology of mafic–ultramafic bodies from the Sulu UHP terrane, China

Two Rongcheng eclogite‐bearing peridotite bodies (Chijiadian and Macaokuang) occur as lenses within the country rock gneiss of the northern Sulu terrane. The Chijiadian ultramafic body consists of garnet lherzolite, whereas the Macaokuang body is mainly meta‐dunite. Both ultramafics are characterized by high MgO contents, low fertile element concentrations and total REE contents, which suggests that they were derived from depleted, residual mantle. High FeO contents, an LREE‐enriched pattern and trace‐element contents indicate that the bulk‐rock compositions of these ultramafic rocks were modified by metasomatism. Oxygen‐isotope compositions of analysed garnet, olivine, clinopyroxene and orthopyroxene from these two ultramafic bodies are between +5.2‰ and +6.2‰ (δ¹⁸O), in the range of typical mantle values (+5.1 to +6.6‰). The eclogite enclosed within the Chijiadian lherzolite shows an LREE‐enriched pattern and was formed by melts derived from variable degrees (0.005–0.05) of partial melting of peridotite. It has higher δ¹⁸O values (+7.6‰ for garnet and +7.7‰ for omphacite) than those of lherzolite. Small O‐isotope fractionations (ΔCpx‐Ol: 0.4‰, ΔCpx‐Grt: 0.1‰, ΔGrt‐Ol: 0.3–0.4‰) in both eclogite and ultramafic rocks suggest isotopic equilibrium at high temperature. The P–T estimates suggest that these rocks experienced subduction‐zone ultrahigh‐pressure (UHP) metamorphism at ～700–800 °C, 5 GPa, with a low geothermal gradient. Zircon from the Macaokuang eclogite contains inclusions of garnet and diopside. The 225 ± 2 Ma U/Pb age obtained from these zircon may date either the prograde conditions just before peak metamorphism or the UHP metamorphic event, and therefore constrains the timing of subduction‐related UHP metamorphism for the Rongcheng mafic–ultramafic bodies.