Redistribution Of REE Research Articles

Albitization and redistribution of REE and Y in IOCG systems: Insights from Moonta-Wallaroo, Yorke Peninsula, South Australia

Abstract Trace element concentrations, particularly rare earth elements and yttrium (REY) in feldspars and accessory minerals, have been determined in a suite of albitized igneous, metasedimentary and metasomatite rocks from the Moonta-Wallaroo district, Olympic Cu–Au Province, South Australia. Results show that changes in REY-fractionation trends and concentrations in feldspars and common accessories are associated with key textures in albite-bearing associations from different lithologies. In granitic rocks, pseudomorphic replacement of pre-existing feldspars is typified by porous albite with cleavage-oriented intergrowths of sericite and pore-attached hematite. These observations are comparable with albitization features of granitic terranes elsewhere. A mineral association (albite-sericite ± chlorite), similar to that from granitoids, is observed as pervasive spots in limestone, inferring prograde skarnoid reactions at low fluid/rock ratio in an impure carbonate. In metasedimentary and metasomatite rocks with comparable Na2O content (~ 5–6 wt.%), fine-grained granoblastic albite suggests growth under high fluid/rock ratios irrespective of lithology. In such cases, albite with the highest REY content (ΣREY ~ 200 ppm) accounts for the entire REY budget, e.g., in albite–biotite-schist with the lowest abundance of accessory minerals. Nanoscale investigation confirms this albite to be a REY carrier (elements incorporated within the crystal lattice); no pore-attached inclusions are observed. In contrast, albite with the lowest REY-concentration (~ 14 ppm) is encountered in the metasomatite. In such rocks, recording the highest ΣREY (~ 1000 ppm) in whole-rock, partitioning of REY is favoured among the abundant accessories (titanite, apatite) and calc-silicates (actinolite, clinozoisite) rather than albite. Comparable low-REY albite is also found in granitoid-derived albitite (Na2O ~ 5 wt.%), in which abundant accessories and discrete REY-minerals formed during albitization account for the high ΣREY content (~ 700 ppm) in whole rock. The role of coupled dissolution–reprecipitation reactions (CDRR) is critical for REY (re)distribution within albitized igneous rocks, where REY-release from early magmatic accessories and/or feldspars assists REY-enrichment into late albite. The presence of abundant nanopore-attached inclusions in plagioclase demonstrates the nanoscale nature of CDRR-driven albitization in granitoids, consistent with published experimental work on altered granites. Such porosity offers sites for REY entrapment seen within discrete REY-minerals in new-formed K-feldspar. Similarly, release and uptake of REY, concurrent with albitization, is seen in formation of coarser REY-minerals (xenotime, bastnasite, synchysite) during CDRR-driven replacement of accessory Fe–Ti-oxides by symplectites of chlorite and hematite. Based on the differences identified between the albitization pathways in igneous and metasedimentary rocks, we discuss how albitization proceeds via a series of complex fluid–mineral reactions, each involving the redistribution, accumulation and retention of REY. These reactions are critical for defining the endowment and deportment of REY in rocks that have undergone sodic alteration. Contrary to previous models, albitization appears controlled by pH rather than redox conditions. Despite regional differences in local geological environment and alteration style across the Olympic Cu–Au Province, albitization, the initiation of hydrothermal alteration, is a pre-requisite stage for REY-enrichment in Iron-Oxide–Copper–Gold (IOCG) systems. REY distribution patterns in feldspars may thus have value in mineral exploration as criteria enabling alteration associated with mineralization to be distinguished from the regional background. Strong albitization without superposition of later potassic alteration may not, however, be automatically linked to the formation of giant IOCG deposits. Albitization enhances rock permeability and in a strongly faulted structural environment without a suitable trap, hydrothermal fluids may be more readily lost from the system.

Time scales of diffusive re-equilibration in bi-mineralic systems with and without a fluid or melt phase

Diffusion is a fundamental mass transfer process in magmatic and metamorphic systems. Simple recipes for evaluating time scales for diffusive re-equilibration of a trace element in bi-mineralic aggregates with and without the presence of intergranular fluid or melt are obtained through approximate solutions to diffusion equations. Diffusive re-equilibration times for the trace element depend on average grain sizes of the two minerals, diffusion coefficients and partition coefficients for the element in the two minerals, and volume fractions or volume fluxes of the minerals and fluid or melt in the system. There are two time scales for diffusive re-equilibration in fluid-bearing bi-mineralic systems. The fast time scale is proportional to fluid fraction and dominated by the mineral that has a faster diffusion rate. The slow time scale is bounded by the time scales of diffusion in the two minerals and determines the overall time scale of diffusive re-equilibration for the system. Presence of small amount of fluid or melt does not lead to a reduction in the time scale of diffusive re-equilibration for the bi-mineralic aggregate. Percolation of fluid or melt drives the system further away from equilibrium and increases the length and time scales for diffusive re-equilibration in the system. The time scales for subsolidus re-equilibration in bi-mineralic aggregates are determined by the minor’s rule: the mineral that contains a lesser amount of the trace element of interest in the system contributes more to the overall diffusive time.Applications to REE redistribution between clinopyroxene and orthopyroxene and between plagioclase and orthopyroxene highlight the importance of REE diffusion and partitioning in pyroxene and plagioclase. The time scales for subsolidus re-equilibration of REE in noritic rocks are dominated by light REE diffusion in orthopyroxene and by middle and heavy REE diffusion in plagioclase. The time scales for subsolidus re-equilibration of REE in two-pyroxene bearing rocks are controlled primarily by REE diffusion in orthopyroxene. The time scales for diffusive re-equilibration of REE in melt-bearing two-pyroxene aggregates are determined by diffusion in clinopyroxene for light REE and by diffusion in orthopyroxene for middle to heavy REE. Presence of melt flow further expands the role of clinopyroxene. This contrasting behavior in diffusive time scale may provide a simple explanation for the ubiquitous chemical disequilibrium in light REE between clinopyroxene and orthopyroxene observed in mantle peridotites from a wide range of tectonic settings.

LREE-redistribution among fluorapatite, monazite, and allanite at high pressures and temperatures

The REE enrichment process in fluorapatite and the REE redistribution among fluorapatite, monazite, and allanite were studied in a series of three sets of experimental runs at P-T conditions of 0.5 to 4 GPa and 650 to 900 °C. The first two sets of experimental runs utilized fluorapatite as a P-source, synthetic monazite or allanite as the REE sources, albite, quartz, and NaF-H2O or NaCl-H2O. The third set of runs was carried out with powdered Ca3(PO4)2, allanite, quartz, (±Al2O3), and a NaF-H2O solution.

Redistribution of REE, Y, Th, and U at high pressure: Allanite-forming reactions in impure meta-quartzites (Sesia Zone, Western Italian Alps)

Accessory phases are important hosts of trace elements; allanite may contain >90% of the REE in a bulk rock. The mobility and redistribution of several trace elements, notably HREE, Th, U, and Y is thus controlled by reactions involving allanite and other REE phases, as well as several rock-forming minerals. As these elements are commonly concentrated in mature clastic sediments, a suite of impure quartzite was studied. Two eclogite facies samples from the Monometamorphic Cover Complex of the Sesia Zone (Western Italian Alps) are presented in some detail, as they reveal a remarkably rich spectrum of reaction relationships that involve REE phases. Two allanite-forming reactions were inferred from textures and phase compositions monazite + Ca - silicate ( ? ) + fluid → allanite + apatite + thorite ; (1) monazite + thorite + Ca - silicate ( ? ) + fluid → Th - rich allanite + auerlite ± apatite . (2) Petrographic observations and thermodynamic models suggest that allanite entered the HP assemblage at ~530 °C and 17–18 kbar during prograde metamorphism. In one sample, allanite is rimmed by epidote rich in Y and HREE that grew at the expense of xenotime. Two net transfer reactions were derived xenotime + allanite + fluid → Y - rich epidote + apatite + thorite ; (3) xenotime + allanite + fluid → Y - rich epidote + aeschynite + thorite + ( phosphate ? ) . (4) Textural relationships and trace element analyses of coexisting allanite/monazite and xenotime/Y-rich epidote reveal systematic partitioning of the REE. Partition coefficients for the HREE are compatible with equilibrium fractionation, whereas those for the LREE show patterns that seem to be inherited from the precursor phases, in this case zircon with variable LREE composition.

Geochemistry of the Late Neoproterozoic Hadb adh Dayheen ring complex, Central Arabian Shield: Implications for the origin of rare-metal-bearing post-orogenic A-type granites

The Hadb adh Dayheen ring complex (HDRC), Central Arabian Shield, is an alkaline to peralkaline A-type granite complex. It consists of an inner core of monzogranite followed outward by porphyritic alkali feldspar granite (hornblende biotite granite and aegirine riebeckite granite). Field and textural observations indicate that the different granite types were separated from magma reservoir, at different stages, and emplaced at higher levels along pre-existing fractures. The geochemical characteristics indicate that their magma was most plausibly originated by partial melting of juvenile lower crust following collision between East and West Gondwana at the final stage of the Arabian Shield evolution. The alkali feldspar granites have high abundances of albite and fluorite and wide variation of HFSE and REE that indicate interaction with hydrothermal F-rich fluids. Although there are many geochemical, mineralogical and textural evidence of secondary metasomatic alteration superimposed on the granitic rocks, they show textural features such as the arrangement of albite inclusions along growth planes in quartz (snowball texture) and aegirine that indicate early magmatic crystallization of albite. Also, the strong linear positive correlation of Ta vs. Nb and Zr vs. Hf emphasize that the behavior and enrichment of Ta and Nb are largely controlled by magmatic processes. The events that can explain the evolution of these rocks are: (1) during magmatic evolution, F dissolved in the magma and lowered the crystallization temperature causing REE and HFSE to form complexes and thus behave as incompatible elements, (2) prolonged crystallization of the major mineral phases (quartz and feldspar) formed a late-stage magmatic fluid enriched in volatiles (H 2O, F) and trace elements, (3) accessory minerals crystallized from such a phase in the interstices between the major mineral phases, and (4) post-magmatic re-equilibration and formation of secondary albite (Na-metasomatism) has probably led to the redistribution of some major elements and limited redistribution of HFSE and REE.

The Gumeshevo skarn-porphyry copper deposits in the Central Urals, Russia: Evolution of the ore-magmatic system as deduced from isotope geochemistry (Sr, Nd, C, O, H)

The Early Devonian Gumeshevo deposit is one of the largest ore objects pertaining to the dioritic model of the porphyry copper system paragenetically related to the low-K quartz diorite island-arc complex. The (87Sr/86Sr)t and (ɛNd)t of quartz diorite calculated for t = 390 Ma are 0.7038–0.7045 and 5.0–5.1, respectively, testifying to a large contribution of the mantle component to the composition of this rock. The contents of typomorphic trace elements (ppm) are as follows: 30–48 REE sum, 5–10 Rb, 9–15 Y, and 1–2 Nb. The REE pattern is devoid of Eu anomaly. Endoskarn of low-temperature and highly oxidized amphibole-epidote-garnet facies is surrounded by the outer epidosite zone. Widespread retrograde metasomatism is expressed in replacement of exoskarn and marble with silicate (chlorite, talc, tremolite)-magnetite-quartz-carbonate mineral assemblage. The 87Sr/86Sr ratios of epidote in endoskarn and carbonate in retrograde metasomatic rocks (0.7054–0.7058 and 0.7053–0.7065, respectively) are intermediate between the Sr isotope ratios of quartz dioritic rocks and marble (87Sr/86Sr = 0.70784 ± 2). Isotopic parameters of the fluid equilibrated with silicates of skarn and retrograde metasomatic rocks replacing exoskarn at 400°C are δ18O = +7.4 to +8.5‰ and δD = −49 to −61‰ (relative to SMOW). The δ13C and δ18O of carbonates in retrograde metasomatic rocks after marble are −5.3 to +0.6 (relative to PDB) and +13.0 to +20.2% (relative to SMOW), respectively. Sulfidation completes metasomatism, nonuniformly superimposed on all metasomatic rocks and marbles with formation of orebodies, including massive sulfide ore. The δ34S of sulfides is 0 to 2‰ (relative to CDT);87Sr/86Sr of calcite from the late calcite-pyrite assemblage replacing marble is 0.704134 ± 6. The δ13C and 87Sr/86Sr of postore veined carbonates correlate positively (r = 0.98; n = 6). The regression line extends to the marble field. Its opposite end corresponds to magmatic (in terms of Bowman, 1998b) calcite with minimal δ13C, δ18O, and 87Sr/86Sr values (−6.9 ‰, +6.7‰, and 0.70378 ± 4, respectively). The aforementioned isotopic data show that magmatic fluid was supplied during all stages of mineral formation and interacted with marble and other rocks, changing its Sr, C, and O isotopic compositions. This confirms the earlier established redistribution of major elements and REE in the process of metasomatism. A contribution of meteoric and metamorphic water is often established in quartz from postore veins.

Geochemistry and origin of ferruginous nodules in weathered granodioritic gneisses, Mysore Plateau, Southern India

Fe-nodules occur within saprolites formed from weathering of granodioritic gneisses in the rain-shadow region of the Mysore Plateau adjacent to the Sahyadri Mountains in Southern India. These nodules and their host saprolites were studied for their geochemistry, including chemical speciation, to understand nodule formation and chemical redistribution processes during rock weathering. From their mode of occurrence, and mineralogical and geochemical data, we infer that the nodules originated by a two-stage process in which the initial extensive weathering of gneisses likely facilitated subsequent ferrolysis weathering and nodule formation. Nodules originated by precipitation of goethite, hematite and gibbsite along with several amorphous phases within the matrix of weathered gneisses. This is possible only under hydromorphic conditions, suggesting that parts of the plateau must have gone through a humid phase prior to the present aridity. In the saprolites, Al, Fe, and Ti become enriched because of the removal of Si, Ca, Na, and K. However within the nodule, Fe, Ti, Cr, and Ni are deposited after their chemical transport from the saprolite. Titanium, known for its immobile nature, was also mobilized and concentrated under the conditions of nodule formation. The most important elements in the nodule constitution are Fe, Al, Ti, and Mn, each having both crystalline and amorphous phases. Fe–Ti and Mn oxyhydroxides grain coatings in the saprolites and discrete amorphous Mn and Ti phases in the nodules seem to have scavenged trace elements from the weathering profile. REE were mobilized during weathering and nodule genesis in which Ce and Ti show a strong geochemical coherence. The enrichment of only HREE in saprolite, and both HREE and LREE with significant Ce in the nodule, indicate the control of evolving secondary minerals in the REE redistribution during rock weathering. Strong enrichment of Ce in the weathering profile and in nodules has important implications to the REE chemistry of river waters.

Redistribution of REE in association with formation of secondary uranium minerals

Redistribution of REE in association with formation of secondary uranium minerals

Northwest Africa 011: A “eucritic” basalt from a non‐eucrite parent body

Abstract— We have carried out a detailed petrographic, mineralogical, and trace element study of Northwest Africa (NWA) 011. This meteorite bears many similarities to the eucrites it was initially identified with, although oxygen isotopic compositions rule out a genetic relationship. Like many eucrites, NWA 011 crystallized from a source with approximately chondritic proportions of REE, although a slightly LREE‐enriched bulk composition with a small positive Eu anomaly, as well as highly fractionated Fe/Mg ratios and depleted Sc abundances (Korotchantseva et al. 2003), suggest that the NWA 011 source experienced some pyroxene and/or olivine fractionation. Thermal metamorphism resulted in homogenization of REE abundances within grains, but NWA 011 did not experience the intergrain REE redistribution seen in some highly metamorphosed eucrites. Despite a similarity in oxygen isotopic compositions, NWA 011 does not represent a basaltic partial melt from the acapulcoite/lodranite parent body. The material from which NWA 011 originated may have been like some CH or CB chondrites, members of the CR chondrite clan, which are all related through oxygen isotopic compositions. The NWA 011 parent body is probably of asteroidal origin, possibly the basaltic asteroid 1459 Magnya.

Redistribution of U, Pb and REE in association with alteration of uranium minerals from the Koongarra deposit, Northern Territory, Australia

Summary In order to investigate migration behavior of REE in uranium matrix by alteration, and to understand a chronological history of the alteration processes, in-situ isotopic analysis of U, Pb and REE by using a Sensitive High Resolution Ion MicroProbe (SHRIMP) was applied to the Koongarra uranium deposit sample (Northern Territory, Australia) which contains uraninite and two kinds of secondary uranium minerals (curite and sklodowskite). Highly discordant U-Pb data from all of the uranium minerals suggest that the secondary uranium minerals were formed by sequential alteration of primary uraninite 50-580 Ma ago, and subsequently affected by recent weathering. The difference of REE abundance patterns between primary uraninite and secondary uranium minerals show geochemical evidence of REE redistribution during the secondary mineralization by the interaction of primary ore body with meteoric water.

Scale and timing of Rare Earth Element redistribution in the Taconian foreland of New England

Clastic sedimentary rocks, deposited on eastern North America in response to the Taconian Orogeny, commonly have Sm/Nd isotope relationships indicating substantial isotope disturbance near or subsequent to the time of sedimentation that may be associated with severe depletion in light rare earth elements (LREE). Affected units [Normanskill Formation (Austin Glen and Pawlet Members), Frankfort Formation and Perry Mountain Formation] are widely separated both geographically (western New York to western Maine) and stratigraphically (Middle Ordovician to Silurian). A model is proposed for the most likely explanation of the observed REE and Sm/Nd isotope relationships involving a two-stage process. In the first stage, REE are redistributed on a mineralogical scale (dissolution/precipitation on a sample scale) often with the involvement of REE-enriched trace phases such as apatite and monazite. This stage typically takes place during diagenesis but may also take place later during metamorphism and/or recent weathering, and results in isotope re-equilibration on a sample scale. The second stage occurs when one or more of these phases is redissolved and REE are transported on large advective scales. Where LREE-enriched phases are involved, this gives rise to LREE depletion in whole rocks. The timing of this second stage cannot be constrained from Sm/Nd isotope data and may take place at any time subsequent to the isotope re-equilibration. Such complex histories of REE redistribution may result in serious errors in estimating Nd model ages but not in estimating the Nd isotope composition at the age of sedimentation. Thus, Sm/Nd ratios even of unmetamorphosed sedimentary rocks have to be carefully evaluated before the calculation of depleted mantle model ages for the provenance.

Assessing the impact of black shale processes on REE and the U–Pb isotope system in the southern Appalachian Basin

Upper Devonian Java and Huron shales from the southern Appalachian Basin exhibit evidence of REE redistribution and resetting of the U–Pb isotopic system at the time of deposition (ca. 365 Ma). This alteration to the primary detrital signature of these shales is indicative of black shale diagenetic/depositional processes that in effect obscure paleoenvironmental and provenance information that may be recorded. The most direct evidence of these black shale processes is the rotated nature of the whole-rock REE patterns from this sequence of presumably source related shales. The neo-formation of REE-bearing diagenetic phases such as apatite and possibly carbonate has led to an unusually large range in the whole-rock 147Sm/ 144Nd and the Ce/Ce* for this sequence of shales. Changes to these whole-rock ratios will effectively alter the Nd model age and create a Ce/Ce* that records evidence of diagenetic processes rather than information about the paleooceanographic conditions of the basin. Simultaneously, the sequestration of U at the time of deposition and subsequent fixation in diagenetic phases such as apatite has effectively reset the 238U– 206Pb isotopic system at 340±50 Ma overprinting the Pb isotopic signature of the source area. The trace-element and isotopic signatures recorded by the Java and Huron formation shales from the study area reveal a syn-/postdepositional history dominated by what can be referred to as black shale processes. The diagenetic conditions that develop at and below the sediment water interface during the deposition of organic-rich shale are unique and consequently leave behind a unique geochemical fingerprint that can potentially overprint paleoenvironmental and provenance information.

Geochemistry of the Upper Neoproterozoic and Lower Cambrian siliciclastic rocks and U-Pb dating on detrital zircons in the Central Iberian Zone, Spain

Sandstones and shales from the Upper Neoproterozoic (UN) succession in the Central Iberian Zone (CIZ) show parallel REE patterns and relatively restricted and similar ranges and average values of some element ratios such as Al2O3/TiO2,Ti/Nb, Eu/Eu*, (La/Yb)n, (Gd/Yb)n and Th/U. This remarkable geochemical homogeneity for related medium- and fine-grained rocks is unusual, and strongly suggests a recycled source area. However, the Lower Cambrian (LC) equivalent rocks are, in general terms, geochemically less mature, more heterogeneous and more fractionated. Their average REE patterns are practically coincident, probably as a consequence of REE redistribution related to the reworking of sediments during a stage of sea level fall in Lower Cambrian times. Ti and Zr abundances, chemical index of alteration (CIA) values and element ratios such as Al2O3/TiO2, K/Rb, Ti/Nb and Rb/Zr can be used for discriminating purposes between the UN and LC siliciclastic rocks. Detrital zircons from a UN and a LC sandstone display morphological differences. However, U-Pb data are discordant and cannot be interpreted in a straightforward manner. Nevertheless, age data are compatible with a model in which the continent of Gondwana would have supplied zircons, showing a bimodal age distribution, in variable proportions to the respective sandstone units.

Residence and redistribution of REE, Y, Zr, Th and U during granulite-facies metamorphism: behaviour of accessory and major phases in peraluminous granulites of central Spain

Accessory minerals are thought to play a key role in controlling the behaviour of certain trace elements such as REE, Y, Zr, Th and U during crustal melting processes under high-grade metamorphic conditions. Although this is probably the case at middle crustal levels, when a comparison is made with granulite-facies lower crustal levels, differences are seen in trace element behaviour between accessory minerals and some major phases. Such a comparison can be made in Central Spain where two granulite-facies terranes have equilibrated under slightly different metamorphic conditions and where lower crustal xenoliths are also found. Differences in texture and chemical composition between accessory phases found in leucosomes and leucogranites and those of melanosomes and protholiths indicate that most of the accessory minerals in melt-rich migmatites are newly crystallized. This implies that an important redistribution of trace elements occurs during the early stages of granulite-facies metamorphism. In addition, the textural position of the accessory minerals with respect to the major phases is crucial in the redistribution of trace elements when melting proceeds via biotite dehydration melting reactions. In granulitic xenoliths from lower crustal levels, the situation seems to be different, as major minerals show high concentration of certain trace elements, the distribution of which is thus controlled by reactions involving final consumption of Al-Ti-phlogopite. A marked redistribution of HREE–Y–Zr between garnet and xenotime (where present) and zircon, but also of LREE between feldspars (K-feldspar and plagioclase) and monazite, is suggested.

Trace element geochemistry during chemical weathering

The granite weathering in Longnan, Jiangxi, is represented by mineralogical changes of feldspars → montmorillonite, illite → kaolinite, halloysite → bauxite, with Na, Ca, Si, P, V, U and Sr being in a mobile state while Ti, Al, Fe, Sc, Th, Zr and Hf remaining relatively conservative. With the exception of Zr/Hf, Nb/Ta, Th/Sc, Zr/Nd and Sm/Nb, changes are notable in ratios between most of the trace elements. Re-distribution of REE and Y has taken place during the chemical weathering, and the REE patterns of weathered samples in the profile, with original characters of the parent rock still recognizable, has undergone some fractionation. Generally, the extent of chemical weathering is the critical factor determining the mineralogical and chemical characteristics of the profiles and this must be taken into account in any study of tracing the provenance on the basis of mineralogical and trace element characteristics of the sediments.

Contrasting geochemical and Sm-Nd isotopic compositions of Archean metasediments from the Kongling high-grade terrain of the Yangtze craton: evidence for cratonic evolution and redistribution of REE during crustal anatexis

Twenty-three clastic metasediments from the Kongling high-grade terrain of the Yangtze craton, South China were analyzed for major, trace and rare earth elements and Sm-Nd isotopic ratios. Associated dioritic-tonalitic-trondhjemitic (DTT) and granitic gneisses as well as amphibolites were also analyzed in order to constrain provenance. The results show that the clastic metasediments can be classified into 3 distinct groups in terms of mineralogical, geochemical and Sm-Nd isotopic compositions. Group A is characterized by having no to slight negative Eu anomalies (Eu/Eu∗ = 0.82–1.07), being high in Cr (191–396 ppm) and Ni (68–137 ppm), and low in Th (3.3–7.8 ppm) and REE (ΣREE = 99–156 ppm). These characteristics are similar to those of metasediments from Archean greenstone belts. In addition, the Group A metasediments have the value of the Chemical Index of Alteration (CIW) close to felsic gneisses. Their Sm-Nd isotopic, REE and trace element compositions can be interpreted by mixtures of the DTT gneisses and amphibolites. Dating of detrital zircons from 2 Group A samples by SHRIMP reveals a major concordant age group of 2.87–3.0 Ga, which is identical to the age of the trondhjemitic gneiss. These results strongly suggest that Group A was principally the first-cycle erosion product of the local Kongling DTT gneiss and amphibolite. Moreover, the higher than amphibolite Cr content and slight Eu depletion exhibited by some samples from this group infer that ultramafic rocks like komatiite and granite of probably 3.0–3.3 Ga in age also played a role. Group B is characterized by the presence of graphite and shows a more evolved composition similar to post-Archean shales with a prominent negative Eu anomaly (Eu/Eu∗ = 0.48–0.77) and high CIW. On paired Cr/Th vs La/Co and Co/Th plots, Group B samples conform to a two-end member mixing line of the Kongling granitic gneiss and amphibolite. However, data on Nd model age and CIW suggest that the granite component should be younger than the sampled granitic gneiss and derived from a distal source. Both Groups A and B exhibit a clear positive correlation between CIW and T DM and a negative one between CIW and Eu/Eu∗. These correlations point to the crustal evolution of the Yangtze craton towards coupled increasing CIW and Eu depletion with decreasing age. This in turn reflects the change of granitoid magmatism from local Na-rich dioritic-tonalitic-trondhjemitic rocks to widespread K-feldspar granite. The change led to the intracrustal differentiation, stabilization and growth of the craton. Group C is restite and contains abundant sillimanite and garnet and unusually high ilmenite (7–11vol%), which can be seen to be dehydration melting products of biotite under the microscope. This group shows extremely varied REE distributions from LREE enriched to depleted and from negative to strong positive (Eu/Eu∗ = 1.63) Eu anomalies. Compared to Groups A and B, Group C is severely depleted in Na 2O, K 2O, LREE, Rb and Ba, whereas TiO 2, Co, V, Sc and HREE and Y are considerably enriched. This is accompanied by anomalous high Sm/Nd (0.21–0.28), 147Sm/ 144Nd (0.1361–0.1738) and 143Nd/ 144Nd (0.511589–0.511958) ratios. T DM correlates clearly with Sm/Nd ratio and 2 out of 3 samples give significantly older to unrealistic T DM (3.9–4.9 Ga). The results document redistribution of REE and an open behavior of the Sm-Nd isotope system during the biotite dehydration melting of metasediments.

Behavior of accessory phases and redistribution of Zr, REE, Y, Th, and U during metamorphism and partial melting of metapelites in the lower crust: an example from the Kinzigite Formation of Ivrea-Verbano, NW Italy

This study is aimed at understanding the behavior of monazite, xenotime, apatite and zircon, and the redistribution of Zr, REE, Y, Th, and U among melt, rock-forming and accessory phases in a prograde metamorphic sequence, the Kinzigite Formation of Ivrea-Verbano, NW Italy, that may represent a section from the middle to lower continental crust. Metamorphism ranges from middle amphibolite to granulite facies and metapelites show evidence of intense partial melting and melt extraction. The appearance of melt controls the grain size, fraction of inclusions and redistribution of REE, Y, Th, and U among accessories and major minerals. The textural evolution of zircon and monazite follows, in general, the model of Watson et al. (1989). Apatite is extracted from the system dissolved into partial melts. Xenotime is consumed in garnet-forming reactions and is the first source for the elevated Y and HREE contents of garnet. Once xenotime is exhausted, monazite, apatite, zircon, K-feldspar, and plagioclase are progressively depleted in Y, HREE, and MREE as the modal abundance of garnet increases. Monazite is severely affected by two retrograde reactions, which may have consequences for U-Pb dating of this mineral. Granulite-grade metapelites (stronalites) are significantly richer in Ti, Al, Fe, Mg, Sc, V, Cr, Zn, Y, and HREE, and poorer in Li, Na, K, Rb, Cs, Tl, U, and P, but have roughly the same average concentration of Cu, Sr, Pb, Zr, Ba, LREE, and Th as amphibolite-grade metapelites (kinzigites). The kinzigite-stronalite transition is marked by the sudden change of Th/U from 5–6 to 14–15, the progressive increase of Nb/Ta, and the decoupling of Ho from Y. Leucosomes were saturated in zircon, apatite, and (except at the lowest degree of partial melting) monazite. Their REE patterns, especially the magnitude of the Eu anomaly, depend on the relative proportion of feldspars and monazite incorporated into the melt. The presence of monazite in the source causes an excellent correlation of LREE and Th, with nearly constant Nd/Th ≈ 2.5–3. The U depletion and increase in Th/U characteristic of granulite facies only happens in monazite-bearing rocks. It is attributed to enhancement of the U partitioning in the melt due to elevated Cl activity followed by the release of a Cl-rich F-poor aqueous fluid at the end of the crystallization of leucosomes. Halide activity in partial melts was buffered by monazite and apatite. Since the U (and K) depletion does not substantially affect the heat-production of metapelites, and mafic granulites maintain similar Th/U and abundance of U and Th as their unmetamorphosed equivalents, it seems that geochemical changes associated to granulitization have only a minor influence on heat-production in the lower crust.

REE-bearing minerals in the albitites of central Sardinia, Italy

AbstractRecent studies on albitite rocks located in the granodiorite complex of Central Sardinia have revealed that epidote has a widespread occurrence as a light rare-earth element (LREE)-bearing accessory common phase. Titanite has been recorded as a heavy rare earth element (HREE)-bearing mineral. The Hercynian granodiorite complex of Central Sardinia is composed chiefly of quartz, Ca-plagioclase, K-feldspar and biotite and of a wide variety of secondary assemblages, mainly allanite, titanite and zircon. Albitic plagioclase and quartz are the main mineral components of the albitites. Additional minerals include, besides allanite and epidote, a more calcic-plagioclase (oligoclase), K-feldspar, chlorite, titanite and more rarely muscovite. The mineral assemblages and REE-bearing minerals of albitites were analysed by wavelength dispersive spectrometry (WDS). Chemical data suggest that there is a near complete solid-solution between epidote and allanite whereas little variations in HREE of titanites were detected. In epidote-group minerals a pronounced zoning in REE was observed while titanite was recorded unzoned. Textural relations were studied by SEM to distinguish primary from secondary epidotes. Chemical criteria to recognize magmatic from alteration epidotes were also applied. The alteration epidotes mainly occur and generally originate from plagioclase alteration and from leaching of magmatic allanite. Comparison of textures using both the SEM technique and EPMA data showed that the characteristic ‘patchy zoning’, observed in epidotes, corresponds with different amounts of REE in these minerals.The schematic model proposed for the epidote-forming reactions during the metasomatic processes that affected the granodiorites involves: (i) the instability of the anorthitic component of plagioclase; (ii) the simultaneous formation of albite; (iii) the leaching of the magmatic allanite with a redistribution of REE in the epidotes of the albitites.

Mineral chemistry and the petrogenesis of eucrites: I. Noncumulate eucrites

Ion microprobe analyses of REE and other selected trace and minor elements, coupled with electron microprobe measurements of major elements, were made in pigeonite, plagioclase, and phosphates of eight noncumulate eucrites from the various chemical groups previously recognized.REE concentrations are homogeneous in individual pigeonite and plagioclase grains of equilibrated eucrites but, except for Ibitira which is highly equilibrated, show intergrain variations. REE zoning was observed in some pyroxene and plagioclase grains of Pasamonte and ALHA76005 (two polymict eucrites with high abundance of unequilibrated clasts) and in some plagioclase grains of Sioux County and Chervony Kut (two equilibrated eucrites). Parent melt REE compositions were calculated for Pasamonte, Sioux County, and Chervony Kut, using the lowest REE abundances observed in the cores of igneously-zoned pyroxene and plagioclase grains and appropriate REE partition coefficients; they are remarkably similar to their respective whole rock abundances. The calculations also indicate that some plagioclase grains in Chervony Kut may be cumulus material. In ALHA76005, a positive Ce anomaly indicative of terrestrial REE redistribution was often observed in both pyroxene and plagioclase analyses. Coupled major and trace element analyses reveal that there are two types of zoned pyroxenes in Pasamonte: one was formed by igneous processes and the other owes its zoning to secondary alteration.The data generally support the model of Stolper (1977) for the origin of noncumulate eucrites, i.e., that the Stannem trend and main group eucrites were formed by different degrees of partial melting and the Nuevo Laredo trend by fractional crystallization. However, they also suggest chemical variability among eucrite magmas. The LREE/HREE ratios recorded in pyroxene and plagioclase indicate that noncumulate eucrites most likely derived from a source region with REEs in chondritic proportions.A search for 26Mg excesses from the decay of 26Al in Chervony Kut and Ibitira, the eucrites with the oldest reported ages, and in Pasamonte was negative.

Ion microprobe investigation of plagioclase and orthopyroxene from lunar Mg-suite norites: Implications for calculating parental melt REE concentrations and for assessing postcrystallization REE redistribution

The lunar Mg-suite, which includes dunites, troctolites, and norites, makes up to 20–30% of the Moon's crust down to a depth of ∼ 60 km. The remainder is largely anorthosite. This report focuses on norites (which consist mostly of orthopyroxene and plagioclase) because we have found that both phases are effective recorders of their parental melt compositions. In an earlier report, we analyzed orthopyroxene from twelve samples (three from Apollo 14, two from A-15, and seven from A-17) by SIMS for eight REE (La, Ce, Nd, Sm, Eu, Dy, Er, Yb). Inversion of these data to estimated melt compositions yielded extremely high REE concentrations similar to KREEP. In this study, we report SIMS REE data for plagioclase from these same twelve samples. The major objective of this study is to estimate parental REE concentrations from both orthopyroxene and plagioclase data to see if both data inversions produce concordant melt compositions and thus better constrain the composition of melts parental to Mg-suite norites. The estimated REE concentrations from both phases show some evidence of slight postcrystallization REE redistribution. Comparison of the observed ratio of REE for pyroxene/ plagioclase to the ratio of the Ds for pyroxene/plagioclase is consistent with REE redistribution which involves LREE diffusing from pyroxene into plagioclase and HREE diffusing from plagioclase into pyroxene. However, apparently these postcrystallization exchanges have not seriously affected our ability to estimate melt REE concentrations. The estimated melt REE concentrations using both plagioclase and orthopyroxene, are similar to high-K KREEP especially for melts parental to A-15 norites. This study provides support for mineral trace element inversion estimates for parental melts. Even though these lunar crustal lithologies experienced high temperature annealing, apparently the cores of plagioclase and pyroxene continue to carry a record of their igneous crystallization history.