Diffusion-limited REE uptake by eclogite garnets and its consequences for Lu–Hf and Sm–Nd geochronology

Garnets from the Zermatt-Saas Fee eclogites contain narrow central peaks for Lu + Yb + Tm ± Er and at least one additional small peak towards the rim. The REE Sm + Eu + Gd + Tb ± Dy are depleted in the cores but show one prominent peak close to the rim. These patterns cannot be modeled using Rayleigh fractionation accompanied by mineral breakdown reactions. Instead, the patterns are well explained using a transient matrix diffusion model where REE uptake is limited by diffusion in the matrix surrounding the porphyroblast. Observed profiles are well matched if a roughly linear radius growth rate is used. The secondary peaks in the garnet profiles are interpreted to reflect thermally activated diffusion due to temperature increase during prograde metamorphism. The model predicts anomalously low ¹⁷⁶Lu/¹⁷⁷Hf and ¹⁴⁷Sm/¹⁴⁴Nd ratios in garnets where growth rates are fast compared to diffusion of the REE, and these results have important implications for Lu–Hf and Sm–Nd geochronology using garnet.     

Origins of yttrium and rare earth element distributions in metamorphic garnet

Highly variable distributions of yttrium and rare earth elements (Y+REEs) are documented in pelitic garnet from the Picuris Mountains, New Mexico, and from Passo del Sole, Switzerland, and in mafic garnet from the Franciscan Complex, California. The wide variety of these Y+REE zoning patterns, and those described previously in other occurrences, imply diverse origins linked to differing degrees of mobility of these elements through the intergranular medium during garnet growth. In the Picuris Mountains, large, early‐nucleating crystals have radial profiles of Y+REE dominated by central peaks and annular maxima, in patterns that vary systematically with atomic number. Superimposed on these features are narrow spikes in HREEs and MREEs, located progressively rimward with decreasing atomic number. In contrast, profiles in small, late‐nucleating crystals contain only broad central maxima for all Y+REEs. In garnet from Passo del Sole, Y+REE zoning varies radically from sample to sample: in some rocks, crystals of all sizes display only central peaks for all Y+REEs; in others, profiles exhibit irregular fluctuations in Y+REE contents that match up with small‐scale patchy zoning in Y and Ca X‐ray maps. In the Franciscan Complex, Y+REE in garnet cores fluctuate unsystematically, but mantles and rims display concentric oscillatory zoning for both major elements and Y+REEs. Our interpretation of the complexity of Y+REE distributions in metamorphic garnet centres on the concept that these distributions vary primarily in response to the length scales over which these elements can equilibrate during garnet growth. Very short length scales of equilibration, due to low intergranular mobility, produce overprint zoning characterized by small‐scale irregularities. Higher but still restricted mobility yields diffusion‐controlled uptake, characterized by patterns of central peaks and annular maxima that vary with atomic number and are strongly influenced by T–t paths during garnet growth. Still greater mobility permits progressively greater, potentially rock‐wide, equilibration with major‐ and accessory‐phase assemblages, leading to mineralogical controls: an unchanging mineral assemblage during garnet growth produces bell‐shaped profiles resembling those produced by Rayleigh fractionation, whereas changes in major‐ and/or accessory‐phase assemblages produce profiles with distinct annuli and sharp discontinuities in concentration. The very high mobility associated with influxes of Y+REE‐bearing fluids can cause these element distributions to be dominated by factors external to the rock, yielding profiles characterized by abrupt shifts or oscillations that are not correlated to changes in mineral assemblages.     

Zonal REE + Y profiles in garnet and their genetic implications: A case study of metapelites from the northern Ladoga region

The objective of this study is to provide insights into the REE and Y behavior during garnet porphyroblast formation in staurolite-bearing schists as a constituent of Late Paleoproterozoic metapelites of the Ladoga Complex. The MnNCKFMASH P–T pseudosection for a single sample and Grt–Bt thermometry indicate that the garnet core grew at 520°C and under 7.0–7.2 kbar in the Grt–Bt–Pl–Chl–Ms–Zo field, whereas the garnet rim was equilibrated at 590–600°C and under 3.5–4.0 kbar. The measured zoning profiles are strongly depleted in REE + Y in the garnet core containing high Mn and Ca concentrations. The intermediate zone of garnet is enriched in La, Ce, Pr, and Nd (inner LREE + Nd annulus), as well as in Dy, Er, Yb, Lu, and Y (outer HREE + Y + Dy annulus). According to pseudosection analysis, these peaks were probably produced owing to breakdown of epidote-group minerals (allanite, REE-rich epidote) at T < 535°C and P > 6.5 kbar. Towards the rim, the HREE + Y contents gradually decrease, whereas MREE (Sm, Eu, Gd) display an inverse trend. The rim also exhibits a negative Eu anomaly. The former tendency reflects an increase in temperature during garnet crystallization and partitioning of elements between garnet and monazite. It is thought that the latter is linked to oppositely directed change in garnet-monazite partition coefficients for HREE and MREE with increasing temperature.     

Experimental petrology constraints on the recycling of mafic cumulate: a focus on Cr-spinel from the Rum Eastern Layered Intrusion,Scotland

The ¹⁷⁶Lu–¹⁷⁶Hf and ¹⁴⁷Sm–¹⁴³Nd decay systems are routinely used to determine garnet (Grt)–whole-rock (WR) ages; however, the ¹⁷⁶Lu–¹⁷⁶Hf age of garnet is typically older than the ¹⁴⁷Sm–¹⁴³Nd age determined from the same aliquots. Here we present experimental data for Lu³⁺ and Hf⁴⁺ diffusion in garnet as functions of temperature, pressure and oxygen fugacity and show that the diffusivity of Hf⁴⁺ in almandine/spessartine garnet is significantly slower than that of Lu³⁺. The diffusive closure temperature (T _C) of Hf⁴⁺ is significantly higher than that of Nd³⁺, and although this property is partly responsible for the observed ¹⁷⁶Lu–¹⁷⁶Hf and ¹⁴⁷Sm–¹⁴³Nd Grt–WR age discrepancies, the difference between the T _C-s of Lu³⁺ and Hf⁴⁺ could lead to apparent Grt–WR ¹⁷⁶Lu–¹⁷⁶Hf ages that are skewed from the age of Hf⁴⁺ closure in garnet. In addition, the slow diffusivity of Hf⁴⁺ indicates that the bulk of metamorphic garnets retain a substantial fraction of prograde radiogenic ¹⁷⁶Hf throughout peak metamorphic conditions, a phenomenon that further complicates the interpretation of ¹⁷⁶Lu–¹⁷⁶Hf garnet ages and invalidates the use of analytical T _C expressions. We argue that the diffusion of trivalent rare earth elements in garnet becomes much faster when their concentration level falls below a few hundred ppm, as in the experiments of Tirone et al. (Geochim Cosmochim Acta 69: 2385–2398, 2005), and further argue that this low-concentration mechanism is appropriate for modeling the susceptibility of ¹⁴⁷Sm–¹⁴³Nd garnet ages to diffusive resetting.     

Pressure-Dependence of Rare Earth Element Distribution in Amphibolite- and Granulite- Grade Garnets. A LA-ICP-MS Study

Using an excimer (KrF) laser ablation ICP-MS system, we studied the distribution of REE in garnets from metapelites and metabasites from Ivrea-Verbano (Western Alps, Italy) and from the Peña Negra Anatectic Complex (Central Iberia), finding systematic variations that correlate well with the metamorphic grade. Chondrite-normalized REE patterns of garnets from amphibolite-grade metapelites have lower-than-chondrite levels from La to Sm, a very small or no Eu anomaly, and a steep rise in the abundance of heavy REE as the atomic number increases. Metapelitic garnets from the amphibolite-granulite transition have a marked Eu negative anomaly and are enriched in MREE such that Sm is 10-15 times chondrite and the pattern is almost flat from Dy to Yb-Lu. In garnets from granulite-grade metapelites, the intensity of the Eu anomaly and the relative concentration of Nd, Sm, Gd and Tb increase, with almost flat chondrite-normalized patterns from Sm to Lu. Garnets from mafic granulites are remarkably similar to those of metapelitic garnets equilibrated at the same pressure, except for the Eu anomaly. The apparent paradox of enhanced uptake of larger REE ions with increasing pressure is attributed to the 3M²⁺ 2REE³⁺+ vacancy substitution, which produces a net decrease in the dimensions of the unit-cell of garnet. Variations in REE patterns depend essentially on the pressure and have little dependence on either temperature, bulk-composition of garnet, or REE whole-rock composition, so they could represent a new approach for geobarometric studies. The best numerical parameter to express pressure-related variations of REE distribution in garnets is the Gd/Dy ratio which does not seem perceptibly affected by disequilibrium partitioning. The regression equation between GASP pressure and the average Gd/Dy^garnet is P = 3.6 + 5.6 Gd/Dy. This equation seems to be reliable for garnets: (1)equilibrated within a pressure range of 4-9 kbar, (2) coexisting with modal monazite; and (3) with unit-cell dimensions under 11.46 Å.     

Reconstruction of phosphate formation environments (from data on distribution of lanthanides)

The criteria for the evaluation of the REE composition of phosphorites and sedimentary rocks have been determined. These data are required to reconstruct depositional environments. Literature data on the geochemistry of some phosphorite deposits of Eurasia are considered. The REE patterns of Mesozoic phosphorites of the East European Platform are studied. On the basis of REE contents, the ratios of lanthanides and fields on the La–(Nd + Sm)–(Y + Dy), La–(Ce + Nd + Sm)–(Y + Dy), and LREE–MREE–(HREE×10) diagrams have been determined as indicators of climate and the depth and facies conditions of sedimentation.     

Modification of the Sm–Nd isotopic system in garnet induced by retrogressive fluids

Garnet, as a major constitutive mineral of eclogite, is important for Sm–Nd dating of eclogite due to its high Sm/Nd ratio and its stability during retrogression. However, a comprehensive study of the petrography, mineral chemistry, garnet water content, and Sm–Nd isotopic composition of eclogites from the Bixiling massif, Central Dabie Zone (CDZ), reveals significant modification of the Sm–Nd isotopic system in garnet as a result of retrogression. This problem constitutes a challenge for Sm–Nd dating of the Bixiling eclogites, with the Sm–Nd isochron ages of 218 ± 4 to 210 ± 9 Ma reported in the literature being younger than 226 ± 3 Ma, which is the generally accepted peak metamorphic age of the CDZ. Petrographic analysis reveals heterogeneity in colour within single fractured garnet grains. There are light‐pink garnet (Grt‐P) and red garnet (Grt‐R) types that possess distinct chemical compositions. Compared to Grt‐P, Grt‐R has higher Fe and andradrite contents but lower Al and grossular contents. Grt‐P also has lower water contents (15–35 ppm) than Grt‐R (34–65 ppm), which, together with the spatial association between Grt‐R and fractures, suggests that the colour change is related to fluid alteration. Grt‐P is an ultra‐high‐pressure (UHP) mineral, and Grt‐R is the product of the interaction between Grt‐P and a fluid during retrogression. Moreover, Grt‐R features lower Sm and Nd contents but higher Sm/Nd ratios than Grt‐P. The Sm–Nd isochrons defined by UHP minerals (Grt‐P+Omp+Rt or Grt‐P+Cpx+WR) from three eclogite samples yield consistent ages of 226.0 ± 3.8 Ma, 225.0 ± 3.9 Ma and 226.2 ± 6.9 Ma, which are identical to the peak metamorphic age of 226 ± 3 Ma for the CDZ. The retrogressed garnet (i.e., Grt‐R), omphacite and rutile, together define a pseudoisochron with younger ages of 218.9 ± 5.9 to 202.8 ± 4.8 Ma, which are geologically meaningless. The increase in the Sm/Nd ratio with constant or lower ¹⁴³Nd/¹⁴⁴Nd ratios during the transformation of Grt‐P to Grt‐R was probably the cause of these younger ages.     

Sm-Nd chronology of porphyroblastic garnets from granulite facies metabasic rocks in Calabria (Southern Italy): inferences for preserved isotopic memory and resetting

Metabasic rocks related to pre-Cambrian protoliths from the lower portion of the deep crust of the Serre (Calabria, southern Italy) contain porphyroblastic garnet up to 5–6 cm in diameter. Garnet forms coronas around the inclusions of clinopyroxene and is in contact with various matrix minerals. Both inner and outer coronas formed under granulite facies conditions after the thermal peak during the Hercynian reworking. Six porphyroblastic garnets (≥1 cm in diameter) from four samples have been dated with the Sm-Nd method to constrain the distinct metamorphic stages and, possibly, to investigate the diffusion of Sm and Nd in garnet. They show in the core major element flat profiles whereas one of these, analyzed for REEs, preserves only a feeble zoning. This suggests that the diffusion rates of REEs are effective at the crystal scale. The apparent Nd ages range from 354 to 88 Ma, without any reproducibility in each and in all rock samples. The oldest age of 354 Ma is interpreted as the primary isotopic signatures linked to prograde metamorphism. The interpretation of younger ages (309, 272, 215, 143 and 88 Ma) requires a detailed discussion about: (i) possible modification of chemical and isotopic composition of the rocks during and after garnet growth, (ii) possible contamination by inclusions in garnet, (iii) inherited isotopic disequilibrium, (iv) new growth or recrystallization of garnet and (v) possible isotopic resetting of large crystals which, in principle, is hampered by the slow diffusion of REE’s in garnet. Some of the Nd ages are similar to U-Pb ages of zircon from the metabasic rocks of deep crustal rocks of the Serre (350, 300 and 280 Ma). This convergence of apparent ages can hardly be considered as simply fortuitous. Thus, since: (i) corona formation was fluid-assisted and (ii) all porphyroblasts were broken up into several fragmented subgrains by sets of fractures resulting in smaller volumes, the volume diffusion and the possible role of high-T fluids on the resetting of Sm-Nd ages are discussed. The calculated ages of 354, 309 and 272 Ma are considered as geologically meaningful and related to the thermal peak and subsequent decompression and cooling stage of the Variscan metamorphism.     

Retention of Sm–Nd isotopic ages in garnets subjected to high-grade thermal reworking: implications for diffusion rates of major and rare earth elements and the Sm–Nd closure temperature in garnet

Garnet is a vital mineral for determining constrained P–T–t paths as it can give both the P–T and t information directly. However, estimates of the closure temperature of the Sm–Nd system in garnet vary considerably leading to significant uncertainties in the timing of peak conditions. In this study, five igneous garnets from an early Proterozoic 2414 ± 6 Ma garnet—cordierite bearing s-type granite—which was subjected to high-T reworking have been dated to examine their diffusional behaviour in the Sm–Nd system. Garnets 8, 7, 6 and 2.5 mm in diameter were compositionally profiled and then dated, producing two-point Sm–Nd isochron ages of 2412 ± 10, 2377 ± 5, 2370 ± 5 and 2365 ± 8 and 2313 ± 11 Ma, respectively. A direct correlation exists between grain size and amount of resetting highlighting the effect of grain size on closure temperature. Major element EMPA and LA-ICPMS REE traverses reveal homogenous major element profiles and relict igneous REE profiles. The retention of REE zoning and homogenisation of major element zoning suggest that diffusion rates of REEs are considerably slower than that of the major cations. The retention of REE zoning and the lack of resetting in the largest grains suggest that Sm–Nd closure temperature in garnet is a function of grain size, thermal history and REE zoning in garnet.     

Thermodynamic modeling of REE behavior in oxidized hydrothermal fluids of high sulfate sulfur concentrations

Thermodynamic calculations using the HCh software were made for mineral equilibriums including REEs in the fluoride–sulfide–chloride–carbonate–sulfate–system in the presence of Na, Ca, and P with fluids of various acidities–alkalinities [11]. The obtained thermodynamic characteristics of thenardite allowed us to carry out the calculations for this phase under complicated hydrothermal conditions simulating the presence of oxidized fluids at 500–100°C and 2000–125 bar. Among other solid phases, REEs–fluorite, monazite, and REE–F–apatite were formed as CaF₂–(Ln,Y)F₃, LnPO₄, and Ca₅(PO₄)₃F–(Ln,Y)₃(PO₄)₃ ideal solid solutions, respectively, where Ln is La, Ce, Pr, Nd, Sm, Eu, and Gd. Xenotime, anhydrite, elemental sulfur, and calcite were found as well.     

Submarine groundwater discharge is an important net source of light and middle REEs to coastal waters of the Indian River Lagoon, Florida, USA

Porewater (i.e., groundwater) samples were collected from multi-level piezometers across the freshwater-saltwater seepage face within the Indian River Lagoon subterranean estuary along Florida’s (USA) Atlantic coast for analysis of the rare earth elements (REE). Surface water samples for REE analysis were also collected from the water column of the Indian River Lagoon as well as two local rivers (Eau Gallie River, Crane Creek) that flow into the lagoon within the study area. Concentrations of REEs in porewaters from the subterranean estuary are 10-100 times higher than typical seawater values (e.g., Nd ranges from 217 to 2409 pmol kg⁻¹), with submarine groundwater discharge (SGD) at the freshwater-saltwater seepage face exhibiting the highest REE concentrations. The elevated REE concentrations for SGD at the seepage face are too high to be the result of simple, binary mixing between a seawater end-member and local terrestrial SGD. Instead, the high REE concentrations indicate that geochemical reactions occurring within the subterranean estuary contribute substantially to the REE cycle. A simple mass balance model is used to investigate the cycling of REEs in the Indian River Lagoon and its underlying subterranean estuary. Mass balance modeling reveals that the Indian River Lagoon is approximately at steady-state with respect to the REE fluxes into and out of the lagoon. However, the subterranean estuary is not at steady-state with respect to the REE fluxes. Specifically, the model suggests that the SGD Nd flux, for example, exported from the subterranean estuary to the overlying lagoon waters exceeds the combined input to the subterranean estuary from terrestrial SGD and recirculating marine SGD by, on average, ∼100 mmol day⁻¹. The mass balance model also reveals that the subterranean estuary is a net source of light REEs (LREE) and middle REEs (MREE) to the overlying lagoon waters, but acts as a sink for the heavy REEs (HREE). Geochemical modeling and statistical analysis further suggests that this fractionation occurs, in part, due to the coupling between REE cycling and iron redox cycling within the Indian River Lagoon subterranean estuary. The net SGD flux of Nd to the Indian River Lagoon is ∼7-fold larger than the local effective river flux to these coastal waters. This previously unrecognized source of Nd to the coastal ocean could conceivably be important to the global oceanic Nd budget, and help to resolve the oceanic “Nd paradox” by accounting for a substantial fraction of the hypothesized missing Nd flux to the ocean.     

Diffusion in garnet: a review

With improvements on high-pressure experimental techniques in multi-anvil apparatus and the development of new analytical tools, major progress has been made on diffusion in garnets in the past several decades. The data obtained in the experimental determination of diffusion coefficients in garnets are of fundamental importance for diffusion modeling and timescales of geological and planetary processes. In this review, we have compiled experimental data on self-diffusion (Si, O, cations), trace element diffusion (Li, Y, Ga, Cr, Sr, REEs), and interdiffusion (Ca–Fe/Mg, Si–Al) in garnet in the light of new advances and recent applications. In addition, some empirical relationships among diffusion parameters (pre-exponential factor D ₀, activation energy E, ionic radius) are also discussed. We hope that this review can provide a useful data digest and guide to future study of diffusion in garnet.     

Zoned (Cretaceous and Cenozoic) garnet and the timing of high grade metamorphism, Southern Alps, New Zealand

New (garnet Sm–Nd and Lu–Hf) and existing (Rb–Sr, ⁴⁰Ar/³⁹Ar, U–Pb and Sm–Nd) ages and data on deformational fabrics and mineral compositions show for the first time that the garnet growth and ductile deformation in the Alpine Schist belt and Southern Alps orogen, New Zealand are diachronous and partly Cenozoic in age. The dominant metamorphic isograds in the Alpine Schist formed during crustal thickening at a previously unsuspected time, at c. 86 Ma, immediately prior to the opening of the Tasman Sea at c. 84–82 Ma. Obvious changes in the textures and compositional zoning patterns of garnet are not always reliable indicators of polymetamorphism, and fabric elements can be highly diachronous. A detailed timing history for the growth of a single garnet is recorded by a Sm–Nd garnet–whole rock age of 97.8 ± 8.1 Ma for the inmost garnet core (zone 1), Lu–Hf ages of 86.2 ± 0.2 Ma and 86.3 ± 0.2 Ma for overgrowth zones 2 and 3, a step‐leach Sm–Nd age of 12 ± 37 Ma for zone 4, and growth of the garnet rim (zone 5) over the Alpine Fault mylonite foliation during the modern phase of oblique collision that began at c. 5–6 Ma. Plate convergence along the New Zealand portion of the Gondwana margin continued after c. 105 Ma, almost certainly culminating in the oblique collision of a large oceanic plateau (Hikurangi Plateau). The metamorphism of the Alpine Schist at c. 86 Ma is evidence of that hit. The mid‐ to late‐Cretaceous extension that is widespread elsewhere in the New Zealand region is attributed to upper plate extension and slab roll‐back. The effects of the collision with the Hikurangi Plateau may have contributed to the changing plate motions in the region leading up to the opening of the Tasman Sea at c. 82 Ma.     

High‐resolution geochemical record of fluid–rock interaction in a mid‐crustal shear zone: a comparative study of major element and oxygen isotope transport in garnet

Garnet grains from an intensely metasomatized mid‐crustal shear zone in the Reynolds Range, central Australia, exhibit a diverse assortment of textural and compositional characteristics that provide important insights into the geochemical effects of fluid–rock interaction. Electron microprobe X‐ray maps and major element profiles, in situ secondary ion mass spectrometry oxygen isotope analyses, and U–Pb and Sm–Nd geochronology are used to reconstruct their thermal, temporal and fluid evolution. These techniques reveal a detailed sequence of garnet growth, re‐equilibration and dissolution during intracontinental reworking associated with the Ordovician–Carboniferous (450–300 Ma) Alice Springs Orogeny. A euhedral garnet porphyroblast displays bell‐shaped major element profiles diagnostic of prograde growth zoning during shear zone burial. Coexisting granulitic garnet porphyroclasts inherited from precursor wall rocks show extensive cation re‐equilibration assisted by fracturing and fragmentation. Oxygen isotope variations in the former are inversely correlated with the molar proportion of grossular, suggesting that isotopic fractionation is linked to Ca substitution. The latter generally show close correspondence to the isotopic composition of their precursor, indicating slow intergranular diffusion of O relative to Fe²⁺, Mg and Mn. Peak metamorphism associated with shearing (～550 °C; 5.0–6.5 kbar) occurred at c. 360 Ma, followed by rapid exhumation and cooling. Progressive Mn enrichment in rim domains indicates that the retrograde evolution caused partial garnet dissolution. Accompanying intra‐mineral porosity production then stimulated limited oxygen isotope exchange between relict granulitic garnet grains and adjacent metasomatic biotite, resulting in increased garnet δ¹⁸O values over length scales <200 μm. Spatially restricted oxygen interdiffusion was thus facilitated by increased fluid access to reaction interfaces. The concentration of Ca in channelled fracture networks suggests that its mobility was enhanced by a similar mechanism. In contrast, the intergranular diffusion of Fe²⁺, Mg and Mn was rock‐wide under the same P–T regime, as demonstrated by a lack of local spatial variations in the re‐equilibration of these components. The extraction of detailed reaction histories from garnet must therefore take into account the variable length‐ and time‐scales of elemental and isotopic exchange, particularly where the involvement of a fluid phase enhances the possibility of measureable resetting profiles being generated for slowly diffusing components such as Ca and O, even at low ambient temperatures and relatively fast cooling rates.     

Genesis for Rare Earth Elements Enrichment in the Permian Manganese Deposits in Zunyi,Guizhou Province,SW China

The Zunyi manganese deposits, which formed during the Middle to Late Permian period and are located in northern Guizhou and adjacent areas, are the core area of a series of large-medium scale manganese enrichment minerogenesis in the southern margin and interior of the Yangtze platform, Southern China. This study reports the universal enrichment of rare earth elements(REEs) in Zunyi manganese deposits and examines the enrichment characteristics, metallogenic environment and genesis of REEs. The manganese ore bodies present stratiform or stratoid in shape, hosted in the silicon–mud–limestones of the Late Permian Maokou Formation. The manganese ores generally present lamellar, massive, banded and brecciated structures, and mainly consist of rhodochrosite, ropperite, tetalite, capillitite, as well as contains paragenetic gangue minerals including pyrite, chalcopyrite, rutile, barite, tuffaceous clay rock, etc. The manganese ores have higher ΣREE contents range from 158 to 1138.9 ppm(average 509.54 ppm). In addition, the ΣREE contents of tuffaceous clay rock in ore beds vary from 1032.2 to 1824.5 ppm(average 1396.42 ppm). The REEs from manganese deposits are characterized by La, Ce, Nd and Y enriched, and existing in the form of independent minerals(e.g., monazite and xenotime), indicating Zunyi manganese deposits enriched in light rare earth elements(LREE). The Ce_(anom) ratios(average-0.13) and lithofacies and paleogeography characteristics indicate that Zunyi manganese deposits were formed in a weak oxidation-reduction environment. The(La/Yb)_(ch), Y/Ho,(La/Nd)_N,(Dy/Yb)_N, Ce/Ce* and Eu/Eu* values of samples from the Zunyi manganese deposits are 5.53–56.92, 18–39, 1.42–3.15, 0.55–2.20, 0.21–1.76 and 0.48–0.86, respectively, indicating a hydrothermal origin for the manganese mineralization and REEs enrichment. The δ~(13) C_(V-PDB)(-0.54 to-18.1‰) and δ~(18) O_(SMOW)(21.6 to 26.0‰) characteristics of manganese ores reveal a mixed source of magmatic and organic matter. Moreover, the manganese ore, tuffaceous clay rock and Emeishan basalt have extremely similar REE fractionation characteristic, suggesting REEs enrichment and manganese mineralization have been mainly origin from hydrothermal fluids.     

Fluorite as an Sm–Nd geochronometer of hydrothermal processes: Dating of mineralization hosted in the Strel’tsovka uranium ore field,eastern Baikal region

The possibility of using hydrothermal fluorite as an Sm–Nd geochronometer is based on the results of an REE pattern study of this mineral (Chernyshev et al., 1986). As a result of REE fractionation, in many cases, the Sm/Nd ratio achieves a multifold increase compared with its level in terrestrial rocks, and the radiogenic shift of the ¹⁴³Nd/¹⁴⁴Nd isotope ratio reaches 10–20 ε_Nd units over a short time interval (as soon as tens of Ma). This is a necessary prerequisite for Sm–Nd isochron dating of fluorite. Zonal polychrome fluorite from a vein referred to the final stage of large-scale uranium mineralization at the Sterl’tsovka deposit in the ore field of the same name located in the eastern Transbaikal region has been dated using the ¹⁴³Nd/¹⁴⁴Nd method. To optimize isochron construction, local probes with high and contrasting Sm/Nd ratios have been sampled from the polished surfaces of two samples, taking into account the REE pattern of zonal fluorite. Sm–Nd isochron dating has been carried out separately for each sample. The ¹⁴⁷Sm/¹⁴⁴Nd и ¹⁴³Nd/¹⁴⁴Nd ratios vary within the intervals 0.5359–2.037 and 0.512799–0.514105, respectively. Two isochrons, each based on six fluorite probes, have been obtained with the following parameters, which coincide within 2σ uncertainty limits: (1) t = 134.8 ± 1.3 Ma, (¹⁴³Nd/¹⁴⁴Nd)₀ = 0.512310 ± 13, MWSD = 0.43 and (2) t = 135.8 ± 1.6 Ma, (¹⁴³Nd/¹⁴⁴Nd)₀ = 0.512318 ± 10, MWSD = 1.5. The mean age of fluorite based on two isochron datings is 135.3 ± 1 Ma. Comparison of this value with the most precise dating of pitchblende related to the ore stage in the Strel’tsovka ore field (135.5 ± 1 Ma) shows that four mineralization stages, distinguished by geological and mineralogical data, that were completed with the formation of polychrome fluorite veins 135.3 ± 1 Ma ago, represent a single and indivisible hydrothermal process whose duration does not exceed 1 Ma.     

Sm-Nd isotope systematics in garnet from different lithologies (Eastern Alps): age results, and an evaluation of potential problems for garnet Sm-Nd chronometry [Chem. Geol. 185 (2002) 255-281]

Interpretation of Sm-Nd garnet ages is frequently impaired by one of the following restrictions: (a) high-LREE inclusions, (b) isotopic disequilibrium, and (c) the uncertainty about the closure temperature. These issues are addressed by way of an evaluation of garnet Sm-Nd data from different rock types of the Austroalpine basement units, Eastern Alps, including metabasic eclogites, mica schist and paragneiss, metapegmatite and metagranite.Nd concentration in handpicked garnet varies between 0.021 and 23.1 ppm in metabasites, 0.49 and 17.4 ppm in metapelites and between 0.024 and 4.6 ppm in metapegmatites and metagranites. The overall range of ¹⁴⁷Sm/¹⁴⁴Nd is 0.15-2.5 in garnet from metabasites, 0.12-3.03 in metapelite garnet and 0.66-7.21 in Mn-rich garnet from metapegmatites and metagranites. A clear negative correlation between Nd concentration and Sm/Nd is observed in garnets from all these lithologies. Therefrom, it is concluded that even optically “clean” garnet separates may contain high-LREE microinclusions, such as epidote-allanite, zoisite, apatite, sphene, monazite or zircon. However, very low Nd concentrations correlated with low Sm/Nd as well as high Nd concentrations (>5 ppm) correlated with fairly high Sm/Nd ratios (0.8) have also been observed. Apart from replicate analyses within as well as between samples with a common PT-history, leaching experiments are a useful technique to elucidate any distorting influence of unequilibrated inclusions on the garnet age, especially if the observed Sm/Nd ratio is low (<0.5). Leaching of garnet separates with HCl (2.5, 5.8 M) produces no obvious element fractionation, but may improve Sm/Nd, and hence age precision, considerably. Isotopic disequilibrium between garnet and other matrix minerals is observed preferentially in basic eclogites, derived from gabbroic precursors.Sm-Nd garnet analysis allows the recognition of several distinct garnet-forming events in the Eastern Alps.(a) A Variscan high-P event is documented in metabasites from the northern-central Ötztal basement around 360-350 Ma, whereas garnet from sillimanite-bearing gneisses dates the Variscan thermal peak in the western part of the same subunit around 345-330 Ma.(b) A long-lived, Permian to Triassic event (285-225 Ma), correlated with crustal extension and low-P metamorphism, is documented by spessartine-rich garnet from metapegmatites as well as almandine-rich garnet cores from mica schist.(c) Age data of garnet from eo-Alpine (Cretaceous) deeply subducted rocks of the southern/eastern Austroalpine units are related to near-peak PT, eclogite- to amphibolite-facies metamorphic conditions (peak: 2 GPa/685 °C), and/or incipient isothermal decompression, due to fast, tectonically driven exhumation (110/100-85 Ma). At cooling rates of 20-30 °C/Ma (exhumation rates: 3-5 km/Ma), the Sm-Nd closure temperature (T_c) for mm-sized garnet in these rocks is estimated at 650-680 °C.     

Separating metamorphic events in the Fosdick migmatite–granite complex,West Antarctica

The Fosdick migmatite–granite complex in West Antarctica records evidence for two high‐temperature metamorphic events, the first during the Devonian–Carboniferous and the second during the Cretaceous. The conditions of each high‐temperature metamorphic event, both of which involved melting and multiple melt‐loss events, are investigated using phase equilibria modelling during successive melt‐loss events, microstructural observations and mineral chemistry. In situ SHRIMP monazite and TIMS Sm–Nd garnet ages are integrated with these results to constrain the timing of the two events. In areas that preferentially preserve the Devonian–Carboniferous (M₁) event, monazite grains in leucosomes and core domains of monazite inclusions in Cretaceous cordierite yield an age of c. 346 Ma, which is interpreted to record the timing of monazite growth during peak M₁ metamorphism (～820–870 °C, 7.5–11.5 kbar) and the formation of garnet–sillimanite–biotite–melt‐bearing assemblages. Slightly younger monazite spot ages between c. 331 and 314 Ma are identified from grains located in fractured garnet porphyroblasts, and from inclusions in plagioclase that surround relict garnet and in matrix biotite. These ages record the growth of monazite during garnet breakdown associated with cooling from peak M₁ conditions. The Cretaceous (M₂) overprint is recorded in compositionally homogeneous monazite grains and rim domains in zoned monazite grains. This monazite yields a protracted range of spot ages with a dominant population between c. 111 and 96 Ma. Rim domains of monazite inclusions in cordierite surrounding garnet and in coarse‐grained poikiloblasts of cordierite yield a weighted mean age of c. 102 Ma, interpreted to constrain the age of cordierite growth. TIMS Sm–Nd ages for garnet are similar at 102–99 Ma. Mineral equilibria modelling of the residual protolith composition after Carboniferous melt loss and removal of inert M₁ garnet constrains M₂ conditions to ～830–870 °C and ～6–7.5 kbar. The modelling results suggest that there was growth and resorption of garnet during the M₂ event, which would facilitate overprinting of M₁ compositions during the M₂ prograde metamorphism. Measured garnet compositions and Sm–Nd diffusion modelling of garnet in the migmatitic gneisses suggest resetting of major elements and the Sm–Nd system during the Cretaceous M₁ overprint. The c. 102–99 Ma garnet Sm–Nd ‘closure’ ages correspond to cooling below 700 °C during the rapid exhumation of the Fosdick migmatite–granite complex.     

Precise Determination of Sm and Nd Concentrations and Nd Isotopic Compositions in Highly Depleted Ultramafic Reference Materials

In this study, a high‐precision method for the determination of Sm and Nd concentrations and Nd isotopic composition in highly depleted ultramafic rocks without a preconcentration step is presented. The samples were first digested using the conventional HF + HNO₃ + HClO₄ method, followed by the complete digestion of chromite in the samples using HClO₄ at 190–200 °C and then complete dissolution of fluoride formed during the HF decomposition step using H₃BO₃. These steps ensured the complete digestion of the ultramafic rocks. The rare earth elements (REEs) were separated from the sample matrix using conventional cation‐exchange chromatography; subsequently, Sm and Nd were separated using the LN columns. Neodymium isotopes were determined as NdO⁺, whereas Sm isotopes were measured as Sm⁺, both with very high sensitivity using single W filaments with TaF₅ as an ion emitter. Several highly depleted ultramafic rock reference materials including USGS DTS‐1, DTS‐2, DTS‐2b, PCC‐1 and GSJ JP‐1, which contain extremely low amounts of Sm and Nd (down to sub ng g^?1 level), were analysed, and high‐precision Sm and Nd concentration and Nd isotope data were obtained. This is the first report of the Sm‐Nd isotopic compositions of these ultramafic rock reference materials except for PCC‐1.     

Non-Henry’s Law behavior of REE partitioning between fluorapatite and CaF2-rich melts: Controls of intrinsic vacancies and implications for natural apatites

The partitioning of rare-earth elements (REEs: Gd and multiple REEs), Sr, and Mn between fluorapatite and CaF₂-rich melts was investigated over a wide range of REE concentrations (i.e., from 0.8 ± 0.1 to 25,000 ± 2600 ppm Gd in fluorapatite) in two different sample assemblies (i.e., tightly covered Pt crucibles and sealed Pt capsules) at 1220 °C and atmospheric pressure. Attainment of equilibrium is indicated by selected reversal experiments. The partition coefficient D(Gd) decreases from ∼2 to ∼0.5 with increasing Gd in fluorapatite, hence a marked non-Henry’s Law behavior, but becomes independent of composition at and above ∼5000 and ∼1000 ppm Gd for experiments in Pt crucibles and Pt capsules, respectively. Non-Henry’s Law behavior is also observed in experiments involving multiple REEs. All REE patterns are convex upward in shape with maxima between Nd and Gd, and D(La)/D(Nd) and D(Nd)/D(Yb) decrease systematically with increasing total REEs in fluorapatite, suggesting that REE fractionations are partly related to non-Henry’s Law behavior. These experimental results and local structural data from previous electron paramagnetic resonance spectroscopic studies suggest that the non-Henry’s Law behavior of REE partitioning between fluorapatite and melt is controlled by intrinsic Ca²⁺ vacancies in the c-axis channels. The D(Sr) and D(Mn) values are independent of composition and, therefore, do not deviate from the Henry’s Law in their respective compositional ranges investigated in this study.Nonstoichiometry, such as Ca²⁺ and F⁻ vacancies in the c-axis channels, is well known in natural apatites, particularly in biogenic apatites. Therefore, the observed non-Henry’s Law behavior of REE partitioning is expected to have important implications for REE geochemical modeling involving apatites and for the uptake of REEs by natural apatites. Particularly, the non-Henry’s Law behavior of REE partitioning is at least partly responsible for the commonly observed, bell-shaped REE patterns in fossil biogenic apatites.