Protracted diagenetic alteration of REE contents in fossil bioapatites: Direct evidence from Lu-Hf isotope systematics

Fossil bones and teeth are potentially important repository for geochemical proxy data and a target for radiometric dating. The concentration of many trace elements in bones and teeth increases by orders of magnitude after death and it is this diagenetic incorporation that forms the basis for several areas of geochemical study. The use of bones and teeth in this context relies on two assumptions: first, that target metal ions are incorporated rapidly after death, reflecting a known environmental signal, and second, that after early incorporation, the bone or tooth remains as an essentially closed system, resistant to later diagenetic change. A wide literature has developed exploring these assumptions, but relatively little direct evidence has been used to assess the long-term diagenetic stability of trace elements within bones and teeth. In this study, we use the Lu-Hf isotope system to show that bones and teeth of Cretaceous and Triassic age from both terrestrial and marine settings experience continued, long-term diagenetic change, most likely through gradual addition of trace elements. Modelling suggests that diagenetic addition after initial recrystallisation may account for >50% of the total REE content in the sampled bones, the extent depending on initial uptake conditions. Tooth enamel and enameloid may be more resistant to late diagenetic changes, but dentine is probably altered to the same extent as bone. These results have significant implications for the use of bones and teeth as hosts of chronological, palaeoceanographic, palaeoenvironmental and taphonomic information, particularly in Mesozoic and Palaeozoic contexts.     

Competitive binding of REE to humic acid and manganese oxide: Impact of reaction kinetics on development of cerium anomaly and REE adsorption

The competitive binding of rare earth elements (REE) to purified humic acid (HA) and MnO₂ was studied experimentally using various HA/MnO₂ ratios over a range of pH (3 to 8). MnO₂, humic acid and REE solutions were simultaneously mixed to investigate the kinetics of the competitive reactions. Aqueous REE–HA complex is the dominant species whatever the experiment time, pH and HA/MnO₂ ratio. The value of the distribution coefficients between MnO₂ and solution (log K_d^Ree/Mno₂) increases with the HA/MnO₂ ratio, indicating that part of the REE–HA complexes are adsorbed onto MnO₂. The development of a Ce anomaly appears strongly limited in comparison with inorganic experimental conditions. Throughout the experimental run time, for HA/MnO₂ ratios of less than 0.4, MnO₂ acts as a competitor leading to a partial dissociation of the REE–HA complex. The majority of the dissociated REE is readsorbed onto the MnO₂ surface. The readsorption of REE is expressed by an increased Ce anomaly on the log K_d^Ree/Mno₂ pattern as well as a change in shape of the coefficient distribution of REE between soluble HA and solution pattern (log K_d^Ree/HA decrease for the heavy rare earth elements — HREE). Thus, REE are not only bound to MnO₂ as a REE–HA complex, but also as REE(III). Moreover, the competition between HA and MnO₂ for REE binding is shown to be higher at low pH (< 6) and low DOC/Mn ratio. This study partially confirms previous work that demonstrated the control of REE adsorption by organic matter, while shedding more light on the impact of pH as well as complexation reaction competition on long-term REE partitioning between solid surface and organic solutions. The latter point is important as regards to REE speciation under conditions typical of rock and/or mineral alteration.     

Models of diffusion-limited uptake of trace elements in fossils and rates of fossilization

Many fossils are assumed to take up trace elements by a process of combined diffusion plus adsorption (DA), yet in principle composition profiles can be explained by several different diffusion-limited processes, including diffusion plus reaction or recrystallization (DR) and double-medium diffusion (DMD). The DA and DMD models are supported by REE and U composition profiles across fossil teeth, measured by laser-ablation ICP-MS, that show error-function - like diffusion profiles into enamel from the dentine-enamel interface and concentrations in the interior of enamel that are at original biogenic levels or higher. Published composition and age profiles in some Pleistocene bones may be better explained by a DR model. All three diffusion models imply linear behavior between age and distance squared, vastly simplifying U-series dating methods for Pleistocene fossils. Modeled uptake rates for fossil teeth yield a strict minimum bound on durations of about one decade to one century. The similarity of diffusion profiles in teeth, irrespective of depositional ages ranging from ∼30 ka to >30 Ma, implies that uptake occurred quickly, with a maximum duration of a few tens of kyr for typical fossil enamel; faster uptake is implied for typical fossil bone and dentine. Disparities in these uptake estimates compared to some archeological bone may reflect sampling and preservation bias for paleontological vs. archeological materials.     

Surface-structure-controlled sectoral zoning of the rare earth elements in fluorite from Long Lake, New York, and Bingham, New Mexico, USA

The concentration and distribution of rare earth elements (REE) in sectorally zoned fluorite crystals from Long Lake, New York, and the Hansonburg Mining District, Bingham, New Mexico, have been studied using cathodoluminescence and synchrotron X-ray fluorescence microanalysis (SXRFMA). In cubo-octahedral samples from Long Lake, New York, Ce, Nd, Gd, Dy, Ho, Er, and Tm are preferentially partitioned into the |111| sector relative to the |100| sector. Partition coefficients (K_d = concentration in |111| sector/concentration in |100| sector) range between 3.5 for Ce, to 1.4 for Tm, with a general decrease in K_d as elements deviated from the ionic radius of Ca²⁺, for which REE substitute in fluorite. Diffusion of the REE has occurred, as evidenced by gradual changes in composition over distances of 0.2 to 0.3 mm at sector boundaries.In Bingham samples, three different partition coefficients were determined for Dy: K_d|100|/|111| = 2.83, K_{d |100|/|110|} = 1.77, and K_{d |110|/|111|} = 1.60. These are mean K_d values for a 95% confidence interval. In another sample from the same deposit, Dy, Er, and Gd were found to be preferentially incorporated into the |100| sector relative to the |210| sector with average K_{d |100|/|210|} of 3.1, 2.4, and 2.9, respectively. In a third sample, Nd was found to be preferentially incorporated into the |110| sector relative to the |321| sector with an average K_{d |110|/|321|} value of 2.3.Compositional heterogeneities in a given sector (concentric zoning) have been resolved using SXRFMA but are significantly less than the concentration difference across sector boundaries. Often fluorite exists in a wide variety of morphologies, as is the case in the Hansonburg Mining District of Bingham. We suggest caution when using the REE as petrogenetic indicators because fluorite trace element chemistry can vary greatly among crystals within a deposit depending on the internal morphology of a particular crystal.     

Submicroscopic accessory minerals overprinting clay mineral REE patterns (celadonite–glauconite group examples)

Samples of glauconite, representing different stages of glauconitisation, as well as different formation environments, were analysed for rare earth elements (REE) and other trace elements using a combination of bulk sample and spatially-resolved in situ techniques. The results indicate that the high-sensitivity, spatially-resolved technique of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) produces values up to two orders of magnitude lower than the bulk sample analyses. This suggests that submicroscopic rare earth element-bearing phases are distributed within the glauconite aggregates comprising the bulk samples. Analytical scanning electron microscopy (ASEM) revealed the presence of micrometre-sized grains of apatite and pore filling precipitates of an unidentified (REE, Ca)-phosphate (approximate composition Ca_0.3–0.4(Ce_0.4La_0.1–0.2Nd_0.1)PO₄) in some glauconite grains.The inherent REE concentrations of the glauconite aggregates (i.e., glauconite crystallites without accidental mechanical inclusions or authigenic, not layer silicate mineral precipitates) was found to be relatively low (e.g., typically less than 100 ppm), and this value decreased with increasing glauconitisation (smectite–mica transformation through a series of recrystallisation processes). These results suggest that the REEs substitute for Ca in the interlayer space of the layer silicate structure and, therefore, the REE content decreases as Ca is progressively removed from the interlayer (smectite–mica transition).LA-ICP-MS, when combined with electron probe microanalysis (EPMA) or ASEM, offers an opportunity to exclude submicroscopic accessory minerals from glauconite trace element analyses, and so produces reliable trace element data for the respective minerals which host those elements.These results illustrate that accessory minerals are difficult to eliminate from clay samples, and that care needs to be taken in the interpretation of clay mineral REE distributions, irrespective of the aggregation state of the studied clay (i.e., whether finely dispersed within the sedimentary rock, or forming millimetre-sized aggregates). Model calculations showed that authigenic apatite associated with the studied green marine clays tends to have higher REE content than “bioapatites”, the total REE content being above 10 000 ppm.     

The aqueous geochemistry of the rare earth elements and yttrium. Part 7. REE,Th and U contents in thermal springs associated with the Idaho batholith

Concentrations of the rare earth elements (REE), Th and U have been determined in thermal waters emerging from a number of locations in and around the Idaho Batholith. Previous investigators have suggested that the source of heat for the geothermal systems studied is the radioactive decay of K, Th and U which are enriched in the rocks through which the fluids flow. Thus, knowledge of the behavior of REE, Th and U in these systems may contribute to a better understanding of the potential consequences of the interaction of hydrothermal fluids with deeply buried nuclear waste. Such studies may also lead to the possible use of REE as an exploration tool for geothermal resources. The thermal waters investigated may be characterized as near-neutral to slightly alkaline, dilute, NaHCO₃-dominated waters with relatively low temperatures of last equilibration with their reservoir rocks (<200°C). REE, Th and U concentrations were measured using Fe(OH)₃ coprecipitation, followed by ICP-MS, which yielded detection limits of 0.01–0.003 μg/l for each element, depending on the volume of fluid sample taken. The concentrations of REE, Th and U measured (from <0.1 up to a few μg/l) are 3–5 orders of magnitude less than chondritic, in agreement with concentrations of these elements measured in other similar continental geothermal systems. The REE exhibit light REE-enriched patterns when normalized to chondrite, but when normalized to NASC or local granites, they exhibit flat or slightly heavy REE-enriched trends. These findings indicate that the REE are either taken up in proportion to their relative concentrations in the source rocks, or that the heavy REE are preferentially mobilized. Concentrations of REE and Th are often higher in unfiltered, compared to filtered samples, indicating an important contribution of suspended particulates, whereas U is apparently truly dissolved. In some of the hot springs the REE concentrations exhibit marked temporal variations, which are greater than the variations observed in major element concentrations, alkalinity and temperature. There are also variations in the fluid concentrations of REE, Th and U related to general location within the study area which may be reflective of variations in the concentrations of these elements in the reservoir rocks at depth. Thermal waters in the southern and central parts of the field area all contain ∑REE concentrations exceeding 0.1 μg/l (up to as high as 3 μg/l), Th exceeding 0.2 μg/l and U generally <0.4 μg/l. In contrast, thermal waters from the northern area contain lower ∑REE (<0.6 μg/l) and Th (<0.1 μg/l), but higher U (>3.0 μg/l). Using experimentally measured and theoretically estimated thermodynamic data, the distribution of species for La, Ce and Nd have been calculated and also the solubility of pure, endmember (La, Ce, Nd) phosphate phases of the monazite structure in selected hot spring fluids. These calculations indicate that, at the emergence temperatures, CO²⁻₃ and OH⁻ complexes of the REE are the predominant species in the thermal waters, whereas at the deep-aquifer temperatures, OH complexes predominate. In these thermal waters, monazite solubility is strongly prograde with respect to temperature, with solubility often decreasing several orders of magnitude upon cooling from the deep-aquifer to the emergence temperature. At the surface temperature, calculated monazite solubilities are, within the uncertainty of the thermodynamic data, comparable to the REE concentrations measured in the filtered samples, whereas at the deep-aquifer temperature, monazite solubilities are generally several orders of magnitude higher than the REE concentrations measured in the filtered or unfiltered samples. Therefore, a tentative model is suggested in which the thermal fluids become saturated with respect to a monazite-like phase (or perhaps an amorphous or hydrated phosphate) upon ascent and cooling, followed by subsequent precipitation of that phase. The temporal variations in REE content can then be explained as a result of sampling variable mixtures of particulate matter and fluid and/or variable degrees of attainment of equilibrium between fluid and solid phosphate.     

Solid–water partitioning of elements in Czech freshwaters

Partitioning of 41 elements between solids and water was studied by filtration and dialysis in situ in Czech freshwaters. Field-based distribution (partition) coefficients, K_D, between suspended particulate matter (SPM) and filtrate (‘dissolved’ fraction) differed by 4 orders of magnitude. The highest K_D values (log K_D>2.0 l/g) were exhibited by Zr, Al, Ce, Pb, La, Ti, Fe, Sm, Th and Cr which are extremely insoluble in near-neutral water or generally poorly soluble (Zr,Ti). The K_Ds decrease with element and DOC loading due to the relative increase of the element in the low molecular fraction. Log K_D mostly increased linearly with pH within a range from 3.5 to 9. K_D^U decreased at pH >6 due to carbonate complexation. The colloidal fraction (>1 kDa <0.4 μm) in a reservoir with a pH of 6.8 was mainly preferred by Fe, Pb, Be, Nb, Y, Al, Ni, U and Zr. When the colloidal fraction is not differentiated from true solution, then incorrect information about partitioning may be obtained and the highest K_D may decrease.     

Adsorption of REE(III)-humate complexes onto MnO2: Experimental evidence for cerium anomaly and lanthanide tetrad effect suppression

Experiments were conducted to evaluate the impact of organic complexation on the development of Ce anomalies and the lanthanide tetrad effect during the adsorption of rare-earth elements (REE) onto MnO₂. Two types of aqueous solutions—NaCl and NaNO₃—were tested at pH 5 and 7.5. Time-series experiments indicate that a steady-state is reached within less than 10 h when REE occur as free inorganic species, whereas steady state is not reached before 10 d when REE occur as REE-humate complexes. The distribution coefficients (K_d^REE) between suspended MnO₂ and solution show no or only very weak positive Ce anomaly or lanthanide tetrad effect when REE occur as humate complexes, unlike the results obtained in experiments with REE occurring as free inorganic species. Monitoring of dissolved organic carbon (DOC) concentrations show that log K_d^REE_organic/K_d^DOC ratios are close to 1.0, implying that the REE and humate remain bound to each other upon adsorption. Most likely, the Ce anomaly reduction/suppression in the organic experiments arises from a combination of two processes: (i) inability of MnO₂ to oxidize Ce(III) because of shielding of MnO₂ surfaces by humate molecules and (ii) Ce(IV) cannot be preferentially removed from solution due to quantitative complexation of the REE by organic matter. We suggest that the lack of lanthanide tetrad effect arises because the adsorption of REE-humate complexes onto MnO₂ occurs dominantly via the humate side of the complexes (anionic adsorption), thereby preventing expression of the differences in Racah parameters for 4f electron repulsion between REE and the oxide surface. The results presented here explain why, despite the development of strongly oxidizing conditions and the presence of MnO₂ in the aquifer, no (or insignificant) negative Ce anomalies are observed in organic-rich waters. The present study demonstrates experimentally that the Ce anomaly cannot be used as a reliable proxy of redox conditions in organic-rich waters or in precipitates formed at equilibrium with organic-rich waters.     

Rare earth element partitioning between titanite and silicate melts: Henry’s law revisited

We present detailed experimental results on the partitioning of rare earth elements (REE) between titanite and a range of different silicate melts. Our results show that Henry’s law of trace element partitioning depends on bulk composition, the available partners for heterovalent substitution, crystal composition, and melt composition. We illustrate that the partition coefficients for Sm depend very strongly on the bulk concentration of Sm in the system. The substitution mechanism, by which rare earth elements are incorporated into the crystal structure, plays an important role for trace element partitioning and also for the onset of Henry’s law. Our data show that there are clear differences between substitution mechanisms of major elements compared to elements which are present only as traces. Our experiments also clearly show that the onset of Henry’s law depends on the concentrations of the sum of all trace elements which are incorporated into the crystal by the same substitution mechanism. For geochemical modelling of magmatic processes involving titanite, and indeed other accessory phases, it is of crucial importance to first evaluate whether the REE, and other trace elements, are present as traces or as major elements, only then appropriate D values may be chosen.     

Nd and Sr isotope compositions in modern and fossil bones - Proxies for vertebrate provenance and taphonomy

Rare earth elements (REE), while not essential for the physiologic functions of animals, are ingested and incorporated in ppb concentrations in bones and teeth. Nd isotope compositions of modern bones of animals from isotopically distinct habitats demonstrate that the ¹⁴³Nd/¹⁴⁴Nd of the apatite can be used as a fingerprint for bedrock geology or ambient water mass. This potentially allows the provenance and migration of extant vertebrates to be traced, similar to the use of Sr isotopes. Although REE may be enriched by up to 5 orders of magnitude during diagenesis and recrystallization of bone apatite, in vivo¹⁴³Nd/¹⁴⁴Nd may be preserved in the inner cortex of fossil bones or enamel. However, tracking the provenance of ancient or extinct vertebrates is possible only for well-preserved archeological and paleontological skeletal remains with in vivo-like Nd contents at the ppb-level. Intra-bone and -tooth REE analysis can be used to screen for appropriate areas. Large intra-bone Nd concentration gradients of 10¹-10³ are often measured. Nd concentrations in the inner bone cortex increase over timescales of millions of years, while bone rims may be enriched over millenial timescales. Nevertheless, ε_Nd values are often similar within one ε_Nd unit within a single bone. Larger intra-bone differences in specimens may either reflect a partial preservation of in vivo values or changing ε_Nd values of the diagenetic fluid during fossilization. However, most fossil specimens and the outer rims of bones will record taphonomic ¹⁴³Nd/¹⁴⁴Nd incorporated post mortem during diagenesis. Unlike REE patterns, ¹⁴³Nd/¹⁴⁴Nd are not biased by fractionation processes during REE-uptake into the apatite crystal lattice, hence the ε_Nd value is an important tracer for taphonomy and reworking. Bones and teeth from autochthonous fossil assemblages have small variations of ±1 ε_Nd unit only. In contrast, fossil bones and teeth from over 20 different marine and terrestrial fossil sites have a total range of ε_Nd values from -13.0 to 4.9 (n = 80), often matching the composition of the embedding sediment. This implies that the surrounding sediment is the source of Nd in the fossil bones and that the specimens of this study seem not to have been reworked. Differences in ε_Nd values between skeletal remains and embedding sediment may either indicate reworking of fossils and/or a REE-uptake from a diagenetic fluid with non-sediment derived ε_Nd values. The latter often applies to fossil shark teeth, which may preserve paleo-seawater values. Complementary to ε_Nd values, ⁸⁷Sr/⁸⁶Sr can help to further constrain the fossil provenance and reworking.     

Rare Earth Element Enrichment in Late Archean Manganese Deposits from the Iron Ore Group,East India

The major, trace and rare earth element (REE) composition of Late Archean manganese, ferromanganese and iron ores from the Iron Ore Group (IOG) in Orissa, east India, was examined. Manganese deposits, occurring above the iron formations of the IOG, display massive, rhythmically laminated or botryoidal textures. The ores are composed primarily of iron and manganese, and are low in other major and trace elements such as SiO₂, Al₂O₃, P₂O₅ and Zr. The total REE concentration is as high as 975 ppm in manganese ores, whereas concentrations as high as 345 ppm and 211 ppm are found in ferromanganese and iron ores, respectively. Heavy REE (HREE) enrichments, negative Ce anomalies and positive Eu anomalies were observed in post‐Archean average shale (PAAS)‐normalized REE patterns of the IOG manganese and ferromanganese ores. The stratiform or stratabound shapes of ore bodies within the shale horizon, and REE geochemistry, suggest that the manganese and ferromanganese ores of the IOG were formed by iron and/or manganese precipitation from a submarine, hydrothermal solution under oxic conditions that occurred as a result of mixing with oxic seawater. While HREE concentrations in the Late Archean manganese and ferromanganese ores in the IOG are slightly less than those of the Phanerozoic ferromanganese ores in Japan, HREE resources in the IOG manganese deposits appear to be two orders of magnitude higher because of the large size of the deposits. Although a reliable, economic concentration technique for HREE from manganese and ferromanganese ores has not yet been developed, those ores could be an important future source of HREE.     

Partitioning of rare earth elements between garnet and andesite melt: an autoradiographic study of P-T-X effects

High-pressure equilibrium studies were conducted in piston-cylinder apparatus to determine rare earth element (REE) partitioning between garnet and H₂O-vapor-saturated liquidus, from 20 kbar/980°C to 30 kbar/1060 °C. Ag capsules were employed to eliminate loss of Fe. Partition coefficients (K_D's) were determinined with autoradiographic techniques employing beta-active isotopes of Ce, Sm, and Tm. Major elements in garnet were determined by microprobe analysis. Synthesis and reversal runs of 24 hr or greater duration were used to bracket values of K_D's within analytical uncertainty.The K_D values for all three REE are constant over the radiogenic concentration range of 1 to 350 ppm, suggesting that the high abundance of natural REE in the starting materials may suppress possible deviations from Henry's Law behavior reported in similar autoradiographic studies of synthetic systems with no natural REE. Changes in K_D with increasing pressure and temperature at near-liquidus conditions suggest that the dominant control of K_D is the average size of cations occupying the 8-fold sites in garnet. Specifically, the substitution of 8-fold Ca for Mg and Fe causes an increase in K_D values greater than that attributable to the coincident effects of pressure and temperature. The inverse correlation of increasing K_D with REE ionic radius supports the interpretation that the average size of the 8-fold cation controls the relative variation of K_D among REE.These experimental K_D values produce less relative fractionation in melts between light REE and heavy REE than do previous K_D's derived from data on coexisting natural garnet phenocryst/rockmatrix pairs. Models for the derivation of orogenic andesites from partial melting of subducted basaltic eclogite are qualitatively improved by these new K_D's. Existing calculations of K_D values necessary for the viability of the eclogite fractionation are also in good agreement with these experimental K_D values.     

Trace element partitioning between apatite and silicate melts

We present new experimental apatite/melt trace element partition coefficients for a large number of trace elements (Cs, Rb, Ba, La, Ce, Pr, Sm, Gd, Lu, Y, Sr, Zr, Hf, Nb, Ta, U, Pb, and Th). The experiments were conducted at pressures of 1.0 GPa and temperatures of 1250 °C. The rare earth elements (La, Ce, Pr, Sm, Gd, and Lu), Y, and Sr are compatible in apatite, whereas the larger lithophile elements (Cs, Rb, and Ba) are strongly incompatible. Other trace elements such as U, Th, and Pb have partition coefficients close to unity. In all experiments we found D_Hf > D_Zr, D_Ta ≈ D_Nb, and D_Ba > D_Rb > D_Cs. The experiments reveal a strong influence of melt composition on REE partition coefficients. With increasing polymerisation of the melt, apatite/melt partition coefficients for the rare earth elements increase for about an order of magnitude. We also present some results in fluorine-rich and water-rich systems, respectively, but no significant influence of either H₂O or F on the partitioning was found. Furthermore, we also present experimentally determined partition coefficients in close-to natural compositions which should be directly applicable to magmatic processes.     

A kinetic approach to describe trace-element distribution between particles and solution in natural aquatic systems

The partitioning of radioactive trace elements between seawater and particulate matter from surface sediments and sediment traps was investigated in laboratory experiments. For the elements Na, Zn, Se, Sr, Cd, Sn, Sb, Cs, Ba, Hg, Th and Pa (group I) constant distribution coefficients (K_d) were found after a few days of equilibration, whereas the elements Be, Mn, Co and Fe (group II) showed an increasing K_d over the whole time of observation of 108 days. The time dependence of K_d is described by an adsorption-desorption equilibrium (group I elements), followed by a lattice transport reaction step (group II elements). The reaction rate constants are compared to Mn oxidation rates and to adsorption rate constants derived from in situ measurements of the $\text{U}\text{Th}$ disequilibrium as available from literature.     

Petrography and geochemistry of Jurassic sandstones from the Jhuran Formation of Jara dome,Kachchh basin,India: Implications for provenance and tectonic setting

Sandstones of Jhuran Formation from Jara dome, western Kachchh, Gujarat, India were studied for major, trace and rare earth element (REE) geochemistry to deduce their paleo-weathering, tectonic setting, source rock characteristics and provenance. Petrographic analysis shows that sandstones are having quartz grains with minor amount of K-feldspar and lithic fragments in the modal ratio of Q ₈₉:F ₇:L ₄. On the basis of geochemical results, sandstones are classified into arkose, sub-litharenite, wacke and quartz arenite. The corrected CIA values indicate that the weathering at source region was moderate to intense. The distribution of major and REE elements in the samples normalized to upper continental crust (UCC) and chondrite values indicate similar pattern of UCC. The tectonic discrimination diagram based on the elemental concentrations and elemental ratios of Fe₂O₃ + MgOvs. TiO₂, SiO₂ vs. log(K₂O/Na₂O), Sc/Cr vs. La/Y, Th–Sc–Zr/10, La–Th–Sc plots Jhuran Formation samples in continental rift and collision settings. The plots of Ni against TiO₂, La/Sc vs. Th/Co and V–Ni–Th ?10 reveals that the sediments of Jhuran Formation were derived from felsic rock sources. Additionally, the diagram of (Gd/Yb) _N against Eu/Eu ^? suggest the post-Archean provenance as source possibly Nagar Parkar complex for the studied samples.     

Geochemistry and origin of massif-type anorthosites

Samples of Proterozoic anorthosite complexes from the Adirondack Mountains of New York, Burwash Area of Ontario, and the Nain Complex of Labrador, ranging in composition from anorthosite to anorthositic gabbro, have been analyzed for major elements, Rb, Sr, Ba and nine rare-earth elements (REE), in order to set limits on the compositions and origins of their parent magmas. Similar rock types from the different areas have similar major and trace element compositions. The anorthosites have high Sr/Ba ratios, low REE abundances (Ce about 10, Yb about 0.5–1.5 times chondrites) and large positive Eu anomalies. The associated anorthositic gabbros have lower Sr/Ba ratios, REE abundances nearly an order of magnitude higher than the anorthosites, and small to negligible positive Eu anomalies.Model calculations using the adcumulate rocks with the lowest REE abundances and published distribution coefficients yield parent liquids having REE abundances and patterns similar to those of the associated anorthositic gabbros with the highest REE abundances. Rocks with intermediate REE abundances are the result of incorporation of a liquid component by a plagioclase-rich cumulate similar to the adcumulate samples. The analytical data and model calculations both suggest parent liquids having compositions of 50–54% SiO₂, greater than 20% Al₂O₃, about 1% K₂O, atomic Mg/(Mg+Fe²⁺) ratios (Mg No.'s) of less than 0.4, 15–30 ppm Rb, 400–600 ppm Sr and 400–600 ppm Ba, 40–50 times chondrites for Ce and 8–10 times chondrites for Yb.The low atomic Mg/(Mg+Fe²⁺) values for these rocks combined with geophysical evidence suggesting there are not large quantities of ferromagnesian material at depth, indicate that the anorthositic masses are not products of fractional crystallization of mafic melt derived from melting of the mantle. Rather, it is suggested that they are a result of partial melting of tholeiitic compositions at depths shallower than the basalt-eclogite transformation, leaving a pyroxene-dominated residue.     

Aluminum-dependent trace element partitioning in clinopyroxene

As technical advances have dramatically increased our ability to analyze trace elements, the need for more reliable data on the compositional dependence of trace element partitioning between minerals and melt has become increasingly important. The late-Cretaceous Carmacks Group of south central Yukon comprises a succession of primitive high-Mg ankaramitic lavas characterized by shoshonitic chemical affinities and containing large complexly zoned clinopyroxene phenocrysts. The compositional zonation of the clinopyroxene phenocrysts is characterized by relatively Fe-rich (Mg^# = Mg/(Mg + Fe) = 0.85), but mottled, cores surrounded by mantles of cyclically-zoned clinopyroxene whose Mg^# varies repeatedly between 0.9 and 0.80. These cyclically zoned clinopyroxene mantles appear to record the repeated influx and mixing of batches of primitive with more evolved magma in a deep sub-crustal (∼1.2 GPa) magma chamber(s). Laser ablation ICP-MS was used to analyze the trace element variation in these zoned clinopyroxenes. The results indicate more than a threefold variation in the absolute concentrations of Th, Zr, rare earth elements (REE), and Y within individual clinopyroxene phenocrysts, with no apparent change in the degree of REE or high field strength element (HFSE) fractionation. The variation in absolute abundances of trace elements correlates closely with the major element composition of the clinopyroxene, with the most enriched clinopyroxene having the lowest Mg^# and highest Al contents. The problem is that the amount of crystal fractionation required to explain the major element variation (∼20%) in these clinopyroxene phenocrysts cannot explain the increase in the abundance of the incompatible trace elements, which would require more than 70% crystal fractionation, if constant partition coefficients are assumed. The anomalous increase in incompatible trace elements appears to reflect an increase in their partition coefficients with increasing Al^IV in the clinopyroxene; with an increase in Al₂O₃ from 1.5 to 4.0 wt.% during ∼20% crystal fractionation over a temperature decrease of ∼100°C being associated with more that a threefold increase in the partition coefficients of Th, Zr, REE, and Y. The magnitude of these increases may indicate that the substitution of these trace elements into clinopyroxene is better modeled in some natural systems by a local charge balance model, rather than the distributed charge model that better replicates the results of annealed experiments. These findings indicate that the effect of Al on the partition coefficients of incompatible trace elements in clinopyroxene may be under appreciated in natural magmatic systems and that the application of experimentally determined clinopyroxene partition coefficients to natural systems must be done with caution.     

REE concentrations of garnet and omphacite in eclogites from the Dabie Mountain, central China

Distributions of the rare-earth elements (REE) in omphacite and garnet and REE behaviors during metamorphic processes were discussed. The REE concentrations of garnet and omphacite in six eclogite samples from the Dabie Mountain, central China, were measured by inductively coupled plasma-mass spectrometry (ICP-MS). The correlation of δEu ratios between garnet and omphacite indicated that chemical equilibrium of REE distribution between garnet and omphacite could be achieved during ultra-high pressure (UHP) metamorphism. Most of the partition coefficients (Kd=CiOmp/CiGrt) of light rare-earth elements (LREE) are higher than 1. However the partition coefficients of heavy rare-earth elements (HREE) are lower than 1. This indicated that the LREE inclined to occupy site M2 in omphacite, but the HREEs tended to occupy eightfold coordinated site in garnet during the eclogite formation. The REE geochemistry of the eclogites indicated that LREE could be partially lost during the prograde metamorphic process of protolith, but be introduced into the rocks during the symplectite formation. LREE are more active than HREE during the UHP metamorphism. The results are favorable to highlighting the REE behavior and evolution of UHP metamorphic rocks.     

Lanthanide-humic substances complexation. I. Experimental evidence for a lanthanide contraction effect

The interaction of the lanthanides (Ln) with humic substances (HS) was investigated with a novel chemical speciation tool, Capillary Electrophoresis-Inductively Coupled Plasma Mass Spectrometry (CE-ICP-MS). By using an EDTA-ligand competition method, a bi-modal species distribution of LnEDTA and LnHS is attained, separated by CE, and detected online by sector field ICP-MS. We quantified the binding of all 14 rare earth elements (REEs), Sc and Y with Suwannee river fulvic acid, Leonardite coal humic acid, and Elliot soil humic acid under environmental conditions (pH 6-9, 0.001-0.1 mol L⁻¹ NaNO₃, 1-1000 nmol L⁻¹ Ln, 10-20 mg L⁻¹ HS). Conditional binding constants for REE-HS interaction (K_c) ranged from 8.9 < log K_c < 16.5 under all experimental conditions, and display a lanthanide contraction effect, Δ_LK_c: a gradual increase in K_c from La to Lu by 2-3 orders of magnitude as a function of decreasing ionic radius. HS polyelectrolyte effects cause K_c to increase with increasing pH and decreasing ionic strength. Δ_LK_c increases significantly with increasing pH, and likely with decreasing ionic strength. Based on a strong correlation between Δ_LK_c values and denticity for organic acids, we suggest that HS form a range of tri- to tetra-dentate complexes under environmental conditions. These results confirm HS to be a strong complexing agent for Ln, and show rigorous experimental evidence for potential REE fractionation by HS complexation.     

Non-modal melting in an upwelling mantle column: Steady-state models with applications to REE depletion in abyssal peridotites and the dynamics of melt migration in the mantle

Simple models for trace element fractionation during concurrent melting and melt migration in an upwelling steady-state mantle were developed. Based on petrologic considerations, we divided the mantle column into two regions: a single-lithology lower region that consists of partially molten garnet and spinel lherzolites and a double-lithology upper region where high-porosity dunite channels or melt-filled fractures are embedded in a porous lherzolite/harzburgite matrix. Analytical solutions for the case of a constant and uniform relative melting suction rate and a linearly variable relative melt suction rate were obtained. Key parameters and the first order characteristics of melting and melt migration in a 1-D steady-state mantle column were examined through forward calculations and Monte Carlo simulations. Melting in the upwelling single-lithology column is equivalent to non-modal batch melting, whereas melting and melt migration in the double-lithology region can be viewed as a nonlinear combination of batch melting and fractional melting, depending on the amount of melt extracted to the channel. The degree of melting (F), the degree of melting at the depth of melt-channel initiation (F_d) and the relative rate of melt suction (R) are important in controlling the extent of depletion of the incompatible trace element in the matrix. Spatially variable R affects the abundance of an incompatible trace element in the melt and residual solid the most in near fractional melting. There is a strong nonlinear trade off among the three parameters. Given F_d, it is possible to constrain F and R from incompatible trace element abundances in residual peridotite.To explore the dynamics of melt migration in the mantle, we used the two melting models developed in this study and published REE and Y abundances in diopside in abyssal peridotites from the Central Indian Ridge to infer their melting and melt migration history. Overall, the degrees of melting inferred from the trace element data are not sensitive to the value of F_d used in the inversion and ranges from 10% to 15%. The relative rate of melt suction depends slightly on the choice of F_d and ranges from 0.85 to 1.0 for F_d = 0.05 and 0.75 to 0.97 for F_d = 0. Further, the estimated R is inversely correlated with F, a robust feature independent of the choice of F_d. The upward decrease of R in an upwelling mantle column can be understood in terms of melt focusing in the lower part of the double-lithology region. And finally, given F and R, we found that the permeability and porosity of the lherzolite/harzburgite matrix also increase as a function of F in the melting column, with melt fractions ranging from 0.2% to 0.7% for a grain size of 5 mm.