Melting of hydrous pyroxenites with alkali amphiboles in the continental mantle: 2. Trace element compositions of melts and minerals

The trace element compositions of melts and minerals from high-pressure experiments on hydrous pyroxenites containing K-richterite are presented. The experiments used mixtures of a third each of the natural minerals clinopyroxene, phlogopite and K-richterite, some with the addition of 5% of an accessory phase ilmenite, rutile or apatite. Although the major element compositions of melts resemble natural lamproites, the trace element contents of most trace elements from the three-mineral mixture are much lower than in lamproites. Apatite is required in the source to provide high abundances of the rare earth elements, and either rutile and/or ilmenite is required to provide the high field strength elements Ti, Nb, Ta, Zr and Hf. Phlogopite controls the high levels of Rb, Cs and Ba.Since abundances of trace elements in the various starting mixtures vary strongly because of the use of natural minerals, we calculated mineral/melt partition coefficients (D_Min/melt) using mineral modes and melting reactions and present trace element patterns for different degrees of partial melting of hydrous pyroxenites. Rb, Cs and Ba are compatible in phlogopite and the partition coefficient ratio phlogopite/K-richterite is high for Ba (1 3 6) and Rb (12). All melts have low contents of most of the first row transition elements, particularly Ni and Cu ((0.1–0.01) × primitive mantle). Nickel has high D_Min/melt for all the major minerals (12 for K-richterite, 9.2 for phlogopite and 5.6 for Cpx) and so behaves at least as compatibly as in melting of peridotites. Fluorine/chlorine ratios in melts are high and D_Min/melt for fluorine decreases in the order apatite (2.2) > phlogopite (1.5) > K-richterite (0.87). The requirement for apatite and at least one Ti-oxide in the source of natural lamproites holds for mica pyroxenites that lack K-richterite. The results are used to model isotopic ageing in hydrous pyroxenite source rocks: phlogopite controls Sr isotopes, so that lamproites with relatively low ⁸⁷Sr/⁸⁶Sr must come from phlogopite-poor source rocks, probably dominated by Cpx and K-richterite. At high pressures (>4 GPa), peritectic Cpx holds back Na, explaining the high K₂O/Na₂O of lamproites.     

Determination of zircon/melt trace element partition coefficients from SIMS analysis of melt inclusions in zircon

Partition coefficients (^zircon/meltD_M) for rare earth elements (REE) (La, Ce, Nd, Sm, Dy, Er and Yb) and other trace elements (Ba, Rb, B, Sr, Ti, Y and Nb) between zircon and melt have been calculated from secondary ion mass spectrometric (SIMS) analyses of zircon/melt inclusion pairs. The melt inclusion-mineral (MIM) technique shows that D_REE increase in compatibility with increasing atomic number, similar to results of previous studies. However, D_REE determined using the MIM technique are, in general, lower than previously reported values. Calculated D_REE indicate that light REE with atomic numbers less than Sm are incompatible in zircon and become more incompatible with decreasing atomic number. This behavior is in contrast to most previously published results which indicate D > 1 and define a flat partitioning pattern for elements from La through Sm. The partition coefficients for the heavy REE determined using the MIM technique are lower than previously published results by factors of ≈15 to 20 but follow a similar trend. These differences are thought to reflect the effects of mineral and/or glass contaminants in samples from earlier studies which employed bulk analysis techniques.D_REE determined using the MIM technique agree well with values predicted using the equations of Brice (1975), which are based on the size and elasticity of crystallographic sites. The presence of Ce⁴⁺ in the melt results in elevated D_Ce compared to neighboring REE due to the similar valence and size of Ce⁴⁺ and Zr⁴⁺. Predicted ^zircon/meltD values for Ce⁴⁺ and Ce³⁺ indicate that the Ce⁴⁺/Ce³⁺ ratios of the melt ranged from about 10⁻³ to 10⁻². Partition coefficients for other trace elements determined in this study increase in compatibility in the order Ba < Rb < B < Sr < Ti < Y < Nb, with Ba, Rb, B and Sr showing incompatible behavior (D_M < 1.0), and Ti, Y and Nb showing compatible behavior (D_M > 1.0).The effect of partition coefficients on melt evolution during petrogenetic modeling was examined using partition coefficients determined in this study and compared to trends obtained using published partition coefficients. The lower D_REE determined in this study result in smaller REE bulk distribution coefficients, for a given mineral assemblage, compared to those calculated using previously reported values. As an example, fractional crystallization of an assemblage composed of 35% hornblende, 64.5% plagioclase and 0.5% zircon produces a melt that becomes increasingly more enriched in Yb using the D_Yb from this study. Using D_Yb from Fujimaki (1986) results in a melt that becomes progressively depleted in Yb during crystallization.     

Zonation des éléments en traces au cours de la croissance des cristaux dans les bains silicatés: l'exemple de Rb,Cs, Sr et Ba dans le système Qz-Ab-Or-H2O

An indirect method was used to study Na, K, Rb, Cs, Sr and Ba partition coefficients between crystals and silicate melt. Equilibria between a hydrothermal solution and the melt at 800°C and 2 kb and between a hydrothermal solution and crystals at 750°C and 2 kb were separately achieved.For major element partitioning (Na and K), the results obtained here are in good agreement with those of Tuttle and Bowen (1958) which allow us to follow crystal evolution during a fractional crystallization process where the growth of zoned crystals takes place.For minor elements Rb, Cs, Sr, Ba, melt/aqueous solution partition coefficients depend on Na/K as well as the silica content of the melt. These effects are rather small for Rb and Cs, but are much more important for the alkaline earths. The feldspar/aqueous solution partition coefficients also depend on Na/K.The variations of the partition coefficients feldspar/melt are complex in the part of the Qz-Ab-Or diagram located below the cotectic line.During fractional crystallization following the Rayleigh law (assuming that there are no kinetic phenomena) Sr (D > 10) is almost totally removed from the melt in the early stages whereas Cs (D < 0.1) remains in the melt during the whole process. Rb and Ba have partition coefficients closer to unity. The variation of these coefficients, due to changes in bulk composition of liquid and crystals during fractional crystallization, can lead to complex zoning with possible concentration maxima at some stages. Similar phenomena can be expected in non-ideal natural solid solutions, even if no discontinuities can be detected in the physicochemical evolution of the parent magma.     

Bottled drinking water: Water contamination from bottle materials (glass,hard PET,soft PET), the influence of colour and acidification

A test comparing concentrations of 57 chemical elements (Ag, Al, As, B, Ba, Be, Bi, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Hf, Ho, I, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, Ni, Pb, Pr, Rb, Sb, Se, Sm, Sn, Sr, Ta, Tb, Te, Th, Ti, Tl, Tm, U, V, W, Y, Yb, Zn and Zr) determined by inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) in 294 samples of the same bottled water (predominantly mineral water) sold in the European Union in glass and PET bottles demonstrates significant (Wilcoxon rank sum test, α = 0.05) differences in median concentrations for Sb, Ce, Pb, Al, Zr, Ti, Th, La, Pr, Fe, Zn, Nd, Sn, Cr, Tb, Er, Gd, Bi, Sm, Y, Lu, Dy, Yb, Tm, Nb and Cu. Antimony has a 21× higher median value in bottled water when sold in PET bottles (0.33 vs. 0.016 μg/L). Glass contaminates the water with Ce (19× higher than in PET bottles), Pb (14×), Al (7×), Zr (7×), Ti, Th (5×), La (5×), Pr, Fe, Zn, Nd, Sn, Cr, Tb (2×), Er, Gd, Bi, Sm, Y, Lu, Yb, Tm, Nb and Cu (1.4×). Testing an additional 136 bottles of the same water sold in green and clear glass bottles demonstrates an important influence of colour, the water sold in green glass shows significantly higher concentrations in Cr (7.3×, 1.0 vs. 0.14 μg/L), Th (1.9×), La, Zr, Nd, Ce (1.6×), Pr, Nb, Ti, Fe (1.3×), Co (1.3×) and Er (1.1×).     

Synthesis and Preliminary Characterisation of New Silicate, Phosphate and Titanite Reference Glasses

Eleven synthetic silicate and phosphate glasses were prepared to serve as reference materials for in situ microanalysis of clinopyroxenes, apatite and titanite, and other phosphate and titanite phases. Analytical results using different micro-analytical techniques showed that the glass fragments were homogeneous in major and trace elements down to the micrometre scale. Trace element determinations using inductively coupled plasma-mass spectrometry (ICP-MS), multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS), laser-ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) and secondary ionisation mass spectrometry (SIMS) showed good agreement for most elements (Li, Be, B, Cs, Rb, Ba, Sr, Ga, Pb, U, Th, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Er, Tm, Yb, Lu, Zr, Hf, Ta, Nb) studied and provide provisional recommended values.     

Melt-vapor solubilities and elemental partitioning in peraluminous granite-pegmatite systems: experimental results with Macusani glass at 200 MPa

Vapor-saturated experiments at 200 MPa with peraluminous, lithophile-element-rich rhyolite obsidian from Macusani, Peru, reveal high miscibility of H₂O and silicate melt components. The H₂O content of melt at saturation (11.5+-0.5 wt.%) is almost twice that predicted by existing melt speciation models. The corresponding solubility of melt components in vapor decreases from 15 wt.% dissolved solids (750°–775° C) to 9 wt.% at 600° C. With regard to major and most minor components, macusanite melt dissolves congruently in vapor. Among the elements studied (B, P, F, Li, Rb, Cs, Be, Sr, Ba, Nb, Zr, Hf, Y, Pb, Th, U, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, and Tm), only boron has a vapor/melt partition coefficient (D[B]) consistently 1 at superliquidus temperatures (>645° C). Phosphorus and fluorine behave similarly, with D[P] and D[F]<0.5. Little or no significant vapor/melt fractionation is evident among most periodic groups (alkalis, alkaline earths, Zr/Hf, or the REE). The temperature dependence of vapor/melt partition coefficients is generally greatest for cations with charge +3 (except Nb and U); most vapor/melt partition coefficients for trace elements increase with decreasing temperature to the liquidus. Crystallization proceeds by condensation of crystalline phases from vapor; most coexisting melts are aphyric. Changes in the major element content of melt are dominated by the mineral assemblage crystallized from vapor, which includes subequal proportions of white mica, quartz, albite, and orthoclase. The volumetric proportion of (mica + or-thoclase)/albite increases slightly with decreasing T, creating a sodic, alkaline vapor. Vapor deposition of topaz (T500° C), which consumes F from melt, returns K/Na ratios of melt to near unity with the vapor-deposition of albite. The abundances of most trace elements in residual melt change little with the crystallization of major phases, but in some cases are strongly controlled by the deposition of accessory phases including apatite (T550° C), which depletes the melt in P and REE. Below the liquidus, boron increasingly favors the vapor over melt with decreasing temperatures.     

Experimental and computational study of trace element distribution between orthopyroxene and anhydrous silicate melt: substitution mechanisms and the effect of iron

Although orthopyroxene (Opx) is present during a wide range of magmatic differentiation processes in the terrestrial and lunar mantle, its effect on melt trace element contents is not well quantified. We present results of a combined experimental and computational study of trace element partitioning between Opx and anhydrous silicate melts. Experiments were performed in air at atmospheric pressure and temperatures ranging from 1,326 to 1,420°C in the system CaO–MgO–Al₂O₃–SiO₂ and subsystem CaO–MgO–SiO₂. We provide experimental partition coefficients for a wide range of trace elements (large ion lithophile: Li, Be, B, K, Rb, Sr, Cs, Ba, Th, U; rare earth elements, REE: La, Ce, Nd, Sm, Y, Yb, Lu; high field strength: Zr, Nb, Hf, Ta, Ti; transition metals: Sc, V, Cr, Co) for use in petrogenetic modelling. REE partition coefficients increase from $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 Although orthopyroxene (Opx) is present during a wide range of magmatic differentiation processes in the terrestrial and lunar mantle, its effect on melt trace element contents is not well quantified. We present results of a combined experimental and computational study of trace element partitioning between Opx and anhydrous silicate melts. Experiments were performed in air at atmospheric pressure and temperatures ranging from 1,326 to 1,420°C in the system CaO–MgO–Al₂O₃–SiO₂ and subsystem CaO–MgO–SiO₂. We provide experimental partition coefficients for a wide range of trace elements (large ion lithophile: Li, Be, B, K, Rb, Sr, Cs, Ba, Th, U; rare earth elements, REE: La, Ce, Nd, Sm, Y, Yb, Lu; high field strength: Zr, Nb, Hf, Ta, Ti; transition metals: Sc, V, Cr, Co) for use in petrogenetic modelling. REE partition coefficients increase from $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 to $ D_{\text{Lu}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.109 $ D_{\text{Lu}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.109 , D values for highly charged elements vary from $ D_{\text{Th}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0026 $ D_{\text{Th}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0026 through $ D_{\text{Nb}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0033 $ D_{\text{Nb}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0033 and $ D_{\text{U}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0066 $ D_{\text{U}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0066 to $ D_{\text{Ti}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.058 $ D_{\text{Ti}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.058 , and are all virtually independent of temperature. Cr and Co are the only compatible trace elements at the studied conditions. To elucidate charge-balancing mechanisms for incorporation of REE into Opx and to assess the possible influence of Fe on Opx-melt partitioning, we compare our experimental results with computer simulations. In these simulations, we examine major and minor trace element incorporation into the end-members enstatite (Mg₂Si₂O₆) and ferrosilite (Fe₂Si₂O₆). Calculated solution energies show that R²⁺ cations are more soluble in Opx than R³⁺ cations of similar size, consistent with experimental partitioning data. In addition, simulations show charge balancing of R³⁺ cations by coupled substitution with Li⁺ on the M1 site that is energetically favoured over coupled substitution involving Al–Si exchange on the tetrahedrally coordinated site. We derived best-fit values for ideal ionic radii r ₀, maximum partition coefficients D ₀, and apparent Young’s moduli E for substitutions onto the Opx M1 and M2 sites. Experimental r ₀ values for R³⁺ substitutions are 0.66–0.67 ? for M1 and 0.82–0.87 ? for M2. Simulations for enstatite result in r ₀ = 0.71–0.73 ? for M1 and ~0.79–0.87 ? for M2. Ferrosilite r ₀ values are systematically larger by ~0.05 ? for both M1 and M2. The latter is opposite to experimental literature data, which appear to show a slight decrease in $ r_{0}^{{{\text{M}}2}} $ r_{0}^{{{\text{M}}2}} in the presence of Fe. Additional systematic studies in Fe-bearing systems are required to resolve this inconsistency and to develop predictive Opx-melt partitioning models for use in terrestrial and lunar magmatic differentiation models.     

Experimental measurements of zircon/melt trace-element partition coefficients

Zircon was grown from trace-element doped hydrous peralkaline rhyolite melts with buffered oxygen fugacities in cold-seal experiments at 0.1 and 0.2 GPa and 800 °C and piston-cylinder experiments at 1.5 GPa and 900-1300 °C. Zircon and glass were present in all run products, and small monazite crystals were present in eight of the 12 experiments. Average diameters of zircon crystals ranged from 5 to 20 μm at 800 °C to 30-50 μm at 1300 °C. Zircon crystals have thin rims, and adjacent glass has a narrow (∼1 μm thick) compositional boundary layer. Concentrations obtained through in-situ analysis of cores of run product zircon crystals and melt pools were used to calculate trace-element partition coefficients D^zircon/melt for P, Sc, Ti, V, Y, La, Ce, Pr, Nd, Eu, Gd, Ho, Yb, Lu, Hf, Th, and U. In most cases Lu was the most (D 12-105) and La the least (0.06-0.95) compatible elements. D values from this study fall within the range of previously measured values for Rare Earth Elements (REE). However, D values measured experimentally show less fractionation than those recently measured using natural phenocryst/matrix pairs. For example, D_Lu/D_La measured experimentally in this study range between 27 and 206 compared to a value of 706,522 for a natural zircon/dacite pair [Sano, Y., Terada, K., and Fukuoka, T. 2002 High mass resolution ion microprobe analysis of rare earth elements in silicate glass, apatite and zircon: lack of matrix dependency. Chem. Geol.184, 217-230]. Although D values from this study show good agreement with the lattice strain model, D values from natural phenocryst/matrix pairs combined with measured zircon compositions better reproduce host-rock (magma) compositions of igneous rocks. They also yield more reasonable estimates of magma compositions when combined with compositions of ‘‘out-of-context” zircons. For example, compositions of the Hadean detrital zircons from Jack Hills, Australia yield LREE-enriched magmas when combined with D values from phenocryst/matrix pairs yields, but yield LREE-depleted magmas when experimentally determined D values are used. We infer that experimentally measured D^zircon/melt values represent disequilibrium partitioning resulting from rapid zircon growth during short laboratory timescales. Rapid growth causes development of observed diffusive boundary layers in the melt adjacent to zircon crystals. D values from phenocryst/matrix pairs are therefore recommended for petrogenetic modeling.     

Two-liquid partition coefficients: Experimental data and geochemical implications

Partition coefficients for Cs, Ba, Sr, Ca, Mg, La, Sm, Lu, Mn, Ti, Cr, Ta, Zr, and P between immiscible basic and acidic liquids in the system K₂O-Al₂O₃-FeO-SiO₂ were experimentally determined at 1,180 °C and 1 atm. Phosphorus is most strongly enriched in the basic melt (by a factor of 10), followed by rare earth elements, Ta, Ca, Cr, Ti, Mn, Zr, Mg, Sr, and Ba (enriched by a factor of 1.5). Of the elements studied, only Cs is enriched in the acidic melt. The two-liquid partition coefficients of Zr, Ta, Sm, and Mn are constant for concentrations ranging from <0.1% to as high as 1 wt.-%, suggesting that Henry's law is applicable in silicate melts (at least for these elements) to concentrations well above typical trace element levels in rocks. The strong relative preference of many elements for the basic melt implies that the structural characteristics of basic melts more readily permit stable coordination of cations by oxygen. Partitioning of elements between crystal and liquid in a magma must therefore be influenced by the composition (and consequent structure) of the liquid.Application of the two-liquid partition coefficients to possible occurrences of liquid immiscibility in magmas reveals that typical basalt-rhyolite associations are probably not generated by two-liquid phase separation. However, liquid immiscibility cannot be discounted as a possible origin for lamprophyric rocks containing felsic segregations.     

Instrumental Neutron Activation Analysis of Two French Geochemical Reference Samples - Basalt BR and Biotite Mica-Fe

Instrumental neutron activation analysis results for 20 trace elements (Sc, Cr, Co, Ni, Rb, Cs, Ba, La, Ce, Nd, Sm, Eu, Gd, Tb, Tm, Yb, Lu, Hf, Ta, Th) and for two major elements (Na and Fe) in two geochemical reference samples issued by the "Centre de Recherches Pétrographiques et Géochimiques" are reported and compared with available literature values. In general our results agree well with recommended or proposed values.     

Trace element partitioning between amphibole and hydrous silicate glasses at 0.6–2.6 GPa

Partitioning behavior between amphibole and silicate glass of thirty-three minor and trace elements (Sc, Ti, V, Cr, Co, Rb, Sr, P, Y, Zr, Nb, Cs, Ba, K, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, Pb, Th, and U) have been determined experimentally. Products of crystallization of hydrous basalt melts from 0.6 GPa/860 °C up to 2.6 GPa/970 °C were obtained in a multi-anvil apparatus. Major and trace element compositions of amphibole and glass were determined with a combination of electron microprobe and laser ablation inductively coupled plasma mass spectrometry. The main mineral phase is calcic amphibole, and the coexisting glass compositions are tonalite, granodiorite, and granite. The compatibility of rare earth elements increase at 915 °C and then decrease at 970 °C, but the compatibility of most of these elements shows a continued, significant increase with increasing pressure. For high-field strength elements, large ion lithophile elements, actinide compatibility decrease with increasing temperature or pressure, but transition metals show a continued increase in compatibility within the temperature–pressure conditions. From mathematical and graphical fitting, we determined best-fit values for the ideal ionic radius (r₀, 1.01–1.04 Å), the strain-free partition coefficient (D₀, 1.18–1.58), and apparent Young’s modulus (E, 142–370 GPa) for the M4 site in amphibole according to the lattice strain model. The \(D_{0}^{M4}\) for rare earth elements rises at 915 °C and then drops at 970 °C at 0.6 GPa. However, the \(D_{0}^{M4}\) values are positively proportional to the pressure for rare earth elements in the amphibole-glass pairs at 0.6–2.6 GPa and 970 °C. Furthermore, the derived best-fit values for \(r_{0}^{M4}\) and \(E^{M4}\) are almost constant and trend to increase with rising temperature and pressure, respectively. The partition coefficient is distinctly different for different melt compositions. The rare earth elements become more enriched in amphibole if the quenched glass is granodiorite or granite compared to the tonalitic glasses.

     

A comparative evaluation of minerals and trace elements in the ashes from lignite, coal refuse, and biomass fired power plants

Coal being a limited source of energy, extraction of energy from other sources like lignite, coal-refuse, and biomass is being attempted worldwide. The minerals and inorganic elements present in fuel feeds pose different technological and environmental concerns. Lignite ash, refuse ash, and biomass ash collected from Indian power plants burning lignite, coal-refuse, and mustard stalk, respectively, were analyzed for physico-chemical characteristics and trace elements. The lignite ash has high SiO₂, CaO, MgO, Al₂O_3, and SO₃; the refuse ash has high SiO₂ and Fe₂O₃, but low SO₃; the biomass ash has high SiO₂ (but low Al₂O₃), and high CaO, MgO, K₂O, Na₂O, SO₃, and P₂O₅. A substantial presence of chloride (2.1%) was observed in the biomass ash. Quartz is the most abundant mineral species. Other minerals are mullite, hematite, gehlenite, anhydrite, and calcite in the lignite ash; orthoclase in the refuse ash; albite, sanidine, gehlenite, anhydrite, and calcite in the biomass ash. Ashes with high concentrations (> 100 mg/kg) of trace elements are: lignite ash (V < La < Mn < Cr < Ni < Nd < Ba < Ce, Zn < Sr); refuse ash (Cr < Ce < V < Rb < Mn < Sr, Zn < Ba); biomass ash (Cu < Zn < Ba, Sr). Based on Earth crust normalization, Co, Ni, As, Se, Mo, Zn, Pb, U, and REEs (except Pr and Er) are enriched in the lignite ash; molybdenum, Zn, Cs, Pb, Th, U, La, Ce, and Lu in the refuse ash; and Mo, Zn, Sr, Cs, Pb, and Lu in the biomass ash. Elements As, Zn, Mo, Ni, Pb, Rb, Cr, V, Ba, Sr, and REEs are correlated with Al, indicating the possibilities of their association with aluminum silicates minerals. Similarly, barium, Cs, Th, and U are correlated with iron oxides; molybdenum and Sr may also be associated with sulfates and chlorides. Due to the alkaline nature of these ashes, the high concentrations of As and Se in the lignite ash; molybdenum in the biomass ash; and Se in the refuse ash may pose environmental concerns.     

Determination of fluid/melt partition coefficients by LA-ICPMS analysis of co-existing fluid and silicate melt inclusions: Controls on element partitioning

Analyses of co-existing silicate melt and fluid inclusions, entrapped in quartz crystals in volatile saturated magmatic systems, allowed direct quantitative determination of fluid/melt partition coefficients. Investigations of various granitic systems (peralkaline to peraluminous in composition, log fO₂ = NNO−1.7 to NNO+4.5) exsolving fluids with various chlorinities (1-14 mol/kg) allowed us to assess the effect of these variables on the fluid/melt partition coefficients (D). Partition coefficients for Pb, Zn, Ag and Fe show a nearly linear increase with the chlorinity of these fluid (D_Pb ∼ 6 ∗ m_Cl, D_Zn ∼ 8 ∗ m_Cl, D_Ag ∼ 4 ∗ m_Cl, D_Fe ∼ 1.4 ∗ m_Cl, where m_Cl is the molinity of Cl). This suggests that these metals are dissolved primarily as Cl-complexes and neither oxygen fugacity nor the composition of the melt affects significantly their fluid/melt partitioning. By contrast, partition coefficients for Mo, B, As, Sb and Bi are highest in low salinity (1-2 mol/kg Cl) fluids with maximum values of D_Mo ∼ 20, D_B ∼ 15, D_As ∼ 13, D_Sb ∼ 8, D_Bi ∼ 15 indicating dissolution as non-chloride (e.g., hydroxy) complexes. Fluid/melt partition coefficients of copper are highly variable, but highest between vapor like fluids and silicate melt (D_Cu ? 2700), indicating an important role for ligands other than Cl. Partition coefficients for W generally increase with increasing chlorinity, but are exceptionally low in some of the studied brines which may indicate an effect of other parameters. Fluid/melt partition coefficients of Sn show a high variability but likely increase with the chlorinity of the fluid (D_Sn = 0.3-42, D_W = 0.8-60), and decrease with decreasing oxygen fugacity or melt peraluminosity.     

Trace element partitioning between carbonatitic melts and mantle transition zone minerals: Implications for the source of carbonatites

The occurrence of CO₂-rich lavas (carbonatites, kimberlites) and carbonate-rich xenoliths provide evidence for the existence of carbonatitic melts in the mantle. To model the chemical composition of such melts in the deep mantle, we experimentally determined partition coefficients for 23 trace elements (including REE, U-Th, HFSE, LILE) between deep mantle minerals and carbonatite liquids at 20 and 25 GPa and 1600 °C. Under these conditions, majoritic garnet and CaSiO₃ perovskite are the main reservoirs for trace elements. This study used both femtosecond LA-ICP-MS and SIMS techniques to measure reliable trace element concentrations. Comparison of the two techniques shows a general agreement, except for Sc and Ba. Our experimentally determined partition coefficients are consistent with the lattice strain model. The data suggest an effect of melt structure on partition coefficients in this pressure range. For instance, strain-free partition coefficient (D₀) for majorite-carbonatite melts do not follow the order of cation valence, , observed for majorite-CO₂-free silicate melts. The newly determined partition coefficients were combined with trace element composition of majoritic garnets found as inclusions in diamond to model trace element patterns of deep-seated carbonatites. The result compares favorably with natural carbonatites. This suggests that carbonatites can originate from the mantle transition zone.     

Instrumental Neutron Activation Analysis Of French Geochemical Reference Samples

Instrumental neutron activation analytical data, for eighteen trace elements (Ba, Co, Cr, Cs, Hf, Rb), Sb, Sc, Ta, Th, La, Ce, Nd, Sm, Eu, Tb, Yb, Lu), Hd₂O and Fe₂0₃ in eleven French geoche-mical reference samples are presented and discussed briefly.     

Partitioning of trace elements between rutile and silicate melts: Implications for subduction zones

Mineral/melt trace element partition coefficients were determined for rutile (TiO₂) for a large number of trace elements (Zr, Hf, Nb, Ta, V, Co, Cu, Zn, Sr, REE, Cr, Sb, W, U, Th). Whilst the high field strength elements (Zr, Hf, Nb, Ta) are compatible in rutile, other studied trace elements are incompatible (Sr, Th, REE). In all experiments we found D_Ta > D_Nb, D_Hf > D_Zr and D_U > D_Th. Partition coefficients for some polyvalent elements (Sb, W, and Co) were sensitive to oxygen fugacity. Melt composition exerts a strong influence on HFSE partition coefficients. With increasing polymerization of the melt, rutile/melt partition coefficients for the high field strength elements Zr, Hf, Nb and Ta increase about an order of magnitude. However, D_Nb/D_Ta and D_Hf/D_Zr are not significantly affected by melt composition. Because D_U ? D_Th, partial melting of rutile-bearing eclogite in subducted lithosphere may cause excesses of ²³⁰Th over ²³⁸U in some island arc lavas, whereas dehydration of subducted lithosphere may cause excesses of ²³⁸U over ²³⁰Th. From our partitioning results we infer partition coefficients for protactinium (Pa) which we predict to be much lower than previously anticipated. Contrary to previous studies, our data imply that rutile should not significantly influence observed ²³¹Pa-²³⁵U disequilibria in certain volcanic rocks.     

Determination of melt influence on divalent element partitioning between anorthite and CMAS melts

We propose a theory for crystal-melt trace element partitioning that considers the energetic consequences of crystal-lattice strain, of multi-component major-element silicate liquid mixing, and of trace-element activity coefficients in melts. We demonstrate application of the theory using newly determined partition coefficients for Ca, Mg, Sr, and Ba between pure anorthite and seven CMAS liquid compositions at 1330 °C and 1 atm. By selecting a range of melt compositions in equilibrium with a common crystal composition at equal liquidus temperature and pressure, we have isolated the contribution of melt composition to divalent trace element partitioning in this simple system. The partitioning data are fit to Onuma curves with parameterizations that can be thermodynamically rationalized in terms of the melt major element activity product (a_Al2O3)(a_SiO2)² and lattice strain theory modeling. Residuals between observed partition coefficients and the lattice strain plus major oxide melt activity model are then attributed to non-ideality of trace constituents in the liquids. The activity coefficients of the trace species in the melt are found to vary systematically with composition. Accounting for the major and trace element thermodynamics in the melt allows a good fit in which the parameters of the crystal-lattice strain model are independent of melt composition.     

Distribution of REE,LILE, and HFSE between biotite,feldspar, and the melt in the granulite facies migmatite,nimnyr block,Aldan shield

The behavior of trace elements under conditions of partial melting of granitoid rocks has been studied. The element’s partition coefficients between minerals and the melt D_i^min/melt depends, in the first place, on the composition of the primary melt. In biotite the HREE D_i are a little below 1, while those of LREE, especially D_i for Ce, are 1–3 orders of magnitude less. This leads to an efficient differentiation of REEs in anatexic melts especially when biotite is the main mineral phase of restite. On the contrary, there are feldspars, the D_i of which cannot provide such a magnitude of differentiation. Unlike garnets and pyroxenes, whose stability in restite permits enrichment of anatexic melts produced in migmatization zones with Nb, Ti, and Cr, the presence of biotite in restite causes depletion of melts with those elements as well as with Rb. Feldspars, under conditions of their fractional crystallization or during differentiation of an anatexic melt, deplete the latter with Sr, Ba, and Rb, but enrich it with Nb, Ti, Cr, Y, Zr, and V.     

Trace elements in minerals as indicators of the evolution of alkaline ultrabasic dike series: LA-ICP-MS data for the magmatic provinces of northeastern Fennoscandia and Germany

In this paper we report the results of the analysis of rare earth (REE), large-ion lithophile (LILE), and high field strength (HFSE) elements in minerals from the alkaline lamprophyre dikes of the Kola region and the Kaiserstuhl province by the local method of laser ablation inductively coupled plasma mass spectrometry. The contents of Y, Li, Rb, Ba, Th, U, Ta, Nb, Sr, Hf, Zr, Pb, Be, Sc, V, Cr, Ni, Co, Cu, Zn, Ga, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu were measured in olivine, melilite, clinopyroxene, amphibole, phlogopite, nepheline, apatite, perovskite, and the host fine-grained groundmass. The obtained data on trace element partitioning among the mineral phases of the alkaline ultrabasic rocks of the dike series indicate that the main mineral hosts for the HFSEs and REEs in alkaline picrites, olivine melanephelinites, and melilitites are perovskite and apatite comprising more than 90% of these elements. Among major rock-forming minerals, melilite, clinopyroxene, and highly magnesian amphibole make a significant contribution to the balance of REEs during the evolution of melanephelinite melts. The partition coefficients of Ni, Co, Cu, Zn, Sc, V, Cr, Ga, Y, Li, Rb, Ba, Th, U, Ta, Nb, Sr, Hf, Zr, Pb, Be, and all of the REEs were calculated for olivine, clinopyroxene, amphibole, phlogopite, nepheline, perovskite, and apatite on the basis of mineral/groundmass ratios. Variations in the composition of complex zoned clinopyroxene phenocrysts reflect the conditions of polybaric crystallization of melanephelinite melt, which began when the magmas arrived at the base of the lower crust and continued during the whole period of their ascent to the surface. The formation of green cores in clinopyroxene is an indicator of mixing between primary melanephelinite melts and phonolite magmas under upper mantle conditions. The estimation of the composition of primary melts for the rocks of the alkaline ultrabasic series of the Kola province indicated a single primary magma for the whole series. This magma produced pyroxene cumulates and complementary melilitolites, foidolites, and nepheline syenites.     

Trace element partitioning between mica- and amphibole-bearing garnet lherzolite and hydrous basanitic melt: 1. Experimental results and the investigation of controls on partitioning behaviour

Thirty five minor and trace elements (Li, Be, B, Sc, Cu, Zn, Ga, Ge, As, Rb, Nb, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, La, Ce, Nd, Sm, Tb, Ho, Tm, Lu, Hf, Ta, W, Tl, Pb, Bi, Th and U) in experimentally produced near-liquidus phases, from a primitive nelpheline basanite from Bow Hill in Tasmania (Australia), were analysed by LAM ICP-MS. A number of halogens (F, Cl and I) were also analysed by electron microprobe. The analyses were used to determine mineral/melt partition coefficients for mica, amphibole, garnet, clinopyroxene, orthopyroxene and olivine for conditions close to multiple saturation of the basanite liquidus with garnet lherzolite (approximately 2.6 GPa and 1,200°C with 7.5 wt% of added H₂O). A broader range of conditions was also investigated from 1.0 GPa and 1,025°C to 3.5 GPa and 1,190°C with 5–10 wt% of added H₂O. The scope and comprehensiveness of the data allow them to be used for two purposes, these include the following: an investigation of some of the controlling influences on partition coefficients; and the compilation of a set partition coefficients that are directly relevant to the formation of the Bow Hill basanite magma by partial melting of mantle peridotite. Considering clinopyroxene, the mineral phase for which the most data were obtained, systematic correlations were found between pressure and temperature, mineral composition, cation radius and valence, and ΔG ^coulb (the coulombic potential energy produced by substituting a cation of mismatched valence into a crystallographic site). ΔG ^coulb is distinctly different for different crystallographic sites, including the M2 and M1 sites in clinopyroxene. These differences can be modelled as a function of variations in optimum valence (expressed as 1 sigma standard deviations) within individual M1 and M2 site populations.