The effect of Ca-Tschermaks component on trace element partitioning between clinopyroxene and silicate melt

We have studied the influence of Ca-Tschermaks (Calcium Tschermaks or CaTs) content of clinopyroxene on the partitioning of trace elements between this phase and silicate melt at fixed temperature and pressure. Ion probe analyses of experiments carried out in the system Na₂O–CaO–MgO–Al₂O₃–SiO₂, at 0.1 MPa and 1218°C, produced crystal-melt partition coefficients (D) of 36 trace elements (Li, Cl, Sc, Ti, V, Cr, Fe, Co, Ge, Sr, Y, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta and W), for clinopyroxene compositions between 10 and 32 mol% CaTs. Partition coefficients for 2+ to 5+ cations show, for each charge, a near parabolic dependence of log D on ionic radius of the substituting cation, for partitioning into both the M1 and M2 sites of clinopyroxene. Fitting the results to the elastic strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal-melt partition coefficients from elastic moduli. Nature 372, 452–454] we obtain results for the strain-free partition coefficients of theoretical cations (D₀), with site radius r₀, and for the site's Young's Modulus (E).

In agreement with earlier data our results show that increasing ^ivAl concentration in cpx is matched by increasing D, E_M1, E_M2 and D₀ for tri-, tetra- and pentavalent cations. The degree of fractionation between chemically similar elements (i.e. Ta/Nb, Zr/Hf) also increases. In contrast, D values for mono-, di- and hexavalent cations decrease with increasing ^ivAl in the cpx. The large suite of trace elements used has allowed us to study the effects of cation charge on D₀, r₀ and E. We have found that D₀ and r₀ decrease with increasing cation charge, e.g. r₀=0.66 Å for 4+ cations and 0.59 Å for 5+ cations substituting into M1. Values of E_M1 and E_M2 increase with cation charge as well as with increasing ^ivAl content. The increase in E_M2 is linear and close to the trend set by Hazen and Finger [Hazen, R.M., Finger, L.W., 1979. Bulk modulus-volume relationship for cation–anion polyhedra. J. Geophys. Res. 84 (10) 6723–6728] for oxides. E_M1 values are much higher and do not fit the trend predicted by the Hazen and Finger relationship.     

SIMS determination of trace element partition coefficients between garnet, clinopyroxene and hydrous basaltic liquids at 2–7.5 GPa and 1080–1200°C

Trace element partition coefficients (D's) for up to 13 REE, Nb, Ta, Zr, Hf, Sr and Y have been determined by SIMS analysis of seven garnets, four clinopyroxenes, one orthopyroxene and one phlogopite crystallized from an undoped basanite and a lightly doped (200 ppm Nb, Ta and Hf) quartz tholeiite. Experiments were conducted at 2–7.5 GPa, achieving near-liquidus crystallization at relatively low temperatures of 1080–1200°C under strongly hydrous conditions (5–27 wt.% added water). Garnet and pyroxene D_REE show a parabolic pattern when plotted against ionic radius, and conform closely to the lattice strain model of Blundy and Wood (Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454). Comparison, at constant pressure, between hydrous and anhydrous values of the strain-free partition coefficient (D₀) for the large cation sites of garnet and clinopyroxene reveals the relative importance of temperature and melt water content on partitioning. In the case of garnet, the effect of lower temperature, which serves to increase D₀, and higher water content, which serves to decrease D₀, counteract each other to the extent that water has little effect on garnet–melt D₀ values. In contrast, the effect of water on clinopyroxene–melt D₀ overwhelms the effect of temperature, such that D₀ is significantly lower under hydrous conditions. For both minerals, however, the lower temperature of the hydrous experiments tends to tighten the partitioning parabolas, increasing fractionation of light from heavy REE compared to anhydrous experiments.

Three sets of near-liquidus clinopyroxene–garnet two-mineral D values increase the range of published experimental determinations, but show significant differences from natural two-mineral D's determined for subsolidus mineral pairs. Similar behaviour is observed for the first experimental data for orthopyroxene–clinopyroxene two-mineral D's when compared with natural data. These differences are in large part of a consequence of the subsolidus equilibration temperatures and compositions of natural mineral pairs. Great care should therefore be taken when using natural mineral–mineral partition coefficients to interpret magmatic processes.

The new data for strongly hydrous compositions suggest that fractionation of Zr–Hf–Sm by garnet decreases with increasing depth. Thus, melts leaving a garnet-dominated residuum at depths of about 200 km or greater may preserve source Zr/Hf and Hf/Sm. This contrasts with melting at shallower depths where both garnet and clinopyroxene will cause Zr–Hf–Sm fractionation. Also, at shallower depths, clinopyroxene-dominated fractionation may produce a positive Sr spike in melts from spinel lherzolite, but for garnet lherzolite melting, no Sr spike will result. Conversely, clinopyroxene megacrysts with negative Sr spikes may crystallize from magmas without anomalous Sr contents when plotted on mantle compatibility diagrams. Because the characteristics of strongly hydrous silicate melt and solute-rich aqueous fluid converge at high pressure, the hydrous data presented here are particularly pertinent to modelling processes in subduction zones, where aqueous fluids may have an important metasomatic role.     

Laser Ablation ICPMS study of trace element partitioning between plagioclase and basaltic melts: an experimental approach

Plagioclase-melt partition coefficients (D) for 34 trace elements at natural concentration levels were determined experimentally in a natural MORB composition at atmospheric pressure using thin Pt-wire loops. Experiments were carried out at three temperatures (1,220, 1,200, and 1,180°C), and at three different oxygen fugacities (fO₂ = IW, QFM, air) in order to assess the effect of fO₂ on the partitioning of elements with multiple valence (Fe, Eu, Cr). Run products were analyzed by laser-ablation ICP-MS. Most trace element Ds increase slightly as temperature decreases, except for D _Zr, D _Fe, D _Eu and D _Cr that vary systematically with fO₂. Applying the Lattice Strain Model to our data suggests the presence of Fe²⁺ entirely in the octahedral site at highly to moderate reducing conditions, while Fe³⁺ was assigned wholly to the tetrahedral site of the plagioclase structure. Furthermore, we provide a new quantitative framework for understanding the partitioning behaviour of Eu, which occurs as both 2+ and 3+ cations, depending on fO₂and confirm the greater compatibility of Eu²⁺, which has an ionic radius similar to Sr, relative to Eu³⁺ in plagioclase and the higher Eu²⁺/ Eu³⁺ under reducing conditions. For petrogenetic basaltic processes, a combined fractionation of Eu²⁺–Sr and Fe–Mg by plagioclase has considerable potential as an oxybarometer for natural magmatic rocks.     

The influence of Cr on the garnet–spinel transition in the Earth''s mantle: experiments in the system MgO–Cr2O3–SiO2 and thermodynamic modelling

The position of the transition from spinel peridotite to garnet peridotite in a simplified chemical composition has been determined experimentally at high pressures and high temperatures. The univariant reaction MgCr₂O₄+2Mg₂Si₂O₆=Mg₃Cr₂Si₃O₁₂+Mg₂SiO₄, has a negative slope in P–T space between 1200 °C and 1600 °C. The experimental results, combined with assessed thermodynamic data for MgCr₂O₄, MgSiO₃ and Mg₂SiO₄ give the entropy and enthalpy of formation of knorringite garnet (Mg₃Cr₂Si₃O₁₂). Thermodynamic calculations in simplified chemical compositions indicate that Cr shifts the garnet-in reaction to much higher pressures than previously anticipated. Moreover, in Cr-bearing systems a pressure–temperature field exists where garnet and spinel coexist. The width of this divariant field strongly depends on the Cr/(Cr+Al) of the system.     

Mutual replacement reactions in alkali feldspars II: trace element partitioning and geothermometry

Perthitic alkali feldspar primocrysts in layered syenites in the Klokken intrusion in South Greenland, underwent dissolution–reprecipitation reactions in a circulating post-magmatic aqueous fluid at ~450°C, and are to a large degree pseudomorphs. These ‘mutual replacement’ reactions provide a perfect natural experiment with which to study trace element partitioning between sodium and potassium feldspars growing simultaneously. The reactant ‘phase’ was a cryptoperthitic feldspar consisting of low albite and low microcline in a coherent sub-μm ‘braid’ intergrowth and the product phases were ‘strain-free’ incoherent subgrains of low albite and low microcline forming microporous patch perthites on scales up to 200 μm. The driving force for the reaction was reduction of coherency strain energy. The mechanisms of this process are described in Part I. Five mixed braid perthite–patch perthite crystals were analysed for major and trace elements using laser ablation-inductively coupled plasma mass spectrometry with a 19 μm beam diameter. This gave bulk analyses of the braid texture, which were in the range Ab_73–54Or_45–27An_4.3–0.8, but could resolve Ab- and Or-rich patches in patch perthite. The major element bulk compositions of the crystals were retained during the replacement reactions. Major components in patches plot on tielines in the Ab–Or–An ternary system that pass through or very close to the parent braid perthite composition and indicate local equilibrium on the scale of a few tens of mm. Many trace elements, including REE, were lost to the fluid during the deuteric reactions, but the effect is large only for Fe and Ti. Cs, Pb and Sr were added to some crystals. Plots of log distribution coefficient D for Rb, Ba, Pb, Eu²⁺, La and Ce between Or- and Ab-rich patches against ionic radius are straight lines, assuming eightfold coordination, and to a first approximation are independent of ionic charge. K also lies on these lines, and the smaller ions Na and Ca lie close to them. The best linear fits were obtained using ionic radii for ^[8]K and ^[8]Ca, but there is ambiguity as to whether ^[7]Na or ^[5]Na is most appropriate. The linear relationship shows that the listed trace elements are in the feldspar M-site rather than in inclusions. Tl is in M although an exact D could not be obtained. The very large Cs ion partitions strongly into the Or-rich phase but its D value appears to be less than predicted by extrapolation. The near-linearity arises because partitioning is occurring between two solids into sites which have similar Young’s moduli, so that the parabolas that normally represent trace element partitioning between crystals and liquids (which have negligible shear strength) approximately cancel out. Ga and Be are in T-sites, as well as some of the Fe and Ti present, although part is in oxide inclusions. The site of Sc is unclear, but if structural it is likely to be T. Partitioning on M-sites is a potential geothermometer but because the effective size of the irregular M-site is defined by its K and (Na + Ca) contents, which are controlled by ternary solvus relationships, its calibration is not independent of conventional two-feldspar geothermometers. Trace elements may however provide a useful means of confirming that feldspar pairs are in equilibrium, and of recognising feldspar intergrowths produced by non-isochemical replacement rather than exsolution. Two-feldspar geothermometry for the ternary phases in the low-albite microcline patch perthites gives temperatures above the stability range of microcline, markedly so if a correction is made for Si–Al ordering. This is probably because current geothermometers are too sensitive to low concentrations of An in ordered Or-rich feldspars. This interpretation is supported by two-feldspar assemblages growing at known temperatures in geothermal systems and sedimentary basins. This paper and the earlier Part I are dedicated in the memory of J. V. Smith and W. L. Brown, both of whom died in 2007, in acknowledgement of their unrivalled contributions to the study of the feldspar minerals over more than half a century. An erratum to this article can be found at     

Carbon–oxygen isotope and trace element constraints on how fluids percolate faulted limestones from the San Andreas Fault system: partitioning of fluid sources and pathways

Understanding the way fluids flow in fault zones is of prime importance to develop correct models of earthquake mechanics, especially in the case of the abnormally weak San Andreas Fault (SAF) system. Because fluid flow can leave detectable signatures in rocks, geochemistry is essential to bring light on this topic. The present detailed study combines, for the first time, C–O isotope analyses with a comprehensive trace element data set to examine the geometry of fluid flow within a significant fault system hosted by a carbonate sequence, from a single locality across the Little Pine Fault–SAF system. Such a fault zone contains veins, deformation zones, and their host rocks. Stable isotope geochemistry is used to establish a relative scale of integrated fluid–rock ratios. Carbonate δ¹⁸O varies between 28‰ and 15‰ and δ¹³C between 5‰ and −7‰. From highest to lowest delta values, thus from least to most infiltrated, are the host rocks, the vein fillings, and the deformation zone fillings, respectively. Infiltration increases toward fault core. The fluids are H₂O–CO₂ mixtures. Two fluid sources, one internal and the other external, are found. The external fluid is inferred to come essentially from metamorphism of the Franciscan formation underneath. The internal (local) fluid is provided by a 30% volume reduction of the host limestones resulting from pressure solution and pore size reduction. Most trace elements, including the lanthanides, show enrichment at the 100-m scale in host carbonate rocks as fluid–rock ratios increase toward the fault core. In contrast, the same trace element concentrations are low, relative to host rocks, in veins and deformation zone carbonate fillings, and this difference in concentration increases as fluid–rock ratio increases toward the fault core. We suggest that the fluid trace elements are scavenged by complexation with organic matter in the host rocks. Elemental complexation is especially illustrated by large fractionation of Y–Ho and Nb–Ta geochemical pairs. Complexation associated with external fluid flow has a significant effect on trace element enrichment (up to 700% relative enrichment) while concentration by pressure solution associated with volume decrease of host rocks has a more limited effect (up to 40% relative enrichment). Our observations from the millimeter to the kilometer scale call for the partitioning of fluid sources and pathways, and for a mixed focused–pervasive fluid flow mechanism. The fluid mainly flows within veins and deformation zones and, simultaneously, within at least 10 cm from these channels, part of the fluid flows pervasively in the host rock, which controls the fluid composition. Scavenging of the fluid rare earth elements (REE) by host rocks is responsible for the formation of REE-depleted vein and deformation zone carbonate fillings. Fluid flow is not only restricted to veins or deformation zones as commonly believed. An important part of fluid flow takes place in host rocks near fault zones. Hence, the nature of the lithologies hosting fault zones must be considered in order to take into account the role of fluids in the seismic cycle.     

Volatile (S,Cl and F) and fluid mobile trace element compositions in melt inclusions: implications for variable fluid sources across the Kamchatka arc

Volatile element, major and trace element compositions were measured in glass inclusions in olivine from samples across the Kamchatka arc. Glasses were analyzed in reheated melt inclusions by electron microprobe for major elements, S and Cl, trace elements and F were determined by SIMS. Volatile element–trace element ratios correlated with fluid-mobile elements (B, Li) suggesting successive changes and three distinct fluid compositions with increasing slab depth. The Eastern Volcanic arc Front (EVF) was dominated by fluid highly enriched in B, Cl and chalcophile elements and also LILE (U, Th, Ba, Pb), F, S and LREE (La, Ce). This arc-front fluid contributed less to magmas from the central volcanic zone and was not involved in back arc magmatism. The Central Kamchatka Depression (CKD) was dominated by a second fluid enriched in S and U, showing the highest S/K₂O and U/Th ratios. Additionally this fluid was unusually enriched in ⁸⁷Sr and ¹⁸O. In the back arc Sredinny Ridge (SR) a third fluid was observed, highly enriched in F, Li, and Be as well as LILE and LREE. We argue from the decoupling of B and Li that dehydration of different water-rich minerals at different depths explains the presence of different fluids across the Kamchatka arc. In the arc front, fluids were derived from amphibole and serpentine dehydration and probably were water-rich, low in silica and high in B, LILE, sulfur and chlorine. Large amounts of water produced high degrees of melting below the EVF and CKD. Fluids below the CKD were released at a depth between 100 and 200 km due to dehydration of lawsonite and phengite and probably were poorer in water and richer in silica. Fluids released at high pressure conditions below the back arc (SR) probably were much denser and dissolved significant amounts of silicate minerals, and potentially carried high amounts of LILE and HFSE. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Distribution of Fe and Mg between coexisting garnet and hornblende in synthetic and natural systems: an empirical calibration of the garnet–hornblende Fe–Mg geothermometer

Multiple regression analysis of a compilation of the Fe²⁺–Mg distribution between garnet and hornblende from experimental runs on basaltic to intermediate compositions (n=22) and coexisting garnet–clinopyroxene–hornblende from natural (intermediate to basaltic) rocks (n=43) has been performed to define ln K_{D(Fe²⁺/Mg)}^Grt–Hbl as a function of temperature and garnet composition. The regression of data covering a large span in pressure (5–16 kbar), temperature (515–1025°C) and composition yields the ln K_{D(Fe²⁺/Mg)}^Grt–Hbl–P–T compositional relationship (r²=0.93):

where

Application of this expression to natural garnet–hornblende pairs in intermediate to basaltic and semipelitic rock types from various settings gives temperatures that are consistent with other methods.     

Trace element fractionation during high-grade metamorphism and crustal melting—constraints from ion microprobe data of metapelitic, migmatitic and igneous garnets and implications for Sm–Nd garnet chronology

Rare earth element (REE) and other trace element (Y, Sr, Ti, Cr, V, Na) abundances in garnet from a garnet-bearing metapelite, a pelitic migmatite, a syn-tectonic granite and a post-tectonic leucogranite were measured by secondary ion mass spectrometry (SIMS) in order to identify the effective variables on the trace element distribution between garnet and the host rock. Garnet from the garnet-bearing metapelite, the pelitic migmatite and the syn-tectonic granite is zoned with respect to REE. The cores are enriched by a factor of 2–3 relative to the rims. For the garnets from the garnet-bearing metapelite equilibrium distribution following a simple Rayleigh fractionation is responsible for the decreasing concentrations in REE from core to rim. Garnet from the pelitic migmatite shows a more complex trace element pattern following distinct enrichment and depletion patterns for Ti, V, Cr and REE from core to rim. These features suggest disequilibrium between garnet and the associated melt in which the enrichment of trace elements probably correspond to a period of open-system behaviour in these rocks at a time when the garnet, originally nucleated in the metamorphic environment was incorporated into the melt. The garnet from the syn-tectonic granite shows stepwise decreasing concentrations in REE from core to rim: a REE-rich core can be distinguished from a broad REE-depleted rim. Notably, from core to rim an inflection of the Yb / Er and Yb / Dy ratios is visible. Whereas the decrease of HREE abundance in the core region of the garnet from the syn-tectonic granite may arise from equilibrium partitioning during garnet growth, the inflection can be interpreted as a result of partial melting. Garnet cores with high Yb / Er and Yb / Dy >  1 nucleated in the metamorphic environment without the presence of a melt whereas the rims with lower Yb / Er and Yb / Dy <  1 crystallized in the presence of a melt. Garnet from the leucogranite has lower REE abundances and is considered to be of igneous origin. In contrast to garnet from the other samples, its core has low trace element abundances, whereas its rim is significantly enriched in REE but depleted in Ti. These features suggest that only the outermost rim was in equilibrium with the melt. For this garnet, liquid diffusion controlled partitioning is more likely to explain the extreme trace element variation. An evaluation of Sm and Nd concentrations in garnet and a comparison of Sm–Nd and U–Pb garnet ages and U–Pb monazite ages form the terrane indicate that the observed LREE systematics in the different garnet species are a primary feature and are not homogenized by volume diffusion during high grade amphibolite facies conditions.     

Geochemistry of eclogites from the Dabie–Sulu terrane, eastern China: New insights into protoliths and trace element behaviour during UHP metamorphism

The major and trace element compositions of nine eclogites from the Dabie–Sulu ultrahigh pressure (UHP) metamorphic terrane in eastern China were determined for both whole rock and the main constituent minerals, garnet and clinopyroxene. The results indicate that the eclogite protoliths originated from a basaltic magma, which formed in a continental setting as shown by isotopic and immobile element data. Based on the garnet REE characteristics, the eclogites can be roughly divided into two groups. Group 1 has LREE enrichment with no Eu anomaly for whole rock, and smooth LREE depletion but HREE enrichment pattern for garnet, whereas group 2 shows a depletion of LREE with a pronounced positive Eu anomaly and flat HREE pattern for both whole rock and garnet. From these features, we suggest that the protoliths for group 2 are Fe–Ti–gabbros with relatively high cumulus plagioclase and Fe–Ti oxide, whereas the group 1 eclogites are probably from basalts. Therefore, the unusual garnet REE pattern observed in group 2 can be considered as an important signature for identifying gabbro protoliths for eclogites. The identification of gabbro protoliths from the eclogites in the Dabie–Sulu terrane provides evidence for Neoproterozoic rift magmatism in the northern margin of the Yangtze craton. During ultrahigh pressure metamorphism in the Dabie–Sulu terrane, LILEs (including Ba, Rb, Th, U, K) had high mobility, but REEs and HFSEs were immobile, and trace element distribution equilibrium was approached between garnet and clinopyroxene. An estimate of mass balance indicates that garnet and clinopyroxene host the majority of HREEs and Y, and clinopyroxene is a significant host for Sr, but minor and accessory minerals predominantly account for LREEs, Th, U, and Zr.     

The influence of redox processes on trace element mobility in a sandy aquifer—an experimental approach

This study is concerned with the geochemical behavior of Cu, Zn, As, Mo, Ba, La and Ce under the reducing conditions of a bank infiltration system. To identify and interpret individual processes laboratory experiments were performed on columns containing sandy sediments of an anoxic pleistocene aquifer from the Ruhr valley (western Germany). The flow rate being the key variable was varied from 0.21 to 0.46 and 0.82 m/d (meters per day), whereas the concentration of the reducing agent (acetate) remained constant. A second experiment lasting 80 weeks was carried out at a flow rate of 0.80 m/d, in order to characterize interactions between the pore water and solid phase. The results of these experiments show that the geochemistry of the trace elements involved can be explained to a large extent by the major redox processes of manganese, iron and sulfate turnover. The trace elements As, Mo, Ce and La were released into the pore water as a result of the reduction of Mn- and Fe-(hydr)oxides within the zone of major redox processes. Cu and Zn were removed from the infiltrating water within the first centimeters of the column by sulfide (co)precipitation, whereas the mobility of Mo was controlled by sulfidic fixation further down the flow path. As a result of the decreasing S²⁻-concentrations along the flow path, dissolved As(III) was re-oxidized (E_H>− 250 mV) and precipitated as As(V) in a barium–arsenate-phase.     

赣中古塘地区锡石LA-ICP-MS U-Pb年代学及微量元素地球化学特征

江西中部相山矿田及其周边铀多金属成矿作用复杂。近些年,在其南部古塘地区地表新发现了一处锡石矿化带,赋存于加里东期花岗岩中。通过对该矿点锡石开展原位LA-ICP-MS U-Pb定年和微量元素分析,获得其²⁰⁷Pb/²⁰⁶Pb-²³⁸U/²⁰⁶Pb谐和年龄为150.44±2.78 Ma、下交点年龄为150.64±2.78 Ma,两者相近,可以代表该锡石矿的成矿年龄,与矿化带周边的燕山期山心单元花岗岩成岩年龄（152.4±1.1 Ma）相近。微量元素中,高场强元素Ti、Nb、Ta富集明显。与Sn容易发生类质同象的Mn、Nb、Hf、Ta等4种元素彼此正相关性明显,Fe和Mo呈正相关关系,却与Nb、Mn、Hf、Ta均呈现负相关性。在W-Fe图解中,处于花岗岩岩浆热液型锡矿床的右侧,说明研究区成矿物质应该主要来自岩浆热液,而且成矿温度较高。古塘地区锡石矿与山心单元花岗岩虽然具有相近的成矿、成岩年龄,但由于后者具有极高的氧逸度,不利于Sn元素的富集,而与Mo成矿有关;与山心单元花岗岩中可见辉钼矿矿囊而未发现锡矿化的地质现象保持一致。

     

Mobilization and redistribution of major and trace elements in two weathering profiles developed on serpentinites in the Lomié ultramafic complex, South-East Cameroon

The behaviour of major and trace elements have been studied along two serpentinite weathering profiles located in the Kongo-Nkamouna and Mang North sites of the Lomié ultramafic complex.The serpentinites are characterized by high SiO₂ and MgO contents, very low trace, rare earth and platinum-group element contents. Lanthanide and PGE contents are higher in the Nkamouna sample than in Mang North. Normalized REE patterns according to the CI chondrites reveal that: (i) all REE are below chondrites abundances in the Mang North sample; (ii) the (La/Yb)_N ratio value is higher in the Nkamouna sample (23.72) than in the Mang one (1.78), this confirms the slightly more weathered nature of the Nkamouna sample. Normalized PGE patterns according to the same CI chondrites reveal a negative Pt anomaly in the Mang sample. The Nkamouna sample is characterized by a flat normalized PGE pattern.All element contents increase highly from the parent rock to the coarse saprolite.In the weathering profiles, Fe₂O₃ contents decrease from the bottom to the top contrarily to Al₂O₃, SiO₂ and TiO₂. The contents of alkali and alkaline oxides are under detection limit.Concerning trace elements, Cr, Ni, Co, Cu, Zn and Sc decrease considerably from the bottom to the top while Zr, Th, U, Be, Sb, Sn, W, Ta, Sr, Rb, Hf, Y, Li, Ga, Nb and Pb increase towards the clayey surface soil. Chromium, Ni and Co contents are high in the weathered materials in particular in the saprolite zone and in the nodules.REE contents are high in the weathered materials, particularly in Nkamouna. Their concentrations decrease along both profiles. Light REE are more abundant than heavy REE. Normalized REE patterns according to the parent rock reveal positive Ce anomalies in all the weathered materials and negative Eu anomalies only at the bottom of the coarse saprolite (Nkamouna site). Positive Ce anomalies are higher in the nodular horizon of both profiles. An additional calculation method of lanthanide anomalies, using NASC data, confirms positive Ce anomalies ([Ce/Ce^*]_NASC = 1.15 to 60.68) in several weathered materials except in nodules ([Ce/Ce^*]_NASC = 0.76) of the upper nodular horizon (Nkamouna profile). The (La/Yb)_N ratios values are lower in the Nkamouna profile than in Mang site.PGE are more abundant in the weathered materials than in the parent rock. The highest contents are obtained in the coarse saprolite and in the nodules. The elements with high contents along both profiles are Pt (63–70 ppb), Ru (49–52 ppb) and Ir (41 ppb). Normalized PGE patterns show positive Pt anomalies and negative Ru anomalies.The mass balance evaluation, using thorium as immobile element, reveals that:

– major elements have been depleted along the weathering profile, except for Fe, Mn and Ti that have been enriched even only in the coarse saprolite;

– all the trace elements have been depleted along both profiles, except for Cr, Co, Zn, Sc, Cu, Ba, Y, Ga, U and Nb that have been enriched in the coarse saprolite;

– rare earth elements have been abundantly accumulated in the coarse saprolite, before their depletion towards the top of the profiles;

– platinum-group elements have been abundantly accumulated in the coarse saprolite but have been depleted towards the clayey surface soil.

Moreover, from a pedogenetical point of view, this study shows that the weathering profiles are autochtonous, except in the upper part of the soils where some allochtonous materials are revealed by the presence of zircon grains.     

Lu–Hf geochronology and trace element distribution in garnet: Implications for uplift and exhumation of ultra-high pressure granulites in the Sudetes, SW Poland

Combining Lu–Hf garnet geochronology with in situ trace element analyses in garnet allowed us to gain new insight into the metamorphic evolution of UHP–UHT rocks in the Stary Gierałtów region, in the Polish Sudetes. Prograde garnet growth recorded by Rayleigh-type heavy REE (HREE) zoning in the felsic granulites indicates that the obtained 386.6 ± 4.9 Ma Lu–Hf age represents the time of garnet crystallization on a prograde UHP metamorphic path. The surrounding rocks were metamorphosed at the same time as indicated by 381.2 ± 6.7 Ma Sm–Nd garnet age obtained for the mid-crustal metapelites. The second metamorphic episode, which affected most of the lower crust in the Orlica–Śnieżnik Massif (OSM) occurred at ca. 340 Ma as determined by U–Pb zircon and Sm–Nd garnet dating of granulites in this and previous studies is interpreted as a high temperature event, which took place on a retrograde path.

Trace element distribution in garnets from the layered granulites showed significant differences in distribution of medium and HREE in garnets from mafic and felsic protoliths over the course of the metamorphic evolution. This had strong impact on the isotopic dating results and led to “decoupling” of the Sm–Nd and Lu–Hf clocks, which recorded timing of the two different metamorphic episodes separated by as much as 40 Ma. Moreover, the preservation of the HREE growth zonation profile in garnets from the felsic granulites whose minimum metamorphic temperature was established at 900 °C implies that the Lu–Hf system under relatively dry conditions does not undergo significant diffusional re-equilibration even at such extreme temperatures and therefore it sill provides the age of prograde garnet growth. Under hydrous conditions, at least some resetting will take place, as documented by the partially relaxed HREE zonation profile in the amphibolitised mafic granulite, which yielded a 10 Ma younger age. The HREE distribution study appeared to be a particularly valuable and essential tool, which allowed us to distinguish garnet growth from post-growth complexities and hence, provide improved age interpretation. Medium REE, on the other hand, did not show any obvious correlation with the isotopic signature of garnet.

Two distinct metamorphic episodes recorded in the Stary Gierałtów region show that buoyancy-driven uplift of UHP rocks can be arrested at the base of a continental crust if not supported by any additional force. In our case study, the UHP rocks would have never reached the surface if their uplift had not been resumed after a long pause under a different tectonic regime. The multistage, discontinuous uplift revealed by the UHP rocks of the OSM provides a new scenario for the exhumation of continental crust from mantle depths distinct from the fast-track exhumation histories recognized in UHP terranes elsewhere.     

Selenium and other trace element in phosphorites: A comparison between those of the Bayovar-Sechura and other provenances

Data of trace element composition of phosphorites are scarce and incomplete. Phosphorites of different origins can vary substantially in trace element contents. In this paper 20 trace element concentrations of 35 sample phosphorites are reported. The geographical provenance is: Bayovar-Sechura (Peru), Khouribga, Youssoufia and Boucraa (Morocco), Gafsa (Tunisia), Florida (USA), Idaho and Phosphoria Formation (USA), North Carolina (USA), Algeria, Israel, Senegal, Syria and Togo. Aqua regia extracts were used to estimate the “pseudototal” values, following standard procedures (ISO 11466, 2002) and measured by ICP-AES and ICP-MS.     

Annual trace element cycles in calcite–aragonite speleothems: evidence of drought in the western Mediterranean 1200–1100 yr BP

Each of two calcitic stalagmites from Grotte de Clamouse, Herault, southern France, displays a discrete aragonite layer dated at around 1100 yr BP. The layer of fanning aragonite ray crystals is immediately preceded by calcite with Mg and Sr compositions that are uniquely high for the past 3 kyr. Trace element compositions close to the boundary between original aragonite and calcite are consistent with quasi‐equilibrium partitioning of trace elements between the phases. Study of modern dripwaters demonstrates that pronounced covariation of Mg/Ca and Sr/Ca ratios in dripwater occurs owing to large amounts of calcite precipitation upflow of the drips that fed the stalagmites. Trace element to Ca ratios are enhanced during seasonally dry periods. Ion microprobe data demonstrate a pronounced covariation of trace elements, including Mg and Sr in calcite, and Sr, U and Ba in aragonite. The mean peak spacing is close to the long‐term mean of annual growth rates determined by differences in U‐series ages and so the trace element peaks are interpreted as annual. The trace element chemistry of the stalagmites on annual to inter‐annual scales thus directly reflects the amounts of prior calcite precipitation, interpreted as an index of aridity. The longer‐term context is a multi‐decadal period of aridity (1200–1100 yr BP) possibly correlated with an analogous episode in Central America. The arid period culminated in the nucleation of aragonite, but within a decade was followed by a return to precursor conditions. Copyright © 2005 John Wiley & Sons, Ltd.     

Mobility of arsenic and trace element inventories in sediment cores from Masuda City,southwestern Japan

The vertical distribution of arsenic and other trace and major elements has been studied in four sediment cores from Masuda City, Nagashima and Okite in the Shimane Prefecture of southwestern Japan. The sediment cores were also subjected to leaching techniques and ¹⁴C dating. The stratigraphic sequences in the cores consist of silt and sandy silt at top, passing downward into gray to black clays. Elevated values of As, Pb, Zn, Cu, Ni, Cr, and V are present in several horizons while abundances of these elements tend to be higher in the black and gray clays, probably due to adsorption onto clay sediments. Higher concentrations of Fe and total sulfur (TS) occur in black clays. The correlations of the trace metals with iron suggest their adsorption onto Fe (oxy)hydroxides, whereas correlations with sulfur in some cores indicate that they were precipitated as Fe-sulfides. Age determinations suggest that clay horizons at ∼5 m depth were deposited at around 5,000 and 6,000 years BP (¹⁴C ages) during the transgressive phase of sea level change. The results of the leaching techniques in the core samples show that higher amounts of As were extracted with deionized water. Even at neutral pH, As can be released from sediments to groundwater, and therefore groundwater pollution is a concern in Masuda City and the surrounding area.     

The determination of trace elements in Fe–Mn oxide coatings on pebbles using LA-ICP-MS

Iron–manganese oxide coatings form on a wide range of geologic samples where they have the ability to adsorb elements and potentially act as a mineral exploration/environmental monitoring tool. In this study, Fe–Mn oxide coatings on stream pebbles were collected from streams in four study areas located across the province of Newfoundland and Labrador, Canada. The study locations were in areas of former copper mines (Tilt Cove and Betts Cove), carbonate geology (Robinsons River), and a metropolitan area (Rennies River). Collected pebbles underwent a simple sample preparation procedure and were then analyzed for a wide range of elements by LA-ICP-MS after optimization of the operating conditions. Water samples accompanied the pebbles, and these were analyzed for pH, dissolved oxygen, conductivity, and a large selection of elements by ICP-MS. Multivariate statistics, in the form of Principal Component Factor Analysis (PCFA) was performed on both data sets. Graphs of the factor scores from the PCFA produced groupings of the samples that were related to geologic/environmental inputs. The loading of variables in each factor was related to the adsorption of the element either to the MnO₂ or Fe₂O₃ phase with most elements except Cr and Cu displaying preferential adsorption to MnO₂. Elemental Fe–Mn oxide coating concentrations were a result of the element's affinity (chalcophile, lithophile, or siderophile), pH of the environment, stream water concentration, and amount of each oxide phase present. Even with these complications, LA-ICP-MS analysis of Fe–Mn oxides was able to identify areas of heavy metal pollution and locate geologic inputs.     

福建尤溪丁家山矿区闪锌矿中微量元素及其对晶体结构影响研究

应用矿相显微镜、显微电子能谱分析、粉晶X射线衍射等分析手段,研究了丁家山闪锌矿中微量元素的存在状态和富集特征。通过闪锌矿晶体化学式的对比,研究发现闪锌矿可以分为两个世代,它们的成矿温度存在明显差异。通过微量元素比值推断该矿床为高中温内生矿床,并经受过后期改造。闪锌矿受类质同象离子置换的影响,其晶胞参数与微量元素含量关系密切。同时在该矿区首次发现了白钨矿。     

Magmatic-to-hydrothermal crystallization in the W–Sn mineralized Mole Granite (NSW, Australia): Part II: Evolving zircon and thorite trace element chemistry

The Sn–W mineralized Mole Granite in Eastern Australia hosts zircon populations that crystallized at several stages during a protracted magmatic to hydrothermal evolution. Thirty-four elements have been quantified by laser-ablation inductively-coupled-plasma mass-spectrometric microanalysis with the aim of relating the chemistry of zircon to its growth environment. Trace element contents are highly variable for all textural occurrences. Zircon inclusions in earliest quartz phenocryst suggest that zircon was a liquidus phase that crystallized probably deep in the crust. Trace element contents are conspicuously high, showing only a slight positive Ce anomaly but a pronounced negative Eu-anomaly. Successive crystallization stages of magmatic zircon are characterized by progressive depletion in trace element contents, notably the rare earth elements, with an increasingly important positive Ce-anomaly. This evolution reflects saturation of REE accepting minerals such as monazite, thorite, xenotime and possibly apatite and is affected little by the exsolution of a magmatic–hydrothermal fluid. Zircon that is interpreted to have precipitated from aqueous fluids in Sn–W-bearing quartz veins shows REE patterns indistinguishable from those of late magmatic zircon. When combined with experimental evidence on the fluid–melt partitioning of REE, it indicates that the REE distribution coefficients for zircon/melt and zircon/fluid are largely comparable.

The second example of hydrothermal zircon crystallized some 2 My after the host granite. These crystals reveal an intragranular zonation of increasing trace element concentrations from core to rim. Therefore, REE abundances and patterns alone are not conclusive indicators of the geological environment in which zircon crystallized. Nevertheless, variations in trace element contents of zircon that relate to the chemistry of the melt or fluid from which zircon crystallized, as measured in cogenetic melt and fluid inclusions, are promising for future petrogenetic modeling.

Lead and Cs are strongly incompatible in hydrothermal zircon, with estimated zircon–fluid distribution coefficients D ≤ 0.001, while Sn and Li are moderately incompatible, D_Sn  0.6 and D_Li  0.1, and Ce is compatible, D_Ce  14. Moreover, hydrothermal zircon has a more pronounced negative Eu-anomaly and higher Ta/Nb and U/Th ratios than the magmatic zircons of the Mole Granite.