Element Partition Coefficients Research Articles

Cobalt and nickel distribution and controlling factors in the Bushveld layered complex

The Bushveld Complex is the largest known layered intrusion in the world and has been extensively studied. However, there remains an absence of systematic investigations of cobalt (Co) and nickel (Ni) distribution at various scales. Elements Co and Ni behave varying degrees of compatibility within chromite, silicates, and sulfides, making them effective proxies for elucidating chemical competition and interaction among these minerals. This study aims to characterize Co and Ni distribution in olivine, pyroxenes, chromite, and whole rocks from different seams of the Bushveld Complex and to reveal their controlling factors. Our results indicate large variations of whole-rock Co and Ni concentrations, with a decreasing sequence of dunites (Co: 156–222 ppm; Ni: 2208–2750 ppm) > harzburgites (Co: 87.8–174 ppm; Ni: 152–2050 ppm) > pyroxenites (Co: 58.7–143 ppm; Ni: 387–1947 ppm) > norites (Co: 16.0–113 ppm; Ni: 153–646 ppm) > anorthosites (Co: 3.20–16.3 ppm; Ni: 19.7–97.2 ppm). In general, olivine has higher Ni contents (717–4496 ppm) and lower Co (105–239 ppm) than chromite (Ni: 524–1948 ppm; Co: 236–563 ppm). Pyroxenes have apparently low Co (orthopyroxene: 39.7–184 ppm; clinopyroxene: 17.2–114 ppm) and Ni contents (orthopyroxene: 224–1195 ppm; clinopyroxene: 177–831 ppm). Chromite in chromitites has lower Co content than that in other rocks. The whole-rock and mineral Co and Ni variations in the stratigraphic profile are closely related with lithology, mineral assemblages and element partition coefficients in minerals. The Co contents in the chromite and pyroxenes vary alternately with the chromitites and rock seams, with lower Co contents in ore samples than that in silicate rocks. Whole rocks and mineral separates in the Merensky Reef exhibit the highest Ni contents (whole-rock: up to 4000 ppm; orthopyroxene: 1035–1195 ppm; clinopyroxene: 730–831 ppm; chromite: 1760–1948 ppm), which are likely attributed to sulfide segregation and diffusion between sulfides and other minerals. In addition, the sulfide segregation may also be a main factor resulting in Co-Ni decoupling in pyroxenes from the Main Zone of the Bushveld Complex.

Trace element partitioning in the lunar magma ocean: an experimental study

Modeling the behavior of trace elements during lunar magma ocean solidification is important to further our understanding of the chemical evolution of the Moon. Lunar magma ocean evolution models rely on consistent datasets on how trace elements partition between a lunar silicate melt and coexisting minerals at different pressures, temperatures, and redox conditions. Here we report new experimental trace element partition coefficients (D) between clinopyroxene (cpx), pigeonite, orthopyroxene, plagioclase, olivine (ol), and silicate melt at conditions relevant for the lunar magma ocean. The data include Dcpx−melt at ambient and high pressures (1.5 GPa and 1310 °C), and partition coefficients at ambient pressure for pig, opx, ol, and pl. Overall, clinopyroxene is a phase that may control the fractionation of key geochemical trace element ratios, such as Lu/Hf and Sm/Nd, during the evolution of the lunar magma ocean. We explore the impact of the new silicate Dmineral−melt on the trace element evolution of the lunar magma ocean and we find that accessory phosphate minerals, such as apatite or whitlockite are of critical importance to explain the observed trace element and isotopic signature of the KREEP reservoir on the Moon. The new partition coefficients were applied to calculate the trace element evolution of the residual melts of the crystallizing lunar magma ocean and we propose a new trace element composition for the urKREEP reservoir. The new data will be useful for future thermo-chemical models in order to adequately predict the duration of the lunar magma ocean and the age of the Moon.

Trace element partitioning in basaltic systems as a function of oxygen fugacity

Along with temperature, pressure and melt chemistry, magmatic oxygen fugacity (fO2) has an important influence on liquid and solid differentiation trends and melt structure. To explore the effect of redox conditions on mineral stability and mineral-melt partitioning in basaltic systems we performed equilibrium, one-atmosphere experiments on a picrite at 1200–1110 °C with fO2 ranging from NNO-4 log units to air. Clinopyroxene crystallizes from 1180 °C to near-solidus, along with plagioclase, olivine and spinel. Olivine Mg# increases with increasing fO2, eventually reacting to pigeonite. Spinel is absent under strongly reducing conditions. Mineral-melt partition coefficients (D) of redox-sensitive elements (Cr, Eu, V, Fe) vary systematically with fO2 and, in some cases, temperature (e.g. DCr in clinopyroxene). Clinopyroxene sector zoning is common; sectors along a- and b-axes have higher AlIV, AlVI, Cr and Ti and lower Mg than c-axis sectors. In terms of coupled substitutions, clinopyroxene CaTs (MgSi = AlVIAlIV) prevails under oxidized conditions (≥ NNO), where Fe3+ balances the charge, but is limited under reduced conditions. Overall, AlIV is maximised under high temperature, oxidizing conditions and in slowly grown (a–b) sectors. High AlIV facilitates incorporation of REE (REEAlIV = CaSi), but DREE (except DEu) show no systematic dependence on fO2 across the experimental suite. In sector zoned clinopyroxenes enrichment in REE3+ in Al-rich sectors is quantitatively consistent with the greater availability of suitably-charged M2 lattice sites and the electrostatic energy penalty required to insert REE3+ onto unsuitably-charged M2 sites. By combining our experimental results with published data, we explore the potential for trace element oxybarometry. We show that olivine-melt DV, clinopyroxene-melt DV/DSc and plagioclase-melt DEu/DSr all have potential as oxybarometers and we present expressions for these as a function of fO2 relative to NNO. The crystal chemical sensitivity of heterovalent cation incorporation into clinopyroxene and the melt compositional sensitivity of the Eu2+–Eu3+ redox potential limit the use of clinopyroxene-melt and plagioclase-melt, however, olivine-melt DV affords considerable precision and accuracy as an oxybarometer that is independent of temperature, and crystal and melt composition. Variation of DV and DV/DSc with fO2 for olivine and clinopyroxene contains information on redox speciation of V in coexisting melt. By comparing the redox speciation constraints from partitioning to data from Fe-free synthetic systems and XANES spectroscopy of quenched glasses, we show that homogenous equilibria involving Fe and V species modify V speciation on quench, leading to a net overall reduction in the average vanadium valence. Mineral-melt partitioning of polyvalent species can be a useful probe of redox speciation in Fe-bearing systems that is unaffected by quench effects.

Trace element partitioning between apatite and silicate melts: Effects of major element composition, temperature, and oxygen fugacity, and implications for the volatile element budget of the lunar magma ocean

Apatite, as an accessory phase in igneous and metamorphic rocks, has important petrological significance due to its capacity to accommodate appreciable amounts of many trace elements in its mineral structure. To better constrain trace element partitioning between apatite and silicate melts, we conducted experiments that produced apatites approaching fluorapatite (FlAp), hydroxylapatite (OHAp) and chlorapatite (ClAp) endmembers separately at 1050 and 1100 °C, 1 GPa pressure, under oxygen fugacity (fO2) about one log unit below iron-wüstite buffer to four log unit above fayalite-magnetite-quartz buffer. We report the results of 12 experiments which demonstrate that ClAp exhibits lower trace element partition coefficients compared with FlAp and OHAp, especially for Rare Earth Elements (REEs) under all run conditions explored, suggesting trace element partitioning is sensitive to anion site occupancy. Divalent cations are less sensitive to anion occupancy. Positive Eu partitioning anomalies (DEu/DEu*, where Eu is the chondrite normalized abundance and Eu* is the interpolated value from neighboring elements ordered by atomic number) are observed in ClAp experiments under relatively low fO2s, whereas negative Eu anomalies are exhibited by FlAp and OHAp under the same fO2 conditions. We infer that anionic occupancies have a direct impact on the substitution mechanisms of trace elements in apatite, thereby influencing their partition coefficients. Beyond the anions, correlations of apatite compositional components (XCa, XNa, XP and XSi) with partition coefficients suggest they exert crystal chemical controls on trace element partitioning. Based on these observations, we developed parameterized lattice strain models to predict the partitioning of divalent and trivalent elements as a function of temperature and apatite composition, and an fO2-dependent apatite-melt Eu partitioning model and oxybarometer. We further developed a Eu in apatite-plagioclase oxybarometer that enables us to calculate the fO2 of apatite and plagioclase-bearing magmatic and subsolidus systems, and evaluated the influence of subsolidus reequilibration on the new oxybarometer. Applied to one of our experiments, winonaite HaH193, and samples from Sept Iles layered intrusion, the oxybarometer recovers their anticipated fO2s, ranging from about two log units below the iron-wüstite buffer to the fayalite-magnetite-quartz buffer. Using the new REE and fO2-dependent Eu partitioning models, we constrained the petrogenesis of lunar KREEP basalt and estimated the relative volatile content in the late lunar magma ocean (LMO) cumulates. The model suggests a relative depletion of Cl in the LMO cumulates, consistent with Cl isotopic analyses and volatile abundance measurements in previous work, suggesting that differential loss of volatiles occurred before or during the late-stage evolution of the LMO.

Purification of High-Purity Tin via Vertical Zone Refining

The present investigation delves into the potential of vertical zone refining as an effective purification technique for achieving high-purity tin (Sn) metal. The utilization of vertical zone refining offers distinct advantages over traditional horizontal zone refining, as it allows for enhanced control over the molten zone and solid–liquid interface, ultimately leading to superior impurity separation efficiency. The present study reveals that the solute partition coefficients (k0) of various impurity elements, such as Zn, Ag, Al, Mg, Ca, Ni, In, Co, Cu, As, Pb, Fe, and Bi, during the vertical zone refining process consistently demonstrate values below one. Notably, the partition coefficient of Sb deviates slightly from the others, being greater than one but approaching one. The authors achieve exceptional levels of purity in both the bottom and middle regions of the rod by subjecting the Sn melt to nine passes of vertical zone refining at a heating temperature of 405 °C and a downward pulling rate of 10 µm/s, resulting in purities exceeding 6N4. Furthermore, by evaluating the effective partition coefficients (keff), it was determined that impurity elements, such as Cu and Bi, closely approach their equilibrium partition coefficients, reaching values of approximately 0.492 and 0.327, respectively. To further enhance the purity of Sn metal and maximize product yield, we propose the utilization of electrolytic refining and vacuum distillation, with particular emphasis on the efficient separation of five specific elements, including Cu, Fe, As, Pb, and Sb. By elucidating these findings, this study not only contributes valuable insights into the efficacy of vertical zone refining as a purification technique for high-purity tin metal, but also offers important recommendations for refining strategies and impurity element separation.

Compositional variation and Sn isotope fractionation of cassiterite during magmatic-hydrothermal processes

Cassiterite (SnO2) precipitates over a wide physicochemical range during magmatic-hydrothermal processes. Significant variations in chemical and Sn isotopic compositions of cassiterite have been increasingly reported from hydrothermal deposits worldwide. However, the mechanisms responsible for such notable changes in cassiterite geochemistry remain to be fully addressed. Toward this end, we investigated the chemical and Sn isotopic compositions of distinct generations of cassiterite from a highly-evolved magmatic-hydrothermal-metallogenic system (Xianghualing Sn polymetallic deposit, South China). Cassiterite is widespread in the albite granite, greisen, skarn, and sulfide ore of this deposit, covering most of the known cassiterite-bearing rock/ore types. Based on distinct morphologies and mineral paragenesis, three generations of the Xianghualing cassiterite are identified: (1) Cst 1 occurs in albite granite and greisen; (2) Cst 2 occurs in skarn; and (3) Cst 3 is present in sulfide ore. A lattice strain model indicates that inter-element compositional differences of cassiterite are dual-controlled by cassiterite element partition coefficients and melt/fluid compositions for sufficient and deficient elements, respectively. The variations in Zr, Hf, Nb, and Ta elements in cassiterite are recognized as thermo-indicators of the melt/fluid physicochemical conditions. Their concentrations are influenced by pre- and syn-precipitated Zr-Hf-Nb-Ta-enriched minerals that have a wide crystallization temperature range. Due to differentiations of multiple cationic valences, concentrations and interelement ratios of Sb, Fe, V, and U can be utilized to monitor the relative melt/fluid redox state of different cassiterite generations. Tin stable isotopic compositions are notably fractionated in the Xianghualing cassiterite samples, with δamuSn values relative to standard NIST 3161a ranging from −0.16‰ to 0.19‰. By comparison with compiled Sn isotopes of other hydrothermal deposits, kinetic disequilibrium fractionation is proposed as the main control on cassiterite Sn isotopes fractionation. A Rayleigh fractionation model generates fractionation factors of 1.00010–1.00025, consistent with fractionation factors predicted by first principles calculations (1.00013 to 1.00037). Thus, progressive precipitation of Sn-enriched minerals due to the change of physicochemical conditions during magmatic-hydrothermal processes will cause lighter Sn isotopic compositions in residual melt/fluid. This study highlights that cassiterite chemical and Sn stable isotopes are novel indicators to magmatic-hydrothermal processes.

Fingerprinting crustal anatexis with apatite trace element, halogen, and Sr isotope data

The geochemistry of apatite is a valuable tool for granite petrogenetic study. Here we explore the capability of apatite for fingerprinting anatectic reactions during crustal melting. We conducted a detailed petrographic, trace element, volatile, and Sr isotopic study of the apatites from four groups of leucosomes and leucogranites that formed by amphibole dehydration melting (group I), hydration melting (group II), muscovite dehydration melting (group III), and feldspar accumulation (Group IV) from the central Himalayan orogen. The coexistence of primary CO2-rich fluid and multiphase solid inclusions in apatite indicates fluid–melt immiscibility and suggests that C–O–H fluids were present during hydration melting. We observe marked differences in major and trace element, as well as halogen (F and Cl) contents in apatite from different groups, corresponding to different melting reactions. Apatite REE, Y, Mn, F, and F/Cl exhibit a decrease, whereas Sr/Y and Cl increase, from muscovite dehydration melting to hydration melting, and to amphibole dehydration melting. Amphibole dehydration melting results in similar CaO, Sr, and Eu/Eu* in apatite to hydration melting, but the latter leads to lower (La/Yb)N in apatite. These geochemical differences in apatite can be explained by different minerals participating in the melting reactions and varying melt polymerization resulting from the different melting reactions. The degree of melt polymerization decreases in the sequence from muscovite dehydration melting to hydration melting, and to amphibole dehydration melting. A higher degree of melt polymerization results in higher values for trace element partition coefficients between apatite and melt, and therefore the enhanced incorporation of REE, Y and Mn in apatite. Higher Sr and Eu/Eu* in apatite reflect the consumption of a larger amount of plagioclase in the melting reaction. The F and Cl contents in partial melts were calculated based on apatite composition, which exhibit an increasing trend from hydration melting to muscovite hydration melting, and to amphibole hydration melting. Such a trend can be explained by different proportions of hydrous minerals (muscovite and amphibole) participating in the melting reactions, with amphibole responsible for the high Cl content in melt and apatite. In addition, the apatite Sr isotopic compositions record the Sr isotopic disequilibrium during partial melting and exhibit distinct evolutional trends resulting from different anatectic reactions. Muscovite dehydration melting forms melt with higher 87Sr/86Sr than the restite due to radiogenic Sr released by muscovite. Apatite therefore records progressively decreasing 87Sr/86Sr during melt evolution before the isotopic homogenization between the partial melt and the restite. In contrast, apatites crystallized from the melt of hydration melting show an evolutional trend of increasing 87Sr/86Sr. In summary, the elemental and isotopic compositions of apatite can be related to different types of melting reactions, and can therefore be used as an indicator of the mechanisms of melt formation during crustal anatexis. We demonstrate such an application through the case study of group IV apatite from feldspar accumulation, and also explore its utility in granite petrogenetic studies.

Lithospheric thinning beneath the Tengchong volcanic field, Southern China: Insight from Cenozoic calc-alkaline basalts

The Tengchong Cenozoic volcanic field lies in SE margin of the Tibetan Plateau. The basalts of the Tengchong field exhibit evident spatial-temporal variations, but consensus on their meaning has not been reached yet. In this study, we collected basalts from western, central and eastern areas in the Tengchong volcanic field and measured the whole-rock and olivine major and trace elements of basalts. Tengchong basalts exhibit remarkable chemical and isotopic diversity, showing a strong correlation with eruption locations and ages. Specifically, basalts in the western and eastern areas (formed at 7.2–2.8 Ma) are characterized by high 87Sr/86Sr and low 3He/4He ratios, while those in the central area (formed at 0.6–0.02 Ma) feature low 87Sr/86Sr and high 3He/4He ratios. Based on the temperature- and pressure-dependent elemental partition coefficients, this phenomenon is interpreted as mainly caused by the difference in lithospheric thickness among these areas. On the one hand, the estimated primary magmas in the eastern and western areas show higher SiO2, Na2O, (La/Sm)N, Hf/Lu and Ba/Zr ratios than those in the central area. On the other hand, the Ni contents in olivine phenocrysts are higher in the western and eastern areas than in the central area. As different amounts of extension result in different degrees of decompression of the asthenosphere, finally influencing the compositional variation of magmas, these results indicate that the lithosphere in the eastern and western areas is thicker than that in the central area. In addition, basalts erupted in the eastern and western areas are older than those in the central area, suggesting lithospheric thinning. We propose that lithospheric extension due to slab rollback may have caused lithospheric thinning. In addition, according to the different deformation modes of the crust and lithospheric mantle, our study supports mantle-crust decoupling south of ∼26°N in SE margin of the Tibetan Plateau.

Multivariate statistical analysis of trace elements in apatite: Discrimination of apatite with different origins

Partial least squares-discriminant analysis (PLS-DA) was used to construct the link between trace element contents of magmatic or hydrothermal apatite and deposit and rock types. Apatite with different origins is discriminated by characteristic chemical composition. In average, ore magmatic apatite has higher light REE and Th, and lower Sr than barren rock apatite, independent of deposit types. Hydrothermal apatite has lower La, Ce, Pr, and Nd contents than magmatic apatite, probably because fluids prefer migrating light rare earth element out of apatite. Hydrothermal apatite from iron oxide copper gold (IOCG) and iron oxide apatite (IOA) deposits is discriminated by high Mn and Sr relative to magmatic apatite, probably because these elements are fluid mobile. Barren magmatic apatite from granitoid-related deposits is well separated from ore magmatic apatite by higher Sr, Eu, Gd, Tb, Dy, and lower Mn contents, which are likely related to the relatively low degree of differentiation and high aluminum saturation index of parental magma.Magmatic apatite from IOA deposits is discriminated by relatively high Nd, Sm, Gd, Tb, Dy, and low Mn and U contents, which are possibly related to the crystallization of Mn-compatible magnetite microlites and peraluminous magmas. Magmatic apatite from granitoid-related W deposits is relatively rich in Y, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. The relative enrichment of Sr in magmatic apatite from granitoid-related Cu-Pb-Zn and Pb-Zn deposits is likely due to less fractionation of Sr-compatible plagioclase. Melt of sediment component accounts for high Mn and Th in magmatic apatite from granitoid-related Mo deposits. Magmatic apatite from porphyry deposits is discriminated by relatively high V, Sr, and Eu contents. Magmatic apatite from porphyry Mo deposits has relatively high Pr, Nd, and Sm and low Sr contents compared to other types of porphyry deposits due to the more evolved magma. Hydrothermal apatite from IOA deposits is discriminated by high V and Sr, whereas those from IOCG deposits have high Sm, Eu, Gd, Tb, and U contents, because the lower temperature of IOCG cause precipitation of REE in Cl-rich fluid. Relatively low Gd and Tb in hydrothermal apatite from skarn deposits are possibly due to the crystallization of amphibole.Apatite in carbonatite has high contents of trace elements possibly because high contents of Ca and P in melts cause high apatite-melt partition coefficients of trace elements. Apatite from sedimentary and metamorphic rocks is discriminated by relative enrichment of Sr and Eu. Compared to igneous rocks, apatite from sedimentary rocks has low REE contents, reflecting low REE budget in surface waters. Breakdown of some minerals to release and remobilize REE and U during metamorphism can interpret high heavy REE and U contents in apatite from high-grade metamorphic rocks relative to those from low- and medium-grade metamorphic rocks. The ability to discriminate apatite from different types of deposits and rocks indicates the application potential of apatite chemistry in mineral exploration. A flowchart was proposed to identify apatite with unknown origins.

Experimental investigation of trace element partitioning between amphibole and alkali basaltic melt: Toward a more general partitioning model with implications for amphibole fractionation at deep crustal levels

Abstract Time-series experiments were carried out in a piston-cylinder apparatus at 0.8 GPa and 1030–1080 °C using a hydrous K-basalt melt as the starting material to determine the element partition coefficients between amphibole and silicate glass. Major, minor, and trace element compositions of amphibole and glass were determined with a combination of electron microprobe and laser ablation inductively coupled plasma mass spectrometry. Results show that the main mineral phase is calcic amphibole, and the coexisting glass compositions range from basaltic trachyandesite to andesite. We estimated the ideal radius, the maximum partition coefficient and the apparent Young’s modulus of the A, M1-M2-M3, and M4-M4′ sites of amphibole. The influence of melt and amphibole composition, temperature, and pressure on the partition coefficients between amphiboles and glasses has also been investigated by comparing our data with a literature data set spanning a wide range of pressures (0.6–2.5 GPa), temperatures (780–1100 °C), and compositions (from basanite to rhyolite). Finally, we modeled a deep fractional crystallization process using the amphibole-melt partition coefficients determined in this study, observing that significant amounts of amphibole crystallization (>30 wt%) well reproduce the composition of an andesitic melt similar to that of the calc-alkaline volcanic products found in Parete and Castelvolturno boreholes (NW of Campi Flegrei, Italy).

Melting relations of Ca–Mg carbonates and trace element signature of carbonate melts up to 9 GPa – a proxy for melting of carbonated mantle lithologies

Abstract. The most profound consequences of the presence of Ca–Mg carbonates (CaCO3–MgCO3) in the Earth's upper mantle may be to lower the melting temperatures of the mantle and control the melt composition. Low-degree partial melting of a carbonate-bearing mantle produces CO2-rich, silica-poor melts compositionally imposed by the melting relations of carbonates. Thus, understanding the melting relations in the CaCO3–MgCO3 system facilitates the interpretation of natural carbonate-bearing silicate systems. We report the melting relations of the CaCO3–MgCO3 system and the partition coefficient of trace elements between carbonates and carbonate melt from experiments at high pressure (6 and 9 GPa) and temperature (1300–1800 ∘C) using a rocking multi-anvil press. In the absence of water, Ca–Mg carbonates are stable along geothermal gradients typical of subducting slabs. Ca–Mg carbonates (∼ Mg0.1–0.9Ca0.9–0.1CO3) partially melt beneath mid-ocean ridges and in plume settings. Ca–Mg carbonates melt incongruently, forming periclase crystals and carbonate melt between 4 and 9 GPa. Furthermore, we show that the rare earth element (REE) signature of Group-I kimberlites, namely strong REE fractionation and depletion of heavy REE relative to the primitive mantle, is resembled by carbonate melt in equilibrium with Ca-bearing magnesite and periclase at 6 and 9 GPa. This suggests that the dolomite–magnesite join of the CaCO3–MgCO3 system might be useful to approximate the REE signature of carbonate-rich melts parental to kimberlites.

Spinel Harzburgite-Derived Silicate Melts Forming Sulfide-Bearing Orthopyroxenite in the Lithosphere. Part 1: Partition Coefficients and Volatile Evolution Accompanying Fluid- and Redox-Induced Sulfide Formation

We report abundances of major trace and volatile elements in an orthopyroxenite vein cutting a sub-arc, mantle-derived, spinel harzburgite xenolith from Kamchatka. The orthopyroxenite contains abundant sulfides and is characterized by the presence of glass (formerly melt) both interstitially and as inclusions in minerals, comparable with similar veins from the West Bismarck arc. The glass formed by quenching of residual melts following crystallization of abundant orthopyroxene, amphibole, and minor olivine and spinel. The interstitial glass has a low-Ti, high-Mg# andesite composition, with a wide range of H2O and S contents but more limited F and Cl variations. We calculate trace element partition coefficients using mineral and glass data, including those for halogens in amphibole, which agree with experimental results from the literature. Despite having a similar, high-Mg# andesite composition, the orthopyroxene-hosted glass inclusions usually contain much more H2O and S than the interstitial glass (4–7 wt% and ∼2,600 ppm, respectively). The initial vein-forming melts were oxidized, recording oxygen fugacity conditions up to ∼1.5 log units above the fayalite–magnetite–quartz oxygen buffer. They intruded the sub-arc mantle lithosphere at ≥1,300°C, where they partially crystallized to form high-Mg# andesitic derivative melts at ca. 1,050–1,100°C. Comparison with literature data on glass-free orthopyroxenite veins from Kamchatka and the glass-bearing ones from West Bismarck reveals fundamental similarities indicating common parental melts, which were originally produced by low-degree melting (≤5%) of spinel harzburgite at ≥1,360°C and ≤1.5 GPa. This harzburgite source likely contained ≤0.05 wt% H2O and a few ppm of halogens. Volatile evolution inferred from glass compositions shows that (i) redox exchange between S6+ in the original melt and Fe2+ in the host mantle minerals, together with (ii) the formation of an S-bearing, (H2O, Cl)-rich hydrothermal fluid from the original melt, provides the conditions for the formation of abundant sulfides in the orthopyroxenites during cooling. During this process, up to 85% of the original melt S content (∼2,600 ppm) is locally precipitated as magmatic and hydrothermal sulfides. As such, melts derived from spinel harzburgite sources can concentrate chalcophile and highly siderophile metals in orthopyroxenite dykes and sills in the lithosphere.

Pressure-induced structural evolution in boron-bearing model rhyolitic glasses under compression: Implications for boron isotope compositions and properties of deep melts in Earth’s interior

The pressure-induced structural evolutions of boron-bearing model rhyolitic melts under high pressures enable to infer the detailed geochemical processes (melting and fluid-rock-melt interactions) occurring in Earth interiors and to control the melt properties (viscosity and the boron isotope composition, δ11B) of complex magmatic melts, providing insights into the boron cycle toward the deeper part of the upper mantle (∼10 GPa). Despite the importance, the structures of multicomponent boron-bearing silicate melts above 3 GPa are currently unavailable. Here, we explore the structures, particularly, coordination transformation of constituent elements in boron-bearing nepheline and albite glasses – a model rhyolitic melts - upon compression to a depth of ∼270 km (∼9.2 GPa) in the mantle using multi-nuclear solid-state nuclear magnetic resonance (NMR) spectroscopy. The results showed that the conversion of [3]B into [4]B is prominent upon compression up to 6 GPa. In contrast, the formation of [5,6]Al is accompanied by the formation of oxygen tricluster above 6 GPa, where all the nonbridging oxygens are consumed. We quantify how the melt composition affects tendency to form highly coordinated B, Al, and Si upon compression. Particularly, the increase in the [4]B population tends to be larger for the glasses with low Si content as pressure increases to 9.2 GPa. We reveal the relationship between such structural adaptations of the compressed melts at high pressure and the melt properties, including viscosity and element partition coefficient in boron-bearing melts. The current NMR results also unravel the structural origins of 11B/10B ratios in rhyolitic melts at high pressure. Considering a preferential partitioning of 10B to [4]B, an increase in [4]B population in the melts leads to an pressure-induced enrichment of 10B. As the increase in Si/B ratio in the melts tends to decrease the pressure-induced increase in [4]B fraction, the contribution of boron coordination transformation on the 11B/10B ratios in silicate melt would be somewhat minor in deep mantle melts with increasing Si content. The detailed boron environments in rhyolitic melts at high pressure yield useful constraints for the isotope composition (11B/10B) of dense mantle melts, thereby enabling quantification of deep boron cycle.

Element Partitioning and Li‐O Isotope Fractionation Between Silicate Minerals and Crustal‐Derived Carbonatites and Their Implications

AbstractIn order to investigate element partitioning and Li‐O isotope fractionation between silicate minerals and carbonatite melts at variable levels from mantle to crust, we document elemental and Li‐O isotopic data for major minerals from crust‐derived carbonatites at Eppawala, Sri Lanka. Partition coefficients (D) of elements between olivine or clinopyroxene and carbonatite melts are consequently estimated. The estimated D values indicate that Li, Zn, Co, Cr, Mn, and Ni behave compatibly in olivine, while P and Sc are slightly compatible, and V and Al are mildly incompatible. Partition coefficients of elements between clinopyroxene and carbonatite melts are defined here, including highly compatible Li, Sc, Ti, V, Al, and Na, moderately compatible Zn, Co, Cr, and Ga, and incompatible Mn, Ni, P, and Cu. They are systematically higher than literature values obtained from mantle conditions, but their relative compatibilities at different systems are consistent. This indicates that element partitioning between silicates and carbonatite melts is highly temperature‐ and pressure‐dependent and can be used to evaluate geochemical proxies of carbonatite metasomatism, and evolution and mineralization of carbonatite melts. Profile analyses on olivine grains reveal that Fe‐loving elements in olivine could well preserve features of crystal growth and modal metasomatic interaction, while Li and O isotope fractionations are strongly controlled by element diffusion and Li isotopes are robust indicators of cryptic metasomatic interaction.

Improved volume variable cluster model method for crystal-lattice optimization: effect on isotope fractionation factor

The isotopic fractionation factor and element partition coefficient can be calculated only after the geometric optimization of the molecular clusters is completed. Optimization directly affects the accuracy of some parameters, such as the average bond length, molecular volume, harmonic vibrational frequency, and other thermodynamic parameters. Here, we used the improved volume variable cluster model (VVCM) method to optimize the molecular clusters of a typical oxide, quartz. We documented the average bond length and relative volume change. Finally, we extracted the harmonic vibrational frequencies and calculated the equilibrium fractionation factor of the silicon and oxygen isotopes. Given its performance in geometrical optimization and isotope fractionation factor calculation, we further applied the improved VVCM method to calculate isotope equilibrium fractionation factors of Cd and Zn between the hydroxide (Zn–Al layered double hydroxide), carbonate (cadmium-containing calcite) and their aqueous solutions under superficial conditions. We summarized a detailed procedure and used it to re-evaluate published theoretical results for cadmium-containing hydroxyapatite, emphasizing the relative volume change for all clusters and confirming the optimal point charge arrangement (PCA). The results showed that the average bond length and isotope fractionation factor are consistent with those published in previous studies, and the relative volume changes are considerably lower than the results calculated using the periodic boundary method. Specifically, the average Si–O bond length of quartz was 1.63 Å, and the relative volume change of quartz centered on silicon atoms was − 0.39%. The average Zn–O bond length in the Zn–Al-layered double hydroxide was 2.10 Å, with a relative volume change of 1.96%. Cadmium-containing calcite had an average Cd–O bond length of 2.28 Å, with a relative volume change of 0.45%. At 298 K, the equilibrium fractionation factors between quartz, Zn–Al-layered double hydroxide, cadmium-containing calcite, and their corresponding aqueous solutions were Delta ^{30/28} {text{Si}}_{{{text{Qtz-H}}_{4} {text{SiO}}_{4} }} = 2.20{permil} , Delta^{18/16} {text{O}}_{ {text{Qtz}}{-} ( {text{H}}_{2} {text{O}} )_{text{n}}} = 36.05{permil}, Delta^{66/64} {text{Zn}}_{ {text{Zn}} {-} {text{Al LDH-Zn}} ( {text{H}}_{2} {text{O}} )_{text{n}}^{2+}} = 1.12{permil} and Delta^{114/110} {text{Cd}}_{ {text{(Cd--Cal)-Cd}} ( {text{H}}_{2} {text{O}} )_ {text{n}}^{2 +} } = - 0.26{permil} respectively. These results strongly support the reliability of the improved VVCM method for geometric optimization of molecular clusters.

Trace element partitioning during incipient melting of phlogopite-peridotite in the spinel and garnet stability fields

Potassium-rich magmatism represents subordinate magma volumes worldwide but has been observed in many geodynamic settings. Most potassic magmas are thought to derive from very-low degrees of melting of metasomatized mantle lithologies. We performed piston-cylinder experiments to determine trace element partition coefficients between incipient potassic silicate melts and phlogopite ± pargasite peridotite in the spinel (1 GPa) and garnet stability fields (3 GPa). Most of the rare Earth elements (REEs) are compatible in pargasite but incompatible in phlogopite. Although garnet remains the mineral phase most efficiently fractionating heavy from light REEs (DYbgrt/melt/DLagrt/melt > 750), orthopyroxene can also significantly fractionate REEs, e.g., achieving DYbopx/melt/DLaopx/melt > 100 at 3 GPa. Mineral-liquid partition coefficients vary by about one order of magnitude between incipient melts derived from the spinel and garnet stability fields. We thus show that trace element partitioning at the onset of melting is controlled more by pressure (through melt composition) than by the extent of melting. With increasing pressure, Rb and Ba exhibit different behaviors in phlogopite, with DBaphl/melt > DRbphl/meltat 1 GPa and the opposite at 3 GPa. At 1 GPa, a decrease of melt polymerization (lower NBO/T) with increasing melt fraction translates into a significant decrease of most phlogopite partition coefficients. Finally, we show that resolvable inter-element fractionations do occur when phlogopite- (and pargasite)-bearing peridotite are melted, indicating that trace element ratios are not always faithfully representative of that of their sources but bear the imprint of varied P–T conditions of melting and contrasted pre-metasomatic histories. This self-consistent partition coefficient dataset thus gives a new scope to understand the complex petrogenesis of K-rich magmas in orogenic settings.

Partitioning of Ti, Al, P, and Cr between olivine and a tholeiitic basaltic melt: Insights on olivine zoning patterns and cation substitution reactions under variable cooling rate conditions

The mechanism governing the kinetic growth of olivine in dynamic volcanic settings has been the subject of considerable attention in recent years. Under variable cooling rate (CR) and undercooling (−ΔT) regimes, the textual maturation of olivine proceeds from skeletal/dendritic crystals to polyhedral morphologies by infilling of the crystal framework. Owing to the establishment of a diffusion-controlled growth regime, a sharp diffusive boundary layer develops in the melt next to the advancing olivine surface. In this context, we have quantified the apparent partitioning of Ti, Al, P, and Cr between olivine and a Hawaiian tholeiitic basaltic melt at P = 1 atm, fO2 = QFM-2 buffer, and CR = 4, 20, and 60 °C/h over a constant -ΔT = 85 °C. Differences in charge and/or size between the substituent minor cations and the major species in the olivine crystallographic site dominate the energetics of homovalent and heterovalent cation substitutions. While the entry of Ti in the olivine lattice site accounts for the simple exchange [TSi4+] ↔ [TTi4+], more complex charge-balancing coupled-substitution mechanisms have been determined for the incorporation of Al, P, and Cr, i.e., [MMg2+, TSi4+] ↔ [MAl3+, TAl3+], [2 TSi4+] ↔ [TP5+, TAl3+], and [MMg2+, TSi4+] ↔ [MCr3+, TAl3+], respectively. In order to maintain charge balance, the disequilibrium uptake of minor cations in rapidly growing crystals is controlled by the same substitution mechanisms observed under equilibrium crystallization. This finding is consistent with the achievement of a local interface equilibrium at the olivine-melt interface independently of the diffusive boundary in the melt. A statistical approach based on multivariate analysis of olivine/melt compositional parameters confirms that the control of melt structure on the partitioning of Ti, Al, P, and Cr is almost entirely embodied in the olivine structure and chemistry via charge compensation reactions. Therefore, the magnitude of minor element partition coefficients is weakly dependent on diffusion kinetics in the melt but rather strongly governed by olivine zoning patterns resulting from fast crystal growth rates.

Trace element partitioning between anhydrite, sulfate melt, and silicate melt

AbstractAnhydrite has become increasingly recognized as a primary igneous phase since its discovery in pumices from the 1982 eruption of El Chichón, Mexico. Recent work has provided evidence that immiscible sulfate melts may also be present in high-temperature, sulfur-rich, arc magmas. In this study we present partition coefficients for 37 trace elements between anhydrite, sulfate melt and silicate melt based on experiments at 0.2–1 GPa, 800–1200 °C, and fO2 > NNO+2.5.Sulfate melt–silicate melt partition coefficients are shown to vary consistently with ionic potential (the ratio of nominal charge to ionic radius, Z/r) and show peaks in compatibility close to the ionic potential of Ca and S. Partition coefficients for many elements, particularly REE, are more than an order of magnitude lower than previously published data, likely related to differences in silicate melt composition between the studies. Several highly charged cations, including V, W, and Mo are somewhat compatible in sulfate melt but are strongly incompatible in anhydrite. Their concentrations in quench material from natural samples may help to fingerprint the original presence of sulfate melt.Partition coefficients for 2+ and 3+ cations between anhydrite and silicate melt vary primarily as a function of the calcium partition coefficients (DCaAnh−Sil) and can be described in terms of exchange reactions involving the Ca2+ site in anhydrite. Trivalent cations are dominantly charge-balanced by Na1+. Most data are well fit using a simple lattice-strain model, although some features of the partitioning data, including DLaAnh−Sil>DCeAnh−Sil, suggest the occurrence of two distinct anhydrite Ca-sites with slightly different optimum radii at the experimental conditions.The ratio DSrAnh−Sil>DCaAnh−Sil is shown to be relatively insensitive to silicate melt composition and should vary from 0.63–0.53 between 1200–800 °C, based on a simple, “one-site” lattice strain model. Comparison to DSrAnh−Sil and DCaAnh−Sil calculated for natural anhydrite suggests that in most cases, including the S-rich eruptions of Pinatubo and El Chichón, the composition of anhydrite is consistent with early crystallization of anhydrite close to the liquidus of silicate melt with a composition approximately that of the bulk erupted material. This illustrates how anhydrite (and perhaps sulfate melt) provides a mechanism to transport large quantities of sulfur from significant depth to the eruptive environment.

Effect of Solidifying Structure on Centerline Segregation of S50C Steel Produced by Compact Strip Production

Medium-high carbon steels having a high quality are widely used in China. It is advantageous to produce high value-added hot-rolled plates with the crystal refined and chemical composition homogenized in the casting slabs. However, element segregation occurs easily during high-medium carbon steels’ production. Generally, the centerline segregation is improved by enlarging the equiaxed zone with low-superheat casting and electromagnetic stirring (EMS). Studies were conducted on centerline segregation of S50C steel slabs with a thickness of 52 mm produced by the compact strip production (CSP) process in China without EMS equipped. By sampling along the width at different position, the secondary dendrite arm spacing (SDAS) was measured after etching and picture processing, based on which the cooling rate was calculated. It was found that the cooling rate increased from the center to the surfaces of the slabs ranging in 1~20 K/s, 10 times faster than that of a conventional process. The faster cooling rate led to a refined solidifying structure and columnar dendrite through the center of the slabs. The SDAS tended to increase from surfaces to the center, ranging only 32~120 μm smaller than that of a conventional process in 100~300 μm, indicating a finer solidifying structure by the CSP process. Results by EPMA indicated that elements C, Si, and Mn distribute in dispersed spots, increasing towards the center, and the centerline segregation changed in a narrow range: for C mainly in 1.0~1.1, Si in 0.98~1.08, Mn in 0.96~1.02, respectively, meaning a more chemical homogenization than that of thick slabs. Elements’ segregation originated from solute redistribution between solid and liquid. According to thermodynamic calculation, δ region of S50C is so narrow that the solute redistribution mainly occurred between γ-Fe and liquid during solidification. As the equilibrium partition coefficient of element C was the smallest, it was easy for C to be rejected to the residual liquid in the inter-dendritic space, leading to obvious segregation, relatively. Besides, as a result of high-cooling intensity, the solidifying structure became so fine that the Fourier number increased and the volume of the residual liquid decreased, making centerline segregation alleviated effectively both in volume and degree. Although bulging was observed during the industrial experiment, the centerline segregation was still inhibited obviously as the refining solidifying structure with permeability ranged only in 0.1~2.3 μm2 from the surfaces to centerline, which showed a good resistance on the residual flow towards the centerline.

Sectoral and growth rate control on elemental uptake by individual calcite crystals

Heterogeneous distribution of trace elements (impurities) within individual calcite crystals is a phenomenon commonly observed in natural and laboratory systems. Changes in thermodynamic intensive parameters (mostly chemical potential and temperature) cannot always explain the inhomogeneous impurity patterns in calcite crystals and it has been suggested that growth rate and crystallographic orientation may exert strong effects on elemental incorporation into calcite. In addition, there are a number of experimental studies on micro-scale element (E) distribution between non-equivalent pairs of calcite vicinal faces (known as sectoral zoning); however, the variability of partition coefficients (e.g., KE = (E/Ca)calcite/(E/Ca)fluid) within individual crystals remains undetermined.In this study, we have extended the work on elemental distribution between crystal sectors to evaluation of partition coefficients of trace and minor elements (Li, B, Mg, and Sr) in calcite crystal faces (10–14) and (01−12), whose growth rates were assessed. Growth entrapment model (GEM) and lattice strain theory were applied to explain KE heterogeneity by varying near-surface diffusivity of Mg and Sr and by varying surface enrichment factor for Li, B, Mg, and Sr. Decoupling of sectoral and growth rate effects reveals that sectoral zoning plays a key role in elemental distribution. More specifically, KLi and KB vary by more than one order of magnitude and KMg varies by a factor of two within individual crystal faces. Strontium sectoral distribution is different from those of Li, B, and Mg and KSr varies by up to a factor of two. These behaviors likely reflect different mechanisms of incorporation of Li, B, Mg, and Sr into calcite.