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There is increasing evidence to suggest that high field strength elements (HFSE) could be mobile to some extent in hydrothermal fluid due to the influence of halogens (e.g., fluorine and chlorine). However, in natural hydrothermal (fluid) systems, \"coupled dissolution reprecipitation\" (CDR) reactions at fluid-mineral interfaces that have been emphasized in the past decade may play a key role in controlling the final textures and mineral assemblages. The influences of the CDR reactions in hydrothermal systems on HFSE enrichment or depletion at the mineral scale are enigmatic. In this study, we show that enrichment of Nb and Zr can occur in magnetite on the mineral scale formed by hydrothermal fluids at medium-to-lower temperature in a skarn system. Four stages of mineralization and alteration of magnetite have been identified in the Baishiya iron skarn deposit of the East Kunlun Mountains of China. Magnetite formed in stage 1 (S1) developed obvious oscillatory zonation, whereas that formed in stages 2 (S2) and 3 (S3) shows hydrothermal alteration and metasomatic textures, and that in stage 4 (S4) developed euhedral crystals with simple zoning. Systematic variations in the trace element compositions of different magnetite grains analyzed by EMPA and LA-ICP-MS suggest that the magnetite from S1 to S3 may have formed in a metasomatic process at relatively constant temperature, whereas the magnetite from S4 formed by re-equilibrium processes at lower temperature. The magnetite from each stage can be divided into light and dark domains based on backscattered electron images. The dark domains in the magnetite from S1 and S2 have higher Nb/Ta (8.52-27.00) and Zr/Hf (18.22-52.64) ratios and silicon contents than the light domains (0.55-5.66 and 2.54-16.43, respectively). Compared with other magnetite ores, the ores from S1 and S2 are depleted of V and Ni. This depletion may be induced by increased oxygen and co-crystallized sulfide. However, these variations are unlikely to be responsible for the enrichment of Nb and Zr in magnetite at equilibrium conditions. Conversely, the dark domains of the magnetite from S1 and S2 are porous, irregular, and/or oscillatory with quartz inclusions, indicating nonequilibrium conditions. These textural features could be attributed to the CDR reactions that are ubiquitous in skarn systems. The increased silicon concentrations in magnetite due to the CDR reactions could affect the lattice parameters of the magnetite structure, leading to an overall change in the volume of magnetite ores. The reduplicative processes of volume change, dissolution, and porosity formation within magnetite are further improved due to an increased oxygen fugacity and co-crystallized sulfide (e.g., decreased temperature or increased sulfur fugacity) at far-from-equilibrium or local equilibrium conditions, resulting in oscillatory magnetite dark domains of S1. Ripening of the transient porosity can trap nanoscale precipitates of columbite and zircon within pores of Si-magnetite, and this precipitation could be attributed to the co-crystallized phlogopite that would incorporate fluorine from the hydrothermal fluid, and subsequently decrease the solubility of Nb and Zr in the skarn system. This scenario highlights that Nb and Zr could be scavenged and enriched into in the reaction fronts (porosity) by controlling the reaction pathway at a local scale that does not reflect the overall fluid-rock interaction history of the mineral assemblage.

Indirect calculation of magma crystallization temperatures is an important subject for geologists to know the petrogenesis of igneous rocks. During magma evolution from generation to crystallization, several processes control the behavior of elements. In this research, we obtained two new methods for the thermometry of magma by using high field strength elements (HFSEs; Zr, Hf, Ce, Y, and Ti) abundances in igneous rocks. The first was T(K) = −15,993/(lnCZr + lnCHf − 21.668), where CZr and CHf are the bulk-rock Zr and Hf contents in ppm, and T is the temperature in Kelvin. This equation was specially formulated to address metaluminous to peraluminous rocks with M < 2 [(Na + K + 2Ca)/(Al × Si)] (cation ratio) and SiO2 > 63 wt.%. The second was T(K) = −20,914/(ln(CHf + CY + CCe) + (ln(CZr/TiO2) − 31.153). CHf, CY, and CCe, and CZr are Hf, Y, Ce, and Zr contents (ppm) in the whole rocks. The second equation is more suitable for peralkaline to alkaline rocks with M > 2 and a wide range of SiO2. Both equations are applicable for temperatures from 750 °C to 1400 °C. These two equations are simple and robust thermometry methods and predict similar values in the range of TZr thermometry, which has previously been suggested for magma crystallization temperature.

The La Pedriza pluton stands out as the most extensively fractionated granite (Rb lt; 629; Sr lt; 2 and Ba lt; 2 ppm) of the Spanish Central System Batholith. These granites show a strong enrichment in some rare metal contents (Nb = 44, Y = 136, Yb = 10.7, U = 17, Ta = 7, Sc = 15 ppm). The petrography and geochemistry (including Sr- Nd isotopes) reveal that the pluton is composed of at least four units. These are classified as I-type peraluminous leucogranites (A/CNK=1.03-1.17), P-poor (P2O5lt;0.2 wt%) and Na2O-rich (lt; 4.24 wt%) exhibiting differences in their HFSE and REE contents and εNd compositions. Moreover, the units of the La Pedriza granite display different trends of fractional crystallization. REE spectra of the two most fractionated units suggest the involvement of a fluorine-rich melt in the last stages favouring the crystallization of xenotime and niobotantalates. Intermediate meta-igneous granulite protoliths are proposed as source rocks. The most evolved units of the La Pedriza pluton show chemical features convergent to A-type granites; these are explained by extensive fractional crystallization of a P-poor, I-type granite magma.

Melt inclusion data from primitive arc basalts from Mexico and Kamchatka show clear positive correlations of \"fluid mobile element\"/H2O ratios with the Cl/H2O ratio, suggesting that the trace element content of subduction zone fluids is strongly enhanced by complexing with chloride. This effect is observed for large-ion lithophile (LILE) elements, (e.g., Rb and Sr), but also for the light rare earth elements (REE, e.g., La and Ce) as well as for U. The correlations of these elements with Cl/H2O cannot be explained by the addition of sediment melts or slab melts to the mantle source, since Cl has no effect on the solubility or partitioning of these elements in silicate melt systems. On the other hand, the observed relationship of trace element abundance with Cl is consistent with a large body of experimental data showing greatly enhanced partitioning into aqueous fluid upon addition of chloride. Accordingly, it appears that a dilute, Cl-bearing aqueous fluid is the main carrier of LILE, light REE, and U from the slab to the source of melting in arcs. Moreover, elevated Ce/H2O ratios clearly correlate with fluid salinity and therefore are not suitable as a \"slab geothermometer\". From a synopsis of experimental and melt inclusion data, it is suggested that the importance of sediment or slab melting in the generation of arc magmas is likely overestimated, while the effects of trace element scavenging from the mantle wedge may be underestimated. Moreover, establishing reliable data sets for the fluid/mineral partition coefficients of trace elements as a function of pressure, temperature, and salinity requires additional efforts, since most of the commonly used experimental strategies have severe drawbacks and potential pitfalls.

We present new experimentally determined trace element partition coefficients between spinel and silicate melt. The experiments were performed at atmospheric pressure and at temperatures between 1220 and 1450 °C. To study the effect of redox conditions on trace element partitioning, we performed experiments under different redox conditions, with f O 2 ranging from log −12 to log −0.7. The effect of different spinel compositions is also investigated. Our results show that spinel of all compositions readily incorporates the transition metals Ni, Co and Ga and the corresponding partition coefficients are >1. D Ni,Co,Ga are not significantly affected by changing melt composition, crystal composition or redox conditions. However, the multivalent trace elements V and Mo show a strong effect of redox conditions on their partitioning behavior with D V and D Mo highest at very reducing conditions and considerably lower at more oxidizing conditions. Partition coefficients for the high field strength elements Ti, Zr, Hf, Nb, and Ta and the elements Sc and Lu strongly depend on crystal composition, with D Ti and D Sc >1 for very Fe 3+ - or Cr-rich (and Al-poor) spinels, but one to two orders of magnitude lower in systems with Al-rich spinels. We present some examples on how our data may be used to reconstruct redox conditions of spinel formation. We also present some results on the partitioning of Pt and Rh between spinel and melt. D Rh depends strongly on redox conditions, while D Pt is not significantly affected.

Peralkaline granites and pegmatites are a prime repository of REE and HFSE, critical raw materials. Although it is accepted that magmatic processes are fundamental in concentrating these metals, the role of hydrothermal fluids in concentrating and fractionating these elements remains unclear. This paper investigates the global reproducibility of the magmatic-hydrothermal evolution of alkaline silica-saturated systems using alkali pyroxene and amphiboles from six alkaline complexes. These minerals contain significant amounts of REE and other HFSE, and pyroxene is stable throughout the magmatic and hydrothermal stages. Amphibole consists of mostly unzoned arfvedsonite, leakeite, and katophorite, while pyroxene is always aegirine. Two types of aegirine were defined. In all complexes, type-I aegirine is zoned; its core is enriched in Ca, REE, Zr, Hf, Sc and Sn, and the rims in Na, Fe3+ and contains secondary rare-metal bearing minerals and fluid inclusions. Type-II aegirine replaces amphibole and is oscillatory zoned. We interpret the amphiboles and REE-rich cores of type-I aegirine to have grown during the magmatic stage, whereas the rims of REE-poorer type-I and II aegirine are formed during the hydrothermal stage. During magmatic crystallization, REE intake into amphiboles and pyroxene as well as LREE-HREE fractionation were favored by their crystallographic properties and by competition among them and other minerals. During subsequent hydrothermal stages, REE and other HFSE were remobilized, locally reconcentrated and fractionated in mineral pseudomorphs and secondary pyroxene. These observations point out the importance of studying rock-forming minerals such as pyroxenes and amphiboles to unravel geological events controlled by common processes globally.

In natural corundum, a strong geochemical correlation is sometimes observed between Be and heavy high field strength elements (HHFSEs) such as Nb, Ta and W, and it has been hypothesized that trace elements are hosted in primary inclusions. However, no known mineral enriched in both Be and HHFSEs stable at these geological conditions can explain this correlation. To understand how Be and HHFSEs are distributed in natural corundum down to the atomic scale, two natural Be-bearing sapphire crystals from Afghanistan and Nigeria are studied using laser ablation inductively coupled plasma and time-of-flights secondary ion mass spectrometry, atom probe tomography and transmission electron microscopy. In addition to common trace elements such as Mg, Ti, and Fe, Be and W are detected in the metamorphic sapphire from Afghanistan, whereas Be, Nb and Ta are detected in the magmatic sapphire from Nigeria. Nanoclustering in both samples shows fractionation of Be and high field strength elements (including Ti) by atomic mass, suggesting a secondary process controlled by solid-state diffusion. The homogeneously distributed W and the secondary nano-precipitates bearing Nb and Ta indicates that HHFSEs can be incorporated into the corundum structure during crystallization, most likely through preferred adsorption on the growth surface. The strong correlation between Be and HHFSEs across the growth zones is probably due to Be being attracted by HHFSEs to partially balance the charge when incorporated into the corundum structure. The enrichment of high field strength elements by growth kinetics may result in supersaturated concentrations during crystallization, allowing them to precipitate out when the host corundum is heated above its formation temperature by basaltic magma. Comparison with previous transmission electron microscope studies suggests the same process for incorporating Be and HHFSEs also applies to other natural corundums from different localities.

Eudialyte-group minerals (EGM) attract global interest as potential resources for high-field-strength elements (e.g. Zr, Nb, Ta, and rare-earth elements), i.e. critical materials for modern technologies. They are particularly valued for their relative enrichment in the most critical lanthanides, i.e. Nd and heavy rare earth elements (Gd–Lu). However, rare earth element ( REE ) substitution mechanisms into the EGM structure are still poorly understood. Light and heavy REE may occupy different sites and there may be ordering and/or defect clustering in the structure. This study uses X-ray absorption spectroscopy to determine the structural state of REE in EGM from prospective eudialyte-bearing complexes. Yttrium K -edge and Nd L 3 -edge spectra were collected as proxies for heavy and light REE , respectively, and compared to natural and synthetic REE -bearing standards. Extended X-ray absorption fine structure data yield best fits for Y in six-fold coordination with Y–O distances of 2.24–2.32 Å, and a second coordination sphere comprising Fe, Na, Ca, Si and O at radial distances of 3.6–3.8 Å. These findings are consistent with dominant Y 3+ substitution for Ca 2+ on the octahedral M 1 site in all the samples studied, and exclude preferential substitution of Y 3+ onto the smaller octahedral Z site or the large low-symmetry N 4 site. Using lattice strain theory, we constructed relative partitioning models to predict site preferences of lanthanides we have not measured directly. The models predict that all REE are favoured on the Ca-dominant M 1 site and that preferential partitioning of heavy over light REE increases in EGM containing significant Mn in the M 1-octahedral rings (oneillite subgroup). Thus, the flat REE profiles that make EGM such attractive exploration targets are not due to preferential partitioning of light and heavy REE onto different sites. Instead, local ordering of Mn- and Ca-occupied M 1 sites may influence the capacity of EGM to accommodate heavy REE .

Titanite from various rocks of the Karkonosze granitoid pluton (South-Eastern Poland) was studied, in order to evaluate its precision in recording magma evolution processes. The rocks are of lamprophyric, dioritic, granodioritic and granitic composition, including hybrid structures such as microgranular magmatic enclaves and composite dykes. Based on textures, chemistry and Zr-in-titanite geothermometry, titanites can be divided into magmatic and post-magmatic populations. Late- to post-magmatic titanite is present in almost all rock types, especially in the most evolved ones (where magmatic titanite is absent) and can be characterized by low trace element and high Al and F contents. Magmatic titanite crystallized in temperatures between 610 and 870 °C, after apatite and relatively simultaneously with amphibole and zircon. Titanite from lamprophyre exhibits compositional features typical of titanites formed in mafic rocks: low Al and F, high Ti4+/(Al + Fe3+), LREE (light rare earth elemet)-enriched chondrite-normalized REE patterns, low Y/Zr, Nb/Zr, Lu/Hf, high (Ce + Nd)/Y, Th/U and Zr. Titanite from hybrid rocks inherited these characteristics, indicating major contribution of the mantle-derived magma especially during early stages of magmatic evolution. Titanite compositional variations, as well as a wide range of crystallization temperatures in hybrid granodiorites point to prolonged crystallization from distinct magma domains of variable mafic versus felsic melt proportions. The extent of compositional variations decreases through subsequent stages of magmatic evolution, and titanite with the least contribution of the mafic component is characterized by higher total REE, Al and F contents, lower Ti4+/(Al + Fe3+), (Ce + Nd)/Y and Th/U ratios, LREE-depleted chondrite-normalized REE patterns and higher Y/Zr, Nb/Zr and Lu/Hf ratios. Titanite composition from the intermediate and late stage hybrids bears signature of decreasing amount of the mafic melt and higher degree of its evolution, however, the exact distinction between the former and the latter is very limited.

Rare earth mineralization in the Bear Lodge alkaline complex (BLAC) is mainly associated with an anastomosing network of carbonatite dikes and veins, and their oxidized equivalents. Bear Lodge carbonatites are LREE-dominant, with some peripheral zones enriched in HREEs. We describe the unique chemistry and mineralogy one such peripheral zone, the Cole HFSE(+HREE) Occurrence (CHO), located ∼2 km from the main carbonatite intrusions. The CHO consists of anatase, xenotime-(Y), brockite, fluorite, zircon, and K-feldspar, and contains up to 44.88% TiO2, 3.12% Nb2O5, 6.52% Y2O3, 0.80% Dy2O3, 2.63% ThO2, 6.0% P2O5, and 3.73% F. Electron microprobe analyses of xenotime-(Y) overgrowths on zircon show that oscillatory zoning is a result of variable Th and Ca content. Cheralite-type substitution, whereby Th and Ca are incorporated at the expense of REEs, is predominant over the more commonly observed thorite-type substitution in xenotime-(Y). Th/Ca-rich domains are highly beam sensitive and accompanied by high-F concentrations and low-microprobe oxide totals, suggesting cheralite-type substitution is more easily accommodated in fluorinated and hydrated/hydroxylated xenotime-(Y). Analyses of xenotime-(Y) and brockite show evidence of VO43- substitution for PO43- with patches of an undefined Ca-Th-Y-Ln phosphovanadate solid-solution composition within brockite clusters. Fluorite from the CHO is HREE-enriched with an average Y/Ho ratio of 33.2, while other generations of fluorite throughout the BLAC are LREE-enriched with Y/Ho ratios of 58.6-102.5. HFSE(+HREE) mineralization occurs at the interface between alkaline silicate intrusions and the first outward occurrence of calcareous Paleozoic sedimentary rocks, which may be local sources of P, Ti, V, Zr, and Y. U-Pb zircon ages determined by LA-ICP-MS reveal two definitive 207Pb/206Pb populations at 2.60-2.75 and 1.83-1.88 Ga, consistent with derivation from adjacent sandstones and Archean granite. Therefore, Zr and Hf are concentrated by a physical process independent of the Ti/Nb-enriched fluid composition responsible for anatase crystallization. The CHO exemplifies the extreme fluid compositions possible after protracted LREE-rich crystal fractionation and subsequent fluid exsolution in carbonatite-fluid systems. We suggest that the anatase+xenotime-(Y)+brockite+fluorite assemblage precipitated from highly fractionated, low-temperature (<200 °C), F-rich fluids temporally related to carbonatite emplacement, but after significant fractionation of ancylite and Ca-REE fluorocarbonates. Low-temperature aqueous conditions are supported by the presence of fine-grained anatase as the sole Ti-oxide mineral, concentrically banded botryoidal fluorite textures, and presumed hydration of phosphate minerals. Fluid interaction with Ca-rich lithologies is known to initiate fluorite crystallization which may cause destabilization of (HREE, Ti, Nb)-fluoride complexes and precipitation of REE+Th phosphates and Nb-anatase, a model valuable to the exploration for economic concentrations of HREEs, Ti, and Nb.