Nb–Ta mineralization in Ti-oxide minerals from the Bagolyhegy Metarhyolite Formation (Bükk Mountains, NE Hungary)

The foliated low-grade metamorphic rocks of the Triassic Bagolyhegy Metarhyolite Formation, mainly of pyroclastic origin, host post-metamorphic quartz-albite veins containing abundant tourmaline and occasionally rutile/ilmenite. The study of the Ti-oxide-mineralized veins with SEM-EDX revealed an unusual mineral assemblage comprising fine-grained Nb–Ta-bearing oxides (columbite-tantalite series, fluorcalciomicrolite and other Nb–Ti–Y–Fe-REE-oxide minerals) intergrown with Nb-rich polymorphs of TiO2 (anatase, rutile), ilmenite and zircon enriched with hafnium. This high field strength elements (HFSE)-bearing paragenesis is unexpected in this lithology, and was not described from any formation in the Paleozoic-Mesozoic rock suite of the Bükk Mountains (NE Hungary) before. The host metavolcanics are significantly depleted in all HFSE compared to the typical concentrations in felsic volcanics and the mineralized quartz-albite veins have even lower Ti–Nb–Ta concentration than the host rock, so the mineralization does not mean any enrichment. From proximal outcrops of the Triassic Szentistvánhegy Metavolcanics, potassic metasomatized lenses with albite-quartz vein fillings containing rutile/ilmenite are known. We studied them for comparison, but they only contain REE mineralization (allanite-monazite-xenotime); the Nb–Ta-content of Ti-oxide minerals is undetectably low. LA-ICP-MS measurements for U–Pb dating of Hf-rich zircon of the Nb–Ta-rich mineral assemblage gave 71.5 ± 5.9 Ma as lower intercept age while dating of allanite of the REE mineralized quartz-albite veins gave 113 ± 11 Ma as lower intercept age. The REE-bearing vein fillings formed during a separate mineralization phase in the Early Cretaceous, while the Nb–Ta mineralization was formed by post-metamorphic alkaline fluids in the Late Cretaceous., controlled by fault zones and fractures.

Mantle source of tephritic porphyry in the Tarim Large Igneous Province constrained from Mg, Zn, Sr, and Nd isotope systematics: Implications for deep carbon cycling

The nature and source of magmatism associated with large igneous provinces (LIPs) remain disputed. Here we investigate the role of recycled materials that contributed to mantle heterogeneity in the Tarim Large Igneous Province (TLIP) in China through integrated Zn−Mg−Sr−Nd isotopes of a rare tephritic rock suite. The Sr−Nd isotopes [(87Sr/86Sr)i = 0.70368−0.70629; εNd(t) = −0.25−4.64] and δ26Mg values (−0.23‰ to −0.34‰) of the tephritic porphyries are consistent with a normal mantle origin. In contrast, the whole rock and pyroxene phenocrysts yield δ66Zn values of +0.28‰ to +0.46‰ and +0.30‰ to +0.39‰, which are slightly heavier than those of the terrestrial mantle (+0.16 ± 0.06‰) and mid-oceanic-ridge basalts (MORBs) (+0.27 ± 0.05‰). We exclude the possibility that the heavy Zn isotopes of the Wajilitag tephritic porphyries are caused by magmatic processes such as fractional crystallization and partial melting and correlate the isotopic features to the role of altered oceanic crust along with magnesite in the mantle source. The Wajilitag tephritic porphyry displays trace-element patterns similar to those of the melts from natural hornblendite, especially those of hornblendite + peridotite. Additionally, the geochemical characteristics such as enrichment in Nb and Ta, depletion in K, high TiO2, and constant Na2O/K2O ratios also suggest that the tephritic porphyries were derived from an amphibole-bearing source contributed by altered oceanic crust along with sedimentary carbonates. Our study provides insight into the contribution of subducted materials to the mantle heterogeneity beneath the TLIP and highlights the role of subduction in the deep carbon cycle and subducted slab-lithosphere-plume interaction in the generation of LIPs.

Jadeitite and Related Rocks in Serpentinite Mélanges from the Rio San Juan Complex, Dominican Republic: Evidence for Both Isochemical Replacement and Metasomatic Desilication of Igneous Protoliths with Fluid-Assisted Jadeite Growth

—This study presents an overview of the systematic petrography, mineralogy, and geochemistry of jadeitite and jadeite-rich rocks found as blocks in the serpentinite mélanges of the Rio San Juan Complex (RSJC) of the northern Dominican Republic. The RSJC is one of the remnants of the subduction/accretionary complex of the Great Caribbean Arc that once spanned the gap between North and South America, moved relatively eastward to its present position as the Lesser Antilles island arc, and left collisional fragments along the two continental margins. Our systematic collection of heterogeneous samples ranges from jadeitite s.str. (sensu stricto) with ≥90 vol.% jadeite to quartz-rich rocks with jadeite and lawsonite. Two suites of rock types can be recognized. In the matrix-quartz-free rock suite, albite is the principal vein-filling or interstitial phase. Quartz is present only as inclusions in the cores of some jadeite crystals. In the matrix-quartz-bearing rock suite, quartz is abundant and albite is relatively rare. The first-order question concerning jadeite-rich rocks is whether jadeite precipitated from a high-pressure aqueous fluid (“vein precipitation” or “P-type”) or whether the jadeite-rich rock formed through comprehensive metasomatic replacement of an igneous protolith (“R-type”). Some examples occur as discordant veins and are clearly P-type. For most, however, classification has been equivocal. The systematic data on the petrography and whole-rock chemistry of jadeite rocks from the RSJC presented in this paper leads to significant clarification. A major argument against R-type genesis is that the metasomatic mass transfer required to produce jadeitite and jadeite-rich rocks from any normal igneous protolith is prohibitively complex. Using whole-rock, major-element compositions, we show that many members of the matrix-quartz-bearing rock suite from the RSJC can be derived by isochemical HP/LT metamorphism of normal oceanic plagiogranites subducted together with oceanic crust. Isocon analysis shows, furthermore, that more jadeite-rich rock types and also members of the matrix-quartz-free suite can be derived from such plagiogranites primarily by straightforward desilication, a realistic scenario in a serpentine-rich environment. The quartz inclusions found in jadeite crystals of the matrix-quartz-free suite corroborate a genetic path in which the plagioclase in a plagiogranite protolith reacts to jadeite + quartz. Later desilication and the formation of albite in the Si-undersaturated rock matrix leave tell-tale quartz inclusions as relics in jadeite crystals.

Resolving changes in arc magma volatile budgets over Myr timescales leading up to porphyry Cu formation

<p>The crustal-scale magmatic systems of Andean-style arcs produce thick volcanic deposits and abundant plutons that are emplaced into the crust. They can also generate spatially- and temporally-restricted, economically-important porphyry Cu deposits. These deposits are formed at the magmatic-hydrothermal transition and require significant amounts of volatiles and metals to be concentrated in the sub-volcanic environment. Thus, understanding the magmatic and tectonic processes acting within an arc segment and their effect on the volatile budgets of crustal magmas could be essential for identifying the constraining factors controlling the potential of a magmatic system to produce a porphyry deposit.</p><p>In this study we examine the magmatic evolution of the Rio Blanco-Los Bronces district, ~30 km northeast of Santiago, Chile, which is host to the Earth’s largest resource of Cu. Eocene to Early Miocene volcanic rocks were intruded by the Miocene San Francisco Batholith that, in turn, partially hosts intrusions related to the Late Miocene to Early Pliocene Rio Blanco-Los Bronces porphyry deposit cluster. We apply a combination of whole-rock, apatite and zircon geochemistry and zircon geochronology to the intrusive rock suite of the district to provide temporally- constrained geochemical information over the entire duration of batholith assembly and ore formation.</p><p>U-Pb geochronology reveals incremental assembly of the San Francisco Batholith by individual magma batches over >14Myr (~18 – 4 Ma), with ore formation occurring in discrete pulses in the last 3 Myr before cessation of intrusive activity within the district. Progressive changes in the trace element chemistry indicate crustal thickening and deeper magma evolution within the arc segment as a result of the subduction of the Juan Fernandez ridge. A temporal shift to elevated SO<sub>3</sub> and Cl contents is recorded by zircon-hosted apatite inclusions from the intrusions with highest values occurring in porphyry intrusions directly associated with the ore forming events. These data suggest variable volatile budgets of magmas during zircon crystallisation and hint at crustal-scale controls on the porphyry ore-forming potential of an arc segment.</p><p> </p>

The Syenite–Carbonatite Complex of Ihouhaouene (Western Hoggar, Algeria): Interplay Between Alkaline Magma Differentiation and Hybridization of Cumulus Crystal Mushes

The 2 Ga-old Ihouhaouene alkaline complex (Western Hoggar, Algeria) is among the oldest known carbonatite occurrences on Earth. The carbonatites are calciocarbonatites hosted by syenites, the predominant rock type in the complex. Both rock types are characterized by medium-grained to pegmatitic textures and contain clinopyroxene, apatite, and wollastonite, associated with K-feldspar in syenites and a groundmass of calcite in carbonatites. The rock suite shows a continuous range of compositions from 57–65 wt.% SiO2 and 0.1–0.4 wt.% CO2 in red syenites to 52–58 wt.% SiO2 and 0.1–6.5 wt.% CO2 in white syenites, 20–35 wt.% SiO2 and 11–24 wt.% CO2 in Si-rich carbonatites (>10% silicate minerals), and <20 wt.% SiO2 and 24–36 wt.% CO2 in Si-poor carbonatites (<5% silicate minerals). Calculation of mineral equilibrium melts reveals that apatite and clinopyroxene are in disequilibrium with each other and were most likely crystallized from different parental magmas before being assembled in the studied rocks. They are subtle in the red syenites, whereas the white syenites and the Si-rich carbonatites bear evidence for parental magmas of highly contrasted compositions. Apatite was equilibrated with LREE-enriched (Ce/Lu = 1,690–6,182) carbonate melts, also characterized by elevated Nb/Ta ratio (>50), whereas clinopyroxene was precipitated from silicate liquids characterized by lower LREE/HREE (Ce/Lu = 49–234) and variable Nb/Ta ratios (Nb/Ta = 2–30). The Si-poor carbonatites resemble the Si-rich carbonatites and the white syenites with elevated REE contents in apatite equilibrium melts compared to clinopyroxene. However, apatite equilibrium melt in Si-poor carbonatite shows a majority of subchondritic values (Nb/Ta<10) and clinopyroxene has chondritic-to-superchondritic values (Nb/Ta = 15–50). Although paradoxical at first sight, this Nb-Ta signature may simply reflect the segregation of the carbonatite from highly evolved silicate melts characterized by extremely low Nb/Ta values. Altogether, our results suggest an evolutionary scheme whereby slow cooling of a silico-carbonated mantle melt resulted in the segregation of both cumulus minerals and immiscible silicate and carbonate melt fractions, resulting in the overall differentiation of the complex. This process was however counterbalanced by intermingling of partially crystallized melt fractions, which resulted in the formation of hybrid alkaline cumulates composed of disequilibrium cumulus phases and variable proportions of carbonate or K-feldspar.

Convective isolation of Hadean mantle reservoirs through Archean time

Although Earth has a convecting mantle, ancient mantle reservoirs that formed within the first 100 Ma of Earth’s history (Hadean Eon) appear to have been preserved through geologic time. Evidence for this is based on small anomalies of isotopes such as182W,142Nd, and129Xe that are decay products of short-lived nuclide systems. Studies of such short-lived isotopes have typically focused on geological units with a limited age range and therefore only provide snapshots of regional mantle heterogeneities. Here we present a dataset for short-lived182Hf−182W (half-life 9 Ma) in a comprehensive rock suite from the Pilbara Craton, Western Australia. The samples analyzed preserve a unique geological archive covering 800 Ma of Archean history. Pristine182W signatures that directly reflect the W isotopic composition of parental sources are only preserved in unaltered mafic samples with near canonical W/Th (0.07 to 0.26). Early Paleoarchean, mafic igneous rocks from the East Pilbara Terrane display a uniform pristine µ182W excess of 12.6 ± 1.4 ppm. Fromca. 3.3Ga onward, the pristine182W signatures progressively vanish and are only preserved in younger rocks of the craton that tap stabilized ancient lithosphere. Given that the anomalous182W signature must have formed byca. 4.5 Ga, the mantle domain that was tapped by magmatism in the Pilbara Craton must have been convectively isolated for nearly 1.2 Ga. This finding puts lower bounds on timescale estimates for localized convective homogenization in early Earth’s interior and on the widespread emergence of plate tectonics that are both important input parameters in many physical models.

A new statistical approach to the geochemical systematics of Italian alkaline igneous rocks

The ultra-alkaline rocks have exotic features that frustrated many attempts to group them in a single classification diagram. A consistent classification would be very useful to define a possible consanguinity, an argument that feed a living debate. This paper investigates the petrologic characteristics of the Cenozoic Italian ultra-alkaline rock-suite using -Rank Entropy Anentropy (RHA) and Principal Component Analysis (PCA)-. The RHA formula is the succession of component’s symbols arranged according to the diminishing of their elemental content in the analysis (whole rock composition). Other two parameters considered are an expression of the anentropy and entropy of the system. The PCA allows the definition of new latent variables based on geochemical compositions through linear combinations of the major oxides. Using both statistical methods was possible to create discrete groups of rock-types, associated by genetic relationship. The groups plotted in the Mg-Ca-Al ternary diagram depicts two main evolutionary arrays. We interpret the chemical variance in term of a general magmatic processes based on immiscibility and crystal fractionation. A comparison with similar association worldwide give a more general prospective to the magmato-tectonic assignment of these rocks, which is highly controversial in Italy.

Mineralogical and Chemical Characterization of Zr-REE-Nb Ores from Khalzan Buregtei (Mongolia)—Approaches to More Efficient Extraction of Rare Metals from Alkaline Granitoids

Alkaline rocks are worldwide observed as hosts for rare metal (Zr-REE-Nb) minerals. The classification of the ore bearing rock type is challenging due to the fact that textures and mineral assemblage are obscured by post-magmatic alteration. In addition, the alteration causes fine and intricate intergrowth of the ore minerals with associated gangue. Hence, intensive comminution is necessary to liberate the ore minerals, which is one parameter hampering the economical use of this deposit type. This study provides a quantitative mineralogical investigation of the ore bearing rock suite at Khalzan Buregtei as an example of rare metal deposits. R1-R2 multication parameters are shown to be highly appropriate as quantitative mineralogical indicators based on readily available major element datasets to visualize and quantify alteration types of the ore bearing rock suite. The ore minerals were found to be associated with a cluster-forming assemblage of post-magmatic phases. Automated mineralogy was applied to quantify the textural properties of the ore mineral clusters. This finding permits efficient pre-concentration of rare metal ore at coarser particle size fraction, requiring less energy consuming comminution.

NEW RESULTS OF POLYMETALLIC, PGE AND REE MINERALIZATION RESEARCH IN THE SUWAŁKI ANORTHOSITE MASSIF (NE POLAND)

Suwałki Anortosite Massif (SAM) occurs in the crystalline basement of NE Poland within 200 km of the magmatic, Mesoproterozoic AMCG (anorthosite–mangerite–charnockite–granite) rock suite terrane called the Mazury Complex. SAM was discovered as a result of the drilling research of the prominent negative magnetic and gravimetric anomalies. There is an extensive negative anomaly of both potential fields related to the anorthosite massif. Gravimetric anomaly is surrounded by the bands of positive anomalies caused by rocks with elevated densities, such as granitoids, monzondiorites and granodiorites. A negative magnetic anomaly is surrounded by the bands of positive anomalies with significant amplitudes, particularly strongly marked from the south, west and north. Positive magnetic anomalies are associated with the presence of rocks with proven strong magnetic susceptibility due to the content of ferrolites (ilmenite-magnetite rocks) with accompanying Fe-Cu-Ni-Co sulphide mineralization. Fe-Ti-(V) ore deposits in the SAM were discovered in the early 1960s, in the region of Krzemianka and Udryn, but also Jeleniewo and Jezioro Okrągłe, under a thick overburden of Phanerozoic sedimentary rocks within small positive magnetic anomalies. These deposits were documented in about 100 deep boreholes to a depth of 2300 m, and the resources in C1 + C2 category were estimated for about 1.5 billion tons of titanium-magnetite ores with vanadium, mainly in the Krzemianka and Udryn ore fields. The model age obtained by the Re-Os NTIMS method for Fe-Ti-V ores and sulphides from the Krzemianka and Jezioro Okrągłe ore deposits was 1559 ±37 Ma with an initial ratio of 187Os/188Os = 1.16 ±0.06. This age was recognized as the age of the entire Suwałki Massif. Despite many years of research, the deep structure and the form of the massif has not been fully recognized. At present, geophysical and geological 3D modelling of borehole data is carried out using the OasisMontaj (Geosoft) software package. The 3D model is generated in the GeoModeller 3D application (Intrepid Geophysics) in order to recognize the geological correctness and interpretation of magnetic-gravity anomalies of the whole massif and its cover.