Complex Zone Research Articles

The occurrence of cobaltite nanoparticles in pyrite from the De’erni deposit, NW China

Cobalt (Co) is a critical metal that occurs in many types of deposits, Co minerals and sulfide hosts are the main forms of Co occurrence. Pyrite is the most important cobalt-bearing mineral in the De’erni Cu-Zn-Co ultramafic-hosted volcanogenic massive sulfide deposits. However, the occurrence and enrichment of Co in pyrite remain unclear. In this study, a combination of LA-ICP-MS and STEM techniques was employed to conduct a detailed mineralogical investigation of pyrite in the De’erni deposit. The results revealed significant variations in cobalt content among pyrite samples from different mineral assemblages. Pyrite associated with magnetite (Mag), pyrrhotite (Po), chalcopyrite (Ccp), arsenopyrite (Apy), and bornite (Bn) (Py-Mag-Po-Ccp-Apy-Bn suite of mineral assemblages) exhibited the highest cobalt content, which ranged from 672.6 ppm to 2007 ppm. Cobalt occurs in two forms in the pyrite from the De’erni deposit: as cobaltite nanoparticles (NPs) and as a substitute for iron (Fe) in the pyrite lattice. The enrichment mechanism of cobalt in pyrite was explored at the deposit and mineral scales. The results indicate that a decrease in ore-forming fluid temperature and an increase in cobalt content may be significant factors contributing to cobalt enrichment at the deposit scale. Lattice defects may play a crucial role in cobalt enrichment within the pyrite lattice. Furthermore, the discovery of cobaltite NPs in pyrite could provide new insights for explaining the complex zonation of the cobalt element in pyrite.

Ages and geochemistry of garnet reveal multi-types of iron-copper mineralization in the Eastern Tianshan, NW China

The Aqishan-Yamansu Fe-Cu-Au metallogenic belt in the Eastern Tianshan, NW China, hosts numerous Fe and Fe-Cu deposits that may have different genetic models, such as volcanic-hosted and skarn/IOCG types. These variations in genetic models are attributed to whether the mineralization is associated with hydrothermal activity related to volcanic or intrusive rocks. This study primarily focuses on garnets formed during the early skarn alteration in the Shuanglong Fe-Cu and Shaquanzi Fe deposits within this belt. Garnets from the Shuanglong deposit can be divided into two types and exhibit general homogeneity, with SL-Grt1 being Fe-rich and subsequently replaced by the Fe-poor SL-Grt2. Garnets from the Shaquanzi deposit display complex zonation patterns, SQZ-Grt1 show core–oscillatory zoned rim and SQZ-Grt2 show core–mantle–oscillatory zoned rim. Laser-ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) dating of SL-Grt1 and SL-Grt2 produced lower intercept 206Pb/238U ages ranging from 318.0 ± 6.4 Ma to 303.7 ± 16.4 Ma, coinciding with the multi-stage granite occurrence. In contrast, SQZ-Grt1 and SQZ-Grt2 yielded ages between 328.0 ± 2.6 Ma and 320.4 ± 1.7 Ma, corresponding to the timing of the hosted rhyolite. SL-Grt1 show light rare earth element (LREE) enrichment, and low concentrations of high field strength elements (HFSE), such as V and Zr, and appears to have formed rapidly within an open system. Conversely, SL-Grt2 is characterized by heavy rare earth element (HREE) enrichment and elevated HFSE contents, which could be formed slowly in a closed system. The variable composition in the SQZ-Grt1 and SQZ-Grt2 record cyclical changes in fluid kinetics (vigorous fluid flow vs. fluid stagnation). The cyclical zones in SQZ-Grt2 with HREE and HFSE concentrations below the detection limit indicate multiple inputs of external seawater. The distinct characteristics between Shuanglong and Shaquanzi garnets may reflect the difference between the single magma intrusion and complex volcanic activity. Combining previously published chronological data, this study elucidates a transition from the Middle Carboniferous volcanic-hosted Fe deposits (335–320 Ma) to the Late Carboniferous intrusion-related skarn or IOCG type Fe-Cu deposits (310–300 Ma) in the Aqishan-Yamansu belt.

The evolution of Archean crust undisturbed for three billion years: A case study from the Bahalda Pluton, Singhbhum Craton, eastern India

The Archean Bahalda Pluton (Singhbhum Craton, eastern India) is an I-type mafic granodiorite, surrounded by Paleoarchean TTG and TTG-derived granites of the Singhbhum Suite. The Singhbhum Suite is highly unusual amongst Eo- and Paleo-Archean terranes because most of the Singhbhum Craton escaped post-Archean deformation and metamorphism. The Bahalda granodiorite contains accessory zircon, titanite, and fluorapatite, which are rarely studied together but are a powerful tool for exploring magmatic and post-magmatic processes. U-Pb zircon and titanite dating indicate a ca. 3.35 Ga emplacement age of the Bahalda granodiorite. Subsequent ca. 3.27–3.05 Ga U-Pb fluorapatite ages are interpreted as recording low-grade metamorphic or hydrothermal event(s). The Bahalda fluorapatite and titanite are LREE-enriched compared to the HREE. The complex zonation of fluorapatite suggests that primary igneous fluorapatite was recrystallised with the removal of REE and overgrown by REE-depleted rims. This is in agreement with the apatite trace element systematics which imply fluorapatite cores are of mafic I-type granitoid affinity, with rims of low- and medium-grade metamorphic / metasomatic affinity. No textural evidence of titanite alteration was detected, but some domains have minor REE depletion compared to crystal interiors. The titanite and fluorapatite data display similar trends in LREE vs Sr/Y space due to metamorphic/hydrothermal alteration. The evolution of the Bahalda Pluton, which did not exceed greenschist facies for 3 Gyr, invites comparison with other stabilized cratons from the Mesoarchean.

Main minerals of the Araxá alkali-carbonatite complex, Minas Gerais State, Brazil

The Araxá alkali-carbonatitic complex is a significant source of niobium and phosphate and accounts for approximately 75% of global niobium production. The complex contains magmatic niobium ore minerals, such as natrium-pyrochlore and calcium-pyrochlore, and hydrothermal niobium ore minerals in the form of kenopyrochlore and natrium-pyrochlore. The magmatic micas in the complex are tetraferriphlogopites that exhibit Mg-rich cores surrounded by one or two rims of tetraferriphlogopites formed by hydrothermal alteration. These rims have lower IVAl and Mg apfu (atom per formula unit) values but higher IVFe3+ and Fe2+ contents than the original phlogopite. Microphlogopitite dikes that formed during several episodes of magmatism between 83.48 and 77.4 Ma contain tetraferriphlogopites, phlogopite, eastonite, biotite, and annite-siderophyllite. These micas exhibit variations in Mg2+ and Fe2+ concentrations owing to the magmatic differentiation and subsequent hydrothermal alteration, resulting in rims with higher Mg and lower Fe2+ concentrations than the mica core. The Araxá complex also contains magmatic magnetite that has been further altered by hydrothermal processes, resulting in the formation of ilmenite and the oxidation and crystallization of titaniferous hematite. Magnetite within the microphlogopitites displays variations in the concentrations of Fe3+ and Ti, likely owing to the timing of the intrusion of the microphlogopitites into the Araxá complex. The degree of oxidation of the oxidized ilmenite of the Araxá complex varies based on the intrusions, which occurred before or during hydrothermal activity. Apatite is concentrated in carbonatites, which form a ring around the core of the complex, and disseminated in phlogopite-rich rocks hosting norsethite carbonatite veins in the center of the complex. The apatite in the core rocks exhibits complex zonation with unexpected changes in Ca, P, and Sr concentrations. Apatite in the carbonatite ring was generated during the differentiation of the carbonatite magma, whereas that in the core rocks exsolved from the phosphorus-saturated carbonatite magma (in press). The carbonate minerals dolomite, norsethite, and calcite exhibit compositions grouped around their end-members, suggesting that they formed during different stages of magmatic source differentiation. Strontium differentiation occurs in the magmas corresponding to each endmember, and carbocernaite is exsolved from the Sr-saturated crystals, thus forming micro-inclusions in some carbonate crystals that have been displaced by late-magmatic hydrothermal fluids.

Sheared Peridotites from Northern Lesotho: Metasomatism-Induced Deformation and Craton Destabilization

Abstract Sheared peridotite xenoliths are snapshots of deformation processes that occur in the cratonic mantle shortly before their entrainment by kimberlites. The process of deformation that caused the shearing has, however, been highly debated since the 1970s and remains uncertain. To investigate the processes involved in the deformation, we have studied 12 sheared peridotites from Late Cretaceous (90 Ma) kimberlites in northern Lesotho, on the southeast margin of the Kaapvaal craton. Various deformation textures are represented, ranging from porphyroclastic to fluidal mosaic. Our sample suite consists of eleven garnet peridotites, with various amounts of clinopyroxene, and one garnet-free spinel peridotite with a small amount of clinopyroxene. All of the peridotites are depleted in Fe, and the Mg# of olivine and orthopyroxene range from 91 to 94. Three groups of sheared peridotites are present and have been identified primarily on the basis of Ca contents of olivine and orthopyroxene. The porphyroclasts preserve pre-deformation P–T conditions of 3.5 to 4.5 GPa and 900°C to 1100°C (Group I), 5 to 5.5 GPa and 1200°C to 1250°C (Group II) and 6 ± 0.5 GPa and 1400 ± 50°C (Group III). Group III samples lie above the 40 mW/m2 conductive geothermal gradient, indicating thermal perturbation prior to deformation. The sheared peridotites from Lesotho were affected by various metasomatic events. Pre-deformation metasomatism, involving melts and fluids, is recorded in the porphyroclasts. In Group II and III samples, the clinopyroxene porphyroclasts have similar compositions to Cr-rich and Cr-poor clinopyroxene megacrysts, respectively, that have previously described from southern African kimberlites. This suggests a relationship between them. Younger pre-deformation metasomatism is preserved in a zoned garnet from Group II (enrichment in Ti, Zr, Y + HREE) and orthopyroxene in a Group I sample. The latter exhibits a complex zonation, with a highly enriched (Fe, Ti) inner rim and a less-enriched outer rim. These enrichments must have occurred shortly before deformation. Metasomatism during deformation is revealed by the complex chemical changes recorded in olivine neoblasts with, depending on the sample, increasing or decreasing contents of Ti, Ca, Al, Cr, Mn and Na. Crystallographic preferred orientations of olivine neoblasts are consistent with bimodal, B, C, E, AG-type fabrics and indicate the presence of a hydrous metasomatic agent. We suggest that, akin to the shallower sheared peridotites (Group I), Groups II and III were influenced by early (proto-)kimberlite melt pulses and propose the following model: (proto-)kimberlitic melts invaded the lower lithosphere. These melts followed narrow shear zone networks, produced by deformation at the lithosphere–asthenosphere boundary, heated and metasomatized the surrounding peridotites and were responsible for megacryst crystallization. Sheared peridotites from close to the melt conduits (Group III) have compositions comparable to Cr-poor megacrysts, while those located at a greater distance (Group II) resemble Cr-rich megacrysts. Reactive infiltration of volatile-rich proto-kimberlite melts caused rheologically weakening of olivine in the lithospheric mantle. The consequence of this positive feedback mechanism of metasomatism, weakening and deformation—due to the high magmatic and metasomatic activity in the Late Cretaceous—is the progressive perforation of the lower Kaapvaal lithosphere by rheologically weak zones and the destruction of the protecting dry and depleted layer at its base. This could have caused the observed thinning and destabilization of the lower lithosphere below the southern margin of the Kaapvaal craton.

Magmatic-hydrothermal evolution of long-lived Nb-Ta-(Sn) mineralization in Lianyunshan, NE Hunan, South China

The Lianyunshan Complex (LYSC) is a Nb-Ta-Li-Be rare metals mining area in northeastern Hunan, South China. The deposit is composed of a granite-type rare-metal pegmatite mineralization that occurs as dikes around the LYSC. The present study examines the genetic relationship, fluid evolution, and metallogeny of the co-developed ore-free pegmatite (OFP) and ore-bearing pegmatite (OBP) in granite-related pegmatite-type Nb-Ta rare-metal deposits in the LYSC. Four minerals: columbite-tantalite (coltan), zircon, cassiterite, and monazite were investigated for their chemical and isotopic compositions. The coltan grains range from homogeneous crystals to zoned varieties with growth rims that result from equilibrium and disequilibrium reactions due to local changes in the physical and chemical conditions. These structures were altered by later metasomatic replacement processes related to the hydrothermal fluid activity and produced structures such as alteration rims, patches, irregular zonations, and complex zonations, with a corresponding increase in Ta. Coltan in OBP yielded two weighted mean 206Pb/238U ages of 135.9 ± 2.1 Ma and 120.5 ± 1.2 Ma, corresponding to magmatic (early-stage) and hydrothermal (late-stage) Nb-Ta mineralization ages, respectively. The cassiterite gives a weighted mean U-Pb mineralization age of 130.5 ± 3.9 Ma, which is interpreted as the magmatic-hydrothermal age (transitional stage). Zircon grains in OBP give a lower weighted mean U-Pb age of 121.5 ± 0.8 Ma, resulting from metamictization by the later fluid-assisted alteration and recrystallization in the late-stage hydrothermal event. Monazite grains from OFP yielded a weighted mean 206Pb/238U age of 137.1 ± 0.5 Ma, while zircon gives a mean U-Pb age of 130.3 ± 0.6 Ma. The ages of 137 and 130 Ma obtained for the OFP represent the magmatic (early-stage) and magmatic-hydrothermal stage (transitional) of OFP crystallization in the LYSC. Calculated zircon εHf (t) values and TDM2 ages from OFP (−7.6 to −5.4 and 1663−1532 Ma, respectively) and OBP (−8.7 to −8.2 and 1735−1704 Ma, respectively) are akin to those of the schist and metasandstone strata of the metasedimentary Lengjiaxi metasedimentary group—a melt source material to the LYSC composite batholith. We propose a long-lived ∼15 m.y. Nb-Ta-(Sn) mineralization model for the Lianyunshan complex.

Identifying superimposed W–Sn mineralization events using cassiterite microtextures, trace-element chemistry, and geochronology

Numerous large deposits are formed by multiple mineralization events, however, how to identify superimposed mineralization events is poorly understood. The Xiangdong deposit is a large quartz vein-hosted W–Sn deposit within the Dengfuxian composite granite in South China. Previous studies have suggested that there are two discrete W–Sn mineralization events in the deposit, whereas the ore-forming conditions and processes of the two mineralization events are still unclear. To address these ambiguities, this contribution characterized the microtextures, trace-element chemistry, and geochronology of cassiterite assemblages within W–Sn-rich quartz veins. Based on cathodoluminescence (CL) images, cassiterite crystals were classified into two types with textural differences — Cst 1 and Cst 2. Cassiterite 1 is subhedral to irregular and exhibits complex zonation, whereas Cst 2 is euhedral and exhibits oscillatory zonation. Trace-element concentrations and maps of cassiterite obtained via LA–ICP–MS indicate that Cst 1 has high Fe, W, U, and Sb, but low Nb, Ta, and Zr concentrations, whereas Cst 2 has high Nb, Ta, and Zr, but low Fe, W, U, and Sb concentrations. This indicates that Cst 2 formed from higher temperature and more oxidizing hydrothermal fluids than Cst 1. Laser ablation ICP–MS U–Pb geochronological results of Cst 1 and Cst 2 demonstrate they precipitated at 150.0 ± 2.6 Ma and 136.3 ± 5.5 Ma, respectively. This contribution demonstrates that integrated textural and compositional studies of cassiterite assemblages are critical to identifying hydrothermal events that superimposed W–Sn mineralization, and to constrain ore-forming mechanisms and the physicochemical conditions of the environment.

The Role of Magma Mixing in the Petrogenesis of Eocene Ultrapotassic Lavas, Western Yunnan, SW China

AbstractMagma mixing is a widespread magmagenic process. However, its significance in the formation of ultrapotassic magmas has been largely overlooked so far as they are commonly thought to originate directly from the mantle and ascend rapidly through the crust. The Hezhong ultrapotassic lavas in Western Yunnan (SW China) are (basaltic) trachy-andesitic in composition. These rocks display porphyritic textures with olivine, clinopyroxene (Cpx), spinel, and phlogopite occurring as both phenocryst and glomerocryst. Disequilibrium textures and complex zonation of crystals are commonly observed. Specifically, based on the textural and compositional characteristics, olivines can be classified into three different populations: two populations are characterized by highly to moderately magnesian olivines with normal chemical core-rim zonation (Fo~94–86 to Fo~89–79 and Fo~91–89 to Fo~86–84, respectively). The third population lacks obvious crystal zonation, but individual crystals exhibit some compositional variety at lower Fo contents (Fo83–76). Similarly, four populations of Cpx and two populations of spinel phenocrysts are recognized in terms of texture and composition. Notably, Cpx with reverse zoning contains a ‘green-core’ surrounded by a colourless mantle and rim. Hence, based on the variations of mineral assemblage, types of inclusions, and chemical compositions, all phenocryst/glomerocryst minerals can be divided into three groups. Mineral Group I (MG I) consists of high Fo cores of olivine, cores of the zoned spinel, and phlogopite. MG II only includes the green cores of reversed zoned Cpx (green-core Cpx), and MG III is composed of micro phenocrysts without obvious zoning and rims of large phenocrysts. Comparing these mineral groups with relevant minerals occurring in typical temporally and spatially associated igneous rocks, we suggest that the MG I and II could have been derived from magmas with compositions resembling an olivine lamproite and a trachyte, respectively. The overall bulk-rock geochemical and isotopic features of Hezhong lavas also agree with a mixing process between these two endmembers. Hence, we infer that mixing between these two magmas played a key role in the petrogenesis of the ultrapotassic Hezhong lavas and that the MG III crystallized from the mixed magmas. Our study highlights the complex formation of ultrapotassic magmas inferring that caution must be taken when using bulk chemical magma compositions are to deduce source signatures.

Long-lived Nb-Ta mineralization in Mufushan, NE Hunan, South China: Geological, geochemical, and geochronological constraints

The Mufushan Complex (MFSC), located in northeastern Hunan, is a significant producer of Nb-Ta-Li-Be rare metals in South China. The present study examines the genetic relationship, material provenance, fluid evolution, and metallogeny of the co-developed ore-free pegmatite (OFP) and ore-bearing pegmatite (OBP) in granite-related pegmatite-type Nb-Ta rare-metal deposits in MFSC. Three minerals (columbite-tantalite (coltan), zircon, and monazite) were chosen for analysis. The coltan grains display both primary crystallization structures (crystal homogeneity, oscillatory zonings, and primary growth rims) resulting from equilibrium and disequilibrium reactions due to localized changes in the physicochemical conditions and environment, as well as later replacement structures (alteration rims, patches, irregular zonations, and complex zonations) from metasomatic replacement processes related to hydrothermal fluid activity. The coltan yielded two weighted mean 206Pb/238U ages of 138.1 ± 2.1 Ma and 125.3 ± 2.0 Ma corresponding to magmatic and hydrothermal Nb-Ta mineralization ages. For the OFP, zircons also yielded two weighted mean 206Pb/238U ages of 138.4 ± 0.8 Ma and 131.5 ± 0.7 Ma, whereas monazite gave a weighted mean U-Pb age 142.9 ± 1.2 Ma. The ages of 142–138 Ma and 131 Ma represent the early and late stages of OFP crystallization and barren pegmatites in the MFSC, respectively. Zircon Lu-Hf isotopic compositions link rare-metal metallogenesis to the Lengjiaxi Group, which was the source material to the Mufushan composite batholith. Calculated εHf(t) values and TDM2 ages from the OFP (−7.6 to −3.6 and 1676–1418 Ma, respectively) and the OBP (−14.1 to +4.9 and 2976–1548 Ma, respectively) are akin to those of schists and metasandstones of the metasedimentary Lengjiaxi Group. We propose a long-lived (ca. 13-Myr) event involving two metallogenic episodes of Nb-Ta mineralization in the Mufushan region. This study demonstrates the potential of zircon, coltan, and monazite for fingerprinting minerals and classifying the mineralization potential of pegmatite veins.

Metal(loid) Deportment in Sulfides from the High-Grade Core of the Bingham Canyon Porphyry Cu-Mo-Au Deposit, Utah

Abstract Porphyry deposits supply the bulk of the world’s Cu and Mo and significant amounts of Au, as well as other minor and trace metal(loid)s, including Ag, Re, Te, Pd, Se, Bi, Zn, and Pb. Porphyry deposits are gaining in importance as a source of critical raw materials with the increasing global demand for these commodities. To date, minor and trace metal(loid)s are still commonly recovered as by-products from porphyry ores without prior characterization of their host mineralogy that could inform more efficient processing and improved recoveries. We report a comprehensive metal(loid) deportment study on a complete vein paragenetic series in samples from the northwestern high-grade zone of the Bingham Canyon Cu-Mo-Au porphyry deposit, Utah. The polyphase Bingham stock comprises an early premineralization equigranular monzonite phase that was intruded by a series of five successive, ore-related porphyry intrusions. Veins with hypogene Cu-(Fe) sulfide assemblages from all five porphyry intrusions were characterized for their trace metal(loid) contents by laser ablation-inductively coupled-mass spectrometry (LA-ICP-MS). It was found that bornite and digenite contain elevated Bi, Ag, Te, and Se relative to chalcopyrite, whereas the latter contains elevated concentrations of Co, Ga, and In. A stepwise decline in sulfide abundance occurs over the porphyry intrusion sequence and is more pronounced in digenite and bornite than in chalcopyrite. The related diminishing concentration per rock volume (inventory) of Bi, Ag, Te, and Se in the youngest porphyry dikes could have been caused in part by a geochemical change in the mineralizing fluid supply across successive intrusive-hydrothermal cycles. Element mapping of exsolved digenite within bornite revealed characterstic partitioning of metal(loid)s between bornite and digenite; most notably Ag, but also Te and Au are enriched in digenite relative to enclosing bornite. Bornite domains within these composite grains reveal complex zonation of Sn, In, and Bi, which are attributed to stress-induced diffusion within bornite, resulting from the digenite exsolution process. The selective partitioning of metal(loid)s between bornite and digenite is likely a common feature in many porphyry Cu deposits, given the fundamental mineralogical characteristics of these two sulfides. Our results contribute to an improved understanding of the distribution (from mineral to deposit scale) of critical trace metal(loid)s in porphyry deposits, particularly those containing exsolved digenite. This knowledge can be applied to determine more accurately the value of ore resources, to improve geometallurgical models and by-product recoveries, and to help limit the environmental effects of metal(loid) dispersion.

Post-caldera volcanism reveals shallow priming of an intra-ocean arc andesitic caldera: Hunga volcano, Tonga, SW Pacific

Intra-oceanic arcs are typically associated with intermediate (andesitic) cone volcanoes. However, caldera volcanoes may also form in these settings from very large eruptions, resulting in sudden changes to the magma reservoir. These reservoirs can then produce either semi-continuous or intermittent low-intensity volcanism between major caldera-producing or caldera-deepening eruptions, providing insights into the post-caldera evolution of the system. Hunga volcano (Kingdom of Tonga, Southwest Pacific) is a large mainly submarine edifice that produced a series of caldera-forming eruptions ~900 years ago. Since then, numerous smaller-scale subaerial and submarine eruptions occurred, the most recent forming new islands in 2009 and 2014/15. Pyroclastic deposits associated with these latest eruptions have identical (range ~ 0.1 wt% of all major oxides) andesitic composition that overlap with the primitive end of the slightly wider compositional range of the caldera-forming episodes. Texturally simple plagioclase, clinopyroxene and orthopyroxene phenocrysts in pre-, syn- and post-caldera pyroclasts point to a single shallow storage reservoir at 5–8 km depth. Lack of complex zonation indicates that this reservoir is constantly resupplied by low-flux inputs of basaltic andesite magma and is large enough that convective mixing rapidly homogenises new inputs. The reservoir feeds intermittent, low-intensity, post-caldera volcanism with constant andesite composition, driven possibly by magmatic overpressure and “leakage” of gas-rich magma pockets around the edges of the caldera. More primitive and compositionally variable basaltic andesites formed a lava-dominated edifice prior to the caldera-forming event. This suggests a causal link between magma supply dynamics and caldera priming relating to the maturing of the plumbing system and formation of a sustained subvolcanic andesite magma reservoir.

Species composition and turnover models provide robust approximations of biodiversity in marine conservation planning

Robust design of Marine Protected Areas in ocean environments is often challenging due to inadequate knowledge of biodiversity patterns, reflecting difficulties in the prediction of species distributions from sampling data that are often sparse or inadequate. Models that combine species and environmental data, such as Gradient Forests (GF), provide one analytical approach to this problem, efficiently combining available information to produce spatial models of species turnover throughout an area of interest. Spatial estimates of species turnover can then be classified to estimate spatial patterns in species composition; however, the performance of GF-based classifications within a conservation planning context has not previously been evaluated. Here we assess the utility for conservation planning (using the software Zonation) of a GF-based hierarchical classification that summarises spatial patterns in demersal fish composition in the oceans around New Zealand. Progressively more complex Zonation analyses assessed the effects of (i) varying the number of classification groups, (ii) adding information describing species turnover, and (iii) adding information describing spatial variation in demersal fish species richness. The best-performing GF-based conservation ranking used layers describing the distributions of 30 classification groups, demersal fish species turnover between these groups, and species richness. Conservation outcomes from this ranking were only marginally less efficient than those from a more conventional ranking that used 217 individual species distribution layers (7% less efficient). This indicates that GF-based classifications may provide a practical alternative for marine conservation planning. Additional advantages arise from the greater ease with which a single classification layer summarising complex biodiversity patterns can facilitate decision-making in participatory stakeholder processes.

Large-scale liquid immiscibility in the Hongge layered intrusion hosting a giant Fe-Ti oxide deposit in SW China

The Hongge layered intrusion hosts the largest magmatic Fe-Ti oxide ore deposit in China and provides a valuable opportunity for improving the current understanding of magma differentiation and associated ore-forming processes. In this study, we present geochemical data for apatite- and plagioclase-hosted inclusions in gabbros from the Hongge Upper Zone. The apatite-hosted melt inclusions have a large compositional range with 27.7–60.4 wt% SiO2 and 1.31–25.7 wt% FeOt, which is difficult to be achieved through fractional crystallization but can be well explained by an unmixing process and trapping of immiscible melts along the binodal of a two-liquid field. Only Fe-rich melt inclusions (with 23.8–33.1 wt% SiO2 and 17.7–35.8 wt% FeOt) are observed in plagioclase, which can be attributed to the preferential trapping of immiscible Fe-rich melts by crystallizing plagioclase. The cumulus clinopyroxene and plagioclase display complex zonations with different compositional domains, indicating that disequilibrium crystallization might have happened. We argue that efficient separation of immiscible liquids occurred in the magma chamber and contributed to the concentration of the ore-forming elements Fe and Ti in the remaining immiscible Fe-rich melt. Large amounts of Fe-Ti oxides crystallized from the collected Fe-rich melt forming the major Fe-Ti oxide ore layers of the Hongge intrusion.

Provenance of Albian to Cenomanian exotics-bearing turbidites in the Western Carpathians: a heavy mineral analysis

Throughout the Cretaceous, Tethyan oceanic branches gradually closed, and various ophiolites became obducted and eroded. Their remnants, however, provide an abundance of exotic clasts of unknown origin. Sandstone samples from the oldest, Albian exotics-bearing strata of the Pieniny Klippen Belt and Central Western Carpathians were analysed for heavy minerals. These samples were dominated by a high content of chrome-spinels, zircon, tourmaline, apatite and rutile. Titanite, kyanite, monazite, epidote, sillimanite and staurolite were much less abundant. Garnet was generally also rare; however, it was locally common, as were blue amphiboles, pyroxenes and kyanite. The spinels found in the samples were predominantly derived from harzburgites (supra-subduction peridotites and volcanic rocks). The blue amphiboles represented glaucophanes to ferroglaucophanes, and were derived from HP/LT metabasites. Pyroxenes (enstatite, less commonly augite and diopside) most likely came from coeval volcanics. Most of the tourmalines were derived from metasedimentary rocks and locally from granitoids. Furthermore, some have a complex zonation with two phases of tourmaline, or tourmaline intergrown with quartz. These were likely derived from ophiolitic sources. The results from our analysis indicate a dominance of ophiolites and older sediments with local input of continental crust metamorphic rocks. A resulting palaeogeographic reconstruction involves secondary doubling of the Neotethys suture zone and its lateral shift north of the Central Western Carpathians, which formed a common source for exotics in the Pieniny Klippen Belt and the Central Western Carpathians.

Ti-in-quartz: Evaluating the role of kinetics in high temperature crystal growth experiments

We present results from 25 hydrothermal quartz growth experiments, all conducted at 800 °C and 1 kbar but with varying starting materials and run times, to address discrepancies between calibrations of the titanium-in-quartz (TitaniQ) thermobarometer. In our experiments, a gold capsule is loaded with silica glass, water, and either rutile or anatase as the TiO2 source. In most experiments, there is also a large quartz seed crystal contained in an open inner capsule. The use of rutile versus anatase has a significant influence on the (re)crystallization pathways of the SiO2 and TiO2 components. When rutile is used, quartz overgrowths have abundant open cavities and complex zonations. The rutile does not completely dissolve because rutile is the stable TiO2 polymorph, and yet, new rutile forms at the quartz seed-overgrowth interface and on the outer surface of quartz crystals. This suggests crystallization of quartz near Ωrut ∼ 1, but wide-ranging Ti concentrations and zonations in quartz are indicative of kinetic effects. When powdered anatase is used, the quartz overgrowths look markedly different, lacking the open cavities and instead exhibiting step edges and terraces. The Ti concentrations in quartz from these experiments are also wide-ranging but reach larger values.Our results span the range of previous calibrations and indicate that Ti concentrations in quartz are sensitive to the TiO2/SiO2 ratio of the fluid as opposed to the absolute concentration (or activity) of dissolved TiO2. We present a kinetic model for quartz and rutile growth from a fluid where the input parameters are the initial degrees of supersaturation with respect to quartz and rutile, the total reactive surface area, and rate constants that link the degree of supersaturation to net precipitation rates. The model can explain many of the salient features of our experimental results, as well as those from previous studies, but requires that the rate constant multiplied by the reactive surface area for rutile is less than that of quartz, and that rutile solubility depends on the SiO2 concentration of the fluid, as documented in the recent literature. Complete quartz-rutile equilibrium may not have been established in any of the experimental studies, but low-pressure experiments with slowly grown quartz seem to be more reliable than extrapolations from high-pressure experiments for thermobarometry of shallow natural systems.

Detritic tourmalines with complex zonation in the Cretaceous exotic flysches of the Western Carpathians: Where did they come from?

The period of the Cretaceous marked a time of convergence in the Tethyan realm, characterized by both collisions and local ophiolitic obduction. Sedimentary records from this period are full of detritic materials of unknown provenance, so-called exotics. Among these exotic rocks and minerals was tourmaline with complex zonation which began to appear in considerable amounts. Research conducted in Albian to Senonian exotics of the Western Carpathians has shown that there are two kinds of complex-zoned grains: 1) grains with a fabric consisting of several tourmaline phases, which are chaotically arranged as laths and 2) grains displaying a fine intergrowth of tourmaline and quartz. The first type of tourmaline shows a continuous trend of Al and its substitution by Fe3+ at the Y and Z sites, thus shifting from a schorl-dravitic composition to a bosiite one. The second type consists of a dominant presence of schorl-dravitic tourmaline, however, with a scarce occurrence of Al-enriched oxy-dravitic, foititic and magnesio-foititic compositions.Tourmaline with complex zonation occurs in metamorphics, which include HP and UHP facies, evaporitic complexes, and hydrothermal deposits. They also appear locally in granites and pegmatites. In most of the rocks, saline and boron-rich fluids played a substantial role (in the high-pressure metamorphics there was an influx of fluids during their exhumation). Because the examined exotics are rich in ophiolitic material, including HP to UHP rock pebbles it is substantiated to assume that the also represented the main source of the complex-zoned tourmaline. They may have also combined with Permian-Lower Triassic evaporites where the dismembered ophiolites are often embedded. Hydrothermal veins and granitoids did not represent a regionally significant and widespread source at that time.

Petrogenesis of Nb–(Ta) aplo-pegmatites and fine-grained granites from the Early Cretaceous Huangshan rare-metal granite suite, northeast Jiangxi Province, southeast China

The Early Cretaceous (ca. 130 Ma) Nb-rich and Ta-poor Huangshan suite, South China, includes a series of medium-grained granites that contain Nb-rich mica and very low columbite contents, which are indicative of a potential Nb resource. In addition, the Huangshan suite contains fine-grained granites and aplo-pegmatites in which disseminated Nb–Ta columbite is an ore. Two types of fine-grained microcline-bearing and albite-rich leucogranite sills and dikes were identified. Sills and dikes of leucogranites and aplo-pegmatites intrude the medium-grained granites and surrounding hornfels. The aplo-pegmatites consist of large microcline and quartz crystals that are typically broken and embedded within a foliated albite-rich matrix. Niobium-rich and Mn-poor columbite with Ta# [Ta/(Ta + Nb)] ≤ 0.5 and Mn# [Mn/(Mn + Fe)] < 0.2, which is characterized by complex zonation, is the major accessory mineral in the fine-grained granites and aplo-pegmatites. The Huangshan columbites display an unusual pattern of Ta# variation at nearly constant Mn#. Fractional crystallization along cannot explain the observed trends, but they can be accounted for by recurrent mixing between two distinct and independently evolving magmas. One end-member is deemed to be an evolved Nb-rich magma, and the other is a Ta-enriched magma of the peraluminous rare-metal granite series (i.e., Yichun trend). Major and trace element features also support this model of recurrent magma mixing.

In situ Sr Isotope Compositions of Plagioclase from a Complete Stratigraphic Profile of the Bushveld Complex, South Africa: Evidence for Extensive Magma Mixing and Percolation

The cumulates of the Bushveld Complex, which form the largest layered intrusion on Earth, are known to have crystallized from several isotopically distinct magma pulses. Here, we present in situ Sr isotope compositions combined with the corresponding mineral chemistry of plagioclase from all lithological zones, covering > 6 km of stratigraphy, to constrain the petrogenesis of the complex. The in situ data coupled with high-resolution elemental maps of individual plagioclase grains reveal complex zonation patterns with respect to mineral chemistry and Sr isotope composition. This suggests that interstitial plagioclase in the Bushveld Complex crystallized from multiple, isotopically distinct influxes of melt percolating through a mafic cumulate framework and displacing the resident melt. Similarly, cumulus plagioclase grains are the result of continual ingress of a distinct magma, which picked up previously formed plagioclase crystals. Sr isotope compositions across the layered sequence seem to be largely decoupled from differentiation indices, such as Mg#, anorthite content or trace element ratios. As these observations cannot be explained by bulk assimilation, we propose that the elevated Sr isotopic signature of the Bushveld cumulates may have resulted from the interaction of the parental magma with a fluid derived from the up to 2 km thick dolomitic footwall, which caused a major shift in Sr isotope composition without significantly affecting the degree of differentiation or trace element signature. The decarbonation and/or assimilation of dolomite during the intrusion of the Bushveld Complex may be of major importance, not only for the petrogenesis but also for the emplacement of the layered intrusion, because devolatilization is directly linked to space creation owing to volume loss, thus producing a lopolith.

Polymetamorphism in garnet micaschists of the Saualpe Eclogite Unit (Eastern Alps, Austria), resolved by automated SEM methods and EMP–Th–U–Pb monazite dating

ABSTRACTPolymetamorphic garnet micaschists from the Austroalpine Saualpe Eclogite Unit (Kärnten, Austria, Eastern Alps) display complex microstructural and mineral–chemical relationships. Automated scanning electron microscopy routines with energy dispersive X‐ray (EDX) spectral mapping were applied for monazite detection and garnet mineral–chemical characterization. When the Fe, Mg, Mn and Ca element wt% compositions are used as generic labels for garnet EDX spectra, complex zonations and porphyroblast generations can be resolved in complete thin sections for selective electron‐microprobe analyses. Two garnet porphyroblast generations and diverse monazite age populations have been revealed in low‐Ca and high‐Al‐metapelites. Garnet 1 has decreasing Mn, constant Ca and significantly increasing Mg from cores to rims. Geothermobarometry of garnet 1 assemblages signals a crystallization along a M1 prograde metamorphism at ~650 °C/6–8 kbar. Sporadic monazite 1 crystallization started at c. 320 Ma. Subsequent pervasive 300–250 Ma high‐Y and high‐Gd monazite 1 formation during decompression coincided with the intrusion of Permian and Early Triassic pegmatites. Monazite 1 crystallized along the margin of garnet 1. Coronas of apatite and allanite around the large 320–250 Ma monazite signal a retrogressive stage. These microstructures suggest a Carboniferous‐to‐Early‐Permian age for the prograde M1 event with garnet 1. Such a M1 event at an intermediate‐P/T gradient has not yet been described from the Saualpe, and preceded a Permo‐Triassic low‐P stage. The M2 event with garnet 2 postdates the corona formation around Permian monazite. Garnet 2 displays first increasing XCa at decreasing XMg, then increasing XCa and XMg, and finally decreasing XCa with increasing XMg, always at high Ca and Mg, and low Mn. This records a P–T evolution which passed through eclogite facies conditions and reached maximum temperatures at ~750 °C/14 kbar during decompression‐heating. A monazite 2 population (94–86 Ma) with lower Y and Gd contents crystallized at decreasing pressure during the Cretaceous (Eo‐Alpine) metamorphism M2 at a high‐P/T gradient. The Saualpe Eclogite Unit underwent two distinct clockwise metamorphic cycles at different P–T conditions, related to continental collisions under different thermal regimes. This led to a characteristic distribution pattern of monazite ages in this unit which is different from other Austroalpine basement areas.

Nephelinite lavas at early stage of rift initiation (Hanang volcano, North Tanzanian Divergence)

North Tanzanian Divergence is the first stage of continental break-up of East African Rift (<6 Ma) and is one of the most concentrated areas of carbonatite magmatism on Earth, with singular Oldoinyo Lengai and Kerimasi volcanoes. Hanang volcano is the southernmost volcano in the North Tanzanian Divergence and the earliest stage of rift initiation. Hanang volcano erupted silica-undersaturated alkaline lavas with zoned clinopyroxene, nepheline, andradite-schorlomite, titanite, apatite, and pyrrhotite. Lavas are low MgO-nephelinite with low Mg# and high silica content (Mg# = 22.4–35.2, SiO2 = 44.2–46.7 wt%, respectively), high incompatible element concentrations (e.g. REE, Ba, Sr) and display Nb–Ta fractionation (Nb/Ta = 36–61). Major elements of whole rock are consistent with magmatic differentiation by fractional crystallization from a parental melt with melilititic composition. Although fractional crystallization occurred at 9–12 km and can be considered as an important process leading to nephelinite magma, the complex zonation of cpx (e.g. abrupt change of Mg#, Nb/Ta, and H2O) and trace element patterns of nephelinites recorded magmatic differentiation involving open system with carbonate–silicate immiscibility and primary melilititic melt replenishment. The low water content of clinopyroxene (3–25 ppm wt. H2O) indicates that at least 0.3 wt% H2O was present at depth during carbonate-rich nephelinite crystallization at 340–640 MPa and 1050–1100 °C. Mg-poor nephelinites from Hanang represent an early stage of the evolution path towards carbonatitic magmatism as observed in Oldoinyo Lengai. Paragenesis and geochemistry of Hanang nephelinites require the presence of CO2-rich melilititic liquid in the southern part of North Tanzanian Divergence and carbonate-rich melt percolations after deep partial melting of CO2-rich oxidized mantle source.