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White mica and tourmaline are the dominant hydrothermal alteration minerals at the world-class Panasqueira W-Sn-Cu deposit in Portugal. Thus, understanding the controls on their chemical composition helps to constrain ore formation processes at this deposit and determine their usefulness as pathfinder minerals for mineralization in general. We combine whole-rock geochemistry of altered and unaltered metasedimentary host rocks with in situ LA-ICP-MS measurements of tourmaline and white mica from the alteration halo. Principal component analysis (PCA) is used to better identify geochemical patterns and trends of hydrothermal alteration in the datasets. The hydrothermally altered metasediments are enriched in As, Sn, Cs, Li, W, F, Cu, Rb, Zn, Tl, and Pb relative to unaltered samples. In situ mineral analyses show that most of these elements preferentially partition into white mica over tourmaline (Li, Rb, Cs, Tl, W, and Sn), whereas Zn is enriched in tourmaline. White mica has distinct compositions in different settings within the deposit (greisen, vein selvages, wall rock alteration zone, late fault zone), indicating a compositional evolution with time. In contrast, tourmaline from different settings overlaps in composition, which is ascribed to a stronger dependence on host rock composition and also to the effects of chemical zoning and microinclusions affecting the LA-ICP-MS analyses. Hence, in this deposit, white mica is the better recorder of the fluid composition. The calculated trace-element contents of the Panasqueira mineralizing fluid based on the mica data and estimates of mica-fluid partition coefficients are in good agreement with previous fluid-inclusion analyses. A compilation of mica and tourmaline trace-element compositions from Panasqueira and other W-Sn deposits shows that white mica has good potential as a pathfinder mineral, with characteristically high Li, Cs, Rb, Sn, and W contents. The trace-element contents of hydrothermal tourmaline are more variable. Nevertheless, the compiled data suggest that high Sn and Li contents are distinctive for tourmaline from W-Sn deposits.
The Devonian Las Chacras-Potrerillos batholith comprises six nested monzonitic to granitic intrusions with metaluminous to weakly peraluminous composition and a Sr-Nd isotopic signature indicating a dominantly juvenile mantle-derived source. The chemically most evolved units in the southern batholith contain a large number of intra-granitic, pod-shaped tourmaline-bearing pegmatites. This study uses in situ chemical and boron isotopic analyses of tourmaline from nine of these pegmatites to discuss their relationship to the respective host intrusions and the implications of their B-isotope composition for the source and evolution of the magmas. The tourmalines reveal a diversity in element composition (e.g., FeO, MgO, TiO2, CaO, MnO, F) which distinguishes individual pegmatites from one another. However, all have a narrow 5 11 B range of -13.7 to -10.5%0 (n = 100) which indicates a relatively uniform magmatic system and similar temperature conditions during tourmaline crystallization. The average delta(11) B value of -11.7%0 is typical for S-type granites and is within the range reported for peraluminous granites. pegmatites, and metamorphic units of the Ordovician basement into which the Las Chacras-Potrerillos batholith intruded. The B-isotope evidence argues for a crustal boron source like that of the Ordovician basement, in contrast to the metaluminous to weakly peraluminous composition and juvenile initial Sr and Nd isotope ratios of the Las Chacras-Potrerillos batholith magmas. We propose that the boron was not derived from the magma source region but was incorporated from dehydration melting of elastic metasedimentary rocks higher up in the crustal column.
The early Cretaceous Paraná–Etendeka Large Igneous Province is attributed to the impact of the Tristan mantle plume on the base of the continental lithosphere and the associated opening of the South Atlantic Ocean during the breakup of West Gondwana. Although the geochemistry of the Paraná and Etendeka volcanic rocks has been extensively studied, there is still disagreement on the role of the mantle plume in the production of the magma types observed, because some of their primary compositions are obscured by continental crustal contamination. However, there are related plutonic rocks that preserve mantle signatures. The Doros Complex is a shallow-level mafic intrusion within the Etendeka Province of Namibia. New 39Ar/40Ar step-heating ages for Doros gabbros from this study (weighted mean of 130 ± 1 Ma; 2σ error) confirm contemporaneity with the Paraná–Etendeka magmatic event. The Doros suite yields mean ɛNd values of +5·3 ± 1·0 (1σ; n = 11), initial 87Sr/86Sr = 0·70418 ± 0·00017 (n = 11) and 206Pb/204Pb = 18·11 ± 0·06 (n = 13) at 132 Ma. The clustering of isotopic data and trends in incompatible trace element ratios indicate that all the magmas in the complex were derived from the same mantle source components, during the same melting episode. By quantitative isotopic modelling of mixing processes, we constrain the Doros parental magma to comprise 60–80% melt of a depleted asthenospheric mantle component and 20–40% melt of a more enriched, Tristan plume-derived, asthenospheric component. No lithospheric mantle component is required to explain the Doros magma compositions. The chilled margin to the complex is the only rock type that shows evidence of significant continental crustal contamination, by assimilation of the metasedimentary host-rock upon emplacement. The identification of a substantial Tristan plume component in the Doros source confirms the integral role of the deep-seated thermal anomaly in Paraná–Etendeka magmatism. We show, in addition, that the Doros suite has consistent, strong geochemical affinities with the Tafelkop group ‘ferropicrite’ lavas of the Etendeka Province. This provides crucial evidence in support of Doros as the eruptive site for the Tafelkop lavas, thereby linking the Doros magmatism to the earliest eruptive phase in the Etendeka event. The distinctive chemistry of this magma group has been attributed to relatively deep decompression melting of pyroxenite-bearing material in the heterogeneous Tristan plume head, related to the initial impact of the plume on the base of the lithosphere.
The Sierra Nevada de Santa Marta in NW Colombia is an isolated massif at the northernmost end of the Andes chain near the boundary with the Caribbean plate. Previous geologic mapping and K-Ar dating have shown that Jurassic plutonic and volcanic units make up a large part of the Santa Marta Massif (SMM). These rocks have been considered to be part of a Jurassic magmatic arc extending from NW Colombia to northern Chile, but without any geochemical basis for comparison. This paper reports on a geochemical and Sr-Nd-Pb isotope study of the Jurassic rocks in the SMM and provides 12 new U-Pb zircon ages from in-situ laser ICP-MS dating. The plutonic and volcanic units span a range from 45 to 78 wt.% SiO2, with a dominance of intermediate to felsic compositions with SiO2 > 57 wt.%. They classify as calc-alkaline, medium to high-K, metaluminous rocks with trace-element features typical for arc-derived magma series. In terms of their major and trace-element compositions, the SMM Jurassic units overlap with contemporary plutonic and volcanic rocks from other regions of the Central and Eastern Cordilleras of Colombia, and confirm an arc affinity. The new U-Pb ages range from 176 +/- 1 Ma to 192 +/- 2 Ma (n = 12), with most between 180 and 188 Ma (n = 7). The initial Sr isotope ratios (at 180 Ma) are between 0.7012 and 0.7071 (n = 29), with 3 outliers attributed to mobilization of Rb and/or Sr, Nearly all samples have negative( )epsilon Nd-(180) values between - 10.3 and 0.0 (n = 30), the two exceptions being only slightly positive (1.1 and 1.9). Measured Pb isotope ratios fall in a narrow range, with Pb-206/Pb-204 from 18.02 to 19.95, (207) Pb/(204) Pb from 15.56 to 15.67 and Pb-208/Pb-204 from 37.76 to 39.04 (n = 28). In the regional context of previous studies, these results confirm early Jurassic ages and an arc affinity for the widespread magmatism exposed in the eastern and northeastern Colombian Andes. We also note patterns in the distribution and composition of magmas. The magmatic activity in the Central Cordillera tends to be younger than in the Eastern Cordillera and is spatially more restricted to the vicinity of regional fault systems. In terms of composition, Jurassic igneous rocks in the Eastern Cordillera have systematically lower epsilon Nd-(180) values than those from the Central Cordillera, whereas the Pb isotope ratios overlap. We ascribe the Nd isotope variations to heterogeneity in the mantle source and/or degree of crustal contamination, whereas the Pb isotope ratios are crust-dominated and similar throughout the region. The spatio-temporal and compositional evolution of Jurassic magmatic rocks in the Northern Andes reflect the major plate kinematic readjustment between the Triassic and the Early Jurassic in the proto-Andean margin.
The early Cretaceous Koegel Fontein intrusive complex is situated near the Atlantic coast in South Africa, about 350 km northwest of Cape Town. The complex comprises felsic units of granite and syenite with compositionally related dykes, and a single intrusive plug of diorite. Existing zircon U-Pb ages of 144 +/- 2 Ma for the syenite and 133.9 +/- 1.3 Ma for the granite suggest that the emplacement of the complex took place over a period of about 10 My. This study provides additional and independent ages of the Koegel Fontein complex by Ar-40/Ar-39 dating to confirm the onset and duration of magmatism and better define the sequence of igneous units that comprise it. New laser step-heating Ar-40/Ar-3(9) ages on plagioclase and biotite from the main intrusive units in the complex are presented here, including samples previously dated by U-Pb dating. The Ar-40/Ar-39 ages for the granite and syenite units (131.1 +/- 0.9 Ma and 143.3 +/- 0.9, respectively) are in good agreement with the zircon U-Pb ages. Other units not previously dated include the Rooivleitjie alkaline granite (150.7 +/- 0.6 Ma), two quartz-porphyry dykes (143.0 +/- 0.9 and 139.4 +/- 1.7 Ma) and the Zout Rivier diorite plug (133.0 +/- 1.0 Ma). The new results confirm an early onset of magmatism at Koegel Fontein relative to that of the Etendeka Province some 1000 km to the north, which is consistent with the regional south-to-north propagation of South Atlantic rifting. The youngest Ar-40/Ar-3(9) ages at Koegel Fontein (134 to 131 Ma, Rietpoort Granite and 133 Ma, Zout Rivier diorite) correspond to the age of the first magnetic seafloor-spreading anomaly offshore, and we suggest that the longevity of Koegel Fontein magmatism relates to a superposition of pre-drift magmatism onshore and spreading-related magmatism as continental separation began.
Small-scale variations in mineral chemistry, textures, and platinum group element (PGE) mineralization were investigated in the Lower and Middle Group chromitite layers LG6, LG6a, MG1, MG2, and MG2 II from vertical drill core profiles at the Thaba mine in the northwestern limb of the Bushveld Complex. We present detailed geochemical profiles of chromite composition and chromite crystal size distribution curves to shed light on the processes of chromite accumulation and textural modification as well as mineralization. Multiple samples within each layer were assayed for PGE concentrations, and the respective platinum group mineral association was determined by mineral liberation analysis (MLA). There is strong evidence for postcumulus changes in the chromitites. The crystal size distribution curves suggest that the primary chromite texture was coarsened by a combination of adcumulus growth and textural equilibration, while compaction of the crystal mush played only a minor role. Mineral compositions were also modified by postcumulus processes, but because of the very high modal amount of chromite and its local preservation in orthopyroxene oikocrysts, that phase retained much primary information. Vertical variations of chromite composition within chromitite layers and from one layer to another do not support the idea of chromite accumulation from crystal-rich slurries or crystal settling from a large magma chamber. Instead, we favor a successive buildup of chromitite layers by repeated injections of relatively thin layers of chromite-saturated magmas, with in situ crystallization occurring at the crystal mush-magma interface. The adcumulus growth of chromite grains to form massive chromitite required addition of Cr to the layers, which we attribute to downward percolation from the overlying magma. The PGE concentrations are elevated in all chromitite layers compared to adjacent silicate rocks and show a systematic increase upward from LG6 (avg 807 ppb Ir + Ru + Rh + Pt + Pd + Au) to MG2 II (avg 2,062 ppb). There are also significant internal variations in all layers, with enrichments at hanging and/or footwalls. The enriched nature of chromitites in PGEs compared to host pyroxenites is a general feature, independent of the layer thickness. The MLA results distinguish two principal groups of PGE mineral associations: the LG6, LG6, and MG1 are dominated by the malanite series, laurite, and PGE sulfarsenides, while the MG2 and MG2 II layers are characterized by laurite and PGE sulfides as well as Pt-Fe-Sn and PGE-Sb-Bi-Pb alloys. Differences in the PGE associations are attributed to postcumulus alteration of the MG2 and MG2 II layer, while the chromitites below, particularly LG6 and LG6a, contain a more pristine association.
Britholite group minerals (REE,Ca)(5)[(Si,P)O-4](3)(OH,F) are widespread rare-earth minerals in alkaline rocks and their associated metasomatic zones, where they usually are minor accessory phases. An exception is the REE deposit Rodeo de los Molles, Central Argentina, where fluorbritholite-(Ce) (FBri) is the main carrier of REE and is closely intergrown with fluorapatite (FAp). These minerals reach an abundance of locally up to 75 modal% (FBri) and 20 modal% (FAp) in the vein mineralizations. The Rodeo de los Molles deposit is hosted by a fenitized monzogranite of the Middle Devonian Las Chacras-Potrerillos batholith. The REE mineralization consists of fluorbritholite-(Ce), britholite-(Ce), fluorapatite, allanite-(Ce), and REE fluorcarbonates, and is associated with hydrothermal fluorite, quartz, albite, zircon, and titanite. The REE assemblage takes two forms: irregular patchy shaped REE-rich composites and discrete cross-cutting veins. The irregular composites are more common, but here fluorbritholite-(Ce) is mostly replaced by REE carbonates. The vein mineralization has more abundant and better-preserved britholite phases. The majority of britholite grains at Rodeo de los Molles are hydrothermally altered, and alteration is strongly enhanced by metamictization, which is indicated by darkening of the mineral, loss of birefringence, porosity, and volume changes leading to polygonal cracks in and around altered grains. A detailed electron microprobe study of apatite-britholite minerals from Rodeo de los Molles revealed compositional variations in fluorapatite and fluorbritholite-(Ce) consistent with the coupled substitution of REE3+ + Si4+ = Ca2+ + P5+ and a compositional gap of similar to 4 apfu between the two phases, which we interpret as a miscibility gap. Micrometer-scale intergrowths of fluorapatite in fluorbritholite-(Ce) minerals and vice versa are chemically characterized here for the first time and interpreted as exsolution textures that formed during cooling below the proposed solvus.