Isotopic constraints on the age and source of ore-forming fluids of the Bou Azzer arsenide ores (Morocco)

The Bou Azzer district in Morocco has a long mining history since the beginning of the XXst century during which it has become the only world producer of Co from primary, hydrothermal Co arsenide ores. Orebodies are structurally controlled, and mainly distributed along fault contacts between Cryogenian ophiolite-related serpentinite bodies and intrusive quartz diorite or, locally, ophiolitic gabbros or Ediacaran volcanic rocks. Ore formation took place through a multi-stage mineralizing process that included an early stage composed by gold, quartz, chlorite, muscovite and calcite, followed by the main arsenide and sulfarsenide stage (subdivided into three substages, IIa: Ni-rich, Co ores, IIb: Co-Fe ores and IIc: Fe-Co ores), and ending with an epithermal stage characterized by the precipitation of sulfides along with quartz and calcite. Field relations and most previous geochronologic dating pointed to a post Pan-African age of ore formation, mainly coincident with the Hercynian orogeny. The isotopic study presented in this paper includes S, Pb, Rb/Sr and Sm/Nd data of a set of ore mineral samples from three deposits (Aghbar, Tamdrost and Aït Ahmane), as well as of regional samples representative of the different lithologies occurring in the Bou Azzer area. The isotope data set was completed with S isotope analyses of arsenide and sulfarsenide minerals from five ore deposits (Filon 7/5, Aghbar, Tamdrost, Ightem and Aït-Ahmane) and of some whole-rock regional samples. Results show that ores formed during multi-episodic hydrothermal events connected with hercynian reactivation of Devonian-Carboniferous faults, supporting previous geochronologic dating. The obtained Pb, Sr, Nd and S isotopic signatures of ore minerals and regional rocks further show that ophiolite-related lithologies became isotopically modified by interaction with crustal material and afterwards acted as the main source of ore-forming elements. Nevertheless, isotopic data do not fully concur with such a simple scenario but are quite consistent with a rather complex interpretation based on multi-source origin of some elements and isotopes scavenged from a number of isotopically different lithologies both from the inferred basement and the volcanic and sedimentary cover. © 2022 The Author(s

The origin of the Palaeoproterozoic AMCG complexes in the Ukrainian shield: New U-Pb ages and Hf isotopes in zircon

© 2017 Elsevier B.V.The Ukrainian shield hosts two Palaeoproterozoic anorthosite-mangerite-charnockite-granite (AMCG) complexes (the Korosten and Korsun-Novomyrhorod complexes) that intruded Palaeoproterozoic continental crust in north-western and central parts of the shield, respectively. We report results of U-Pb zircon and baddeleyite dating of 16 samples from the Korosten plutonic complex (KPC), and 6 samples from the Korsun-Novomyrhorod plutonic complex (KNPC). Fifteen zircon samples from both complexes were also analysed for Hf isotopes. These new, together with previously published data indicate that the formation of the KPC started at c. 1815 Ma and continued until 1743 Ma with two main phases of magma emplacement at 1800–1780 and 1770–1758 Ma. Each of the main phases of magmatic activity included both basic and silicic members. The emplacement history of the KNPC is different from that of the KPC. The vast majority of the KNPC basic and silicic rocks were emplaced between c. 1757 and 1750 Ma; the youngest stages of the complex are represented by monzonites and syenites that were formed between 1748 and 1744 Ma. Both Ukrainian AMCG complexes are closely associated in space and time with mantle-derived mafic and ultramafic dykes. The Hf isotope ratios in the zircons indicate a predominantly crustal source for the initial melts with some input of juvenile Hf from mantle-derived tholeiite melts. The preferred model for the formation of the Ukrainian AMCG complexes involves the emplacement of large volumes of hot mantle-derived tholeiitic magma into the lower crust. This resulted in partial melting of mafic lower-crustal material, mixing of lower crustal and tholeiitic melts, and formation of ferromonzodioritic magmas. Further fractional crystallization of the ferromonzodioritic melts produced the spectrum of basic rocks in the AMCG complexes. Emplacement of the ferromonzodioritic and tholeiitic melts into the middle crust and their partial crystallization caused abundant melting of the ambient crust and formation of the large volumes of granitic rocks present in the complexes

The origin of the Palaeoproterozoic AMCG complexes in the Ukrainian shield: New U-Pb ages and Hf isotopes in zircon

© 2017 Elsevier B.V.The Ukrainian shield hosts two Palaeoproterozoic anorthosite-mangerite-charnockite-granite (AMCG) complexes (the Korosten and Korsun-Novomyrhorod complexes) that intruded Palaeoproterozoic continental crust in north-western and central parts of the shield, respectively. We report results of U-Pb zircon and baddeleyite dating of 16 samples from the Korosten plutonic complex (KPC), and 6 samples from the Korsun-Novomyrhorod plutonic complex (KNPC). Fifteen zircon samples from both complexes were also analysed for Hf isotopes. These new, together with previously published data indicate that the formation of the KPC started at c. 1815 Ma and continued until 1743 Ma with two main phases of magma emplacement at 1800–1780 and 1770–1758 Ma. Each of the main phases of magmatic activity included both basic and silicic members. The emplacement history of the KNPC is different from that of the KPC. The vast majority of the KNPC basic and silicic rocks were emplaced between c. 1757 and 1750 Ma; the youngest stages of the complex are represented by monzonites and syenites that were formed between 1748 and 1744 Ma. Both Ukrainian AMCG complexes are closely associated in space and time with mantle-derived mafic and ultramafic dykes. The Hf isotope ratios in the zircons indicate a predominantly crustal source for the initial melts with some input of juvenile Hf from mantle-derived tholeiite melts. The preferred model for the formation of the Ukrainian AMCG complexes involves the emplacement of large volumes of hot mantle-derived tholeiitic magma into the lower crust. This resulted in partial melting of mafic lower-crustal material, mixing of lower crustal and tholeiitic melts, and formation of ferromonzodioritic magmas. Further fractional crystallization of the ferromonzodioritic melts produced the spectrum of basic rocks in the AMCG complexes. Emplacement of the ferromonzodioritic and tholeiitic melts into the middle crust and their partial crystallization caused abundant melting of the ambient crust and formation of the large volumes of granitic rocks present in the complexes

ADAMTS13 phenotype in plasma from normal individuals and patients with thrombotic thrombocytopenic purpura

The activity of ADAMTS13, the von Willebrand factor cleaving protease, is deficient in patients with thrombotic thrombocytopenic purpura (TTP). In the present study, the phenotype of ADAMTS13 in TTP and in normal plasma was demonstrated by immunoblotting. Normal plasma (n = 20) revealed a single band at 190 kD under reducing conditions using a polyclonal antibody, and a single band at 150 kD under non-reducing conditions using a monoclonal antibody. ADAMTS13 was not detected in the plasma from patients with congenital TTP (n = 5) by either antibody, whereas patients with acquired TTP (n = 2) presented the normal phenotype. Following immunoadsorption of immunoglobulins, the ADAMTS13 band was removed from the plasma of the patients with acquired TTP, but not from that of normal individuals. This indicates that ADAMTS13 is complexed with immunoglobulin in these patients. The lack of ADAMTS13 expression in the plasma from patients with hereditary TTP may indicate defective synthesis, impaired cellular secretion, or enhanced degradation in the circulation. This study differentiated between normal and TTP plasma, as well as between congenital and acquired TTP. This method may, therefore, be used as a complement in the diagnosis of TTP

The Variscan gabbros from the Spanish Central System: A case for crustal recycling in the sub-continental lithospheric mantle?

15 páginas, 12 figuras, 4 tablas.-- El Pdf del artículo es la versión post-print.The gabbroic intrusions that crop out along the Spanish Central System (SCS) are geochemically heterogeneous, including primitive and evolved rocks. Differentiation is mainly related to fractionation of Cr-spinel and olivine, but mixing with coeval granitic magmas or crustal assimilation may have also played a role in the evolution of the most differentiated rocks. The most primitive uncontaminated gabbros show arc-like trace element chondrite and primitive-mantle normalised patterns, characterised by large ion lithophile elements (LILE)-light rare earth elements (LREE) enrichment, Sr and Pb positive and Nb–Ta–Ti negative anomalies. However, paleogeographic constraints suggest that the SCS was located far from subduction zones, so these geochemical signatures could be better explained by a recycling of continental crustal components within the mantle. The most primitive SCS gabbros expand the Sr–Nd isotopic compositional range of the Variscan basic magmatism in the Central Iberian Zone to more depleted values. This reflects a heterogeneous sub-continental lithospheric mantle under central Spain ranging from a depleted mantle (εNd = + 3.1, 87Sr/86Sr = 0.704) towards an isotopically enriched component (εNd = − 1.6, 87Sr/86Sr = 0.706). Geochemical modelling suggests that mantle enrichment could be explained by minor lower crustal metapelitic granulite contamination (~ 2%). Additionally, the Sr–Nd–Pb isotopic ratios of the most primitive gabbros match the composition of the European subcontinental lithospheric mantle recorded in ultramafic xenoliths from western and central Europe.This work is included in the objectives of, and supported by, the CGL-2008-05952 project of the Ministerio de Educación y Ciencia of Spain and the CCG07-UCM/AMB-2652 project of the Complutense University of Madrid.Peer reviewe

Oxygen isotope composition of magnetite in iron ores of the Kiruna type in Chile and Sweden

Magnetite-apatite iron ores of the Kiruna type, unaffected by deformation, have structures and textures similar to those of igneous rocks. The best examples are the El Laco deposits in northern Chile which resemble lava flows, pyroclastic deposits and dikes. El Laco magnetites have d18O values between 2.3 and 4.2‰ (V-SMOW). Magnetite from ore with a magmatic texture has a mean of 3.7‰, and the mean for magnetite intergrown with pyroxene in veins is 2.4‰. Oxygen isotope data given here, fluid inclusion results and geological evidence indicate that ore formation took place in a cooling magmatic system. Major orebodies resembling lava flows and near-vent pyroclastic deposits crystallized from magma at ca. 1000°C. Fluids from cooling magma deposited magnetite and pyroxene (±apatite) at ca. 800°C in fissures and open spaces, now present as veins cutting major orebodies. There is little evidence for significant magnetite precipitation during hydrothermal conditions. A large province of magnetite-apatite iron ore in central Chile (the Cretaceous iron belt) and the Kiruna district in northern Sweden also contain primary ore of magmatic appearance. Major deposits in the Chilean iron belt and Kiruna contain magmatic-textured magnetites with the following d18O means: Algarrobo = 2.2‰, Romeral = 1.2‰, Cerro Imán = 1.6‰, and Kiirunavaara = 1.5‰. We consider all oxygen isotope data for unoxidized, magmatic-textured magnetite as representative of the Fe-rich magmas. Magnetites affected by hydrothermal alteration, recrystallization and subaerial oxidation have modified isotope signatures

Sandstone-hosted Pb-Zn deposits along the margin of the Scandinavian Caledonides and their possible relationship with nearby Pb-Zn vein mineralisation

Numerous sandstone-hosted Pb-Zn deposits occur along the present-day erosional front of the eastern Scandinavian Caledonides. The largest deposit is Laisvall (64.3 Mt at 4.0% Pb, 0.6% Zn and 9.0 g/t Ag) and since mineralisations generally share similar characteristics (reminding of both SEDEX and MVT-style) the term Laisvall-type has often been used. Typically, mineralised zones occur along sedimentary bedding and consist of disseminated galena and sphalerite and lesser amounts of calcite, fluorite, baryte, pyrite and sericite forming a cement that fill interstitial pores in Neoproterozoic/Eocambrian (e.g. Laisvall) to Cambrian (e.g. Vassbo) sandstones. Deposits occur both in autochtonous and allochtonous sedimentary rocks, and a broad consensus exists about their epigenetic nature, their spatial relationships to syn-sedimentary faults and that ore fluids have scavenged metals from the crystalline basement. However, the detailed ore depositional history and the timing of ore deposition have remained more controversial. New analyses aimed to complement earlier Rb-Sr data (crush-leach technique using sphalerite) fail to support a published three-point isochron age of 467 ± 5 Ma. This is probably due to syn-ore mixing between fluids carrying isotopically variable strontium and inherited problems to analyse sphalerite grains that strictly were deposited from a single ore pulse. Tentatively, strontium in the ores originate from a mix of components derived from the basement, seawater and the local sedimentary host sequences. The lead component has highly radiogenic compositions, and data define sub-parallel linear arrays interpreted to essentially represent mixing of isotopically different types of lead released from regional basement rocks. There are obvious similarities when comparing features of deposits representing two Pb-Zn ore styles, the sandstone-hosted dissemination and the fracture-controlled mineralisation in the granite-dominated basement occurring further east of the Caledonian margin. These include low temperature brines responsible for mineral deposition, the mineralogy and the nature of Rb-Sr and Pb isotope data. We suggest that these types of mineralisation have a common origin and time of emplacement, but it is elusive to propose a well-constrained age. Nonetheless, field observations and other evidence suggest that ore formation is due to large-scale fluid flow triggered by the transition from an extensional to compressional tectonic setting at about 500 Ma. Connected to this mid-Cambrian stage was the development of syn-sedimentary faults and fractures in the basement and in overlying consolidated sandstones. The opening of such zones of weakness enabled a movement of ore-forming fluids infilling pore space in sandstones (disseminated ore) and fractures in the basement (vein ore)

Multi-isotope approach for the identification of metal and fluid sources of the Arroyo Rojo VMS deposit, Tierra del Fuego, Argentina

The Arroyo Rojo deposit, located in Tierra del Fuego, is the most important polymetallic, volcanic-hosted massive sulphide in the rhyolitic belt of the Fuegian Andes. The best intercepts in drill holes indicate a true thickness of 18.6 m and concentrations of 2.2% Cu, 3.9% Pb, 14.5% Zn, 140 g/t Ag, 1.1 g/t Au). This deposit, located near the town of Ushuaia, is hosted in a Middle Jurassic volcanic and volcanoclastic sequence. Massive and semimassive bodies display stacked lenticular morphologies with disseminated mineralization in both the footwall and hanging wall. The associated hydrothermal alteration system is partially conformable with the layering of the volcanic rocks. The ores and host rocks display a penetrative tectonic foliation and were metamorphosed to greenschist facies. Previous studies have not resulted in a consensus regarding the nature and the source of ore-forming fluids and the style of deposition of the sulphides at Arroyo Rojo. In this study, both stable and radiogenic isotopes were used develop a better understanding of these aspects of the deposit. Hydrogen and oxygen isotopes indicate that an evolved seawater mixed with significant contributions from other fluid reservoirs such as magmatic and/or metamorphic waters was the most likely source of the ore-forming fluids. These fluids underwent significant interaction with the underlying volcanic and sedimentary rocks, which promoted partial (Sr isotopes) or full (Pb isotopes) homogenization of radiogenic isotopes. δ34SCDT values suggest that the sulphur was derived from several sources: biogenic reduction of seawater sulphate (BSR) in a restricted to closed basin was mixed with a heavier component derived from inorganic reduction of seawater sulphate (TRS) and possibly from sulphur leached from igneous footwall rocks and/or direct contribution from magmatic fluids. Lateral infiltration of hydrothermal fluids resulted in the formation of a halo of semimassive to disseminated ore due to the replacement of porous, reactive glassy and breccia tuffs. As a result of the hydrothermal circulation, two styles of mineralization are observed in the Arroyo Rojo deposit: a stringer zone and a halo of semimassive to disseminated ore corresponding to sub-seafloor replacement, and syn-sedimentary mineralization consisting of massive sulphides. This model is consistent with the geodynamic context of the study area: a narrow, deep-marine volcano-tectonic rift parallel to the Andean side of South America and related to the initial break-up of Gondwana (ca. 145 Ma).Fil: Biel, C.. Universidad de Zaragoza; EspañaFil: Subías, I.. Universidad de Zaragoza; EspañaFil: Fanlo, I.. Universidad de Zaragoza; EspañaFil: Billström, K.. Swedish Museum of Natural History; SueciaFil: Acevedo, Rogelio Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Austral de Investigaciones Científicas; Argentin