The Niederschlag fluorite-(barite) deposit, Erzgebirge/Germany—a fluid inclusion and trace element study

The Niederschlag fluorite-barite vein deposit in the Western Erzgebirge, Germany, has been actively mined since 2013. We present the results of a first comprehensive study of the mineralogy, petrography, fluid inclusions, and trace element geochemistry of fluorite related to the Niederschlag deposit. Two different stages of fluorite mineralization are recognized. Stage I fluorite is older, fine-grained, associated with quartz, and forms complex breccia and replacement textures. Conversely, the younger Stage II fluorite is accompanied by barite and often occurs as banded and coarse crystalline open-space infill. Fluid inclusion and REY systematics are distinctly different for these two fluorite stages. Fluid inclusions in fluorite I reveal the presence of a low to medium saline (7–20% eq. w (NaCl+CaCl2)) fluid with homogenization temperatures of 140–180 °C, whereas fluorite II inclusions yield distinctly lower (80–120 °C) homogenization temperatures with at least two high salinity fluids involved (18–27% eq. w (NaCl+CaCl2)). In the absence of geochronological data, the genesis of the earlier generation of fluorite-quartz mineralization remains enigmatic but is tentatively related to Permian magmatism in the Erzgebirge. The younger fluorite-barite mineralization, on the other hand, has similarities to many fluorite-barite-Pb-Zn-Cu vein deposits in Europe that are widely accepted to be related to the Mesozoic opening of the northern Atlantic Ocean.European Social Fund http://dx.doi.org/10.13039/50110000489

Distribution and solubility limits of trace elements in hydrothermal black smoker sulfides: An in-situ LA-ICP-MS study

The key for understanding the trace metal inventory of currently explored VHMS deposits lies in the understanding of trace element distribution during the formation of these deposits on the seafloor. Recrystallization processes already occurring at the seafloor might liberate trace elements to later hydrothermal alteration and removement. To investigate the distribution and redistribution of trace elements we analyzed sulfide minerals from 27 black smoker samples derived from three different seafloor hydrothermal fields: the ultramafic-hosted Logatchev hydrothermal field on the Mid-Atlantic Ridge, the basaltic-hosted Turtle Pits field on the mid-atlantic ridge, and the felsic-hosted PACMANUS field in the Manus basin (Papua New Guinea). The sulfide samples were analyzed by mineral liberation analyser for the modal abundances of sulfide minerals, by electron microprobe for major elements and by laser ablation-inductively coupled plasma-mass spectrometry for As, Sb, Se, Te, and Au. The samples consist predominantly of chalcopyrite, sphalerite, pyrite, galena and minor isocubanite as well as inclusions of tetrahedrite–tennantite. Laser ablation spectra were used to evaluate the solubility limits of trace elements in different sulfide minerals at different textures. The solubility of As, Sb, and Au in pyrite decreases with increasing degree of recrystallization. When solubility limits are reached these elements occur as inclusions in the different sulfide phases or they are expelled from the mineral phase. Most ancient VHMS deposits represent felsic or bimodal felsic compositions. Samples from the felsic-hosted PACMANUS hydrothermal field at the Pual ridge (Papua New Guinea) show high concentrations of Pb, As, Sb, Bi, Hg, and Te, which is likely the result of an additional trace element contribution derived from magmatic volatiles. Co-precipitating pyrite and chalcopyrite are characterized by equal contents of Te, while chalcopyrite that replaced pyrite (presumably during black smoker growth) is enriched in Te relative to pyrite. These higher Te concentrations may be related to higher fluid temperature

The Niederschlag fluorite-(barite) deposit, Erzgebirge/Germany—a fluid inclusion and trace element study

<jats:title>Abstract</jats:title><jats:p>The Niederschlag fluorite-barite vein deposit in the Western Erzgebirge, Germany, has been actively mined since 2013. We present the results of a first comprehensive study of the mineralogy, petrography, fluid inclusions, and trace element geochemistry of fluorite related to the Niederschlag deposit. Two different stages of fluorite mineralization are recognized. Stage I fluorite is older, fine-grained, associated with quartz, and forms complex breccia and replacement textures. Conversely, the younger Stage II fluorite is accompanied by barite and often occurs as banded and coarse crystalline open-space infill. Fluid inclusion and REY systematics are distinctly different for these two fluorite stages. Fluid inclusions in fluorite I reveal the presence of a low to medium saline (7–20% eq. w (NaCl+CaCl<jats:sub>2</jats:sub>)) fluid with homogenization temperatures of 140–180 °C, whereas fluorite II inclusions yield distinctly lower (80–120 °C) homogenization temperatures with at least two high salinity fluids involved (18–27% eq. w (NaCl+CaCl<jats:sub>2</jats:sub>)). In the absence of geochronological data, the genesis of the earlier generation of fluorite-quartz mineralization remains enigmatic but is tentatively related to Permian magmatism in the Erzgebirge. The younger fluorite-barite mineralization, on the other hand, has similarities to many fluorite-barite-Pb-Zn-Cu vein deposits in Europe that are widely accepted to be related to the Mesozoic opening of the northern Atlantic Ocean.</jats:p&gt

Fluorite Mineralization Related to Carbonatitic Magmatism in the Western Transbaikalia: Insights from Fluid Inclusions and Trace Element Composition

Fluorite mineralization associated with different types of magmatism is common in the Western Transbaikalia. This study deals with Arshan, Yuzhnoe, and Ulan-Ude fluorite occurrences, which are the most significant examples of carbonatite-related fluorite mineralization in the region. The present paper focused on new fluorite geochemistry and fluid inclusion data, is aimed at revealing conditions of the fluorite mineralization formation, highlighting its genetic relationship with magmatism, compared to other deposits of this type. All the three locations belong to the Late Mesozoic Central Asian carbonatite province. Fluorites here are characterized by high rare earth elements (REE), Sr, and elevated La/Yb values. Fluid inclusions data imply that the formation of fluorite mineralization is a long process extending from late magmatic to the hydrothermal stage. Early fluorite crystallized from sulfate-carbonate orthomagmatic fluids at temperatures up to 500 °C. True hydrothermal fluorite was formed from the same fluids that were probably mixed with meteoric waters, which caused the temperature to drop to below 420 °C and led to an increase in the chloride component. The REE compositions of fluorite from the studied locations are similar to compositions of REE-rich fluorites from carbonatite-related deposits around the world

Structure and evolution of the volcanic rift zone at São Lourenço peninsula, Madeira

Ponta de São Lourenço is the deeply eroded eastern end of Madeira’s east–west trending rift zone, located near the geometric intersection of the Madeira rift axis with that of the Desertas Islands to the southeast. It dominantly consists of basaltic pyroclastic deposits from Strombolian and phreatomagmatic eruptions, lava flows, and a dike swarm. Main differences compared to highly productive rift zones such as in Hawai’i are a lower dike intensity (50–60 dikes/km) and the lack of a shallow magma reservoir or summit caldera. 40Ar/39Ar age determinations show that volcanic activity at Ponta de São Lourenço lasted from >5.2 to 4 Ma (early Madeira rift phase) and from 2.4 to 0.9 Ma (late Madeira rift phase), with a hiatus dividing the stratigraphy into lower and upper units. Toward the east, the distribution of eruptive centers becomes diffuse, and the rift axis bends to parallel the Desertas ridge. The bending may have resulted from mutual gravitational influence of the Madeira and Desertas volcanic edifices. We propose that Ponta de São Lourenço represents a type example for the interior of a fading rift arm on oceanic volcanoes, with modern analogues being the terminations of the rift zones at La Palma and El Hierro (Canary Islands). There is no evidence for Ponta de São Lourenço representing a former central volcano that interconnected and fed the Madeira and Desertas rifts. Our results suggest a subdivision of volcanic rift zones into (1) a highly productive endmember characterized by a central volcano with a shallow magma chamber feeding one or more rift arms, and (2) a less productive endmember characterized by rifts fed from deep-seated magma reservoirs rather than from a central volcano, as is the case for Ponta de São Lourenço

A Comparative study of five reference materials and the Lombard meteorite for the determination of the platinum-group elements and gold by LA-ICP-MS

A range of independently characterised reference materials (RMs) for LA-ICP-MS, used for the determination of the platinum-group elements (PGE) and Au in a sulfide matrix, were analysed and compared: 8b, PGE-A, NiS-3, Po727-T1, Po724-T and the Lombard meteorite. The newly developed RM NiS-3 was used as the RM for the calibration of all LA-ICP-MS analyses and the measured concentrations of the other RMs compared against their published concentrations. This data were also used to assess the consistency of concentrations calibrated against the different RMs. It was found that Po727-T1 and 8b produced results that were comparable, within uncertainty, for all elements. Po727-T1 also produced consistent results with NiS-3 for all elements. All other RMs showed differences for some elements, especially Ru in Po724-T, and Os, Ir and Au in PGE-A. The homogeneity of the PGE and Au in each RM was assessed, by comparing the precision of multiple LA-ICP-MS spot analyses with the average uncertainty of the signal. Po724-T, Po727-T1 and the Lombard meteorite were found to be homogeneous for all elements, but 8b, PGE-A and NiS-3 were heterogeneous for some elements. This is the first direct comparison between a range of independently characterised PGE and Au LA-ICP-MS RMs.14 page(s

A Comparative Study of Five Reference Materials and the Lombard Meteorite for the Determination of the Platinum-Group Elements and Gold by LA-ICP-MS

A range of independently characterised reference materials (RMs) for LA-ICP-MS, used for the determination of the platinum-group elements (PGE) and Au in a sulfide matrix, were analysed and compared: 8b, PGE-A, NiS-3, Po727-T1, Po724-T and the Lombard meteorite. The newly developed RM NiS-3 was used as the RM for the calibration of all LA-ICP-MS analyses and the measured concentrations of the other RMs compared against their published concentrations. This data were also used to assess the consistency of concentrations calibrated against the different RMs. It was found that Po727-T1 and 8b produced results that were comparable, within uncertainty, for all elements. Po727-T1 also produced consistent results with NiS-3 for all elements. All other RMs showed differences for some elements, especially Ru in Po724-T, and Os, Ir and Au in PGE-A. The homogeneity of the PGE and Au in each RM was assessed, by comparing the precision of multiple LA-ICP-MS spot analyses with the average uncertainty of the signal. Po724-T, Po727-T1 and the Lombard meteorite were found to be homogeneous for all elements, but 8b, PGE-A and NiS-3 were heterogeneous for some elements. This is the first direct comparison between a range of independently characterised PGE and Au LA-ICP-MS RMs

Metal budget and origin of aqueous brines depositing deep-seated Zn-Pb mineralization linked to hydrocarbon reservoirs, North German Basin

The origin, evolution, and interplay of brine and hydrocarbon fluid systems play a crucial role in the formation of deep sediment-hosted base metal ore deposits. Here we investigate ratios of halogens, noble gases, stable C and S isotopes, and metal budgets of aqueous brines, which deposited deep-seated and near-surface hydrothermal Zn-Pb mineralization hosted by Zechstein carbonates in the Lower Saxony Basin (North German Basin), by studies of fluid inclusions in sphalerite and quartz. Major and trace element geochemistry and noble gas isotopic signatures of brine inclusions revealed that the ore-forming fluids were highly reactive and experienced prolonged interactions with host rocks in the constricted, over-pressured metal source regions and consequently evolved from near-neutral, oxidized brines towards more reduced, acidic high-salinity brines. Quartz-hosted halite-saturated fluid inclusions with T-h <200 degrees C contain Zn and Pb concentrations up to ca. 9400 mu g g(-1) and 5200 mu g g(-1), respectively, and indicate the efficiency of metal scavenging processes. The interactions with Westphalian coals and C-org-rich shales influenced the redox state as well as the trace and critical element budget of the sphalerite-hosted fluid inclusions, with enrichment in Ge, Pd, Sb, Tl, Bi, and Ag. The salinities of metalliferous fluids originated primarily from seawater evaporation, however in addition a significant halite-dissolution component is present in the southern part of the Lower Saxony Basin. High concentrations of radiogenic noble gases and potassium in the sphalerite-hosted fluid inclusions are ascribed to strong interactions with the Paleozoic siliciclastic sedimentary pile and crystalline basement rocks. Reflux of the strongly modified, sulfur-poor, Zn-Pb-bearing acidic brines, proceeded via re-activated structurally controlled pathways into sour gas or gas-saturated brine pools in the Zechstein Ca2 carbonate unit. Here, mixing of the ascending metal-rich brines with H2S derived from thermochemical sulfate reduction (TSR), resulted in the deposition of deep-seated Zn-Pb ores in the Lower Saxony Basin. The overall timing of the Zn-Pb ore formation can be constrained to the Upper Cretaceous basin inversion.ISSN:0026-4598ISSN:1432-186

Coupled Fe and S isotope variations in pyrite nodules from Archean shale

Iron and sulfur isotope compositions recorded in ancient rocks and minerals such as pyrite (FeS2) have been widely used as a proxy for early microbial metabolisms and redox evolution of the oceans. However, most previous studies focused on only one of these isotopic systems. Herein, we illustrate the importance of in-situ and coupled study of Fe and S isotopes on two pyrite nodules in a c. 2.7 Ga shale from the Bubi Greenstone Belt (Zimbabwe). Fe and S isotope compositions were measured both by bulk-sample mass spectrometry techniques and by ion microprobe in-situ methods (Secondary Ion Mass Spectrometry, SIMS). Spatially-resolved analysis across the nodules shows a large range of variations at micrometer-scale for both Fe and S isotope compositions, with δ56Feδ56Fe and δ34Sδ34S values from −2.1 to +0.7‰+0.7‰ and from −0.5 to +8.2‰+8.2‰, respectively, and Δ33SΔ33S values from −1.6 to +2.9‰+2.9‰. The Fe and S isotope variations in these nodules cannot be explained by tandem operation of Dissimilatory Iron Reduction (DIR) and Bacterial Sulfate Reduction (BSR) as was previously proposed, but rather they reflect the contributions of different Fe and S sources during a complex diagenetic history. Pyrite formed from two different mineral precursors: (1) mackinawite precipitated in the water column, and (2) greigite formed in the sediment during early diagenesis. The in-situ analytical approach reveals a complex history of the pyrite nodule growth and allows us to better constrain environmental conditions during the Archean

Timing, petrogenesis, and setting of granites from the southern Beishan late Palaeozoic granitic belt, Northwest China and implications for their tectonic evolution

<div><p>Late Palaeozoic granites are widely distributed in the southeastern Beishan area, which is located in the central part of the southern Central Asian Orogenic Belt (CAOB). U–Pb zircon dates of five late Palaeozoic granitic plutons from the southeastern Beishan area yield Permian ages: 285 ± 2 Ma (Shuwojing and Western Shuwojing plutons), 269 ± 3 Ma (Jianquanzi and Jiuquandihongshan plutons), and 260 ± 1 Ma (Jiujing pluton). The early Permian Shuwojing pluton, an unfractionated calc-alkaline biotite monzogranite with slightly positive εNd(<i>t</i>) (+0.7 and +0.6) and low initial ⁸⁷Sr/⁸⁶Sr (0.70722 and 0.70712), and the early Permian Western Shuwojing pluton, a high-K calc-alkaline biotite granite with slightly negative εNd(<i>t</i>) (−0.2 and −0.1) and low initial ⁸⁷Sr/⁸⁶Sr (0.70390 and 0.70919), are likely derived from a mixture of depleted (juvenile) mantle and upper continental crustal (or sedimentary) material. The mid-Permian Jianquanzi and Jiuquandihongshan monzogranites have highly fractionated potassium-rich calc-alkaline characteristics with negative εNd(<i>t</i>) (−4.3) and very high initial ⁸⁷Sr/⁸⁶Sr (0.71949), reflecting a continental crustal component. The compositionally diverse Jiujing pluton and the granodiorite and high-Sr monzogranite phases display adakite-like compositions with relatively low εNd(<i>t</i>) (−0.1 and −2.2) and high initial ⁸⁷Sr/⁸⁶Sr (0.70822 and 0.70913). The Jiujing low-Sr monzogranite has higher initial ⁸⁷Sr/⁸⁶Sr (0.73464) and lower εNd(<i>t</i>) (−2.8), indicating a significant continental crustal component in its genesis. This work, combined with the regional geology and previous studies, suggest that the early to middle Permian southern Beishan plutons formed in a post-collisional environment, probably an intracontinental rift environment linked to asthenospheric upwelling in response to the break-off of a subducted slab. In the late Permian, the southern Beishan area was in a compressive tectonic regime and thickening of the continental crust resulted in the formation of the Jiujing adakite-like granite.</p></div