Cenozoic intra-plate magmatism in the Darfur volcanic province: mantle source, phonolite-trachyte genesis and relation to other volcanic provinces in NE Africa

Chemical and Sr, Nd and Pb isotopic compositions of Late Cenozoic to Quaternary small-volume phonolite, trachyte and related mafic rocks from the Darfur volcanic province/NW-Sudan have been investigated. Isotope signatures indicate variable but minor crustal contributions. Some phonolitic and trachytic rocks show the same isotopic composition as their primitive mantle-derived parents, and no crustal contributions are visible in the trace element patterns of these samples. The magmatic evolution of the evolved rocks is dominated by crystal fractionation. The Si-undersaturated strongly alkaline phonolite and the Si-saturated mildly alkaline trachyte can be modelled by fractionation of basanite and basalt, respectively. The suite of basanite–basalt–phonolite–trachyte with characteristic isotope signatures from the Darfur volcanic province fits the compositional features of other Cenozoic intra-plate magmatism scattered in North and Central Africa (e.g., Tibesti, Maghreb, Cameroon line), which evolved on a lithosphere that was reworked or formed during the Neoproterozoic.     

Early Holocene M~6 explosive eruption from Plosky volcanic massif (Kamchatka) and its tephra as a link between terrestrial and marine paleoenvironmental records

We report tephrochronological and geochemical data on early Holocene activity from Plosky volcanic massif in the Kliuchevskoi volcanic group, Kamchatka Peninsula. Explosive activity of this volcano lasted for ~1.5 kyr, produced a series of widely dispersed tephra layers, and was followed by profuse low-viscosity lava flows. This eruptive episode started a major reorganization of the volcanic structures in the western part of the Kliuchevskoi volcanic group. An explosive eruption from Plosky (M~6), previously unstudied, produced tephra (coded PL2) of a volume of 10–12 km³ (11–13 Gt), being one of the largest Holocene explosive eruptions in Kamchatka. Characteristic diagnostic features of the PL2 tephra are predominantly vitric sponge-shaped fragments with rare phenocrysts and microlites of plagioclase, olivine and pyroxenes, medium- to high-K basaltic andesitic bulk composition, high-K, high-Al and high-P trachyandesitic glass composition with SiO₂ = 57.5–59.5 wt%, K₂O = 2.3–2.7 wt%, Al₂O₃ = 15.8–16.5 wt%, and P₂O₅ = 0.5–0.7 wt%. Other diagnostic features include a typical subduction-related pattern of incompatible elements, high concentrations of all REE (>10× mantle values), moderate enrichment in LREE (La/Yb ~ 5.3), and non-fractionated mantle-like pattern of LILE. Geochemical fingerprinting of the PL2 tephra with the help of EMP and LA-ICP-MS analyses allowed us to map its occurrence in terrestrial sections across Kamchatka and to identify this layer in Bering Sea sediment cores at a distance of >600 km from the source. New high-precision ¹⁴C dates suggest that the PL2 eruption occurred ~10,200 cal BP, which makes it a valuable isochrone for early Holocene climate fluctuations and permits direct links between terrestrial and marine paleoenvironmental records. The terrestrial and marine ¹⁴C dates related to the PL2 tephra have allowed us to estimate an early Holocene reservoir age for the western Bering Sea at 1,410 ± 64 ¹⁴C years. Another important tephra from the early Holocene eruptive episode of Plosky volcano, coded PL1, was dated at 11,650 cal BP. This marker is the oldest geochemically characterized and dated tephra marker layer in Kamchatka to date and is an important local marker for the Younger Dryas—early Holocene transition. One more tephra from Plosky, coded PL3, can be used as a marker northeast of the source at a distance of ~110 km.     

Modeling the effect of stratification on cemented layer formation in sulfide-bearing mine tailings

Reactive transport simulations have been applied to investigate possible effects of stratification on the potential of sulfide-bearing mine tailings to form protective cemented layers. The simulations are based on characteristic strata found at a German tailings site, including sulfide-enriched heavy mineral layers, mica-enriched silt layers, and homogeneously mixed layers. The simulated secondary phases (jarosite, gypsum, amorphous ferric arsenate, amorphous Fe hydroxide, alunite, amorphous silica, and kaolinite) are similar to those observed in the field. Using scanning electron microscope analyses of cemented layers, it has been observed that the pore area becomes disconnected if the porosity is decreased to values below 15%, which would indicate a strong decrease in permeability. Stratification was found to play a crucial role in cemented layer formation. Cemented layers are absent or insignificant in systems with a homogeneous distribution of Fe-bearing sulfides. They are extensively developed in systems with (a) an arsenopyrite-rich layer or (b) a mica-enriched layer situated immediately below an Fe-sulfide enriched layer. The modeling results have clearly demonstrated that the key processes operating in scenario (a) are very different from the key processes in scenario (b). In scenario (a), the oxidation of arsenopyrite is followed by the precipitation of amorphous ferric arsenate, which can be solely responsible for significant pore reduction. In scenario (b), the presence of a large amount of reactive aluminosilicates (e.g. biotite and Ca-bearing plagioclase) immediately below the Fe-sulfide rich layer appears to be crucial. Key processes are extensive formation of Acid Rock Drainage (ARD) followed by enhanced (pH-driven) weathering of aluminosilicates, resulting in the accumulation of secondary phases directly below the Fe-sulfide rich layer. In both scenarios, a cemented layer is formed that effectively retards the further downward movement of the oxidation front. The presented details on the role of stratification in the formation of cemented layers could be considered in the construction of mining heaps as a possible measure to stimulate natural attenuation.     

Carbonate diagenesis and feldspar alteration in fracture-related bleaching zones (Buntsandstein,central Germany): possible link to CO<Subscript>2</Subscript>-influenced fluid–mineral reactions

Fracture-related bleaching of Lower Triassic Buntsandstein red beds of central Germany was related to significant carbonate diagenesis and feldspar alteration caused by CO₂-rich fluids. Using cathodoluminescence microscopy and spectroscopy combined with electron microprobe analysis and stable carbon isotope study, two major fluid–mineral interactions were detected: (1) zoned, joint-filling calcites and zoned pore-filling calcite cements, the latter replacing an earlier dolomite, were formed during bleaching. During the calcite formation and dolomite–calcite transformation, iron was incorporated into the calcite cement crystal cores due to Fe availability from the coeval bleaching. The dedolomitisation was ultimately associated with a volume increase. The related permeability decrease implies a certain degree of sealing and increasing retention of CO₂, and the volume increase offers a minor CO₂ sink. Carbonate-rich sandstone, therefore, can provide advantages for underground CO₂ storage especially when situated in the fringes of the reservoir. (2) Alkali-feldspar alteration due to the bleaching fluids is reflected in cathodoluminescence spectra predominantly by the modulation of a brown luminescence emission peak (~620 nm). This peak represents a newly discovered effect related to alkali-feldspar alteration not solely associated with bleaching. Its modulation by the bleaching is interpreted to be due to Na depletion or a lattice defect in the Si–O bonds of the SiO₄-tetrahedron. Alteration reflected by this luminescence feature has a destructive effect on the feldspars implying the possibility of diminished rock integrity due to bleaching and, hence, CO₂-rich fluids. Two further CL spectral changes related to bleaching occur, (a) decreased intensity between around 570 nm assigned to Mn-depletion, and (b) increased amplitude and wavelength shift of the red (~680 nm) band. Converging evidence from carbonate and feldspar diagenesis, stable carbon isotope data and analysis of fracture directions suggests that CO₂ fluids contributed to a significant extent to the bleaching phenomena and alteration in the studied Buntsandstein strata.     

Insights from trace element geochemistry as to the roles of subduction zone geometry and subduction input on the chemistry of arc magmas

Subduction zones of continental, transitional, and oceanic settings, relative to the nature of the overriding plate, are compared in terms of trace element compositions of mafic to intermediate arc rocks, in order to evaluate the relationship between subduction parameters and the presence of subduction fluids. The continental Chilean Southern Volcanic Zone (SVZ) and the transitional to oceanic Central American Volcanic Arc (CAVA) show increasing degrees of melting with increasing involvement of slab fluids, as is typical for hydrous flux melting beneath arc volcanoes. At the SVZ, the central segment with the thinnest continental crust/lithosphere erupted the highest-degree melts from the most depleted sources, similar to the oceanic-like Nicaraguan segment of the CAVA. The northern part of the SVZ, located on the thickest continental crust/lithosphere, exhibits features more similar to Costa Rica situated on the Caribbean Large Igneous Province, with lower degrees of melting from more enriched source materials. The composition of the slab fluids is characteristic for each arc system, with a particularly pronounced enrichment in Pb at the SVZ and in Ba at the CAVA. A direct compositional relationship between the arc rocks and the corresponding marine sediments that are subducted at the trenches clearly shows that the compositional signature of the lavas erupted in the different arcs carries an inherited signal from the subducted sediments.     

Experimental study of mechanical and hydraulic properties of bedded rock salt from the Jintan location

A series of triaxial compression tests, triaxial extension tests, and triaxial compression creep tests were conducted to evaluate the strength, deformability, and permeability of rock salt from the Jintan location. Based on a previous analysis, the measured data can be physically modeled very well as shown by the constitutive model Hou/Lux and indicate that China’s representative bedded rock salt from the Jintan location is characterized by good ductility and deformation properties, similar to the European high-purity rock salt. Based on a comparison of compression as well as extension failure strength determined at rock salt from Jintan location, a similarity of compression and extension failure strength could be demonstrated. Permeation flow seems to be an anisotropic process because the permeability measured at samples prior to failure by compression tests differs to those measured at samples prior to failure by extension tests. The anisotropy of damage and destruction of rock salt has a significant influence on permeability. In case of triaxial compression tests, the measured permeability increases two to six orders of magnitude because of consistent direction of injection and cracks. In case of triaxial extension tests, however, the permeability increases less with a maximum of two orders in magnitude. The test results are significant for understanding the load-bearing behavior of rock salt from Jintan location and investigations with reference to the stability and tightness of underground caverns.     

Retention of uranium in complexly altered zircon: An example from Bancroft,Ontario

Mesoproterozoic (~ 1050 Ma; Stenian) zircon crystals from the Saranac Prospect, Bancroft, Ontario, contain up to ~ 1 wt.% U and ~ 0.15 wt.% Th and, correspondingly, they are for the most part extensively radiation-damaged (calculated total α-doses 2.3?35.3 × 10¹⁸/g). The crystals show textures of complex, intense chemical alteration that is attributed to multiple, low-T replacement events along fluid-controlled reaction fronts. Centers of crystals appear totally replaced; the primary zoning is virtually erased and the material has high porosity and numerous inclusions. Interior regions surrounding the central reworked areas still exhibit primary igneous-type zoning; in those regions the alteration emanates from fractures and then follows the more radiation-damaged growth zones. Altered areas are typically recognized by their high porosity, low BSE intensity, and deficient analytical totals. Those regions often have lost a significant fraction of their radiogenic Pb. They are in general somewhat depleted in Zr, Si, and U, and are notably enriched in Ca and Fe. Element maps reveal elevated concentrations of Al and Y within filled fractures. Our observations indicate that the fluid-driven ion exchange is mainly controlled by the accessibility of micro-areas with elevated levels of radiation damage to transporting fluids via “fast pathways”. Most importantly, there is apparent Zr?Si?U equilibrium between initially existing and newly formed zircon. The retention of U after the chemical replacement (94 ± 14% relative to the original U content in the respective zones) does not significantly fall below the retention of two major cations Zr (95 ± 4%) and Si (95 ± 2%). In spite of the partially extreme hydrothermal alteration overprinting, the original U zoning in the crystals is well preserved. These observations suggest that preferential chemical leaching of U from zircon is clearly not a general feature of this mineral. This in turn seems to question the general validity of hydrothermal experiments to low-T, fluid-driven alteration of zircon in geological environments. The observed apparent immobility of U may affect the interpretation of U?Pb discordance in zircon, and the performance assessment of this mineral as potential waste form for actinides.     

Symplectite formation during decompression induced garnet breakdown in lower crustal mafic granulite xenoliths: mechanisms and rates

The complex microstructure of kelyphitic rims around garnet in lower crustal garnet granulite xenoliths from the Bakony–Balaton Highland Volcanic Field, Central Pannonian Basin has been studied in order to identify controls on garnet breakdown. Symplectites comprised of a vermicular intergrowth of submicron sized anorthite, orthopyroxene and spinel replace garnet at a sharp reaction front. Based on element distribution maps the transformation of garnet to symplectite is isochemical. Phase diagram calculations indicate that this reaction was induced by a pressure decrease and/or a temperature increase. In site-specific TEM foils prepared by focused ion beam technique and oriented parallel and perpendicular to the reaction front 200 nm wide rods of anorthite and 20 nm wide rods of spinel are identified. The rods are oriented approximately perpendicular to the replacement front and are embedded in an orthopyroxene matrix. The regular spacing of the symplectite phases along the reaction front suggests that their growth is controlled by diffusion. The kinetics of symplectite formation has been modelled based on irreversible thermodynamics. During interaction of the xenolith with the host basalt the microstructure and chemistry of the An–Opx–Spl symplectite was significantly modified and it was partially replaced by an olivine bearing symplectite. In contrast to primary symplectite formation, these processes were metasomatic in nature including addition of sodium, titanium and some trace elements from the basaltic melt and can clearly be discerned from the garnet breakdown. Based on these observations it is inferred that symplectite formation took place within the deep crust during the extension of the Pannonian Basin between 15 and 30 km depth at high temperature (850–1,050°C) prior to the volcanic transport to the surface.