Experimental constraints on ultrapotassic magmatism from the Bohemian Massif (durbachite series, Czech Republic)

The equilibrium phase relations of a mafic durbachite (53 wt.% SiO₂) from the Třebíč pluton, representative of the Variscan ultrapotassic magmatism of the Bohemian Massif (338–335 Ma), have been determined as a function of temperature (900–1,100°C), pressure (100–200 MPa), and H₂O activity (1.1–6.1 wt.% H₂O in the melt). Two oxygen fugacity ranges were investigated: close to the Ni–NiO (NNO) buffer and 2.6 log unit above NNO buffer (∆NNO + 2.6). At 1,100°C, olivine is the liquidus phase and co-crystallized with phlogopite and augite at 1,000°C for the whole range of investigated pressure and water content in the melt. At 900°C, the mineral assemblage consists of augite and phlogopite, whereas olivine is not stable. The stability field of both alkali feldspar and plagioclase is restricted to low pressure (100 MPa) at nearly water-saturated conditions (<3–4 wt.% H₂O) and T < 900°C. A comparison between experimental products and natural minerals indicates that mafic durbachites have a near-liquidus assemblage of olivine, augite, Ti-rich phlogopite, apatite and zircon, followed by alkali feldspar and plagioclase, similar to the mineral assemblage of minette magma. Natural amphibole, diopside and orthopyroxene were not reproduced experimentally and probably result from sub-solidus reactions, whereas biotite re-equilibrated at low temperature. The crystallization sequence olivine followed by phlogopite and augite reproduces the sequence inferred in many mica-lamprophyre rocks. The similar fractionation trends observed for durbachites and minettes indicate that mafic durbachites are probably the plutonic equivalents of minettes and that K- and Mg-rich magmas in the Bohemian Massif may have been generated from partial melting of a phlogopite–clinopyroxene-bearing metasomatized peridotite. Experimental melt compositions also suggest that felsic durbachites can be generated by simple fractionation of a more mafic parent and mixing with mantle-derived components at mid crustal pressures.     

Mineralogy and major-trace element geochemistry of the Haymana manganese mineralizations,Ankara, Turkey

The study area comprises Çayirli, Harapa?illari and Ortabel (ÇHO) districts in the Haymana town 25 km SW of the Ankara city. In this study, geologic setting, mineralogical and geochemical characteristics of manganese mineralizations are examined and their origin is discussed. Data were obtained from field observations, various polished and thin section determinations and chemical analyses of 25 ore samples. Major and trace element analyses were conducted with ICP-ES and ICP-MS methods at ACME Laboratories (Canada). ÇHO manganese ores are found in reddish radiolarites and partly interbedded marls of the Ankara ophiolitic melange of lower Cretaceous-upper Senonian age. In these extremely folded rocks, manganese is observed as band and lenses. All samples are composed of pyrolusite and quartz. Circular pyrolusites around the gangue form a ring texture and radiolarite ores yield spherical sections. In addition, breccia-like texture is observed between pyrolusite and quartz. Geologic setting, mineralogical and textural data indicate an exogene environment. Major and trace element abundances and correlation among them imply that ÇHO mineralizations are of hydrothermal origin and linked to the same source. Evaluation of all these data shows that ÇHO manganese mineralizations are of hydrothermal type sedimentary mineralization and they were deposited in distal part of the source.     

Aerobic oxidation of mackinawite (FeS) and its environmental implication for arsenic mobilization

Oxidation of mackinawite (FeS) and concurrent mobilization of arsenic were investigated as a function of pH under oxidizing conditions. At acidic pH, FeS oxidation is mainly initiated by the proton-promoted dissolution, which results in the release of Fe(II) and sulfide in the solution. While most of dissolved sulfide is volatilized before being oxidized, dissolved Fe(II) is oxidized into green rust-like precipitates and goethite (α-FeOOH). At basic pH, the development of Fe(III) (oxyhydr)oxide coating on the FeS surface inhibits the solution-phase oxidation following FeS dissolution. Instead, FeS is mostly oxidized into lepidocrocite (γ-FeOOH) via the surface-mediated oxidation without dissolution. At neutral pH, FeS is oxidized via both the solution-phase oxidation following FeS dissolution and the surface-mediated oxidation mechanisms. The mobilization of arsenic during FeS oxidation is strongly affected by FeS oxidation mechanisms. At acidic pH (and to some extent at neutral pH), the rapid FeS dissolution and the slow precipitation of Fe (oxyhydr)oxides results in arsenic accumulation in water. In contrast, the surface-mediated oxidation of FeS at basic pH leads to the direct formation of Fe (oxyhydr)oxides, which provides effective adsorbents for As under oxic conditions. At acidic and neutral pH, the solution-phase oxidation of dissolved Fe(II) accelerates the oxidation of the less adsorbing As(III) to the more adsorbing As(V). This study reveals that the oxidative mobilization of As may be a significant pathway for arsenic enrichment of porewaters in sulfidic sediments.     

Ferrous phosphate surface precipitates resulting from the reduction of intragrain 6-line ferrihydrite by Shewanella oneidensis MR-1

The reductive biotransformation of 6-line ferrihydrite located within porous silica (intragrain ferrihydrite) by Shewanella oneidensis MR-1 was investigated and compared to the behavior of 6-line ferrihydrite in suspension (free ferrihydrite). The effect of buffer type (PIPES and NaHCO₃), phosphate (P), and an electron shuttle (AQDS) on the extent of reduction and formation of Fe(II) secondary phases was investigated under anoxic conditions. Electron microscopy and micro X-ray diffraction were applied to evaluate the morphology and mineralogy of the biogenic precipitates and to study the distribution of microorganisms on the surface of porous silica after bioreduction. Kinetic reduction experiments with free and intragrain ferrihydrite revealed contrasting behavior with respect to the buffer and presence of P. The overall amount of intragrain ferrihydrite reduction was less than that of free ferrihydrite [at 5 mmol L⁻¹ Fe(III)_T]. Reductive mineralization was not observed in the intragrain ferrihydrite incubations without P, and all biogenic Fe(II) concentrated in the aqueous phase. Irrespective of buffer and AQDS addition, rosettes of Fe(II) phosphate of approximate 20-30 μm size were observed on porous silica when P was present. The rosettes grew not only on the silica surface but also within it, forming a coherent spherical structure. These precipitates were well colonized by microorganisms and contained extracellular materials at the end of incubation. Microbial extracellular polymeric substances may have adsorbed Fe(II) promoting Fe(II) phosphate nucleation with subsequent crystal growth proceeding in different directions from a common center.     

Unsteady diagenetic processes and sulfur biogeochemistry in tropical deltaic muds: Implications for oceanic isotope cycles and the sedimentary record

Sedimentary S cycling is usually conceptualized and interpreted within the context of steadily accreting (1-D) transport-reaction regimes. Unsteady processes, however, are common in many sedimentary systems and can result in dramatically different S reaction balances and diagenetic products than steady conditions. Globally important common examples include tropical deltaic topset and inner shelf muds such as those extending from the Amazon River ∼1600 km along the Guianas coast of South America. These deposits are characterized by episodic reworking of the surface seabed over vertical depths of ∼0.1-3 m. Reworked surface sediments act as unsteady, suboxic batch reactors, unconformably overlying relict anoxic, often methanic deposits, and have diagenetic properties largely decoupled from net accumulation of sediment. Despite well-oxygenated water and an abundant reactive organic matter supply, physical disturbance inhibits macrofauna, and benthic communities are dominated by microbial biomass across immense areas. In the surficial suboxic layer, molecular biological analyses, tracer experiments, sediment C/S/Fe compositions, and δ³⁴S, δ¹⁸O of pore water indicate close coupling of anaerobic C, S, and Fe cycles. δ¹⁸O- can increase by 2-3‰ during anaerobic recycling without net change in δ³⁴S-, demonstrating reduction coupled to complete anaerobic reoxidation to and a δ¹⁸O- reduction + reoxidation fractionation factor?12‰ (summed magnitudes). S reoxidation must be coupled to Fe-oxide reduction, contributing to high dissolved Fe²⁺ (∼1 mM) and Fe mobilization-export. The reworking of Amazon-Guianas shelf muds alone may isotopically alter δ¹⁸O- equivalent in mass to?25% of the annual riverine delivery of to the global ocean. Unsteady conditions result in preservation of unusually heavy δ³⁴S isotopic compositions of residual Cr reducible S, ranging from 0‰ to >30‰ in physically reworked deposits. In contrast, bioturbated facies adjacent to physically reworked regions accumulate isotopically light S (δ³⁴S to −20‰) in otherwise similar decomposition regimes. The isotopic patterns of both physically and biologically reworked regions can be simulated with simple diagenetic models. Heavy S isotopic signatures are largely a consequence of unsteady diffusion and progressive anaerobic burndown into underlying deposits, whereas isotopically depleted bioturbated deposits predominantly reflect biogenic diffusive scaling and isotopic distillation/diffusive pumping associated with reoxidation in burrow walls immediately adjacent to reduced zones. The S isotopic transition from unsteady physically controlled regions of the Amazon delta moving laterally into bioturbated facies mimics the transition of S isotopic patterns temporally in the geologic record during the rise of bioturbation. No special role for S disproportionation is required to explain these differences. The potential role of unsteady, suboxic diagenesis and dynamic reworking of sediments has been largely ignored in models of the evolution of surficial elemental cycling and interpretations of the geologic record.     

The growth of the continental crust: Constraints from zircon Hf-isotope data

A worldwide database of over 13,800 integrated U–Pb and Hf-isotope analyses of zircon, derived largely from detrital sources, has been used to examine processes of crustal evolution on a global scale, and to test existing models for the growth of continental crust through time. In this study we introduce a new approach to quantitatively estimating the proportion of juvenile material added to the crust at any given time during its evolution. This estimate is then used to model the crustal growth rate over the 4.56 Ga of Earth's history. The modelling suggests that there was little episodicity in the production of new crust, as opposed to peaks in magmatic ages. The distribution of age-Hf isotope data from zircons worldwide implies that at least 60% of the existing continental crust separated from the mantle before 2.5 Ga. However, taking into consideration new evidence coming from geophysical data, the formation of most continental crust early in Earth's history (at least 70% before 2.5 Ga) is even more probable. Thus, crustal reworking has dominated over net juvenile additions to the continental crust, at least since the end of the Archean. Moreover, the juvenile proportion of newly formed crust decreases stepwise through time: it is about 70% in the 4.0–2.2 Ga time interval, about 50% in the 1.8–0.6 Ga time interval, and possibly less than 50% after 0.6 Ga. These changes may be related to the formation of supercontinents.     

Provenance of Lower Cretaceous Wölong Volcaniclastics in the Tibetan Tethyan Himalaya: Implications for the final breakup of Eastern Gondwana

Lower Cretaceous volcanic lithic arenites, widely distributed in the Tethyan Himalaya, provide insights into the continental breakup of Eastern Gondwana. In southern Tibet they are represented by the Wölong Volcaniclastics. The volcanic rocks that contributed clastic material to the lower parts of this unit were predominantly alkali basalts, whereas rhyolitic/dacitic volcanism becomes the predominant source of the upper strata. Geochemical analyses of basaltic grains and of detrital Cr-spinels from the Wölong Volcaniclastics demonstrate the alkaline character of the volcanism and suggest “within-plate” tectonic setting for the volcanism. Zircon U–Pb ages confirm that this volcanism continued from ～ 140 Ma to ～ 119 Ma. Hf-isotope data on these Early Cretaceous zircons indicate that their parental magmas were mantle-derived, but in the later stage of magmatic activity mantle-derived magmas were mixed with partial melts derived from the continental crust.The Lower Cretaceous volcaniclastics occur along a broad belt paralleling the northern margin of Greater India. The onset of volcaniclastic deposition in the Himalayas appears to become progressively younger toward the west, but it ended synchronously during the Late Albian (～ 102 Ma). The low volume of volcanic rocks and their intra-plate tectonic setting suggest that they are the result of decompressional melting along extensional deep-seated fractures cross-cutting the continental crust, and reflect changes in regional intra-plate tectonic stresses when Greater India began to separate from the Australia–Antarctica supercontinent.     

Biological influences on modern sulfates: Textures and composition of gypsum deposits from Guerrero Negro,Baja California Sur,Mexico

Gypsum (CaSO₄·2H₂O) deposits from a range of sedimentary environments at Guerrero Negro, Baja California Sur, Mexico were investigated for microscale texture and composition in order to differentiate features formed under substantial microbial influence from those for which microbial effects were relatively minor or absent. Gypsum deposits were classified according to their sedimentary environment, textures, crystal habit, brine composition and other geochemical factors. The environments studied included subaqueous sediments in anchialine pools and in solar salterns, as well as subsurface sediments of mudflats and saltpans. Gypsum that developed in the apparent absence of biofilms included crystals precipitated in the water column and subsedimentary discs that precipitated from phreatic brines. Subsedimentary gypsum developed in sabkha environments exhibited a sinuous microtexture and poikilitically enclosed detrital particles. Water column precipitates had euhedral prismatic habits and extensive penetrative twinning. Gypsum deposits influenced by biofilms included bottom nucleated crusts and gypsolites developing in anchialine pools and saltern ponds. Gypsum precipitating within benthic biofilms, and in biofilms within subaerial sediment surfaces provided compelling evidence of biological influences on crystal textures and habits. This evidence included irregular, high relief surface textures, accessory minerals (S°, Ca-carbonate, Sr/Ca-sulfate and Mg-hydroxide) and distinctive crystal habits such as equant forms and crystals having distorted prism faces.     

Field evidences of secondary surface ruptures occurred during the 20 February 1956 Eskişehir earthquake in the NW Anatolia

Surface rupture and source fault of the 20 February 1956 Eskişehir earthquake have been a matter of debate that potentially contributes towards the understanding of the active deformation and seismic risk in the highly populated NW Anatolia. Field observations on the two fault segments (namely Kavacık and Uludere faults) in the north of the Eskişehir graben revealed evidences of co-seismic surface rupture and mass movements during the Eskişehir earthquake. Surface rupture was observed as a 2.5m wide, a 100m long and ca. 20 cm deep asymmetric depression in the Gümüşlü valley, 2 km east of the Uludere village. A trench dug on this depression confirms a prominent high-angle south dipping fault (dominantly left lateral strike slip) and two faint north-dipping antithetics as clear noticeable shear zones in organic-rich thick soil. Mass failures are particularly observed in spring depressions filled with loose torrent and carbonaceous material in front of the fault scarp. Some rock slides of several tens of meters in size that obviously require significantly high ground shaking were also developed on steep fault scarps. The orientation of the principal stress tensor as deduced from the surface rupture of the Eskişehir earthquake displays clear inconsistency with the geometry of prominent faults in the area. We concluded that this disagreement may be explained by a curved surface rupture. The western and eastern tips of this rupture are EW trending and the probable NW-running part in the middle would correspond to the bounding zone between two right-stepping faults.