Geochemical studies of the SUBO 18 (Enkingen) drill core and other impact breccias from the Ries crater,Germany

Suevite and melt breccia compositions in the boreholes Enkingen and Polsingen are compared with compositions of suevites from other Ries boreholes and surface locations and discussed in terms of implications for impact breccia genesis. No significant differences in average chemical compositions for the various drill cores or surface samples are noted. Compositions of suevite and melt breccia from southern and northeastern sectors of the Ries crater do not significantly differ. This is in stark contrast to the published variations between within‐crater and out‐of‐crater suevites from northern and southern sectors of the Bosumtwi impact structure, Ghana. Locally occurring alteration overprint on drill cores—especially strong on the carbonate‐impregnated suevite specimens of the Enkingen borehole—does affect the average compositions. Overall, the composition of the analyzed impact breccias from Ries are characterized by very little macroscopically or microscopically recognized sediment‐clast component; the clast populations of suevite and impact melt breccia are dominated consistently by granitic and intermediate granitoid components. The Polsingen breccia is significantly enriched in a dioritic clast component. Overall, chemical compositions are of intermediate composition as well, with dioritic‐granodioritic silica contents, and relatively small contributions from mafic target components. Selected suevite samples from the Enkingen core have elevated Ni, Co, Cr, and Ir contents compared with previously analyzed suevites from the Ries crater, which suggest a small meteoritic component. Platinum‐group element (PGE) concentrations for some of the enriched samples indicate somewhat elevated concentrations and near‐chondritic ratios of the most immobile PGE, consistent with an extraterrestrial contribution of 0.1–0.2% chondrite‐equivalent.     

Cu- and Mn-bearing tourmalines from Brazil and Mozambique: crystal structures, chemistry and correlations

Cu- and Mn-bearing tourmalines from Brazil and Mozambique were characterised chemically (EMPA and LA-ICP-MS) and by X-ray single-crystal structure refinement. All these samples are rich in Al, Li and F (fluor-elbaite) and contain significant amounts of CuO (up to ~1.8 wt%) and MnO (up to ~3.5 wt%). Structurally investigated samples show a pronounced positive correlation between the <Y-O> distances and the (Li + Mn²⁺ + Cu + Fe²⁺) content (apfu) at this site with R ² = 0.90. An excellent negative correlation exists between the <Y-O> distances and the Al₂O₃ content (R ² = 0.94). The samples at each locality generally show a strong negative correlation between the X-site vacancies and the (MnO + FeO) content. The Mn content in these tourmalines depends on the availability of Mn, on the formation temperature, as well as on stereochemical constraints. Because of a very weak correlation between MnO and CuO we believe that the Cu content in tourmaline is essentially dependent on the availability of Cu and on stereochemical constraints.     

The Gradenbach Observatory—monitoring deep-seated gravitational slope deformation by geodetic, hydrological, and seismological methods

The Gradenbach mass movement (GMM) is an example of DGSD (deep-seated gravitational slope deformation) in crystalline rocks of the Eastern Alps (12.85°E, 47.00°N). The main body of the GMM covers an area of 1.7 km² and its volume is about 120?×?10⁶ m³. A reconstruction of the deformation history yields a mean displacement of?～?22 m from 1962 to 2011. In 1965/66, 1975, 2001, and 2009 high sliding velocities, exceeding several meters per year, interrupt the quasi-stationary periods of slow movement (≤0.3 m/year). Since 1999 the displacement of the main body of the GMM has been observed by GPS. Time series of extensometer readings, precipitation, snow cover water equivalent, water discharge, and hydrostatic water level observed in boreholes were re-processed and are presented in this paper. Continuous recording of seismic activity by a seismic monitoring network at the GMM began in the summer of 2006. Deformation has been monitored since 2007 by an embedded strain rosette based on fiber optics technology and a local conventional geodetic deformation network. The velocity of the GMM could be modeled to a large extent by a quantitative relation to hydro-meteorological data. During the phase of high sliding velocity in spring 2009, the seismic activity in the area increased significantly. Several types of seismic events were identified with some of them preceding the acceleration of the main body by about 6 weeks. The potential inherent in the Gradenbach Observatory data to supply early warning and hazard estimation is discussed.     

Regional sulfate–hematite–sulfide zoning in the auriferous Mariana anticline, Quadrilátero Ferrífero of Minas Gerais, Brazil

The distribution of mineral deposits, characterised as barite deposits, hematite-rich auriferous deposits and auriferous tourmaline–sulfide deposits, displays a regional sulfate–hematite–sulfide zoning along the thrust-delineated limbs of the Mariana anticline, in the south-eastern part of the Quadrilátero Ferrífero of Minas Gerais, Brazil. Cross-cut relationships of barite veins and sulfide lodes indicate that sulfidation occurred in a late-tectonic context, which is here attributed to the collapse of the ～0.6-Ga Brasiliano thrust front. Reconnaissance S-isotopic data from barite and pyrite (Antônio Pereira barite deposit and its adjacent gold deposit, respectively), and arsenopyrite (Passagem de Mariana gold deposit), suggest a new interpretation for the hydrothermal fluid overprint in the Mariana anticline. The Antônio Pereira barite has Δ³³S values that are near zero, constraining the sulfate source to rocks younger than 2.45 Ga. The barite-δ³⁴S values are between +19.6 and +20.8?‰. The Passagem arsenopyrite and tourmaline have Co/Ni ratios that define a positive linear trend with the Antônio Pereira pyrite. The latter has homogenous δ³⁴S values, between +8.8 and +8.9?‰, which are compatible with thermochemical reduction of aqueous sulfate with the S-isotopic composition of the Antônio Pereira barite.     

Infrared reflectivity spectra of single crystal cassiterites

The infrared reflectivity spectra of two natural cassiterite single crystals from Portugal and Vietnam have been studied and analysed in the frequency range of 15–4000 cm^–1 at room temperature. The optical mode parameters are deduced by simulation of the experimental spectra using the factorised form of the dielectric function. The difference with synthetic SnO₂ spectra is a dip near 500 cm^–1 understood as the activation of an infrared forbidden E _g mode due to the amount of Fe³⁺ and Ti⁴⁺ impurities. Another result of this work is the derivation of the correct values of the static dielectric constant of cassiterite.     

Platinum-group element distribution in base-metal sulfides of the Merensky Reef from the eastern and western Bushveld Complex, South Africa

Base-metal sulfides in magmatic Ni-Cu-PGE deposits are important carriers of platinum-group elements (PGE). The distribution and concentrations of PGE in pentlandite, pyrrhotite, chalcopyrite, and pyrite were determined in samples from the mineralized portion of four Merensky Reef intersections from the eastern and western Bushveld Complex. Electron microprobe analysis was used for major elements, and in situ laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) for trace elements (PGE, Ag, and Au). Whole rock trace element analyses were performed on representative samples to obtain mineralogical balances. In Merensky Reef samples from the western Bushveld, both Pt and Pd are mainly concentrated in the upper chromitite stringer and its immediate vicinity. Samples from the eastern Bushveld reveal more complex distribution patterns. In situ LA-ICP-MS analyses of PGE in sulfides reveal that pentlandite carries distinctly elevated PGE contents, whereas pyrrhotite and chalcopyrite only contain very low PGE concentrations. Pentlandite is the principal host of Pd and Rh in the ores. Palladium and Rh concentrations in pentlandite reach up to 700 and 130 ppm, respectively, in the samples from the eastern Bushveld, and up to 1,750 ppm Pd and up to 1,000 ppm Rh in samples from the western Bushveld. Only traces of Pt are present in the base-metal sulfides (BMS). Pyrrhotite contains significant though generally low amounts of Ru, Os, and Ir, but hardly any Pd or Rh. Chalcopyrite contains most of the Ag but carries only extremely low PGE concentrations. Mass balance calculations performed on the Merensky Reef samples reveal that in general, pentlandite in the feldspathic pyroxenite and the pegmatoidal feldspathic pyroxenite hosts up to 100 % of the Pd and Rh and smaller amounts (10–40 %) of the Os, Ir, and Ru. Chalcopyrite and pyrrhotite usually contain less than 10 % of the whole rock PGE. The remaining PGE concentrations, and especially most of the Pt (up to 100 %), are present in the form of discrete platinum-group minerals such as cooperite/braggite, sperrylite, moncheite, and isoferroplatinum. Distribution patterns of whole rock Cu, Ni, and S versus whole rock Pd and Pt show commonly distinct offsets. The general sequence of “offset patterns” of PGE and BMS maxima, in the order from bottom to top, is Pd in pentlandite?→?Pd in whole rock?→?(Cu, Ni, and S). The relationship is not that straightforward in general; some of the reef sequences studied only partially show similar trends or are more complex. In general, however, the highest Pd concentrations in pentlandite appear to be related to the earliest, volumetrically rather small sulfide liquids at the base of the Merensky Reef sequence. A possible explanation for the offset patterns may be Rayleigh fractionation.     

Geochemistry and mineralogy of shallow alluvial aquifers in Daudkandi upazila in the Meghna flood plain, Bangladesh

The shallow alluvial aquifers of the delta plains and flood plains of Bangladesh, comprises about 70% of total land area are mostly affected by elevated concentrations of arsenic (As) in groundwater exposing a population of more than 35 million to As toxicity. Geochemical studies of shallow alluvial aquifer in the Meghna flood plain show that the uppermost yellowish grey sediment is low in As (1.03 mg/kg) compared to the lower dark grey to black sediment (5.24 mg/kg) rich in mica and organic matter. Sequential extraction data show that solid phase As bound to poorly crystalline and amorphous metal (Fe, Mn, Al)-oxyhydroxides is dominant in the grey to dark grey sediment and reaches its maximum level (3.05 mg/kg) in the mica rich layers. Amount of As bound to sulphides and organic matter also peaks in the dark grey to black sediment. Vertical distributions of major elements determined by X-ray fluorescence (XRF) show that iron (Fe₂O₃), aluminum (Al₂O₃) and manganese (MnO) follow the general trend of distribution of As in the sediments. Concentrations of As, Mn, Fe, HCO₃ ⁻, SO₄ ²⁻ and NO₃ ⁻ in groundwater reflect the redox status of the aquifer and are consistent with solid phase geochemistry. Mineralogical analysis by X-ray diffraction (XRD) and scanning electron microscopy (SEM) fitted with energy dispersive X-ray spectrometer (EDS) revealed dominance of crystalline iron oxides and hydroxides like magnetite, hematite and goethite in the oxidised yellowish grey sediment. Amorphous Fe-oxyhydroxides identified as grain coating in the mica and organic matter rich sediment suggests weathering of biotite is playing a critical role as the source of Fe(III)-oxyhydroxides which in turn act as sink for As. Presence of authigenic pyrite in the dark grey sediment indicates active reduction in the aquifer.     

The tropospheric distribution of formaldehyde during TROPOZ II

A series of 149 measurements of the HCHO mixing ratio were made between 0 and 10 km altitude and 70° N to 60° S latitude during TROPOZ II. The data show a vertical decrease of the HCHO mixing ratio with altitude at all latitudes and a broad latitudinal maximum in the HCHO mixing ratio between 30° N and 30° S at all altitudes. The measured mixing ratios of HCHO are considerably higher than those expected from CH₄ oxidation alone, but agree broadly with the average latitude by altitude distribution of HCHO derived by a 2D model including emissions of C₁–C₇ hydrocarbons. A number of the regional scale deviations of the measured HCHO distribution from the average modelled one can be explained in terms of the local wind field.