Oxidation of the Kaapvaal lithospheric mantle driven by metasomatism

The oxidation state, reflected in the oxygen fugacity (fO₂), of the subcratonic lithospheric mantle is laterally and vertically heterogeneous. In the garnet stability field, the Kaapvaal lithospheric mantle becomes progressively more reducing with increasing depth from Δlog fO₂ FMQ-2 at 110 km to FMQ-4 at 210 km. Oxidation accompanying metasomatism has obscured this crystal-chemical controlled depth-fO₂ trend in the mantle beneath Kimberley, South Africa. Chondrite normalized REE patterns for garnets, preserve evidence of a range in metasomatic enrichment from mild metasomatism in harzburgites to extensive metasomatism by LREE-enriched fluids and melts with fairly unfractionated LREE/HREE ratios in phlogopite-bearing lherzolites. The metasomatized xenoliths record redox conditions extending up to Δlog fO₂ = FMQ, sufficiently oxidized that magnesite would be the stable host of carbon in the most metasomatized samples. The most oxidized lherzolites, those in or near the carbonate stability field, have the greatest modal abundance of phlogopite and clinopyroxene. Clinopyroxene is modally less abundant or absent in the most reduced peridotite samples. The infiltration of metasomatic fluids/melts into diamondiferous lithospheric mantle beneath the Kaapvaal craton converted reduced, anhydrous harzburgite into variably oxidized phlogopite-bearing lherzolite. Locally, portions of the lithospheric mantle were metasomatized and oxidized to an extent that conversion of diamond into carbonate should have occurred. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Stratigraphy and geochemistry of pillow basalts within the ophiolitic mélange of the Izmir–Ankara–Erzincan suture zone: implications for the geotectonic character of the northern branch of Neotethys

The Izmir-Ankara-Erzincan suture zone of Turkey is a broad zone of ophiolitic mélange containing numerous fragmented blocks ranging in age from Triassic to Cretaceous. Stratigraphic sequences for various mélange units are compared, together with the geochemistry of associated basaltic pillow lavas of Cretaceous age. A review of geochemical data for the pillow lavas demonstrate: (a) a dominant group of alkalic basalts with enriched incompatible elements, variable Zr/Y and Zr/Nb ratios, and (b) a range of tholeiitic basalts with slightly depleted to mildly enriched (normalized) rare earth patterns, (La/Yb)_N 0.4-3.0, and generally low Zr/Y ratios. The alkalic basalts can be chemically matched to Pacific Ocean seamounts, although the close association of red radiolarites and cherts suggests that many basalts represent the margins of such structures, rather than the main seamount edifice. Nd-Sr isotope data are typical for ocean island basalts and represent an admixture of a dominant EM-1 source and a depleted MORB-like source. Enhanced δ¹⁸O compositions are a consequence of submarine alteration and not crustal contamination. Tholeiitic compositions have affinities with both N- and E-type MORB, although most are probably representative of tholeiitic ocean islands. Overall the basalts are mainly representative of structures built on the ocean floor, rather than the oceanic crust itself, being scraped off the subducting crust and preserved in the mélange of the accretionary wedge.     

A Common Reference Material for Cadmium Isotope Studies – NIST SRM 3108

Research into natural mass‐dependent stable isotope fractionation of cadmium has rapidly expanded in the past few years. Methodologies are diverse with MC‐ICP‐MS favoured by all but one laboratory, which uses thermal ionisation mass spectrometry (TIMS). To quantify the isotope fractionation and correct for instrumental mass bias, double‐spike techniques, sample‐calibrator bracketing or element doping has been used. However, easy comparison between data sets has been hampered by the multitude of in‐house Cd solutions used as zero‐delta reference in different laboratories. The lack of a suitable isotopic reference material for Cd is detrimental for progress in the long term. We have conducted a comprehensive round‐robin assay of NIST SRM 3108 and the Cd isotope offsets to commonly used in‐house reference materials. Here, we advocate NIST SRM 3108 both as an isotope standard and the isotopic reference point for Cd and encourage its use as ‘zero‐delta’ in future studies. The purity of NIST SRM 3108 was evaluated regarding isobaric and polyatomic molecular interferences, and the levels of Zn, Pd and Sn found were not significant. The isotope ratio ¹¹⁴Cd/¹¹⁰Cd for NIST SRM 3108 lies within ～ 10 ppm Da^?1 of best estimates for the Bulk Silicate Earth and is validated for all measurement technologies currently in use.     

Bias of ostracod stable isotope data caused by drying of sieve residues from water

Stable isotope analysis of ostracod shells is used routinely for palaeoenvironmental studies of ostracod-bearing records. Sample treatment usually involves the disaggregation of sediments and sieving; before the sieving residues were washed with water onto petri dishes and oven-dried. In our study, we compared δ¹⁸O and δ¹³C values of shells that were oven-dried from water and from ethanol alternatively. Large isotopic differences of up to 3‰ were determined for δ¹⁸O values, whereas differences in δ¹³C values were less pronounced with differences of up to 1.6‰. Stable isotope values of shells dried from water were lower for both oxygen and carbon as a result of calcite crystals precipitated on the shell surfaces during the drying process. Therefore, ostracod shells for stable isotope analysis should not be prepared by drying from water. Instead, shells should be dried from ethanol to obtain reliable stable isotope data; likewise freeze-drying is expected to provide trustworthy results.     

Present-day and future precipitation in the Baltic Sea region as simulated in a suite of regional climate models

Here we investigate simulated changes in the precipitation climate over the Baltic Sea and surrounding land areas for the period 2071–2100 as compared to 1961–1990. We analyze precipitation in 10 regional climate models taking part in the European PRUDENCE project. Forced by the same global driving climate model, the mean of the regional climate model simulations captures the observed climatological precipitation over the Baltic Sea runoff land area to within 15% in each month, while single regional models have errors up to 25%. In the future climate, the precipitation is projected to increase in the Baltic Sea area, especially during winter. During summer increased precipitation in the north is contrasted with a decrease in the south of this region. Over the Baltic Sea itself the future change in the seasonal cycle of precipitation is markedly different in the regional climate model simulations. We show that the sea surface temperatures have a profound impact on the simulated hydrological cycle over the Baltic Sea. The driving global climate model used in the common experiment projects a very strong regional increase in summertime sea surface temperature, leading to a significant increase in precipitation. In addition to the common experiment some regional models have been forced by either a different set of Baltic Sea surface temperatures, lateral boundary conditions from another global climate model, a different emission scenario, or different initial conditions. We make use of the large number of experiments in the PRUDENCE project, providing an ensemble consisting of more than 25 realizations of climate change, to illustrate sources of uncertainties in climate change projections.     

Thermal conductivity measurements of road construction materials in frozen and unfrozen state

A series of thermal conductivity measurements for various materials was performed in a large climate chamber. The size of the chamber allowed the preparation of relatively large samples in a controlled thermal environment. Three types of thermal sensors were used: (1) two needle probes; (2) a grid of temperature sensors, evenly distributed inside the sample; (3) two additional thermal probes, which were simplified versions of an instrument originally developed for measuring thermal properties of the ice/dust mixture expected to exist at the surface of a comet nucleus. They consist of a series of individual temperature sensors integrated into a glass fibre rod. Each of these sensors can be operated in an active (heated) or passive (only temperature sensing) mode. The following sample materials were used: fine-grained reddish sand, coarse-grained moist sand, gravels with various grain size distributions from < 1 cm up to about 6 cm, and for comparison and calibration pure water (with convection suppressed by adding agar-agar), compact ice, and compact granite. Of particular interest are the measurements with composite samples, like stones embedded in an agar-agar matrix. We describe the evaluation methods and present the results of the thermal conductivity measurements.     

Precambrian crystalline basement in southern Mongolia as revealed by SHRIMP zircon dating

Single zircon ages determined by ion microprobe (SHRIMP II) for granitoid gneisses from the southern slope of the Baga Bogd massif (Gobi-Altai, southern Mongolia) reveal several episodes of zircon growth, ranging from late Palaeoproterozoic to late Cambrian. The oldest events are documented by a zircon crystallization age for a gneiss protolith at 1519 ± 11 Ma and by a xenocrystic zircon from a dark grey augen-gneiss yielding an age of c. 1701 Ma. Discrete igneous events are recorded in granite-gneisses with protolith emplacement ages of 983 ± 6, 956 ± 3 and 954 ± 8 Ma. These ages provide the first record of early Neoproterozoic magmatic activity in this region. A much younger and discrete magmatic event is recorded by several dioritic to granitic orthogneisses which are tectonically interlayered with the older gneisses and have protolith emplacement ages between 502 and 498 Ma. These late Cambrian granitoids of calc-alkaline affinity are likely to have been emplaced along an active continental margin and suggest that the Baga Bogd Precambrian crustal fragment was either docked against the southward (present-day coordinates) growing margin of the CAOB or was a large enough crustal entity to develop an arc along its margin. We speculate that the Precambrian gneisses of this massif may be part of a crustal fragment rifted off the Tarim Craton.     

Hydrothermal alteration and zeolitization of the Fohberg phonolite,Kaiserstuhl Volcanic Complex,Germany

The subvolcanic Fohberg phonolite (Kaiserstuhl Volcanic Complex, Germany) is an economic zeolite deposit, formed by hydrothermal alteration of primary magmatic minerals. It is mined due to the high (>40 wt%) zeolite content, which accounts for the remarkable zeolitic physicochemical properties of the ground rock. New mineralogical and geochemical studies are carried out (a) to evaluate the manifestation of hydrothermal alteration, and (b) to constrain the physical and chemical properties of the fluids, which promoted hydrothermal replacement. The alkaline intrusion is characterized by the primary mineralogy: feldspathoid minerals, K-feldspar, aegirine–augite, wollastonite, and andradite. The rare-earth elements-phase götzenite is formed during the late-stage magmatic crystallization. Fluid-induced re-equilibration of feldspathoid minerals and wollastonite caused breakdown to a set of secondary phases. Feldspathoid minerals are totally replaced by various zeolite species, calcite, and barite. Wollastonite breakdown results in the formation of various zeolites, calcite, pectolite, sepiolite, and quartz. Zeolites are formed during subsolidus hydrothermal alteration (<150 °C) under alkaline conditions. A sequence of Ca–Na-dominated zeolite species (gonnardite, thomsonite, mesolite) is followed by natrolite. The sequence reflects an increase in \(\log [(a_{{{\text{Na}}^{ + } }} )/(a_{{{\text{H}}^{ + } }} )]\) and decrease in \(\log [(a_{{{\text{Ca}}^{2 + } }} )/(a_{{{\text{H}}^{ + } }}^{2} )]\) of the precipitating fluid. Low radiogenic ⁸⁷Sr/⁸⁶Sr values indicate a local origin of the elements necessary for secondary mineral formation from primary igneous phases. In addition, fractures cut the intrusive body, which contain zeolites, followed by calcite and a variety of other silicates, carbonates, and sulfates as younger generations. Stable isotope analysis of late-fracture calcite indicates very late circulation of meteoric fluids and mobilization of organic matter from surrounding sedimentary units.     

Particle size distribution and dissolution properties of metals in cyclone fly ash

The particles in the examined cyclone fly ash were all smaller than 0.25 mm. in diameter, and particles smaller than 0.075 mm. in diameter accounted for 88.4 % of the ash weight. This result indicates that cyclone fly ash consists of particles with a small diameter. The metals in the cyclone fly ash were enriched in small particles. The highest concentrations for zinc, copper, lead, cadmium and molybdenum in the cyclone fly ash were found in the smallest particle size fraction (< 0.075 mm.) and for Barium, chromium, nickel, Vanadium and Cobalt in the second to smallest particle size fraction (0.075-0.125 mm.). From an environmental and toxicological standpoint, the smallest particles are of the greatest concern when ash is handed at landfill disposal sites (transport and disposal especially in stormy weather conditions), and some studies have reported risks to workers from prolonged exposure to ash. The results of the comparison of various dissolution methods for metals showed that the digestion procedures with nitric acid alone (USEPA 3051) or with a mixture of nitric acid + hydrogen peroxide (USEPA 3050B) slightly underestimated the metal concentrations in the cyclone fly ash. Although the use of hydrofluoric acid is often necessary for the determination of a number of elements associated with siliceous minerals, its use can result in loss of trace elements during dissolution.     

A neutron diffraction study of alkali cation migration in montmorillonites

Neutron powder diffraction measurements on lithium and cesium saturated montmorillonite samples before and after heat treatment at 300°C are studied, in order to undertake a complete refinement of crystal structure and unravel the migration mechanism for the interlayer cations of Li or Cs. Rietveld analysis of the corresponding diffraction patterns finds that montmorillonite crystallizes in the C2/m space group with unit cell dimensions consistent with the size of the specific interlayer cation. We show that thermal treatment affects the two types of samples in a different way. This is with respect to their unit cell dimensions and the migration of Li from the 2b to the 2c clay lattice site, in constrast to the Cs positioning which remains effectively unchanged.