Carbon-13 exchange between CO2 and CH4 under geothermal conditions

On the basis of recently reported data on the kinetics of carbon-13 exchange between CO₂ and CH₄ at temperatures above 500°C, first order rate constants $\text{log k = 11.16?10,190/T}$ were derived allowing variations in Δ, the difference in the isotopic composition of coexisting CO₂ and CH₄, to be evaluated as a function of initial composition and cooling rate of the rising geothermal fluid. Observed Δ-values in geothermal discharges are likely to represent frozen in compositions attained after minimum residence times of 20 ka at 400°C or 10 Ma at 300°C. The carbon-13 contents of any biogenic gases are unlikely to have been affected by thermal re-equilibration at temperatures below 200°C. The chemical equilibrium involving CO₂ and CH₄ can be expected to proceed about a hundred times faster than isotopic equilibration.     

Early Triassic potassic volcanism in the Afyon Zone of the Anatolides/Turkey: implications for the rifting of the Neo-Tethys

Afyon Zone, which was derived from the Anatolide–Tauride platform during closure of the Neo-Tethys, is made up of pre-Mesozoic basement and unconformably overlying Triassic–Early Tertiary cover series. The Afyon Zone contains widespread metavolcanic rocks, which are dominated by rhyolite, dacite, and trachyandesite. They form a distinct volcanic succession, which is separated from the underlying Silurian–Lower Carboniferous metacarbonates and meta-siliciclastics by a regional unconformity. Trachyandesitic metavolcanics are made up of massive lava flows, pyroclastics and epiclastics, less frequently, domes and dikes, which were developed on a deeply eroded subaerial landmass. U/Pb and Pb/Pb zircon geochronology yielded Lower Triassic (~250 Ma) ages, which are interpreted as extrusion age of trachyandesitic volcanics. Based on the stratigraphic, geochronological, and geochemical data, we suggest that these Lower Triassic magmatic rocks represent an extensional tectonic setting on the northern active margin of the Gondwana, which led to the development of the northern branch of the Neo-Tethys.     

Occurrence of naphthalenesulfonates and their condensates with formaldehyde in a landfill leachate and their transport behavior in groundwater of the Upper Rhine Valley, Germany

. Naphthalenesulfonates and their condensation products with formaldehyde are manufactured in the chemical industry for broad application as tanning agents, dispersing agents, and as superplasticizers for concrete. With the disposal of waste they have found their way into the aquatic environment. Five monomeric naphthalenesulfonates and a group of dimeric sulfonated naphthalene-formaldehyde condensates (SNFC) were identified in the leachate and in groundwater observation wells downstream in the plume of the Karlsruhe-West landfill, situated in the Upper Rhine Valley in southwest Germany. For the main monomer of technical SNFC products, 2-naphthalenesulfonate (2-NS), the concentration in the leachate was 170 µg l^–1, which decreased to 9.5 µg l^–1 at a distance of about 300 m from the boundary of the landfill. In the Merdingen tracer test field, the transport of these compounds was studied under more controlled conditions in two tracer experiments with (1) two model compounds, and (2) a technical SNFC product and uranine as a reference tracer. In these experiments, the monomeric naphthalenesulfonates and the SNFC with n=2 behave as conservative tracers. Thus, the findings of the landfill study were supported by these results. Higher molecular SNFC were strongly retarded, which is attributed to adsorption to soil particles. The results of the second tracer experiment suggest a degradation of 2-NS and 2,6-naphthalenedisulfonate (2,6-NDS) after adaptation of the microorganisms in the groundwater aquifer as a consequence of the first tracer experiment.     

<Superscript>57</Superscript>Fe Mössbauer spectroscopy,X-ray single-crystal diffractometry,and electronic structure calculations on natural alexandrite

Natural alexandrite Al₂BeO₄:Cr from Malyshevo near Terem Tschanka, Sverdlovsk, Ural, Russia, has been characterized by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe, X-ray single-crystal diffractometry and by electronic structure calculations in order to determine oxidation state and location of iron. The sample contains 0.3 wt% of total iron oxide. The ⁵⁷Fe Mössbauer spectrum can be resolved into three doublets. Two of them with hyperfine parameters typical for octahedrally coordinated high-spin Fe³⁺ and Fe²⁺, respectively, are assigned to iron substituting for Al in the octahedral M2-site. The third doublet is attributed to Fe³⁺ in hematite. Electronic structure calculations in the local spin density approximation are in reasonable agreement with experimental data provided that expansion and/or distortion of the coordination octahedra are presumed upon iron substitution. The calculated hyperfine parameters of Fe³⁺ are almost identical for the M1 and M2 positions, but the calculated ligand-field splitting is by far too large for high-spin Fe³⁺ on M1.     

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.