Sources and transport of carbon and nitrogen in the River Sava watershed, a major tributary of the River Danube

Carbon and nitrogen dynamics were examined throughout the River Sava watershed, a major tributary of the River Danube, in 2005 and 2006. The River Sava exported 2.1 × 10¹¹ mol C/yr as dissolved inorganic carbon (DIC), and emitted 2.5 × 10¹⁰ mol C/yr as CO₂ to the atmosphere. Stable carbon isotope ratios indicate that up to 42% of DIC originated from carbonate weathering and 23% from degradation of organic matter. Loads of dissolved and particulate organic carbon increased with discharge and export rates were calculated to be 2.1 × 10¹⁰ mol C/yr and up to 4.1 × 10⁹ mol C/yr, respectively. Isotopic compositions (δ¹³C and δ¹⁵N) and C/N ratios indicated that soil organic matter was the dominant source of particulate organic matter for 59% of the samples. Eighteen percent of the samples were dominated by plankton, 12% by periodic inputs of fresh terrestrial plant detritus with C/N > 15, and about 11% of the samples were dominated by the contribution of aquatic vascular plants. Nitrate inputs were controlled by land use in the River Sava watershed. δ¹⁵N_NO3 values <6‰ were found in predominantly forested watersheds, while values >6‰ typically represented watersheds with a higher percentage of agricultural and/or urban land use. Elevated δ¹⁵N_NO3 values (up to +25.5‰) at some sites were probably due to the combined effects of low-flow and inputs from sewage and/or animal waste.     

Pressure–temperature evolution of lawsonite eclogite in Sivrihisar; Tavşanlı Zone–Turkey

The Cretaceous blueschist belt, Tavşanlı Zone, representing the subducted and exhumed northern continental margin of the Anatolide–Tauride platform is exposed in Western Anatolia. The Sivrihisar area east of Tavşanlı is made up of tectonic units consisting of i) metaclastics and conformably overlying massive marbles (coherent blueschist unit), ii) blueschist-eclogite unit, iii) marble–calcschist intercalation and iv) metaperidotite slab. The metaclastics are composed of jadeite–lawsonite–glaucophane and jadeite–glaucophane–chloritoid schists, phengite phyllites, and calcschists with glaucophane–lawsonite metabasite layers. The blueschist-eclogite unit representing strongly sheared, deeply buried and imbricated tectonic slices of accreted uppermost levels of the oceanic crust with minor metamorphosed serpentinite bodies consists of lawsonite-bearing eclogitic metabasites (approximately 90% of the field), lawsonite eclogites, metagabbros, serpentinites, pelagic marbles, omphacite–glaucophane–lawsonite metapelites and metacherts. The mineral assemblage of the lawsonite eclogite (garnet + omphacite > 70%) is omphacite, garnet, lawsonite, glaucophane, phengite and rutile. Lawsonite eclogite lenses are enclosed by garnet–lawsonite blueschist envelopes.Textural evidence from lawsonite eclogites and country rocks reveals that they did not leave the stability field of lawsonite during subduction and exhumation. The widespread preservation of lawsonite in eclogitic metabasites and eclogites can be attributed to rapid subduction and subsequent exhumation in a low geothermal gradient of the oceanic crust material without experiencing a thermal relaxation. Peak P–T conditions of lawsonite eclogites are estimated at 24 ± 1 kbar and 460 ± 25 °C. These P–T conditions indicate a remarkably low geotherm of 6.2 °C/km corresponding to a burial depth of 74 km.     

Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (δ¹⁸O_H2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O₂ and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ± 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate–water oxygen isotope fractionation, ε¹⁸O_SO4–H2O, of ~ 3.8‰ for the anaerobic experiments. Aerobic oxidation produced apparent ε_SO4–H2O values (6.4‰) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O₂ into sulfate. δ³⁴S_SO4 values are ~ 4‰ lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in δ³⁴S_SO4 of ~? 1.5 ± 0.2‰ was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions.     

Isotopic constraints on the genesis and age of autochthonous glaucony in the Oligo-Miocene Torquay Group, south-eastern Australia

The Oligo‐Miocene Torquay Group at Bird Rock in south‐eastern Australia comprises a sequence of fine‐grained skeletal carbonates and argillaceous and glauconitic sandstones, deposited in a cool‐water, mid‐shelf environment. The Bird Rock glaucony is autochthonous and consists predominantly of randomly interstratified glauconitic smectite, which constitutes bioclast infills and faecal pellet replacements. The results of Rb–Sr and oxygen isotopic analysis of samples taken from a single glauconitic horizon (the BW horizon) indicate that the glaucony developed through a series of simultaneous dissolution–crystallization reactions, which occurred during very early diagenesis in a closed or isochemical system, isolated from the ambient marine environment. The constituent ions of the glaucony were derived primarily from terrigenous clay minerals, but considerable potassium may have been sourced indirectly from sea water, through potassium enrichment of clay precursors. The pore fluids associated with glauconitization were marine derived, but progressively modified by the dissolution–crystallization of detrital clay minerals and autochthonous glaucony. Rb–Sr data for the BW horizon indicate that dating glauconies may be somewhat problematic, as co‐genetic glauconitic minerals can show a range of initial strontium compositions, which reflect the incorporation of strontium derived from mineralogical precursors and/or contemporaneous sea water. Rb–Sr isochrons indicate that the glaucony of the BW horizon formed at 23 ± 3 Ma. This age is in good agreement with both the established biostratigraphy and a ⁸⁷Sr/⁸⁶Sr age for the horizon (23 ± 1 Ma), but could only be determined using the independent age constraint and the estimate of the ⁸⁷Sr/⁸⁶Sr ratio of contemporaneous sea water provided by analysis of associated biogenic carbonate.     

The Budget of Turbulent Kinetic Energy in the Urban Roughness Sublayer

Full-scale observations from two urban sites in Basel, Switzerland were analysed to identify the magnitude of different processes that create, relocate, and dissipate turbulent kinetic energy (TKE) in the urban atmosphere. Two towers equipped with a profile of six ultrasonic anemometers each sampled the flow in the urban roughness sublayer, i.e. from street canyon base up to roughly 2.5 times the mean building height. This observational study suggests a conceptual division of the urban roughness sublayer into three layers: (1) the layer above the highest roofs, where local buoyancy production and local shear production of TKE are counterbalanced by local viscous dissipation rate and scaled turbulence statistics are close to to surface-layer values; (2) the layer around mean building height with a distinct inflexional mean wind profile, a strong shear and wake production of TKE, a more efficient turbulent exchange of momentum, and a notable export of TKE by transport processes; (3) the lower street canyon with imported TKE by transport processes and negligible local production. Averaged integral velocity variances vary significantly with height in the urban roughness sublayer and reflect the driving processes that create or relocate TKE at a particular height. The observed profiles of the terms of the TKE budget and the velocity variances show many similarities to observations within and above vegetation canopies.