Tracking the lithium isotopic evolution of the mantle using carbonatites

Carbonatites are mantle-derived, intraplate magmas that provide a means of documenting isotopic variations of the Earth's mantle through time. To investigate the secular Li isotopic evolution of the mantle and to test whether Li isotopes document systematic recycling of material processed at or near the Earth's surface into the mantle, we analyzed the Li isotopic compositions of carbonatites and spatially associated mafic silicate rocks. The Li isotopic compositions of Archean (2.7 Ga) to Recent carbonatites (δ⁷Li = 4.1 ± 1.3 (n = 23, 1σ)) overlap the range typical for modern mantle-derived rocks, and do not change with time, despite ongoing crustal recycling. Thus, the average Li isotopic composition of recycled crustal components has not deviated greatly from the mantle value (~ + 4) and/or Li diffusion is sufficiently fast to attenuate significant heterogeneities over timescales of 10⁸ years. Modeling of Li diffusion at mantle temperatures suggests that limited δ⁷Li variation in the mantle through time reflects the more effective homogenization of Li in the mantle compared to radiogenic isotope systems. The real (but limited) variations in δ⁷Li that exist in modern mantle-derived magmas as well as carbonatites studied here may reflect isotopic fractionation associated with shallow-level processes, such as crustal assimilation and diffusive isotopic fractionation in magmatic systems, with some of the scatter possibly related to low-temperature alteration.     

Nitrogen recycling in subducted oceanic lithosphere: The record in high- and ultrahigh-pressure metabasaltic rocks

This paper provides the first measurements of the nitrogen (N) concentrations and isotopic compositions of high- and ultrahigh-pressure mafic eclogites, aimed at characterizing the subduction input flux of N in deeply subducting altered oceanic crust (AOC). The samples that were studied are from the Raspas Complex (Ecuador), Lago di Cignana (Italy), the Zambezi Belt (Zambia) and Cabo Ortegal (Spain), together representing subduction to 50-90 km depths. The eclogites contain 2-20 ppm N with δ¹⁵N_air values ranging from −1 to +8‰. These values overlap those of altered oceanic crust, but are distinct from values for fresh MORB (for the latter, ∼1.1 ppm N and δ¹⁵N_air ∼ −4‰). Based on N data in combination with other trace element data, the eclogite suites can be subdivided into those that are indistinguishable from their likely protolith, AOC, with or without superimposed effects of devolatilization (Lago di Cignana, Cabo Ortegal), and those that have experienced metasomatic additions during subduction-zone metamorphism (Zambezi Belt, Raspas). For the former group, the lack of a detectable loss of N in the eclogites, compared to various altered MORB compositions, suggests the retention of N in deeply subducted oceanic crust. The metasomatic effects affecting the latter group can be best explained by mixing with a (meta)sedimentary component, resulting in correlated enrichments of N and other trace elements (in particular, Ba and Pb) thought to be mobilized during HP/UHP metamorphism. Serpentinized and high-pressure metamorphosed peridotites, associated with the eclogites at Raspas and Cabo Ortegal, contain 3-15 ppm N with δ¹⁵N_air values ranging from +3 to +6‰, significantly higher than the generally accepted values for the MORB mantle (δ¹⁵N_air ∼ −5‰). Based on their relatively high N contents and their homogeneous and positive δ¹⁵N values, admixing of sedimentary N is also indicated for the serpentinized peridotites.One possible pathway for the addition of sediment-derived N into eclogites and peridotites involves mixing with fluids along the slab-mantle wedge interface. Alternatively, sedimentary N could be incorporated into peridotites during serpentinization at bending-related faults at the outer rise and, during later deserpentinization, released into fluids that then infiltrate overlying rocks. Deep retention of N in subducting oceanic crust should be considered in any attempt to balance subduction inputs with outputs in the form of arc volcanic gases. If materials such as these eclogites and serpentinized peridotites are eventually subducted to beyond sub-arc depths into the deeper mantle, containing some fraction of their forearc-subarc N inventory (documented here), they could deliver isotopically heavy N into the mantle to potentially be sampled by plume-related magmas.     

Spatial distribution of polyfluoroalkyl compounds in dab (Limanda limanda) bile fluids from Iceland and the North Sea

The spatial distribution of polyfluoroalkyl compounds (PFCs) was investigated in dab (Limanda limanda) bile fluids collected from Iceland and the North Sea. Concentrations of various PFCs, including perfluorinated sulfonates (C₄-C₆, C₈ PFSAs), perfluorinated carboxylic acids (C₉-C₁₄ PFCAs) and n-methyl perfluorooctane sulfonamidoethanol (MeFOSE), were quantified. Perfluorooctane sulfonate (PFOS) was the predominant compound with highest concentrations along the Danish and German coast (mean 9.36 ng/g wet weight (ww)). Significantly lower PFOS concentrations were found at the other sampling stations in the North Sea and Iceland (p < 0.01, t-test). Conversely, the spatial distribution of the PFCAs in Iceland and the North Sea was more uniform. The most abundant PFCA was perfluorononanoic acid (PFNA), while the mean concentration decreased with increasing chain length from 4.7 ng/g ww for PFNA to 0.04 ng/g ww for perfluorotetradecanoic acid (PFTeDA). Overall, the different spatial distribution of PFCs indicates different origin of sources and different transportation mechanism.     

A study to explain the emission of nitric oxide from a marsh soil

In the period 18–21 September 1989, soil NO emission was studied at Halvergate Marshes, Norfolk (U.K.) within the framework of the BIATEX-LOVENOX joint field experiment. Using a dynamic chamber technique, 186 measurements at four plots were performed showing a net NO flux of 7.2–14.6×10^–12 kgN m^–2 s^–1. Soil samples from a soil profile (1.0 m) at a representative site and from the uppermost layer (0.1 m) of each of the four plots were sent to the laboratory for (a) detailed physical and chemical soil analysis, (b) determination of NO production rates, NO uptake rate constants, and NO compensation mixing ratios, and (c) characterization of the microbial processes involved. A diffusive model (Galbally and Johansson, 1989) was applied to the laboratory results to infer NO fluxes of the individual soil samples. When we compared these fluxes with those measured in the field, we found agreement within a factor 2–4. Furthermore, laboratory studies showed, that NO was produced and consumed only in the upper soil layer (0–0.1 m depth) and that the NO production and consumption activities observed in the Halvergate marsh soil were most probably due to the anaerobic metabolism of denitrifying bacteria operating in anaerobic microniches within the generally aerobic soil.     

Modelling of a medium-term dynamics in a shallow tidal sea, based on combined physical and neural network methods

The paper presents an approach towards a medium-term (decades) modelling of water levels and currents in a shallow tidal sea by means of combined hydrodynamic and neural network models. The two-dimensional version of the hydrodynamic model Delft3D, forced with realistic water level and wind fields, is used to produce a two-year-database of water levels and currents in the study area. The linear principal component analysis (PCA) of the results is performed to reveal dominating spatial patterns in the analyzed dataset and to significantly reduce the dimensionality of the data. It is shown that only a few principal components (PCs) are necessary to reconstruct the data with high accuracy (over 95% of the original variance). Feed-forward neural networks are set up and trained to effectively simulate the leading PCs based on water level and wind speed and direction time series in a single, arbitrarily chosen point in the study area. Assuming that the spatial modes resulting from the PCA are ‘universally’ applicable to the data from time periods not modelled with Delft3D, the trained neural networks can be used to very effectively and reliably simulate temporal and spatial variability of water levels and currents in the study area. The approach is shown to be able to accurately reproduce statistical distribution of water levels and currents in various locations inside the study area and thus can be viewed as a reliable complementary tool e.g., for computationally expensive hydrodynamic modelling. Finally, a detailed analysis of the leading PCs is performed to estimate the role of tidal forcing and wind (including its seasonal and annual variability) in shaping the water level and current climate in the study area.     

The role of the Kupferschiefer in the formation of hydrothermal base metal mineralization in the Spessart ore district, Germany: insight from detailed sulfur isotope studies

The Spessart district (SW Germany), located at the southwestern margin of the Permian Kupferschiefer basin in Central Europe, hosts abundant stratabound and structurally controlled base metal mineralization. The mineralization styles identified are (1) stratabound Cu-Pb-Zn-(Ag) ores in Zechstein sedimentary rocks, (2) structurally controlled Cu-As-(Ag) ores in Zechstein sedimentary rocks, (3) crosscutting Co-Ni-(Bi)-As and Cu-Fe-As veins, (4) stratabound metasomatic Fe-Mn carbonate ores in Zechstein dolomite, (5) barren barite veins, and (6) Fe-Mn-As veins in Permian rhyolites. Building on previous work that involved mineralogical, textural, and chemical characterization of the major mineralization types, we have performed a comprehensive sulfur isotope study that applied both conventional and novel laser-ablation multi-collector inductively coupled plasma mass spectrometry techniques. The δ³⁴S values of sulfide minerals from the different ore types are consistently negative and highly variable, in the range between −44.5‰ and −3.9‰, whereas the δ³⁴S values of barite are all positive in the range between 4.7‰ and 18.9‰. Remarkably, stratabound and structurally controlled mineralization in Zechstein sedimentary rocks has the least negative δ³⁴S values, whereas vein-type deposits have consistently more negative δ³⁴S values. The observed pattern of sulfide δ³⁴S values can be best interpreted in terms of fluid mixing at the basement-cover interface. Hydrothermal fluids originating from the crystalline basement migrated upward along subvertical fault zones and were periodically injected into groundwaters that were flowing in the post-Variscan sedimentary cover. These groundwaters had interacted with the Zechstein sedimentary rocks, resulting in fluids characterized by elevated concentrations of reduced sulfur (with negative δ³⁴S values) and alkaline pH. Repeated mixing between both chemically contrasting fluids caused rapid and efficient precipitation of sulfide ore minerals in hydrothermal veins with highly variable but distinctly negative δ³⁴S values.     

Two-site CCD observations and spectroscopy of HD 207331: A new δ Scuti variable in Cygnus

The results of an observational campaign on the new δ Scuti pulsator HD 207331 are reported. The star was observed photometrically from August 26 to September 2, 2009 from the Observatorio San Pedro Mártir (0.84-m telescope, Mexico) and the Observatorio del Teide (0.80-m telescope, Spain). An overall run of 53.8 h of useful data was collected from the two sites. Four oscillation frequencies for HD 207331 have been found above a 99% confidence level. These results confirm the multiperiodic pulsation nature of the star suggested in previous observations with sparse data. Spectroscopic observations carried out in 2009 allowed us to derive its spectral type and luminosity class as well as to estimate its rotation rate. A simple comparison with models is performed.