Input of particulate heavy metals from rivers and associated sedimentary deposits on the Gulf of Lion continental shelf

Fluxes of the heavy metals chromium (Cr), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), cadmium (Cd) and zinc (Zn) delivered by rivers to the Gulf of Lion (NW Mediterranean Sea) were estimated over a three year study of the River Rhone and its smaller tributaries. Most of the particulate metal fluxes (80–90%) delivered by these rivers occurred within a very short period of time (less than 12%), a typical trend for the Mediterranean environment, where highly contrasting hydrological regimes were observed over the year. Temporal and spatial variations in the fluxes of these particulate metals were driven by the fluxes in both water discharge and suspended particulate matter load. On the shelf, these particulate metal fluxes, largely arising from the Rhone watershed, were two to ten times more important than those resulting from atmospheric deposition. Co, Cr and Ni in the rivers and on the shelf surface sediments were mainly natural and associated with the finest particles. Cd and Phosphorus appeared to be associated with the silt fraction and to be enriched in the prodelta areas. Pb, Zn and Cu were more closely associated with the organic matter content and also showed enrichment in the organic rich prodeltaic sediments. Anthropogenic influences diminished offshore, except for Pb and Zn which could be supplied from the atmosphere by man-made aerosols. Although most of the metals tended to be enriched in the prodelta areas, these did not constitute a permanent sink due to resuspension processes affecting these shallow depths. A resuspension experiment conducted on sediment cores from the Rhone prodelta demonstrated that metal deposited on the surface layer, especially those associated with the organic matter, may be resuspended; this should be taken into account for a complete understanding of the biogeochemical cycle of these metals.     

High-pressure single-crystal X-ray diffraction and synchrotron Mössbauer study of monoclinic ferrosilite

The phase and spin transitions in single-crystal monoclinic ferrosilite, FeSiO₃, were investigated using X-ray diffraction and Mössbauer spectroscopy up to lower-mantle pressures and room temperature in a helium pressure medium. Using single-crystal X-ray diffraction, we measured the equation of state of ferrosilite up to about 43 GPa. We observed a P2₁/c-to-C2/c phase transition between 1.5 and 1.7 GPa and a phase transition from C2/c to a distinct P2₁/c structure between 30 and 34 GPa. With time-domain Mössbauer spectroscopy, we determined the hyperfine parameters of ferrous iron up to 95 GPa. The phase transitions were correlated with discontinuities in Mössbauer spectral features. We observed the onset of high-spin-to-low-spin transitions in the M1 and M2 sites at ～37 GPa and ～74 GPa, respectively. Understanding the electronic structure of iron in a well-characterized single crystal of ferrosilite may help interpret the behavior of iron in complex dense silicate phases.     

Pb/Pb age determinations on the Newania and Sevattur carbonatites of India: evidence for multi-stage histories

The ages of Indian carbonatites are still controversial. Most of the earlier datings were done by K/Ar methods. We therefore analysed Pb/Pb ratios in carbonatites from carbonatite-alkalic complexes of Newania (NW India, Rajasthan State) and Sevattur (SW India, Tamil Nadu State) to constrain the age and geological history of these rocks. Newania carbonatites are intrusive into Precambrian Untala granite-gneiss and mainly dolomitic in composition (rauhaugite) followed by a later phase of ankerite carbonatite, while thin calcite carbonatite (sövite) dykelets are the youngest in the sequence. The analysed whole-rock samples are characterised by ²⁰⁶Pb/²⁰⁴Pb ratios between 60 and 176 and ²⁰⁷Pb/²⁰⁴Pb ratios between 22 and 40, which are extremely high in comparison to common igneous rocks and even for carbonatite compositions. One sample, New 37, shows the extreme ratios of ²⁰⁶Pb/²⁰⁴Pb = 574 and ²⁰⁷Pb/²⁰⁴Pb = 73. This requires a μ-value of about 2000 for the last 1550 Ma. If the samples are classified according to their petrographic/geochemical characteristics this results in an isochron age of 1551 ± 46 Ma for the ankerite carbonatites (six samples). The dolomites (6 samples) yield an isochron age of 2.27 Ga. Although these results fit quite well into the geological evolution scheme of the area, the extreme long age hiatus between dolomite carbonatite and ferrocarbonatite formation events raises severe problems for their petrologic interpretation.

The Proterozoic Sevattur carbonatite complex (SCC, Tamil Nadu) was emplaced contemporaneously with a large number of carbonatite complexes within the Precambrian gneissic terrane of the Eastern Ghats Mobile Belt. The main mass is composed of dolomite carbonatite (rauhaugite) with a few dikes of calcite carbonatite (sövite) and ankerite carbonatite within it. All eight samples together yield an isochron of 805 ± 10 Ma. This isochron is mainly determined on ankerite carbonatites with μ-values up to 1900 for the last 800 Ma. Taking only ankerite carbonatites into account, the resulting age is 801 ± 11 Ma. The ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb ratios of these samples are similar to the main group of Newania and far beyond the isotopic composition of common igneous rocks.

Our investigations show that in carbonatitic rock systems extremely high lead isotopic ratios can be established due to the crystallization of uranium-rich mineral phases. In both cases the observed high to extremely high initial Pb isotope ratios require the residence of the lead in intermediate high-μ reservoirs either within the upper mantle or the crust prior to the carbonatite formation. A high-temperature event, which completely reset the Rb/Sr and K/Ar isotopic systems of Nevania carbonatites, seems to have no influence on the lead isotopic systematics.     

Experimental investigations on the formation of excess air in quasi-saturated porous media

The formation of an excess of dissolved gas (“excess air”) in quasi-saturated media was studied by analyzing and interpreting dissolved noble gas concentrations in laboratory column experiments. Using quartz sand filled columns of 1 m length, two different experimental designs were realized. In the first, groundwater recharge was simulated by a unidirectional vertical water flow through the columns. In the second, groundwater level fluctuations in an aquifer zone without active infiltration were reproduced by cyclic water level fluctuations in the columns. The reproducible generation of excess air under these defined, near natural conditions was successful. Partial or complete dissolution of air bubbles entrapped in the quartz sand could be identified as the mechanism responsible for the generation of excess air. Depending on the experimental design, supersaturation of the dissolved atmospheric noble gases ranging between 1.4% ΔNe and 16.2% ΔNe was found. The measured noble gas patterns were interpreted using inverse modeling and conceptual gas exchange models and were compared to results of numerical simulations of gas bubble dissolution in water filled soil columns. The gas composition in most of the samples resembles either unfractionated pure atmospheric excess air or is fractionated in accordance with closed-system equilibration between entrapped air and surrounding water. In addition to the amount of entrapped air, the hydrostatic pressure exerted on the entrapped air bubbles is the dominating parameter responsible for the total amount of dissolved air. The composition of the excess air component is controlled by the water flow regime, the bubble size distribution, the initially dissolved gas concentrations and the initially entrapped gas composition.     

Basal plane reactivity of phyllosilicates studied in situ by hydrothermal atomic force microscopy (HAFM)

The basal plane reactivities of the sheet silicates apophyllite and phlogopite have been studied by hydrothermal atomic force microscopy (HAFM) in situ in aqueous solutions at temperatures from 20 to 140 °C. At pH 4-5.6 (T = 20-100 °C), the apophyllite basal surface undergoes a swelling process which forms square hillocks on the surface. The reaction comprises three sequential morphological transformations that cause swelling to increase from 0.15 to 2.5 nm. In the first two transformations, interlayer cations are replaced by hydronium ions from the solution; the third transformation involves a depolymerization and partial cross-linking of the protonated silicate sheets. The reaction of phlogopite with acidic aqueous solutions (pH 1.5-2) at high temperature (T = 100-140 °C) causes the nucleation of numerous monolayer etch pits on the pristine surface. Where the 2D pits recur at the same lateral position, they can accumulate to a total pit depth of up to 50 nm. The formation of an altered layer has also been detected at these conditions. The alteration affects the uppermost 4-5 layers. The layers are expanded, corrugated, highly unstable, and readily peel off the surface. Etch pit formation has been detected even underneath the altered layer. On the basis of HAFM data, dissolution rates and activation energies were calculated. The presented data show that the basal surface of phlogopite plays an important role in the dissolution process at least at elevated temperatures and that the absolute amount of released material has comparable contributions from both basal surfaces and edge surfaces.     

Geochronology and geochemistry of a dyke–host rock association and implications for the formation of the Bavarian Pfahl shear zone, Bohemian Massif

To place constraints on the formation and deformation history of the major Variscan shear zone in the Bavarian Forest, Bavarian Pfahl zone, SW Bohemian Massif, granitic dykes and their feldspar-phyric massive host rock (so-called palite), zircons were dated by the U–Pb isotope dilution and Pb-evaporation methods. The dated samples comprise two host rocks and four dykes from a K-rich calc-alkaline complex adjoining the SW part of the Bavarian Pfahl shear zone. The palites, which appear to be the oldest magmatic rocks emplaced in the shear zone, yield ages of 334±3, 334.5±1.1 Ma (average ²⁰⁷Pb/²⁰⁶Pb-evaporation zircon ages) and 327–342 Ma (range of U/Pb zircon ages) suggesting a Lower Carboniferous age for the initiation of the Pfahl zone. Absence of inherited older cores in all investigated zircons indicates that incorporation of crustal zircon material has played virtually no role or that the melting temperature was very high. Determination of the dyke emplacement age is complicated by partial Pb-loss in most of the fractions analysed. This Pb-loss can be ascribed to higher U content of the dyke zircons compared to those from host rock. Upper discordia intercept ages of the different dykes range from 322±5 to 331±9 Ma. The dykes are pre- to synkinematic with respect to penetrative regional mylonitisation along the Pfahl zone, and the upper intercept ages provide a maximum age for this tectonic event.     

Recognition of early Carboniferous alkaline granite in the southern Altai orogen: post-orogenic processes constrained by U–Pb zircon ages, Nd isotopes, and geochemical data

The Altai orogen forms the southern part of the Central Asian Orogenic Belt (CAOB), the world’s largest accretionary orogen. However, its tectonic evolution, particularly during the late Paleozoic, is still not well understood. U–Pb zircon analyses for the Bulgen alkaline granite yield crystallization ages of 358?±?4?Ma (SHRIMP) and 354?±?4?Ma (LA-ICP-MS). These ages are significantly younger than published emplacement ages for subduction/collision-related syn-orogenic granitoids (460–375?Ma) in this region. The Bulgen granite has high SiO₂, total alkalis, rare earth elements, HFSE (Th, Zr, Hf, Nb, and Ce), and low Ba, Sr with pronounced negative anomalies in Eu, Ba, Sr, P, and Ti, showing a clear A-type geochemical signature. The granite records high εNd(t) values of +6.3 to +6.4 and young model ages (T _DM) of ca. 600?Ma. The Bulgen alkaline granite is largely undeformed as opposed to the early-middle Paleozoic counterparts, which form elongated deformed bodies parallel to the prevailing tectonic fabric (NW direction). Available data suggest that magmatism in the southern Altai region evolved from early-middle Paleozoic I-type tholeiitic and calc-alkaline granitoids to late Paleozoic A-type alkaline granitoids. The high εNd(t) values of the Bulgen alkaline granite indicate a homogeneous juvenile mantle source, whereas the early-middle Paleozoic granitoids are characterized by lower and more variable εNd(t) values (?2.6 to +4.2). These differences provide an important insight into the late Paleozoic orogenic processes of the Chinese Altai and indicate a significant change of the tectonic regime from a syn-orogenic regional compression setting to a post-orogenic extensional one. Major tectonic movements in this region ceased after the early Carboniferous.     

Geochemical characteristics from tests of four modern planktonic foraminiferal species in the Indonesian Throughflow region and their implications

Test geochemistry of planktonic foraminifera is an indispensable tool in reconstructing past ocean hydrological changes. It is essential to investigate region-specific implications of test geochemistry,although those established from other regions can be broadly applied. In this study, characteristics of6180 and Mg/Ca from tests of four planktonic foraminiferal species, Globigerinoides ruber sensu stricto(s.s.), Globigerinoides sacculifer, Pulleniatina obliquiloculata and Neogloboquadrina dutertrei, from 60 coretop sediment samples retrieved from the Indonesian Throughflow(ITF) region were studied. These geochemical data were compared with modern hydrographic profiles in order to assess their relations and to investigate potential implications of test geochemical parameters in reconstructing past oceanographic change in the ITF region. Calcification depths of these four species were first estimated based on comparison between measured test δ180 and predicted calcite δ¹⁸O that was calculated from modern temperature and salinity. The results indicate that G. ruber s.s. and G. sacculifer calcify within the mixedlayer at 0-50 m and 20-75 m, respectively, whereas P. obliquiloculata and N. dutertrei calcify within the thermocline at around 75 to 125 m. A combined study of excess Mg/Ca(difference between measured and predicted Mg/Ca) and salinity suggests that salinity exerts a negligible impact on test Mg/Ca of these foraminiferal species in the ITF region. Comparison of test Mg/Ca-derived temperatures with temperature profiles of the upper 200 m of the water column from the seas of the ITF region also indicate calcification depths of these species, which match well with the above estimations using test δ¹⁸O. It further indicates that G. sacculifer may be more sensitive in reflecting changes in the depth of the mixedlayer, highlighting a potential use of Mg/Ca temperature difference between G. ruber s.s. and G. sacculifer in reconstructing the depth of the mixed-layer in the ITF region.     

High resolution climate simulations over the Arctic

The regional atmospheric climate model HIRHAM has been applied to the Arctic. Simulations for the whole year 1990 and for an ensemble of winter months (January of 1985-1995) have been performed. The comparison of the simulations with observational data analyses shows that the general spatial patterns are in good agreement with the data, in both the vertical structure and the annual cycle. For an additional validation of the model results, a multivariate classification of large-scale circulation patterns has been applied to the January ensemble model simulations.