Palaeoceanographic changes in the North Atlantic during the Mid-Pleistocene Transition (MIS 31-19) as inferred from planktonic foraminiferal and calcium carbonate records

Marine sediments from the Integrated Ocean Drilling Project (IODP) Site U1314 (56.36°N, 27.88°W), in the subpolar North Atlantic, were studied for their planktonic foraminifera, calcium carbonate content, and Neogloboqudrina pachyderma sinistral (sin.) δ13C records in order to reconstruct surface and intermediate conditions in this region during the Mid-Pleistocene Transition (MPT). Variations in the palaeoceanography and regional dynamics of the Arctic Front were estimated by comparing CaCO3 content, planktonic foraminiferal species abundances, carbon isotopes and ice-rafted debris (IRD) data from Site U1314 with published data from other North Atlantic sites. Site U1314 exhibited high abundances of the polar planktonic foraminifera N. pachyderma sin. and low CaCO3 content until Marine Isotope Stage (MIS) 26, indicating a relatively southeastward position of the Arctic Front (AF) and penetration of colder and low-salinity surface arctic water-masses. Changing conditions after MIS 25, with oscillations in the position of the AF, caused an increase in the northward export of the warmer North Atlantic Current (NAC), indicated by greater abundances of non-polar planktonic foraminifera and higher CaCO3. The N. pachyderma sin. δ13C data indicate good ventilation of the upper part of the intermediate water layer in the eastern North Atlantic during both glacial and interglacial stages, except during Terminations 24/23, 22/21 and 20/1. In addition, for N. pachyderma (sin.) we distinguished two morphotypes: non-encrusted and heavily encrusted test. Results indicate that increases in the encrusted morphotype and lower planktonic foraminiferal diversity are related to the intensification of glacial conditions (lower sea-surface temperatures, sea-ice formation) during MIS 22 and 20.

Phosphate release kinetics in calcareous grassland and forest soils in response to H+ addition

Phosphate release kinetics in soils are of global interest because sustainable plant nutrition with phosphate will be a major concern in the future. Dissolution of phosphate-containing minerals induced by a changing rhizosphere equilibrium through proton input is one important mechanism that releases phosphate into bioavailable forms. Our objectives were (i) to determine phosphate release kinetics during H+ addition in calcareous soils of the Schwäbische Alb, Germany, and to assess the influence of (ii) land-use type (grassland vs. forest) and (iii) management intensity on reactive phosphate pools and phosphate release rate constants during H+ addition. Phosphate release kinetics were characterized by a large fast-reacting phosphatepool, which could be attributed to poorly-crystalline calcium phosphates, and a small slow-reacting phosphate pool probably originating from carbonate-bearing hydroxylapatite. Both reactive phosphate pools—as well as total phosphate concentrations (TP) in soil—were greater in grassland than in forest soils. In organically fertilized grassland soils, concentrations of released phosphate were higher than in unfertilized soils, likely because organic fertilizers contain poorly-crystalline phosphate compounds which are further converted into sparingly soluble phosphate forms. Because of an enriched slow-reacting phosphate pool, mown pastures were characterized by a more continuous slow phosphate release reaction in contrast to clear biphasic phosphate release patterns in meadows. Consequently, managing phosphate release kinetics via management measures is a valuable tool to evaluate longer-term P availability in soil in the context of finite rock phosphate reserves on earth.

Nutrient Transport in the Mammary Gland: Calcium, Trace Minerals and Water Soluble Vitamins.

Milk nutrients are secreted by epithelial cells in the alveoli of the mammary gland by several complex and highly coordinated systems. Many of these nutrients are transported from the blood to the milk via transcellular pathways that involve the concerted activity of transport proteins on the apical and basolateral membranes of mammary epithelial cells. In this review, we focus on transport mechanisms that contribute to the secretion of calcium, trace minerals and water soluble vitamins into milk with particular focus on the role of transporters of the SLC series as well as calcium transport proteins (ion channels and pumps). Numerous members of the SLC family are involved in the regulation of essential nutrients in the milk, such as the divalent metal transporter-1 (SLC11A2), ferroportin-1 (SLC40A1) and the copper transporter CTR1 (SLC31A1). A deeper understanding of the physiology and pathophysiology of these transporters will be of great value for drug discovery and treatment of breast diseases.

Dating brittle tectonic movements with cleft monazite: Fluid-rock interaction and formation of REE minerals

[1] Two millimeter-sized hydrothermal monazites from an open fissure (cleft) that developed late during a dextral transpressional deformation event in the Aar Massif, Switzerland, have been investigated using electron microprobe and ion probe. The monazites are characterized by high Th/U ratios typical of other hydrothermal monazites. Deformation events in the area have been subdivided into three phases: (D1) main thrusting including formation of a new schistosity, (D2) dextral transpression, and (D3) local crenulation including development of a new schistosity. The two younger deformational structures are related to a subvertically oriented intermediate stress axis, which is characteristic for strike slip deformation. The inferred stress environment is consistent with observed kinematics and the opening of such clefts. Therefore, the investigated monazite-bearing cleft formed at the end of D2 and/or D3, and during dextral movements along NNW dipping planes. Interaction of cleft-filling hydrothermal fluid with wall rock results in rare earth element (REE) mineral formation and alteration of the wall rock. The main newly formed REE minerals are Y-Si, Y-Nb-Ti minerals, and monazite. Despite these mineralogical changes, the bulk chemistry of the system remains constant and thus these mineralogical changes require redistribution of elements via a fluid over short distances (centimeter). Low-grade alteration enables local redistribution of REE, related to the stability of the accessory phases. This allows high precision isotope dating of cleft monazite. 232Th/208Pb ages are not affected by excess Pb and yield growth domain ages between 8.03 ± 0.22 and 6.25 ± 0.60 Ma. Monazite crystallization in brittle structures is coeval or younger than 8 Ma zircon fission track data and hence occurred below 280°C.

High-resolution sequence stratigraphic correlation in the Upper Jurassic (Kimmeridgian)–Upper Cretaceous (Cenomanian) peritidal carbonate deposits (Western Taurides, Turkey)

Upper Jurassic (Kimmeridgian)±Upper Cretaceous (Cenomanian) inner platform carbonates in the Western Taurides are composed of metre-scale upward-shallowing cyclic deposits (parasequences) and important karstic surfaces capping some of the cycles. Peritidal cycles (shallow subtidal facies capped by tidal-¯at laminites or fenestrate limestones) are regressive- and transgressive-prone (upward-deepening followed by upward-shallowing facies trends). Subtidal cycles are of two types and indicate incomplete shallowing. Submerged subtidal cycles are composed of deeper subtidal facies overlain by shallow subtidal facies. Exposed subtidal cycles consist of deeper subtidal facies overlain by shallow subtidal facies that are capped by features indicative of prolonged subaerial exposure. Subtidal facies occur characteristically in the Jurassic, while peritidal cycles are typical for the Lower Cretaceous of the region. Within the foraminiferal and dasyclad algal biostratigraphic framework, four karst breccia levels are recognized as the boundaries of major second-order cycles, introduced for the ®rst time in this study. These levels correspond to the Kimmeridgian±Portlandian boundary, mid-Early Valanginian, mid-Early Aptian and mid-Cenomanian and represent important sea level falls which affected the distribution of foraminiferal fauna and dasyclad ¯ora of the Taurus carbonate platform. Within the Kimmeridgian±Cenomanian interval 26 third-order sequences (types 1 and 2) are recognized. These sequences are the records of eustatic sea level ¯uctuations rather than the records of local tectonic events because the boundaries of the sequences representing 1±4 Ma intervals are correlative with global sea level falls. Third-order sequences and metre-scale cyclic deposits are the major units used for long-distance, high-resolution sequence stratigraphic correlation in the Western Taurides. Metre-scale cyclic deposits (parasequences) in the Cretaceous show genetical stacking patterns within third-order sequences and correspond to fourth-order sequences representing 100±200 ka. These cycles are possibly the E2 signal (126 ka) of the orbital eccentricity cycles of the Milankovitch band. The slight deviation of values, calculated for parasequences, from the mean value of eccentricity cycles can be explained by the currently imprecise geochronology established in the Cretaceous and missed sea level oscillations when the platform lay above fluctuating sea level.

Geochemical synthesis for the Effingen Member in boreholes at Oftringen, Gösgen and Küttigen

The Effingen Member is a low-permeability rock unit of Oxfordian age (ca. 160 Ma) that occurs across northern Switzerland. It comprises sandy calcareous marls and (argillaceous) limestones. This report describes the hydrogeochemistry, mineralogy and supporting physical properties of the Effingen Member in three boreholes in the Jura-Südfuss area: Oftringen, Gösgen and Küttigen, where it is 220–240 m thick. The top of the Effingen Member is at 420, 66 and 32 m depths at the three sites. Core materials are available from Oftringen and Gösgen, whereas information from Küttigen is limited to cuttings, in-situ hydrogeological testing and geophysical logging. Hydrogeological boundaries of the Effingen Member vary between locations. Ground-water flows were identified during drilling at the top (Geissberg Member), but not at the base, of the Effingen Member at Oftringen, at the base (Hauptrogenstein Formation) of the Effingen Member at Gösgen, and in a limestone layer (Gerstenhübel unit) within the Effingen Member at Küttigen. The marls and limestones of the Effingen Member have carbonate contents of 46–91 wt.-% and clay-mineral contents of 5–37 wt.-%. Pyrite contents are up to 1.6 wt.-%, but no sulphate minerals were detected by routine analyses. Clay minerals are predominantly mixed-layer illite-smectite, illite and kaolinite, with sporadic traces of chlorite and smectite. Veins filled with calcite ± celestite occur through the Effingen Member at Oftringen but not at Gösgen or Küttigen. They formed at 50–70 ºC from externally derived fluids, probably of Miocene age. Water contents are 0.7–4.2 wt.-%, corresponding to a water-loss porosity range of 1.9–10.8 vol.-%. Specific surface areas, measured by the BET method, are 2–30 m2/g, correlating with clay-mineral contents. Water activity has been measured and yielded surprisingly low values down to 0.8. These cannot be explained by pore-water salinity alone and include other effects, such as changes in the fabric due to stress release or partial saturation. Observed variations in measurements are not fully understood. Cation exchange capacity (CEC) and exchangeable cation populations have been studied by the Ni-en method. CEC, derived from the consumption of the index cation Ni, is 9–99 meq/kgrock at a solid:liquid ratio of 1, correlating with the clay-mineral content. Cation concentrations in Ni-en extract solutions are in the order Na+≥Ca2+>Mg2+>K+>Sr2+. However, the analytical results from the Ni-en extractions have additional contributions from cations originating from pore water and from mineral dissolution reactions that occurred during extraction, and it was not possible to reliably quantify these contributions. Therefore, in-situ cation populations and selectivity coefficients could not be derived. A suite of methods have been used for characterising the chemical compositions of pore waters in the Effingen Member. Advective displacement was used on one sample from each Oftringen and Gösgen and is the only method that produces results that approach complete hydrochemical compositions. Aqueous extraction was used on core samples from these two boreholes and gives data only for Cl- and, in some cases, Br-. Out-diffusion was used on core samples from Oftringen and similarly gives data for Cl- and Br- only. For both aqueous extraction and out-diffusion, reaction of the experimental water with rock affected concentrations of cations, SO42 and alkalinity in experimental solutions. Another method, centrifugation, failed to extract pore water. Stable isotope ratios (δ18O and δ2H) of pore waters in core samples from Oftringen were analysed by the diffusive exchange method and helium contents of pore water in Oftringen samples were extracted for mass spectrometric analysis by quantitative outgassing of preserved core samples. Several lines of evidence indicate that drillcore samples might not have been fully saturated when opened and subsampled in the laboratory. These include comparisons of water-loss porosities with physical porosities, water-activity measurements, and high contents of dissolved gas as inferred from ground-water samples. There is no clear proof of partial saturation and it is unclear whether this might represent in-situ conditions or is due to exsolution of gas due to the pressure release since drilling. Partial saturation would have no impact on the recalculation of pore-water compositions from aqueous extraction experiments using water-loss porosity data. The largest uncertainty in the pore-water Cl- concentrations recalculated from aqueous extraction and out-diffusion experiments is the magnitude of the anion-accessible fraction of water-loss porosity. General experience of clay-mineral rich formations suggests that the anion-accessible porosity fraction is very often about 0.5 and generally in a range of 0.3 to 0.6 and tends to be inversely correlated with clay-mineral contents. Comparisons of the Cl- concentration in pore water obtained by advective displacement with that recalculated from aqueous extraction of an adjacent core sample suggests a fraction of 0.27 for an Oftringen sample, whereas the same procedure for a Gösgen sample suggests a value of 0.64. The former value for anion-accessible porosity fraction is presumed to be unrepresentative given the local mineralogical heterogeneity at that depth. Through-diffusion experiments with HTO and 36Cl- suggest that the anion-accessible porosity fraction in the Effingen Member at Oftringen and Gösgen is around 0.5. This value is proposed as a typical average for rocks of the Effingen Member, bearing in mind that it varies on a local scale in response to the heterogeneity of lithology and pore-space architecture. The substantial uncertainties associated with the approaches to estimating anion-accessible porosity propagate into the calculated values of in-situ pore-water Cl- concentrations. On the basis of aqueous extraction experiments, and using an anion-accessible porosity fraction of 0.5, Cl- concentrations in the Effingen Member at Oftringen reach a maximum of about 14 g/L in the centre. Cl- decreases upwards and downwards from that, forming a curved depth profile. Cl- contents in the Effingen Member at Gösgen increase with depth from about 3.5 g/L to about 14 g/L at the base of the cored profile (which corresponds to the centre of the formation). Out-diffusion experiments were carried out on four samples from Oftringen, distributed through the Effingen Member. Recalculated Cl- concentrations are similar to those from aqueous extraction for 3 out of the 4 samples, and somewhat lower for one sample. Concentrations of other components, i.e. Na+, K+, Ca2+, Mg2+, Sr2+, SO42- and HCO3- cannot be obtained from the aqueous extraction and out-diffusion experimental data because of mineral dissolution and cation exchange reactions during the experiments. Pore-water pH also is not constrained by those extraction experiments. The only experimental approach to obtain complete pore-water compositions for samples from Oftringen and Gösgen is advective displacement of pore water. The sample from Oftringen used for this experiment is from 445 m depth in the upper part of the Effingen Member and gave eluate with 16.5 g/L Cl- whereas aqueous extraction from a nearby sample indicated about 9 g/L Cl-. The sample from Gösgen used for advective displacement is from 123 m depth in the centre of the Effingen Member sequence and gave eluate with about 9 g/L Cl- whereas aqueous extraction gave 11.5 g/L Cl-. In both cases the pore waters have Na-(Ca)-Cl compositions and SO42- concentrations of about 1.1 g/L. The Gösgen sample has a Br/Cl ratio similar to that of sea water, whereas this ratio is lower for the Oftringen sample. Taking account of uncertainties in the applied experimental approaches, it is reasonable to place an upper limit of ca. 20 g/L on Cl- concentration for pore water in the Effingen Member in this area. There are major discrepancies between pore-water SO42- concentrations inferred from aqueous extraction or out-diffusion experiments and those obtained from advective displacement in both the Oftringen and Gösgen cases. A general conclusion is that all or at least part of the discrepancies are attributable to perturbation of the sulphur system and enhancement of SO42- by sulphate mineral dissolution and possibly minor pyrite oxidation during aqueous extraction and out-diffusion. Therefore, data for SO42- calculated from those pore-water sampling methods are considered not to be representative of in-situ conditions. A reference pore-water composition was defined for the Effingen Member in the Jura Südfuss area. It represents the probable upper limits of Cl- contents and corresponding anion and cation concentrations that are reasonably constrained by experimental data. Except for Cl- and possibly Na+ concentrations, this composition is poorly constrained especially with respect to SO42- and Ca2+ concentrations, and pH and alkalinity. Stable isotope compositions, δ18O and δ2H, of pore waters in the Effingen Member at Oftringen plot to the right of the meteoric water line, suggesting that 18O has been enriched by water-rock exchange, which indicates that the pore waters have a long residence time. A long residence time of pore water is supported by the level of dissolved 4He that has accumulated in pore water of the Effingen Member at Oftringen. This is comparable with, or slightly higher than, the amounts of 4He in the Opalinus Clay at Benken. Ground waters were sampled from flowing zones intersected by boreholes at the three locations. The general interpretation is that pore waters and ground-water solutes may have similar origins in Mesozoic and Cenozoic brackish-marine formations waters, but ground-water solutes have been diluted rather more than pore waters by ingress of Tertiary and Quaternary meteoric waters. The available hydrochemical data for pore waters from the Effingen Member at these three locations in the Jura-Südfuss area suggest that the geochemical system evolved slowly over geological periods of time, in which diffusion was an important mechanism of solute transport. The irregularity of Cl- and δ18O profiles and spatial variability of advective ground-water flows in the Malm-Dogger system suggests that palaeohydrogeological and hydrochemical responses to changing tectonic and surface environmental conditions were complex.

Manganiferous minerals of the epidote group from the Archaean basement of West Greenland

The chemical compositions and crystal structures of Mn3+-containing minerals from the epidote group in Greenland rocks are investigated and described in detail. They occur in hydrothermally altered Archaean mafic sequences within the gneissic complex of the North Atlantic craton of West Greenland. The Mn-containing minerals have a characteristic red to pink colour. A detailed microchemical study shows a significant inter- and intra-sample variation in Mn content. The samples from different parageneses can be classified as Mn-bearing epidote and Mn-bearing clinozoisite. The intra-sample variation in the content of Al, Fe and Mn is on a very fine scale, but still allows for identification of a negative correlation between Mn and Fe. Textures indicate different stages of growth. Crystal chemical data are compared with literature data and illustrate the basic systematic differences between the influence of Fe and Mn on the crystal structure of the epidote group minerals.

Continuous eclogite melting and variable refertilisation in upwelling heterogeneous mantle

Large-scale tectonic processes introduce a range of crustal lithologies into the Earth's mantle. These lithologies have been implicated as sources of compositional heterogeneity in mantle-derived magmas. The model being explored here assumes the presence of widely dispersed fragments of residual eclogite (derived from recycled oceanic crust), stretched and stirred by convection in the mantle. Here we show with an experimental study that these residual eclogites continuously melt during upwelling of such heterogeneous mantle and we characterize the melting reactions and compositional changes in the residue minerals. The chemical exchange between these partial melts and more refractory peridotite leads to a variably metasomatised mantle. Re-melting of these metasomatised peridotite lithologies at given pressures and temperatures results in diverse melt compositions, which may contribute to the observed heterogeneity of oceanic basalt suites. We also show that heterogeneous upwelling mantle is subject to diverse local freezing, hybridization and carbonate-carbon-silicate redox reactions along a mantle adiabat.

Superspace description of wagnerite-group minerals (Mg,Fe,Mn) 2 (PO 4 )(F,OH)

Reinvestigation of more than 40 samples of minerals belonging to the wagnerite group (Mg, Fe, Mn)2(PO4)(F,OH) from diverse geological environments worldwide, using single-crystal X-ray diffraction analysis, showed that most crystals have incommensurate structures and, as such, are not adequately described with known polytype models (2b), (3b), (5b), (7b) and (9b). Therefore, we present here a unified superspace model for the structural description of periodically and aperiodically modulated wagnerite with the (3+1)-dimensional superspace group C2/c(0[beta]0)s0 based on the average triplite structure with cell parameters a [asymptotically equal to] 12.8, b [asymptotically equal to] 6.4, c [asymptotically equal to] 9.6 Å, [beta] [asymptotically equal to] 117° and the modulation vectors q = [beta]b*. The superspace approach provides a way of simple modelling of the positional and occupational modulation of Mg/Fe and F/OH in wagnerite. This allows direct comparison of crystal properties.

Resolving diffusion in clay minerals at different time scales: Combination of experimental and modeling approaches

Since no single experimental or modeling technique provides data that allow a description of transport processes in clays and clay minerals at all relevant scales, several complementary approaches have to be combined to understand and explain the interplay between transport relevant phenomena. In this paper molecular dynamics simulations (MD) were used to investigate the mobility of water in the interlayer of montmorillonite (Mt), and to estimate the influence of mineral surfaces and interlayer ions on the water diffusion. Random Walk (RW) simulations based on a simplified representation of pore space in Mt were used to estimate and understand the effect of the arrangement of Mt particles on the meso- to macroscopic diffusivity of water. These theoretical calculations were complemented with quasielastic neutron scattering (QENS) measurements of aqueous diffusion in Mt with two pseudo-layers of water performed at four significantly different energy resolutions (i.e. observation times). The size of the interlayer and the size of Mt particles are two characteristic dimensions which determine the time dependent behavior of water diffusion in Mt. MD simulations show that at very short time scales water dynamics has the characteristic features of an oscillatory motion in the cage formed by neighbors in the first coordination shell. At longer time scales, the interaction of water with the surface determines the water dynamics, and the effect of confinement on the overall water mobility within the interlayer becomes evident. At time scales corresponding to an average water displacement equivalent to the average size of Mt particles, the effects of tortuosity are observed in the meso- to macroscopic pore scale simulations. Consistent with the picture obtained in the simulations, the QENS data can be described using a (local) 3D diffusion at short observation times, whereas at sufficiently long observation times a 2D diffusive motion is clearly observed. The effects of tortuosity measured in macroscopic tracer diffusion experiments are in qualitative agreement with RW simulations. By using experimental data to calibrate molecular and mesoscopic theoretical models, a consistent description of water mobility in clay minerals from the molecular to the macroscopic scale can be achieved. In turn, simulations help in choosing optimal conditions for the experimental measurements and the data interpretation. (C) 2014 Elsevier B.V. All rights reserved.

Environmental control on the occurrence of high-coercivity magnetic minerals and formation of iron sulfides in a 640 ka sediment sequence from Lake Ohrid (Balkans)

The bulk magnetic mineral record from Lake Ohrid, spanning the past 637 kyr, reflects large-scale shifts in hydrological conditions, and, superimposed, a strong signal of environmental conditions on glacial–interglacial and millennial timescales. A shift in the formation of early diagenetic ferrimagnetic iron sulfides to siderites is observed around 320 ka. This change is probably associated with variable availability of sulfide in the pore water. We propose that sulfate concentrations were significantly higher before  ∼  320 ka, due to either a higher sulfate flux or lower dilution of lake sulfate due to a smaller water volume. Diagenetic iron minerals appear more abundant during glacials, which are generally characterized by higher Fe / Ca ratios in the sediments. While in the lower part of the core the ferrimagnetic sulfide signal overprints the primary detrital magnetic signal, the upper part of the core is dominated by variable proportions of high- to low-coercivity iron oxides. Glacial sediments are characterized by high concentration of high-coercivity magnetic minerals (hematite, goethite), which relate to enhanced erosion of soils that had formed during preceding interglacials. Superimposed on the glacial–interglacial behavior are millennial-scale oscillations in the magnetic mineral composition that parallel variations in summer insolation. Like the processes on glacial–interglacial timescales, low summer insolation and a retreat in vegetation resulted in enhanced erosion of soil material. Our study highlights that rock-magnetic studies, in concert with geochemical and sedimentological investigations, provide a multi-level contribution to environmental reconstructions, since the magnetic properties can mirror both environmental conditions on land and intra-lake processes.