Impact of the azores front propagation on deep ocean particle flux

The Azores Current originating as a branch of the Gulf Stream is a highly dynamic system in the subtropical North Atlantic. The associated front forms the northeastern boundary of the North Atlantic Subtropical Gyre. In this study we analyzed 42 years of assimilated modeled temperature fields to localize the position of the Azores Front at 22°W and observed a fast north- and southward propagation between 30°N and 37°N on monthly to decadal time scales. The North Atlantic Oscillation with correlated changes of the wind direction was identified as one driving mechanism. As the front is acting as a guide for Rossby waves, the signal of the front??s propagation is transferred to the western Atlantic and, among other atmospheric forcing mechanisms, induces a shifting of the Northern Wall of the Gulf Stream with one year delay. Shallower mixed layer depths in the northern frontal region of the Azores Current caused by the rise of the isotherms lead to nutrient supply and primary production different from those found in the southern frontal region of the current system. A high interannual variability is manifested in deep ocean particle flux, derived from a sediment trap in 2000 m water depth at the mooring site KIEL276 (33°N, 22°W) from 1993 to 2008, which is directly related to the phytoplankton bloom in the euphotic zone. This variability is explained by the propagation of the front and strong variations in the catchment areas of the sediment trap due to the associated eddy activity in the frontal region.     

Climate change and the resilient society: utopia or realistic option for German regions?

For the last five years, climate change has been increasingly perceived as a challenge for regional development. Compared to other nations, Germany is relatively ‘safe’, but the German regions are prone to different impacts of climate change; some of them might be positive but most will be negative in the long run. Strategic concepts are therefore needed to reduce the negative impacts and use the potential positive effects. Due to enforced research funding, several German regions are currently developing adaptation strategies within transdisciplinary research projects. Based on a comparative case study analysis of three of these projects, this paper looks for the benefits of resilience thinking in the context of climate change adaptation. The analysis shows that the case study regions try to increase their resilience to climate change by strengthening the properties of (1) resistance, (2) recovery and (3) creativity. But the discussion also reveals that only parts, certain sectors or subjects, of the region can increase their distinct resilience. Regional stakeholder networks as established within the case study regions can make a significant contribution to linking different sectors and levels of action. Therefore, this approach seems to be applicable for integrating the need for adaptation within the whole region. It is believed that the regionalized communication of potential climate change impacts raises awareness for climate change adaptation, helps to develop appropriate adaptation measures and encourages action. Hence, different approaches can indeed lead to more resilient structures. But the resilient society at regional level remains utopia.     

Climate change and the resilient society: utopia or realistic option for German regions?

For the last five years, climate change has been increasingly perceived as a challenge for regional development. Compared to other nations, Germany is relatively ‘safe’, but the German regions are prone to different impacts of climate change; some of them might be positive but most will be negative in the long run. Strategic concepts are therefore needed to reduce the negative impacts and use the potential positive effects. Due to enforced research funding, several German regions are currently developing adaptation strategies within transdisciplinary research projects. Based on a comparative case study analysis of three of these projects, this paper looks for the benefits of resilience thinking in the context of climate change adaptation. The analysis shows that the case study regions try to increase their resilience to climate change by strengthening the properties of (1) resistance, (2) recovery and (3) creativity. But the discussion also reveals that only parts, certain sectors or subjects, of the region can increase their distinct resilience. Regional stakeholder networks as established within the case study regions can make a significant contribution to linking different sectors and levels of action. Therefore, this approach seems to be applicable for integrating the need for adaptation within the whole region. It is believed that the regionalized communication of potential climate change impacts raises awareness for climate change adaptation, helps to develop appropriate adaptation measures and encourages action. Hence, different approaches can indeed lead to more resilient structures. But the resilient society at regional level remains utopia.     

Iron speciation and isotope fractionation during silicate weathering and soil formation in an alpine glacier forefield chronosequence

The chemical weathering of primary Fe-bearing minerals, such as biotite and chlorite, is a key step of soil formation and an important nutrient source for the establishment of plant and microbial life. The understanding of the relevant processes and the associated Fe isotope fractionation is therefore of major importance for the further development of stable Fe isotopes as a tracer of the biogeochemical Fe cycle in terrestrial environments. We investigated the Fe mineral transformations and associated Fe isotope fractionation in a soil chronosequence of the Swiss Alps covering 150 years of soil formation on granite. For this purpose, we combined for the first time stable Fe isotope analyses with synchrotron-based Fe-EXAFS spectroscopy, which allowed us to interpret changes in Fe isotopic composition of bulk soils, size fractions, and chemically separated Fe pools over time in terms of weathering processes. Bulk soils and rocks exhibited constant isotopic compositions along the chronosequence, whereas soil Fe pools in grain size fractions spanned a range of 0.4‰ in δ⁵⁶Fe. The clay fractions (<2 μm), in which newly formed Fe(III)-(hydr)oxides contributed up to 50% of the total Fe, were significantly enriched in light Fe isotopes, whereas the isotopic composition of silt and sand fractions, containing most of the soil Fe, remained in the range described by biotite/chlorite samples and bulk soils. Iron pools separated by a sequential extraction procedure covered a range of 0.8‰ in δ⁵⁶Fe. For all soils the lightest isotopic composition was observed in a 1 M NH₂OH-HCl-25% acetic acid extract, targeting poorly-crystalline Fe(III)-(hydr)oxides, compared with easily leachable Fe in primary phyllosilicates (0.5 M HCl extract) and Fe in residual silicates. The combination of the Fe isotope measurements with the speciation data obtained by Fe-EXAFS spectroscopy permitted to quantitatively relate the different isotope pools forming in the soils to the mineral weathering reactions which have taken place at the field site. A kinetic isotope effect during the Fe detachment from the phyllosilicates was identified as the dominant fractionation mechanism in young weathering environments, controlling not only the light isotope signature of secondary Fe(III)-(hydr)oxides but also significantly contributing to the isotope signature of plants. The present study further revealed that this kinetic fractionation effect can persist over considerable reaction advance during chemical weathering in field systems and is not only an initial transient phenomenon.     

Iron isotope fractionation during proton- and ligand-promoted dissolution of primary phyllosilicates

We studied stable iron isotope fractionation during dissolution of a biotite and chlorite enriched mineral fraction from granite by HCl and 5 mM oxalic acid in a pH range of 4-5.9. Batch experiments covered a time period from 2 h to 100 days and were performed at initial potassium concentrations of 0, 0.5, and 5 mM to induce different levels of biotite exfoliation. All experiments were kept anoxic to investigate solely the dissolution step without the influence of oxidation and precipitation of secondary Fe oxyhydroxides. Oxalic acid increased the release of Fe by a factor of ∼15 compared with the HCl experiments. Addition of 0.5 mM K to initial solutions in proton-promoted dissolution decreased the release of Fe by 30-65% depending on the dissolution stage. In ligand-controlled dissolution, K reduced the Fe release only to a minor extent. All solutions of the early dissolution stages were enriched in light Fe isotopes by up to −1.4‰ in δ⁵⁶Fe compared with the isotopic composition of biotite and chlorite mineral separates, which we explained by a kinetic isotope effect. In proton-promoted dissolution, early released fractions of K-enriched experiments were significantly lighter (−0.7‰ to −0.9‰) than in the initially K-free experiments. The evolution of Fe isotope ratios in solution was modeled by a linear combination of kinetic isotope effects during two independent dissolution processes attacking different crystallographic sites. In ligand-controlled dissolution, K did not influence the kinetic isotope effect and the Fe isotope composition in solution in the late dissolution stages remained slightly lighter than the bulk composition of the biotite/chlorite enriched mineral fraction. This study demonstrates that the initial Fe weathering flux should be enriched in light Fe isotopes and that Fe isotope data in combination with dissolution kinetics and stoichiometry provide new insights into dissolution mechanisms.     

Effect of citrate on the local Fe coordination in ferrihydrite, arsenate binding, and ternary arsenate complex formation

In oxic environments contaminated with arsenate (As(V)), small polyhydroxycarboxylates such as citrate may impact the structure of precipitating ferrihydrite (Fh) and thus the surface speciation of As(V). In this study, ‘2-line’ Fh was precipitated from ferric nitrate solutions that were neutralized to pH 6.5 in the presence of increasing citrate concentrations and in the absence or presence of As(V). The initial citrate/Fe and As/Fe ratios were 0-50 mol% and 5 mol%, respectively. The reaction products, enriched with up to 0.32 mol citrate per mole Fe, were characterized by X-ray diffraction, transmission electron microscopy, and Fe and As K-edge X-ray absorption spectroscopy. Citrate decreased the particle size of Fh by impairing the polymerization of Fe(O,OH)₆ octahedra via edge and corner linkages. In the presence of citrate and As(V), coordination numbers of Fe decreased by up to 28% relative to pure Fh. Citrate significantly reduced the static disorder of Fe-O bonds, implying a decreased octahedral distortion in Fh. Mean bond distances in Fh were not affected by citrate and remained constant within error at 1.98 Å for Fe-O, 3.03 Å for Fe-Fe1, and 3.45 Å for Fe-Fe2. Likewise, citrate had no effect on the As-Fe (3.31 Å) bond distance in As(V) coprecipitated with Fh. The As K-edge EXAFS data comply with the formation of (i) only monodentate binuclear (²C) As(V) surface complexes and (ii) combinations of ²C, monodentate mononuclear (¹V), and outersphere As(V) surface complexes. Our results suggest that increasing citrate concentrations led to a decreasing ¹V/²C ratio and/or that citrate increasingly impaired the formation of outersphere As(V) complexes. Moreover, citrate stabilized colloidal suspensions of Fh (pH 4.3-6.6, I ∼0.45 M) and reduced Fh formation at the expense of soluble Fe(III)-citrate complexes. At initial citrate/Fe ratios ?25 mol%, between 8% and 41% of total Fe was bound in Fe(III)-citrate complexes after Fh formation. Polynuclear Fe(III)-citrate species were found to bind As(V) via surface complexes indistinguishable by EXAFS from those of As(V) adsorbed to or coprecipitated with Fh. Our study implies that low molecular weight polyhydroxycarboxylates may enhance the mobility of As(V) in aqueous systems of high ionic strength (e.g., neutralizing acid mine drainage) by colloidal stabilization of suspended Fh particles and the formation of ternary As(V) complexes.     

Ultrasonic velocities of North Sea chalk samples: influence of porosity, fluid content and texture

We have studied 56 unfractured chalk samples of the Upper Cretaceous Tor Formation of the Dan, South Arne and Gorm Fields, Danish North Sea. The samples have porosities of between 14% and 45% and calcite content of over 95%. The ultrasonic compressional‐ and shear‐wave velocities (V_P and V_S) for dry and water‐saturated samples were measured at up to 75 bar confining hydrostatic pressure corresponding to effective stress in the reservoir. The porosity is the main control of the ultrasonic velocities and therefore of the elastic moduli. The elastic moduli are slightly higher for samples from the South Arne Field than from the Dan Field for identical porosities. This difference may be due to textural differences between the chalk at the two locations because we observe that large grains (i.e. filled microfossils and fossil fragments) that occur more frequently in samples from the Dan Field have a porosity‐reducing effect and that samples rich in large grains have a relatively low porosity for a given P‐wave modulus. The clay content in the samples is low and is mainly represented by either kaolinite or smectite; samples with smectite have a lower P‐wave modulus than samples with kaolinite at equal porosity. We find that ultrasonic V_P and V_S of dry chalk samples can be satisfactorily estimated with Gassmann's relationships from data for water‐saturated samples. A pronounced difference between the V_P/V_S ratios for dry and water‐saturated chalk samples indicates promising results for seismic amplitude‐versus‐offset analyses.     

Rutile chemistry and thermometry as provenance indicator: An example from Chios Island,Greece

In the present study we focused on detrital rutile separated from 12 psammitic samples that belong to three different sedimentary successions (Carboniferous, Permo-Carboniferous, Permo-Triassic) occurring on Chios Island, Greece. The Ti, Cr, Al, Fe, Nb, Zr, Si, and V contents of the rutiles were obtained by electron-microprobe analyses to trace their provenance.The Cr and Nb concentrations of the analysed rutile grains show a wide range and indicate that this mineral in the Carboniferous succession is mainly derived from metamafic rocks, whereas in the Permo-Carboniferous and Permo-Triassic successions stem from a metapelitic source. The calculated formation temperatures using the Zr-in-rutile thermometer range from ca. 520 to 850 °C with “hotter” rutile being encountered in the Permo-Carboniferous and Permo-Triassic successions. This feature together with the rutile chemistry indicate a change in source-rock lithology through time, which could either reflect an increasing depth of erosion of an exhumed ‘Variscan’ nappe pile of heterogeneous composition in the hinterland or a change in the style of accretion and erosion of different terranes at the southern margin of Laurussia during the subduction of a branch of the Palaeotethys Ocean in the Late Palaeozoic. In general, this study underscores the importance of rutile chemistry and thermometry in quantitative single-mineral provenance analysis and in chemostratigraphic analysis of clastic sedimentary rocks.