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.     

Deep‐sea channel evolution and stratigraphic architecture from inception to abandonment from high‐resolution Autonomous Underwater Vehicle surveys offshore central California

The Lucia Chica channel system is an avulsion belt with four adjacent channels that progressively avulsed to the north‐east from a single, upslope feeder channel. Avulsion occurred from underfilled channels, leaving open channels that were reactivated by flows stripped from younger, adjacent channels. Differences in relief (height from channel thalweg to levée crest), sinuosity and levée stratigraphy between adjacent channels correspond to relative channel age, and indicate a change in channel morphology and architecture with time. Potential triggers for the change over time include differences in gradient, flow behaviour and characteristics, and channel evolution. Gradient does not appear to be a major control on channel formation and avulsion because adjacent channels formed on the same gradient. Based on available ultra‐high‐resolution remote imaging obtained with an Autonomous Underwater Vehicle, differences in adjacent channel morphology are interpreted to be primarily a result of differences in channel maturity. The interpreted sequence of channel maturity involves erosional channel inception through scouring and incipient channels (defined by linear trains of scours) prior to development of continuous thalwegs. Channel narrowing, formation and growth of levées, increasing channel relief and development of sinuosity occurred as channels evolved. The evolutionary sequence interpreted from the high‐resolution Lucia Chica dataset provides a unique perspective on intrinsic controls of architecture for single channel elements. In addition to helping bridge the gap between outcrop and industry‐standard reflection‐seismic data resolutions and scopes, interpretations in this study also expose potential problems with hierarchical classifications in three‐dimensional imaging of distributary systems, and provide potentially important analogues for evolutionary morphologies not resolved in other deep‐water channel systems.     

A multi‐method field experiment to determine local groundwater flow in a glacier forefield

We implemented multiple independent field techniques to determine the direction and velocity of groundwater flow at a specific stream reach in a glacier forefield. Time‐lapse experiments were conducted using two electrical resistivity tomography (ERT) lines installed in a cross pattern. A circular array of groundwater tubes was also installed to monitor groundwater flow via discrete salt injections. Both inter‐borehole and ERT results confirmed this stream section as a losing reach and enabled quantification of the flow direction. Both techniques yielded advection velocities varying between 5.7 and 21.8 m/day. Estimates of groundwater flow direction and velocity indicated that groundwater infiltrates from the stream nearby and not from the adjacent lateral moraine. Groundwater age estimated from radon concentration measurements supported this hypothesis. Despite uncertainties inherent to each of the methods deployed, the combination of multiple field techniques allowed drawing consistent conclusions about local groundwater flow. We thus regard our multi‐method approach as a reliable way to characterize the two‐dimensional groundwater flow at sites where more invasive groundwater investigation techniques are difficult to carry out and local heterogeneities can make single measurements unreliable. Copyright © 2014 John Wiley & Sons, Ltd.     

Changes of cloud microphysical properties during the transition from supercooled to mixed-phase conditions during CIME

A ground-based seeding experiment using carbon dioxide and propane sprayed from pressurized bottles was carried out under supercooled cloud conditions on a small spatial and short time scale. Water vapor deposition on the artificially generated dry ice and propane ice germs as the main ice formation process (nucleation and growth) is consistent with the experimental results. After nucleation, diffusional growth of the ice particles, partly at the expense of evaporating small droplets, was identified during the mixing of the seeding line with the ambient supercooled cloud. Within the seeding plume, ice water contents up to 80% of the total condensed water are observed, although the size of the formed ice particles did not exceed 25 μm. From the changes of the ice and supercooled liquid phase with time under mixed-phase conditions, liquid water content (LWC) evaporation, ice water content (IWC) formation, and ice crystal growth rates are estimated, which are not affected by the artificial nucleation process. Thus, these rates are assessed to be applicable for a growing ice phase of small ice particles in a young mixed-phase cloud, where other growth mechanisms, like riming or aggregation, are negligible.     

Boninites as windows into trace element mobility in subduction zones

Boninites are subduction-related rocks originating from re-melting of highly depleted mantle sources left after extraction of tholeiitic melts. Due to their depleted nature, the incompatible trace element inventory of boninites is virtually entirely inherited from slab components without a significant contribution from the refractory mantle wedge. Thus, boninites constitute an excellent window into processes controlling trace element mobilization at the slab-mantle wedge interface. In order to constrain the behaviour of trace elements in subduction zones with a special emphasis on high field strength elements, we analyzed low-Ca boninites and associated tholeiitic basalts from Cape Vogel, Papua New Guinea (PNG) and compare them with compositions of high-Ca boninites and associated tholeiitic basalts from Cyprus. High-precision HFSE (Nb, Ta, Zr, Hf, W) concentration data of the boninites and associated tholeiitic basalts were obtained by isotope dilution. Major, trace element, and Sr-Nd-Hf-Pb isotope compositions clearly document a significant contribution of slab-derived melts involved in the petrogenesis of the PNG boninites, whereas only fluid-like subduction components were involved in the petrogenesis of the PNG basalts and the Cyprus suite. Low-Ca boninites from PNG are derived from a more refractory mantle source (∼21% depletion) than the high-Ca boninites from Cyprus (∼11% depletion) and their respective tholeiitic precursors (<10% depletion). In agreement with the more depleted nature of their mantle source, boninites exhibit a significantly stronger overprint by slab components. High-precision HFSE data indicate that, in comparison to LILE, a somewhat lower but measurable mobilization of all investigated HFSE in both slab-derived fluids and melts is evident. Modelling calculations demonstrate that the subduction components dominate the LILE budget and also largely control LREE and HFSE abundances in the boninite sources. Notably, the increasing influence of slab-derived fluids results in a decrease of the negative Nb-Ta anomaly, most likely reflecting a similar mobility of Nb-Ta and LREE at higher pressures near the critical point of fluid-melt miscibility. Ratios of Zr/Hf and Nb/Ta in the melt-like slab components dominating in the sources of the PNG boninites were probably fractionated in equilibrium with garnet-amphibolitic mafic oceanic crust. HFSE ratios in the Cyprus boninites are best explained by dehydration of subducted pelagic sediments in the absence of Ti-rich phases such as rutile. Our results also confirm previous assertions that the mobility of HFSE decreases in the order Sb > W-Mo > Nb-Ta > Zr-Hf. Furthermore, Mo-W systematics may provide a potential novel tracer for the amount, composition and redox state of subducted pelagic sediments that contribute to the geochemical budget of intra-oceanic arc systems.     

Earthquakes in Switzerland and surrounding regions during 2008

This report of the Swiss Seismological Service summarizes the seismic activity in Switzerland and surrounding regions during 2008. During this period, 451 earthquakes and 75 quarry blasts were detected and located in the region under consideration. The three strongest events occurred in the Valais, near Lac des Toules (M_L 3.6), and in Graubünden, near Ilanz (M_L 3.7) and Paspels (M_L 4.0). Although felt by the population, they were not reported to have caused any damage. However, with a total of only 15 events with M_L ≥ 2.5, the seismic activity in the year 2008 was far below the average over the previous 33 years.     

Vodyanitskii mud volcano,Sorokin trough,Black Sea: Geological characterization and quantification of gas bubble streams

Vodyanitskii mud volcano is located at a depth of about 2070 m in the Sorokin Trough, Black sea. It is a 500-m wide and 20-m high cone surrounded by a depression, which is typical of many mud volcanoes in the Black Sea. 75 kHz sidescan sonar show different generations of mud flows that include mud breccia, authigenic carbonates, and gas hydrates that were sampled by gravity coring. The fluids that flow through or erupt with the mud are enriched in chloride (up to ∼650 mmol L⁻¹ at ∼150-cm sediment depth) suggesting a deep source, which is similar to the fluids of the close-by Dvurechenskii mud volcano. Direct observation with the remotely operated vehicle Quest revealed gas bubbles emanating at two distinct sites at the crest of the mud volcano, which confirms earlier observations of bubble-induced hydroacoustic anomalies in echosounder records. The sediments at the main bubble emission site show a thermal anomaly with temperatures at ∼60 cm sediment depth that were 0.9 °C warmer than the bottom water. Chemical and isotopic analyses of the emanated gas revealed that it consisted primarily of methane (99.8%) and was of microbial origin (δD-CH₄ = −170.8‰ (SMOW), δ¹³C-CH₄ = −61.0‰ (V-PDB), δ¹³C-C₂H₆ = −44.0‰ (V-PDB)). The gas flux was estimated using the video observations of the ROV. Assuming that the flux is constant with time, about 0.9 ± 0.5 × 10⁶ mol of methane is released every year. This value is of the same order-of-magnitude as reported fluxes of dissolved methane released with pore water at other mud volcanoes. This suggests that bubble emanation is a significant pathway transporting methane from the sediments into the water column.     

Periglacial trimlines and nunataks of the Last Glacial Maximum: the Gap of Dunloe,southwest Ireland

During the last main phase of glaciation (26–13 ka) an ice‐cap developed in southwest Ireland and ice, from a dispersal centre in the vicinity of Kenmare, flowed north through the Gap of Dunloe in the Macgillycuddy's Reeks. On surrounding hillsides a weathering limit separates ice‐moulded bedrock, on low ground, from frost‐weathered terrain above. Assessment of bedrock dilation joint characteristics, Schmidt hammer R‐value data and clay‐sized mineral contents of basal soil samples, demonstrate significant contrasts in the degree of weathering above and below this limit. The weathering limit declines in altitude along former ice flow‐lines and is confluent with morainic deposits on the eastern side of the Gap. This supports the assertion that the high‐level weathering limit is a periglacial trimline that marks the former maximum upper limit of the body of ice which occupied the Gap of Dunloe during the Last Glacial Maximum (LGM). Reconstruction of the former ice‐surface profile from periglacial trimline limits on the eastern side of the Gap yields a mean estimate for basal shear stress of 106.5 kPa. This value suggests that the ice mass which occupied the Gap of Dunloe at the LGM was warm based and flowed on a bedrock substrate. Copyright © 2004 John Wiley & Sons, Ltd.     

The effects of tropical storm Dennis on coastal phytoplankton

The effects of tropical storm Dennis were documented in the coastal waters of South Carolina during August 1981. Phytoplankton photosynthesis vs. irradiance curves showed initial depression of the parameter a followed by three- to five-fold increase of both a and the asymptotic maximum rate of photosynthesis P_m^B. Productivity rates were depressed in most samples immediately after the storm. Surface samples at the inshore stations were around 50 mg C m^?3 h^?1 at saturating light intensities, while the offshore station rates were around 10 mg C m^?3 h^?1. After a 10-day lag these rates had increased to about 200 mg C m^?3 h^?1 inshore and 75 mg C m^?3 h^?1 offshore. These changes are thought to be primarily caused by changes in species composition. Some of the dominant diatom species changed and dinoflagellate species were introduced. No significant changes in nutrient concentrations were observed. Transient depressions of water temperature, salinity and light intensity may have contributed to the observed changes.