Alpine climate during the Holocene: a comparison between records of glaciers,lake sediments and solar activity

The European Alps are very sensitive and vulnerable to climate change. Recent improvements in Alpine glacier length records and climate reconstructions from annually laminated sediments of Alpine Lake Silvaplana give the opportunity to investigate the relationship between these two data sets of Alpine climate. Two different time frames are considered: the last 500–1000 years as well as the last 7400 years. First, we found good agreement between the two different climate archives during the past millennium: mass accumulation rates and biogenic silica concentration are largely in phase with the glacier length changes of Mer de Glace and Unterer Grindelwaldgletscher, and with the records of glacier length of Grosser Aletschgletscher and Gornergletscher. Secondly, the records are compared with temporally highly resolved data of solar activity. The Sun has had a major impact on the Alpine climate variations in the long term, i.e. several centuries to millennia. Solar activity varies with the Hallstatt periodicity of about 2000 years. Hallstatt minima are identified around 500, 2500 and 5000 a. Around these times grand solar minima (such as the Maunder Minimum) occurred in clusters coinciding with colder Alpine climate expressed by glacier advances. During the Hallstatt maxima around 0, 2000 and 4500 a, the Alpine glaciers generally retreated, indicating a warmer climate. This is supported by archaeological findings at Schnidejoch, a transalpine pass in Switzerland that was only accessible when glaciers had retreated. On shorter timescales, however, the influence of the Sun cannot be as easily detected in Alpine climate change, indicating that in addition to solar forcing, volcanic influence and internal climate variations have played an important role. Copyright © 2011 John Wiley & Sons, Ltd.     

The Stokes and Vening-Meinesz functionals in a moving tangent space

The regularized solution of the external sphericalStokes boundary value problem as being used for computations of geoid undulations and deflections of the vertical is based upon theGreen functions S ₁(₀, ₀, , ) ofBox 0.1 (R = R ₀) andV ₁(₀, ₀, , ) ofBox 0.2 (R = R ₀) which depend on theevaluation point {₀, ₀} S _R0 ² and thesampling point {, } S _R0 ² ofgravity anomalies (, ) with respect to a normal gravitational field of typegm/R (free air anomaly). If the evaluation point is taken as the meta-north pole of theStokes reference sphere S _R0 ² , theStokes function, and theVening-Meinesz function, respectively, takes the formS() ofBox 0.1, andV ₂() ofBox 0.2, respectively, as soon as we introduce {meta-longitude (azimuth), meta-colatitude (spherical distance)}, namely {A, } ofBox 0.5. In order to deriveStokes functions andVening-Meinesz functions as well as their integrals, theStokes andVening-Meinesz functionals, in aconvolutive form we map the sampling point {, } onto the tangent plane T₀S _R0 ² at {₀, ₀} by means ofoblique map projections of type(i) equidistant (Riemann polar/normal coordinates),(ii) conformal and(iii) equiareal.Box 2.1.–2.4. andBox 3.1.– 3.4. are collections of the rigorously transformedconvolutive Stokes functions andStokes integrals andconvolutive Vening-Meinesz functions andVening-Meinesz integrals. The graphs of the correspondingStokes functions S ₂(),S ₃(r),,S ₆(r) as well as the correspondingStokes-Helmert functions H ₂(),H ₃(r),,H ₆(r) are given byFigure 4.1–4.5. In contrast, the graphs ofFigure 4.6–4.10 illustrate the correspondingVening-Meinesz functions V ₂(),V ₃(r),,V ₆(r) as well as the correspondingVening-Meinesz-Helmert functions Q ₂(),Q ₃(r),,Q ₆(r). The difference between theStokes functions / Vening-Meinesz functions andtheir first term (only used in the Flat Fourier Transforms of type FAST and FASZ), namelyS ₂() – (sin /2)^–1,S ₃(r) – (sinr/2R ₀)^–1,,S ₆(r) – 2R ₀/r andV ₂() + (cos /2)/2(sin² /2),V ₃(r) + (cosr/2R ₀)/2(sin² r/2R ₀),, illustrate the systematic errors in theflat Stokes function 2/ or flatVening-Meinesz function –2/². The newly derivedStokes functions S ₃(r),,S ₆(r) ofBox 2.1–2.3, ofStokes integrals ofBox 2.4, as well asVening-Meinesz functionsV ₃(r),,V ₆(r) ofBox 3.1–3.3, ofVening-Meinesz integrals ofBox 3.4 — all of convolutive type — pave the way for the rigorousFast Fourier Transform and the rigorousWavelet Transform of theStokes integral / theVening-Meinesz integral of type equidistant, conformal and equiareal.     

Heavy metals in Changjiang estuarine and offshore sediments: responding to human activities

The Changjiang (Yangtze) estuarine and offshore sediments were analyzed for total heavy metals concentrations and chemical fractions.Distributions of heavy metals show typical banded diffusion pattern,with high concentrations near the river mouth and following a decreasing trend in the offshore direction.According to chemical fractions,Fe/Mn oxide fraction is the major non-residual fraction in the Changjiang estuarine and offshore sediments.Higher percentage of non-residual fraction of Pb implies that,the industrial contaminations transported via the atmosphere and river input,may affect the non-residual fraction of heavy metals.Over past fifteen years,the concentration of Pb normalizing to Al presents significant increasing trend,corresponding to the effect of human activities.By comparison of heavy metals fractions in 2003 to 2006,it has been realized that increasing water and sediment may cause a higher percentage non-residual fraction of Cu in the southern part of offshore muddy sediments.     

Speeding Up the Analytical Workflow for Coltan Fingerprinting by an Integrated Mineral Liberation Analysis/LA‐ICP‐MS Approach

Coltan (the African trade name for columbite‐tantalite, a tantalum ore) is one of several raw materials that finance the civil wars in the eastern provinces of the Democratic Republic of the Congo. To improve the transparency along the tantalum trade chain, a ‘certificate of origin’ for so‐called ‘conflict minerals’ has been recommended by the United Nations. Accordingly, the German Federal Institute for Geosciences and Natural Resources (BGR) has developed an analytical fingerprint procedure for coltan. Mineral formation age, modal mineralogy and chemical composition are important fingerprint parameters. The original workflow to obtain these parameters was streamlined and is now based on mineral liberation analysis and LA‐ICP‐MS. The use of an ICP‐MS instrument with a detector system covering an extended linear dynamic range and the application of an internal standard‐independent calibration strategy allowed data for major and trace element determination and mineral formation age estimates to be obtained simultaneously. The analytical results of this new approach were compared with analytical techniques of the original workflow and showed excellent agreement in terms of mineralogical and chemical characterisation and mineral formation age of coltan samples. Within a test, samples of different origin were allocated correctly and simple, binary mixtures were also identified successfully.     

Micro-scale tracing of Fe and Si isotope signatures in banded iron formation using femtosecond laser ablation

We have detected micrometre-scale differences in Fe and Si stable isotope ratios between coexisting minerals and between layers of banded iron formation (BIF) using an UV femtosecond laser ablation system connected to a MC-ICP-MS. In the magnetite–carbonate–chert BIF from the Archean Old Wanderer Formation in the Shurugwi Greenstone Belt (Zimbabwe), magnetite shows neither intra- nor inter-layer trends giving overall uniform δ⁵⁶Fe values of 0.9‰, but exhibits intra-crystal zonation. Bulk iron carbonates are also relatively uniform at near-zero values, however, their individual δ⁵⁶Fe value is highly composition-dependent: both siderite and ankerite and mixtures between both are present, and δ⁵⁶Fe end member values are 0.4‰ for siderite and −0.7‰ for ankerite. The data suggest either an early diagenetic origin of magnetite and iron carbonates by the reaction of organic matter with ferric oxyhydroxides catalysed by Fe(III)-reducing bacteria; or more likely an abiotic reaction of organic carbon and Fe(III) during low-grade metamorphism. Si isotope composition of the Old Wanderer BIF also shows significant variations with δ³⁰Si values that range between −1.0‰ and −2.6‰ for bulk layers. These isotope compositions suggest rapid precipitation of the silicate phases from hydrothermal-rich waters. Interestingly, Fe and Si isotope compositions of bulk layers are covariant and are interpreted as largely primary signatures. Moreover, the changes of Fe and Si isotope signatures between bulk layers directly reflect the upwelling dynamics of hydrothermal-rich water which govern the rates of Fe and Si precipitation and therefore also the development of layering. During periods of low hydrothermal activity, precipitation of only small amounts of ferric oxyhydroxide was followed by complete reduction with organic carbon during diagenesis resulting in carbonate–chert layers. During periods of intensive hydrothermal activity, precipitation rates of ferric oxyhydroxide were high, and subsequent diagenesis triggered only partial reduction, forming magnetite–carbonate–chert layers. We are confident that our micro-analytical technique is able to detect both the solute flux history into the sedimentary BIF precursor, and the BIF’s diagenetic history from the comparison between coexisting minerals and their predicted fractionation factors.     

Devonian–Carboniferous slivers within the basement area of north-east Oscar II Land, Spitsbergen

Formed during an early compressional period in the opening of North Atlantic Ocean, a Tertiary fold-thrust belt extends along the mid-to- southern part of the western coast of Spitsbergen. Complex thrust structures involve the basement (Caledonian and older) and many shallow dipping thrust faults dissect the overlying cover rocks (Devonian and younger) in Oscar II Land in the northern part of the belt. Some of these faults occur within the basement rocks with slivers or fault blocks of the cover rocks from south-western Brøggerhalvøya to innermost St. Jonsfjorden in north-eastern Oscar II Land. Six of the slivers contain Carboniferous rocks and one is a fault-bounded block with Devonian rocks. These steeply west-dipping faults form a complex fault system- EOFC (Engelskbukta-Osbornbreen Fault Complex) - within the basement area. The lithological units of the basement are separated by faults within the EOFC, which is structurally continuous with the Brøggerhalvøya fold-thrust zone to the north and is thought to continue to the fold-thrust zone on the south-eastern coast of St. Jonsfjorden. Some previous authors considered that the two lithologically contrasting Vendian diamictites and intervening Moefjellet Formation are stratigraphically continuous and defined two separate tilloid successions in the present area. This interpretation has been extended over the whole of western Spitsbergen. However, the present study indicates that these two tilloid formations and the Moefjellet Formation are separated by the faults, probably thrusts, within the EOFC and are not in a continuous stratigraphic relation. Therefore, the two-stage history of Vendian glaciation seems questionable.     

The experimental calibration of the iron isotope fractionation factor between pyrrhotite and peralkaline rhyolitic melt

A first experimental study was conducted to determine the equilibrium iron isotope fractionation between pyrrhotite and silicate melt at magmatic conditions. Experiments were performed in an internally heated gas pressure vessel at 500 MPa and temperatures between 840 and 1000 °C for 120-168 h. Three different types of experiments were conducted and after phase separation the iron isotope composition of the run products was measured by MC-ICP-MS. (i) Kinetic experiments using ⁵⁷Fe-enriched glass and natural pyrrhotite revealed that a close approach to equilibrium is attained already after 48 h. (ii) Isotope exchange experiments—using mixtures of hydrous peralkaline rhyolitic glass powder (∼4 wt% H₂O) and natural pyrrhotites (Fe_1 − xS) as starting materials— and (iii) crystallisation experiments, in which pyrrhotite was formed by reaction between elemental sulphur and rhyolitic melt, consistently showed that pyrrhotite preferentially incorporates light iron. No temperature dependence of the fractionation factor was found between 840 and 1000 °C, within experimental and analytical precision. An average fractionation factor of Δ ⁵⁶Fe/⁵⁴Fe_{pyrrhotite-melt} = −0. 35 ± 0.04‰ (2SE, n = 13) was determined for this temperature range. Predictions of Fe isotope fractionation between FeS and ferric iron-dominated silicate minerals are consistent with our experimental results, indicating that the marked contrast in both ligand and redox state of iron control the isotope fractionation between pyrrhotite and silicate melt. Consequently, the fractionation factor determined in this study is representative for the specific Fe²⁺/ΣFe ratio of our peralkaline rhyolitic melt of 0.38 ± 0.02. At higher Fe²⁺/ΣFe ratios a smaller fractionation factor is expected. Further investigation on Fe isotope fractionation between other mineral phases and silicate melts is needed, but the presented experimental results already suggest that even at high temperatures resolvable variations in the Fe isotope composition can be generated by equilibrium isotope fractionation in natural magmatic systems.     

Cosmogenic <Superscript>10</Superscript>Be-derived denudation rates of the Eastern and Southern European Alps

Denudation rates from cosmogenic ¹⁰Be measured in quartz from recent river sediment have previously been used in the Central Alps to argue that rock uplift occurs through isostatic response to erosion in the absence of ongoing convergence. We present new basin-averaged denudation rates from large rivers in the Eastern and Southern European Alps together with a detailed topographic analysis in order to infer the forces driving erosion. Denudation rates in the Eastern and Southern Alps of 170–1,400 mm ky⁻¹ are within a similar range to those in the Central Alps for similar lithologies. However, these denudation rates vary considerably with lithology, and their variability generally increases with steeper landscapes, where correlations with topographic metrics also become poorer. Tertiary igneous rocks are associated with steep hillslopes and channels and low denudation rates, whereas pre-Alpine gneisses usually exhibit steep hillslopes and higher denudation rates. Molasse, flysch, and schists display lower mean basin slopes and channel gradients, and, despite their high erodibility, low erosion rates. Exceptionally low denudation rates are also measured in Permian rhyolite, which has high mean basin slopes. We invoke geomorphic inheritance as a major factor controlling erosion, such that large erosive glaciers in the late Quaternary cold periods were more effective in priming landscapes in the Central Alps for erosion than in the interior Eastern Alps. However, the difference in tectonic evolution of the Eastern and Central Alps potentially adds to differences in their geomorphic response; their deep structures differ significantly and, unlike the Central Alps, the Eastern Alps are affected by ongoing tectonic influx due to the slow motion and rotation of Adria. The result is a complex pattern of high mountain erosion in the Eastern Alps, which has evolved from one confined to the narrow belt of the Tauern Window in late Tertiary time to one affecting the entire underthrust basement, orogenic lid, and parts of the Southern Alps today.     

Petroleum degradation and associated microbial signatures at the Chapopote asphalt volcano, Southern Gulf of Mexico

At the Chapopote Knoll in the Southern Gulf of Mexico, deposits of asphalt provide the substrate for a prolific cold seep ecosystem extensively colonized by chemosynthetic communities. This study investigates microbial life and associated biological processes within the asphalts and surrounding oil-impregnated sediments by analysis of intact polar membrane lipids (IPLs), petroleum hydrocarbons and stable carbon isotopic compositions (δ¹³C) of hydrocarbon gases. Asphalt samples are lightly to heavily biodegraded suggesting that petroleum-derived hydrocarbons serve as substrates for the chemosynthetic communities. Accordingly, detection of bacterial diester and diether phospholipids in asphalt samples containing finely dispersed gas hydrate suggests the presence of hydrocarbon-degrading bacteria. Biological methanogenesis contributes a substantial fraction to the methane captured as hydrate in the shallow asphalt deposits evidenced by significant depletion in ¹³C relative to background thermogenic methane. In sediments, petroleum migrating from the subsurface stimulates both methanogenesis and methanotrophy at a sulfate-methane transition zone 6-7 m below the seafloor. In this zone, microbial IPLs are dominated by archaeal phosphohydroxyarchaeols and archaeal diglycosidic diethers and tetraethers. Bacterial IPLs dominate surface sediments that are impregnated by severely biodegraded oil. In the sulfate-reduction zone, diagnostic IPLs indicate that sulfate-reducing bacteria (SRB) play an important role in petroleum degradation. A diverse mixture of phosphohydroxyarchaeols and mixed phospho- and diglycosidic archaeal tetraethers in shallow oil-impregnated sediments point to the presence of anaerobic methane-oxidizing ANME-2 and ANME-1 archaea, respectively, or methanogens. Archaeal IPLs increase in relative abundance with increasing sediment depth and decreasing sulfate concentrations, accompanied by a shift of archaeol-based to tetraether-based archaeal IPLs. The latter shift is suggested to be indicative of a community shift from ANME-2 and/or methanogenic archaea in shallower sediments to ANME-1/methanogenic archaea and possibly benthic archaea in deeper sediments.