Denudation rates of small transient catchments controlled by former glaciation: The Hörnli nunatak in the northeastern Swiss Alpine Foreland

Extensive glaciers repeatedly occupied the northern Alpine Foreland during the Pleistocene and left a strongly glacially overprinted low slope landscape. Only few islands appeared as nunataks standing above the surface of the large piedmont glacier lobes. These nunatak areas kept their original shape, manifested in steep catchments with mean slopes up to 33 . Even though not glaciated, these catchments where significantly affected by base-level changes occurring as a consequence of phases of glacier advances and retreats. Both domains, the glacially eroded and non-eroded, are therefore prone to different mechanisms and time-scales of fluvial and colluvial re-adjustment. In this study we investigate these effects by exploring the spatial distribution and magnitude of denudation in the Hörnli region of the eastern Swiss Alpine Foreland in the present Interglacial. The area represents both domains in a relatively small area with largely uniform tectonic, lithologic and climatic conditions. The differences in Holocene andscape evolution are investigated using topographic analyses and catchment-averaged denudation rates derived from 10Be concentrations in fluvial quartz sand. We find that in formerly non-glaciated, fluvially dominated catchments close hillslope-channel coupling prevails and that these catchments yield high average denudation rates of 350 mm/ka. Glacially overprinted catchments yielded catchment-wide denudation rates an order of magnitude lower. These low denudation rates are hypothesized to be the consequence of both (i) a dominance of slow hillslope processes and (ii) admixture of high concentration, pre-LGM glacial sediment. This suggests that a) a careful field investigation must accompany the denudation rate studies and b) that the concept of area-weighted cosmogenic nuclide denudation rates must be considered in light of the predominant catchment processes.

In situ dehydration behavior of zeolite-like pentagonite: A single-crystal X-ray study

The structural modifications upon heating of pentagonite, Ca(VO)(Si4O10)·4H2O (space group Ccm21, a=10.3708(2), b=14.0643(2), c=8.97810(10) Å, V=1309.53(3) Å3) were investigated by in situ temperature dependent single-crystal X-ray structure refinements. Diffraction data of a sample from Poona district (India) have been measured in steps of 25 up to 250 °C and in steps of 50 °C between 250 and 400 °C. Pentagonite has a porous framework structure made up by layers of silicate tetrahedra connected by V4+O5 square pyramids. Ca and H2O molecules are extraframework occupants. Room temperature diffraction data allowed refinement of H positions. The hydrogen-bond system links the extraframework occupants to the silicate layers and also interconnects the H2O molecules located inside the channels. Ca is seven-fold coordinated forming four bonds to O of the tetrahedral framework and three bonds to extraframework H2O. The H2O molecule at O9 showing a high displacement parameter is not bonded to Ca. The dehydration in pentagonite proceeds in three steps. At 100 °C the H2O molecule at O8 was released while O9 moved towards Ca. As a consequence the displacement parameter of H2O at O9 halved compared to that at room temperature. The unit-cell volume decreased to 1287.33(3) Å3 leading to a formula with 3H2O per formula unit (pfu). Ca remained seven-fold coordinated. At 175 °C Ca(VO)(Si4O10)·3H2O transformed into a new phase with 1H2O molecule pfu characterized by doubling of the c axis and the monoclinic space group Pn. Severe bending of specific TOT angles led to contraction of the porous three-dimensional framework. In addition, H2O at O9 was expelled while H2O at O7 approached a position in the center of the channel. The normalized volume decreased to 1069.44(9) Å3. The Ca coordination reduced from seven- to six-fold. At 225 °C a new anhydrous phase with space group Pna21 but without doubling of c had formed. Release of H2O at O7 caused additional contraction of TOT angles and volume reduction (V=1036.31(9) Å3). Ca adopted five-fold coordination. During heating excursion up to 400 °C this anhydrous phase remained preserved. Between room temperature and 225 °C the unit-cell volume decreased by 21% due to dehydration. The dehydration steps compare well with the thermo-gravimetric data reported in the literature.

High-temperature induced dehydration, phase transition and exsolution in amicite: A single-crystal X-ray study

Temperature dependent single-crystal X-ray data were collected on amicite K4Na4(Al8Si8O32)·11H2O from Kola Peninsula (Russia) in steps of 25 °C from room temperature to 175 °C and of 50 °C up to 425 °C. At room temperature amicite has space group I2 with a = 10.2112(1), b = 10.4154(1), c = 9.8802(1) Å, β = 88.458(1)°, V = 1050.416(18) Å3. Its crystal structure is based on a Si–Al ordered tetrahedral framework of the GIS type with two systems of eight-membered channels running along the a and c axes. Extraframework K and Na cations are ordered at two fully occupied sites. Above 75 °C amicite was found to partly dehydrate into two separate but coherently intergrown phases, both of space group I2/a, one K-rich ∼K8(Al8Si8O32) ·4H2O (at 75 °C: a = 10.038(2), b = 9.6805(19), c = 9.843(2) Å, β = 89.93(3)°, V = 956.5(3) Å3) and the other Na-rich ∼Na8(Al8Si8O32)·2H2O (at 75 °C: a = 9.759(2), b = 8.9078(18), c = 9.5270(19) Å, β = 89.98(3)°, V = 828.2(3) Å3). Upon further heating above 75 °C the Na- and K-phases lost remaining H2O with only minor influence on the framework structure and became anhydrous at 175 °C and 375 °C, respectively. The two anhydrous phases persisted up to 425 °C. Backscattered electron images of a heated crystal displayed lamellar intergrowth of the K- and Na-rich phases. Exposed to ambient humid conditions K- and Na-rich phases rehydrated and conjoined to the original one phase I2 structure.

In situ dehydration behavior of veszelyite (Cu,Zn)2Zn(PO4)(OH)3·2H2O: A single-crystal X-ray study

The rare mixed copper-zinc phosphate mineral veszelyite (Cu,Zn)2Zn(PO4)(OH)3·2H2O space group P21/c, a = 7.5096(2), b = 10.2281(2), c = 9.8258(2) Å, β = 103.3040(10)°, V = 734.45(3) Å3 was investigated by in situ temperature-dependent single-crystal X-ray structure refinements. The atomic arrangement of veszelyite consists of an alternation of octahedral and tetrahedral sheets. The Jahn-Teller distorted CuO6 octahedra form sheets with eight-membered rings. The tetrahedral sheet composed of PO4 and ZnO3(OH) tetrahedra shows strong topological similarities to that of cavansite, gismondine, and kipushite.Diffraction data of a sample from Zdravo Vrelo, near Kreševo (Bosnia and Herzegovina) have been measured in steps of 25 up to 225 °C. Hydrogen positions and the hydrogen-bond system were determined experimentally from the structure refinements of data collected up to 125 °C. At 200 °C, the hydrogen-bonding scheme was inferred from bond-valence calculations and donor-acceptor distances. The hydrogen-bond system connects the tetrahedral sheet to the octahedral sheet and also braces the Cu sheet.At 150 °C, the H2O molecule at H2O2 was released and the Cu coordination (Cu1 and Cu2) decreased from originally six- to fivefold. Cu1 has a square planar coordination by four OH groups and an elongate distance to O3, whereas Cu2 has the Jahn-Teller characteristic elongate bond to H2O1. The unit-cell volume decreased 7% from originally 734.45(3) to 686.4(4) Å3 leading to a formula with 1 H2O pfu. The new phase observed above 150 °C is characterized by an increase of the c axis and a shortening of the b axis. The bending of T-O-T angles causes an increasing elliptical shape of the eight-membered rings in the tetrahedral and octahedral sheets. Moreover a rearrangement of the hydrogen-bond system was observed.At 225 °C, the structure degrades to an X-ray amorphous residual due to release of the last H2O molecule at H2O1. The stronger Jahn-Teller distortion of Cu1 relative to Cu2 suggests that Cu1 is fully occupied by Cu, whereas Cu2 bears significant Zn. H2O1 is the fifth ligand of Cu2. Zn at Cu2 is not favorable to adopt planar fourfold coordination. Thus, if the last water molecule is expelled the structure is destabilized.This study contributes to understanding the dehydration mechanism and thermal stability of supergene minerals characterized by Jahn-Teller distorted octahedra with mixed Cu, Zn occupancy.

In situ dehydration behavior of zeolite-like cavansite: A single-crystal X-ray study

To track dehydration behavior of cavansite, Ca(VO)(Si4O10)·4H2O space group Pnma, a = 9.6329(2), b = 13.6606(2), c = 9.7949(2) Å, V = 1288.92(4) Å3 single-crystal X-ray diffraction data on a crystal from Wagholi quarry, Poona district (India) were collected up to 400 °C in steps of 25 °C up to 250 °C and in steps of 50 °C between 250 and 400 °C. The structure of cavansite is characterized by layers of silicate tetrahedra connected by V4+O5 square pyramids. This way a porous framework structure is formed with Ca and H2O as extraframework occupants. At room temperature, the hydrogen bond system was analyzed. Ca is eightfold coordinated by four bonds to O of the framework structure and four bonds to H2O molecules. H2O linked to Ca is hydrogen bonded to the framework and also to adjacent H2O molecules. The dehydration in cavansite proceeds in four steps.At 75 °C, H2O at O9 was completely expelled leading to 3 H2O pfu with only minor impact on framework distortion and contraction V = 1282.73(3) Å3. The Ca coordination declined from originally eightfold to sevenfold and H2O at O7 displayed positional disorder.At 175 °C, the split O7 sites approached the former O9 position. In addition, the sum of the three split positions O7, O7a, and O7b decreased to 50% occupancy yielding 2 H2O pfu accompanied by a strong decrease in volume V = 1206.89(8) Å3. The Ca coordination was further reduced from sevenfold to sixfold.At 350 °C, H2O at O8 was released leading to a formula with 1 H2O pfu causing additional structural contraction (V = 1156(11) Å3). At this temperature, Ca adopted fivefold coordination and O7 rearranged to disordered positions closer to the original O9 H2O site.At 400 °C, cavansite lost crystallinity but the VO2+ characteristic blue color was preserved. Stepwise removal of water is discussed on the basis of literature data reporting differential thermal analyses, differential thermo-gravimetry experiments and temperature dependent IR spectra in the range of OH stretching vibrations.

Orbital changes, variation in solar activity and increased anthropogenic activities: controls on the Holocene flood frequency in the Lake Ledro area, Northern Italy

Adding to the on-going debate regarding vegetation recolonisation (more particularly the timing) in Europe and climate change since the Lateglacial, this study investigates a long sediment core (LL081) from Lake Ledro (652ma.s.l., southern Alps, Italy). Environmental changes were reconstructed using multiproxy analysis (pollen-based vegetation and climate reconstruction, lake levels, magnetic susceptibility and X-ray fluorescence (XRF) measurements) recorded climate and land-use changes during the Lateglacial and early-middle Holocene. The well-dated and high-resolution pollen record of Lake Ledro is compared with vegetation records from the southern and northern Alps to trace the history of tree species distribution. An altitudedependent progressive time delay of the first continuous occurrence of Abies (fir) and of the Larix (larch) development has been observed since the Lateglacial in the southern Alps. This pattern suggests that the mid-altitude Lake Ledro area was not a refuge and that trees originated from lowlands or hilly areas (e.g. Euganean Hills) in northern Italy. Preboreal oscillations (ca. 11 000 cal BP), Boreal oscillations (ca. 10 200, 9300 cal BP) and the 8.2 kyr cold event suggest a centennial-scale climate forcing in the studied area. Picea (spruce) expansion occurred preferentially around 10 200 and 8200 cal BP in the south-eastern Alps, and therefore reflects the long-lasting cumulative effects of successive boreal and the 8.2 kyr cold event. The extension of Abies is contemporaneous with the 8.2 kyr event, but its development in the southern Alps benefits from the wettest interval 8200-7300 cal BP evidenced in high lake levels, flood activity and pollen-based climate reconstructions. Since ca. 7500 cal BP, a weak signal of pollen-based anthropogenic activities suggest weak human impact. The period between ca. 5700 and ca. 4100 cal BP is considered as a transition period to colder and wetter conditions (particularly during summers) that favoured a dense beech (Fagus) forest development which in return caused a distinctive yew (Taxus) decline.We conclude that climate was the dominant factor controlling vegetation changes and erosion processes during the early and middle Holocene (up to ca. 4100 cal BP).

Mass-movement and flood-induced deposits in Lake Ledro, southern Alps, Italy: implications for Holocene palaeohydrology and natural hazards

High-resolution seismic profiles and sediment cores from Lake Ledro combined with soil and riverbed samples from the lake's catchment area are used to assess the recurrence of natural hazards (earthquakes and flood events) in the southern Italian Alps during the Holocene. Two well-developed deltas and a flat central basin are identified on seismic profiles in Lake Ledro. Lake sediments have been finely laminated in the basin since 9000 cal. yr BP and frequently interrupted by two types of sedimentary events (SEs): light-coloured massive layers and dark-coloured graded beds. Optical analysis (quantitative organic petrography) of the organic matter present in soil, riverbed and lacustrine samples together with lake sediment bulk density and grain-size analysis illustrate that light-coloured layers consist of a mixture of lacustrine sediments and mainly contain algal particles similar to the ones observed in background sediments. Light-coloured layers thicker than 1.5 cm in the main basin of Lake Ledro are synchronous to numerous coeval mass-wasting deposits remoulding the slopes of the basin. They are interpreted as subaquatic mass-movements triggered by historical and pre-historical regional earthquakes dated to AD2005, AD1891, AD1045 and 1260, 2545, 2595, 3350, 3815, 4740, 7190, 9185 and 11 495 cal. yr BP. Darkcoloured SEs develop high-amplitude reflections in front of the deltas and in the deep central basin. These beds are mainly made of terrestrial organic matter (soils and lignocellulosic debris) and are interpreted as resulting from intense hyperpycnal flood event. Mapping and quantifying the amount of soil material accumulated in the Holocene hyperpycnal flood deposits of the sequence allow estimating that the equivalent soil thickness eroded over the catchment area reached up to 5mm during the largest Holocene flood events. Such significant soil erosion is interpreted as resulting from the combination of heavy rainfall and snowmelt. The recurrence of flash flood events during the Holocene was, however, not high enough to affect pedogenesis processes and highlight several wet regional periods during the Holocene. The Holocene period is divided into four phases of environmental evolution. Over the first half of the Holocene, a progressive stabilization of the soils present through the catchment of Lake Ledro was associated with a progressive reforestation of the area and only interrupted during the wet 8.2 event when the soil destabilization was particularly important. Lower soil erosion was recorded during the mid-Holocene climatic optimum (8000-4200 cal. yr BP) and associated with higher algal production. Between 4200 and 3100 cal. yr BP, both wetter climate and human activities within the drainage basin drastically increased soil erosion rates. Finally, from 3100 cal. yr BP to the present-day, data suggest increasing and changing human land use.

Lake sediments as natural seismographs: A compiled record of Late Quaternary earthquakes in Central Switzerland and its implication for Alpine deformation

Central Switzerland lies tectonically in an intraplate area and recurrence rates of strong earthquakes exceed the time span covered by historic chronicles. However, many lakes are present in the area that act as natural seismographs: their continuous, datable and high-resolution sediment succession allows extension of the earthquake catalogue to pre-historic times. This study reviews and compiles available data sets and results from more than 10 years of lacustrine palaeoseismological research in lakes of northern and Central Switzerland. The concept of using lacustrine mass-movement event stratigraphy to identify palaeo-earthquakes is showcased by presenting new data and results from Lake Zurich. The Late Glacial to Holocene mass-movement units in this lake document a complex history of varying tectonic and environmental impacts. Results include sedimentary evidence of three major and three minor, simultaneously triggered basin-wide lateral slope failure events interpreted as the fingerprints of palaeoseismic activity. A refined earthquake catalogue, which includes results from previous lake studies, reveals a non-uniform temporal distribution of earthquakes in northern and Central Switzerland. A higher frequency of earthquakes in the Late Glacial and Late Holocene period documents two different phases of neotectonic activity; they are interpreted to be related to isostatic post-glacial rebound and relatively recent (re-)activation of seismogenic zones, respectively. Magnitudes and epicentre reconstructions for the largest identified earthquakes provide evidence for two possible earthquake sources: (i) a source area in the region of the Alpine or Sub-Alpine Front due to release of accumulated north-west/south-east compressional stress related to an active basal thrust beneath the Aar massif; and (ii) a source area beneath the Alpine foreland due to reactivation of deep-seated strike-slip faults. Such activity has been repeatedly observed instrumentally, for example, during the most recent magnitude 4.2 and 3.5 earthquakes of February 2012, near Zug. The combined lacustrine record from northern and Central Switzerland indicates that at least one of these potential sources has been capable of producing magnitude 6.2 to 6.7 events in the past.

A 2000 year long seasonal record of floods in the southern European Alps

Knowledge of past natural flood variability and controlling climate factors is of high value since it can be useful to refine projections of the future flood behavior under climate warming. In this context, we present a seasonally resolved 2000 year long flood frequency and intensity reconstruction from the southern Alpine slope (North Italy) using annually laminated (varved) lake sediments. Floods occurred predominantly during summer and autumn, whereas winter and spring events were rare. The all-season flood frequency and, particularly, the occurrence of summer events increased during solar minima, suggesting solar-induced circulation changes resembling negative conditions of the North Atlantic Oscillation as controlling atmospheric mechanism. Furthermore, the most extreme autumn events occurred during a period of warm Mediterranean sea surface temperature. Interpreting these results in regard to present climate change, our data set proposes for a warming scenario, a decrease in summer floods, but an increase in the intensity of autumn floods at the South-Alpine slope.

A TEX 86 lake record suggests simultaneous shifts in temperature in Central Europe and Greenland during the last deglaciation

High-resolution quantitative temperature records from continents covering glacial to interglacial transitions are scarce but important for understanding the climate system. We present the first decadal resolution record of continental temperatures in Central Europe during the last deglaciation (similar to 14,60010,600cal. yrB.P.) based on the organic geochemical palaeothermometer TEX86. The TEX86-inferred temperature record from Lake Lucerne (Vierwaldstattersee, Switzerland) reveals typical oscillations during the Late Glacial Interstadial, followed by an abrupt cooling of 2 degrees C at the onset of Younger Dryas and a rapid warming of 4 degrees C at the onset of the Holocene, within less than 350years. The remarkable resemblance with the Greenland and regional stable oxygen isotope records suggests that temperature changes in continental Europe were dominated by large-scale reorganizations in the northern hemispheric climate system.

Holocene flood frequency across the Central Alps – solar forcing and evidence for variations in North Atlantic atmospheric circulation

The frequency of large-scale heavy precipitation events in the European Alps is expected to undergo substantial changes with current climate change. Hence, knowledge about the past natural variability of floods caused by heavy precipitation constitutes important input for climate projections. We present a comprehensive Holocene (10,000 years) reconstruction of the flood frequency in the Central European Alps combining 15 lacustrine sediment records. These records provide an extensive catalog of flood deposits, which were generated by flood-induced underflows delivering terrestrial material to the lake floors. The multi-archive approach allows suppressing local weather patterns, such as thunderstorms, from the obtained climate signal. We reconstructed mainly late spring to fall events since ice cover and precipitation in form of snow in winter at high-altitude study sites do inhibit the generation of flood layers. We found that flood frequency was higher during cool periods, coinciding with lows in solar activity. In addition, flood occurrence shows periodicities that are also observed in reconstructions of solar activity from C-14 and Be-10 records (2500-3000, 900-1200, as well as of about 710, 500, 350, 208 (Suess cycle), 150, 104 and 87 (Gleissberg cycle) years). As atmospheric mechanism, we propose an expansion/shrinking of the Hadley cell with increasing/decreasing air temperature, causing dry/wet conditions in Central Europe during phases of high/low solar activity. Furthermore, differences between the flood patterns from the Northern Alps and the Southern Alps indicate changes in North Atlantic circulation. Enhanced flood occurrence in the South compared to the North suggests a pronounced southward position of the Westerlies and/or blocking over the northern North Atlantic, hence resembling a negative NAO state (most distinct from 4.2 to 2.4 kyr BP and during the Little Ice Age). South-Alpine flood activity therefore provides a qualitative record of variations in a paleo-NAO pattern during the Holocene. Additionally, increased South Alpine flood activity contrasts to low precipitation in tropical Central America (Cariaco Basin) on the Holocene and centennial time scale. This observation is consistent with a Holocene southward migration of the Atlantic circulation system, and hence of the ITCZ, driven by decreasing summer insolation in the Northern hemisphere, as well as with shorter-term fluctuations probably driven by solar activity. (C) 2013 Elsevier Ltd. All rights reserved.

Frequent floods in the European Alps coincide with cooler periods of the past 2500 years

Severe floods triggered by intense precipitation are among the most destructive natural hazards in Alpine environments, frequently causing large financial and societal damage. Potential enhanced flood occurrence due to global climate change would thus increase threat to settlements, infrastructure, and human lives in the affected regions. Yet, projections of intense precipitation exhibit major uncertainties and robust reconstructions of Alpine floods are limited to the instrumental and historical period. Here we present a 2500-year long flood reconstruction for the European Alps, based on dated sedimentary flood deposits from ten lakes in Switzerland. We show that periods with high flood frequency coincide with cool summer temperatures. This wet-cold synchronism suggests enhanced flood occurrence to be triggered by latitudinal shifts of Atlantic and Mediterranean storm tracks. This paleoclimatic perspective reveals natural analogues for varying climate conditions, and thus can contribute to a better understanding and improved projections of weather extremes under climate change.

Temporal and Spatial Coexistence of Archaeal and Bacterial amoA Genes and Gene Transcripts in Lake Lucerne

Despite their crucial role in the nitrogen cycle, freshwater ecosystems are relatively rarely studied for active ammonia oxidizers (AO). This study of Lake Lucerne determined the abundance of both amoA genes and gene transcripts of ammonia-oxidizing archaea (AOA) and bacteria (AOB) over a period of 16 months, shedding more light on the role of both AO in a deep, alpine lake environment. At the surface, at 42 m water depth, and in the water layer immediately above the sediment, AOA generally outnumbered AOB. However, in the surface water during summer stratification, when both AO were low in abundance, AOB were more numerous than AOA. Temporal distribution patterns of AOA and AOB were comparable. Higher abundances of amoA gene transcripts were observed at the onset and end of summer stratification. In summer, archaeal amoA genes and transcripts correlated negatively with temperature and conductivity. Concentrations of ammonium and oxygen did not vary enough to explain the amoA gene and transcript dynamics. The observed herbivorous zooplankton may have caused a hidden flux of mineralized ammonium and a change in abundance of genes and transcripts. At the surface, AO might have been repressed during summer stratification due to nutrient limitation caused by active phytoplankton.

Searching the Rhone delta channel in Lake Geneva since François‐Alphonse Forel

In the late 19th century, F.A. FOREL led investigations of the Rhone River delta area of Lake Geneva that resulted in the dis- covery of a textbook example of a river-fed delta system containing impressive subaquatic channels. Well ahead of the marine counterparts, scientific observations and interpretations of water currents shaping the delta edifice for the first time documented how underflow currents carry cold, suspension-laden waters from the river mouth all the way to the deep basin. These early investigations of the Rhone delta laid the basis for follow-up studies in the 20th and 21th centuries. Sediment coring, water-column measurements, manned submersible diving, seismic reflection profiling and bathymetric sur- veying eventually provided a rich database to unravel the key erosional and depositional processes, further documenting the impact of human-induced changes in the catchment. With the merging of old and new scientific knowledge, today a comprehensive understanding prevails of how a delta changes through time, how its channels are formed, and what potential natural hazards may be related to its evolution. New and efficient bathymetric techniques, paired with novel coring operations, provided a time-series of morphologic evolution showing and quantifying the high dynamics of the delta/channel evolution in an unprecedented temporal and spatial reso- lution. Future investigations will continue to further quantify these dynamic processes and to link the evolution of the subaquatic domain with changes and processes in the catchment and with natural hazards. Its size, easy access, and large variety of states and processes will continue to make the Rhone delta area a perfect ‘laboratory’ in which general processes can be studied that could be upscaled or downscaled to other marine and lacustrine deltas.