Physico-chemical and biological sediment properties determining erosion resistance of contaminated riverine sediments – Temporal and vertical pattern at the Lauffen reservoir/River Neckar, Germany

In order to contribute to a reliable, easy-to-handle and economically viable erosion risk assessment of contaminated riverine sites, the present study aims to implement master-variables best characterising the sediment stability. Thus, a wide range of sediment properties was related to the critical shear stress for mass erosion, determined in the SETEG (Stroemungskanal zur Ermittlung der tiefenabhaengigen Erosionsstabilitaet von Gewaessersedimenten) pressurised channel, with special emphasis on vertical and temporal gradients in the Lauffen reservoir on the River Neckar. Over the course of 1 year, positive impacts of some macrofauna species and benthic diatoms on the sediment stability were detected for the sediment surface (0.5 cm). However, a high seasonal variability of biological parameters caused varying relations with erosion resistance in the upper sediment layers as shown for the colloidal carbohydrates. Considering only deeper sediment layers (5–35 cm), a more general pattern could be revealed with correlations between the critical shear stress and single sediment properties such as depth, grain size, total organic carbon (TOC), cation exchange coefficient (CEC), carbohydrates and proteins. Firstly, the influence of physico-chemical and biological properties on erosion resistance became evident, even over depths at 0–35 cm. Secondly, inter-particle forces are most important for erosion resistance. These are enhanced in fine-grained sediment layers, offering high binding capacities but also strengthened by polymeric substances permeating the void space and coating particles. These covariance patterns of sedimentological and biological parameters are addressed by multivariate statistical tests (principal component analysis), resulting in a higher magnitude of the correlation coefficient between critical shear stress and the master-variables in main component II (polymeric substances, grain size, TOC, CEC; R=0.77) compared to single correlations.     

Thermodynamic properties and stability of AlF-bearing titanite CaTiOSiO4–CaAlFSiO4

Calorimetric and experimental data on AlF-bearing titanite are presented that yield thermodynamic properties of CaAlFSiO₄, as well as activity-composition relations of binary titanite CaTiOSiO₄-CaAlFSiO₄. The heat capacity of synthetic CaAlFSiO₄ was measured with differential scanning calorimetry between 170 and 850 K: C_P=689.96-0.38647T+2911300T^-2-8356.1T^-0.5+0.00016179T² Based on low-temperature heat capacity calculations with lattice vibrational theory (Debye model), the calorimetric entropy of CaAlFSiO₄ can be expected to lie between 104.7 and 118.1 J mol^-1 K^-1. The temperature of the P2₁/a to A2/a phase change was determined calorimetrically for a titanite with X_Al=0.09 (T_transition=390 K). The decrease of the transition temperature at a rate of about 11 K per mol% CaAlFSiO₄ is in good agreement with previous TEM investigations. The displacement of the reaction anorthite + fluorite = CaAlFSiO₄ in the presence of CaTiOSiO₄ was studied with high P-T experiments. Titanite behaves as a non-ideal, symmetrical solid-solution. The thermodynamic properties of CaAlFSiO₄ consistent with a multi-site mixing model are: % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavTnhis1MBaeXatLxBI9gBam % XvP5wqSXMqHnxAJn0BKvguHDwzZbqegm0B1jxALjhiov2Daebbnrfi % fHhDYfgasaacH8srps0lbbf9q8WrFfeuY-Hhbbf9v8qqaqFr0xc9pk % 0xbba9q8WqFfea0-yr0RYxir-Jbba9q8aq0-yq-He9q8qqQ8frFve9 % Fve9Ff0dmeaabaqaciaacaGaaeqabaWaaeaaeaaakeaafaqaaiWaca % aabaGaeeyrauKaeeOBa4MaeeiDaqNaeeiAaGMaeeyyaeMaeeiBaWMa % eeiCaaNaeeyEaKNaeeiiaaIaee4Ba8MaeeOzayMaeeiiaaIaeeOzay % Maee4Ba8MaeeOCaiNaeeyBa0MaeeyyaeMaeeiDaqNaeeyAaKMaee4B % a8MaeeOBa4MaeeiiaaIaeeikaGIaeeyzauMaeeiBaWMaeeyzauMaee % yBa0MaeeyzauMaeeOBa4MaeeiDaqNaee4CamNaeeykaKIaeeiiaaIa % emizaq2aaSbaaSqaaiabdAgaMbqabaGccqWGibasdaahaaWcbeqaai % abicdaWaaaaOqaaiabg2da9iabgkHiTiabikdaYiabiEda3iabisda % 0iabicdaWiabc6caUiabiIda4iabgglaXkabiodaZiabc6caUiabic % daWiabbccaGiabbUgaRjabbQeakjabb2gaTjabb+gaVjabbYgaSnaa % CaaaleqabaGaeyOeI0IaeGymaedaaaGcbaGaee4uamLaeeiDaqNaee % yyaeMaeeOBa4MaeeizaqMaeeyyaeMaeeOCaiNaeeizaqMaeeiiaaIa % ee4CamNaeeiDaqNaeeyyaeMaeeiDaqNaeeyzauMaeeiiaaIaeeyzau % MaeeOBa4MaeeiDaqNaeeOCaiNaee4Ba8MaeeiCaaNaeeyEaKNaeeii % aaIaee4uam1aaWbaaSqabeaacqqGWaamaaaakeaacqqG9aqpcqqGXa % qmcqqGWaamcqqG0aancqqGUaGlcqqG5aqocqGHXcqScqqGXaqmcqqG % UaGlcqqGXaqmcqqGGaaicqqGkbGscqqGTbqBcqqGVbWBcqqGSbaBda % ahaaWcbeqaaiabgkHiTiabigdaXaaakiabbUealnaaCaaaleqabaGa % eyOeI0IaeGymaedaaaGcbaGaeeyta0KaeeyyaeMaeeOCaiNaee4zaC % MaeeyDauNaeeiBaWMaeeyzauMaee4CamNaeeiiaaIaeeiCaaNaeeyy % aeMaeeOCaiNaeeyyaeMaeeyBa0MaeeyzauMaeeiDaqNaeeyzauMaee % OCaiNaeeiiaaYaamWaaeaacqWGxbWvdaWgaaWcbaGaemisaG0aaWba % aWqabeaacqGHsislaaaaleqaaOGaeeivaqLaem4vaC1aaSbaaSqaai % abdohaZbqabaaakiaawUfacaGLDbaaaeaacqGH9aqpcqaIXaqmcqaI % ZaWmcqGGUaGlcqaI2aGncqGHXcqScqaIWaamcqGGUaGlcqaI0aanca % aMe8UaeeOsaOKaeeyBa0Maee4Ba8MaeeiBaW2aaWbaaSqabeaacqGH % sislcqaIXaqmaaaaaaaa!E403!

Climatic and limnological changes at Lake Karakul (Tajikistan) during the last ~29 cal ka

We present results of analyses on a sediment core from Lake Karakul, located in the eastern Pamir Mountains, Tajikistan. The core spans the last ~29 cal ka. We investigated and assessed processes internal and external to the lake to infer changes in past moisture availability. Among the variables used to infer lake-external processes, high values of grain-size end-member (EM) 3 (wide grain-size distribution that reflects fluvial input) and high Sr/Rb and Zr/Rb ratios (coinciding with coarse grain sizes), are indicative of moister conditions. High values in EM1, EM2 (peaks of small grain sizes that reflect long-distance dust transport or fine, glacially derived clastic input) and TiO₂ (terrigenous input) are thought to reflect greater influence of dry air masses, most likely of Westerly origin. High input of dust from distant sources, beginning before the Last Glacial Maximum (LGM) and continuing to the late glacial, reflects the influence of dry Westerlies, whereas peaks in fluvial input suggest increased moisture availability. The early to early-middle Holocene is characterised by coarse mean grain sizes, indicating constant, high fluvial input and moister conditions in the region. A steady increase in terrigenous dust and a decrease in fluvial input from 6.6 cal ka BP onwards points to the Westerlies as the predominant atmospheric circulation through to present, and marks a return to drier and even arid conditions in the area. Proxies for productivity (TOC, TOC/TN, TOC _Br ), redox potential (Fe/Mn) and changes in the endogenic carbonate precipitation (TIC, δ¹⁸O _Carb ) indicate changes within the lake. Low productivity characterised the lake from the late Pleistocene until 6.6 cal ka BP, and increased rapidly afterwards. Lake level remained low until the LGM, but water depth increased to a maximum during the late glacial and remained high into the early Holocene. Subsequently, the water level decreased to its present stage. Today the lake system is mainly climatically controlled, but the depositional regime is also driven by internal limnogeological processes.     

Effects of spring warming and mixing duration on diatom deposition in deep Tiefer See,NE Germany

Monitoring during three meteorologically different spring seasons in 2012, 2013, and 2014 revealed that temperature increase in spring, which influences spring lake mixing duration, markedly affected nutrient availability and diatom deposition in a sediment trap close to the bottom of deep Tiefer See, NE Germany. Deposition of Stephanodiscus taxa and small Cyclotella taxa was much higher after late ice out and a deep, short lake mixing period in spring 2013, compared to that after gradual warming and lengthy lake mixing periods in spring 2012 and 2014, when only brief or marginal ice cover occurred. Availability of dissolved Si and P was 33 and 20 % higher, respectively, in 2013 compared to 2014. The observed relation between high (low) diatom deposition and short (lengthy) mixing duration in spring was applied to varved sediments deposited between AD 1924 and 2008. Low detrital Si content in trapped material and a sediment core enabled use of µXRF-counts of Si as a proxy for diatom silica. The spring mixing duration for 1951–2008 was derived from FLake-model calculations. The spring warming duration related to lake mixing was approximated from air temperatures for 1924–2008 using the dates when daily mean air temperature exceeded 5 °C (start) and 10 °C (end). Diatom silica deposition showed a significant (p < 0.0001) inverse linear relationship with the modeled spring mixing duration (R² = 0.36) and the spring warming duration (R² = 0.28). In both cases, the relationship is strengthened when data from the period of low diatom production (1987–2005) is excluded (R² = 0.59 and R² = 0.35). Part of this low diatom production is related to external nutrient supply that favored growth of cyanobacteria at the expense of diatoms. This approach shows that diatom Si deposition was strongly influenced by the availability of light and nutrients, related to the duration of lake mixing and warming in spring, during most of the studied period. The remaining unexplained variability, however, indicates that additional factors influence Si deposition. Further tests in other deep, temperate lakes are necessary to verify if this relation is a common feature and consequently, if diatom Si can be used as a proxy for spring mixing duration in such lakes.     

Comparison of two algorithms for calculating photolysis frequencies including the effects of clouds

Summary Two complex models to determine photolysis frequencies for chemical transport models are used to study the effects of input data and the consideration of relevant physical processes on the derived photolysis frequencies. Within the model CTM photolysis frequencies are calculated on a coarse latitudinal grid with climatological input data (monthly mean or seasonal mean values) and are then interpolated linearly in space to derive photolysis frequencies for each grid cell of the chemical transport model. These clear sky photolysis frequencies are then corrected to account for cloud effects. The model STAR calculates photolysis frequencies for each grid cell considering the relevant physical processes on the basis of actual profiles computed with a mesoscale meteorological model and other available geophysical data.The comparison of the O₃ and NO₂ photolysis frequencies shows that the approach used within the CTM model compares to STAR only under certain conditions, as climatological input data can be less suitable for episodic photolysis frequencies calculations. The ozone column content significantly alters the photolysis frequency of ozone itself and climatological Dobson data limit the quality of the calculations. The temperature dependence of the quantum yields and the absorption cross sections lead to increased uncertainties when climatological temperature profiles are used. This is especially the case for sunrise/sunset conditions. The use of one surface albedo for all landuse types and seasons within the CTM model restricts the quality of the calculations close to the surface. If clouds are present the CTM model over-/underestimates the cloud effects on the photolysis frequencies and differences up to an order of magnitude are found for below cloud values.With 11 Figures     

Experimente zum Einfluß des Gesteinsglas-Chemismus auf die Zeolithbildung durch hydrothermale Umwandlung

In the formation of zeolites by hydrothermal alteration volcanic glasses are the starting material in most cases. The experiments aimed at demonstrating in what way the chemistry of the volcanic glass influences:

1. the alteration rate of the volcanic glass to zeolites,
2. the kind of zeolites being formed and their formation conditions.

Three volcanic glasses were used, a basaltic, a phonolitic, and a rhyolitic one. The experimental conditions were as similar as possible to the natural alteration conditions. Solutions being used: H₂O dist (pH ～5.5), 0.01 n NaOH (pH ～10.5), and solutions of similar chemistry to the natural ones. The temperatures were 180 °, 200 °, 250 ° C. The experiments were carried out both in closed and in open systems. The experimental results show a difference in the alteration rate and in the zeolites being formed between the basaltic and the phonolitic glasses on the one hand and the rhyolitic one on the other. In case of the closed system the SiO₂-poor volcanic glasses react more rapidly than the SiO₂-rich one. The zeolites being formed are chabazite, phillipsite, analcime respectively mordenite, analcime. In case of the open system the influence of the chemistry of the volcanic glass on the alteration rate and the zeolite being formed is less significant. Which zeolite is formed at a given temperature depends on: the chemistry of the starting material, the chemistry of the reacting solution and wether there is a closed or an open system.     

Ar/Ar geochronology of Neogene phreatomagmatic volcanism in the western Pannonian Basin,Hungary

Neogene alkaline basaltic volcanic fields in the western Pannonian Basin, Hungary, including the Bakony–Balaton Highland and the Little Hungarian Plain volcanic fields are the erosional remnants of clusters of small-volume, possibly monogenetic volcanoes. Moderately to strongly eroded maars, tuff rings, scoria cones, and associated lava flows span an age range of ca. 6 Myr as previously determined by the K/Ar method. High resolution ⁴⁰Ar/³⁹Ar plateau ages on 18 samples have been obtained to determine the age range for the western Pannonian Basin Neogene intracontinental volcanic province. The new ⁴⁰Ar/³⁹Ar age determinations confirm the previously obtained K/Ar ages in the sense that no systematic biases were found between the two data sets. However, our study also serves to illustrate the inherent advantages of the ⁴⁰Ar/³⁹Ar technique: greater analytical precision, and internal tests for reliability of the obtained results provide more stringent constraints on reconstructions of the magmatic evolution of the volcanic field. Periods of increased activity with multiple eruptions occurred at ca. 7.95 Ma, 4.10 Ma, 3.80 Ma and 3.00 Ma.     

First lacustrine varve chronologies from Mexico: impact of droughts,ENSO and human activity since AD 1840 as recorded in maar sediments from Valle de Santiago

We present varve chronologies for sediments from two maar lakes in the Valle de Santiago region (Central Mexico): Hoya La Alberca (AD 1852–1973) and Hoya Rincón de Parangueo (AD 1839–1943). These are the first varve chronologies for Mexican lakes. The varved sections were anchored with tephras from Colima (1913) and Paricutín (1943/1944) and ²¹⁰Pb ages. We compare the sequences using the thickness of seasonal laminae and element counts (Al, Si, S, Cl, K, Ti, Mn, Fe, and Sr) determined by micro X-ray fluorescence spectrometry. The formation of the varve sublaminae is attributed to the strongly seasonal climate regime. Limited rainfall and high evaporation rates in winter and spring induce precipitation of carbonates (high Ca, Sr) enriched in ¹³C and ¹⁸O, whereas rainfall in summer increases organic and clastic input (plagioclase, quartz) with high counts of lithogenic elements (K, Al, Ti, and Si). Eolian input of Ti occurs also in the dry season. Moving correlations (5-yr windows) of the Ca and Ti counts show similar development in both sequences until the 1930s. Positive correlations indicate mixing of allochthonous Ti and autochthonous Ca, while negative correlations indicate their separation in sublaminae. Negative excursions in the correlations correspond with historic and reconstructed droughts, El Niño events, and positive SST anomalies. Based on our data, droughts (3–7 year duration) were severe and centred around the following years: the early 1850s, 1865, 1880, 1895, 1905, 1915 and the late 1920s with continuation into the 1930s. The latter dry period brought both lake systems into a critical state making them susceptible to further drying. Groundwater overexploitation due to the expansion of irrigation agriculture in the region after 1940 induced the transition from calcite to aragonite precipitation in Alberca and halite infiltration in Rincón. The proxy data indicate a faster response to increased evaporation for Rincón, the lake with the larger maar dimensions, solar radiation receipt and higher conductivity, whereas the smaller, steeper Alberca maar responded rapidly to increased precipitation.