Monte Carlo Simulations as a Decision Support to Interpret δ15N Values of Nitrate in Groundwater

Intense farming is often associated with the excessive use of manure or fertilizers and the subsequent deterioration of the groundwater quality in many aquifers worldwide. Stable isotopes of dissolved nitrate (δ¹⁵N and δ¹⁸O) are widely used to determine sources of nitrate contamination and denitrification processes in groundwater but are often difficult to interpret. Thus, Monte Carlo simulations were carried out for a site in lower Bavaria, Germany, in order to explain δ¹⁵N observations in a porous groundwater system with two aquifers, the main aquifer (MA) and several smaller perched aquifers (PA). For evaluating potential contributions, frequency distributions of δ¹⁵N were simulated deriving from (I) the mixing of different nitrate sources, related to land use, as input to groundwater, combined with (II) transport of nitrate in groundwater and (III) microbial denitrification. Simulation results indicate a source-driven isotopic shift to heavier δ¹⁵N values of nitrate in groundwater, which may be explained by land use changes toward a more intensified agriculture releasing high amounts of manure. Microbial denitrification may play a role in the PA, with simulated δ¹⁵N distributions close to the observations. Denitrification processes are however unlikely for the MA, as reasonable simulation curve fits for such a scenario were obtained predominantly for unrealistic portions of nitrate sources and related land use. The applied approach can be used to qualitatively and quantitatively evaluate the influence of different potential contributions, which might mask each other due to overlapping δ¹⁵N ranges, and it can support the estimation of nitrate input related to land use.     

Gewinnung biokinetischer Daten von Altwässern mit dem Respirationsfermentor. Teil 1: Methodische Grundlagen und die Bestimmung der spezifischen Wachstumsund Sauerstoffaufnahmerate

Es wird eine Fermentationsvorrichtung für die Messung des Sauerstoffverbrauchs bei wählbaren Sauerstoffpartialdrucken vorgestellt, die in einem geschlossenen Gaskreislauf einen Laboratoriumsfermentor mit Meß- und Regeleinrichtungen sowie Möglichkeiten der Probenahme aufweist. Die Druckregression durch die Kohlendioxidadsorption steuert die synchron registrierte Nachlieferung von Sauerstoffgas. Durch diskontinuierliche Kultivation eines adaptierten Belebtschlammes wurden von einem Braunkohlenpyrolyseabwasser die Sauerstoffverbrauchskurven aufgenommen. Es wurde ein polyauxischer Kurvenverlauf erhalten, wobei auf den Abbau der niederen Fettsauren, im wesentlichen Azetat, 70 … 80% des Gesamtsauerstoffverbrauchs entfielen. Hierfür werden biokinetische Daten bestimmt; ; ; μ_max = 0,56 h^–1 (ausgewählte Werte). Die bei der Erfassung und Errechnung der Daten auftretenden Probleme wurden diskutiert.     

The viscosity of hydrous dacitic liquids: implications for the rheology of evolving silicic magmas

The viscosity of a series of six synthetic dacitic liquids, containing up to 5.04 wt% dissolved water, was measured above the glass transition range by parallel-plate viscometry. The temperature of the 10¹¹ Pa s isokom decreases from 1065 K for the anhydrous liquid, to 864 K and 680 K for water contents of 0.97 and 5.04 wt% H₂O. Including additional measurements at high temperatures by concentric-cylinder and falling-sphere viscometry, the viscosity (η) can be expressed as a function of temperature and water content w according to: where η is in Pa s, T is temperature in K, and w is in weight percent. Within the conditions of measurement, this parameterization reproduces the 76 viscosity data with a root-mean square deviation (RMSD) of 0.16 log units in viscosity, or 7.8 K in temperature. The measurements show that water decreases the viscosity of the dacitic liquids more than for andesitic liquids, but less than for rhyolites. At low temperatures and high water contents, andesitic liquids are more viscous than the dacitic liquids, which are in turn more viscous than rhyolitic liquids, reversing the trend seen for high temperatures and low water contents. This suggests that the relative viscosity of different melts depends on temperature and water content as much as on bulk melt composition and structure. At magmatic temperatures, rhyolites are orders of magnitude more viscous than dacites, which are slightly more viscous than andesites. During degassing, all three liquids undergo a rapid viscosity increase at low water contents, and both dacitic and andesitic liquids will degas more efficiently than rhyolitic liquids. During cooling and differentiation, changing melt chemistry, decreasing temperature and increasing crystal content all lead to increases in the viscosity of magma (melt plus crystals). Under closed system conditions, where melt water content can increase during crystallization, viscosity increases may be small. Conversely, viscosity increases are very abrupt during ascent and degassing-induced crystallization.     

The great sulfur depletion of Earth’s mantle is not a signature of mantle–core equilibration

The extreme depletion of the Earth’s mantle in sulfur is commonly seen as a signature of metal segregation from Earth’s mantle to Earth’s core. However, in addition to S, the mantle contains other elements as volatile as S that are hardly depleted relative to the lithophile volatility trend although they are potentially as siderophile as sulfur. We report experiments in metal-sulfide–silicate systems to show that the CI normalized abundances of S, Pb, and Sn in Earth’s mantle cannot be reproduced by element partitioning in Fe ± S–silicate systems, neither at low nor at high pressure. Much of the volatile inventory of the Earth’s mantle must have been added late in the accretion history, when metal melt segregation to the core had become largely inactive. The great depletion in S is attributed to the selective segregation of a late sulfide matte from an oxidized and largely crystalline mantle. Apparently, the volatile abundances of Earth’s mantle are not in redox equilibrium with Earth’s core.     

Viscosity of andesitic melts—new experimental data and a revised calculation model

The viscosity of a synthetic andesite-like melt was measured in the low viscosity range (10¹-10⁶ Pa s) using the falling sphere(s) method and in the high viscosity range (10⁸-10¹³ Pa s) using parallel-plate viscometry. Falling sphere experiments with melts containing 2.3 and 5.6 wt.% H₂O were carried out in an internally heated gas pressure vessel (IHPV) at 500 MPa confining pressure. The sinking velocity of Pt and Pd spheres and in one case of a corundum sphere was used to measure the melt viscosity. In addition, a creep experiment was performed at ambient pressure using a glass containing 2.73 wt.% H₂O . A more water-rich glass (5.6 wt.% H₂O ) was investigated with a high pressure parallel-plate viscometer at 400 MPa confining pressure in an IPHV. By combining our new data with previous results for a similar melt composition we derived the following expression to describe the viscosity η (in Pa s) as a function of temperature T (in K) and water content w (in wt.%)

     

Molecular characterization of organic matter in sediments from the Keg River formation (Elk Point group), western Canada sedimentary basin

Distributions of free and sulfur-bound biomarkers in organic-rich sediments from the lower and upper Keg River formation (Elk Point group, western Canada) reveal deposition of these sediments under reducing conditions, in agreement with the geological data. The predominance of aryl isoprenoids of Chlorobiaceae origin indicates that photic zone anoxia occurred during time of deposition. A series of novel aryl isoprenoids with a carboxylic acid function was identified by GC–MS and the structure of the predominant 3-methyl-5-(2′,3′,6′-trimethylphenyl)pentanoate was proven by synthesis of an authentic standard. The occurrence of these acids gives evidence that oxidative breakdown at least partially accounts for the diagenetic fate of aromatic carotenoids. Li/EtNH₂ desulfurization of two kerogen concentrates yielded only low amounts of sulfur-bound hydrocarbons, and suggests that either sulfur sequestration was not a predominant process or, more probably, that a major part of the hydrocarbons, initially sulfurized, were released upon maturation, giving further evidence that (poly)sulfide bonds are cleaved at relatively low levels of thermal stress.     

H<Subscript>2</Subscript>O diffusion in peralkaline to peraluminous rhyolitic melts

The diffusion of water in a peralkaline and a peraluminous rhyolitic melt was investigated at temperatures of 714–1,493 K and pressures of 100 and 500 MPa. At temperatures below 923 K dehydration experiments were performed on glasses containing about 2 wt% H₂O _t in cold seal pressure vessels. At high temperatures diffusion couples of water-poor (<0.5 wt% H₂O _t ) and water-rich (~2 wt% H₂O _t ) melts were run in an internally heated gas pressure vessel. Argon was the pressure medium in both cases. Concentration profiles of hydrous species (OH groups and H₂O molecules) were measured along the diffusion direction using near-infrared (NIR) microspectroscopy. The bulk water diffusivity () was derived from profiles of total water () using a modified Boltzmann-Matano method as well as using fittings assuming a functional relationship between and Both methods consistently indicate that is proportional to in this range of water contents for both bulk compositions, in agreement with previous work on metaluminous rhyolite. The water diffusivity in the peraluminous melts agrees very well with data for metaluminous rhyolites implying that an excess of Al₂O₃ with respect to alkalis does not affect water diffusion. On the other hand, water diffusion is faster by roughly a factor of two in the peralkaline melt compared to the metaluminous melt. The following expression for the water diffusivity in the peralkaline rhyolite as a function of temperature and pressure was obtained by least-squares fitting:

The temperature dependence of the speciation of water in NaAlSi3O8-KAlSi3O8 melts: an application of fictive temperatures derived from synthetic fluid-inclusions

 The speciation of water dissolved in glasses along the join NaAlSi₃O₈-KAlSi₃O₈ has been investigated using infrared spectroscopy. Hydrous melts have been hydrothermally synthesized by chemical equilibration of cylinders of bubble-free anhydrous start glasses with water at 1040^° C and 2 kbar. These melts have been isobarically and rapidly (200^° C/s) “drop”-quenched to room temperature and then subsequently depressurized. The speciation of water in the quenched glasses reflects the state of water speciation at a temperature (the so-called fictive temperature) where the quenched-in structure of the glasses closely corresponds to the melt structure at equilibrium. This fictive temperature is detectable as the macroscopically measureable glass transition temperature of these melt compositions. A separate set of experiments using vesicular samples of the same chemistry has precisely defined the glass transition temperature of these melts (±5^° C) on the basis of homogenization temperatures for water-filled fluid inclusions (Romano et al. 1994). The spectroscopic data on the speciation of water in these quenched glasses has been quantified using experimentally determined absorptivities for OH and H₂O for each individual melt composition. The knowledge of glass transition temperatures, together with quantitative speciation data permits an analysis of the temperature dependence of the water speciation over the 113^° C range of fictive temperatures obtained for these water-saturated melts. The variation of water speciation, cast as the equilibrium constant K where K = [H₂O] [O _m ]/[OH]² is plotted versus the fictive temperature of the melt to obtain the temperature dependence of speciation. Such a plot describes a single linear trend of the logarithm of the equilibrium constant versus reciprocal temperature, implying that the exchange of K for Na has little influence on melt speciation of water. The enthalpy derived from temperature dependence is 36.5(±5) kJ/mol. The results indicate a large variation in speciation with temperature and an insensitivity of the speciation to the K–Na exchange. Received: 8 March 1995/Accepted: 6 June 1995     

Macroseismic effects of the north-Italian earthquake of May 6th, 1976, on the territory of Czechoslovakia

Summary The method of treatment of the macroseismic data obtained on the territory of the CSSR after the main 1976 Friuli earthquake is described and the preliminary results are confronted with the geologic structure.