Quantification of organic pollutant degradation in contaminated aquifers using compound specific stable isotope analysis - Review of recent developments

Compound specific stable isotope analysis (CSIA) has been established as a viable tool for proving, characterizing and assessing degradation of organic pollutants within contaminated aquifers. The fractionation of stable isotopes during contaminant degradation leads to observable shifts in stable isotope ratios which can serve as an indicator for in situ pollutant degradation and allow for a quantitative assessment by means of the so-called Rayleigh (distillation) equation.This review highlights the recent developments of the Rayleigh equation approach for quantifying in situ degradation of organic pollutants in contaminated aquifers. The advantages and limitations of the Rayleigh equation approach are discussed and suggestions for improvements are given. Concepts are provided to estimate the uncertainty due to errors or variability of input parameters and how to deal with such uncertainty. Moreover, the applicability of the Rayleigh equation approach is evaluated regarding the heterogeneity and complexity of groundwater systems. For such systems, the review discusses the relevance of non-destructive processes, which affect the concentration (e.g., dispersive mixing) and potentially also the stable isotope ratio of contaminants (e.g., sorption, volatilization), and the resulting implications for the Rayleigh equation approach.     

The hydrogen and carbon isotopic composition of methane from natural gases of various origins

The deuterium concentrations (δD vs SMOW) of biogenic methanes from world-wide occurrences range from ?180 to ?280%. and were found to be depleted in deuterium by approx. 160%. compared to the deuterium concentration of their associated waters. Theoretical considerations support this relationship to be the result of bacterial transformation of CO₂ to methane and is therefore indicative of the biogenic origin of methane.Thermogenic gases with high C₂₊ concentrations (wet gases associated with crude oil) have D/H ratios from ?260 to ?150%. with deuterium contents tending to increase with decreasing wetness. Dry gases which are not associated with petroleum are more enriched in deuterium (?180 to ?130%.) and show an increase in deuterium with increasing rank of the source beds as it is similarly known for carbon-13.Many dry gases in young sedimentary basins were found to contain significant amounts of C₂₊ hydrocarbons. These gases cannot be grouped with either the biogenic or thermogenic gases and their methane is concluded to be of mixed biogenic and thermochemical origin.Using a $\text{δ}{}^{13}\text{C}\text{δD}$ diagrammatic display of the isotope data of methanes the various genetic groups of natural gases can be defined more clearly.     

Engineering Geological Properties of Building Stones from the North-Eastern Part of the Vienna Basin in the Western Carpathians

Geotechnical and Geological Engineering - This research focuses on assessing the most important physical and mechanical properties of rocks that were quarried from the north-eastern part of the...     

Thermodynamics of Al/Al avoidance in the ordering of Al/Si tetrahedral framework structures

The main driving force behind Al/Si ordering in tetrahedral framework aluminosilicates is nearest-neighbour Al/Al avoidance. Computer simulation is used to explore the direct consequences of such Al/Al avoidance. The main result is that the order-disorder transition temperature T _c falls dramatically as the concentration x of Al in the structure is reduced, and if the only interactions are those associated with nearest-neighbour Al/Al avoidance, T _c becomes zero for x less than some critical value x _c , where x _c =0.31 for the feldspar framework and x _c =0.34 for cordierite. Also a large degree of short range order is found above T _c . Both results differ radically from the standard Bragg-Williams model. Plots of entropy and enthalpy of ordering are given as functions of x and T, which may be used to interpret experimental data or for extrapolation into ranges of x and T inaccessible to experiment. Received: 14 May 1997 / Revised, accepted: 2 June 1997     

The structure of the lower crust at the Argentine continental margin, South Atlantic at 44°S

It is well established that the Argentine passive margin is of the rifted volcanic margin type. This classification is based primarily on the presence of a buried volcanic wedge beneath the continental slope, manifested by seismic data as a seaward dipping reflector sequence (SDRS). Here, we investigate the deep structure of the Argentine volcanic margin at 44°S over 200 km from the shelf to the deep oceanic Argentine Basin. We use wide-angle reflection/refraction seismic data to perform a joint travel time inversion for refracted and reflected travel times. The resulting P-wave velocity-depth model confirms the typical volcanic margin structure. An underplated body is resolved as distinctive high seismic velocity (v_p up to 7.5 km/s) feature in the lower crust in the prolongation of a seaward dipping reflector sequence. A remarkable result is that a second, isolated body of high seismic velocity (v_p up to 7.3 km/s) exists landward of the first high-velocity feature. The centres of both bodies are 60 km apart. The high-velocity lower-crustal bodies likely were emplaced during transient magmatic–volcanic events accompanying the late rifting and initial drifting stages. The lateral variability of the lower crust may be an expression of a multiple rifting process in the sense that the South Atlantic rift evolved by instantaneous breakup of longer continental margin segments. These segments are confined by transfer zones that acted as rift propagation barriers. A lower-crustal reflector was detected at 3 to 5 km above the modern Moho and probably represents the lower boundary of stretched continental crust. With this finding we suggest that the continent–ocean boundary is situated 70 km more seaward than in previous interpretations.     

A case study on the correlation of micro-contaminants and potassium in the Leine River (Germany)

River monitoring with focus on the correlation of 41 micro-contaminants with K⁺ and its temporal and spatial variation was carried out in the Leine River (Germany). A positive correlation of concentrations of wastewater-related micro-contaminants and K⁺ is to be expected in receiving waters of wastewater treatment plant (WWTP) effluent since urine is a significant source of K⁺ in WWTP effluent. This correlation was found for compounds, which meet the following criteria: (1) WWTP effluent is the dominating source of the compound, (2) variability of its mass flux in the WWTP is negligible, and (3) the compound is persistent in WWTPs and in the environment. The excellent positive correlation of carbamazepine with K⁺ resulted in the fitting of a universal linear equation to the summer and winter data. For almost all other correlating compounds (1H-benzotriazole, citalopram, diclofenac, metoprolol, sotalol, sulfamethoxazole and tolyltriazole), slopes of the line fittings were steeper in winter (x-axis: K⁺, y-axis: respective micro-contaminant). This has been attributed to a presumed lower degree of degradation and attenuation within WWTPs and in the environment due to low temperatures as well as an increase in consumption of these compounds in the winter months. As part of this research, a sampling event along the entire flow path of the Leine River (∼280 km) was conducted to identify compounds demonstrating stable ratios of various respective micro-contaminants with K⁺. Among other compounds, carbamazepine, sulfamethoxazole, and tolyltriazole demonstrated the best correlations with R² > 0.89. Potassium-equivalents of the individual micro-contaminants depended on land use and population structure of the investigated river section.     

Calcium isotope constraints on the uptake and sources of Ca in a base-poor forest: A new concept of combining stable (δCa) and radiogenic (εCa) signals

Plant-available reserves of major base cations, Ca²⁺ and Mg²⁺, decreased markedly in soils over the past century, thus posing a potential threat to forest ecosystem health. Trees are thought to obtain dissolved Ca²⁺ ions mainly from an easily accessible soil-water reservoir also termed the ‘exchangeable cation pool’. The status of Ca reserves in this soil pool is sensitive to anthropogenic perturbations such as soil acidification induced by acid rain and/or excessive timber harvesting. Here we show that in a base-poor forest of the northeastern USA (i.e. Wachusett Mountain, Massachusetts) the ‘exchangeable Ca pool’ of deeper mineral soils has a unique isotope signature that is significantly enriched in the radiogenic ⁴⁰Ca, due to the dissolution of K-rich silicate minerals such as biotite. Using a simple isotope mass balance, and assuming that the input of Ca from biotite has a ε_Ca signature of ∼16, the results of our calculation indicate that the weathering of biotite may supply a sizeable fraction, up to 25%, of Ca²⁺ ions into the ‘exchangeable cation pool’ of deeper mineral soils. Importantly, samples of local vegetation (i.e. woody tissues of red oak) show no detectable excess of the radiogenic ⁴⁰Ca, and based on our model the upper limit of a possible biotite-derived Ca contribution in vegetation is estimated at ∼5%. We also found no evidence of the radiogenic ⁴⁰Ca signal in the samples of forest floor and the uppermost organic-rich soils (0-15 cm depth), which in turn suggest that over the long-term development of the forest and its organic matter accumulation, the vegetation growth must have also relied primarily on the non-radiogenic Ca sources. Based on our experimental data, such sources may include (i) wet atmospheric deposition, (ii) the organically-complexed Ca in topsoil horizons, and (iii) chemical weathering and/or fungal-mediated dissolution of apatite and Ca-rich plagioclase. Hence, our stable and radiogenic Ca isotope data indicate that the studied base-poor forest is able to bypass the ‘exchangeable cation pool’ of deeper (i.e. below 15 cm) mineral soils, and still manages to meet its nutritional requirements with respect to Ca. Another important implication of this study is that the organically-complexed Ca in the topsoil horizon (0-15 cm depth) has to be tightly bound to the ion exchange sites, otherwise the large radiogenic ⁴⁰Ca signatures present in the ‘exchangeable cation pool’ of deep mineral soils would be swamped by the downward gravitational flux of non-radiogenic Ca from the decaying organic matter and litterfall. Hence, the limited mobility of the organically-complexed Ca in soils and its tight biological cycling could explain the lack of a significant impact of vegetation on the Ca isotope systematics observed in large rivers.     

Influence of subsolidus processes on the chromium number in spinel in ultramafic rocks

The chromium number of spinel Cr#^sp (atomic ratio of Cr/(Cr+Al)) is an important geochemical parameter for the estimation of the degree of partial melting, temperatures, and provenance in peridotites. In this study, a model has been developed in order to determine the effect of subsolidus reactions on the Cr#^sp in ultramafic rocks. The final model includes temperature-dependent distribution coefficients of relevant reactions as well as solubility data and has been applied to lithologies common in mid-ocean ridge settings. Significant changes in the Cr#^sp are predicted from the application of this model during cooling from 1300 to 800°C at mantle pressures. For spinel lherzolites and harzburgites, the Cr#^sp is predicted to decrease proportional to the absolute values of the Cr#^sp at (constantly) increasing spinel mass. Cpx-dunites show the same trend, although to a lower extent. Websterites show a different behavior with a slight increase in the Cr#^sp due to their lack of olivine. Modal abundance of spinel correlates with the magnitude in Cr#^sp change, too. Finally, these results were tested for possible effects on the calculated degree of partial melting as function of the Cr#^sp. Application of the Cr#^sp from a peridotite equilibrated down to 800°C would result in an underestimation of only 1.5 % in the degree of melting, justifying the use of Cr#^sp for estimations of this parameter.     

The Mesozoic–Cenozoic structural framework of the Bay of Kiel area, western Baltic Sea

A dense grid of multichannel high-resolution seismic sections from the Bay of Kiel in the western Baltic Sea has been interpreted in order to reveal the Mesozoic and Cenozoic geological evolution of the northern part of the North German Basin. The overall geological evolution of the study area can be separated into four distinct periods. During the Triassic and the Early Jurassic, E–W extension and the deposition of clastic sediments initiated the movement of the underlying Zechstein evaporites. The deposition ceased during the Middle Jurassic, when the entire area was uplifted as a result of the Mid North Sea Doming. The uplift resulted in a pronounced erosion of Upper Triassic and Lower Jurassic strata. This event is marked by a clear angular unconformity on all the seismic sections. The region remained an area of non-deposition until the end of the Early Cretaceous, when the sedimentation resumed in the area. Throughout the Late Cretaceous the sedimentation took place under tectonic quiescence. Reactivated salt movement is observed at the Cretaceous Cenozoic transition as a result of the change from an extensional to compressional regional stress field. The vertical salt movement influenced the Cenozoic sedimentation and resulted in thin-skinned faulting.