Using Discriminant Analysis and Logistic Regression in Mapping Quaternary Sediments

Mapping the occurrence and thickness of layers within a soil profile is a prerequisite for soil characterization. The objective of this paper is to compare the applicability of two statistical methods—discriminant analysis (DA) and logistic regression (LR)—used to calculate the thickness of Quaternary sediments in a formal way and to identify parameters controlling the occurrence of these sediments. The investigations were carried out in southern Bavaria in an area of about 150 ha presenting a large variability in relief and parent material (Tertiary material, Pleistocene loess, colluvial/alluvial sediments). Comparisons between the two statistical methods were carried out with a training dataset and an evaluation dataset. The results show that DA was preferable under the assumptions of normality and equal variance/covariance matrices. The analyses produced models with 80 % and 79 % correctly reclassified assignments and a canonical correlation coefficient of approximately 0.60. From the simulations, it was found (i) that the determining predictors were altitude, slope, and upslope catchment area (partly expressed as topographical wetness index), SAGA wetness index and specific catchment area; and (ii) that a disadvantage of LR was that trial and error was frequently necessary to find the optimal composition of variables. In this study, a hierarchical combination of binary and ordinal LR was used and revealed (iii) that when the probabilities in LR between adjacent categories were similar, the possibility of incorrect calculations increased and (iv) that visual inspections as well as RMSE showed that DA with weighted depths (5 cm-stepwise DA) provided the best prediction accuracy. This information can help improve soil surveys and the predictability of the spatial heterogeneity in landscapes.     

Adsorption as a cause for iron isotope fractionation in reduced groundwater

Iron isotopes were used to investigate iron transformation processes during an in situ field experiment for removal of dissolved Fe from reduced groundwater. This experiment provided a unique setting for exploring Fe isotope fractionation in a natural system. Oxygen-containing water was injected at a test well into an aquifer containing Fe(II)-rich reduced water, leading to oxidation of Fe(II) and precipitation of Fe(III)(hydr)oxides. Subsequently, groundwater was extracted from the same well over a time period much longer than the injection time. Since the surrounding water is rich in Fe(II), the Fe(II) concentration in the extracted water increased over time. The increase was strongly retarded in comparison to a conservative tracer added to the injected solution, indicating that adsorption of Fe(II) onto the newly formed Fe(III)(hydr)oxides occurred. A series of injection-extraction (push-pull) cycles were performed at the same well. The δ⁵⁷Fe/⁵⁴Fe of pre-experiment background groundwater (−0.57 ± 0.17 ‰) was lighter than the sediment leach of Fe(III) (−0.24 ± 0.08 ‰), probably due to slight fractionation (only ∼0.3 ‰) during microbial mediated reductive dissolution of Fe(III)(hydr)oxides present in the aquifer. During the experiment, Fe(II) was adsorbed from native groundwater drawn into the oxidized zone and onto Fe(III)(hydr)oxides producing a very light groundwater component with δ⁵⁷Fe/⁵⁴Fe as low as −4 ‰, indicating that heavier Fe(II) is preferentially adsorbed to the newly formed Fe(III)(hydr)oxides surfaces. Iron concentrations increased with time of extraction, and δ⁵⁷Fe/⁵⁴Fe linearly correlated with Fe concentrations (R² = 0.95). This pattern was reproducible over five individual cycles, indicating that the same process occurs during repeated injection/extraction cycles. We present a reactive transport model to explain the observed abiotic fractionation due to adsorption of Fe(II) on Fe(III)(hydr)oxides. The fractionation is probably caused by isotopic differences in the equilibrium sorption constants of the various isotopes (K_ads) and not by sorption kinetics. A fractionation factor α_57/54 of 1.001 fits the observed fractionation.     

Zircon U–Pb geochronology of Ordovician magmatism in the polycyclic Ruitor Massif (Internal W Alps)

Among the Middle Penninic basements of the Internal NW-Alps, the Ruitor massif shows the best preserved remnants of pre-Permian metamorphic rocks. Their Barrovian-type mineral associations are somewhat masked by the greenschist to blueschist Alpine metamorphism of Tertiary age. Four Ruitor gneisses have been analysed, showing geochemical characters of granitoids from orogenic zones. Zircon morphology also suggests magmatic protoliths and a crustal source; some of the morphological zircon types suggest anatectic granites. The first U-Pb ages on zircon for this massif have been obtained concurrently through conventional multigrain and ion microprobe dating. Two metavolcanic rocks at 471LJ and 468ᆪ Ma could be slightly older than the porphyritic augen gneisses at 465ᆟ and 460lj Ma. Regional data from the other Internal basement massifs suggest that the Variscan event is poorly recorded, except in Ruitor-type units. Ruitor and Sapey gneisses belonged to the same unit (Nappe des Pontis), which was affected by a 480-450-Ma event including volcanism and anatexis and ended with a late calc-alkaline granite emplacement at 460-450 Ma. The distribution of Variscan basement units roughly parallels Alpine zonation.