The photoelectron spectra of some Tl-Sb sulphosalts

The results of X-ray induced photoelectron spectroscopy (XPS) experiments on several phases of the ternary system Tl-Sb-S are reported. The binding energies of the inner S, Sb and Tl electrons increase with increasing quantities of Sb and decreasing amounts of Tl in these compounds. This is explained by the influences of the proportions of the bonded metals on the effective electron affinity of S. The higher proportions of the more electronegative element bonded to S cause the increase of its effective electron affinity. The results for Tl₂S (carlinite), Tl₃SbS₃, TlSbS₂ (weissbergite), TlAsS₂ (lorandite) and Sb₂S₃ (antimonite) can be interpreted in this way. The results for Tl₄S₃ suggest a predominantly covalent character of bonding for both Tl(III) and Tl(I), which are present in this sulfide. From comparison with Tl₃SbS₄ it could be supposed that Tl(III)-S bond has a more covalent character than Sb(V)-S bond. The results for Tl₃SbS₄ are in agreement with crystal structure data and the results of Moessbauer spectroscopy. For AsS (realgar) the binding energies of the inner electrons of As and S significantly increase, showing that the electrons in molecular orbitals are less strongly bonded to individual atoms, as compared to pure elements. The results for the amorphous TlSb₅S₈ (corresponding in composition to parapierrotite) suggest that in amorphous compound the Tl-S bonding is stronger and the coordination of Tl more regular than in a crystalline one.     

Biological and Physical Clogging in Infiltration Wells: Effects of Well Diameter and Gravel Pack

Gravity-driven infiltration into the shallow subsurface via small-diameter wells (SDWs), i.e., wells with an inner diameter smaller than 7.5 cm (3 inches) and no gravel pack) has proven to be a cost-efficient and flexible tool for managed aquifer recharge (MAR), as it provides relatively high recharge rates with minimal construction effort. SDWs have a significantly smaller open filter area than larger diameter wells with gravel pack, making the infiltration of low-quality waters through these wells more at risk clogging. To investigate their susceptibility for biological and physical clogging, 24 physical models with different well setups were evaluated by infiltrating either nutrient-poor but turbid water or nutrient-rich but clear water. The experiments showed that smaller diameters and the lack of a gravel pack increase the well's susceptibility to both kinds of clogging. However, this effect was observed to be much more pronounced for physical than for biological clogging. Our conclusion is that SDWs show severe disadvantages with respect to the infiltration of highly turbid waters in comparison to large diameter wells with a gravel pack. Nevertheless, this disadvantage is much less severe when it comes to the infiltration of clear but nutrient-rich waters (e.g., treated wastewater). Depending on the economic and geological circumstances of a MAR-project, this disadvantage could be outweighed by the significantly lower construction costs of SDWs.     

Palaeolimnology of Lake Piene-Kuuppalanlampi (Kurkijoki, Karelian Republic, Russia): isolation history, lake ecosystem development and long-term agricultural impact

The post-glacial history of Lake Pieni-Kuuppalanlampi, western Lake Ladoga region, was studied by means of stratigraphic pollen and diatom analyses. Diatoms were analysed to track the isolation history of the basin and the limnological effects of the early land-use phases indicated by pollen analysis. Chrysophycean stomatocysts and Isoëtes spores were also employed in the limnological reconstructions. Sediment dating was provided by six conventional radiocarbon dates.The lower part of the 370-cm long sediment sequence represents early Holocene, large lake conditions: the (freshwater) Yoldia and Ancylus stages of the Baltic basin, with a short-term lagoonal or isolation phase at the end of Yoldia. The basin was isolated due to Ancylus lake regression at 9785 cal B.P. For the small-lake sequence (0–250 cm) we used diatom inferences (WA-method) for hindcasting water chemistry. The post-isolation limnology of Pieni-Kuuppalanlampi reflects the development of vegetation on its small hill-top catchment. In its early development, the lake was mesotrophic, but became more acidic (pH about 6) and oligotrophic after the decline of temperate hardwood trees and the spread of spruce to the area after around 5000 B.P. The lake ecosystem appears to have reacted sensitively to agricultural land-use in the catchment from AD 400–800 onwards: inferred total phosphorus levels and pH both rise during these periods.     

Close binary systems before and after mass transfer: A comparison of observations and theory

From a search through the literature 174 close binaries with known absolute dimensions have been sampled. Distinction is made between systems before and after mass exchange. Mass, period and mass ratio distributions and relations of the group of unevolved binaries (i.e., prior to mass exchange) are transformed into corresponding distributions and relations of evolved binaries. The transformations are based upon theM _1f=g(M _1f) relation derived from an extended set of published theoretical computations of the evolution of close binaries. From this relation the following characteristics of the system after mass exchange are computed:M _1f,M _2f (andq _f),P _f. Five different modes of mass transfer were applied for the computation of the values ofP _f andM _2f. The variation of the period was calculated using the formalism given by Vanbeverenet al. (1979). The results are compared to the observations of binary systems after mass exchange, and are discussed together with an analysis of the effect of several selection effects present in the distributions. The main conclusion is that, during mass exchange in close binaries, more than 50% of the mass is lost to the system in the process of transfer, removing a large amount of angular momentum.This research is supported by the National Foundation of Collective Fundamental Research of Belgium (F.K.F.O.) under No. 2.9009.79.     

Exploring the spatial distribution patterns of South African Cape hakes using generalised additive models

We developed delta generalised additive models (GAMs) to predict the spatial distribution of different size classes of South African hakes, Merluccius capensis and M. paradoxus, using demersal trawl survey data and geographical (latitude and longitude) and environmental features (depth, temperature, bottom dissolved oxygen and sediment type). Our approach consists of fitting, for each hake size class, two independent models, a binomial GAM and a quasi-Poisson GAM, whose predictions are then combined using the delta method. Delta GAMs were validated using an iterative cross-validation procedure, and their predictions were then employed to produce distribution maps for the southern Benguela. Delta GAM predictions confirmed existing knowledge about the spatial distribution patterns of South African hakes, and brought new insights into the factors influencing the presence/absence and abundance of these species. Our GAM approach can be used to produce distribution maps for spatially explicit ecosystem models of the southern Benguela in a rigorous and objective way. Ecosystem models are critical features of the ecosystem approach to fisheries, and distribution maps constructed using our GAM approach will enable a reliable allocation of species biomasses in spatially explicit ecosystem models, which will increase trust in the spatial overlaps and, therefore, the trophic interactions predicted by these models.     

Gas hydrate disturbance fabrics of southern Hydrate Ridge sediments (ODP Leg 204): Relationship with texture and physical properties

Soupy and mousse-like fabrics are disturbance sedimentary features that result from the dissociation of gas hydrate, a process that releases water. During the core retrieval process, soupy and mousse-like fabrics are produced in the gas hydrate-bearing sediments due to changes in pressure and temperature conditions. Therefore, the identification of soupy and mousse-like fabrics can be used as a proxy for the presence of gas hydrate in addition to other evidence, such as pore water freshening or anomalously cool temperature. We present here grain-size results, mineralogical composition and magnetic susceptibility data of soupy and mousse-like samples from the southern Hydrate Ridge (Cascadia accretionary complex) acquired during Leg 204 of the Ocean Drilling Program. In order to study the relationship between sedimentary texture and the presence of gas hydrates, we have compared these results with the main textural and compositional data available from the same area. Most of the disturbed analyzed samples from the summit and the western flank of southern Hydrate Ridge show a mean grain size coarser than the average mean grain size of the hemipelagic samples from the same area. The depositional features of the sediments are not recognised due to disturbance. However, their granulometric statistical parameters and distribution curves, and magnetic susceptibility logs indicate that they correspond to a turbidite facies. These results suggest that gas hydrates in the southern Hydrate Ridge could form preferentially in coarser grain-size layers that could act as conduits feeding gas from below the BSR. Two samples from the uppermost metres near the seafloor at the summit of the southern Hydrate Ridge show a finer mean grain-size value than the average of hemipelagic samples. They were located where the highest amount of gas hydrates was detected, suggesting that in this area the availability of methane gas was high enough to generate gas hydrates, even within low-permeability layers. The mineralogical composition of the soupy and mousse-like sediments does not show any specific characteristic with respect to the other samples from the southern Hydrate Ridge.     

An advanced process for evaluating a linear dielectric constant–bulk electrical conductivity model using a capacitance sensor in field conditions

Abstract

The Hilhorst model was used to convert bulk electrical conductivity (σ_b) to pore water electrical conductivity (σ_p) under laboratory conditions by using the linear relationship between the soil dielectric constant (ε_b) and σ_b. In the present study, applying the linear relationship ε_b–σ_b to data obtained from field capacitance sensors resulted in strong positive autocorrelations between the residuals of that regression. We were able to derive an accurate offset of the relationship ε_b–σ_b and to estimate the evolution of σ_p over time by including a stochastic component to the linear model, rearranging it to a time-varying dynamic linear model (DLM), and using Kalman filtering and smoothing. The offset proved to vary for each depth in the same soil profile. A reason for this might be the changes in soil temperature along the soil profile.

Editor D. Koutsoyiannis; Associate editor M.D. Fidelibus     

Deterioration of Sediment Quality in Seagrass Meadows (<Emphasis Type="Italic">Posidonia oceanica</Emphasis>) Invaded by Macroalgae (<Emphasis Type="Italic">Caulerpa</Emphasis> sp.)

Species of the macroalgae Caulerpa sp. are increasingly being observed in meadows of the endemic Mediterranean seagrass Posidonia oceanica, and in particular Caulerpa taxifolia, has been considered as an invasive species leading to seagrass decline. Studies have so far failed to reveal the underlying mechanisms of the success of the macroalgae, and here, we examine how biogeochemical changes of the environment associated to indigenous (Caulerpa prolifera) and non-indigenous (Caulerpa racemosa and C. taxifolia) species affect the habitat of P. oceanica. Two of the species (C. prolifera and C. racemosa) affect the sediment biogeochemical conditions by increasing organic matter pools, microbial activity, and sulfide pools of the sediments, and limited effects were found for C. taxifolia. Biomass of the macroalgae contributed to the extent of impacts, and high sulfide invasion into the seagrasses and regression of the meadow were pronounced at the location with the highest Caulerpa biomass. This suggests that Caulerpa invasion contributes to seagrass decline probably because Caulerpa thrives better than the seagrasses in the modified environment.     

Polyphase thrusting and dyke emplacement in the central Southern Alps (Northern Italy)

The Triassic succession of the central Southern Alps (Italy) is stacked into several units bounded by south-verging low-angle thrust faults, which are related to two successive steps of crustal shortening. The thrust surfaces are cut by high-angle extensional and strike-slip faults, which controlled the emplacement of hypabissal magmatic intrusions that post-date thrusts motions. Intrusion ages based on SHRIMP U–Pb zircon dating span between 42 ± 1 and 39 ± 1 Ma, suggesting close time relationships with the earliest Adamello intrusion stages and, more in general, with the widespread calc-alkaline magmatism described in the Southern Alps. Fission-track ages of magmatic apatites are indistinguishable from U–Pb crystallization ages of zircons, suggesting that the intrusion occurred in country rocks already exhumed above the partial annealing zone of apatite (depth < 2–4 km). These data indicate that the central Southern Alps were already structured and largely exhumed in the Middle Eocene. Although we describe minor faults affecting magmatic bodies and local reactivations of older structures, no major internal deformations have occurred in the area after the Bartonian. Neogene deformations were instead concentrated farther south, along the frontal part of the belt.