The structural role of Ti in aluminosilicate liquids in the glass transition range: insights from heat capacity and shear viscosity measurements

The shear viscosities and 1 bar heat capacities of glasses and melts along the 67mol% silica isopleth in the system SiO₂-Al₂O₃-Na₂O-TiO₂ have been determined in the temperature ranges 780-1140 K and 305-1090 K respectively. Anomalous behaviour of both these properties is observed for compositions rich in TiO₂ and/or Al₂O₃, an observation attributed to liquid-liquid phase separation followed by anatase crystallization. For samples which do not show anomalous behaviour, it is found that the partial molar heat capacity of the TiO₂ component previously determined in Al-free compositions reproduces our heat capacities to within 1.3%. Viscosity data show that addition of TiO₂ tends to increase viscosity and melt fragility at constant temperature. Furthermore, heat capacity and viscosity data may be combined within the framework of the Adam-Gibbs theory to extract values of the configurational entropy of the liquids and qualitative estimates of the variation of the average energy barrier to viscous flow. Configurational entropy at 900K is inferred to decrease upon addition of TiO₂, in contrast to previous results from Al-free systems. The compositional limit separating normal from anomalous behaviour, as well as the data for homogenous melts have been used to constrain the structural role of Ti in these samples. Our data are consistent with a majority of Ti in five-fold coordination associated with a titanyl bond, in agreement with previous spectroscopic studies. Furthermore, we find no evidence for a Ti-Al interaction in our samples, and we are led to the conclusion that Al and Ti are incompletely mixed, a hypothesis consistent with the observed reduction of configurational entropy upon addition of TiO₂, suggesting an important role of medium range order in controlling the variations in thermodynamic properties.     

Fifty-thousand-year vegetation and climate history of Noel Kempff Mercado National Park, Bolivian Amazon

Pollen and charcoal records from two large, shallow lakes reveal that throughout most of the past 50,000 yr Noel Kempff Mercado National Park, in northeastern lowland Bolivia (southwestern Amazon Basin), was predominantly covered by savannas and seasonally dry semideciduous forests. Lowered atmospheric CO₂ concentrations, in combination with a longer dry season, caused expansion of dry forests and savannas during the last glacial period, especially at the last glacial maximum. These ecosystems persisted until the mid-Holocene, although they underwent significant species reassortment. Forest communities containing a mixture of evergreen and semideciduous species began to expand between 6000 and 3000 ¹⁴C yr B.P. Humid evergreen rain forests expanded to cover most of the area within the past 2000 ¹⁴C yr B.P., coincident with a reduction in fire frequencies. Comparisons between modern pollen spectra and vegetation reveal that the Moraceae-dominated rain forest pollen spectra likely have a regional source area at least 2-3 km beyond the lake shore, whereas the grass- and sedge-dominated savanna pollen spectra likely have a predominantly local source area. The Holocene vegetation changes are consistent with independent paleoprecipitation records from the Bolivian Altiplano and paleovegetation records from other parts of southwestern Amazonia. The progressive expansion in rain forests through the Holocene can be largely attributed to enhanced convective activity over Amazonia, due to greater seasonality of insolation in the Southern Hemisphere tropics driven by the precession cycle according to the Milankovitch Astronomical Theory.     

Geochemical characteristics, Ar–Ar ages and original tectonic setting of the Band-e-Zeyarat/Dar Anar ophiolite, Makran accretionary prism, S.E. Iran

The Makran accretionary prism in southeastern Iran contains extensive Mesozoic zones of melange and large intact ophiolites, representing remnants of the Tethys oceanic crust that was subducted beneath Eurasia. To the north of the Makran accretionary prism lies the Jaz Murian depression which is a subduction-related back-arc basin. The Band-e-Zeyarat/Dar Anar ophiolite is one of the ophiolite complexes; it is located on the west side of the Makran accretionary prism and Jaz Murian depression, and is bounded by two major fault systems. The principal rock units of this complex are a gabbro sequence which includes low- and high-level gabbros, an extensive sheeted diabase dike sequence, late intrusive rocks which consist largely of trondhjemites and diorites, and volcanic rocks which are largely pillow basalts interbedded with pelagic sedimentary rocks, including radiolarian chert. Chondrite- and primitive-mantle-normalized incompatible trace element data and age-corrected Nd, Pb, and Sr isotopic data indicate that the Band-e-Zeyarat/Dar Anar ophiolite was derived from a midocean ridge basalt-like mantle source. The isotopic data also reveal that the source for basalts was Indian-Ocean-type mantle. Based on the rare earth element (REE) data and small isotopic range, all the rocks from the Band-e-Zeyarat/Dar Anar ophiolite are cogenetic and were derived by fractionation from melts with a composition similar to average E-MORB; fractionation was controlled by the removal of clinopyroxene, hornblende and plagioclase. Three ⁴⁰Ar–³⁹Ar plateau ages of 140.7±2.2, 142.9±3.5 and 141.7±1.0 Ma, and five previously published K–Ar ages ranging from 121±4 to 146±5 Ma for the hornblende gabbros suggest that rocks from this ophiolite were formed during the Late Jurassic–Early Cretaceous. Plate reconstructions suggest that the rocks of this complex appear to be approximately contemporaneous with the Masirah ophiolite which has crystallization age of (150 Ma). Like Masirah, the rocks from the Band-e-Zeyarat/Dar Anar ophiolite complex represent southern Tethyan ocean crust that was formed distinctly earlier than crust preserved in the 90–100 Ma Bitlis-Zagros ophiolites (including the Samail ophiolite).     

Structural variations in derivatives of the bacteriochlorophylls of Chlorobiaceae: impact of stratigraphic resolution on depth profiles as revealed by methanolysis

Bacteriochlorophylls c and d, recovered from two sedimentary sequences, were converted to bacteriophaeophorbide methyl esters by methanolysis and analysed by atmospheric pressure chemical ionisation liquid chromatography-multistage mass spectrometry (APCI LC-MSⁿ). The distributions in both settings, a moderately consolidated sediment from Kirisjes Pond, Antarctica, and in a finely laminated microbial mat from Les Salines de la Trinitat, Spain, show significant variations within a narrow depth interval. The overall bacteriophaeophorbide c to d ratios in the two sediments are different, as are the ratios of particular C-3¹ diastereoisomers, indicating distinct differences between the bacterial communities that contributed to each sediment. Furthermore, a shift towards more extensive alkylation in homologues within each sediment is consistent either with changing environmental conditions in the depositional environments, or development-related changes in the structure of the bacterial community, leading to increased competition for light or nutrients.     

Geochronology of anthropogenic pollutants in riparian wetland sediments of the Lippe River (Germany)

Anthropogenic pollutants were determined in a dated sediment core, collected from a riparian wetland of the Lippe River (Ruhr district, Germany). The historical trend in heavy metals, polycyclic aromatic hydrocarbons, organochlorines, polychlorinated biphenyls and linear alkylbenzenes as well as more recent contaminants such as industrial additives, organotins, synthetic musks, methyltriclosan and some other compounds were determined for the time period between 1930 and 1986. Emission sources, information on technical production and usage, as well as on the individual pollution pathways, with appropriate environmental stability, were considered in the interpretation of the sediment contamination over the past 50 years.Contaminants were analysed and interpreted according to two different criteria: (a) the origin of the main contaminants as related to mining and industrial activities as well as municipal sewage and agricultural effluents and (b) the pollution history. Due to a significant appearance of formerly missing contaminants in sediments deposited since 1970, we suggest classifying contaminants as either common (predating 1970) or modern (postdating 1970).In summary, the study provided a comprehensive reconstruction of the pollution history of the Lippe River system.     

Pollution history and recovery of a boreal lake exposed to a heavy bleached pulping effluent load

We examined the effects of heavy pulp mill discharges on the Lake Lievestuoreenjärvi ecosystem and the later recovery of diatom and chironomid communities from age-dated short core samples. Beginning in 1927 the lake received a heavy effluent load from a sulphite pulp mill. Except for the recession during the Second World War and the temporary closure of the mill from 1967 to 1971, the industrial load, containing large quantities of nutrients, organic matter and toxic compounds, increased continuously. In the early 1980s, laboratory documents were falsified by the directors of the mill and the systematic illegal effluent overload led to a collapse of the whole lake ecosystem. In 1985, the outdated plant was finally closed down. Based on the assessment of chemical properties and biological remains of the sediment, we distinguished five developmental phases in the ecological state of the lake. In the pre-industrial phase, the pelagic and profundal benthic communities were dominated by species preferring ultraoligotrophic or oligotrophic lakes. Concomitant with the increasing discharge and deposition of chlorine compounds, resin acids, and mercury, as well as strong acidity and hypolimnetic and epilimnetic anoxia, the ecological status changed in a short period from excellent to bad. Finally, in the early 1960s, the majority of the lake was virtually dead and the aquatic life survived only in the uppermost littoral zone. Since 1985, a fast recovery in the water quality has led to a strong, but temporary eutrophy in pelagic communities. The main peak of eutrophication was caused by the invasion of a species new to the lake,Aulacoseira granulata var.angustissima. Later, the pelagic communities shifted towards oligotrophy, but the original, pre-industrial status has not been re-established. The profundal benthic communities have not achieved the pre-industrial structure, but at present indicate mesotrophy.     

Rainfall thresholds for landsliding in the Himalayas of Nepal

Landsliding of the hillslope regolith is an important source of sediment to the fluvial network in the unglaciated portions of the Himalayas of Nepal. These landslides can produce abrupt increases of up to three orders of magnitude in the fluvial sediment load in less than a day. An analysis of 3 years of daily sediment load and daily rainfall data defines a relationship between monsoonal rainfall and the triggering of landslides in the Annapurna region of Nepal. Two distinct rainfall thresholds, a seasonal accumulation and a daily total, must be overcome before landslides are initiated. To explore the geomorphological controls on these thresholds, we develop a slope stability model, driven by daily rainfall data, which accounts for changes in regolith moisture. The pattern of rainfall thresholds predicted by the model is similar to the field data, including the decrease in the daily rainfall threshold as the seasonal rainfall accumulation increases. Results from the model suggest that, for a given hillslope, regolith thickness determines the seasonal rainfall necessary for failure, whereas slope angle controls the daily rainfall required for failure.     

Apparent and real bias in numerical transfer functions in palaeolimnology

We present an evaluation of the procedure by which model prediction bias is examined in palaeolimnological transfer function inference models. We argue that most of the prediction biases commonly reported in the literature are, in fact, fallacious, and are the artificial consequence of the inappropriate manner in which residuals are traditionally examined. We show that the extent of the specious model bias is entirely predictable from first principles and is essentially determined by the strength of the predictive model. We suggest that the analysis of residuals should always be examined as a function of the model's predictions and we discuss the implications of the old and new approaches.