Speciation of adsorbed yttrium and rare earth elements on oxide surfaces

The distribution of yttrium and the rare earth elements (YREE) between natural waters and oxide mineral surfaces depends on adsorption reactions, which in turn depend on the specific way in which YREE are coordinated to mineral surfaces. Recent X-ray studies have established that Y³⁺ is adsorbed to the rutile (1 1 0) surface as a distinctive tetranuclear species. However, the hydrolysis state of the adsorbed cation is not known from experiment. Previous surface complexation models of YREE adsorption have suggested two to four cation hydrolysis states coexisting on oxide surfaces. In the present study, we investigate the applicability of the X-ray results to rare earth elements and to several oxides in addition to rutile using the extended triple-layer surface complexation model. The reaction producing a hydrolyzed tetranuclear surface species

     

Second-order wave loading on a horizontal rectangular cylinder of substantial draught

Approximate first- and second-order analytical solutions of wave diffraction of a semi-submerged horizontal cylinder of rectangular cross-section are presented. The solutions are based on the assumption that the pressure in the fluid domain underneath the cylinder is linearly dependent on the horizontal space coordinate. Basically, this approach is valid when the clearance between the bottom of the cylinder and the sea bottom is small in comparison with the wave length and is recommended for a cylinder of substantial draught where due to the small clearance other methods are difficult to apply. Boundary conditions are satisfied by a choice of a proper form of the potential functions and by making use of the properties of matching conditions. Theoretical results reveal that the magnitude of the vertical second-order time-dependent loads could be significant and even exceed the corresponding first-order quantities. This phenomenon, which occurs even at moderate steepnesses, as well as the assumption of a linear pressure distribution, are confirmed by experiments performed in a wave tank.     

A Holocene high-resolution record of aquatic productivity,seasonal anoxia and meromixis from varved sediments of Lake Łazduny,North-Eastern Poland: insight from a novel multi-proxy approach

Anthropogenic eutrophication and spreading anoxia in freshwater systems is a global concern. Little is known about anoxia in earlier historic times under weaker human impact, or under prehistoric natural conditions with different trophic, land cover and climatic regimes. We use a novel approach that combines high-resolution hyperspectral imaging with µ-XRF and HPLC-pigment data, which allows us to assess chloropigments (productivity) and bacteriopigments (anoxia) at seasonal subvarve-scale resolution. Our ~9700 cal a bp varved sediment record from NE Poland suggests that productivity increased stepwise from oligotrophic Early Holocene conditions (until ~9200 cal a bp ) to mesotrophic conditions in the Mid- and Late Holocene. Natural eutrophication was mainly a function of progressing landscape evolution with intense weathering under dense forest and warm-moist climatic conditions. Generally, anoxia increased with increasing productivity. Seasonal anoxia and some multi-decadal periods of meromixis were the common mixing patterns throughout the Holocene except for a period of persisting meromixis between ~5200 and 2000 cal a bp. Anthropogenic deforestation around 400 cal a bp resulted in substantially better lake oxygenation despite high productivity. In this small lake, aquatic productivity and lakeshore forest cover (wind shield) were more important factors controlling oxic/anoxic conditions than Holocene temperature variability.     

Late Holocene environmental conditions in Coronation Gulf,southwestern Canadian Arctic Archipelago: evidence from dinoflagellate cysts,other non‐pollen palynomorphs,and pollen

Boxcore 99LSSL‐001 (68.095° N, 114.186° W; 211 m water depth) from Coronation Gulf represents the first decadal‐scale marine palynology and late Holocene sediment record for the southwestern part of the Northwest Passage. The record was studied for organic‐walled microfossils (dinoflagellate cysts, non‐pollen palynomorphs), pollen, terrestrial spores, and sediment characteristics. ²¹⁰Pb, ¹³⁷Cs, and three accelerator mass spectrometry ¹⁴C dates constrain the chronology. Three prominent palaeoenvironmental zones were identified. During the interval AD 1470–1680 (Zone I), the climate was warmer and wetter than at present, and environmental conditions were more favourable to biological activity and northward boreal forest migration, with reduced sea‐ice and a longer open‐water (growing) season. The interval AD 1680–1940 (Zone II) records sea‐ice increase, and generally cool, polar conditions during the Little Ice Age. During AD 1940–2000 (Zone III), organic microfossils indicate an extended open‐water season and decreased sea‐ice, with suggested amelioration surpassing that of Zone I. Although more marine studies are needed to place this record into an appropriate context, the succession from ameliorated (Zone I) to cooler, sea‐ice influenced conditions (Zone II) and finally to 20th‐century warming (Zone III) corresponds well with several terrestrial climatic records from the neighbouring mainland and Victoria Island, and with lower‐resolution marine records to the west. Copyright © 2011 John Wiley & Sons, Ltd.     

A reconstruction of the palaeohydrological conditions of a flood‐plain: a multi‐proxy study from the Grabia River valley mire,central Poland

This study investigated the Grabia River valley mire in central Poland to reconstruct its palaeoenvironmental conditions from the Younger Dryas to the present. We analysed sedimentological, biological and geochemical data from the palaeo‐oxbow lake and valley mire to identify the principal hydrological trends, especially episodes of high water level. During the Lateglacial and Holocene, the Grabia River had a meandering channel, and its hydraulic parameters and the channel dimensions changed in response to climatic oscillations and vegetation development. We identified phases of high flood intensity and high groundwater level that correlate with regional and supraregional climatic events. The frequency and timing of palaeohydroclimatic oscillations show strong similarities to records from other sites in Poland and the rest of Europe. We show that various analytical methods, namely, pollen, plant macrofossils, Cladocera, Chironomidae, sedimentological, geochemical and radiocarbon data, can be effective tools for reconstructing past hydroclimatic changes in palaeo‐oxbow lakes and investigating the effects of past climate changes on river environments. The high sensitivity of the biota, especially Cladocera, to changes in water level permits the reconstruction of palaeoecological changes, especially flood episodes that occurred in the river valley. In particular, the increase in the proportion of sediment‐associated Cladocera and pelagic taxa was closely correlated with floods. Through comparisons with the palaeobiological data, geochemical data allowed the identification of humid phases within the fen associated with a rising groundwater table, direct fluvial activity (floods) and alluvial deposition. We also discuss the limitations of palaeohydrological reconstructions based on these proxies, especially on fossil aquatic invertebrates.     

Root‐related rhodochrosite and concretionary siderite formation in oxygen‐deficient conditions induced by a ground‐water table rise

Sedimentological, mineralogical, stable carbon and oxygen isotope determinations and biomarker analyses were performed on siderite concretions occurring in terrestrial silts to understand their formation and to characterize the sedimentary and diagenetic conditions favouring their growth. High δ¹³C values (6·4‰ on average) indicate that siderite precipitated in an anoxic environment where bacterial methanogenesis operated. The development of anoxic conditions during shallow burial was induced by a change in sedimentary environment from flood plain to swamp, related to a rise of the ground‐water table. Large amounts of decaying plant debris led to efficient oxygen consumption within the pore‐water in the peat. Oxygen depletion, in combination with a decrease in sedimentation rate, promoted anoxic diagenetic conditions under the swamp and favoured abundant siderite precipitation. This shows how a change in sedimentary conditions can have a profound impact on the early‐diagenetic environment and carbonate authigenesis. The concretions contain numerous rhizoliths; they are cemented with calcium‐rhodochrosite, a feature which has not been reported before. The rhodochrosite cement has negative δ¹³C values (?16·5‰ on average) and precipitated in suboxic conditions due to microbial degradation of roots coupled to manganese reduction. The exceptional preservation of the epidermis/exodermis and xylem vessels of former root tissues indicates that the rhodochrosite formed shortly after the death of a root in water‐logged sediments. Rhodochrosite precipitated during the initial stages of concretionary growth in suboxic microenvironments within roots, while siderite cementation occurred simultaneously around them in anoxic conditions. These suboxic microenvironments developed because oxygen was transported from the overlying oxygenated soil into sediments saturated with anoxic water via roots acting as permeable conduits. This model explains how separate generations of carbonate cements having different mineralogy and isotopic compositions, which would conventionally be regarded as cements precipitated sequentially in different diagenetic zones during gradual burial, can form simultaneously in shallow burial settings where strong redox gradients exist around vertically oriented permeable root structures.     

Contrasting sources of Late Paleozoic rhyolite magma in the Polish Lowlands: evidence from U–Pb ages and Hf and O isotope composition in zircon

International Journal of Earth Sciences - The Polish Lowlands, located southwest of the Teisseyre–Tornquist Zone, within Trans-European Suture Zone, were affected by bimodal, but dominantly...     

Plant assemblage from Opole,southern Poland: New data on Late Cretaceous vegetation of the northern part of the European Province

This paper presents the results of studies on plant macroremains found in the upper Turonian of the Folwark Quarry, Opole, Poland, associated with palynological studies of the host rocks. In addition to a few macrofossils (gymnosperm wood, conifer Geinitzia reichenbachii and fern ?Didymosorus) rich sporomorphs (bryophyte, lycopod and fern spores, conifer and angiosperm pollen grains) and marine palynomorphs (mainly dinoflagellate cysts) were recorded. The palynological analysis revealed that the vegetation on the neighbouring land (the East Sudetic Island) in the late Turonian was much more diverse than could be reconstructed based on only macrofossil remains. The latter are taxonomically restricted and dominated by one gymnosperm species (Geinitzia reichenbachii), which make them similar to most neighbouring, coeval Central European assemblages. Its over representation is, thus, a result of taphonomy.     

Characterization of fluid inclusions from mineralized pegmatites of the Damara Belt,Namibia: insight into late-stage fluid evolution and implications for mineralization

Mineralogy and Petrology - Mineralized NYF and LCT pegmatites occur throughout the northeast-trending Neoproterozoic Damara Belt, Namibia. Mineralization in the pegmatites varies geographically,...