A novel ATR‐FTIR technique for identifying colloid composition in natural waters

Although understanding colloid composition has been frequently cited as essential to predicting contaminant transport in natural waters, most current methods to collect and identify colloid composition chemically alter the colloids prior to analysis and fail to identify colloid mineralogy and organic components. This paper presents a new, low‐cost method employing attenuated total reflection Fourier transform infrared spectroscopy (ATR‐FTIR) to identify colloids including organic material in concentrated suspensions. The concentration method employing tangential ultrafiltration at a steady temperature prevents redistribution of dissolved phase and suspended sediments into the colloidal fraction through post‐sampling reactions. ATR‐FTIR allows for direct analysis of concentrated suspensions rather than requiring drying that may alter composition in the colloidal phase, for example, by precipitating carbonates in samples from karst waters. The ability of this technique to monitor variation in colloidal composition is demonstrated through the examination of colloids under two different flow conditions in a karst aquifer and the West Branch of the Susquehanna River in Central Pennsylvania. Copyright © 2014 John Wiley & Sons, Ltd.     

Sulfur and iron speciation in surface sediments along the northwestern margin of the Black Sea

The speciation of sedimentary sulfur (pyrite, acid volatile sulfides (AVS), S⁰, H₂S, and sulfate) was analyzed in surface sediments recovered at different water depths from the northwestern margin of the Black Sea. Additionally, dissolved and dithionite-extractable iron were quantified, and the sulfur isotope ratios in pyrite were measured. Sulfur and iron cycling in surface sediments of the northwestern part of the Black Sea is largely influenced by (1) organic matter supply to the sediment, (2) availability of reactive iron compounds and (3) oxygen concentrations in the bottom waters. Biologically active, accumulating sediments just in front of the river deltas were characterized by high AVS contents and a fast depletion of sulfate concentration with depth, most likely due to high sulfate reduction rates (SRR). The δ³⁴S values of pyrite in these sediments were relatively heavy (−8‰ to −21‰ vs. V-CDT). On the central shelf, where benthic mineralization rates are lower, re-oxidation processes may become more important and result in pyrite extremely depleted in δ³⁴S (−39‰ to −46‰ vs. V-CDT). A high variability in δ³⁴S values of pyrite in sediments from the shelf-edge (−6‰ to −46‰ vs. V-CDT) reflects characteristic fluctuations in the oxygen concentrations of bottom waters or varying sediment accumulation rates. During periods of oxic conditions or low sediment accumulation rates, re-oxidation processes became important resulting in low AVS concentrations and light δ³⁴S values. Anoxic conditions in the bottom waters overlying shelf-edge sediments or periods of high accumulation rates are reflected in enhanced AVS contents and heavier sulfur isotope values. The sulfur and iron contents and the light and uniform pyrite isotopic composition (−37‰ to −39‰ vs. V-CDT) of sediments in the permanently anoxic deep sea (1494 m water depth) reflect the formation of pyrite in the upper part of the sulfidic water column and the anoxic surface sediment. The present study demonstrates that pyrite, which is extremely depleted in ³⁴S, can be found in the Black Sea surface sediments that are positioned both above and below the chemocline, despite differences in biogeochemical and microbial controlling factors.     

The European level in EU governance: territory, authority and trans-scalar networks

This article offers an analysis of the emerging scalar configuration of the governance of the European Union. It discusses how European integration stands for a move from a collection of territorially homogenous systems of rule towards a new assemblage of territories, authorities and rights. The paper first questions the stretchy territoriality of the seemingly obvious European level. Second it analyses the sectoral differences in the evolution of the width and the depth of integration, measured as the transfer of competencies to the EU level between the Rome Treaty (1958) and the Lisbon Treaty (200y). Third it turns to the day-to-day decision-making to assess the relations between players in EU governance and finally it looks more closely at the administrative wheels of the EU machinery.     

Albian-Paleocene flora of the north pacific: Systematic composition, palaeofloristics and phytostratigraphy

Principal attention is focused on phytostratigraphy and comparative palaeofloristics of the Anadyr-Koryak (AKSR) and Northern Alaska (NASR) subregions of the North Pacific Region. The high-resolution Upper Albian-Paleocene phytostratigraphic schemes of these subregions are based on perceived stages of their floral evolution. In the AKSR the scheme includes seven subdivisions of subregional extent: the Early Ginter (upper Albian), Grebenka (upper Albian-Cenomanian-lower Turonian), Penzhina (upper Turonian), Kaivayam (Coniacian), Barykov (Santonian-lower to ?middle Campanian), Gornorechenian (?upper Campanian-lower Maastrichtian), and Koryak (lower to upper Maastrichtian-?Danian) phytostratigraphic horizons. The phytostratigraphic scheme of the NASR includes three subregional phytostratigraphic horizons and five plant-bearing beds. These are the Kukpowruk (?lower to middle-?upper Albian), Niakogon (upper Albian-Cenomanian), Kaolak (Turonian) horizons and beds with the Tuluvak (Coniacian), Early Kogosukruk (upper Santonian-Campanian), Late Kogosukruk (Campanian-Maastrichtian), Early Sagwon (Danian-Selandian), and Late Sagwon (Selandian-Thanetian) floras. The comparative analysis of coeval (or close in age) floras distinguished in the AKSR and NASR shows that they are either similar to each other (floras Early Ginter and Kukpowruk, Grebenka and Niakogon, Penzhina and Kaolak, Koryak and Early Sagwon) or different in systematic composition (floras Kaivayam and Tuluvak, Gornorechenian and Kogosukruk). Similarities between the floras imply that plant assemblages of two subregions evolved under comparable climatic conditions and freely intercommunicated via the Bering Land Bridge during the Albian-Turonian and terminal Maastrichtian-Paleocene. Floras of the AKSR and NASR, which are of different composition, existed in particular intervals of geological history when trans-Beringian plant migrations were limited or even ceased because of palaeoclimatic difference between the subregions. Floras of the AKSR and NASR survived crisis at the Cretaceous-Paleogene boundary without essential evolutionary consequence which does not support a hypothesis of a global ecological crisis at this boundary. From the analysis of the Arctic end-Cretaceous flora and palaeoclimate we conclude that the large Northern Alaskan dinosaurs were driven by lack of resources (food and shelter) to migrate 1200–1300 kilometres to the South to find forage, warmer temperatures and better light conditions before winter set in. A scenario of the Albian-Late Cretaceous florogenesis in the North Pacific Region is proposed. A primary driver of Albian-Late Cretaceous florogenesis was the gradual invasion by novel angiosperm-rich plant communities into the Asiatic continental interiors and a replacement of pre-existing vegetation dominated by ancient ferns and gymnosperms. Plant fossils representing Mesophytic and Cenophytic communities usually do not mix in the individual assemblages.     

Long-term ferry-ADCP observations of tidal currents in the Marsdiep inlet

A unique, five-year long data set of ferry-mounted ADCP measurements in the Marsdiep inlet, the Netherlands, obtained between 1998 and 2003, is presented. A least-squares harmonic analysis was applied to the water transport, (depth-averaged) currents, and water level to study the contribution of the tides. With 144 tidal constituents, maximally 98% of the variance in the water transport and streamwise currents is explained by the tides, whereas for the stream-normal currents this is maximally 50%. The most important constituent is the semi-diurnal M₂ constituent, which is modulated by the second-largest S₂ constituent (about 27% of M₂). Compound and overtides, such as 2MS₂, 2MN₂, M₄, and M₆, are important in the inlet. Due to interaction of M₂ with its quarter-diurnal overtide M₄, the tidal asymmetry in the southern two thirds of the inlet is flood dominant. The amplitudes of all non-astronomic constituents are largest during spring tides, strongly distorting the water level and velocity curves. The M₂ water transport is 40° ahead in phase compared to the M₂ water level, reflecting the progressive character of the tidal wave in the inlet. The currents are strongly rectilinear and they are sheared vertically and horizontally, with the highest currents at the surface above the deepest part of the inlet. During spring tides, near-surface currents can be as large as 1.8 m s^− 1. Due to the relative importance of inertia compared to friction, the M₂ currents near the centre (surface) lag maximal 20° (3°) in phase with the currents near the sides (bottom). The tidal-mean currents are directed into the basin in the shallower channel to the south and out of the basin in the deeper channel to the north.     

Late cretaceous Arman’ flora of Magadan oblast: Paleoclimatic interpretation

The Arman’ flora belongs to the formation of the same name in the Arman’ River basin and Nel’khandzha-Khasyn interfluve. It includes about 80 fossil plant species. The similarity of this flora to the reliably dated fossil floras of northwestern Kamchatka and the Pekul’nei Range dates it to being Turonian and Coniacian in age, which is corroborated by isotopic (U-Pb and ⁴⁰Ar/³⁹Ar) dating of the plant-bearing layers. The CLAMP method is used to estimate quantitative climatic variables, according to which the Arman’ flora existed in a temperate humid climate with warm summers and mild winters. This climate is especially similar to the conditions reconstructed from fossil plants of the Turonian Penzhina flora and the Coniacian Kaivayam and Tylpegyrgynai floras of Northeast Asia.