The S-External pyrenees of Huesca

An Upper Cretaceous-Paleocene series is more or less detached from the Hercynian basement and piled up southward as a Younger Calcareous Chain. A broad belt of Eocene flysch with limestone intercalations terminates eastward against a contemporaneous cross-structure and is affected by a zone of persistent overturning.

---

Zusammenfassung Eine Oberkreide-PalÄozÄn-Serie ist teilweise vom herzynischen Untergrund abgeschert und südwÄrts als Jüngere Kalkkette aufgestaucht. Eine breite Zone von EozÄn-Flysch mit Kalkeinlagerungen endet nach Osten an einer gleichaltrigen Querstruktur. Sie enthÄlt einen durchgehend überkippten Streifen.

---

Résumé La série néocrétacée-paléocène est plus ou moins décollée du socle hercynien et déversée au sud comme «ChaÎne calcaire postérieure». Une large zone de flysch éocène à intercalations calcaires se termine vers l'est contre un accident transversal contemporain et est affectée d'une bande persistante de renversement.

---

. . . .

     

Aeration,nitrogen and salinity as determinants of Spartina alterniflora Loisel. Growth response

A greenhouse experiment was conducted to examine the effects of salinity, nitrogen, and aeration on the growth of Spartina alterniflora Loisel. The experiment was conducted in a factorial arrangement of treatments with salt marsh substrate at three salinity levels (15, 30, 45‰), at two nitrogen levels (0 and 168 kg/ha) and at two aeration levels (zero and oxygen saturation). The maximum biomass was found in the low salinity, nitrogen enhanced, aerated treatment which had 11 times more biomass than the highest (45‰) salinity, nitrogen poor, unaerated treatment. the average effect of nitrogen over the three salinity levels was a 2.01, 1.47, 1.25, and 1.52 times increase in aerial biomass, density, height, and belowground biomass of the plants, respectively. The main effect of aeration was a 2.49, 2.01, 1.57, and 1.85 times increase in the same variables. The combination effect of aeration and nitrogen additions enhanced biomass by 453%. An increase in salinity from 15‰ to 45‰ decreased biomass, density, height and belowground biomass of S. alterniflora by 66, 53, 38, and 61%, respectively. The effect of salinity was more pronounced between 30 and 45‰ than it was between 15 and 30‰. N, P, K, Ca, Mg, Na, Fe, Mn, Zn, Cu, and S concentrations in the aerial living biomass were also examined. There was no evidence to suggest that elemental concentrations (on a per gram basis) were consistently correlated with increased or decreased growth. In relation to salinity, correlations between growth and elemental concentrations were negative while for nitrogen enhanced and/or aerated systems, the correlations were positive.     

Reduction of inorganic compounds in autoclaves by using suspended cellulose

Autoclaves are closed vessels in which liquids can be heated above their ‘normal' boiling points. As a consequence the pressure will rise. This equipment has permitted a variety of processes like the syntheses of organics and the leaching of metal ores. Pressure technologies can be used for accelerating reactions, for specific syntheses or they offer an environmental or economical alternative for existing processes. Wet pressure oxidation of sewage sludge, an organic waste product, has become a proven technology. If less oxygen is added than stoichiometrically required for a complete oxidation, cellulose will break down by a different reaction mechanism, releasing electrons. Under these circumstances reduction of inorganic compounds is possible.     

Water release patterns of heated speleothem calcite and hydrogen isotope composition of fluid inclusions

Speleothem fluid inclusions are a potential paleo-precipitation proxy to reconstruct past rainwater isotopic composition (δ¹⁸O, δD). To get a better insight in the extraction of inclusion water from heated speleothem calcite, we monitored the water released from crushed and uncrushed speleothem calcite, heated to 900 °C at a rate of 300 °C/h, with a quadrupole mass spectrometer. Crushed calcite released water in three not well individualised peaks between 25 and 360 °C, 360 and 650 °C and between 650 and 800 °C while uncrushed calcite released water in two distinct temperature intervals: between 25 and 550 °C and between 550 and 900 °C.Water from two speleothems from the Han-sur-Lesse cave was recovered using three different techniques: i) the crushing and heating to 360 °C technique, ii) the decrepitation by heating to 550 °C and iii) the decomposition by heating to 900 °C technique. Measurements of the δD of water recovered by the decomposition of Han-sur-Lesse calcite heated to 900 °C did not show a 20 to 30‰ offset as found by previous authors. However a difference of 7‰ was observed between water released before and after decomposition of the calcite. Water recovery from the Han-sur-Lesse samples suggests that a simple heating technique (up to 550 °C) without crushing could both (a) recover water with δD representative of that of the drip water and (b) double the water yield as compared to the crushing and heating method.Our study warns for possible contamination of the recovered inclusion water with hydration water of lime, responsible for the recovery of water with very negative δD values.     

Iron-hydroxide clogging of public supply wells receiving artificial recharge: near-well and in-well hydrological and hydrochemical observations

Clogging of water wells by iron-hydroxide incrustations due to mixing of anoxic and oxic groundwater is a common well-ageing problem. The relation between well operation (on and off), the spatial and temporal variations in hydrochemistry outside and inside a supply well, and the distribution of clogging iron-hydroxides were studied in an artificial recharge well field in the Netherlands. Camera inspection, high-resolution multi-level water sampling outside the well and detailed in-well pH/EC/O₂ profiles revealed remarkable patterns. During pumping, the top of the upper well screen abstracted oxic filtrate, although the larger part of the in-well water column was anoxic. The column rapidly turned oxic after shutdown due to a downward short-circuiting of oxic water via the well. Within 15 d it became anoxic due to the slow advance of anoxic lake filtrate created by local changes in flow direction as the neighboring wells continued to pump. Severe clogging occurred where the oxic filtrate entered the well, while half-clogging of the upper well screen occurred due to less inflow of oxic filtrate on the lake side. Transport of iron flocs and bacterial slimes after shutdown seemed to clog the lower part of the well screen. Frequent on/off switching should be avoided in iron-clogged wells.     

Fluid inclusion and cathodoluminescence studies on fluorite from the Kerio valley, Kenya

The Kerio valley lies between the Elgeyo escarpment and the Tugen hills which mark the western margin of the Kenya rift valley. The main fluorite deposits are located in the southern part of the valley at Kimwarer, Choff and Kamnaon.Three types of inclusion fillings were identified: Liquid+Vapour, Liquid+Daughter Minerals and Liquid. The L+V type is dominant. Inclusions occur as clusters, trails along the crystal growth zones and as isolated ones. Low salinities, apparently lower than the 5% wt. NaCl equivalent, were established. Homogenization temperatures suggest that fluorite mineralization took place at different stages and at temperatures between 120 and 180 °C. Isolated readings above 180°C may be referring to the original inclusions in limestone. These measurements and the absence of CO₂ in the inclusions, as well as the occurrence of vugs and crustifications with fluorite, suggest that mineralization took place at relatively shallow depths.Emission spectrum lines representing Eu²⁺, Dy³⁺, Tb³⁺ and Sm³⁺ in fluorite were identified. Sm³⁺ was detected only in the pinkish luminescence of veined fluorite, whereas the pinkish zone in banded fluorite contains Tb³⁺. Eu²⁺ which gives the strongest emission lines in the blue part of the visible spectrum, apparently is responsible for the strong blue cathodoluminescence (CL) in fluorite. The dominance of Eu²⁺ peaks further points to the fact that fluorite mineralization in the Kerio valley took place in an environment that was enriched in Lanthanide Rare Earth Elements (LREE). The presence of rare earths and radioactive elements in fluorite points towards their enrichment in the environment of fluorite mineralization. A juvenile origin of mineral forming solutions is proposed.Two generations of fluorite were established: allotriomorphic fluorite, forming the matrix, and the idiomorphic variety, occurring either in barite or in druzes in early fluorite. Barite in turn forms idiomorphic crystals in allotriomorphic fluorite. Relics of calcite occur in both K-feldspars and in early fluorite. Oxides and hydroxides of Fe, Mn, Ti and Al commonly occur in open spaces in fluorite. Of significance is the presence of gold in fluorite. Fluorite mineralization is of hydrothermal origin in the post-Miocene era and was formed as a result of metasomatic replacement of marble and open space fillings.     

Geochemical and electron paramagnetic characteristics of quartz from a multi-stage vein environment, Cowarra gold deposit, New South Wales

The characterisation of quartz using trace element geochemistry and electron paramagnetic resonance measurements has been tested for different generations of quartz veining in the multi-stage hydrothermal vein system at Cowarra. Quartz closely associated with gold mineralisation can be distinguished from earlier and later quartz generations in the mineralised environment, and both types can be distinguished from regional, barren quartz veins. These separate stages of quartz veins are also recognised from their fluid inclusion characteristics. Geochemical differences in the quartz partly reflect the presence of minor mineral inclusions, particularly sulfides and arsenopyrite.The study highlights the importance of understanding the paragenetic sequence of quartz vein development in a mineralised environment and the need for careful, thorough sampling before attempting geochemical and EPR characterisation of quartz as an exploration technique.     

Burial of redox-sensitive metals and organic matter in the equatorial Indian Ocean linked to precession

Authigenic metals (uranium, cadmium, and molybdenum), organic carbon (OC) and total C₃₇ alkenone (totC₃₇) concentrations were measured for the last 350 kyr in core MD900963, located in the eastern equatorial Arabian Sea. Authigenic metal concentrations on a carbonate-free basis range between 1 and 17 ppm, 0.5 and 6 ppm, and 0.5 and 4 ppm for U, Cd, and Mo, respectively. The profiles are characterized by well-defined 23 kyr cycles between oxic and mildly suboxic conditions. The redox-sensitive metal profiles also follow variations in the concentrations of OC (0.2-0.9%) and alkenones (0.2-6.7 ppm). The coupled variations in inorganic and organic constituents are attributed to a 23-kyr cycle in primary production above site MD900963, as suggested by clear correlations with independent micropaleontologic proxies (primary productivity indices based on foraminifera and coccoliths and fragmentation of foraminiferal shells). The 23-kyr cycles do appear to be primarily driven by productivity rather than changes in bottom water oxygen. Comparison with other records indicates that if this interpretation is correct, productivity variations across much of the Indian Ocean have been dominated by precessional forcing, with high productivity in phase with low summer insolation in the Northern Hemisphere. This interpretation contrasts with the traditional attribution of enhanced productivity in the Indian Ocean with periods of high summer insolation.     

Evidence for compressionally induced high subsidence rates in the Kurile Basin (Okhotsk Sea)

A combined volcanological, geochemical, paleo-oceanological, geochronological and geophysical study was undertaken on the Kurile Basin, in order to constrain the origin and evolution of this basin. Very high rates of subsidence were determined for the northeastern floor and margin of the Kurile Basin. Dredged volcanic samples from the Geophysicist Seamount, which were formed under subaerial or shallow water conditions but are presently located at depths in excess of 2300 m, were dated at 0.84±0.06 and 1.07±0.04 Ma with the laser ⁴⁰Ar/³⁹Ar single crystal method, yielding a minimum average subsidence rate of 1.6 mm/year for the northeast basin floor in the Quaternary. Trace element and Sr–Nd–Pb isotope data from the volcanic rocks show evidence for contamination within lower continental crust and/or the subcontinental lithospheric mantle, indicating that the basement presently at 6-km depth is likely to represent thinned continental crust. Average subsidence rates of 0.5–2.0 mm/year were estimated for the northeastern slope of the Kurile Basin during the Pliocene and Quaternary through the determination of the age and paleo-environment (depth) of formation of sediments from a canyon wall. Taken together, the data from the northeastern part of the Kurile Basin indicate that subsidence began in or prior to the Early Pliocene and that subsidence rates have increased in the Quaternary. Similar rates of subsidence have been obtained from published studies on the Sakhalin Shelf and Slope and from volcanoes in the rear of the Kurile Arc. The recent stress field of the Kurile Basin is inferred from the analysis of seismic activity, focal mechanism solutions and from the structure of the sedimentary cover and of the Alaid back-arc volcano. Integration of these results suggests that compression is responsible for the rapid subsidence of the Kurile Basin and that subsidence may be an important step in the transition from basin formation to its destruction. The compression of the Kurile Basin results from squeezing of the Okhotsk Plate between four major plates: the Pacific, North American, Eurasian and Amur. We predict that continued compression could lead to subduction of the Kurile Basin floor beneath Hokkaido and the Kurile Arc in the future and thus to basin closure.     

Nanoparticles in natural systems II: The natural oxide fraction at interaction with natural organic matter and phosphate

Information on the particle size and reactive surface area of natural samples and its interaction with natural organic matter (NOM) is essential for the understanding bioavailability, toxicity, and transport of elements in the natural environment. In part I of this series (Hiemstra et al., 2010), a method is presented that allows the determination of the effective reactive surface area (A, m²/g soil) of the oxide particles of natural samples which uses a native probe ion (phosphate) and a model oxide (goethite) as proxy. In soils, the natural oxide particles are generally embedded in a matrix of natural organic matter (NOM) and this will affect the ion binding properties of the oxide fraction. A remarkably high variation in the natural phosphate loading of the oxide surfaces (Γ, μmol/m²) is observed in our soils and the present paper shows that it is due to surface complexation of NOM, acting as a competitor via site competition and electrostatic interaction. The competitive interaction of NOM can be described with the charge distribution (CD) model by defining a ≡NOM surface species. The interfacial charge distribution of this ≡NOM surface species can be rationalized based on calculations done with an evolved surface complexation model, known as the ligand and charge distribution (LCD) model. An adequate choice is the presence of a charge of −1 v.u. at the 1-plane and −0.5 v.u. at the 2-plane of the electrical double layer used (Extended Stern layer model).The effective interfacial NOM adsorption can be quantified by comparing the experimental phosphate concentration, measured under standardized field conditions (e.g. 0.01 M CaCl₂), with a prediction that uses the experimentally derived surface area (A) and the reversibly bound phosphate loading (Γ, μmol/m²) of the sample (part I) as input in the CD model. Ignoring the competitive action of adsorbed NOM leads to a severe under-prediction of the phosphate concentration by a factor ∼10 to 1000. The calculated effective loading of NOM is low at a high phosphate loading (Γ) and vice versa, showing the mutual competition of both constituents. Both constituents in combination usually dominate the surface loading of natural oxide fraction of samples and form the backbone in modeling the fate of other (minor) ions in the natural environment.Empirically, the effective NOM adsorption is found to correlate well to the organic carbon content (OC) of the samples. The effective NOM adsorption can also be linked to DOC. For this, a Non-Ideal Competitive adsorption (NICA) model is used. DOC is found to be a major explaining factor for the interfacial loading of NOM as well as phosphate. The empirical NOM-OC relation or the parameterized NICA model can be used as an alternative for estimating the effective NOM adsorption to be implemented in the CD model for calculation of the surface complexation of field samples. The biogeochemical impact of the NOM-PO₄ interaction is discussed.