A generalized least-squares family of algorithms for transient dynamic analysis

By use of the generalized least-squares procedure, in conjunction with a finite element approximation in time, a simple three-time-level family of time integration schemes is derived. This results in fourth-order accurate unconditionally stable algorithms and stable eighth-order accurate non-dissipative algorithms. Numerical examples show the accuracy of the proposed schemes in comparison with the Fox-Goodwin formula and Newmark's average acceleration method.     

A Simplified, Accurate and Fast Method for Lithium Isotope Analysis of Rocks and Fluids, and δ7Li Values of Seawater and Rock Reference Materials

We report a new approach to conduct fast and accurate lithium isotope ratio measurements by MC-ICP mass spectrometry after wet chemical sample preparation. In contrast to most previously published methods our MC-ICP-MS set-up did not use a desolvating system to achieve appropriate ion beam intensities and, therefore, was less affected by matrix-induced shifts of the instrumental mass bias. As the total lithium background and build-up in the sample introduction system was low, previous sample residues could be washed out by an extended uptake of the new sample. Elimination of a nitric acid rinse step increased the sample throughput by a factor of two and allowed the instrumental mass bias drift to be tracked more precisely. δ⁷Li values of powdered silicate rock reference materials and seawater obtained in this study revealed good accuracy and an overall analytical uncertainty of typically 0.5‰ (2s). On the basis of a comparison between our lithium isotope data and compiled literature data, we recommend preliminary average δ⁷Li values for seawater (+30.8‰) and several silicate rock reference materials (BHVO-1: +5.0‰; JA-1: +5.6‰; JB-2: +4.8‰). The compilation of published δ⁷Li values for seawater suggests that the observed large lithium isotope differences are due to inter-method and/or interlaboratory bias. Most recently published δ⁷Li values for seawater show little variation and confirm a constant lithium isotope composition (at the sub ‰ level) of seawater in well mixed ocean basins.     

Ammonia Nitrogen at the Water–Sediment Interface in Puck Bay (Baltic Sea)

The magnitude of the exchange flux at the water–sediment interface was determined on the basis of the ammonia concentration gradient at the near-bottom water–interstitial interface and Fick's first law. It was established that in Puck Bay, ammonia almost always passes from the sediment to water. Ammonia flux varied from 5 to 1434 μmol NH₄-N m⁻² day⁻¹. In total,c. 138·2 tonneammonia year⁻¹pass from sediments of Internal Puck Bay to near-bottom water, the equivalent value for External Puck Bay being 686·9 tonne year⁻¹. In total, about 825 tonne ammonia year⁻¹passes from the sediment to near-bottom water of Puck Bay. In interstitial waters, ammonia occurred in concentrations varying over a wide range (3–1084 μmol NH₄-N dm⁻³).The basic factors affecting the magnitude of ammonia concentration in interstitial waters included: oxidation of organic matter, type of sediment, and inflow of fresh underground waters to the region examined.This paper involves preliminary studies only and constitutes a continuation of the studies on ionic macrocomponents and phosphorus in interstitial waters of Puck Bay undertaken previously.     

Zinc–germanium ores of the Tres Marias Mine,Chihuahua, Mexico

The Tres Marias carbonate-hosted Zn–Ge deposit in Chihuahua, Mexico contains sphalerite with the highest average Ge (960 ppm) and willemite with the highest reported Ge contents of Mississippi-Valley-type (MVT) deposits worldwide. This has prompted current exploration efforts to focus on the deposit as a high-grade source of germanium. The sulfide-rich ore type (>125,000 t at 20% Zn and 250 g/t Ge) contains Fe-rich botryoidal sphalerite (type I) associated with solid hydrocarbons. This type exhibits distinctive intimately intergrown lamellar texture of high-Fe sphalerite (average 9.9 wt.% Fe and 800 ppm Ge) and a somewhat less Fe-rich sphalerite phase (average 5.5 wt.% Fe and 470 ppm Ge). Reddish-brown banded sphalerite (type II, average 5.7 wt.% Fe and 1,320 ppm Ge) is subordinately followed by galena and pyrite. The sulfide-poor “oxidized” zinc ore (up to 50 wt.% Zn; 250 to 300 ppm Ge) is a fine-grained, often friable, alteration product of the sulfide ore and associated limestone and breccia host. While some areas are dominated by carbonates and sulfates, others are enriched in silicates such as hemimorphite and willemite. The gangue assemblage includes goethite, hematite, and amorphous silica or quartz. Minor wulfenite, greenockite, cinnabar, and descloizite also occur. Willemite occurs as interstitial replacement of sphalerite and fracture fillings in the oxidized ore and can be unusually rich in Pb (up to 2.0 wt.%) and Ge (up to 4,000 ppm). Oscillatory zonation reflects trace element incorporation into willemite from the oxidation of primary Ge-bearing sphalerite and galena by siliceous aqueous fluids. The Tres Marias deposit has hybrid characteristics consisting of a primary low-temperature MVT Ge-rich Zn–Pb sulfide ore body, overprinted by Ge-rich hemimorphite, willemite, and Fe oxide mineralization.     

The Younger Dryas climatic conditions in the Za Mnichem Valley (Polish High Tatra Mountains) based on exposure‐age dating and glacier‐climate modelling

Cosmogenic ³⁶Cl was measured in bedrock and moraine boulders in the Za Mnichem Valley (High Tatra Mountains). The post‐LGM deglaciation of the study area occurred about 15.9 ka ago. The northernmost part of the valley slopes was ice‐free around 15 ka ago. The terminal moraine on the valley threshold was finally stabilized 12.5 ka ago during the Younger Dryas cold event (Greenland Stadial 1). At that time, the Za Mnichem glacier was 1.3 km long and had an area of 0.57 km². The AAR equilibrium line of the glacier was located at 1990 m a.s.l., which corresponds to an ELA depression of ～500 m compared to today. The mean summer temperature was colder by 4°–4.5°C than the present‐day temperature. The mean annual temperature was colder by 6°C than today. Such conditions suggest a decrease of the annual precipitation by ～15–25% compared with the present‐day annual average. These data indicate a probable uniform temperature change across central and western Europe, with the precipitation being the most significant factor affecting the mass balance of mountain glaciers. The spatial distribution of balance data suggests increasing continentality towards the east during the Younger Dryas.     

Erythemal UV observations at Belsk,Poland, in the period 1976–2008: Data homogenization,climatology, and trends

Measurements of erythemal irradiance have been carried out continuously at Belsk since May 1975. We present a homogenization procedure of the UV time series for the period of 1976–2008. Long-term oscillations discovered in the homogenized data set agree with those extracted from the reconstructed UV data for all-sky and clear-sky conditions. The UV climatology was established and the UV variability was determined. Positive UV trends were found for the period of 1976-2008 in the annual mean (5.6±0.9% per decade), in the seasonal mean for the warm subperiod of the year (April–October, 5.5±1.0% per decade), and in monthly means (∼2–9% per decade). A satisfactory agreement between the trend extracted from the homogenized ground-based data and that found in satellite UV data for Belsk (1979–2008) supports the reliability of satellite trend analyses over wider areas during snowless periods.     

Fractionation of heavy metals in bottom sediments using Tessier procedure

The study presents the results of Cu, Pb, Zn, Mn and Fe determination in the samples of bottom sediments collected from the Oder and Warta rivers. The sequential extraction of metals in the samples of bottom sediments was performed after introducing the modification of the extraction scheme suggested by Tessier et al. (Anal Chem 51(7):844–851, 1979). The extraction times of particular stages were optimised. The fifth stage was altered by introducing the new methods of performing extraction. The samples of bottom sediments submitted the following granulometric analyses: dry, wet and wet with (HMP) dispersing reagent. Seven granulometric fractions with the following grain sizes were isolated: >2.0, 2.0–1.0, 1.0–0.5, 0.5–0.25, 0.25–0.1, 0.1–0.063 and <0.063 mm. The sequential extraction of particular granulometric fractions was performed. The concentration of metals variability was analysed depending on the method of sample preparation for the chemical analysis, granulometric fraction of sediments subjected to the analysis, extraction conditions and the site of samples collection. The lack of linearity between the metal concentration and the size of granulometric fraction was observed. The highest concentrations of metals were observed in fractions >2.0, 2.0–1.0 and 0.1–0.063 and <0.063 mm while the lowest concentrations occurred in fractions 1.0–0.5, 0.5–0.25, and 0.25–0.1 mm. The atomic absorption spectrometry with flame atomisation (F-AAS) was used for the determination of the investigated elements.     

Spatial distribution of phosphorus forms in sediments in the Gulf of Gdańsk (southern Baltic Sea)

The paper analyses the concentrations of total phosphorus and its forms in sediments from the Gulf of Gdańsk on the basis of studies conducted at 25 sampling sites in 2001–05. The phosphorus speciation analysis was performed by sequential extraction. The extensive spatial variability of P_tot concentrations and speciation was found to be dependent on the physicochemical properties of the sediments, the oxygen conditions in the water and sediments, and the depth of the water column above the sediment surface. In the coastal zone, the sedimentation of riverine suspended matter and the sorption and chemisorption processes exert a considerable influence on P speciation. Over 70% of variation of total phosphorus concentration in sediments in the Gulf of Gdańsk could be explained by changes of proportion of fine fraction of sediments (grain size <0.0625 mm). Maximum P_tot concentrations were recorded in clays and silts in the deep water, stratified part of the Gulf of Gdańsk. In the coastal zone, where sandy sediments are dominant, phosphorus concentrations were much lower; this was due to the considerable dynamics of the bottom water and intensive sea floor transport. P_tot concentrations in the Gulf of Gdańsk sediments ranged from 1.75 to 957.17 μmol g⁻¹ d.w. Of all the forms of phosphorus, the highest concentrations were found for organic phosphorus (Org-P). Of its inorganic forms, the highest concentrations were of phosphorus bound to clay minerals and aluminium oxides (NaOH-P), the lowest ones were of loosely bound phosphorus (NaCl-P). On the basis of determinations of total phosphorus concentrations in sediments of a given type and the available data on the seabed areas covered by particular sediment types in the Gulf of Gdańsk, the mass of total phosphorus in the surficial sediment layer (0–2 cm) was estimated at ca. 15.6×10³ tonnes.