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.     

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.     

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.     

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.     

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.     

Slope processes in the High Arctic: a 30‐year‐long record from Spitsbergen

Ten monitoring sites were established in 1986 near the Scottbreen and Renardbreen glaciers (Bellsund, Spitsbergen) in order to determine the rates of gelifluction on raised marine terraces and on talus cones, accumulation on talus cones, and movement of the protalus rampart. The measurements were performed in 1987, 2007 and 2016. The results obtained revealed a very slow rate of changes on the surface of the analysed area. During 30 years, only one out of 84 points where the gelifluction rate was measured was displaced by 15 cm down‐slope. The maximal annual and average gelifluction rates were calculated at 0.5 cm and 0.18 cm a^?1, respectively. Several measurement points did not change their position over the observation period. As shown by the observations, the gelifluction rate largely does not depend on slope inclination. Studies of talus cones allowed the level of cone increment to be determined as 314.3 kg of scree per square metre. Analysis of factors influencing the rate of mass movement allowed for correlation of the small‐scale gelifluction movement at the analysed sites with the general trends of climate warming. In this part of the Arctic, these trends are manifested by soil desiccation. It appears that slope processes depend on very local topoclimatic factors. Analysis of the obtained data with regard to palaeogeographical and climatic investigations suggests that the ice segregation forms on raised marine terraces developed during the last Holocene cooling, i.e. the Little Ice Age.     

Ionic surfactants adsorption on heterogeneous surfacesAdsorption de tensioactifs ioniques sur les surfaces hétérogènes

The adsorption of surfactants from aqueous solution is a phenomenon of major importance in applications ranging from ore flotation and paint technology to enhanced oil recovery. As this paper will illustrate, the process is very complex and of high scientific interest; its results can be extended to the retention of organic compounds (humic and fulvic acids, pollutants...) on solids in the biosphere. For a good understanding of the mechanisms involved in surfactants adsorption at the hydrophilic solid–aqueous solution interface, thermodynamic models have to take into account: (i) the physical chemistry of the surfactant in aqueous solution for choosing the appropriate reference phase, (ii) the surface heterogeneity of the adsorbing solid, (iii) the intensity of normal adsorbate–adsorbent bonds responsible for adsorption, (iv) the intensity of lateral bonds that favour the formation of surface aggregates through cooperative process and finally, (v) suitable theoretical models to describe adsorption phenomena. Once this has been achieved, two systems can be discussed: systems characterised by strong normal adsorbate–adsorbent bonds, currently used in ore flotation, which lead, in the case of heterogeneous surfaces, to the formation of lamellar aggregates at monolayer concentration and bilayer formation for higher concentrations. Systems characterised by weak normal adsorbate–adsorbent bonds, currently used in enhanced oil recovery and hydrocarbon (bio)remediation, which correspond to: (i) formation of globular micelles at the solid surface near the CMC when the temperature is higher than the Krafft point, (ii) formation of bilayered lamellar aggregates in the opposite case, (iii) three-dimensional condensation on substrate (T<T_Krafft) if the ionic surfactant interacts with cations in the bulk. To cite this article: J.-M. Cases et al., C. R. Geoscience 334 (2002) 675–688.     

Investigation of X-Ray Flares with Long Rising Phases

We have used Yohkoh and GOES X-ray observations to investigate flares with a long rising phase. We have found that a characteristic feature of such flares is a long time interval, Δ t ≥ 20 min, between the temperature maximum and the maximum of the emission measure. We have carried out detailed analysis for 10 limb flares of this type. Time variation of the heating function, E_H(t), has been determined for their loop-top X-ray kernels. The time variation of E_H(t), together with the temperature–density diagnostic diagrams, have been used to explain the large value of the time interval, Δ t. The main point is that for these flares the heating function E_H(t) decreases so slowly after the temperature maximum, that for the long time, Δ t, the energy flux reaching flare foot points is sufficient to maintain significant chromospheric evaporation. Investigation of the flare evolution in the temperature–density diagnostic diagrams allowed us to work out a new method of determination of the density for flare kernels. This method can be applied to all the kernels for which their altitudes can be estimated. The advantage of this method is that for the density determination it is not necessary to assume what is the extension of the emitting plasma along the line of sight.