Determination of indium in natural waters by flow injection inductively coupled plasma mass spectrometry

Two methods have been developed to measure indium (In) in natural waters by flow injection inductively coupled plasma mass spectrometry (ICPMS). One is the isotope dilution technique using an¹¹³In enriched spike and the other utilizes natural yttrium present in the sample as an internal standard. In the former, optimization of the¹¹³In spike to minimize error is often difficult for samples in which In concentrations are variable, whereas in the latter method, a separate determination of Y in the sample is necessary and hence more sample is required. Using about 1 liter of a water sample, 200 fold preconcentration of In was performed by solvent extraction and back extraction technique and then introduced into the ICPMS to measure the¹¹³In/¹¹⁵In or¹¹⁵In/⁸⁹Y ratios. The detection limits were 0.01–0.02 pmol kg⁻¹ for both methods. Application of the methods to seawater samples yielded the concentrations of 0.06–0.15 pmol kg⁻¹ for the Pacific and 0.6–1.5 pmol kg⁻¹ for the Atlantic. The large inter-oceanic variation of In best resembles that of Al amongst the 3B group of elements in the periodic table. River and estuarine samples gave a more variable range of concentrations of 0.01–15 pmol kg⁻¹. Most of the In supplied by rivers is removed by scavenging in the estuarine mixing zone, suggesting that the fluvial input of In to the ocean is small.     

Spatial variations of rare earth elements in north pacific surface water

The concentration of dissolved rare earth elements (REE) were determined at 47 stations in the North Pacific surface waters. Combining with other previous data, we present the surface REE distribution in the North Pacific and discuss the controlling factors. The surface concentrations increase toward the high latitude and continental margin (e.g. [Nd] > 10 pmol kg⁻¹) from the central North Pacific (e.g. [Nd] < 5 pmol kg⁻¹). The North Pacific Deep Water-normalized REE patterns are varied, indicating that two or more factors contribute to the REE distribution. We examined four factors making the regional variation of surface REE concentrations mainly; a) particle scavenging, b) atmospheric dust input, c) vertical mixing and d) lateral transport from the coastal region. Flux calculations for Nd showed that the influence of atmospheric dust was less significant than the vertical input even in the western upwelling zone. Moreover, the longitudinal and latitudinal transitions of surface REE seem to reflect the lateral supply from the coastal areas. We constructed the diagram of surface Er/Lu and Er/Yb molar ratios in order to assess the origin and the input processes of the surface REE. Both molar ratios showed increasing trend toward PEW (Er/Lu (>10.5) and Er/Yb (>1.4)) from PSUW (Er/Lu (>7) and Er/Yb (>1.2)). The high Er/Lu and Er/Yb ratios in PEW indicate that the lateral supply of terrestrial materials from the coastal area is possibly the important factor in PEW, because only weathering and dissolution of rocks can explain such high Er/Lu and Er/Yb ratios to our knowledge.     

Analysis of mechanical behaviour and internal stability of granular materials using discrete element method

Granular materials like sand are widely used in civil engineering. They are composed of different sizes of grains, which generate a complex behaviour, difficult to assess experimentally. Internal instability of a granular material is its inability to prevent the loss of its fine particles under flow effect. It is geometrically possible if the fine particles can migrate through the pores of the coarse soil matrix and results in a change in its mechanical properties. This paper uses the three‐dimensional Particle Flow Code (PFC3D/DEM) to study the stability/instability of granular materials and their mechanical behaviour after suffusion. Stability properties of widely graded materials are analysed by simulating the transport of smaller particles through the constrictions formed by the coarse particles under the effect of a downward flow with uniform pressure gradient. A sample made by an initially stable material according to the Kenney & Lau geometrical criterion was divided into five equal layers. The classification of these layers by this criterion before and after the test shows that even stable granular materials can lose fine particles and present local instability. The failure criterion of eroded samples, in which erosion is simulated by progressive removal of fine particles, evolves in an unexpected way. Internal friction angle increases with the initial porosity, the rate of lost fine particles and the average diameter D₅₀. Copyright © 2016 John Wiley & Sons, Ltd.     

A Compilation of Silicon and Thirty One Trace Elements Measured in the Natural River Water Reference Material SLRS-4 (NRC-CNRC)

The natural river water certified reference material SLRS-4 (NRC-CNRC, National Research Council-Conseil National de Recherches Canada) has been routinely analysed for major and trace elements by six French laboratories. Most measurements were made using inductively coupled plasma-mass spectrometry. For silicon and thirty one trace elements (rare earth elements, Ag, B, Br, Cs, Ga, Ge, Li, P, Pd, Rb, Se, Th, Ti, Tl, W, Y and Zr), no certified values are assigned by NRC-CNRC. We propose some compilation values and related uncertainties according to the results obtained by the different laboratories.     

Organic complexation of rare earth elements in natural waters: Evaluating model calculations from ultrafiltration data

The Stockholm Humic Model (SHM) and Humic Ion-Binding Models V and VI were compared for their ability to predict the role of dissolved organic matter (DOM) in the speciation of rare earth elements (REE) in natural waters. Unlike Models V and VI, SHM is part of a speciation code that also allows us to consider dissolution/precipitation, sorption/desorption and oxidation/reduction reactions. In this context, it is particularly interesting to test the performance of SHM. The REE specific equilibrium constants required by the speciation models were estimated using linear free-energy relationships (LFER) between the first hydrolysis constants and the stability constants for REE complexation with lactic and acetic acid. Three datasets were used for the purpose of comparison: (i) World Average River Water (Dissolved Organic Carbon (DOC) = 5 mg L⁻¹), previously investigated using Model V, was reinvestigated using SHM and Model VI; (ii) two natural organic-rich waters (DOC = 18-24 mg L⁻¹), whose REE speciation has already been determined with both Model V and ultrafiltration studies, were also reinvestigated using SHM and Model VI; finally, (iii) new ultrafiltration experiments were carried out on samples of circumneutral-pH (pH 6.2-7.1), organic-rich (DOC = 7-20 mg L⁻¹) groundwaters from the Kervidy-Naizin and Petit-Hermitage catchments, western France. The results were then compared with speciation predictions provided by Model VI and SHM, successively. When applied to World Average River Water, both Model VI and SHM yield comparable results, confirming the earlier finding that a large fraction of the dissolved REE in rivers occurs as organic complexes This implies that the two models are equally valid for calculating REE speciation in low-DOC waters at circumneutral-pH. The two models also successfully reproduced ultrafiltration results obtained for DOC-rich acidic groundwaters and river waters. By contrast, the two models yielded different results when compared to newly obtained ultrafiltration results for DOC-rich (DOC > 7 mg L⁻¹) groundwaters at circumneutral-pH, with Model VI predictions being closer to the ultrafiltration data than SHM. Sensitivity analysis indicates that the “active DOM parameter” (i.e., the proportion of DOC that can effectively complex with REE) is a key parameter for both Model VI and SHM. However, a survey of ultrafiltration results allows the “active DOM parameter” to be precisely determined for the newly ultrafiltered waters studied here. Thus, the observed discrepancy between SHM predictions and ultrafiltration results cannot be explained by the use of inappropriate “active DOM parameter” values in this model. Save this unexplained discrepancy, the results presented in this study demonstrate that both Model VI and SHM can provide reliable estimates of REE speciation in organic-rich waters. However, it is essential to know the proportion of DOM that can actively complex REE before running these two speciation models.     

A new tool for in situ monitoring of Fe-mobilization in soils

The aim of this study was to design and test a new tool for (i) the quantitative in situ monitoring of Fe(III) reduction in soils and (ii) the tracking of the potential mineralogical changes of Fe-oxides. The tool consists of small (2 × 2 × 0.2 cm) striated polymer plates coated with synthetic pure ferrihydrite or As-doped ferrihydrite (Fh–As). These slides were then inserted within two different horizons (organo-mineral and albic) located in a wetland soil with alternating redox conditions. Dissolution was quantified by X-ray fluorescence (XRF) analyses of total metal contents before and after insertion into the soil. The crystallographic evolution of Fe-oxides was characterized by scanning electron microscope equipped with an energy-dispersive spectrometer (SEM–EDS). Over the months, the ferrihydrite progressively disappeared, at rates comparable to those previously measured in laboratory studies, i.e. in the 1–10 × 10⁻¹² mol Fe m⁻² s⁻¹ range. SEM observations indicate that the supports were highly colonized by bacteria and biofilms in the organo-mineral horizon, suggesting a biological-mediated process, while the albic horizon appeared to be characterized by a mostly chemical-mediated process. In the albic horizon, Fe-sulphide and other micro-precipitates were formed after 7 months of incubation in balance with a quasi dissolution of initial Fe-oxides.     

Geological relationship between Anyui Metamorphic Complex and Samarka terrane,Far East Russia

The Anyui Metamorphic Complex (AMC) of Cretaceous age is composed of metachert, schist, gneiss, migmatite and ultramafic rocks, and forms a dome structure within the northernmost part of the Jurassic accretionary complex of the Samarka terrane. The two adjacent geological units are bounded by a fault, but the gradual changes of grain size and crystallinity index of quartz in chert and metachert of the Samarka terrane and the AMC, together with the gradual lithological change, indicate that at least parts of the AMC are metamorphic equivalents of the Samarka rocks. Radiolarian fossils from siliceous mudstone of the Samarka terrane indicates Tithonian age (uppermost Jurassic), and hence, form a slightly later accretion. This signifies that the accretionary complex in the study area is one of the youngest tectonostratigraphic units of the Samarka terrane. The relationship between the Samarka terrane and AMC, as well as their ages and lithologies, are similar to those of the Tamba–Mino–Ashio terrane and Ryoke Metamorphic Complex in southwest Japan. In both areas the lower (younger) part of the Jurassic accretionary complexes were intruded and metamorphosed by Late Cretaceous granitic magma. Crustal development of the Pacific‐type orogen has been achieved by the cycle of: (i) accretion of oceanic materials and turbidites derived from the continent; and (ii) granitic intrusion by the next subduction and accretion events, accompanied by formation of high T/P metamorphic complexes.