High‐Precision Fe and Mg Isotope Ratios of Silicate Reference Glasses Determined In Situ by Femtosecond LA‐MC‐ICP‐MS and by Solution Nebulisation MC‐ICP‐MS

In this study, a technique for high precision in situ Fe and Mg isotope determinations by femtosecond‐laser ablation‐multi collector‐ICP‐MS (fs‐LA‐MC‐ICP‐MS) was developed. This technique was employed to determine reference values for a series of common reference glasses that may be used for external standardisation of in situ Fe and Mg isotope determinations in silicates. The analysed glasses are part of the MPI‐DING and United States Geological Survey (USGS) reference glass series, consisting of basaltic (BIR‐1G, BCR‐2G, BHVO‐2G, KL2‐G, ML3B‐G) and komatiitic (GOR128‐G and GOR132‐G) compositions. Their Fe and Mg isotope compositions were determined by in situ fs‐LA‐MC‐ICP‐MS and by conventional solution nebulisation multi‐collector ICP‐MS. We determined δ⁵⁶Fe values for these glasses ranging between ‐0.04‰ and 0.10‰ (relative to IRMM‐014) and δ²⁶Mg values ranging between ‐0.40‰ and ‐0.15‰ (relative to DSM‐3). Our fs‐LA‐MC‐ICP‐MS results for both Fe and Mg isotope compositions agreed with solution nebulisation analyses within analytical uncertainties. Furthermore, the results of three USGS reference glasses (BIR‐1G, BHVO‐2G and BCR‐2G) agreed with previous results for powdered and dissolved aliquots of the same reference materials. Measurement reproducibilities of the in situ determinations of δ⁵⁶Fe and δ²⁶Mg values were usually better than 0.12‰ and 0.13‰ (2s), respectively. We further demonstrate that our technique is a suitable tool to resolve isotopic zoning in chemically‐zoned olivine crystals. It may be used for a variety of different applications on isotopically‐zoned minerals, e.g., in magmatic or metamorphic rocks or meteorites, to unravel their formation or cooling rates.     

Optimised Ferrozine Micro‐Method for the Determination of Ferrous and Ferric Iron in Rocks and Minerals

The ferrozine wet chemical method was optimised for the determination of the total iron content and speciation in small geological samples. The ferrozine micro‐method involves dissolution by a mixture of HF and H₂SO₄ followed by spectrophotometric analysis using the complexing agent ferrozine. The method was tested for twenty‐one replicates of eight rock RMs using test portions of 5–14 mg and containing 0.37–5.45 mg total Fe and more than 0.29 mg Fe(II). The optimised ferrozine method was accurate to within 0.23% m/m FeO and 0.34% m/m total Fe, which compares favourably to other wet chemical methods.     

Natural alteration products of sulphide mattes from primary lead smelting

The natural alteration products developed on mattes from lead metallurgy were determined: oxides and hydroxides (HFO, Cu(OH)₂), sulphates (thenardite, gypsum), hydroxysulphates (jarosite, beaverite, brochantite) and carbonates (cerussite, malachite, NaOH·2 PbCO₃). The large range of stability of newly formed phases confirms a significant variety of E_h–pH conditions of natural weathering of matte. Jarosite is stable at pH<3, but some hydroxides and carbonates typically form in neutral and alkaline environments. Consequently, the best dumping conditions for metallurgical mattes are difficult to determine. Such materials can have severe environmental effects and should be dumped in controlled waste-disposal sites. To cite this article: V. Ettler et al., C. R. Geoscience 335 (2003).     

Evolution of water quality in the abandoned iron mines of Lorraine: towards a semi-distributed modelling approach

In Lorraine, flooding of the iron mines leads to a degradation of groundwater quality. Based on a global approach, a numerical simulator has been built that can reproduce and predict the evolution of water quality at the overflow point of the mining basin. In order to specify the spatial distribution of these pollutant concentrations, a new model has been developed. The basin is represented as a network of homogeneous reservoirs. Although encouraging, the results show the need to specify the spatial organisation of water flow in order to reproduce the pollutant concentrations in the different monitored wells. To cite this article: P. Collon et al., C. R. Geoscience 337 (2005).     

Ion Microprobe Determination of Hydrogen Concentration and Isotopic ratio in Extraterrestrial Metallic Alloys

The isotopic ratio of hydrogen was measured in an iron meteorite and terrestrial native iron using an IMS 3f ion microprobe. The extraterrestrial D/H ratio (93 ± 9 × 10^?6) was close to the terrestrial value (105 ± 6 × 10^?6), and both samples had low H concentrations (7 ± 4 and 33 ± 11 ng g^?1 for the iron meteorite and the terrestrial sample, respectively). Experiments on artificially D‐enriched samples showed that the measured hydrogen signal is a combination of indigenous H and terrestrial atmospheric contamination. This contamination comes from the isotope exchange reaction between water adsorbed on the sample surface and atmospheric water, and would be continuously added to the indigenous H in the ion crater by the adsorbed water sinking into the crater during sputtering. Experiments showed that this contamination represents up to 20% of the signal but was within the uncertainty of the measured D/H ratio.     

Iron Isotope Variations in Coastal Seawater Determined by Multicollector ICP-MS

In this paper, we applied a reliable technique for measuring Fe isotope variations in coastal seawater at nanomolar levels. Iron was directly pre-concentrated from acidified seawater samples onto a nitrilotriacetic acid chelating resin and further purified using anion-exchange resin. Sample recovery, determined using a standard addition method, was essentially quantitative. Iron was then determined using a high-resolution multicollector ICP-MS (Neptune) coupled to an ApexQ desolvation introduction system. The external precision for δ⁵⁶Fe values was 0.11‰ (2s) when using total a Fe quantity between 25 and 100 ng. We initially applied this technique to measure the Fe isotope composition of dissolved Fe from several coastal environments in the north-eastern United States and we observed a range of δ⁵⁶Fe values between -0.9‰ and 0.1‰ relative to the IRMM-14 reference material. Iron isotope compositions of several reference water materials for inter-laboratory comparisons were also reported. Our results suggest that iron in coastal seawater, derived from benthic diagenesis and/or groundwater has negative Fe isotopic signatures that are distinct from other iron sources such as atmospheric deposition and rivers.     

Signification des ferruginisations des formations néoprotérozoı̈ques du Nord-Burkina Faso (Afrique de l'Ouest)Meaning of ironstones in the sedimentary Neoproterozoic formations of the northern Burkina Faso (western Africa)

There are many small ferruginous outcrops of different facies, often breccia-like, in the Neoproterozoic sedimentary formations in northern Burkina. These outcrops are made up of goethite and quartz, and are often along with high grades of various elements. It could be a question of gossans. Their large distribution in this part of the Taoudéni Basin offers it prospects as a province geochemically rich in Cu, Pb, Zn, Mo, As, Cd, Co... This basin would be a geochemical bin for ancient formations, which would have been evacuated before the Neoproterozoic. The ironstones would be the mark of further concentrations. To cite this article: A. Blot, C. R. Geoscience 334 (2002) 909–915.     

Premières datations directes de défrichements protohistoriques sur les chaumes secondaires des Vosges (Rossberg,Haut-Rhin). Approche pédoanthracologique

The age of the upland grasslands of the Vosges Mountains is still not well known. On the basis of the study of historical archives, it was assumed that the forest clearings, which led to grasslands establishment, were done by the monks who colonized the Vosges valleys between the 7th and the 8th centuries. Our pedo-anthracological study raises questions about this hypothesis, based on the discovery of Juniperus communis charcoal in soils from the 2nd or 1st century BC. This plant specie is characteristic of grasslands developing into fallows. The occurrence of Juniperus communis charcoals indicates that upland grasslands did exist at least 800 years earlier than it was expected before our study, i.e. at least since the late Iron Age. To cite this article: D. Schwartz et al., C. R. Geoscience 337 (2005).     

New ICP‐MS Results for Trace Elements in Five Iron‐Formation Reference Materials

Iron formations (IFs) typically contain low mass fractions of most trace elements, including the rare earth elements (REE), and few publications describe analytical methods dedicated to this matrix. In this study, we used bomb and table‐top acid dissolution procedures and ICP‐MS to determine the mass fractions of trace elements in IF reference materials FER‐1, FER‐2, FER‐3, FER‐4 and IF‐G. The full digestion of the IF samples with the bomb procedure required the addition of a small amount of water together with the acids. The results obtained by this method mostly agreed statistically with published values. The most remarkable exception was the higher values obtained for the heavy REE in FER‐3. The recoveries of the REE obtained with the table‐top procedure were slightly higher than those of the bomb digestion, except for the values of the heavy REE in FER‐3 and FER‐4, which were up to 30% lower than published values. Sintering of the samples with sodium peroxide was performed to determine the REE, but the results tended to be lower than those derived following acid digestion. On the whole, the recoveries showed dependence on the conditions of digestion, but subtle differences in trace mineral composition between samples also exerted influence on the analytical results for trace elements.     

A land surface model incorporated with soil freeze/thaw and its application in GAME/Tibet

Land surface process is of great importance in global climate change, moisture and heat exchange in the interface of the earth and atmosphere, human impacts on the environment and eco- system, etc. Soil freeze/thaw plays an important role in cold land surface processes. In this work the diurnal freeze/thaw effects on energy partition in the context of GAME/Tibet are studied. A sophisti- cated land surface model is developed, the particular aspect of which is its physical consideration of soil freeze/thaw and vapor flux. The simultaneous water and heat transfer soil sub-model not only reflects the water flow from unfrozen zone to frozen fringe in freezing/thawing soil, but also demon- strates the change of moisture and temperature field induced by vapor flux from high temperature zone to low temperature zone, which makes the model applicable for various circumstances. The modified Picard numerical method is employed to help with the water balance and convergence of the numerical scheme. Finally, the model is applied to analyze the diurnal energy and water cycle char- acteristics over the Tibetan Plateau using the Game/Tibet datasets observed in May and July of 1998. Heat and energy transfer simulation shows that: (i) There exists a negative feedback mechanism between soil freeze/thaw and soil temperature/ground heat flux; (ii) during freezing period all three heat fluxes do not vary apparently, in spite of the fact that the negative soil temperature is higher than that not considering soil freeze; (iii) during thawing period, ground heat flux increases, and sensible heat flux decreases, but latent heat flux does not change much; and (iv) during freezing period, soil temperature decreases, though ground heat flux increases.