Occurrence of noble metals in aluminum- and chromium- rich objects in ordinary chondrites and of baddeleyite (ZrO2) in a chromite inclusion

Abstract— Platinum group elements (PGE) enrichments are found in Fe-Ni blebs (<1 μm) in Al- and Cr-rich objects in the ordinary chondrites Ste. Marguerite, Forest Vale, Montferré. In Ste. Marguerite, high ZrO₂ concentrations (baddeleyite) are also present in a chromite inclusion. Iridium enrichment in this material compared to its metal content is confirmed by INAA. The widespread occurrence of PGE in Al- and Cr-rich objects, mostly present in H-group chondrites of nearly equilibrated types, must be taken into account to understand their conditions of formation.     

A Compilation of Silicon,Rare Earth Element and Twenty‐One other Trace Element Concentrations in the Natural River Water Reference Material SLRS‐5 (NRC‐CNRC)

The natural river water certified reference material SLRS‐5 (NRC‐CNRC) was routinely analysed in this study for major and trace elements by ten French laboratories. Most of the measurements were made using ICP‐MS. Because no certified values are assigned by NRC‐CNRC for silicon and 35 trace element concentrations (rare earth elements, Ag, B, Bi, Cs, Ga, Ge, Li, Nb, P, Rb, Rh, Re, S, Sc, Sn, Th, Ti, Tl, W, Y and Zr), or for isotopic ratios, we provide a compilation of the concentrations and related uncertainties obtained by the participating laboratories. Strontium isotopic ratios are also given.     

Biogeochemical processes in a clay formation in situ experiment: Part E - Equilibrium controls on chemistry of pore water from the Opalinus Clay, Mont Terri Underground Research Laboratory, Switzerland

The chemistry of pore water (particularly pH and ionic strength) is an important property of clay rocks being considered as host rocks for long-term storage of radioactive waste. Pore waters in clay-rich rocks generally cannot be sampled directly. Instead, their chemistry must be found using laboratory-measured properties of core samples and geochemical modelling. Many such measurements have been made on samples from the Opalinus Clay from the Mont Terri Underground Research Laboratory (URL). Several boreholes in that URL yielded water samples against which pore water models have been calibrated. Following a first synthesis report published in 2003, this paper presents the evolution of the modelling approaches developed within Mont Terri URL scientific programs through the last decade (1997-2009). Models are compared to the composition of waters sampled during dedicated borehole experiments. Reanalysis of the models, parameters and database enabled the principal shortcomings of the previous modelling efforts to be overcome. The inability to model the K concentrations correctly with the measured cation exchange properties was found to be due to the use of an inappropriate selectivity coefficient for Na-K exchange; the inability to reproduce the measured carbonate chemistry and pH of the pore waters using mineral-water reactions alone was corrected by considering clay mineral equilibria. Re-examination of the measured Ca/Mg activity ratios and consideration of the mineralogical composition of the Opalinus Clay suggested that Ca/Mg cation exchange rather than dolomite saturation may control the ratio of these ions in solution. This re-examination also suggests that the Ca/Mg ratio decreases with increasing pore-water salinity. Several possible reasons for this are proposed. Moreover, it is demonstrated that feldspar equilibria must not be included in Opalinus Clay modelling because feldspars are present only in very small quantities in the formation and because Na/K ratios measured in pore water samples are inconsistent with feldspar saturation. The principal need to improve future modelling is additional or better data on rock properties, in particular: (i) a more detailed identification of phases in the Opalinus Clay that include redox-sensitive elements together with evaluation of their thermodynamic properties; (ii) an improved understanding of the distribution of celestite throughout the Opalinus Clay for Sr/SO₄ concentrations control; (iii) improvements in analytic and thermodynamic data for Ca-Mg rock cation exchange and mineral chemical properties and (iv) the measurement of composition and stability constants of clay minerals actually present in the formation.     

The geochemistry of gem opals as evidence of their origin

Seventy-seven gem opals from ten countries were analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) through a dilution process, in order to establish the nature of the impurities. The results are correlated to the mode of formation and physical properties and are instrumental in establishing the geographical origin of a gem opal. The geochemistry of an opal is shown to be dependant mostly on the host rock, at least for examples from Mexico and Brazil, even if modified by weathering processes. In order of decreasing concentration, the main impurities present are Al, Ca, Fe, K, Na, and Mg (more than 500 ppm). Other noticeable elements in lesser amounts are Ba, followed by Zr, Sr, Rb, U, and Pb. For the first time, geochemistry helps to discriminate some varieties of opals. The Ba content, as well as the chondrite-normalized REE pattern, are the keys to separating sedimentary opals (Ba > 110 ppm, Eu and Ce anomalies) from volcanic opals (Ba < 110 ppm, no Eu or Ce anomaly). The Ca content, and to a lesser extent that of Mg, Al, K and Nb, helps to distinguish gem opals from different volcanic environments. The limited range of concentrations for all elements in precious (play-of-color) compared to common opals, indicates that this variety must have very specific, or more restricted, conditions of formation. We tentatively interpreted the presence of impurities in terms of crystallochemistry, even if opal is a poorly crystallized or amorphous material. The main replacement is the substitution of Si⁴⁺ by Al³⁺ and Fe³⁺. The induced charge imbalance is compensated chiefly by Ca²⁺, Mg²⁺, Mn²⁺, Ba²⁺, K⁺, and Na⁺. In terms of origin of color, greater concentrations of iron induce darker colors (from yellow to “chocolate brown”). This element inhibits luminescence for concentrations above 1000 ppm, whereas already a low content in U (≤ 1 ppm) induces a green luminescence.     

Magnesium isotope systematics of the lithologically varied Moselle river basin, France

Magnesium and strontium isotope signatures were determined during different seasons for the main rivers of the Moselle basin, northeastern France. This small basin is remarkable for its well-constrained and varied lithology on a small distance scale, and this is reflected in river water Sr isotope compositions. Upstream, where the Moselle River drains silicate rocks of the Vosges mountains, waters are characterized by relatively high ⁸⁷Sr/⁸⁶Sr ratios (0.7128-0.7174). In contrast, downstream of the city of Epinal where the Moselle River flows through carbonates and evaporites of the Lorraine plateau, ⁸⁷Sr/⁸⁶Sr ratios are lower, down to 0.70824.Magnesium in river waters draining silicates is systematically depleted in heavy isotopes (δ²⁶Mg values range from −1.2 to −0.7‰) relative to the value presently estimated for the continental crust and a local diorite (−0.5‰). In comparison, δ²⁶Mg values measured in soil samples are higher (∼0.0‰). This suggests that Mg isotope fractionation occurs during mineral leaching and/or formation of secondary clay minerals. On the Lorraine plateau, tributaries draining marls, carbonates and evaporites are characterized by low Ca/Mg (1.5-3.2) and low Ca/Sr (80-400) when compared to local carbonate rocks (Ca/Mg = 29-59; Ca/Sr = 370-2200), similar to other rivers draining carbonates. The most likely cause of the Mg and Sr excesses in these rivers is early thermodynamic saturation of groundwater with calcite relative to magnesite and strontianite as groundwater chemistry progressively evolves in the aquifer. δ²⁶Mg of the dissolved phases of tributaries draining mainly carbonates and evaporites are relatively low and constant throughout the year (from −1.4‰ to −1.6‰ and from −1.2‰ to −1.4‰, respectively), within the range defined for the underlying rocks. Downstream of Epinal, the compositions of the Moselle River samples in a δ²⁶Mg vs. ⁸⁷Sr/⁸⁶Sr diagram can be explained by mixing curves between silicate, carbonate and evaporite waters, with a significant contribution from the Vosgian silicate lithologies (>70%). Temporal co-variation between δ²⁶Mg and ⁸⁷Sr/⁸⁶Sr for the Moselle River throughout year is also observed, and is consistent with a higher contribution from the Vosges mountains in winter, in terms of runoff and dissolved element flux. Overall, this study shows that Mg isotopes measured in waters, rocks and soils, coupled with other tracers such as Sr isotopes, could be used to better constrain riverine Mg sources, particularly if analytical uncertainties in Mg isotope measurements can be improved in order to perform more precise quantifications.     

Cenozoic Plate interaction of the Australia and Philippine Sea Plates: “hit-and-run” tectonics

Recent studies in northwest New Guinea have shown the presence of at least two marginal basins of different age, both of which formed in back-arc settings. The older basin opened between the Middle Jurassic and Early Cretaceous, a remnant of which is now preserved as the New Guinea Ophiolite. Its obduction started at 40 Ma and it was finally emplaced on the Australian margin at 30 Ma. The younger basin was active during the Oligocene to Middle Miocene and was obducted in the Early Pliocene. Studies of the western edge of the Philippine Sea also reveal an important deformation of the Philippine arc in the Oligocene, which hitherto has remained unexplained. Using information from these systems, paleomagnetic results, kinematic reconstructions and geochemistry of the supra-subduction ophiolite, we present a plate model to explain the region's Eo–Oligocene development. We suggest that an extensive portion of oceanic crust extended the Australian Plate a considerable distance north of the Australian Craton. As Australia began its steady 7–8 cm/year northward drift in the Early Eocene, this lithosphere was subducted. Thus, the portion of the Philippine Sea Plate carrying the Taiwan–Philippine Arc to its present site may have actually been in contact with the ophiolite now in New Guinea and obduction led to deformation of the Philippine Sea Plate itself. Neogene Plate kinematics transported the deformed belt in contact with the Sunda block in the Late Miocene and Pliocene. This interpretation has implications for the origin for the Philippine Sea Plate and the potential incorporation of continental fragments against its boundaries.     

Methyl mercury distributions in relation to the presence of nano- and picophytoplankton in an oceanic water column (Ligurian Sea, North-western Mediterranean)

Recent findings on the distribution of methylated mercury (MeHg_T) in waters have highlighted the importance of organic carbon remineralization on the production of these compounds in the open ocean. Here, we present the first time-series (20 monthly samplings between July 2007 and May 2009) of high-resolution vertical profiles (10-12 depths in a 2350 m water column) of MeHg_T distributions in an open ocean environment, the Ligurian Sea (North-western Mediterranean Sea). Concentrations varied within the sub-picomolar range (general mean: 0.30 ± 0.17 pmol L⁻¹, n = 214) with the lowest values at the surface, increasing with depth up to the oxygen minimum zone, and decreasing slowly at greater depth. Concentrations in the surface waters never exceeded 0.15 pmol L⁻¹, while the highest concentrations (up to 0.82 pmol L⁻¹) were associated to the hypoxycline during the autumn bloom. A detailed vertical MeHg_T profile reveals a “double-peak” pattern, coincidental with the two microbial layers described by Tanaka and Rassoulzadegan (2002), the so-called “microbial food web” in the euphotic zone (<100 m) and the “microbial loop” in the aphotic zone (>100 m). Temporal variations in the MeHg_T abundance and distribution in the water column were linked to seasonality. The highest MeHg_T concentrations were found in the oxygen minimum zone during the period of stratification, and coincide with the greatest abundance of nano- and picophytoplankton (cyanobacteria, nanoflagellates, etc.) in the euphotic layer. None of our deep MeHg_T measurements (∼100 m above the sea bottom) revealed a significant sedimentary source of MeHg_T. We explored the correlation between MeHg_T concentrations and the apparent oxygen utilization, a proxy of organic matter remineralization, over the study period. Results of this study strengthen the hypothesis that net mercury methylation in the open ocean occurs in the water column, is linked to organic matter regeneration, and is promoted by the presence of small-sized nano- and picophytoplankton, that dominate under oligotrophic conditions.     

L'archivage des activités humaines par les neiges et glaces polaires : le cas du plomb

The investigation of the occurrence of lead in dated snow and ice from Greenland and Antarctica has played a major role in our understanding of the history of the pollution of the atmosphere of our planet by this metal. Such studies have however proved to be very demanding, mainly because of the extreme purity of polar snow and ice. Reliable measurements can be obtained only if ultra-clean and highly sensitive procedures are used, as pioneered by Clair Patterson. The Greenland data show evidence of large-scale pollution of the atmosphere of the Northern Hemisphere for lead as early as two millennia ago during Greco–Roman times, especially because of mining and smelting activities in southern Spain. It peaked at the end of the 1960s, with lead concentrations in snow about 200 times higher than natural values, before declining during recent times because of the fall in the use of leaded gasoline. Lead pollution in Antarctica was already significant at the end of the 19th century as a consequence of whaling activities, the traffic of coal-powered ships crossing the Cape Horn, and mining activities in South America, South Africa and Australia. After declining because of the opening of the Panama Canal, the great economic depression and World War II, it reached a maximum during the 1980s, with lead concentrations 20 times higher than natural values. Other studies focus on past natural variations of lead in ancient ice dated from the last climatic cycles. To cite this article: C. Boutron et al., C. R. Geoscience 336 (2004).