Re-Os Isotopic Measurements at the Femtomole Level in Natural Samples

Here we describe a new chemical separation method for Os and an improved mass spectrometric procedure for Re and Os. This technique is based on the selective extraction of OsO₄ from aqueous solution in liquid bromine. Among other advantages, this procedure avoids the cumbersome distillation procedure for Os and uses only commercial "off the shelf" PFA teflon labware. Blank levels for 0.5 g sample sizes are: 0.06 pg and 0.5 pg for Os and Re respectively. Samples containing as little as 1 pg g⁻¹ Os can be analysed reliably with this method. Adaptation to other dissolution methods is also discussed.     

Solar modulation of cosmogenic nuclide production over the last millennium: comparison between C and Be records

For about the last 30 years it has been recognized that the high frequency component of the tree rings ¹⁴C/¹²C record is dominated by the modulation of the cosmic ray flux by the solar wind. In particular, it has been demonstrated that the three most recent periods of low sunspot occurrence were characterized by high values of atmospheric ¹⁴C/¹²C. During the last millennium other periods of high ¹⁴C/¹²C values were observed but their solar origin is still debatable. In the present work we compare these fluctuations with an independent record of cosmogenic ¹⁰Be measured in ice from the South Pole to check the solar origin of the observed ¹⁴C/¹²C variations. In order to compare quantitatively the results obtained on ¹⁰Be and ¹⁴C, it is necessary to take into account the different behaviour of these two cosmogenic isotopes, and especially the damping effect of the carbon cycle in the case of ¹⁴C. As an input to a 12-box numerical model we used the relative fluctuations of the ¹⁰Be concentrations record measured in South Pole ice and converted it into a synthetic ¹⁴C record. We took into account the fact that ¹⁰Be modulation is enhanced in polar regions due to the orientation of the geomagnetic field. As expected, the fluctuations of the modelled ¹⁴C record are much smaller (a factor of 20) than those observed for the raw ¹⁰Be record. In addition, the variations are smoother and shifted in time by a few decades. The ¹⁰Be-based ¹⁴C variations closely resemble the ¹⁴C measurements obtained on tree rings (R = 0.81). In particular, it is easy to identify periods of maximal ¹⁴C/¹²C which correspond to solar activity minima centred at about 1060, 1320 (Wolf), 1500 (Spörer), 1690 (Maunder) and 1820 (Dalton) yr A.D. Cross-correlation calculations suggest that there is no significant lag between the ¹⁰Be-based ¹⁴C and the tree-ring ¹⁴C records. Our study strongly suggests the dominance of the solar modulation on the cosmonuclide production variations during the last millennium.     

Comparison of Cu and Zn cycling in eutrophic lakes with oxic and anoxic hypolimnion

Data on the cycling of Cu and Zn in two eutrophic lakes are presented: Lake Greifen that becomes seasonally anoxic in its hypolimnion and Lake Sempach that is aerated during winter and oxygenated during summer. They suggest that hypolimnetic oxygenation 1) enhances the release of copper from the sediment but 2) also accelerates the entrapment and deposition of Cu and Zn by freshly formed Mn- and Fe-oxides.     

Relationship of Avalonian and Cadomian terranes to Grenville and Pan-African events

Suturing of the supercontinent Rodinia in the Grenville event (˜ 1000 Ma) was followed by rifting in the late Proterozoic (˜ 800-700 Ma), reorganization to Gondwana in the Pan-African (˜ 700-500 Ma) and further accretion to develop Pangea at the end of the Paleozoic. One of the Rodinian rifts followed part of the Grenville suture, it produced the margin of eastern North America and southern Baltica and the contrasting margin of west Gondwana in present South America. The Paleozoic accretionary wedge against the Grenville-age margin of North America and Baltica contains Avalonian/Cadomian terranes that exhibit Pan-African erogenic events ± sediments apparently developed while the terranes were in or near Gondwana. These terranes carry lower-Paleozoic fauna (Acado-Baltic) that are not indigenous to North America and Baltica.U---Pb zircon ages range from 1500-1000 Ma in Grenville terranes and from 800–500 Ma with minor inheritance in Avalonian terranes; they are generally much older in Cadomian terranes, implying very little resetting during Pan-African events. T_DM ages are generally 2000–1200 Ma in Grenville terranes, 1300–600 Ma in Avalonian terranes and 2000–1200 in Cadomian terranes. These summary data show that: (1) the Grenville orogenic event produced almost no juvenile crust; (2) the Avalonian terranes of North America contain crust that evolved primarily in the late Proterozoic, possibly as a mixture of juvenile Pan-African material and Grenville or slightly older material; (3) the Cadomian terranes of Europe consist of old (middle-Proterozoic to Archean) crust with minor juvenile Pan-African material. The Avalonian terranes apparently evolved near, and partly on, the Grenville-age crust now in South America during the intense orogeny associated with rotation of Gondwana away from North America. The Cadomian terranes of Europe, however, appear to be fragments of other parts of Gondwana, probably West Africa.     

Tectonic evolution of the Lachlan Fold Belt, southeastern Australia: constraints from coupled numerical models of crustal deformation and surface erosion driven by subduction of the underlying mantle

We have used a coupled thermo-mechanical finite-element (FE) model of crustal deformation driven by mantle/oceanic subduction to demonstrate that the tectonic evolution of the Lachlan Fold Belt (LFB) during the Mid-Palaeozoic (Late Ordovician to Early Carboniferous) can be linked to continuous subduction along a single subduction zone. This contrasts with most models proposed to date which assume that separate subduction zones were active beneath the western, central and eastern sections of the Lachlan Orogen. We demonstrate how the existing data on the structural, volcanic and erosional evolution of the Lachlan Fold Belt can be accounted for by our model. We focus particularly on the timing of fault movement in the various sectors of the orogen. We demonstrate that the presence of the weak basal decollement on which most of the Lachlan Fold Belt is constructed effectively decouples crustal structures from those in the underlying mantle. The patterns of faulting in the upper crust appears therefore to be controlled by lateral strength contrasts inherited from previous orogenic events rather than the location of one or several subduction zones. The model also predicts that the uplift and deep exhumation of the Wagga-Omeo Metamorphic Belt (WOMB) is associated with the advection of this terrane above the subduction point and is the only tectonic event that gives us direct constraints on the location of the subduction zone. We also discuss the implications of our model for the nature of the basement underlying the present-day orogen.     

A Reflection on Mg, Cd, Ca, Li and Si Isotopic Measurements and Related Reference Materials

This contribution aims to report the reflections we had with the scientific community during two international workshops on reference materials for stable isotopes in Davos (2002) and Nice (2003). After evaluating the isotopic homogeneity of some existing reference materials, based on either certificates, literature data or specific inter-laboratory rounds, we confirm these as primary reference materials or propose new ones relative to which stable isotope compositions should be reported. We propose DSM-3 for Mg, NIST SRM 915a for Ca, L-SVEC for Li and NBS28 for Si. Cadmium does not yet have a well identified delta zero material, although three commercial mono-elemental Cd solutions have yielded the same isotopic composition relative to one another. In order to scale the linearity of any mass spectrometer, some secondary reference materials are also proposed: Cambridge-1 solution for Mg, the "Münster-Cd" and JEPPIM Cd solutions for Cd and the "Big Batch" silicate for Si. The team from Nancy propose to prepare a mixed spike solution for Li isotopes. Well-characterised natural samples such as ocean or continental waters, diatoms, sponges, rocks and minerals are needed to validate the entire analytical procedure, particularly to take into account the effect of sample mineralisation and of chemical manipulations for elemental separation prior to analysis.