Retrograde fluids in the Archean Shawmere anorthosite, Kapuskasing Structural Zone, Ontario, Canada

The Archean Shawmere anorthosite lies within the granulite facies portion of the Kapuskasing Structural Zone (KSZ), Ontario, and is crosscut by numerous linear alteration veins containing calcite + quartz ± dolomite ± zoisite ± clinozoisite ± margarite ±paragonite ± chlorite. These veins roughly parallel the trend of the Ivanhoe Lake Cataclastic Zone. Equilibria involving clinozoisite + margarite + quartz ± calcite ± plagioclase show that the vein minerals were stable at T < 600 °C, XCO₂ < 0.4 at P ≈ 6 kbar. The stabilities of margarite and paragonite in equilibrium with quartz are also consistent with T < 600 °C and XCO₂ < 0.4 at 6 kbar. Additional assemblages consisting of calcite + clinochlore + quartz + talc + margarite indicate T < 500 °C with XCO₂ > 0.9. Thus, vein formation, while clearly retrograde, spanned a range of temperatures, and fluid compositions evolved from H₂O-rich to CO₂-rich. The calcite in the retrograde veins has δ¹⁸O values that range from 8.4 to 11.2‰ (average = +9.7 ± 0.9‰) and δ¹³C values that range from −3.9 to −1.6‰ (average = −3.1 ± 0.6‰). These values indicate that the fluids from which calcite precipitated underwent extensive exchange with the anorthosite and other crustal lithologies. The fluids may have been initially derived either from devolatilization of metamorphic rocks or crystallization of igneous rocks in the adjacent Abitibi subprovince. Vein quartz contains CO₂-rich fluid inclusions (final melting T = −57.0 to −58.7 °C) that range in size from 5 to 17 μm. Measured homogenization temperatures (T h) range from −44.0 to 14.5 °C, however for most inclusions (46 of S1), T h = −44.0 to −21.1 °C (ρCO₂ ≈ 1.13 to 1.05 g/cm³). At 400 to 600 °C, these densities correspond to pressures of 3.5 to 7 kbar, which is the best estimate of pressures of vein formation. It has been argued that some high density CO₂-rich fluid inclusions found in the KSZ were formed during peak metamorphism and thus document the presence of a CO₂-rich fluid during peak granulite facies metamorphism (Rudnick et al. 1984). The association of high density CO₂-rich fluid inclusions with clearly retrograde veins documents the formation of similar composition and density inclusions after the peak of metamorphism. Thus, the coincidence of entrapment pressures calculated from fluid inclusion density measurements with peak metamorphic pressures alone should not be considered strong evidence for peak metamorphic inclusion entrapment. All fluid inclusion results are consistent with an initially semi-isobaric retrograde P–T path. Received: 2 April 1996 / Accepted: 15 November 1996     

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.     

Gaschromatographische Bestimmung von polychlorierten Biphenylen in Wasser nach Headspace-Festphasenmikroextraktion

Gas-chromatographic Determination of Polychlorinated Biphenyls in Water after Headspace Solid-phase Microextraction Headspace-analytical techniques are usually applied to the determination of easily volatile substances in water, whereas semivolatiles are generally isolated by liquid-liquid or solid-phase extraction. In the present paper, a method is presented for isolating high boiling polychlorinated biphenyls (PCB) using headspace solid-phase microextraction at elevated temperature. In spite of their low vapor pressure, the analytes are adsorbed very efficiently on a poly-dimethylsiloxane-coated fiber. Thus, in combination with GC/ECD, a very simple and sensitive solventless determination of PCB is accomplished. Using the simplest possible standard conditions, limits of determination in the lowest nanogram-per-liter range are achieved. Further increased sensitivity down to the ppq (parts per quadrillion) range is possible by stirring and increasing the sample volume and adsorption time. Moderate matrix effects have been observed in some surface and groundwaters.     

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.     

Determining the maximum degree of harmonic coefficients in geopotential models by Monte Carlo methods

Random errors for the harmonic coefficients of a geopotential model are generated from the matrix of normal equations by a parallel computer applying the Gibbs sampler. This leads to random values for the harmonic coefficients. They are transformed by nonlinear, quadratic transformations to random values for the square roots of degree variances, of mean squares of geoid undulations and gravity anomalies. The expected values of these quantities are not equal to the values of these quantities computed by the estimated harmonic coefficients, due to correlations and errors in the estimation. By hypothesis tests estimated harmonic coefficients distorted by correlations and errors are detected. Applying the tests to the geopotential model ITG-CHAMP01 of the Institute of Theoretical Geodesy in Bonn it is concluded that above the degree 62 the harmonic coefficients cannot add any information to the geopotential model.