Preliminary Results from a New 157 nm Laser Ablation ICP-MS Instrument: New Opportunities in the Analysis of Solid Samples

Preliminary results are given from an excimer 157 nm laser ablation multiple-collector inductively coupled plasma-mass spectrometer (LA-MC-ICP-MS), used for the isotopic measurements of solid materials. Elements of geological interest with different volatilities such as Pb and U (e.g. zircon geochronology) and Cu and Zn (as examples of geochemical/biochemical tracers) were analysed. The range of ablation rates of 20-150 nm s^-1 enabled us to ablate the sample down to a depth of 45 μm for a 50 μm diameter pit. The Cu and Zn isotopic measurements gave values that were very stable with, on average, a 0.01 % standard error, comparable with that achieved in liquid mode measurements.     

Feature Environmental geophysics: a site characterization tool for urban regeneration in the post-mining era

The closure and decay of industrial activity involving mining, chemical or light industrial operations has scarred the landscape of urban areas. The Government has major initiatives in urban regeneration to remediate these 'brown-field sites'.     

Timing of deformation in the Norseman-Wiluna Belt, Yilgarn Craton, Western Australia

Establishing relative and absolute time frameworks for the sedimentary, magmatic, tectonic and gold mineralisation events in the Norseman-Wiluna Belt of the Archean Yilgarn Craton of Western Australia, has long been the main aim of research efforts. Recently published constraints on the timing of sedimentation and absolute granite ages have emphasized the shortcomings of the established rationale used for interpreting the timing of deformation events. In this paper the assumptions underlying this rationale are scrutinized, and it is shown that they are the source of significant misinterpretations. A revised time chart for the deformation events of the belt is established. The first shortening phase to affect the belt, D₁, was preceded by an extensional event D_1e and accompanied by a change from volcanic-dominated to plutonic-dominated magmatism at approximately 2685–2675 Ma. Later extension (D_2e) controlled deposition of the ca 2655 Ma Kurrawang Sequence and was followed by D₂, a major shortening event, which folded this sequence. D₂ must therefore have started after 2655 Ma—at least 20 Ma later than previously thought and after the voluminous 2670–2655 Ma high-Ca granite intrusion. Younger transcurrent deformation, D₃–D₄, waned at around 2630 Ma, suggesting that the crustal shortening deformation cycle D₂–D₄ lasted approximately 20–30 Ma, contemporaneous with low-volume 2650–2630 Ma low-Ca granites and alkaline intrusions. Time constraints on gold deposits suggest a late mineralisation event between 2640–2630 Ma. Thus, D₂–D₄ deformation cycle and late felsic magmatism define a 20–30 Ma long tectonothermal event, which culminated with gold mineralisation. The finding that D₂ folding took place after voluminous high-Ca granite intrusion led to research into the role of competent bodies during folding by means of numerical models. Results suggest that buoyancy-driven doming of pre-tectonic competent bodies trigger growth of antiforms, whereas non-buoyant, competent granite bodies trigger growth of synforms. The conspicuous presence of pre-folding granites in the cores of anticlines may be a result from active buoyancy doming during folding.     

Controls on Fe reduction and mineral formation by a subsurface bacterium

The reductive dissolution of FeIII (hydr)oxides by dissimilatory iron-reducing bacteria (DIRB) could have a large impact on sediment genesis and Fe transport. If DIRB are able to reduce FeIII in minerals of high structural order to carry out anaerobic respiration, their range could encompass virtually every O₂-free environment containing FeIII and adequate conditions for cell growth. Previous studies have established that Shewanella putrefaciens CN32, a known DIRB, will reduce crystalline Fe oxides when initially grown at high densities in a nutrient-rich broth, conditions that poorly model the environments where CN32 is found. By contrast, we grew CN32 by batch culture solely in a minimal growth medium. The stringent conditions imposed by the growth method better represent the conditions that cells are likely to encounter in their natural habitat. Furthermore, the expression of reductases necessary to carry out dissimilatory Fe reduction depends on the method of growth. It was found that under anaerobic conditions CN32 reduced hydrous ferric oxide (HFO), a poorly crystalline FeIII mineral, and did not reduce suspensions containing 4 mM FeIII in the form of poorly ordered nanometer-sized goethite (α-FeOOH), well-ordered micron-sized goethite, or nanometer-sized hematite (α-Fe₂O₃) crystallites. Transmission electron microscopy (TEM) showed that all minerals but the micron-sized goethite attached extensively to the bacteria and appeared to penetrate the outer cellular membrane. In the treatment with HFO, new FeII and FeIII minerals formed during reduction of HFO-Fe in culture medium containing 4.0 mmol/L P_i (soluble inorganic P), as observed by TEM with energy-dispersive X-ray spectroscopy, selected area electron diffraction, and X-ray diffraction. The minerals included magnetite (Fe₃O₄), goethite, green rust, and vivianite [Fe₃(PO₄)₂ · 8H₂O]. Vivianite appeared to be the stable end product and the mean coherence length was influenced by the rate of FeIII reduction. When P_i was 0.4 mol/L under otherwise identical conditions, goethite was the only mineral observed to form, and less Fe²⁺ was produced overall. Hence, the ability of DIRB to reduce Fe (hydr)oxides may be limited when the bacteria are grown under nutrient-limited conditions, and the minerals that result depend on the vigor of FeIII reduction.     

Modelling nitrogen and oxygen isotope fractionation during denitrification in a lacustrine redox-transition zone

The stable isotope composition (δ¹⁵N and δ¹⁸O) of nitrate was measured during Summer 1999 in the anaerobic hypolimnion of eutrophic Lake Lugano (Switzerland). Denitrification was demonstrated by a progressive nitrate depletion coupled to increasing δ¹⁵N and δ¹⁸O values for residual nitrate. Maximum δ¹⁵N and δ¹⁸O values amounted to 27.2 and 15.7‰, respectively.¹⁵N and ¹⁸O enrichment factors for denitrification (ε) were estimated using a closed-system model and a dynamic diffusion-reaction model. Using the Rayleigh equation (closed-system approach), we obtained ε values of −11.2 and −6.6‰ for nitrogen and oxygen, respectively. The average ε values derived using the diffusion-reaction model were determined to be −20.7 ± 3.8 for nitrogen and −11.0 ± 1.7 for oxygen. Both N and O isotope fractionation appeared to be lower when denitrification rates where high, possibly in association with high organic carbon availability. In addition, variations in the isotope effects may be attributed to the variable importance of sedimentary denitrification having only a small isotope effect on the water column. The combined measurement of N and O isotope ratios in nitrate revealed that coupled nitrification-denitrification in the open-water was of minor importance. This is the first study of nitrogen and oxygen isotope effects associated with microbial denitrification in a natural lake. Moreover, this study confirms the high potential of δ¹⁸O of nitrate as a valuable biogeochemical tracer in aquatic systems, complementing nitrate δ¹⁵N.     

Intercomparison of Stratospheric Chemistry Models under Polar Vortex Conditions

Several stratospheric chemistry modules from box, 2-D or 3-D models, have been intercompared. The intercomparison was focused on the ozone loss and associated reactive species under the conditions found in the cold, wintertime Arctic and Antarctic vortices. Comparisons of both gas phase and heterogeneous chemistry modules show excellent agreement between the models under constrained conditions for photolysis and the microphysics of polar stratospheric clouds. While the mean integral ozone loss ranges from 4–80% for different 30–50 days long air parcel trajectories, the mean scatter of model results around these values is only about ±1.5%. In a case study, where the models employed their standard photolysis and microphysical schemes, the variation around the mean percentage ozone loss increases to about ±7%. This increased scatter of model results is mainly due to the different treatment of the PSC microphysics and heterogeneous chemistry in the models, whereby the most unrealistic assumptions about PSC processes consequently lead to the least representative ozone chemistry. Furthermore, for this case study the model results for the ozone mixing ratios at different altitudes were compared with a measured ozone profile to investigate the extent to which models reproduce the stratospheric ozone losses. It was found that mainly in the height range of strong ozone depletion all models underestimate the ozone loss by about a factor of two. This finding corroborates earlier studies and implies a general deficiency in our understanding of the stratospheric ozone loss chemistry rather than a specific problem related to a particular model simulation.