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.     

Measurement and interpretation of molecular-level forces of interaction between the siderophore azotobactin and mineral surfaces

The forces of interaction were measured between the siderophore azotobactin and the minerals goethite (α-FeOOH) and diaspore (α-AlOOH) in aqueous solution using force microscopy. Azotobactin, a pyoverdin-type siderophore, was covalently linked to a hydrazide terminated atomic force microscope tip using a standard active ester protein coupling technique. Upon contact with each mineral surface, the adhesion force between azotobactin and goethite was two to three times the value observed for the isostructural Al-equivalent diaspore. The affinity for the solid iron oxide surface reflected in the force measurements correlates with the specificity of azotobactin for aqueous ferric iron. Further, the adhesion force between azotobactin and goethite significantly decreases (4 nN to 2 nN) when small amounts of soluble iron (0.1 μM FeCl₃ · 6H₂O) are added to the system at pH 3.5 suggesting a significant specific interaction between the chelating reactive center of azotobactin and the mineral surface. Changes in the force signature with pH and ionic strength were fairly predictable when considering mineral solubility, the charge character of the mineral surfaces, the molecular structure of azotobactin, and the intervening solution. For example, azotobactin-goethite adhesion values were consistently smaller at pH 3.5 relative to the forces at pH 7. At the lower pH, the large number of protons and the increase in the mineral solubility provides additional electron acceptors (e.g., H⁺ and Fe³⁺(aq)) that are free to compete for the basic oxygen chelating sites in the azotobactin structure. It is believed that this competition disrupts siderophore affinity for the surface resulting in decreased adhesion values.     

Anthropogenic contributions to atmospheric Hg, Pb and As accumulation recorded by peat cores from southern Greenland and Denmark dated using the C “bomb pulse curve”

Mercury concentrations are clearly elevated in the surface and sub-surface layers of peat cores collected from a minerotrophic (“groundwater-fed”) fen in southern Greenland (GL) and an ombrotrophic (“rainwater-fed”) bog in Denmark (DK). Using ¹⁴C to precisely date samples since ca. AD 1950 using the “atmospheric bomb pulse,” the chronology of Hg accumulation in GL is remarkably similar to the bog in DK where Hg was supplied only by atmospheric deposition: this suggests not only that Hg has been supplied to the surface layers of the minerotrophic core (GL) primarily by atmospheric inputs, but also that the peat cores have preserved a consistent record of the changing rates of atmospheric Hg accumulation. The lowest Hg fluxes in the GL core (0.3 to 0.5 μg/m²/yr) were found in peats dating from AD 550 to AD 975, compared to the maximum of 164 μg/m²/yr in AD 1953. Atmospheric Hg accumulation rates have since declined, with the value for 1995 (14 μg/m²/yr) comparable to the value for 1995 obtained by published studies of atmospheric transport modelling (12 μg/m²/yr).The greatest rates of atmospheric Hg accumulation in the DK core are also found in the sample dating from AD 1953 and are comparable in magnitude (184 μg/m²/yr) to the GL core; again, the fluxes have since gone into strong decline. The accumulation rates recorded by the peat core for AD 1994 (14 μg/m²/yr) are also comparable to the value for 1995 obtained by atmospheric transport modelling (18 μg/m²/yr). Comparing the Pb/Ti and As/Ti ratios of the DK samples with the corresponding crustal ratios (or “natural background values” for preanthropogenic peat) shows that the samples dating from 1953 also contain the maximum concentration of “excess” Pb and As. The synchroneity of the enrichments of all three elements (Hg, Pb, and As) suggests a common source, with coal-burning the most likely candidate. Independent support for this interpretation was obtained from the Pb isotope data (²⁰⁶Pb/²⁰⁷Pb = 1.1481 ± 0.0002 in the leached fraction and 1.1505 ± 0.0002 in the residual fraction) which is too radiogenic to be explained in terms of gasoline lead alone, but compares well with values for U.K. coals. In contrast, the lowest values for ²⁰⁶Pb/²⁰⁷Pb in the DK profile (1.1370 ± 0.0003 in the leached fraction and 1.1408 ± 0.0003 in the residual fraction) are found in the sample dating from AD 1979: this shows that the maximum contribution of leaded gasoline occurred approximately 25 yr after the zenith in total anthropogenic Pb deposition.     

Metamorphic and deformational imprint of Cambrian–Lower Ordovician rifting in the Ossa-Morena Zone (Iberian Massif, Spain)

The high-temperature metamorphism recorded in the Valuengo and Monesterio areas constitutes a rare occurrence in the Ossa-Morena Zone of Southwest Iberia, where low-grade metamorphism dominates. The metamorphism of the Valuengo area has been previously considered either Cadomian or Variscan in age, whereas that of Monesterio has been interpreted as a Cadomian imprint. However, these areas share important metamorphic and structural features that point towards a common tectonometamorphic evolution. The metamorphism of the Valuengo and Monesterio areas affects Late Proterozoic and Early Cambrian rocks, and is syn-kinematic with a top-to-the-north mylonitic foliation, which was subsequently deformed by early Variscan folds and thrusts. The U–Pb zircon age (480±7 Ma) we have obtained for an undeformed granite of the Valuengo area is consistent with our geological observations constraining the age of the metamorphism. We propose that this high-temperature metamorphic imprint along a NW–SE ductile extensional shear zone is related to the crustal extension that occurred in the Ossa-Morena Zone during the Cambro-Ordovician rifting. In the same way, the tectonothermal effect of the preorogenic rifting stage may have been wrongly attributed to orogenic processes in other regions as well as in this one.     

Validation of Landslide Susceptibility Maps; Examples and Applications from a Case Study in Northern Spain

A procedure for validating landslide susceptibility maps wasapplied in a study area in northern Spain and the results obtained compared. Validationwas used to carry out sensitivity analysis for individual variables and combinationsof variables. The validity of different map-making methods was tested, as well as theutility of different types of Favourability Functions. The results obtained show thatvalidation is essential to determine the predictive value of susceptibility maps. Italso helps to better select the most suitable function and significant variables, thus improving the efficiency of the mapping process. Validation based on a temporal strategy makes it possible to derive hazard maps from susceptibility maps.     

Kinetics and Mechanism of Trithionate and Tetrathionate Oxidation at Low pH by Hydroxyl Radicals

The oxidation kinetics of trithionate (S₃O₆^2- ) and tetrathionate (S₄O ₆ ^2- ) with hydroxyl radicals (OH^*) have been investigated in systems analogous to acid mine drainage (AMD) environments. The discovery of hydroxyl radical (OH^*) formation on pyrite surfaces (Borda et al., 2003) suggests hydroxyl radicals may affect the oxidation kinetics of intermediate sulfur species such as tetrathionate. Cyclic voltammetry experiments in acidic solutions indicate that the reaction of S₄O ₆ ^2- with OH^* goes through an unknown intermediate, tentatively assigned as S₃O ₄ ^n- . An outer-sphere electron transfer mechanism for the reaction of S₄O ₆ ^2- with OH^* to form S₃O ₄ ^n- is proposed based on experimental results. Oxidation rates for trithionate and tetrathionate in the presence of Fenton's reagent (which forms hydroxyl radicals) are too fast to be directly measured using UV-Vis spectrophotometry, electrochemical, or stop-flow spectrophotometry methods. Competitive reaction kinetics within the context of the Haber—Weiss mechanism suggests that the rate constant for the oxidation of trithionate and tetrathionate with OH^* is in excess of 10⁸ M^-1 sec^-1.     

Stable isotopes in deep-sea corals and a new mechanism for “vital effects”

Offsets from isotopic equilibrium in biogenic carbonates have complicated paleoclimate reconstructions for decades. A new archive of climate, deep-sea corals, is used to evaluate the calcification processes, independent of photosynthesis, that contribute to these offsets. Carbon and oxygen stable isotope data from six modern deep-sea corals show strong linear trends between δ¹³C and δ¹⁸O. Slopes of these trends between samples are similar and range between 1.9 to 2.6 for Δδ¹³C/Δδ¹⁸O. Linear trends intersect isotopic equilibrium for δ¹⁸O and are slightly depleted for δ¹³C. Variations in the isotopic ratios are strongly correlated with the density banding structure. Isotopically depleted aragonite is associated with light, quickly precipitating bands, whereas isotopically enriched points correspond to slowly accumulating, less dense aragonite. The densest white band at the trabecular center is furthest from isotopic equilibrium for both carbon and oxygen. Data from this region fall off the linear trend between δ¹⁸O and δ¹³C. This deviation, where δ¹³C remains constant while the δ¹⁸O continues to decrease, does not support “vital effect” mechanisms that call upon kinetic fractionation to explain offsets from isotopic equilibrium. We propose a new mechanism for vital effects in these deep-sea corals that is based on a thermodynamic response to a biologically induced pH gradient in the calcifying region.     

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.