Old inherited origin for the present near-bimodal topography of Africa

Africa’s landscape is dominated by a manifold of second-order epeirogenic structures superimposed on a first-order bimodal topography. Bivariate regression analysis of Africa’s surface topography shows that this is a complexly folded surface with regionally elevated areas in southern and eastern Africa, and a topographically low northern and western Africa. The apparent spatial relationships between these features are analysed using anomaly correlation between surface topography and free-air gravity anomalies. Occurrences of positively correlated features between gravity and topography in Africa are found to be limited to second-order epeirogenic features. Geophysical modelling and geologic evidence indicate that Africa’s bimodal topography is genetically distinct from these second-order features, and linked to sources as deep as the sublithospheric mantle. The age, measured and modelled elevation of the bimodal topography require that topographic uplift of south-central Africa be episodic. We infer from our findings together with relative sea-level changes, that the near-bimodality of Africa’s topography is an ancient feature inherited at least from upper Paleozoic times. Our reconstructed paleotopography suggests that Africa was largely a low-lying continent dominated by its cratons, and that basement distribution disregards the present-day uplift patterns of Africa.     

Presolar spinel grains from the Murray and Murchison carbonaceous chondrites

With a new type of ion microprobe, the NanoSIMS, we determined the oxygen isotopic compositions of small (<1μm) oxide grains in chemical separates from two CM2 carbonaceous meteorites, Murray and Murchison. Among 628 grains from Murray separate CF (mean diameter 0.15 μm) we discovered 15 presolar spinel and 3 presolar corundum grains, among 753 grains from Murray separate CG (mean diameter 0.45 μm) 9 presolar spinel grains, and among 473 grains from Murchison separate KIE (mean diameter 0.5 μm) 2 presolar spinel and 4 presolar corundum grains. The abundance of presolar spinel is highest (2.4%) in the smallest size fraction. The total abundance in the whole meteorite is at least 1 ppm, which makes spinel the third-most abundant presolar grain species after nanodiamonds (if indeed a significant fraction of them are presolar) and silicon carbide. The O-isotopic distribution of the spinel grains is very similar to that of presolar corundum, the only statistically significant difference being that there is a larger fraction of corundum grains with large ¹⁷O excesses (¹⁷O/¹⁶O > 1.5 × 10⁻³), which indicates parent stars with masses between 1.8 and 4.5 M_⊙.     

Evidence for a large surface ablation zone in central East Antarctica during the last Ice Age

Internal isochronous ice sheet layers, recorded by airborne ice-penetrating radar, were measured along an ice flowline across a large (>1 km high) subglacial hill in the foreground of the Transantarctic Mountains. The layers, dated through an existing stratigraphic link with the Vostok ice core, converge with the ice surface as ice flows over the hill without noticeable change to their separation with each other or the ice base. A two-dimensional ice flow model that calculates isochrons and particle flowpaths and accounts for ice flow over the hill under steady-state conditions requires net ablation (via sublimation) over the stoss face for the predicted isochrons to match the measured internal layers. Satellite remote sensing data show no sign of exposed ancient ice at this site, however. Given the lack of exposed glacial ice, surface balance conditions must have changed recently from the net ablation that is predicted at this site for the last 85,000 years to accumulation.     

Increased sediment accretion rates following invasion byPhragmites australis: The role of litter

Negative connotations of invasive plants worldwide have implicated them as the bearers of unfavorable ecosystem change. We contrasted 5-yr-old and 20-yr-oldPhragmites populations with pre-invasion areas occupied byTypha spp. andPanicum virgatum in an oligohaline tidal marsh of Chesapeake Bay. Peak live biomass was 3 times greater, while standing dead and litter was twice as great in the 20-yr-oldPhragmites. It is this abundance of concentrated litter on the marsh surface of maturePhragmites populations that we implicate as encouraging the trapping of organic and mineral matter. The rate of vertical accretion in 20-yr-oldPhragmites populations is 3–4 mm yr⁻¹ above the adjacent populations. By integrating the constant initial concentration and constant rate of supply models on individual²¹⁰Pb cores, we estimate thatPhragmites populations require a minimum of 7-yr post-colonization to enhance rates of accretion in this system. In ligh of the considerable loss of marsh habitat from relative sea-level rise, this finding contests the view that invasion creates strictly undesirable change at the ecosystem level.     

Surface oxidation of pyrite under ambient atmospheric and aqueous (pH = 2 to 10) conditions: electronic structure and mineralogy from X-ray absorption spectroscopy

The nature of the surface oxidation phase on pyrite, FeS₂, reacted in aqueous electrolytes at pH = 2 to 10 and with air under ambient atmospheric conditions was studied using synchrotron-based oxygen K edge, sulfur L_III edge, and iron L_II,III edge X-ray absorption spectroscopy. We demonstrate that O K edge X-ray absorption spectra provide a sensitive probe of sulfide surface oxidation that is complementary to X-ray photoelectron spectroscopy. Using total electron yield detection, the top 20 to 50 Å of the pyrite surface is characterized. In air, pyrite oxidizes to form predominantly ferric sulfate. In aqueous air-saturated solutions, the surface oxidation products of pyrite vary with pH, with a marked transition occurring around pH 4. Below pH = 4, a ferric (hydroxy)sulfate is the main oxidation product on the pyrite surface. At higher pH, we find iron(III) oxyhydroxide in addition to ferric (hydroxy)sulfate on the surface. Under the most alkaline conditions, the O K edge spectrum closely resembles that of goethite, FeOOH, and the surface is oxidized to the extent that no FeS₂ can be detected in the X-ray absorption spectra. In a 1.667 × 10⁻³ mol/L Fe³⁺ solution with ferric iron present as FeCl₃ in NaCl, the oxidation of pyrite is autocatalyzed, and formation of the surface iron(III) oxyhydroxide phase is promoted at low pH.     

Computational study of tetrahedral Al–Si and octahedral Al–Mg ordering in phengite

 As part of a wider study of the nature and origins of cation order–disorder in micas, a variety of computational techniques have been used to investigate the nature of tetrahedral and octahedral ordering in phengite, K₂ ^[6](Al₃Mg)^[4](Si₇Al)O₂₀(OH)₄. Values of the atomic exchange interaction parameters J _n used to model the energies of order–disorder were calculated. Both tetrahedral Al–Si and octahedral Al–Mg ordering were studied and hence three types of interaction parameter were necessary: for T–T, O–O and T–O interactions (where T denotes tetrahedral sites and O denotes octahedral sites). Values for the T–T and O–O interactions were taken from results on other systems, whilst we calculated new values for the T–O interactions. We have demonstrated that modelling the octahedral and tetrahedral sheets alone and independently produces different results from modelling a whole T–O–T layer, hence justifying the inclusion of the T–O interactions. Simulations of a whole T–O–T layer of phengite indicated the presence of short-range order, but no long-range order was observed. Received: 8 August 2002 / Accepted: 14 February 2003 Acknowledgements The authors are grateful to EPSRC (EJP) and the Royal Society (CIS) for financial support. Monte Carlo simulations were performed on the Mineral Physics Group's Beowulf cluster and the University of Cambridge's High Performance Computing Facility.     

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.     

Atmospheric deposition of Be and Be in New Zealand rain (1996-98)

Beryllium isotope concentrations were determined in monthly rainfall collections at three sites across New Zealand (36 to 45° S), from October 1996 to November 1998. At the northern sites of Leigh (near Auckland) and Gracefield (near Wellington), ⁷Be and ¹⁰Be concentrations are relatively constant at 1.2 to 1.4 × 10⁷ atoms kg⁻¹ rain and 2.1 to 2.6 × 10⁷ atoms kg⁻¹ rain, respectively. These concentrations correspond to annual flux rates of ∼15 and ∼27 × 10⁹ atoms m⁻² y⁻¹, respectively. At the southern site of Dunedin, concentrations are similar to those at the northern sites, but flux rates are significantly lower at ∼ 9 and ∼19 × 10⁹ atoms m⁻² y⁻¹, respectively, because of lower average rainfall east of the Southern Alps mountain range. These results are broadly similar to those reported by Brown et al. (1989) and Knies et al. (1994) for rain from midlatitude sites in the USA sampled from 1986 to 1994. Mean ⁷Be/¹⁰Be ratios for New Zealand (0.47 to 0.61) are, however, significantly lower than for the USA (0.69 to 0.78), due in part to the addition of ¹⁰Be from re-suspended dust. Subtraction of the dust component increases the New Zealand ⁷Be/¹⁰Be ratios to 0.70 (Leigh), 0.65 (Gracefield) and 0.50 (Dunedin). The adjusted results provide evidence for transfer of older stratospheric air to the troposphere in late-spring-summer, an effect which is strongest in the north. The overall reduction of ⁷Be/¹⁰Be from north to south implies an increase in residence time from ∼ 80 to ∼100 d for Be isotopes in the atmosphere above New Zealand.