Thermal evolution of the submonolayer near-surface alloy of ZnPd on Pd (111)

We have performed a high-resolution synchrotron radiation photoelectron spectroscopy study of the initial growth stages of the ZnPd near-surface alloy on Pd(111), complemented by scanning tunnelling microscopy data. We show that the chemical environment for surfaces containing less than half of one monolayer of Zn is chemically distinct from subsequent layers. Surfaces where the deposition is performed at room temperature contain ZnPd islands surrounded by a substrate with dilute Zn substitutions. Annealing these surfaces drives the Zn towards the substrate top-layer, and favours the completion of the first 1 : 1 monolayer before the onset of growth in the next layer.

Early-mid Cretaceous tectonic evolution of eastern Gondwana : from silicic LIP magmatism to continental rupture

The Early–mid Cretaceous marks the confluence of three major continental-scale events in eastern Gondwana: (1) the emplacement of a Silicic Large Igneous Province (LIP) near the continental margin; (2) the volcaniclastic fill, transgression and regression of a major epicontinental seaway developed over at least a quarter of the Australian continent; and (3) epeirogenic uplift, exhumation and continental rupturing culminating in the opening of the Tasman Basin c. 84 Ma. The Whitsunday Silicic LIP event had widespread impact, producing both substantial extrusive volumes of dominantly silicic pyroclastic material and coeval first-cycle volcanogenic sediment that accumulated within many eastern Australian sedimentary basins, and principally in the Great Australian Basin system (>2 Mkm3 combined volume). The final pulse of volcanism and volcanogenic sedimentation at c. 105–95 Ma coincided with epicontinental seaway regression, which shows a lack of correspondence with the global sea-level curve, and alternatively records a wider, continental-scale effect of volcanism and rift tectonism. Widespread igneous underplating related to this LIP event is evident from high paleogeothermal gradients and regional hydrothermal fluid flow detectable in the shallow crust and over a broad region. Enhanced CO2 fluxing through sedimentary basins also records indirectly, large-scale, LIP-related mafic underplating. A discrete episode of rapid crustal cooling and exhumation began c. 100–90 Ma along the length of the eastern Australian margin, related to an enhanced phase of continental rifting that was largely amagmatic, and probably a switch from wide–more narrow rift modes. Along-margin variations in detachment fault architecture produced narrow (SE Australia) and wide continental margins with marginal, submerged continental plateaux (NE Australia). Long-lived NE-trending cross-orogen lineaments controlled the switch from narrow to wide continental margin geometries.

Impacts of climatic factors on evolution of molecular diversity and the natural distribution of wild stocks of the giant freshwater prawn (Macrobrachium rosenbergii)

Natural distributions of most freshwater taxa are restricted geographically, a pattern that reflects dispersal limitation. Macrobrachium rosenbergii is unusual because it occurs naturally in rivers from near Pakistan in the west, across India and Bangladesh to the Malay Peninsula, and across the Sunda Shelf and Indonesian archipelago to western Java. Individuals cannot tolerate full marine conditions, so dispersal between river drainage basins must occur at limited geographical scales when ecological or climatic factors are favorable. We examined molecular diversity in wild populations of M. rosenbergii across its complete natural range to document patterns of diversity and to relate them to factors that have driven evolution of diversity in this species. We found 3 clades in the mitochondrial deoxyribonucleic acid (mtDNA) data set that corresponded geographically with eastern, central, and western sets of haplotypes that last shared a common ancestor 1 × 106 y ago. The eastern clade was closest to the common ancestor of all 3 clades and to the common ancestor with its congener, Macrobrachium spinipes, distributed east of Huxley's Line. Macrobrachium rosenbergii could have evolved in the western Indonesian archipelago and spread westward during the early to mid-Pleistocene to India and Sri Lanka. Additional groups identified in the nuclear DNA data set in the central and western clades probably indicate secondary contact via dispersal between regions and modern introductions that have mixed nuclear and mtDNA genes. Pleistocene sea-level fluctuations can explain dispersal across the Indonesian archipelago and parts of mainland southeastern Asia via changing river drainage connections in shallow seas on wide continental shelves. At the western end of the modern distribution where continental shelves are smaller, intermittent freshwater plumes from large rivers probably permitted larval dispersal across inshore areas of lowered salinity.

Hydrochemical evolution and groundwater flow processes in the Galilee and Eromanga basins, Great Artesian Basin, Australia: A multivariate statistical approach

The Galilee and Eromanga basins are sub-basins of the Great Artesian Basin (GAB). In this study, a multivariate statistical approach (hierarchical cluster analysis, principal component analysis and factor analysis) is carried out to identify hydrochemical patterns and assess the processes that control hydrochemical evolution within key aquifers of the GAB in these basins. The results of the hydrochemical assessment are integrated into a 3D geological model (previously developed) to support the analysis of spatial patterns of hydrochemistry, and to identify the hydrochemical and hydrological processes that control hydrochemical variability. In this area of the GAB, the hydrochemical evolution of groundwater is dominated by evapotranspiration near the recharge area resulting in a dominance of the Na–Cl water types. This is shown conceptually using two selected cross-sections which represent discrete groundwater flow paths from the recharge areas to the deeper parts of the basins. With increasing distance from the recharge area, a shift towards a dominance of carbonate (e.g. Na–HCO3 water type) has been observed. The assessment of hydrochemical changes along groundwater flow paths highlights how aquifers are separated in some areas, and how mixing between groundwater from different aquifers occurs elsewhere controlled by geological structures, including between GAB aquifers and coal bearing strata of the Galilee Basin. The results of this study suggest that distinct hydrochemical differences can be observed within the previously defined Early Cretaceous–Jurassic aquifer sequence of the GAB. A revision of the two previously recognised hydrochemical sequences is being proposed, resulting in three hydrochemical sequences based on systematic differences in hydrochemistry, salinity and dominant hydrochemical processes. The integrated approach presented in this study which combines different complementary multivariate statistical techniques with a detailed assessment of the geological framework of these sedimentary basins, can be adopted in other complex multi-aquifer systems to assess hydrochemical evolution and its geological controls.

Near-infrared spectroscopic study of basic aluminum sulfate and nitrate

The tridecameric Al-polymer [AlO4Al12(OH)24(H2O)12]7+ was prepared by forced hydrolysis of Al3+ up to an OH/Al molar ratio of 2.2. Under slow evaporation crystals were formed of Al13-nitrate. Upon addition of sulfate the tridecamer crystallised as the monoclinic Al13-sulfate. These crystals have been studied using near-infrared spectroscopy and compared to Al2(SO4)3.16H2O. Although the near-infrared spectra of the Al13-sulfate and nitrate are very similar indicating similar crystal structures, there are minor differences related to the strength with which the crystal water molecules are bonded to the salt groups. The interaction between crystal water and nitrate is stronger than with the sulfate as reflected by the shift of the crystal water band positions from 6213, 4874 and 4553 cm–1 for the Al13 sulfate towards 5925, 4848 and 4532 cm–1 for the nitrate. A reversed shift from 5079 and 5037 cm–1 for the sulfate towards 5238 and 5040 cm–1 for the nitrate for the water molecules in the Al13 indicate that the nitrate-Al13 bond is weakened due to the influence of the crystal water on the nitrate. The Al-OH bond in the Al13 complex is not influenced by changing the salt group due to the shielding by the water molecules of the Al13 complex.

Investigation of RuO2/Ta2O5 thin film evolution by thermogravimetry combined with mass spectrometry

The thermal evolution process of RuO2–Ta2O5/Ti coatings with varying noble metal content has been investigated under in situ conditions by thermogravimetry combined with mass spectrometry. The gel-like films prepared from alcoholic solutions of the precursor salts (RuCl3·3H2O, TaCl5) onto titanium metal support were heated in an atmosphere containing 20% O2 and 80% Ar up to 600 °C. The evolution of the mixed oxide coatings was followed by the mass spectrometric ion intensity curves. The cracking of retained solvent and the combustion of organic surface species formed were also followed by the mass spectrometric curves. The formation of carbonyl- and carboxylate-type surface species connected to the noble metal was identified by Fourier transform infrared emission spectroscopy. These secondary processes–catalyzed by the noble metal–may play an important role in the development of surface morphology and electrochemical properties. The evolution of the two oxide phases does not take place independently, and the effect of the noble metal as a combustion catalyst was proved.