Electron spectroscopic studies of perfect and defect metal oxide surfaces

A number of surface sensitive electron spectroscopic techniques have been used during the last few years to study the geometric and electronic structure of well characterized surfaces of metal oxide single crystals. For rocksalt monoxides, the (100) surface has been found to be very nearly a truncation of the bulk lattice; only qualitativelow energy electron diffraction (LEED) measurements have been performed on other oxide crystal structures. The electronic structure of nearly perfect oxide surfaces is generally very similar to that of the bulk, although excitonic surface states have been found on some rocksalt oxides. However, the presence of O-vacancy point defects on transition metal oxide surfaces changes their electronic structure drastically, increasing the d-orbital population of the cations adjacent to the defect. These surface defects are generally the active sites for chemisorption, with nearly perfect surfaces being relatively inert with respect to most of the molecules that have been studied.     

The destruction of mangroves

Coastal developments in Venezuela are leading to the rapid destruction of the mangrove forests. Population pressure leads to an overcrowding of public recreational beaches and the wealthy are increasingly seeking out previously deserted coasts. A rash of summer houses built on stilts over the shallow water is now extending around the mangrove areas, causing pollution, erosion and a progressive deterioration of the coastal environment.     

Stress transfer and nonlinear stress accumulation at subduction-type plate boundaries — Application to the Aleutians

A study of stress accumulation in seismic gaps and of stress transfer along linear plate boundaries is presented. Time-dependent reloading of plate boundaries following seismic ruptures is modeled by a modified Elsasser model of a coupled lithosphere/asthenosphere plate system. This model is applied to study a series of large earthquakes in the Aleutian Islands and the Alaska peninsula in 1938–1965. It is found that the Rat Island earthquake and the 1948 earthquake in the central Aleutians are likely to have been triggered by adjacent ruptures, in the sense that their occurrence would have come at a later time had their neighboring segments not been ruptured. Stresses in the Unalaska Gap and the Shumagin gap are at a relatively high level and these segments of the plate boundary may be expected to rupture in the near future. In general, in the ten years (about 16% of the earthquake cycle for the Aleutians) following an earthquake, the stress recovery in the rupture zone is highly nonlinear, resulting in a much more rapid stress accumulation than the linear case. Even at a later stage of an earthquake cycle, adjacent ruptures can cause an acceleration of loading rate in addition to the coseismic stress jump. A good example is the influence of the 1964 Alaska earthquake on the 1938 rupture zone. A general conclusion of this work is that long term earthquake prediction models must take into account the nonlinear stress accumulation behavior in seismic gaps. Also, we have shown the interaction of adjacent plate boundary segments, which suggests that some large earthquakes may have been triggered by nearby ruptures.     

Distribution of hydrocarbons in the oyster,Pinctada margaratifera,along the coast of Kuwait

Concentrations of total hydrocarbons within the boiling point range of the alkanes n-C₁₄ and n-C₃₂ were determined in oysters, Pinctada margaratifera, from coastal waters of Kuwait. Levels of petroleum-derived hydrocarbons were highest in an area adjacent to the major oil loading facilities. Whether the use of dispersants to treat minor spills increases levels of incorporation of petroleum compounds into the food webs could not be concluded from the data of this study. Levels of total petroleum-type hydrocarbons in the oysters at this site were equivalent to those in mussels, Mytilus sp., from harbours, bays and urban coastal areas of California. The Kuwaiti oysters lacked a C₂₈ pentacyclic triterpane that was present in extracts of mussels from southern California that had been recently exposed to a minor spill or to a natural seepage. Levels of DDE and PCB were comparable to those in relatively unpolluted areas of North America.     

Temporal changes in the contribution of methane-oxidizing bacteria to the biomass of chironomid larvae determined using stable carbon isotopes and ancient DNA

Freshwater lakes are important sources of methane (CH₄) emissions, by organic matter degradation under anaerobic conditions (methanogenesis). Previous studies suggest that lakes contribute up to 16 % of natural emissions. About 60 % of the CH₄ produced is used as an energy source by methane-oxidizing bacteria (MOB—methanotrophs), which could support higher trophic levels, especially Chironomidae (Diptera). Because biogenic methane has a very low stable carbon isotope value, evidence of methane-derived organic-matter assimilation can be tracked by stable carbon isotope analysis in consumers such as chironomids. In some cases, however, chironomid δ¹³C values are not low enough to unambiguously demonstrate methanotroph assimilation and an alternative line of evidence is required. Analysis of ancient DNA (aDNA) from the methanotroph community preserved in lake sediment provides reliable information about past methane oxidation in freshwater lakes. A combination of these two approaches was used to study a sediment core from the deepest zone of Lake Narlay (Jura, France), which covers the last 1,500 years of sediment accumulation. Results show a significant change ca. AD 1600, with an increase in the proportion of MOB in the total bacteria community, and a decrease in chironomid head-capsule δ¹³C. These trends suggest assimilation of MOB by chironomid larvae, and account for up to 36 % of the chironomid biomass. The data also provide information about the feeding behavior of chironomids, with evidence for preferential assimilation of methanotroph type I and the NC10 phylum. The combination of aDNA analysis and carbon stable isotopes strengthens the reliability of inferences about carbon sources incorporated into chironomid biomass.     

Paleo-stratigraphic permeability anisotropy controls supergene mimetic martite goethite deposits

The Hamersley Basin in Western Australia is one of the world's largest iron ore-producing regions, hosting two types of ore in banded iron formations: the high-grade martite-microplaty haematite and the supergene martite-goethite ores. With the high-grade ores almost entirely mined in the last decade, the supergene ores have more recently become the dominant resource of interest. Consequently, understanding the genesis of these martite-goethite deposits is a critical step for exploration. Yet, although various models exist, there is still no consensus on how these mineral resources formed, complicating the prediction of resource volume and location. Here, we show that the paleo-stratigraphic permeability anisotropy (with higher permeability along strata than across) controls the supergene mimetic enrichment transport process and, subsequently, the mineralisation distribution. We introduce a flow model that implicitly represents strata with a potential function that orients the permeability tensor accurately. The numerical solver uses automatic mesh adaptivity to deliver robust solutions. By accurately reproducing the mineralisation patterns in specific deposits, we identify and quantify the paleo-water table level and permeability anisotropy ratio as the two main controlling parameters for the mineralisation distribution. These insights provide new timing constraints for the mineralisation and the physical process of iron enrichment, suggesting much more potential mineralisation volume in the paleo-reconstructed zones than previously anticipated. These flow models allow us to draw geological conclusions with few a priori assumptions required for the genetic model in which the transport component is dominant. The predictive power of this methodology will allow targeted drilling to narrow down the prospective areas and lower exploration costs. Furthermore, the methodology's generality applies to other commodities in sedimentary basins involving supergene processes and will improve our understanding of various genetic models.     

Progressive glacial retreat in the Southern Altiplano (Uturuncu volcano, 22°S) between 65 and 14 ka constrained by cosmogenic He dating

This work presents the first reconstruction of late Pleistocene glacier fluctuations on Uturuncu volcano, in the Southern Tropical Andes. Cosmogenic ³He dating of glacial landforms provides constraints on ancient glacier position between 65 and 14 ka. Despite important scatter in the exposure ages on the oldest moraines, probably resulting from pre-exposure, these ³He data constrain the timing of the moraine deposits and subsequent glacier recessions: the Uturuncu glacier may have reached its maximum extent much before the global LGM, maybe as early as 65 ka, with an equilibrium line altitude (ELA) at 5280 m. Then, the glacier remained close to its maximum position, with a main stillstand identified around 40 ka, and another one between 35 and 17 ka, followed by a limited recession at 17 ka. Then, another glacial stillstand is identified upstream during the late glacial period, probably between 16 and 14 ka, with an ELA standing at 5350 m. This stillstand is synchronous with the paleolake Tauca highstand. This result indicates that this regionally wet and cold episode, during the Heinrich 1 event, also impacted the Southern Altiplano. The ELA rose above 5450 m after 14 ka, synchronously with the Bolling–Allerod.     

Assessing physical vulnerability in large cities exposed to flash floods and debris flows: the case of Arequipa (Peru)

Understanding the physical vulnerability of buildings and infrastructure to natural hazards is an essential step in risk assessment for large cities. We have interpreted high spatial resolution images, conducted field surveys, and utilized numerical simulations, in order to assess vulnerability across Arequipa, south Peru, close to the active El Misti volcano. The emphasis of this study was on flash floods and volcanic or non-volcanic hyperconcentrated flows, which recur on average every 3.5 years across the city. We utilized a geographic information system to embed vulnerability and hazard maps as a step to calculate risk for buildings and bridges along the Río Chili valley and two tributaries. A survey of ~1,000 buildings from 46 city blocks, different in age, construction materials, and land usage, provided architectural and structural characteristics. A similar survey of twenty bridges across the three valleys was based on structural, hydraulic, and strategic parameters. Interpretation of high spatial resolution (HSR) satellite images, which allows for quick identification of approximately 69 % of the structural building types, effectively supplemented field data collection. Mapping vulnerability has led us to pinpoint strategic areas in case of future destructive floods or flows. Calculated vulnerability is high if we examine structural criteria alone. We further consider physical setting with the most vulnerable city blocks located on the lowermost terraces, perpendicular or oblique to the flow path. Statistical analysis conducted on 3,015 city blocks, considering nine criteria identified from HSR images, indicated that building-type heterogeneity and the shape of the city blocks, along with building and street network density, are the most discriminant parameters for assessing vulnerability.     

Hydrochemical and isotopic characteristics of groundwater in the Ndop plain,northwest Cameroon: resilience to seasonal climatic changes

Shallow groundwater (>30 mbgl) is an essential source of drinking water to rural communities in the Ndop plain, northwest Cameroon. As a contribution to water management, the effect of seasonal variation on the groundwater chemistry, hydrochemical controls, drinking quality and recharge were investigated during the peaks of the dry (January) and rainy (September) seasons. Field measurements of physical parameters were preceded by sampling 58 groundwater samples during both seasons for major ions and stable isotope analyses. The groundwater, which was barely acidic (mean pH of 6) and less mineralised (TDS < 272 mg/l), showed no significant seasonal variation in temperature, pH and TDS during the two seasons. The order of cation abundance (meq/l) was Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ and Na⁺ > Mg²⁺ > Ca²⁺ > K⁺ in the dry and rainy seasons, respectively, but that of anions ( \( {\text{HCO}}_{3}^{ - } \)  >  \( {\text{NO}}_{3}^{ - } \)  > Cl^? >  \( {\text{SO}}_{4}^{2 - } \)  > F^?) was similar in both seasons. This suggests a negligible effect of seasonal variations on groundwater chemistry. The groundwater, which was CaMgHCO₃ and NaHCO₃, is chemically evolved rainfall (CaMgSO₄Cl) in the area. Silicate mineral dissolution and cation-exchange were the main controls on groundwater chemistry while there was little anthropogenic influence. The major ions and TDS concentrations classified the water as suitable for human consumption as per WHO guidelines. The narrow cluster of δ¹⁸O and δD of same groundwater from both seasons between the δ¹⁸O and δD values of May–June precipitation along the Ndop Meteoric Water Line indicates meteoric origin, rapid recharge (after precipitation) and timing of recharge between May and June rainfall. Diffuse groundwater recharge mainly occurs at low altitudes (<1,400 m asl) within the plain. Besides major ions and TDS, the similar δ¹⁸O and δD of groundwater from both seasons indicate a consistent groundwater recharge and flow pattern throughout the year and resilience to present day short-term seasonal climatic variations. However, controlled groundwater abstraction is recommended given the increasing demand.