Experimental evidence for a partially dissociated water bilayer on Ru{0001}

Core-level photoelectron spectra, in excellent agreement with ab initio calculations, confirm that the stable wetting layer of water on Ru{0001} contains O-H and H2O in roughly 3:5 proportion, for OHx coverages between 0.25 and 0.7 ML, and T<170 K. Proton disorder explains why the wetting structure looks to low energy electron diffraction (LEED) to be an ordered p(root3xroot3)R30degrees adlayer, even though approximate to3/8 of its molecules are dissociated. Complete dissociation to atomic oxygen starts near 190 K. Low photon flux in the synchrotron experiments ensured that the diagnosis of the nature of the wetting structure quantified by LEED is free of beam-induced damage.

A FORTRAN-90 low-energy electron diffraction program (LEED90 v1.1)

We describe a FORTRAN-90 program to compute low-energy electron diffraction I(V) curves. Plane-waves and layer doubling are used to compute the inter-layer multiple-scattering, while the intra-layer multiple-scattering is computed in the standard way expanding the wavefield on a basis of spherical waves. The program is kept as general as possible, in order to allow testing different parts of multiple-scattering calculations. In particular, it can handle non-diagonal t-matrices describing the scattering of non-spherical potentials, anisotropic vibrations, anharmonicity, etc. The program does not use old FORTRAN flavours, and has been written keeping in mind the advantage for parallelism brought forward by FORTRAN-90.

Theoretical studies of the interface between water and Langmuir films of aliphatic alcohols

The interface between water and Langmuir films of long chain aliphatic molecules is investigated using accurate intermolecular potentials. The stabilities of various ice structures which could form at the interface are examined. Antiferroelectric ice is found to be the most stable, but this stability depends crucially on the first layer of water. Ferroelectric structures are found to collapse upon relaxation. Our model was not able to differentiate between the different nucleation properties of C31H63OH and C30H61OH. A better description of the alcohol–water interaction is probably required to account for this difference.

Reaction of a phospholipid monolayer with gas-phase ozone at the air-water interface: measurement of surface excess and surface pressure in real time

The reaction between gas-phase ozone and monolayers of the unsaturated lipid 1-palmitoy1-2-oleoyl-sn-glycero-3-phosphocholine, POPC, on aqueous solutions has been studied in real time using neutron reflection and surface pressure measurements. The reaction between ozone and lung surfactant, which contains POPC, leads to decreased pulmonary function, but little is known shout the changes that occur to the interfacial material as a result of oxidation. The results reveal that the initial reaction of ozone with POPC leads to a rapid increase in surface pressure followed by a slow decrease to very low values. The neutron reflection measurements, performed on an isotopologue of POPC with a selectively deuterated palmitoyl strand, reveal that the reaction leads to loss of this strand from the air-water interface. suggesting either solubilization of the product lipid or degradation of the palmitoyl strand by a reactive species. Reactions of H-1-POPC on D2O reveal that the headgroup region of the lipids in aqueous solution is not dramatically perturbed by the reaction of POPC monolayers with ozone supporting degradation of the palmitoyl strand rather than solubilization. The results are consistent with the reaction of ozone with the oleoyl strand of POPC at the air water interface leading to the formation of OH radicals. the highly reactive OH radicals produced can then go on to react with the saturated palmitoyl strands leading to the formation or oxidized lipids with shorter alkyl tails.

Can shells of freshwater mussels (Unionidae) be used to estimate low summer discharge of rivers and associated droughts?

This paper examines if shell oxygen isotope ratios (d18Oar) of Unio sp. can be used as a proxy of past discharge of the river Meuse. The proxy was developed from a modern dataset for the reference time interval 1997–2007, which showed a logarithmic relationship between discharge and measured water oxygen isotope ratios(d18Ow). To test this relationship for past time intervals,d18Oar values were measured in the aragonite of the growth increments of four Unio sp. shells; two from a relatively wet period and two from a very dry time interval (1910–1918 and 1969–1977, respectively). Shell d18Oar records were converted into d18Ow values using existing water temperature records. Summer d18Ow values, reconstructed from d18Oar of 1910–1918, showed a similar range as the summer d18Ow values for the reference time interval 1997–2007, whilst summer reconstructed d18Ow values for the time interval 1969–1977 were anomalously high. These high d18Ow values suggest that the river Meuse experienced severe summer droughts during the latter time interval. d18Ow values were then applied to calculate discharge values. It was attempted to estimate discharge from the reconstructed d18Ow values using the logarithmic relationship between d18Ow and discharge. A comparison of the calculated summer discharge results with observed discharge data showed that Meuse low-discharge events below a threshold value of 6 m3/s can be detected in the reconstructed d18Ow records, but true quantification remains problematic.

Oxygen isotope composition of bivalve seasonal growth increments and ambient water in the rivers Rhine and Meuse

The application of oxygen isotope ratios ({delta}18O) from freshwater bivalves as a proxy for river discharge conditions in the Rhine and Meuse rivers is investigated. We compared a dataset of water temperature and water {delta}18O values with a selection of recent shell {delta}18O records for two species of the genus Unio in order to establish: (1) whether differences between the rivers in water {delta}18O values, reflecting river discharge conditions, are recorded in unionid shells; and (2) to what extent ecological parameters influence the accuracy of bivalve shell {delta}18O values as proxies of seasonal, water oxygen isotope conditions in these rivers. The results show that shells from the two rivers differ significantly in {delta}18O values, reflecting different source waters for these two rivers. The seasonal shell {delta}18O records show truncated sinusoidal patterns with narrow peaks and wide troughs, caused by temperature fractionation and winter growth cessation. Interannual growth rate reconstructions show an ontogenetic growth rate decrease. Growth lines in the shell often, but not always, coincide with winter growth cessations in the {delta}18O record, suggesting that growth cessations in the shell {delta}18O records are a better age estimator than counting internal growth lines. Seasonal predicted and measured {delta}18O values correspond well, supporting the hypothesis that these unionids precipitate their shells in oxygen isotopic equilibrium. This means that (sub-) fossil unionids can be used to reconstruct spring-summer river discharge conditions, such as Meuse low-discharge events caused by droughts and Rhine meltwater-influx events caused by melting of snow in the Alps.

Temporal relations of column water vapor and tropical precipitation

Empirical studies using satellite data and radiosondes have shown that precipitation increases with column water vapor (CWV) in the tropics, and that this increase is much steeper above some critical CWV value. Here, eight years of 1-min-resolution microwave radiometer and optical gauge data at Nauru Island are analyzed to better understand the relationships among CWV, column liquid water (CLW), and precipitation at small time scales. CWV is found to have large autocorrelation times compared with CLW and precipitation. Before precipitation events, CWV increases on both a synoptic-scale time period and a subsequent shorter time period consistent with mesoscale convective activity; the latter period is associated with the highest CWV levels. Probabilities of precipitation increase greatly with CWV. Given initial high CWV, this increased probability of precipitation persists at least 10–12 h. Even in periods of high CWV, however, probabilities of initial precipitation in a 5-min period remain low enough that there tends to be a lag before the start of the next precipitation event. This is consistent with precipitation occurring stochastically within environments containing high CWV, with the latter being established by a combination of synoptic-scale and mesoscale forcing.

Cloud statistics and cloud radiative effect for a low-mountain site

In 2007, the Atmospheric Radiation Measurement (ARM) Mobile Facility (AMF) was operated for a nine-month period in the Murg Valley, Black Forest, Germany, in support of the Convective and Orographically-induced Precipitation Study (COPS). The synergy of AMF and COPS partner instrumentation was exploited to derive a set of high-quality thermodynamic and cloud property profiles with 30 s resolution. In total, clouds were present 72% of the time, with multi-layer mixed phase (28.4%) and single-layer water clouds (11.3%) occurring most frequently. A comparison with the Cloudnet sites Chilbolton and Lindenberg for the same time period revealed that the Murg Valley exhibits lower liquid water paths (LWPs; median = 37.5 g m−2) compared to the two sites located in flat terrain. In order to evaluate the derived thermodynamic and cloud property profiles, a radiative closure study was performed with independent surface radiation measurements. In clear sky, average differences between calculated and observed surface fluxes are less than 2% and 4% for the short wave and long wave part, respectively. In cloudy situations, differences between simulated and observed fluxes, particularly in the short wave part, are much larger, but most of these can be related to broken cloud situations. The daytime cloud radiative effect (CRE), i.e. the difference of cloudy and clear-sky net fluxes, has been analysed for the whole nine-month period. For overcast, single-layer water clouds, sensitivity studies revealed that the CRE uncertainty is likewise determined by uncertainties in liquid water content and effective radius. For low LWP clouds, CRE uncertainty is dominated by LWP uncertainty; therefore refined retrievals, such as using infrared and/or higher microwave frequencies, are needed.

Molecular dynamics simulation insight into the mechanism of phenol adsorption at low coverages from aqueous solutions on microporous carbons

MD simulation studies showing the influence of porosity and carbon surface oxidation on phenol adsorption from aqueous solutions on carbons are reported. Based on a realistic model of activated carbon, three carbon structures with gradually changed microporosity were created. Next, a different number of surface oxygen groups was introduced. The pores with diameters around 0.6 nm are optimal for phenol adsorption and after the introduction of surface oxygen functionalities, adsorption of phenol decreases (in accordance with experimental data) for all studied models. This decrease is caused by a pore blocking effect due to the saturation of surface oxygen groups by highly hydrogen-bounded water molecules.

Are the debates on water privatization missing the point? Experiences from Africa, Asia and Latin America

This paper has two principal aims: first, to unravel some of the arguments mobilized in the controversial privatization debate, and second, to review the scale and nature of private sector provision of water and sanitation in Africa, Asia and Latin America. Despite being vigorously promoted in the policy arena and having been implemented in several countries in the South in the 1990s, privatization has achieved neither the scale nor benefits anticipated. In particular, the paper is pessimistic about the role that privatization can play in achieving the Millennium Development Goals of halving the number of people without access to water and sanitation by 2015. This is not because of some inherent contradiction between private profits and the public good, but because neither publicly nor privately operated utilities are well suited to serving the majority of low-income households with inadequate water and sanitation, and because many of the barriers to service provision in poor settlements can persist whether water and sanitation utilities are publicly or privately operated. This is not to say that well-governed localities should not choose to involve private companies in water and sanitation provision, but it does imply that there is no justification for international agencies and agreements to actively promote greater private sector participation on the grounds that it can significantly reduce deficiencies in water and sanitation services in the South.

pH-tunable hydrogelators for water purification: structural optimisation and evaluation

A focused library of potential hydrogelators each containing two substituted aromatic residues separated by a urea or thiourea linkage have been synthesised and characterized. Six of these novel compounds are highly efficient hydrogelators, forming gels in aqueous solution at low concentrations (0.03–0.60 wt %). Gels were formed through a pH switching methodology, by acidification of a basic solution (pH 14 to ≈4) either by addition of HCl or via the slow hydrolysis of glucono-δ-lactone. Frequently, gelation was accompanied by a dramatic switch in the absorption spectra of the gelators, resulting in a significant change in colour, typically from a vibrant orange to pale yellow. Each of the gels was capable of sequestering significant quantities of the aromatic cationic dye, methylene blue, from aqueous solution (up to 1.02 g of dye per gram of dry gelator). Cryo-transmission electron microscopy of two of the gels revealed an extensive network of high aspect ratio fibers. The structure of the fibers altered dramatically upon addition of 20 wt % of the dye, resulting in aggregation and significant shortening of the fibrils. This study demonstrates the feasibility for these novel gels finding application as inexpensive and effective water purification platforms.

Natal nest locations of the Asian house rat (Rattus tanezumi) in lowland rice–coconut cropping systems: a coconut penthouse or rice bunds with water frontage?

CONTEXT. Rattus tanezumi is a serious crop pest within the island of Luzon, Philippines. In intensive flood-irrigated rice field ecosystems of Luzon, female R. tanezumi are known to primarily nest within the tillers of ripening rice fields and along the banks of irrigation canals. The nesting habits of R. tanezumi in complex rice–coconut cropping systems are unknown. AIMS. To identify the natal nest locations of R. tanezumi females in rice–coconut systems of the Sierra Madre Biodiversity Corridor (SMBC), Luzon, during the main breeding season to develop a management strategy that specifically targets their nesting habitat. METHODS. When rice was at the booting to ripening stage, cage-traps were placed in rice fields adjacent to coconut habitat. Thirty breeding adult R. tanezumi females were fitted with radio-collars and successfully tracked to their nest sites. KEY RESULTS. Most R. tanezumi nests (66.7%) were located in coconut groves, five nests (16.7%) were located in rice fields and five nests (16.7%) were located on the rice field edge. All nests were located above ground level and seven nests were located in coconut tree crowns. The median distance of nest sites to the nearest rice field was 22.5m. Most nest site locations had good cover of ground vegetation and understorey vegetation, but low canopy cover. Only one nest location had an understorey vegetation height of less than 20 cm. CONCLUSIONS. In the coastal lowland rice–coconut cropping systems of the SMBC, female R. tanezumi showed a preference for nesting in adjacent coconut groves. This is contrary to previous studies in intensive flood-irrigated rice ecosystems of Luzon, where the species nests mainly in the banks of irrigation canals. It is important to understand rodent breeding ecology in a specific ecosystem before implementing appropriate management strategies. IMPLICATIONS. In lowland rice–coconut cropping systems, coconut groves adjacent to rice fields should be targeted for the 20 management of R. tanezumi nest sites during the main breeding season as part of an integrated ecologically based approach to rodent pest management.

Automatic near real-time selection of flood water levels from high resolution Synthetic Aperture Radar images for assimilation into hydraulic models: a case study

Flood extents caused by fluvial floods in urban and rural areas may be predicted by hydraulic models. Assimilation may be used to correct the model state and improve the estimates of the model parameters or external forcing. One common observation assimilated is the water level at various points along the modelled reach. Distributed water levels may be estimated indirectly along the flood extents in Synthetic Aperture Radar (SAR) images by intersecting the extents with the floodplain topography. It is necessary to select a subset of levels for assimilation because adjacent levels along the flood extent will be strongly correlated. A method for selecting such a subset automatically and in near real-time is described, which would allow the SAR water levels to be used in a forecasting model. The method first selects candidate waterline points in flooded rural areas having low slope. The waterline levels and positions are corrected for the effects of double reflections between the water surface and emergent vegetation at the flood edge. Waterline points are also selected in flooded urban areas away from radar shadow and layover caused by buildings, with levels similar to those in adjacent rural areas. The resulting points are thinned to reduce spatial autocorrelation using a top-down clustering approach. The method was developed using a TerraSAR-X image from a particular case study involving urban and rural flooding. The waterline points extracted proved to be spatially uncorrelated, with levels reasonably similar to those determined manually from aerial photographs, and in good agreement with those of nearby gauges.

Variability in fecal water genotoxicity, determined using the Comet assay, is independent of endogenous N-nitroso compound formation attributed to red meat consumption

Red meat consumption causes a dose-dependent increase in fecal apparent total N-nitroso compounds (ATNC). The genotoxic effects of these ATNCs were investigated using two different Comet assay protocols to determine the genotoxicity of fecal water samples. Fecal water samples were obtained from two studies of a total of 21 individuals fed diets containing different amounts of red meat, protein, heme, and iron. The first protocol incubated the samples with HT-29 cells for 5 min at 4 degrees C, whereas the second protocol used a longer exposure time of 30 min and a higher incubation temperature of 37 degrees C. DNA strand breaks were quantified by the tail moment (DNA in the comet tail multiplied by the comet tail length). The results of the two Comet assay protocols were significantly correlated (r = 0.35, P = 0.003), however, only the second protocol resulted in detectable levels of DNA damage. Inter-individual effects were variable and there was no effect on fecal water genotoxicity by diet (P > 0.20), mean transit time (P = 0.588), or weight (P = 0.705). However, there was a highly significant effect of age (P = 0.019). There was no significant correlation between concentrations of ATNCs in fecal homogenates and fecal water genotoxicity (r = 0.04, P = 0.74). ATNC levels were lower in fecal water samples (272 microg/kg) compared to that of fecal homogenate samples (895 microg/kg) (P < 0.0001). Failure to find dietary effects on fecal water genotoxicity may therefore be attributed to individual variability and low levels of ATNCs in fecal water samples.

Unraveling the electronic structures of low-valent naphthalene and anthracene iron complexes: x-ray, spectroscopic, and density functional theory studies

Naphthalene and anthracene transition metalates are potent reagents, but their electronic structures have remained poorly explored. A study of four Cp*-substituted iron complexes (Cp* = pentamethylcyclopentadienyl) now gives rare insight into the bonding features of such species. The highly oxygen- and water-sensitive compounds [K(18-crown- 6){Cp*Fe(η4-C10H8)}] (K1), [K(18-crown-6){Cp*Fe(η4-C14H10)}] (K2), [Cp*Fe(η4-C10H8)] (1), and [Cp*Fe(η4-C14H10)] (2) were synthesized and characterized by NMR, UV−vis, and 57Fe Mössbauer spectroscopy. The paramagnetic complexes 1 and 2 were additionally characterized by electron paramagnetic resonance (EPR) spectroscopy and magnetic susceptibility measurements. The molecular structures of complexes K1, K2, and 2 were determined by single-crystal X-ray crystallography. Cyclic voltammetry of 1 and 2 and spectroelectrochemical experiments revealed the redox properties of these complexes, which are reversibly reduced to the monoanions [Cp*Fe(η4-C10H8)]− (1−) and [Cp*Fe(η4-C14H10)]− (2−) and reversibly oxidized to the cations [Cp*Fe(η6-C10H8)]+ (1+) and [Cp*Fe(η6-C14H10)]+ (2+). Reduced orbital charges and spin densities of the naphthalene complexes 1−/0/+ and the anthracene derivatives 2−/0/+ were obtained by density functional theory (DFT) methods. Analysis of these data suggests that the electronic structures of the anions 1− and 2− are best represented by low-spin FeII ions coordinated by anionic Cp* and dianionic naphthalene and anthracene ligands. The electronic structures of the neutral complexes 1 and 2 may be described by a superposition of two resonance configurations which, on the one hand, involve a low-spin FeI ion coordinated by the neutral naphthalene or anthracene ligand L, and, on the other hand, a low-spin FeII ion coordinated to a ligand radical L•−. Our study thus reveals the redox noninnocent character of the naphthalene and anthracene ligands, which effectively stabilize the iron atoms in a low formal, but significantly higher spectroscopic oxidation state.