Liquid–Vapor Interface of Formic Acid Solutions in Salt Water: A Comparison of Macroscopic Surface Tension and Microscopic in Situ X-ray Photoelectron Spectroscopy Measurements

The liquid–vapor interface is difficult to access experimentally but is of interest from a theoretical and applied point of view and has particular importance in atmospheric aerosol chemistry. Here we examine the liquid–vapor interface for mixtures of water, sodium chloride, and formic acid, an abundant chemical in the atmosphere. We compare the results of surface tension and X-ray photoelectron spectroscopy (XPS) measurements over a wide range of formic acid concentrations. Surface tension measurements provide a macroscopic characterization of solutions ranging from 0 to 3 M sodium chloride and from 0 to over 0.5 mole fraction formic acid. Sodium chloride was found to be a weak salting out agent for formic acid with surface excess depending only slightly on salt concentration. In situ XPS provides a complementary molecular level description about the liquid–vapor interface. XPS measurements over an experimental probe depth of 51 Å gave the C 1s to O 1s ratio for both total oxygen and oxygen from water. XPS also provides detailed electronic structure information that is inaccessible by surface tension. Density functional theory calculations were performed to understand the observed shift in C 1s binding energies to lower values with increasing formic acid concentration. Part of the experimental −0.2 eV shift can be assigned to the solution composition changing from predominantly monomers of formic acid to a combination of monomers and dimers; however, the lack of an appropriate reference to calibrate the absolute BE scale at high formic acid mole fraction complicates the interpretation. Our data are consistent with surface tension measurements yielding a significantly more surface sensitive measurement than XPS due to the relatively weak propensity of formic acid for the interface. A simple model allowed us to replicate the XPS results under the assumption that the surface excess was contained in the top four angstroms of solution.

The Efficacy of a Novel Microbial 6-Phytase Expressed in Aspergillus oryzae on the Performance and Phosphorus Utilization of Cold- and Warm-Water Fish: Rainbow Trout, Oncorhynchus mykiss , and Nile Tilapia, Oreochromis niloticus

The efficacy and tolerance of a novel microbial 6-phytase were investigated in rainbow trout, Oncorhynchus mykiss, and Nile tilapia, Oreochromis niloticus. Reference diets were sufficient in available phosphorus (P). The test diet limiting in available P was supplemented with phytase at 500, 1000, or 2000 phytase units/kg feed. The enzyme was effective in increasing total P apparent digestibility coefficient in relation to increasing the dose of phytase in rainbow trout and Nile tilapia. Zinc apparent digestibility improved in relation to phytase supplementation in rainbow trout. P release due to phytase supplementation ranged from 0.06 to 0.18% P/kg feed in rainbow trout and from 0.13 to 0.26% P/kg feed in Nile tilapia. A 58-d performance trial was conducted to evaluate tolerance of fish to phytase supplementation. Dietary treatments consisted of a basal diet without phytase or supplemented with 2000 and 200,000 phytase units/kg feed. Results indicate that this novel microbial 6-phytase is well tolerated by fish. Significant improvements for growth as well as feed conversion ratio were observed when the phytase was fed at 2000 phytase units/kg feed. This phytase is proven efficient in releasing P from phytate and could be added when plants are used for fish meal replacement in diets for salmonid and omnivorous fish.

Genetic consequences of habitat fragmentation during a range expansion

We investigate the effect of habitat fragmentation on the genetic diversity of a species experiencing a range expansion. These two evolutionary processes have not been studied yet, at the same time, owing to the difficulties of deriving analytic results for non-equilibrium models. Here we provide a description of their interaction by using extensive spatial and temporal coalescent simulations and we suggest guidelines for a proper genetic sampling to detect fragmentation. To model habitat fragmentation, we simulated a two-dimensional lattice of demes partitioned into groups (patches) by adding barriers to dispersal. After letting a population expand on this grid, we sampled lineages from the lattice at several scales and studied their coalescent history. We find that in order to detect fragmentation, one needs to extensively sample at a local level rather than at a landscape level. This is because the gene genealogy of a scattered sample is less sensitive to the presence of genetic barriers. Considering the effect of temporal changes of fragmentation intensities, we find that at least 10, but often >100, generations are needed to affect local genetic diversity and population structure. This result explains why recent habitat fragmentation does not always lead to detectable signatures in the genetic structure of populations. Finally, as expected, long-distance dispersal increases local genetic diversity and decreases levels of population differentiation, efficiently counteracting the effects of fragmentation.

Pasture degradation modifies the water and carbon cycles of the Tibetan highlands

The Tibetan Plateau has a significant role with regard to atmospheric circulation and the monsoon in particular. Changes between a closed plant cover and open bare soil are one of the striking effects of land use degradation observed with unsustainable range management or climate change, but experiments investigating changes of surface properties and processes together with atmospheric feedbacks are rare and have not been undertaken in the world's two largest alpine ecosystems, the alpine steppe and the Kobresia pygmaea pastures of the Tibetan Plateau. We connected measurements of micro-lysimeter, chamber, 13C labelling, and eddy covariance and combined the observations with land surface and atmospheric models, adapted to the highland conditions. This allowed us to analyse how three degradation stages affect the water and carbon cycle of pastures on the landscape scale within the core region of the Kobresia pygmaea ecosystem. The study revealed that increasing degradation of the Kobresia turf affects carbon allocation and strongly reduces the carbon uptake, compromising the function of Kobresia pastures as a carbon sink. Pasture degradation leads to a shift from transpiration to evaporation while a change in the sum of evapotranspiration over a longer period cannot be confirmed. The results show an earlier onset of convection and cloud generation, likely triggered by a shift in evapotranspiration timing when dominated by evaporation. Consequently, precipitation starts earlier and clouds decrease the incoming solar radiation. In summary, the changes in surface properties by pasture degradation found on the highland have a significant influence on larger scales.

Forests and water: Managing interrelations

Due to their biodiversity, forests generate a range of products and services that are of economic, social or cultural value to human beings. Natural resource management provisions should ensure the creation and maintenance of these goods and services in the long term. However, unsustainable management practices of forests do not only generate short-term benefits but also considerable costs for society. Payment by the beneficiaries of the services would enable us to internalise external costs and promote sustainable management. Two days of conferences on ”Forest and water”, on the multifunctionality of forests, on interactions between forests and water, on sustainable resource management, on payments for environmental services, their institutional and economic perspectives, were the basis of this brochure which presents an in-depth analysis of the information exchanged among conference participants and the public. It is intended for readers who work in international development cooperation and assistance in Switzerland and abroad. It offers additional information for local programmes in the field and at policy level.

Understanding measured water rotational temperatures and column densities in the very innermost coma of Comet 73P/Schwassmann–Wachmann 3 B

Direct sublimation of a comet nucleus surface is usually considered to be the main source of gas in the coma of a comet. However, evidence from a number of comets including the recent spectacular images of Comet 103P/Hartley 2 by the EPOXI mission indicates that the nucleus alone may not be responsible for all, or possibly at times even most, of the total amount of gas seen in the coma. Indeed, the sublimation of icy grains, which have been injected into the coma, appears to constitute an important source. We use the fully-kinetic Direct Simulation Monte Carlo model of Tenishev et al. (Tenishev, V.M., Combi, M.R., Davidsson, B. [2008]. Astrophys. J., 685, 659−677; Tenishev, V.M., Combi, M.R., Rubin, M. [2011]. Astrophys. J., 732) to reproduce the measurements of column density and rotational temperature of water in Comet 73P-B/Schwassmann–Wachmann 3 obtained with a very high spatial resolution of ∼30 km using IRCS/Subaru in May 2006 (Bonev, B.P., Mumma, M.J., Kawakita, H., Kobayashi, H., Villanueva, G.L. [2008]. Icarus, 196, 241−248). For gas released solely from the cometary nucleus at a heliocentric distance of 1 AU, modeled rotational temperatures start at 110 K close to the surface and decrease to only several tens of degrees by 10–20 nucleus radii. However, the measured decay of both rotational temperature and column density with distance from the nucleus is much slower than predicted by this simple model. The addition of a substantial (distributed) source of gas from icy grains in the model slows the decay in rotational temperature and provides a more gradual drop in column density profiles. Together with a contribution of rotational heating of water molecules by electrons, the combined effects allow a much better match to the IRCS/Subaru observations. From the spatial distributions of water abundance and temperature measured in 73P/SW3-B, we have identified and quantified multiple mechanisms of release. The application of this tool to other comets may permit such studies over a range of heliocentric and geocentric distances.

Effect of the Tiger Stripes on the water vapor distribution in Enceladus' exosphere

The jet activity emanating from Enceladus' exosphere south pole region observed by Cassini is a subject of intensive study. The in situ and remote sensing observations performed since 2005 triggered an active modeling campaign. Such modeling is essential for better understanding of the measurements performed by individual instruments as well as to link them for a more complete picture of the volatile and ice grain distribution in Enceladus' exosphere. This paper is focused on the investigation of the effect that diffuse gas sources along the Tiger Stripes have on distribution of the water vapor in Enceladus' exosphere using the updated version of our multiplume model. We have found that accounting for the gas production by Tiger Stripes is critical for interpretation of the Cassini data. According to our calculations, sources along the Tiger Stripes (apart from those originally identified by Spitale and Porco (2007)) must contribute about 23–32% to the total plume source rate, which varies in the range of (6.4–29) ×1027 s−1. The effect of the previously unidentified source suggested in the paper is found to be critical for explaining the Ultraviolet Imaging Spectrograph 2007 and 2010 observations in the whole range of the elapsed times.

Electrochemical CO2 Reduction - A Critical View on Fundamentals, Materials and Applications

The electrochemical reduction of CO2 has been extensively studied over the past decades. Nevertheless, this topic has been tackled so far only by using a very fundamental approach and mostly by trying to improve kinetics and selectivities toward specific products in half-cell configurations and liquid-based electrolytes. The main drawback of this approach is that, due to the low solubility of CO2 in water, the maximum CO2 reduction current which could be drawn falls in the range of 0.01–0.02 A cm–2. This is at least an order of magnitude lower current density than the requirement to make CO2-electrolysis a technically and economically feasible option for transformation of CO2 into chemical feedstock or fuel thereby closing the CO2 cycle. This work attempts to give a short overview on the status of electrochemical CO2 reduction with respect to challenges at the electrolysis cell as well as at the catalyst level. We will critically discuss possible pathways to increase both operating current density and conversion efficiency in order to close the gap with established energy conversion technologies.

Sublimation of water ice mixed with silicates and tholins: Evolution of surface texture and reflectance spectra, with implications for comets

The surfaces of many objects in the Solar System comprise substantial quantities of water ice sometimes mixed with minerals and/or organic molecules. The sublimation of the ice changes the structural and optical properties of these objects. We present laboratory data on the evolution of the structure and the visible and near-infrared spectral reflectance of icy surface analogues of cometary ices, made of water ice, complex organic matter (tholins) and silicates, as they undergo sublimation under low temperature (<-70°C) and pressure (10-⁵mbar) conditions inside the SCITEAS simulation chamber. As the water ice sublimated, we observed in situ the formation of a porous sublimation lag deposit, or sublimation mantle, at the top of the ice. This mantle is a network of filaments made of the non-volatile particles. Organics or phyllosilicates grains, able to interact via stronger inter-particulate forces than olivine grains, can form a foam-like structure having internal cohesiveness, holding olivine grains together. As this mantle builds-up, the band depths of the sub-surface water ice are attenuated until complete extinction under only few millimeters of mantle. Optically thick sublimation mantles are mainly featureless in the near infrared. The absorption bands of the minerals present in the mantle are weak, or even totally absent if minerals are mixed with organics which largely dominate the VIS–NIR reflectance spectrum. During sublimation, ejections of large fragments of mantle, triggered by the gas flow, expose ice particles to the surface. The contrast of brightness between mantled and ice-exposed areas depends on the wavelength range and the dust/ice ratio considered. We describe how the chemical nature of the non-volatiles, the size of their particles, the way they are mixed with the ice and the dust/ice mass ratio influence the texture, activity and spectro-photometric properties of the sublimation mantles. These data provide useful references for interpreting remote-sensing observations of comets and also icy satellites or trans-neptunian objects.

The promoting effect of water on the electroreduction of CO2 in acetonitrile

The promoting effect of water on the electrochemical reduction of carbon dioxide (CO2) from non-aqueous solvents has been studied by means of cyclic voltammetry and in-situ surface-enhanced infrared absorption spectroscopy (SEIRAS). CO2 electroreduction on gold is known to be highly selective towards CO formation in aqueous and in non-aqueous media. The use of non-aqueous solvents is advantageous due to the significantly increased solubility of CO2 compared to aqueous systems. However, in the absence of any proton source, extremely high overpotentials are required for the CO2 electroreduction. In this work, we demonstrate for the first time a tremendous accelerating effect of water additives on the electroreduction of CO2 taking place at gold/acetonitrile interfaces. Already moderate amounts of water, in the concentration range of 0.5 to 0.7 M, are sufficient to decrease significantly the overpotential of CO2 reduction while keeping the CO2 concentration as high as in the pure acetonitrile. The effect of water additives on the mechanism of CO2 electroreduction on gold is discussed on the basis of electrochemical and IR spectroscopic data. The results obtained from gold are compared to analogue experiments carried out on platinum.

Future water quality monitoring--adapting tools to deal with mixtures of pollutants in water resource management.

Environmental quality monitoring of water resources is challenged with providing the basis for safeguarding the environment against adverse biological effects of anthropogenic chemical contamination from diffuse and point sources. While current regulatory efforts focus on monitoring and assessing a few legacy chemicals, many more anthropogenic chemicals can be detected simultaneously in our aquatic resources. However, exposure to chemical mixtures does not necessarily translate into adverse biological effects nor clearly shows whether mitigation measures are needed. Thus, the question which mixtures are present and which have associated combined effects becomes central for defining adequate monitoring and assessment strategies. Here we describe the vision of the international, EU-funded project SOLUTIONS, where three routes are explored to link the occurrence of chemical mixtures at specific sites to the assessment of adverse biological combination effects. First of all, multi-residue target and non-target screening techniques covering a broader range of anticipated chemicals co-occurring in the environment are being developed. By improving sensitivity and detection limits for known bioactive compounds of concern, new analytical chemistry data for multiple components can be obtained and used to characterise priority mixtures. This information on chemical occurrence will be used to predict mixture toxicity and to derive combined effect estimates suitable for advancing environmental quality standards. Secondly, bioanalytical tools will be explored to provide aggregate bioactivity measures integrating all components that produce common (adverse) outcomes even for mixtures of varying compositions. The ambition is to provide comprehensive arrays of effect-based tools and trait-based field observations that link multiple chemical exposures to various environmental protection goals more directly and to provide improved in situ observations for impact assessment of mixtures. Thirdly, effect-directed analysis (EDA) will be applied to identify major drivers of mixture toxicity. Refinements of EDA include the use of statistical approaches with monitoring information for guidance of experimental EDA studies. These three approaches will be explored using case studies at the Danube and Rhine river basins as well as rivers of the Iberian Peninsula. The synthesis of findings will be organised to provide guidance for future solution-oriented environmental monitoring and explore more systematic ways to assess mixture exposures and combination effects in future water quality monitoring.

Litter nutrients and retranslocation in a central African rain forest dominated by ectomycorrhizal trees

In the strongly seasonal, but annually very wet, parts of the tropics, low-water availability in the short dry season leads to a semi-deciduous forest, one which is also highly susceptible to nutrient loss from leaching in the long wet season. Patterns in litterfall were compared between forest with low (LEM) and high (HEM) abundances of ectomycorrhizal trees in Korup National Park, Cameroon, over 26 months in 1990–92. Leaf litter was sorted into 26 abundant species which included six ectomycorrhizal species, and of these three were the large grove-forming trees Microberlinia bisulcata, Tetraberlinia bifoliolata and Tetraberlinia moreliana. Larger-tree species shed their leaves with pronounced peaks in the dry season, whereas other species had either weaker dependence, showed several peaks per year, or were wet-season shedders. Although total annual litterfall differed little between forest types, in the HEM forest (dominated by M. bisulcata) the dry-season peak was more pronounced and earlier than that in the LEMforest. Species differed greatly in their mean leaf litterfall nutrient concentrations, with an approx. twofold range for nitrogen and phosphorus, and 2.5–3.5-fold for potassium, magnesium and calcium. In the dry season, LEM and HEM litter showed similar declines in P and N concentration, and increases in K and Mg; some species, especially M. bisculcata, showed strong dry-wet season differences. The concentration of P (but not N) was higher in the leaf litter of ectomycorrhizal than nonectomycorrhizal species. Retranslocation of N and P was lower among the ectomycorrhizal than nonectomycorrhizal species by approx. twofold. It is suggested that, within ectomycorrhizal groves on this soil low in P, a fast decomposition rate with minimal loss of mineralized P is possible due to the relatively high litter P not limiting the cycle at this stage, combined with an efficient recapture of released P by the surface organic layer of ectomycorrhizas and fine roots. This points to a feedback between two essential controlling steps (retranslocation and mineralization) in a tropical rain forest ecosystem dominated by ectomycorrhizal trees.

VIS-NIR reflectance of water ice/regolith analogue mixtures and implications for the detectability of ice mixed within planetary regoliths

Permanently shadowed regions at the poles of the Moon and Mercury have been pointed out as candidates for hosting water ice at their surface. We have measured in the laboratory the visible and near infrared spectral range (VIS-NIR) bidirectional reflectance of intimate mixtures of water ice and the JSC-1AF lunar simulant for different ice concentrations, particle sizes, and measurement geometries. The nonlinearity between the measured reflectance and the amount of ice in the mixture can be reproduced to some extent by the mixing formulas of standard reflectance models, in particular, those of Hapke and Hiroi, which are tested here. Estimating ice concentrations from reflectance data without knowledge of the mixing coefficientsstrongly dependent on the size/shape of the grainscan result in large errors. According to our results, it is possible that considerable amounts of water ice might be intimately mixed in the regolith of the Moon and Mercury without producing noticeable photometric signatures.

Influence of catchment quality and altitude on the water and sediment composition of 68 small lakes in Central Europe

68 lakes (63 Swiss, 2 French and 3 Italian) located in an altitudinal range between 334 and 2339m spanning a wide range of land-use have been investigated. The aim of the study was to discuss influences of geographic location, vegetation and land-use in the catchment area on the water and sediment chemistry of small lakes. Detailed quantitative description of land-use, vegetation, and climate in the watershed of all lakes was established. Surface and bottom water samples collected from each lake were analyzed for major ions and nutrients. Correlations were interpreted using linear regression analysis. Chemical parameters of water and sediment reflect the characteristics of the catchment areas. All lakes were alkaline since they were situated on calcareous bedrock. Concentrations of nitrogen and phosphorus strongly increase with increasing agricultural land-use. Na and K, however, are positively correlated with the amount of urbanization within the catchment area. These elements as well as dissolved organic carbon (DOC), Mg, Ca, and alkalinity, increase when the catchment is urbanized or used for agriculture. Total nitrogen and organic carbon in the sediments decrease distinctly if large parts of the catchment consist of bare land. No correlations between sediment composition and maximum water depth or altitude of the lakes were found.¶Striking differences in the water compositions of lakes above and below approximately 700 m of altitude were observed. Concentrations of total nitrogen and nitrate, total phosphorus, DOC, Na, K, Mg, Ca, and alkalinity are distinctly higher in most lakes below 700 m than above, and the pH of the bottom waters of these lakes is generally lower. Estimates of total nitrogen concentrations, even in remote areas, indicate that precipitation is responsible for increased background concentrations. At lower altitudes nitrogen concentrations in lakes is explained by the nitrogen loaded rain from urban areas deposited on the catchment, and with high percentages of agricultural land-use in the watershed.

The dust environment of comet 67P/Churyumov-Gerasimenko from Rosetta OSIRIS and VLT observations in the 4.5 to 2.9 AU heliocentric distance range inbound

Context. The ESA Rosetta spacecraft, currently orbiting around cornet 67P/Churyumov-Gerasimenko, has already provided in situ measurements of the dust grain properties from several instruments, particularly OSIRIS and GIADA. We propose adding value to those measurements by combining them with ground-based observations of the dust tail to monitor the overall, time-dependent dust-production rate and size distribution. Aims. To constrain the dust grain properties, we take Rosetta OSIRIS and GIADA results into account, and combine OSIRIS data during the approach phase (from late April to early June 2014) with a large data set of ground-based images that were acquired with the ESO Very Large Telescope (VLT) from February to November 2014. Methods. A Monte Carlo dust tail code, which has already been used to characterise the dust environments of several comets and active asteroids, has been applied to retrieve the dust parameters. Key properties of the grains (density, velocity, and size distribution) were obtained from. Rosetta observations: these parameters were used as input of the code to considerably reduce the number of free parameters. In this way, the overall dust mass-loss rate and its dependence on the heliocentric distance could be obtained accurately. Results. The dust parameters derived from the inner coma measurements by OSIRIS and GIADA and from distant imaging using VLT data are consistent, except for the power index of the size-distribution function, which is alpha = -3, instead of alpha = -2, for grains smaller than 1 mm. This is possibly linked to the presence of fluffy aggregates in the coma. The onset of cometary activity occurs at approximately 4.3 AU, with a dust production rate of 0.5 kg/s, increasing up to 15 kg/s at 2.9 AU. This implies a dust-to-gas mass ratio varying between 3.8 and 6.5 for the best-fit model when combined with water-production rates from the MIRO experiment.