Rainfall intensity affects runoff responses in a semi-arid catchment

The source and hydrochemical makeup of a stream reflects the connectivity between rainfall, groundwater, the stream, and is reflected to water quantity and quality of the catchment. However, in a semi-arid, thick, loess covered catchment, temporal variation of stream source and event associated behaviours are lesser known. Thus, the isotopic and chemical hydrographs in a widely distributed, deep loess, semi-arid catchment of the northern Chinese Loess Plateau were characterized to determine the source and hydrochemical behaviours of the stream during intra-rainfall events. Rainfall and streamflow were sampled during six hydrologic events coupled with measurements of stream baseflow and groundwater. The deuterium isotope (²H), major ions (Cl⁻, SO₄²⁻, NO₃⁻, Ca²⁺, K⁺, Mg²⁺, and Na⁺) were evaluated in water samples obtained during rainfall events. Temporal variation of ²H and Cl⁻ measured in the groundwater and stream baseflow prior to rainfall was similar; however, the isotope compositions of the streamflow fluctuated significantly and responded quickly to rainfall events, likely due to an infiltration excess, overland dominated surface runoff during torrential rainfall events. Time source separation using ²H demonstrated greater than 72% on average, the stream composition was event water during torrential rainfall events, with the proportion increasing with rainfall intensity. Solutes concentrations in the stream had loglinear relationships with stream discharge, with an outling anomaly with an example of an intra-rainfall event on Oct. 24, 2015. Stream Cl⁻ behaved nonconservative during rainfall events, temporal variation of Cl⁻ indicated a flush and washout at the onset of small rainfall events, a dilution but still high concentration pattern in high discharge and old water dominated in regression flow period. This study indicates rainfall intensity affects runoff responses in a semi-arid catchment, and the stored water in the thick, loess covered areas was less connected with stream runoff. Solute transport may threaten water quality in the area, requiring further analysis of the performance of the eco-restoration project.     

The concept of limiting magnitude and the performance of the Isaac Newton telescope for prime focus photography

A quantitative definition of limiting magnitude for stellar photographs is proposed, together with a method of measurement employing a Racine prism. Limiting magnitudes inU, B andV for the Isaac Newton telescope at Herstmonceux derived from a total of 72 prime focus photographs are presented and the results correlated with the size of the photographed image. The limiting magnitude for an extrapolated value of the seeing of 1 isB=22^m.0, in good agreement with a value obtained by scaling the limiting magnitudes of the 200 inch telescope.     

A molal-based model for strong acid chemistry at low temperatures (<200 to 298 K)

Geochemical processes occurring in cold environments on Earth, Mars, and Europa have elicited considerable interest in the application of geochemical models to subzero temperatures. Few existing geochemical models explicitly include acid chemistry and those that do are largely restricted to temperatures ≥0°C or rely on the mole-fraction scale rather than the more common molal scale. This paper describes (1) use of the Clegg mole-fraction acid models to develop a molal-based model for hydrochloric, nitric, and sulfuric acids at low temperatures; (2) incorporation of acid chemistry and nitrate minerals into the FREZCHEM model; (3) validation and limitations of the derived acid model; and (4) simulation of hypothetical acidic brines for Europa.The Clegg mole-fraction acid models were used to estimate activities of water and mean ionic activity coefficients that serve as the database for estimating molal Pitzer-equation parameters for HCl (188 to 298 K), HNO₃ (228 to 298 K), and H₂SO₄ (208 to 298 K). Model eutectics for HNO₃ and H₂SO₄ agree with experimental measurements to within ± 0.2°C. In agreement with previous work, the experimental freezing point depression (fpd) data for pure HCl at subzero temperatures were judged to be flawed and unreliable. Three alternatives are discussed for handling HCl chemistry at subzero temperatures. In addition to defining the solubility of solid-phase acids, this work also adds three new nitrate minerals and six new acid salts to the FREZCHEM model and refines equilibria among water ice, liquid water, and water vapor over the temperature range from 180 to 298 K. The final system is parameterized for Na-K-Mg-Ca-H-Cl-SO₄-NO₃-OH-HCO₃-CO₃-CO₂-H₂O.Simulations of hypothetical MgSO₄-H₂SO₄-H₂O and Na₂SO₄-MgSO₄-H₂SO₄-H₂O brines for Europa demonstrate how freezing can convert a predominantly salt solution into a predominantly acid solution at subzero temperatures. This result has consequences for the effects of salinity, acidity, and temperature as limiting factors for potential life on Europa. Strong acidity would limit life-forms to highly acidophilic organisms.     

The BEAM-project: prediction and assessment of mixture toxicities in the aquatic environment

Freshwater and marine ecosystems are exposed to various multi-component mixtures of pollutants. Nevertheless, most ecotoxicological research and chemicals regulation focus on hazard and exposure assessment of individual substances only, the problem of chemical mixtures in the environment is ignored to a large extent. In contrast, the assessment of combination effects has a long tradition in pharmacology, where mixtures of chemicals are specifically designed to develop new products, e.g. human and veterinary drugs or agricultural and non-agricultural pesticides. In this area, two concepts are frequently used and are thought to describe fundamental relationships between single substance and mixture effects: Independent Action (Response Addition) and Concentration Addition. The question, to what extent these concepts may also be applied in an ecotoxicological and regulatory context may be considered a research topic of major importance, as the concepts would allow to make use of already existing single substance toxicity data for the predictive assessment of mixture toxicities. Two critical knowledge gaps are identified: (a) There is a lack of environmental realism, as a huge part of our current knowledge about the applicability of the concepts is restricted to artificial situations with respect to mixture composition or biological effect assessment. (b) The knowledge on what exactly is needed for using the concepts as tools for the predictive mixture toxicity assessment is insufficient. Both gaps seriously hamper the necessary, scientifically sound consideration of mixture toxicities in a regulatory context.In this paper, the two concepts will be briefly introduced, the necessity of considering the toxicities of chemical mixtures in the environment will be demonstrated and the applicability of Independent Action and Concentration Addition as tools for the prediction and assessment of mixture toxicities will be discussed. An overview of the specific aims and approaches of the BEAM project to fill in the identified knowledge gaps is given and first results are outlined.     

Effects of pressure on aqueous chemical equilibria at subzero temperatures with applications to Europa

Pressure plays a critical role in controlling aqueous geochemical processes in deep oceans and deep ice. The putative ocean of Europa could have pressures of 1200 bars or higher on the seafloor, a pressure not dissimilar to the deepest ocean basin on Earth (the Mariana Trench at 1100 bars of pressure). At such high pressures, chemical thermodynamic relations need to explicitly consider pressure. A number of papers have addressed the role of pressure on equilibrium constants, activity coefficients, and the activity of water. None of these models deal, however, with processes at subzero temperatures, which may be important in cold environments on Earth and other planetary bodies. The objectives of this work were to (1) incorporate a pressure dependence into an existing geochemical model parameterized for subzero temperatures (FREZCHEM), (2) validate the model, and (3) simulate pressure-dependent processes on Europa. As part of objective 1, we examined two models for quantifying the volumetric properties of liquid water at subzero temperatures: one model is based on the measured properties of supercooled water, and the other model is based on the properties of liquid water in equilibrium with ice.The relative effect of pressure on solution properties falls in the order: equilibrium constants(K) > activity coefficients (γ) > activity of water (a_w). The errors (%) in our model associated with these properties, however, fall in the order: γ > K > a_w. The transposition between K and γ is due to a more accurate model for estimating K than for estimating γ. Only activity coefficients are likely to be significantly in error. However, even in this case, the errors are likely to be only in the range of 2 to 5% up to 1000 bars of pressure. Evidence based on the pressure/temperature melting of ice and salt solution densities argue in favor of the equilibrium water model, which depends on extrapolations, for characterizing the properties of liquid water in electrolyte solutions at subzero temperatures, rather than the supercooled water model. Model-derived estimates of mixed salt solution densities and chemical equilibria as a function of pressure are in reasonably good agreement with experimental measurements.To demonstrate the usefulness of this low-temperature, high-pressure model, we examined two hypothetical cases for Europa. Case 1 dealt with the ice cover of Europa, where we asked the question: How far above the putative ocean in the ice layer could we expect to find thermodynamically stable brine pockets that could serve as habitats for life? For a hypothetical nonconvecting 20 km icy shell, this potential life zone only extends 2.8 km into the icy shell before the eutectic is reached. For the case of a nonconvecting icy shell, the cold surface of Europa precludes stable aqueous phases (habitats for life) anywhere near the surface. Case 2 compared chemical equilibria at 1 bar (based on previous work) with a more realistic 1460 bars of pressure at the base of a 100 km Europan ocean. A pressure of 1460 bars, compared to 1 bar, caused a 12 K decrease in the temperature at which ice first formed and a 11 K increase in the temperature at which MgSO₄·12H₂O first formed. Remarkably, there was only a 1.2 K decrease in the eutectic temperatures between 1 and 1460 bars of pressure. Chemical systems and their response to pressure depend, ultimately, on the volumetric properties of individual constituents, which makes every system response highly individualistic.     

Origin and transportation history of lunar breccia 14311

In this paper, we compare the U‐Pb zircon age distribution pattern of sample 14311 from the Apollo 14 landing site with those from other breccias collected at the same landing site. Zircons in breccia 14311 show major age peaks at 4340 and 4240 Ma and small peaks at 4110, 4030, and 3960 Ma. The zircon age patterns of breccia 14311 and other Apollo 14 breccias are statistically different suggesting a separate provenance and transportation history for these breccias. This interpretation is supported by different U‐Pb Ca‐phosphate and exposure ages for breccia 14311 (Ca‐phosphate age: 3938 ± 4 Ma, exposure age: ~550–660 Ma) from the other Apollo 14 breccias (Ca‐phosphate age: 3927 ± 2 Ma, compatible with the Imbrium impact, exposure age: ~25–30 Ma). Based on these observations, we consider two hypotheses for the origin and transportation history of sample 14311. (1) Breccia 14311 was formed in the Procellarum KREEP terrane by a 3938 Ma‐old impact and deposited near the future site of the Imbrium basin. The breccia was integrated into the Fra Mauro Formation during the deposition of the Imbrium impact ejecta at 3927 Ma. The zircons were annealed by mare basalt flooding at 3400 Ma at Apollo 14 landing site. Eventually, at approximately 660 Ma, a small and local impact event excavated this sample and it has been at the surface of the Moon since this time. (2) Breccia 14311 was formed by a 3938 Ma‐old impact. The location of the sample is not known at that time but at 3400 Ma, it was located nearby or buried by hot basaltic flows. It was transported from where it was deposited to the Apollo 14 landing site by an impact at approximately 660 Ma, possibly related to the formation of the Copernicus crater and has remained at the surface of the Moon since this event. This latter hypothesis is the simplest scenario for the formation and transportation history of the 14311 breccia.