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.     

Morphological and microtectonic analysis of Quaternary deformation from Puná and Santa Clara Islands, Gulf of Guayaquil, Ecuador (South America)

This paper presents the neotectonic study of Santa Clara and Puná Islands sited in the Gulf of Guayaquil eastern part. Both islands are located on the south-western segment of the fault zone bounding to the east the North Andean Block. Fault motion and morphostructural analysis were carried out from Pleistocene age terrain. A two step deformation characterises the South Puná tectonics. The first step involves the Zambapala Cordillera uplift that post-dates Pleistocene sediments and pre-dates a marine terrace correlated with the M.I.S. 11 or 13 (440–550 ka). The second step is the formation of a pull-apart that shows evidence of 2.9 km dextral offset since the M.I.S. 11 or 13, giving an offset mean rate of 5.3 to 6.6 mm/yr. This rate is higher than the one calculated on the Pallatanga Fault northeast of the study area, in the Western Andean Cordillera, suggesting that deformation is split in different fault segments from the Gulf of Guayaquil to the continent. The Zambapala Cordillera uplift and transpression deformation requires a compressive event that may have been induced by the subduction process during the early Pleistocene.     

Fan beheading and drainage diversion as evidence of a 3200-2800 BP earthquake event in the Esmeraldas-Tumaco seismic zone: A case study for the effects of great subduction earthquakes

The San Lorenzo area belongs to the Esmeraldas–Tumaco seismic zone where some of the strongest earthquakes of South America occurred during the 20th century. This paper provides evidence for a succession of geomorphic changes characterized by the disruption of the Quaternary drainage network and the reshaping of the Cayapas–Santiago estuary. The rise of the La Boca uplift bordered by the La Boca and San Lorenzo faults is responsible for the southward diversion of the Palabi, Tululbi, Bogotá and Carolina rivers toward the Santiago and Cayapas rivers. The increase of the discharge directed to the Cayapas River generated the change of the channel pattern downstream from the confluence, and the avulsion of a new estuary through the coastal plain. According to the dating of beach ridges the avulsion occurred in the period 3200–2800 BP. This period corresponds also to a faster accretion of the beach ridge margin, interpreted as a response to a small uplift of the shore. The coherency of the three morphologic evidences—diversion of drainage network, avulsion and increase of coastal accretion—suggest a unique morphotectonic event, in relation with the activity of the Esmaraldas–Tumaco seismic zone. The opening of a direct communication through the mangrove margin may have brought favorable conditions for the development of the La Tolita archaeological site after 3000 BP.     

Hyperspectral mapping of alteration assemblages within a hydrothermal vug at the Haughton impact structure,Canada

Meteorite impacts on Earth and Mars can generate hydrothermal systems that alter the primary mineralogies of rocks and provide suitable environments for microbial colonization. We investigate a calcite–marcasite‐bearing vug at the ~23 km diameter Haughton impact structure, Devon Island, Nunavut, Canada, using imaging spectroscopy of the outcrop in the field (0.65–1.1 μm) and samples in the laboratory (0.4–2.5 μm), point spectroscopy (0.35–2.5 μm), major element chemistry, and X‐ray diffraction analyses. The mineral assemblages mapped at the outcrop include marcasite; marcasite with minor gypsum and jarosite; fibroferrite and copiapite with minor gypsum and melanterite; gypsum, Fe³⁺ oxides, and jarosite; and calcite, gypsum, clay, microcline, and quartz. Hyperspectral mapping of alteration phases shows spatial patterns that illuminate changes in alteration conditions and formation of specific mineral phases. Marcasite formed from the postimpact hydrothermal system under reducing conditions, while subsequent weathering oxidized the marcasite at low temperatures and water/rock ratios. The acidic fluids resulting from the oxidation collected on flat‐lying portions of the outcrop, precipitating fibroferrite + copiapite. That assemblage then likely dissolved, and the changing chemistry and pH resulting from interaction with the calcite‐rich host rock formed gypsum‐bearing red coatings. These results have implications for understanding water–rock interactions and habitabilities at this site and on Mars.     

The Spatial and Temporal Characteristics of Pc3 Geomagnetic Activity over Canada in 2000, as a Guide to Planning the Times of Aeromagnetic Surveys

Geomagnetic activity affects aeromagnetic surveys. Geomagnetic variations are quite complex and can be quantified in different ways. A measure of geomagnetic activity that is useful for planning aeromagnetic surveys is the Pc3 pulsation index developed by the Australian Space Weather Agency. Purposeful to developing guidelines for planning aeromagnetic surveys in Canada, we study the variations in Pc3 index amplitude over Canada in 2000. This study shows distinct patterns associated with the sub-auroral zone, the auroral zone, and the polar cap. Average Pc3 index activity is higher during the months of February, July, September, and November in the auroral and sub-auroral zones. The station in the polar cap exhibits maximum activity near midday during the summer months. Detailed analysis of a magnetic storm shows that Pc3 index amplitude during the beginning of the solar storm is least important at the polar cap. The mean Pc3 index also relates to solar wind parameters such as the solar wind velocity and the vertical polarity of the interplanetary magnetic field. Analysis of the morning maximum of the Pc3 index observed in the auroral zone can be used to develop guidelines for planning aeromagnetic surveys in Canada and other areas of the world affected by auroral zones.     

On the determination of the closure parameters in higher-order closure models

In higher-order closure models at least the pressure redistribution and the dissipation of the turbulent kinetic energy and the temperature variance have to be parameterized. Due to this, the introduction of proportionality coefficients — the so-called closure parameters — is forced, which have to be determined before the model is used. We compare a group of models which use the return-to-isotropy hypothesis (Rotta, 1951) to describe the pressure redistribution and assume local isotropy for the smallest eddies in order to parameterize the dissipation. Special concern is given to the method of Mellor and Yamada (1982). Some of the closure parameters are re-derived on the basis of sensitivity studies requiring that both shear production and buoyancy behave in a realistic way if pressure redistribution or dissipation is changed by varying the closure parameters. This set of parameters is compared with those obtained by fitting to experimental data, by use of the Monin-Obukhov similarity theory and by considering ratios of variances, covariances and mean flow gradients, respectively. It is shown that the various sets of closure parameters are at least of the same order. The differences give some insight into the advantages and disadvantages of the various determination procedures. However, the general accordance of the different parameter sets supports the assumption of universal constants.     

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.     

Mass fluxes of xenobiotics below cities: challenges in urban hydrogeology

Urban areas are the focus of major ecological, social and economical activity. They are thus also prime locations of increasing conflict with regard to water use and water protection. As a direct and/or indirect consequence of urban land use and human activity, urban water systems are frequently polluted with organic contaminants including waste water-born xenobiotics such as pharmaceuticals, personal care products (collectively known as PPCPs) and endocrine-active substances. This study reviews new integrated methodologies including flux calculations as well as chemical investigations for determining the impact of human activities on urban water systems and on processes within the urban watershed. The use of indicator substances, representing different contaminant sources and pathways, integral pumping tests and mass balance approaches are suitable alternatives within these environments. The issues are explored using contaminant mass balance examples from Halle/Saale and Leipzig, Germany.