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.     

A Holocene high-resolution record of aquatic productivity,seasonal anoxia and meromixis from varved sediments of Lake Łazduny,North-Eastern Poland: insight from a novel multi-proxy approach

Anthropogenic eutrophication and spreading anoxia in freshwater systems is a global concern. Little is known about anoxia in earlier historic times under weaker human impact, or under prehistoric natural conditions with different trophic, land cover and climatic regimes. We use a novel approach that combines high-resolution hyperspectral imaging with µ-XRF and HPLC-pigment data, which allows us to assess chloropigments (productivity) and bacteriopigments (anoxia) at seasonal subvarve-scale resolution. Our ~9700 cal a bp varved sediment record from NE Poland suggests that productivity increased stepwise from oligotrophic Early Holocene conditions (until ~9200 cal a bp ) to mesotrophic conditions in the Mid- and Late Holocene. Natural eutrophication was mainly a function of progressing landscape evolution with intense weathering under dense forest and warm-moist climatic conditions. Generally, anoxia increased with increasing productivity. Seasonal anoxia and some multi-decadal periods of meromixis were the common mixing patterns throughout the Holocene except for a period of persisting meromixis between ~5200 and 2000 cal a bp. Anthropogenic deforestation around 400 cal a bp resulted in substantially better lake oxygenation despite high productivity. In this small lake, aquatic productivity and lakeshore forest cover (wind shield) were more important factors controlling oxic/anoxic conditions than Holocene temperature variability.     

Quantification of river water infiltration in shallow aquifers using acesulfame and anthropogenic gadolinium

This study has investigated the use of the artificial sweetener acesulfame and the magnetic resonance imaging contrast agent gadolinium as quantitative tracers for river water infiltration into shallow groundwater. The influence of a river on alluvial groundwater in a subalpine catchment in western Europe has been assessed using the ‘classical’ hydrochemical tracer chloride and the trace contaminants acesulfame and anthropogenic gadolinium. Mixing ratios for riverine bank filtrate with ambient groundwater and the uncertainties associated with the temporal and spatial tracer variability were calculated using acesulfame and gadolinium and compared with those obtained using chloride. The temporal variability of tracer concentrations in river water of gadolinium (standard deviation SD: 63%) and acesulfame (SD: 71%) both exceeded that of chloride (SD: 27%), and this was identified as the main source of uncertainty in the mixing analysis. Similar spatial distributions were detected in the groundwater for chloride and gadolinium, but not for acesulfame. Mixing analyses using acesulfame resulted in calculated mixing ratios that differed from those obtained using gadolinium and chloride by up to 83% and 92%, respectively. At the investigated site, which had oxic conditions and moderate temperatures, acesulfame was found to be a less reliable tracer than either gadolinium or chloride, probably because of natural attenuation and input from other sources. There was no statistically significant difference between the mixing ratios obtained using chloride or gadolinium, the mixing ratios obtained using gadolinium were 40–50% lower than those obtained using chloride. This is mainly due to a bias of the mean gadolinium concentration in river water towards higher values. In view of the uncertainties of the two tracers, neither could be preferred over the other for the quantification of bank filtrate in groundwater. At this specific site gadolinium was able to reliably identify river water infiltration and was a more precise tracer than chloride at low mixing ratios (<20%), because of the exclusive occurrence of gadolinium in river water and its high dynamic range. Copyright © 2015 John Wiley & Sons, Ltd.     

High‐resolution stratigraphy of Scandinavian coastal archaeological settlements: the case of Håkonshella,W Norway

The stratigraphy of Scandinavian open‐air archaeological settlements is usually characterized as homogeneous, highly enriched in decomposing organic matter and poor in biogenic carbonates such as shells or bones. As a result, stratigraphies are often difficult to read in the field and settlement sequences may pass unnoticed by archaeologists. Here we show how the integration of bulk analyses, soil micromorphology, X‐ray fluorescence (XRF) core scanning and multivariate statistics can help in overcoming such limitations. We use the case study of Håkonshella 8, a Mesolithic hunter‐fisher‐gatherer settlement located in Bergen (W Norway). Fluctuations in the organic matter content, geochemical proxies (mainly P, Ga, Ti and the Si/Al ratio) and redoximorphic features highlight four cycles of site occupation and abandonment in an otherwise massive anthropogenic deposit. Following these settlement sequences, the site was covered by colluvium from nearby slopes over which a waterlogged soil formed. The approach used in Håkonshella has the potential to improve our capacity to interpret organically enriched anthropic deposits formed in coastal Scandinavia and in similar climatic regions.     

Is robustness really robust? How different definitions of robustness impact decision-making under climate change

Robust decision-making is being increasingly used to support environmental resources decisions and policy analysis under changing climate and society. In this context, a robust decision is a decision that is as much as possible insensitive to a large degree of uncertainty and ensures certain performance across multiple plausible futures. Yet, the concept of robustness is neither unique nor static. Multiple robustness metrics, such as maximin, optimism-pessimism, max regret, have been proposed in the literature, reflecting diverse optimistic/pessimistic attitudes by the decision maker. Further, these attitudes can evolve in time as a response to sequences of favorable (or adverse) events, inducing possible dynamic changes in the robustness metrics. In this paper, we explore the impact of alternative definitions of robustness and their evolution in time for a case of water resources system management under changing climate. We study the decisions of the Lake Como operator, who is called to regulate the lake by balancing irrigation supply and flood control, under an ensemble of climate change scenarios. Results show a considerable variability in the system performance across multiple robustness metrics. In fact, the mis-definition of the actual decision maker’s attitude biases the simulation of its future decisions and produces a general underestimation of the system performance. The analysis of the dynamic evolution of the decision maker’s preferences further confirms the potentially strong impact of changing robustness definition on the decision-making outcomes. Climate change impact assessment studies should therefore include the definition of robustness among the uncertain parameters of the problem in order to analyze future human decisions under uncertainty.     

Sexual reproduction and early life‐history traits of the Mediterranean soft coral Alcyonium acaule

Understanding processes that contribute to a better comprehension of the population dynamics of long‐lived species is critical for the maintenance and potential recovery of such species. Despite the abundance of soft corals in Mediterranean rocky reefs, little information exists on their life histories and reproductive patterns. In this study, we assessed the main reproductive characteristics and early life‐history traits of the long‐lived soft coral Alcyonium acaule. The sex ratio was 1:1; the smallest fertile colonies were one finger in size (2.1 ± 0.6 cm in height), and both colony and polyp fertility increased with colony size. Likewise, the number of eggs and spermary sacs per polyp increased significantly with colony size, whereas the diameter of the female and male sexual products did not. Over 6 years of observations (2007–2012), spawning occurred primarily in July, after the seawater reached 20 °C, in a single spawning episode per year. Approximately 80% of female colonies released eggs, which were retained on the surface of the mother colony by mucous strings for up to a few days. High fertilization rates were observed during spawning in 2008 and 2009 (94.9% and 87.0%, respectively). The timing of development was ~24 h for the blastulae, ~48–72 h for the planulae and 8–22 days for metamorphosis into primary polyps. Survivorship of planulae was relatively high (~50% at 45 days after release), but only 24% of larvae metamorphosed into primary polyps, and their survivorship was moderate after 2 months (65% in 2008 and 74% in 2009). Asexual reproduction was negligible, indicating that sexual reproduction is the main mechanism supporting the maintenance and recovery of populations.     

Linking foraging behavior and diet in a diving seabird

Foraging behavior and diet of breeding seabirds may be analysed simultaneously with the combined use of remote sensing devices and stable isotope analysis. Imperial shag, Phalacrocorax atriceps, breeding at Punta León colony, Argentina, were equipped with global positioning system (GPS) loggers to record foraging trips and blood samples were taken after removal of the devices in order to analyse their nitrogen and carbon stable isotope composition in whole blood and plasma. Whole blood was correlated to plasma isotopic composition for each individual (n = 35), linking diet in the short and medium term. Sexes did not differ in isotopic signatures. The maximum distance reached and the total number of dives that individuals made on two consecutive foraging trips were correlated to their plasma nitrogen isotopic signature. Individuals that went further from the colony and dived fewer times presented more positive signatures, indicative of benthic prey consumption (e.g. Raneya brasiliensis). Diet was predominantly benthic with some individuals incorporating pelagic prey (Engraulis anchoita) and even cephalopods (Octopus tehuelchus). Within breeding pairs (n = 9), different combinations of foraging and prey preferences were observed. Estimated trophic levels of these individuals were similar to those of the same species in other colonies further south along the Patagonian coast.     

Engineering geomorphological characterisation of the Vajont Slide,Italy, and a new interpretation of the chronology and evolution of the landslide

Although the 1963 Vajont Slide in Italy has been extensively studied for over 50 years, its regional geological and geomorphological context has been neglected. In this paper, we use field observations and remote sensing data to elucidate the interaction between endogenic and exogenic processes that brought the north slope of Monte Toc to failure. We present the first detailed pre- and post-failure engineering geomorphology maps of the slide area. The maps delineate two main landslide blocks, several sub-blocks, compressional and extensional zones, and secondary failures in the deposit. The maps provide new insights into the kinematics, dynamics and evolution of the slide. Finally, we discuss the origin of Vajont Gorge and a prehistoric failure that occurred at the same location as the 1963 slide. We propose, as part of a newly developed multi-stage landscape evolution sequence, that the prehistoric failure was a deep-seated gravitational slope deformation (sackung) that initiated during deglaciation and continued to slowly move until the catastrophic failure in 1963. We argue that the gorge was created by these deep-seated slow movements.