Modeling aqueous ferrous iron chemistry at low temperatures with application to Mars

Major uncertainties exist with respect to the aqueous geochemical evolution of the Martian surface. Considering the prevailing cryogenic climates and the abundance of salts and iron minerals on Mars, any attempt at comprehensive modeling of Martian aqueous chemistry should include iron chemistry and be valid at low temperatures and high solution concentrations. The objectives of this paper were to (1) estimate ferrous iron Pitzer-equation parameters and iron mineral solubility products at low temperatures (from < 0 °C to 25 °C), (2) incorporate these parameters and solubility products into the FREZCHEM model, and (3) use the model to simulate the surficial aqueous geochemical evolution of Mars.Ferrous iron Pitzer-equation parameters were derived in this work or taken from the literature. Six new iron minerals [FeCl₂·4H₂O, FeCl₂·6H₂O, FeSO₄·H₂O, FeSO₄·7H₂O, FeCO₃, and Fe(OH)₃] were added to the FREZCHEM model bringing the total solid phases to 56. Agreement between model predictions and experimental data are fair to excellent for the ferrous systems: Fe-Cl, Fe-SO₄, Fe-HCO₃, H-Fe-Cl, and H-Fe-SO₄.We quantified a conceptual model for the aqueous geochemical evolution of the Martian surface. The five stages of the conceptual model are: (1) carbonic acid weathering of primary ferromagnesian minerals to form an initial magnesium-iron-bicarbonate-rich solution; (2) evaporation and precipitation of carbonates, including siderite (FeCO₃), with evolution of the brine to a concentrated NaCl solution; (3) ferrous/ferric iron oxidation; (4) either evaporation or freezing of the brine to dryness; and (5) surface acidification.What began as a dilute Mg-Fe-HCO₃ dominated leachate representing ferromagnesian weathering evolved into an Earth-like seawater composition dominated by NaCl, and finally into a hypersaline Mg-Na-SO₄-Cl brine. Weathering appears to have taken place initially under conditions that allowed solution of ferrous iron [low O₂(g)], but later caused oxidation of iron [high O₂(g)]. Surface acidification and/or sediment burial can account for the minor amounts of Martian surface carbonates. This model rests on a large number of assumptions and is therefore speculative. Nevertheless, the model is consistent with current understanding concerning surficial salts and minerals based on Martian meteorites, Mars lander data, and remotely-sensed spectral analyses.     

Burial, crawling and drifting behaviour of the bivalve Macomona liliana in response to common sediment contaminants

To investigate the effect of sediment contamination on the tellinid bivalve Macomona liliana, juvenile shellfish (about 1.3 mm long) were exposed to copper- and zinc-dosed sand, and sediments collected from several contaminated sites. The behavioural responses measured included burial rate, crawling and drifting. In copper-dosed sediment, a significant reduction in the number of shellfish burying after 10 min occurred at 25 mg Cu kg⁻¹ (dry wt). After a 96-h exposure, shellfish crawled away from sediment with 10 mg Cu kg⁻¹ (dry wt), and when a weak current was provided they left this 10 mg Cu kg⁻¹ (dry wt) sediment by drifting. Zinc-dosed sediment slowed burial at 80 mg Zn kg⁻¹ (dry wt), and stimulated crawling and drifting at 40 mg Zn kg⁻¹ (dry wt). Some of the field-collected contaminated sediments slowed burial and stimulated drifting, but none affected crawling. It appears that juvenile drifting induced by sediment contamination could play a role in determining M. liliana distributions.     

A Gibbs–Pitzer function for high-salinity seawater thermodynamics

A high-salinity Gibbs function for seawater is derived from Pitzer equations of the sea salt components, in conjunction with the 2003 Gibbs function of seawater for low salinities. Various properties, computed from both formulations by thermodynamic rules, are compared with each other, and with high-salinity measurements. The new Gibbs–Pitzer function presented in this paper is valid in the range 0–110 g kg⁻¹ in absolute salinity, −7 to +25 °C in temperature, and 0–100 MPa in applied pressure. The formulation is expressed in the International Temperature Scale 1990 (ITS-90), and is consistent with the International Standard for Fluid Water (IAPWS-95), and with the 2005/2006 equations of state of ice Ih.     

A comfortable night out? Alcohol, drunkenness and inclusive town centres

The Licensing Act (2003) was enacted in England and Wales against the backdrop of media concern about 'binge Britain' and violent town centres avoided by 'social drinkers'. This paper responds to these concerns by asking how to create more inclusive urban centres at night. Findings from focus groups found it was not alcohol consumption or a reluctance to partake in urban life that was detracting residents. Using the notion of 'comfort', the paper instead reveals a strong desire for varied late-night experiences ranging from quiet local venues, to active streets and live venues.     

Pb–Nd isotopic constraints on sedimentary input into the Lesser Antilles arc system

The Lesser Antilles arc is a particularly interesting island arc because it is presently very active, it is located perpendicular to the South American continent and its chemical and isotopic compositions display a strong north–south gradient. While the presence in the south of a thick pile of sedimentary material coming from the old South American continent has long been suspected to explain the geochemical gradient, previous studies failed to demonstrate unambiguously a direct link between the arc lava compositions and the subducted sediment compositions.Here, we present new Nd, Sm, Th, U and Pb concentrations and Nd–Pb isotopic data for over 60 sediments from three sites located in the fore arc region of the Lesser Antilles arc. New data for DSDP Site 543 drill core located east of Dominica Island complement the data published by White et al. [White, W.M., Dupré, B. and Vidal, P., 1985. Isotope and trace element geochemistry of sediments from the Barbados Ridge–Demerara Plain region, Atlantic Ocean. Geochimica et Cosmochimica Acta, 49: 1875–1886.] and confirm their relatively uniform isotopic compositions (i.e., ²⁰⁶Pb/²⁰⁴Pb between 19.13 and 19.53). In contrast, data obtained on DSDP Site 144 located further south, on the edge of the South American Rise and on sediments from Barbados Island are much more variable (²⁰⁶Pb/²⁰⁴Pb ranges from 18.81 to 27.69). The very radiogenic Pb isotopic compositions are found in a 60 m thick black shale unit, which has no age equivalent in the Site 543 drill core. We interpret the peculiar composition of the southern sediments as being due to two factors, (a) the proximity of the South American craton, which contributes coarse grain old detrital material that does not travel far from the continental shelf, and (b) the presence of older sediments including the thick black shale unit formed during Oceanic Anoxic events 2 and 3.The north–south isotopic change known along the Lesser Antilles arc can be explained by the observed geographical changes in the composition of the subducted sediments. About 1% contamination of the mantle wedge by Site 543 sediments explains the composition of the northern islands while up to 10% sediments like those of Site 144 is required in the source of the southern island lavas. The presence of black shales in the subducted pile provides a satisfactory explanation for the very low Δ8/4 values that characterize the Lesser Antilles arc.     

The added value of participatory modelling in fisheries management – what has been learnt?

How can uncertain fisheries science be linked with good governance processes, thereby increasing fisheries management legitimacy and effectiveness? Reducing the uncertainties around scientific models has long been perceived as the cure of the fisheries management problem. There is however increasing recognition that uncertainty in the numbers will remain. A lack of transparency with respect to these uncertainties can damage the credibility of science. The EU Commission's proposal for a reformed Common Fisheries Policy calls for more self-management for the fishing industry by increasing fishers' involvement in the planning and execution of policies and boosting the role of fishers' organisations. One way of higher transparency and improved participation is to include stakeholders in the modelling process itself. The JAKFISH project (Judgment And Knowledge in Fisheries Involving StakeHolders) invited fisheries stakeholders to participate in the process of framing the management problem, and to give input and evaluate the scientific models that are used to provide fisheries management advice. JAKFISH investigated various tools to assess and communicate uncertainty around fish stock assessments and fisheries management. Here, a synthesis is presented of the participatory work carried out in four European fishery case studies (Western Baltic herring, North Sea Nephrops, Central Baltic Herring and Mediterranean swordfish), focussing on the uncertainty tools used, the stakeholders' responses to these, and the lessons learnt. It is concluded that participatory modelling has the potential to facilitate and structure discussions between scientists and stakeholders about uncertainties and the quality of the knowledge base. It can also contribute to collective learning, increase legitimacy, and advance scientific understanding. However, when approaching real-life situations, modelling should not be seen as the priority objective. Rather, the crucial step in a science–stakeholder collaboration is the joint problem framing in an open, transparent way.     

Negative effects of Phaeocystis globosa on microalgae

The potential allelopathic effects of the microalga, Phaeocystis globosa Scherffel, on three harmful bloom algae, Prorocentrum donghaiense Lu, Chattonella marina (Subrahmanyan) Hara et Chihara and Chattonella ovata Hara et Chihara were studied. The growth of C. marina and C. ovata was markedly reduced when the organisms were co-cultured with P. globosa or cultured in cell-free spent medium. Haemolytic extracts from P. globosa cells in the senescence phase had a similar inhibitory effect on the three harmful bloom algae. However, P. globosa had less influence on the brine shrimp, Artemia salina. These results indicate that P. globosa may have an allelopathic effect on microalgae, which would explain the superior competitive abilities of P. globosa. Because the addition of the haemolytic toxins from P. globosa had similar effects on algae as spent media, these compounds may be involved in the allelopathic action of P. globosa.     

Morphology and distribution of dolines on ultramafic rocks from airborne LiDAR data: the case of southern Grande Terre in New Caledonia (SW Pacific)

Dolines are closed geomorphological depressions which are surface manifestations of karstic systems. Usually developed on limestones, they also typify the morphology of the New Caledonian landscape, particularly on the southern massif of the main island (known as Massif du Sud). The specificity of dolines here lies in their development on ultramafic rocks. They are evidences of subsidence, suffosion and collapse phenomena resulting from dissolution weathering of peridotites. However, extensive underground drainage systems are still not yet recognized. Semi‐automatic mapping of dolines is carried out on a 148 km² area of the Massif du Sud from a high accuracy LiDAR digital elevation model. In this area 8601 dolines ranging from 1 m² to 2 km² are identified and morphologically characterized with precision. Most are small, shallow and round‐shaped, yet more complex shapes are locally observed. Size distribution analysis allows the setting of a threshold of 20 000 m² above which surface processes rather than chemical weathering control doline evolution. Doline density analysis reveals high concentrations on flat areas where ferricrete overlies the complete weathering profile, especially in the case of elevated rainy watersheds. Dolines are aligned and elongated along a north 135° ± 5° major fracture direction, which is inherited from the obduction of the Pacific Plate upper mantle in the Late Eocene. Finally, we propose a pioneering morphometric typology of dolines that provides important clues as to pseudokarstic activity. We define collapse, bowl‐shaped and flat bottom dolines. Collapse and bowl‐shaped dolines are assumed to denote active pseudokarst. They may widen and deepen, or eventually be filled by sediments. They are distinguished from flat bottom dolines that are partially to completely filled, which suggests that they are associated with paleo‐pseudokarsts. However the groundwater flow paths associated with the genesis and evolution of dolines must be clarified, thus collapse and bowl‐shaped dolines should be hydrologically monitored. Copyright © 2016 John Wiley & Sons, Ltd.