Ion Transport and the True Transference Number in Nonaqueous Polyelectrolyte Solutions for Lithium Ion Batteries.

Nonaqueous polyelectrolyte solutions have been recently proposed as high Li+ transference number electrolytes for lithium ion batteries. However, the atomistic phenomena governing ion diffusion and migration in polyelectrolytes are poorly understood, particularly in nonaqueous solvents. Here, the structural and transport properties of a model polyelectrolyte solution, poly(allyl glycidyl ether-lithium sulfonate) in dimethyl sulfoxide, are studied using all-atom molecular dynamics simulations. We find that the static structural analysis of Li+ ion pairing is insufficient to fully explain the overall conductivity trend, necessitating a dynamic analysis of the diffusion mechanism, in which we observe a shift from largely vehicular transport to more structural diffusion as the Li+ concentration increases. Furthermore, we demonstrate that despite the significantly higher diffusion coefficient of the lithium ion, the negatively charged polyion is responsible for the majority of the solution conductivity at all concentrations, corresponding to Li+ transference numbers much lower than previously estimated experimentally. We quantify the ion-ion correlations unique to polyelectrolyte systems that are responsible for this surprising behavior. These results highlight the need to reconsider the approximations typically made for transport in polyelectrolyte solutions

Emplacement of inflated Pāhoehoe flows in the Naude’s Nek Pass, Lesotho remnant, Karoo continental flood basalt province: use of flow-lobe tumuli in understanding flood basalt emplacement

Physical volcanological features are presented for a 710-m-thick section, of the Naude’s Nek Pass, within the lower part of the Lesotho remnant of the Karoo Large Igneous Province. The section consists of inflated pāhoehoe lava with thin, impersistent sedimentary interbeds towards the base. There are seven discreet packages of compound and hummocky pāhoehoe lobes containing flow-lobe tumuli, making up approximately 50% of the section. Approximately 45% of the sequence consists of 14 sheet lobes, between 10 and 52-m-thick. The majority of the sheet lobes are in two packages indicating prolonged periods of lava supply capable of producing thick sheet lobes. The other sheet lobes are as individual lobes or pairs, within compound flows, suggesting brief increases in lava supply rate. We suggest, contrary to current belief, that there is no evidence that compound flows are proximal to source and sheet lobes (simple flows) are distal to source and we propose that the presence of flow-lobe tumuli in compound flows could be an indicator that a flow is distal to source. We use detailed, previously published, studies of the Thakurvadi Formation (Deccan Traps) as an example. We show that the length of a lobe and therefore the sections that are ‘medial or distal to source’ are specific to each individual lobe and are dependent on the lava supply of each eruptive event, and as such flow lobe tumuli can be used as an indicator of relative distance from source

Physical Mechanisms for Vertical-CLVD Earthquakes at Active Volcanoes

Many volcanic earthquakes large enough to be detected globally have anomalous focal mechanisms and frequency content. In a previous study, we examined the relationship between active volcanism and the occurrence of a specific type of shallow, non-double-couple earthquake. We identified 101 earthquakes with vertical compensated-linear-vector-dipole (vertical-CLVD) focal mechanisms that took place near active volcanoes between 1976 and 2009. The majority of these earthquakes, which have magnitudes 4.3 less than or equal to MW less than or equal to 5.8, are associated with documented episodes of volcanic unrest. Here we further characterize vertical-CLVD earthquakes and explore possible physical mechanisms. Through teleseismic body-wave analysis and examination of the frequency content of vertical-CLVD earthquakes, we demonstrate that these events have longer source durations than tectonic earthquakes of similar magnitude. We examine the covariance matrix for one of the best-recorded earthquakes and confirm that the isotropic and pure vertical-CLVD components of the moment tensor cannot be independently resolved using our long-period seismic data set. Allowing for this trade-off, we evaluate several physical mechanisms that may produce earthquakes with deviatoric vertical-CLVD moment tensors. We find that physical mechanisms related to fluid flow and volumetric changes are incompatible with seismological, geological, and geodetic observations of vertical-CLVD earthquakes. However, ring-faulting mechanisms explain many characteristics of vertical-CLVD earthquakes, including their seismic radiation patterns, source durations, association with volcanoes in specific geodynamic environments, and the timing of the earthquakes relative to volcanic activity

The status of the world's land and marine mammals: diversity, threat, and knowledge

Knowledge of mammalian diversity is still surprisingly disparate, both regionally and taxonomically. Here, we present a comprehensive assessment of the conservation status and distribution of the world's mammals. Data, compiled by 1700+ experts, cover all 5487 species, including marine mammals. Global macroecological patterns are very different for land and marine species but suggest common mechanisms driving diversity and endemism across systems. Compared with land species, threat levels are higher among marine mammals, driven by different processes (accidental mortality and pollution, rather than habitat loss), and are spatially distinct (peaking in northern oceans, rather than in Southeast Asia). Marine mammals are also disproportionately poorly known. These data are made freely available to support further scientific developments and conservation action

Global patient outcomes after elective surgery: prospective cohort study in 27 low-, middle- and high-income countries.

BACKGROUND: As global initiatives increase patient access to surgical treatments, there remains a need to understand the adverse effects of surgery and define appropriate levels of perioperative care. METHODS: We designed a prospective international 7-day cohort study of outcomes following elective adult inpatient surgery in 27 countries. The primary outcome was in-hospital complications. Secondary outcomes were death following a complication (failure to rescue) and death in hospital. Process measures were admission to critical care immediately after surgery or to treat a complication and duration of hospital stay. A single definition of critical care was used for all countries. RESULTS: A total of 474 hospitals in 19 high-, 7 middle- and 1 low-income country were included in the primary analysis. Data included 44 814 patients with a median hospital stay of 4 (range 2-7) days. A total of 7508 patients (16.8%) developed one or more postoperative complication and 207 died (0.5%). The overall mortality among patients who developed complications was 2.8%. Mortality following complications ranged from 2.4% for pulmonary embolism to 43.9% for cardiac arrest. A total of 4360 (9.7%) patients were admitted to a critical care unit as routine immediately after surgery, of whom 2198 (50.4%) developed a complication, with 105 (2.4%) deaths. A total of 1233 patients (16.4%) were admitted to a critical care unit to treat complications, with 119 (9.7%) deaths. Despite lower baseline risk, outcomes were similar in low- and middle-income compared with high-income countries. CONCLUSIONS: Poor patient outcomes are common after inpatient surgery. Global initiatives to increase access to surgical treatments should also address the need for safe perioperative care. STUDY REGISTRATION: ISRCTN5181700

On The Anomalous Conductivity of Low Permittivity Electrolytes Used in Electrochemical Applications

Most of the battery electrolyte candidates for multivalent-ion systems (e.g. Mg, Ca) present interesting physicochemical properties. In these are included anomalous conductivity, where molar conductivity increases with salt concentration. This phenomenon is related to the electrochemical performance and electrolyte viability. In this thesis, this phenomenon is explained via understanding and quantification of the strong inter-ionic interactions in solution. To this end, computational methods including classical molecular dynamics and electronic structure methods are combined with dielectric relaxation spectroscopy measurements. Two cases studies with ether based electrolytes, one with MgTFSI2 salt and one with Ca(BH4)2 are undertaken. In both cases, the anomalous conductivity originates from changes in salt speciation, i.e. changes in the population of distinct chemical species formed by the ions in the solution. A larger fraction of ionic salt species are promoted at higher salt concentration at the expense of larger, associated clusters. Moreover, it is found that the increase in dielectric constant with increasing salt concentration, due to a significant fraction of polar associated salt species, is likely one of the thermodynamic driving forces for this effect. The findings here are important for the rational design of multivalent electrolytes for electrochemical applications, and help inform salt and solvent selection for advanced electrolyte formulations