Parasitic light absorption, rate laws and heterojunctions in the photocatalytic oxidation of arsenic(III) using composite TiO2/Fe2O3

Composite photocatalyst-adsorbents such as TiO2/Fe2O3 are promising materials for the one-step treatment of arsenite contaminated water. However, no previous study has investigated how coupling TiO2 with Fe2O3 influences the photocatalytic oxidation of arsenic(III). Herein, we develop new hybrid experiment/modelling approaches to study light absorption, charge carrier behaviour and changes in the rate law of the TiO2/Fe2O3 system, using UV-Vis spectroscopy, transient absorption spectroscopy (TAS), and kinetic analysis. Whilst coupling TiO2 with Fe2O3 improves total arsenic removal by adsorption, oxidation rates significantly decrease (up to a factor of 60), primarily due to the parasitic absorption of light by Fe2O3 (88% of photons at 368 nm) and secondly due to changes in the rate law from disguised zero-order kinetics to first-order kinetics. Charge transfer across this TiO2-Fe2O3 heterojunction is not observed. Our study demonstrates the first application of a multi-adsorbate surface complexation model (SCM) towards describing As(III) oxidation kinetics which, unlike Langmuir-Hinshelwood kinetics, includes the competitive adsorption of As(V), and we further highlight the importance of parasitic light absorption and catalyst fouling when designing heterogeneous photocatalysts for As(III) remediation

Organic compound-mineral interactions: using flash pyrolysis to monitor the adsorption of fatty acids on calcite

Fatty acids are near ubiquitous organic compounds in living organisms in the Earth’s biosphere. Following death of an organism in the marine environment its fatty acids may survive descent to the sea bed where they can be juxtaposed with minerals. The aim of this study was to investigate the interaction of fatty acids with the common marine mineral calcite. Adsorption of tetradecanoic acid (C14) on calcite results in a sigmoidal or “s” isotherm. Flash pyrolysis experiments were conducted on samples of fatty acid adsorbed onto calcite and were compared with similar experiments on pure fatty acid and on salts of a fatty acid. Flash pyrolysis of pure tetradecanoic acid generated unsaturated and saturated hydrocarbons and a series of unsaturated and saturated low molecular weight fatty acids. Flash pyrolysis of free tetradecanoic acid salt produced saturated and unsaturated hydrocarbons, an aldehyde and a homologous series of saturated and unsaturated ketones, one of which was a symmetrical mid chain ketone (14-heptacosanone). Flash pyrolysis data from adsorbed tetradecanoic acid samples suggested that adsorption is analogous to the formation of the calcium salt of tetradecanoic acid. A key characteristic of the flash pyrolysis products of adsorbed fatty acids and fatty acid salts was the production of ketones with higher molecular weights than the starting fatty acids. Ketonisation was not observed from the flash pyrolysis of pure acid which implied the catalytic significance of the calcite mineral surface. The abundance of hydrocarbons relative to ketones in the pyrolysates negatively correlated with the proportion of fatty acids adsorbed to the surface of calcite. The ability to use flash pyrolysis to diagnose the nature of fatty acid interactions with mineral surfaces provides a valuable tool for monitoring the fate of these important lipids at the Earth’s surface as they pass into the geosphere and are subjected to diagenetic processes

Zinc isotopic fractionation in Phragmites australis in response to toxic levels of zinc

Stable isotope signatures of Zn have shown great promise in elucidating changes in uptake and translocation mechanisms of this metal in plants during environmental changes. Here this potential was tested by investigating the effect of high Zn concentrations on the isotopic fractionation patterns of Phragmites australis (Cav.) Trin. ex Steud. Plants were grown for 40 d in a nutritive solution containing 3.2 μM (sufficient) or 2 mM (toxic) Zn. The Zn isotopic composition of roots, rhizomes, shoots, and leaves was analysed. Stems and leaves were sampled at different heights to evaluate the effect of long-distance transport on Zn fractionation. During Zn sufficiency, roots, rhizomes, and shoots were isotopically heavy (δ(66)Zn(JMC Lyon)=0.2‰) while the youngest leaves were isotopically light (–0.5‰). During Zn excess, roots were still isotopically heavier (δ(66)Zn=0.5‰) and the rest of the plant was isotopically light (up to –0.5‰). The enrichment of heavy isotopes at the roots was attributed to Zn uptake mediated by transporter proteins under Zn-sufficient conditions and to chelation and compartmentation in Zn excess. The isotopically lighter Zn in shoots and leaves is consistent with long-distance root to shoot transport. The tolerance response of P. australis increased the range of Zn fractionation within the plant and with respect to the environment

Treatment-seeking rates in malaria endemic countries

BACKGROUND: The proportion of individuals who seek treatment for fever is an important quantity in understanding access to and use of health systems, as well as for interpreting data on disease incidence from routine surveillance systems. For many malaria endemic countries (MECs), treatment-seeking information is available from national household surveys. The aim of this paper was to assemble sub-national estimates of treatment-seeking behaviours and to predict national treatment-seeking measures for all MECs lacking household survey data. METHODS: Data on treatment seeking for fever were obtained from Demographic and Health Surveys, Malaria Indicator Surveys and Multiple Cluster Indicator Surveys for every MEC and year that data were available. National-level social, economic and health-related variables were gathered from the World Bank as putative covariates of treatment-seeking rates. A generalized additive mixed model (GAMM) was used to estimate treatment-seeking behaviours for countries where survey data were unavailable. Two separate models were developed to predict the proportion of fever cases that would seek treatment at (1) a public health facility or (2) from any kind of treatment provider. RESULTS: Treatment-seeking data were available for 74 MECs and modelled for the remaining 24. GAMMs found that the percentage of pregnant women receiving prenatal care, vaccination rates, education level, government health expenditure, and GDP growth were important predictors for both categories of treatment-seeking outcomes. Treatment-seeking rates, which varied both within and among regions, revealed that public facilities were not always the primary facility type used. CONCLUSIONS: Estimates of treatment-seeking rates show how health services are utilized and help correct reported malaria case numbers to obtain more accurate measures of disease burden. The assembled and modelled data demonstrated that while treatment-seeking rates have overall increased over time, access remains low in some malaria endemic regions and utilization of government services is in some areas limited

The effect of bacterial growth phase and culture concentration on U(VI) removal from aqueous solution

Bacteria play a key role in controlling the mobility of contaminants, such as uranium (U), in the environment. Uranium could be sourced from disposed radioactive waste, derived either from surface disposal trenches for Low Level Waste (LLW) that, because of the waste type and disposal concept, would typically present acidic conditions or from the geological disposal of LLW or Intermediate Level Waste (ILW) that, because of the waste type and the disposal concept, would typically present alkaline conditions. In disposed radioactive waste, there could be variable amounts of cellulosic material. Bacterial cells may be living in a range of different growth phases, depending on the growth conditions and nutrients available at the time any waste-derived U migrated to the cells. A key knowledge gap to date has been the lack of a mechanistic understanding of how bacterial growth phases (exponential, stationary, and death phase) affect the ability of bacteria to remove U(VI) from solution. To address this, we first characterised the cells using potentiometric titrations to detect any differences in proton binding to proton active sites on Pseudomonas putida cells at each growth phase under aerobic conditions, or under anaerobic conditions favourable to U(IV) reoxidation. We then conducted batch U(VI) removal experiments with bacteria at each phase suspended in 1 and 10 ppm U aqueous solutions with the pH adjusted from 2 to 12 as well as with culture concentrations from 0.01 to 10 g/L, to identify the minimal concentration of bacteria in solution necessary to affect U removal. We found that, in death phase, P. putida cells exhibited double the concentration of proton active sites than bacteria grown to exponential and stationary phase. However, we did not see a difference in the extent of U(VI) removal, from a 10 ppm U solution, between the different growth phases as a function of pH (2 to 12). Culture concentration affected U removal between pH 2–8, where U removal decreased with a decreasing concentration of cells in solution. When the pH was 10–12, ≤55% of U precipitated abiotically. The presence of bacteria in solution (0.01–10 g/L), regardless of growth phase, increased the precipitation of U from ≤55% up to 70–90%, accumulating inside the cells and on the cell walls as ~0.2 μm uranyl phosphate precipitates. These precipitates were also found at low pH with the exception of cells at exponential growth phase. This study demonstrates that growth phase affects the proton-active site concentration but not the extent of U bound to P. putida cells and that growth phase dictates the form of U removed from solution. Since the pH of trench-disposed LLW is controlled by the degradation of cellulosic waste, leading to acidic conditions (pH 4–6), bacterial concentrations would be expected to highly affect the extent of U removed from solution. The cement in grouted ILW and LLW, for geologic disposal, will allow for the development of extremely high pH values in solution (pH 9–13), where even the smallest concentrations of bacteria were able to significantly increase the removal of U from solution under aerobic conditions, or under anaerobic conditions favourable to U(IV) reoxidation

Improved prediction accuracy for disease risk mapping using Gaussian process stacked generalization.

Maps of infectious disease-charting spatial variations in the force of infection, degree of endemicity and the burden on human health-provide an essential evidence base to support planning towards global health targets. Contemporary disease mapping efforts have embraced statistical modelling approaches to properly acknowledge uncertainties in both the available measurements and their spatial interpolation. The most common such approach is Gaussian process regression, a mathematical framework composed of two components: a mean function harnessing the predictive power of multiple independent variables, and a covariance function yielding spatio-temporal shrinkage against residual variation from the mean. Though many techniques have been developed to improve the flexibility and fitting of the covariance function, models for the mean function have typically been restricted to simple linear terms. For infectious diseases, known to be driven by complex interactions between environmental and socio-economic factors, improved modelling of the mean function can greatly boost predictive power. Here, we present an ensemble approach based on stacked generalization that allows for multiple nonlinear algorithmic mean functions to be jointly embedded within the Gaussian process framework. We apply this method to mapping Plasmodium falciparum prevalence data in sub-Saharan Africa and show that the generalized ensemble approach markedly outperforms any individual method

Noncommutative geometry and stochastic processes

The recent analysis on noncommutative geometry, showing quantization of the volume for the Riemannian manifold entering the geometry, can support a view of quantum mechanics as arising by a stochastic process on it. A class of stochastic processes can be devised, arising as fractional powers of an ordinary Wiener process, that reproduce in a proper way a stochastic process on a noncommutative geometry. These processes are characterized by producing complex values and so, the corresponding Fokker-Planck equation resembles the Schroedinger equation. Indeed, by a direct numerical check, one can recover the kernel of the Schroedinger equation starting by an ordinary Brownian motion. This class of stochastic processes needs a Clifford algebra to exist. In four dimensions, the full set of Dirac matrices is needed and the corresponding stochastic process in a noncommutative geometry is easily recovered as is the Dirac equation in the Klein-Gordon form being it the Fokker--Planck equation of the process.Comment: 16 pages, 2 figures. Updated a reference. A version of this paper will appear in the proceedings of GSI2017, Geometric Science of Information, November 7th to 9th, Paris (France

Soil CO2 venting as one of the mechanisms for tolerance of Zn deficiency by rice in flooded soils.

We sought to explain rice (Oryza sativa) genotype differences in tolerance of zinc (Zn) deficiency in flooded paddy soils and the counter-intuitive observation, made in earlier field experiments, that Zn uptake per plant increases with increasing planting density. We grew tolerant and intolerant genotypes in a Zn-deficient flooded soil at high and low planting densities, and found (a) plant Zn concentrations and growth increased with planting density and more so in the tolerant genotype, whereas the concentrations of other nutrients decreased, indicating a specific effect on Zn uptake; (b) the effects of planting density and genotype on Zn uptake could only be explained if the plants induced changes in the soil to make Zn more soluble; and (c) the genotype and planting density effects were both associated with decreases in dissolved CO2 in the rhizosphere soil solution and resulting increases in pH. We suggest the increases in pH caused solubilisation of soil Zn by dissolution of alkali-soluble, Zn-complexing organic ligands from soil organic matter. We conclude that differences in venting of soil CO2 through root aerenchyma were responsible for the genotype and planting density effects

Risk factors for acquisition of hepatitis C virus infection: a case series and potential implications for disease surveillance

Background: Transmission of hepatitis C vims ( HCV) is strongly associated with use of contaminated blood products and injection drugs. Other "non-parental" modes of transmission including sexual activity have been increasingly recognized. We examined risk factors for acquiring HCV in patients who were referred to two tertiary care centers and enrolled in an antiviral therapy protocol. Methods: Interviews of 148 patients were conducted apart from their physician evaluation using a structured questionnaire covering demographics and risk factors for HCV acquisition. Results: Risk factors ( blood products, injection/intranasal drugs, razor blades/toothbrushes, body/ear piercing, occupational exposure, sexual activity) were identified in 141 (95.3%) of participants; 23 (15.5%) had one ( most frequently blood or drug exposure), 41 (27.7%) had two, and 84 (53.4%) had more than two risk factors. No patient reported sexual activity as a sole risk factor. Body piercing accounted for a high number of exposures in women. Men were more likely to have exposure to street drugs but less exposure to blood products than women. Blood product exposure was less common in younger than older HCV patients. Conclusion: One and often multi le risk factors could be identified in nearly all HCV-infected patients seen in a referral practice. None named sexual transmission as the sole risk factor. The development of a more complete profile of factors contributing to transmission of HCV infection may assist in clinical and preventive efforts. The recognition of the potential presence of multiple risk factors may have important implications in the a roach to HCV surveillance, and particularly the use of hierarchical algorithms in the study of risk factors