Kinetics of coupled Fe(II)-catalysed ferrihydrite transformation and U(VI) reduction

Antimony is released into the environment in some natural and man-induced processes. [1]. Yet, its impact on the transformation processes of heavy metal-adsorbing minerals remains poorly understood. In acid-mine drainage systems and shooting ranges, the adsorption of antimony by iron oxides such as ferrihydrite can play a major role. The poorly crystalline 2-line ferrihydrite represents one of the most common Fe oxides in these settings and can transform to goethite (,-FeOOH) or hematite (,-Fe2O3) with time [2]. The rate of transformation depends on the pH, temperature, and on the ions and molecules present during the transformation process [3]. This study focuses on the transformation of synthetic ferrihydrite to crystalline iron oxides in the presence of Sb(V). Transformations were carried out for 1-16 days at 70 ºC and at pH 4, 7 and 12, with different concentrations of Sb(V) (0.00, 0.23, 0.75, 2.25 and 6.00 mM Sb). Samples taken from aqueous suspensions were washed, dried, and characterized by X-ray diffraction (XRD) and atomic absorption spectroscopy (AAS). At pH 12, goethite (Sb concentrations up to 3.7 mg Sb/g) is favored and the transformation is completed after one day. Only a concentration of 6 mM Sb retarded the transformation, where even after 8 days only 50 % of the ferrihydrite was transformed into goethite. Transformations at pH 7 led to a mixture of 75 % hematite and 25 % goethite (4.3 mg Sb/g). However, at concentrations of 6 mM Sb, feroxyhyte (!- FeOOH) (9.1 mg Sb/g) was favored instead. At pH 4, hematite (32.3 mg Sb/g) was favored except for concentrations of 6 mM Sb, were again feroxyhyte (141.1 mg Sb/g) occurred. We assume that increased Sb concentrations favor feroxyhyte and indicate the incorporation of Sb into the structure of feroxyhyte. © The Author

Ferric iron geometry and coordination during hydrolysis and ferrihydrite precipitation

Definitive structural characterisation of ferrihydrite has challenged scientists primarily due to its nanosized particles and inherent long-range structural disorder which challenges analytical methodology (and modelling) typically employed to determine the structure of minerals. Here we report on the application of a synchrotron quick-scanning X-ray absorption spectroscopy (XAS) approach, which allows the collection of Extended X-ray Absorption Fine Structure (EXAFS) spectral data to k = 15 Å-1 in < 1 minute, to obtain unparalleled iron Kedge data on the hydrolysis of FeIII(H2O)6 and ferrihydrite precipitation. Modelling of the pre-edge and EXAFS data: 1) supports theoretical studies which have suggested the existence of a monomeric penta-coordinated FeIII hydrolysis species and; 2) corroborates recently proposed structural models of ferrihydrite that contain tetrahedral FeIII. Modelling results indicate that ferrihydrite consists of 15 to 25 % tetrahedral FeIII and suggest that this geometry must be included in any comprehensive structural model of ferrihydrite and, furthermore, should be considered when evaluating the reactivity, stability and other structure-property relationships of this mineral. © The Authors

Rapamycin does not inhibit HCMV reactivation from dendritic cells in vitro

Human cytomegalovirus (HCMV) infection and reactivation are a major cause of morbidity in immune-suppressed patients. Interestingly, epidemiological studies have shown that patients administered the mammalian target of rapamycin (mTOR) inhibitor, sirolimus (rapamycin), exhibit more favourable outcomes, suggestive of activity against HCMV in vivo. Given its relative lack of activity against lytic infection, it is postulated that rapamycin inhibits HCMV reactivation. Here, we showed that rapamycin administered acutely or chronically has little impact on induction of immediate early (IE) gene expression in experimentally latent dendritic cells or cells from naturally latent individuals. Furthermore, we extended these observations to include other inhibitors of mTORC1 and mTORC 2, which similarly have minimal effects on induction of IE gene expression from latency. Taken together, these data suggest that favourable outcomes associated with sirolimus are attributable to indirect effects that influence HCMV reactivation, rather than a direct mechanistic action against HCMV itself

Atmospheric and Fluvial Nutrients Fuel Algal Blooms in the East China Sea

Chinese coastal waters support vast fisheries and vital economies, but their productivity is threatened by increasingly frequent harmful algal blooms (HABs). Here we provide direct experimental evidence that atmospheric deposition, along with riverine input, opens new niches for bloom-forming dinoflagellates and diatoms in the East China Sea (ECS) by increasing the ratio of nitrogen to phosphorus (N:P), inducing severe P limitation, and altering trace metal micronutrient inventories. Remote sensing analysis of blooms in the region showed that dinoflagellate blooms were associated with increased aerosol optical thickness and decreased sea surface temperature, whereas diatom blooms were primarily associated with seasonally decreased temperature (e.g., during spring blooms). Bottle incubation experiments revealed that aerosol additions approximating 10 days of strong deposition increased iron availability and intensified P limitation, which together promoted dinoflagellate growth in offshore waters. Diatom growth was correlated with elevated trace metal and nutrient content from aerosols. Aerosols did not induce phytoplankton growth at a station within the Yangtze River plume where light was limiting, consistent with remote sensing observations that aerosol effects are stronger in offshore waters. Eutrophication and trace metal enrichment from Yangtze River discharge together with atmospheric deposition may underlie the transition from diatom-dominated spring blooms toward more frequent spring and summer dinoflagellate blooms that has occurred over the past three decades in the ECS

Selective scattering between Floquet-Bloch and Volkov states in a topological insulator

The coherent optical manipulation of solids is emerging as a promising way to engineer novel quantum states of matter. The strong time periodic potential of intense laser light can be used to generate hybrid photon-electron states. Interaction of light with Bloch states leads to Floquet-Bloch states which are essential in realizing new photo-induced quantum phases. Similarly, dressing of free electron states near the surface of a solid generates Volkov states which are used to study non-linear optics in atoms and semiconductors. The interaction of these two dynamic states with each other remains an open experimental problem. Here we use Time and Angle Resolved Photoemission Spectroscopy (Tr-ARPES) to selectively study the transition between these two states on the surface of the topological insulator Bi2Se3. We find that the coupling between the two strongly depends on the electron momentum, providing a route to enhance or inhibit it. Moreover, by controlling the light polarization we can negate Volkov states in order to generate pure Floquet-Bloch states. This work establishes a systematic path for the coherent manipulation of solids via light-matter interaction.Comment: 21 pages, 6 figures, final version to appear in Nature Physic

Stress Biomarkers as Outcomes for HIV+ Prevention: Participation, Feasibility and Findings Among HIV+ Latina and African American Mothers

Mothers living with HIV (MLH) are at high risk for acute and chronic stress, given challenges related to their HIV status, ethnicity, economic and urban living conditions. Biomarkers combined into a composite index show promise in quantifying psychosocial stress in healthy people, but have not yet been examined among MLH. According, we examined potential biomarker correlates of stress [cortisol and catecholamines from home-collected urine and basic health indicators (blood pressure, height and weight, waist-to-hip ratio) measured during an interview] among 100 poor African American and Latina mothers MLH and demographic-matched control mothers without HIV (n = 50). Participants had been enrolled in a randomized controlled trial about 18 months earlier and had either received (MLH-I) or were awaiting (MLH-W) the psychosocial intervention. Participation was high, biomarkers were correctly collected for 93% of cases, and a complete composite biomarker index (CBI) calculated for 133 mothers (mean age = 42). As predicted, MLH had a significantly higher CBI than controls, but there was no CBI difference across ethnicity or intervention group. CBI predicted CD4 counts independently after controlling for age, years since diagnosis, prior CD4 counts, medication adherence, and depression symptoms. The study demonstrates acceptability, feasibility and potential utility of community-based biomarker collections in evaluating individual differences in psychosocial stress

Domains of Chronic Stress, Lifestyle Factors, and Allostatic Load in Middle-Aged Mexican-American Women

Abstract available at publisher's website

Modifiable predictors of depression following childhood maltreatment: a systematic review and meta-analysis

Although maltreatment experiences in childhood increase the risk for depression, not all maltreated children become depressed. This review aims to systematically examine the existing literature to identify modifiable factors that increase vulnerability to, or act as a buffer against, depression, and could therefore inform the development of targeted interventions. Thirteen databases (including Medline, PsychINFO, SCOPUS) were searched (between 1984 and 2014) for prospective, longitudinal studies published in English that included at least 300 participants and assessed associations between childhood maltreatment and later depression. The study quality was assessed using an adapted Newcastle-Ottawa Scale checklist. Meta-analyses (random effects models) were performed on combined data to estimate the effect size of the association between maltreatment and depression. Meta-regressions were used to explore effects of study size and quality. We identified 22 eligible articles (N=12 210 participants), of which 6 examined potential modifiable predictors of depression following maltreatment. No more than two studies examined the same modifiable predictor; therefore, it was not possible to examine combined effects of modifiable predictors with meta-regression. It is thus difficult to draw firm conclusions from this study, but initial findings indicate that interpersonal relationships, cognitive vulnerabilities and behavioral difficulties may be modifiable predictors of depression following maltreatment. There is a lack of well-designed, prospective studies on modifiable predictors of depression following maltreatment. A small amount of initial research suggests that modifiable predictors of depression may be specific to maltreatment subtypes and gender. Corroboration and further investigation of causal mechanisms is required to identify novel targets for intervention, and to inform guidelines for the effective treatment of maltreated children

Cerebral gene expression in response to single or combined gestational exposure to methylmercury and selenium through the maternal diet

Controversy remains regarding the safety of consuming certain types of seafood, particularly during pregnancy. While seafood is rich in vital nutrients, it may also be an important source of environmental contaminants such as methylmercury (MeHg). Selenium (Se) is one essential element present in seafood, hypothesised to ameliorate MeHg toxicity. The aim of the present study was to ascertain the impact of Se on MeHg-induced cerebral gene expression in a mammalian model. Microarray analysis was performed on brain tissue from 15-day-old mice that had been exposed to MeHg throughout development via the maternal diet. The results from the microarray analysis were validated using qPCR. The exposure groups included: MeHg alone (2.6 mg kg−1), Se alone (1.3 mg kg−1), and MeHg + Se. MeHg was presented in a cysteinate form, and Se as Se–methionine, one of the elemental species occurring naturally in seafood. Eight genes responded to Se exposure alone, five were specific to MeHg, and 63 were regulated under the concurrent exposure of MeHg and Se. Significantly enriched functional classes relating to the immune system and cell adhesion were identified, highlighting potential ameliorating mechanisms of Se on MeHg toxicity. Key developmental genes, such as Wnt3 and Sparcl1, were also identified as putative ameliorative targets. This study, utilising environmentally realistic forms of toxicants, delivered through the natural route of exposure, in association with the power of transcriptomics, highlights significant novel information regarding putative pathways of selenium and MeHg interaction in the mammalian brain

Comparative antibacterial potential of selected aldehyde-based biocides and surfactants against planktonic Pseudomonas fluorescens

The antimicrobial efficacy of two aldehydebased biocides (glutaraldehyde, GTA, and orthophthalaldehyde, OPA) and two surfactants (cetyltrimethyl ammonium bromide, CTAB, and sodium dodecyl sulphate, SDS) was tested against planktonic Pseudomonas fluorescens. The antimicrobial effects were evaluated by respiratory activity as a measure of the oxygen uptake rate, adenosine triphosphate (ATP) release, outer membrane proteins (OMP) expression and cellular colour changes. The results were compared with the bacterial characteristics without chemical treatment. Tests in the presence of bovine serum albumin (BSA), in order to mimic a disinfection process in the real situation under dirty conditions, were performed according to the European Standard EN-1276. P. fluorescens was completely inactivated with OPA (minimum bactericidal concentration, MBC = 0.5 mM) and CTAB (MBC = 5 mM) and was resistant to GTA and SDS. Only CTAB promoted cellular disruption and consequent ATP release. The antimicrobial action of the chemicals tested was significantly reduced when BSA was introduced into the bacterial cultures, increasing markedly the MBC values. Additionally, the presence of BSA acted as a disruption protective agent when CTAB was applied and stimulated the bacterial respiratory activity when lower concentrations of SDS were tested. The OMP of the bacterial cells was affected by the application of both surfactants. OMP expression remained unaltered after biocide treatment. Bacterial colour change was noticed after treatment with biocides and surfactants. In summary, P. fluorescens was extremely resistant to GTA and SDS, with antimicrobial action being quenched markedly by the reaction with BSA.Instituto de Biotecnologia e Química Fina (IBQF).Fundação para a Ciência e a Tecnologia (FCT) - (Project CHEMBIO - POCI/BIO/61872/2004