Abstract: The conformational and configurational preferences of Me2PNSNPMe2 (3) and Me2PNSNAsMe2 (4) have been identified using quantum chemical calculations at the DFT/B3LYP/6-311+G* level of theory. An approach in which energetic, structural (geometries and bond orders), electronic (analysis of the electron density) and spectroscopic properties are combined leads to the conclusion that these sulfur-nitrogen-pnictogen chains share many of the properties of their chalcogen-nitrogen analogues but that the through-space intramolecular interactions favouring the Z,Z configuration are even weaker than in these latter compounds. The results of this analysis also lead to an unambiguous assignment of the variable-temperature 31P and 15N NMR spectra of these compounds and their structures both in solution and in the solid state.

Abstract: The use of a Pt electrode coated with a layer of Nafion has been described in previous works as an attractive way to perform the potentiometric detection of hydrogen peroxide. Despite of the attractive features of this approach, the nature of the non-Nernstian response of this system was not properly addressed. In this work, using a mixed potential model, the open circuit potential of the Pt electrode is shown to be under kinetic control of the oxygen reduction reaction (ORR). It is proposed that hydrogen peroxide acts as an oxygenated species that blocks free sites on the Pt surface, interfering with the ORR. Therefore, the effect of the polyelectrolyte coating can be understood in terms of the modulation of the factors that affects the kinetics of the ORR, such as an increase of the H+ concentration, minimization of the effect of the spectator species, etc. Because of the complexity and the lack of models that accurately describe systems with practical applications, this work is not intended to provide a mechanistic but rather a phenomenological view on problem. A general framework to understand the factors that affect the potentiometric response is provided. Experimental evidence showing that the use of polyelectrolyte coatings are a powerful way to control the mixed potential open new ways for the development of robust and simple potentiometric sensors.

Abstract: Uranyl fluoride particles produced via hydrolysis of uranium hexafluoride have been deposited on different substrates: polished graphite disks, silver foil, stainless steel and gold-coated silicon wafer, and measured with micro-Raman spectroscopy (MRS). All three metallic substrates enhanced the Raman signal delivered by UO2F2 in comparison to graphite. The fundamental stretching of the UO band appeared at 867 cm−1 in case of the graphite substrate, while in case of the others it was shifted to lower frequencies (down to 839 cm−1). All applied metallic substrates showed the expected effect of Raman signal enhancement; however the gold layer appeared to be most effective. Application of new substrates provides more information on the molecular structure of uranyl fluoride precipitation, which is interesting for nuclear safeguards and nuclear environmental analysis.

Abstract: Agricultural practices enhancing soil organic carbon (SOC) show potential to buffer negative effects of climate change on forage grass performance. We tested this by subjecting five forage grass varieties differing in fodder quality and drought/flooding resistance to increased persistence in summer precipitation regimes (PR) across sandy and sandy-loam soils from either permanent (high SOC) or temporary grasslands (low SOC) in adjacent parcels. Over the course of two consecutive summers, monoculture mesocosms were subjected to rainy/dry weather alternation either every 3 days or every 30 days, whilst keeping total precipitation equal. Increased PR persistence induced species-specific drought damage and productivity declines. Soils from permanent grasslands with elevated SOC buffered plant quality, but buffering effects of SOC on drought damage, nutrient availability and yield differed between texture classes. In the more persistent PR, Festuca arundinacea FERMINA was the most productive species but had the lowest quality under both ample water supply and mild soil drought, whilst under the most intense soil droughts, Festulolium FESTILO maintained the highest yields. The hybrid Lolium × boucheanum kunth MELCOMBI had intermediate productivity and both Lolium perenne varieties showed the lowest yields under soil drought, but the highest forage quality (especially the tetraploid variety MELFORCE). Performance varied with plant maturity stage and across seasons/years and was driven by altered water and nutrient availability and related nitrogen nutrition among species during drought and upon rewetting. Moreover, whilst permanent grassland soils showed the most consistent positive effects on plant performance, their available water capacity also declined under increased PR persistence. We conclude that permanent grassland soils with historically elevated SOC likely buffer negative effects of increasing summer weather persistence on forage grass performance, but may also be more sensitive to degradation under climate change.

Abstract: Green infrastructure (GI) is already known to be a suitable way to enhance air quality in urban environments. Living wall systems (LWS) can be implemented in locations where other forms of GI, such as trees or hedges, are not suitable. However, much debate remains about the variables that influence their particulate matter (PM) accumulation efficiency. This study attempts to clarify which plant species are relatively the most efficient in capturing PM and which traits are decisive when it comes to the implementation of a LWS. We investigated 11 plant species commonly used on living walls, located close to train tracks and roads. PM accumulation on leaves was quantified by magnetic analysis (Saturation Isothermal Remanent Magnetization (SIRM)). Several leaf morphological variables that could potentially influence PM capture were assessed, as well as the Wall Leaf Area Index. A wide range in SIRM values (2.74–417 μA) was found between all species. Differences in SIRM could be attributed to one of the morphological parameters, namely SLA (specific leaf area). This suggest that by just assessing SLA, one can estimate the PM capture efficiency of a plant species, which is extremely interesting for urban greeners. Regarding temporal variation, some species accumulated PM over the growing season, while others actually decreased in PM levels. This decrease can be attributed to rapid leaf expansion and variations in meteorology. Correct assessment of leaf age is important here; we suggest individual labeling of leaves for further studies. Highest SIRM values were found close to ground level. This suggests that, when traffic is the main pollution source, it is most effective when LWS are applied at ground level. We conclude that LWS can act as local sinks for PM, provided that species are selected correctly and systems are applied according to the state of the art.

Abstract: A soil history of exposure to extreme weather may impact future plant growth and microbial community assembly. Currently, little is known about whether and how previous precipitation regime (PR)-induced changes in soil microbial communities influence plant and soil microbial community responses to a subsequent PR. We exposed grassland mesocosms to either an ambient PR (1 day wet-dry alternation) or a persistent PR (30 days consecutive wet-dry alternation) for one year. This conditioned soil was then inoculated as a 10 % fraction into 90 % sterilized “native” soil, after which new plant communities were established and subjected to either the ambient or persistent PR for 60 days. We assessed whether past persistent weather-induced changes in soil microbial community composition affect soil microbial and plant community responses to subsequent weather persistence. The historical regimes caused enduring effects on fungal communities and only temporary effects on bacterial communities, but did not trigger soil microbial legacy effects on plant productivity when exposed to either current PR. This study provides experimental evidence for soil legacy of climate persistence on grassland ecosystems in response to subsequent climate persistence, helping to understand and predict the influences of future climate change on soil biota.

Abstract: This work reports the use of modified screen-printed carbon electrodes (SPCEs) for the identification of three drugs of abuse and two habitual cutting agents, caffeine and paracetamol, combining voltammetric sensing and chemometrics. In order to achieve this goal, codeine, heroin and morphine were subjected to Square Wave Voltammetry (SWV) at pH 7, in order to elucidate their electrochemical fingerprints. The optimized SPCEs electrode array, which have a differentiated response for the three oxidizable compounds, was derived from Carbon, Prussian blue, Cobalt (II) phthalocyanine, Copper (II) oxide, Polypyrrole and Palladium nanoparticles ink-modified carbon electrodes. Finally, Principal Component Analysis (PCA) coupled with Silhouette parameter assessment was used to select the most suitable combination of sensors for identification of drugs of abuse in presence of cutting agents.

Abstract: Combined mu-XRF, mu-XAFS, and mu-XRD investigations of a uranium-rich tertiary sediment, from a nuclear repository natural analogue site, and a fractured granite bore core section after a column tracer experiment using a Np(V) containing cocktail have been performed. Most mu-XRF/mu-XAFS measurements are recorded in a confocal geometry to provide added depth information. The U-rich sediment results show uranium to be present as a tetravalent phosphate and that U(IV) is associated with As(V). Arsenic present is either As(V) or As(0). The As(0) form thin coatings on the surface of pyrite nodules. A hypothesis for the mechanism of uranium immobilization is proposed, where arsenopyrite acted as reductant of ground water dissolved U(VI) leading to precipitation of less soluble U(IV) and thereby forming As(V). Results for the granite sample show the immobilized Np to be tetravalent and associated with facture material.

Abstract: To provide for the globally increasing demand for proteinaceous food, microbial protein (MP) has the potential to become an alternative food or feed source. Phosphorus (P), on the other hand, is a critical raw material whose global reserves are declining. Growing MP on recovered phosphorus, for instance, struvite obtained from wastewater treatment, is a promising MP production route that could supply protein-rich products while handling P scarcity. The aim of this study was to explore struvite dissolution kinetics in different MP media and characterize MP production with struvite as sole P-source. Different operational parameters, including pH, temperature, contact surface area, and ion concentrations were tested, and struvite dissolution rates were observed between 0.32 and 4.7 g P/L/d and a solubility between 0.23 and 2.22 g P-based struvite/L. Growth rates and protein production of the microalgae Chlorella vulgaris and Limnospira sp. (previously known as Arthrospira sp.), and the purple non‑sulfur bacterium Rhodopseudomonas palustris on struvite were equal to or higher than growth on conventional potassium phosphate. For aerobic heterotrophic bacteria, two slow-growing communities showed decreased growth on struvite, while the growth was increased for a third fast-growing one. Furthermore, MP protein content on struvite was always comparable to the one obtained when grown on standard media. Together with the low content in metals and micropollutants, these results demonstrate that struvite can be directly applied as an effective nutrient source to produce fast-growing MP, without any previous dissolution step. Combining a high purity recovered product with an efficient way of producing protein results in a strong environmental win-win.

Abstract: The heterogeneous precipitation of the eta (MgZn2) phase on the E (Al18Mg3Cr2) dispersoids of the 7075 aluminum alloy was systematically investigated by atomic resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and energy dispersive X-ray spectrometry (EDX). It is found that coarse B particles are heterogeneously precipitated at the E particle interface after water quenching and isothermal aging at 120 degrees C. The incoherent E/Al interface is responsible for the high tendency of heterogeneous precipitation of the B phase. Two different orientation relationships (ORs) between the eta, E and Al matrix are identified: OR1 [2 (11) over bar0](eta)[011](E)//[(1) over bar 12](Al), (01 (1) over bar0)(eta)//(13 (3) over bar)(E)//(201)(Al), OR2 [(1) over bar 12](E)//[0001](eta)//[011](Al), (01 (1) over bar0 )(eta)//(220)(E)//(34 (4) over bar)(Al). The eta phase is preferential to nucleate along the {111}(E) or the {220}(E) planes, depending on its OR. The heterogeneous nucleation of B phase on the E particle could stabilize the E/Al interface by introducing a coherent E/eta interface, which increases the drive force of heterogeneous precipitation. The reorientation of eta phase and mutual diffusion of solute atoms could assist the coherency of the E/eta interface. The present results suggest that increasing the coherency of the E/Al interface is a promising method to suppress the heterogeneous precipitation of the eta phase. (C) 2020 Elsevier B.V. All rights reserved.

Abstract: Thermoelectric materials and magnetocaloric materials are promising candidates for solid-state refrigeration applications. The combination of thermoelectric and magnetocaloric effects could potentially lead to more efficient refrigeration techniques. We designed and successfully synthesized Gd/YbAl3 composites using a YbAl3 matrix with good low-temperature thermoelectric performance and Gd microspheres with a high magnetocaloric performance, using a sintering condition of 750 degrees C and 50 MPa. Using aberration-corrected scanning transmission electron microscopy (STEM), it was discovered that the heterointerface between Gd and YbAl 3 is composed of five sequential interfacial layers: GdAl3, GdAl2, GdAl, Gd3Al2, and Gd3Al. The diffusion of Al atoms plays a crucial role in the formation of these interfacial layers, while Yb or Gd do not participate in the interlayer diffusion. This work provides the essential structural information for further optimizing and designing high-performance composites for thermoelectric-magnetocaloric hybrid refrigeration applications. (C) 2020 Elsevier B.V. All rights reserved.

Abstract: A series of mixed nanocomposite materials was synthetized, containing a Ferrite phase type Zn1-xNixFe2O4 and a Freudenbergite phase type Na2Fe2Ti6O16, where x = 0; 0.2; 0.4; 0.6; 0.8; 1. The choice for this combination is based on the good adsorption properties of Freudenbergite for dye molecules, and the small bandgap energy of Ferrite spinel, allowing activation of the catalysts under visible light irradiation. A two steps synthesis protocol was used to obtain the smart-removal nanocomposites. Firstly, the spinel structure was obtained via the co-precipitation route followed by the addition of the Ti-source and formation of the Freudenbergite system. The role of cations on the formation mechanism and an interesting interchange of cations between spinel and Freudenbergite structures was clarified by a TEM study. Part of the Ti4+ penetrated the spinel structure and, at the same time, part of the Fe3+ formed the Freudenbergite system. The photocatalytic activity was studied under visible light, reaching for the best catalysts a 67% and 40% mineralization degree for methylene blue and rhodamine 6G respectively, after 6 h of irradiation. In the same conditions, the well-known commercial P25 (Degussa) managed to mineralize only 12% and 3% of methylene blue and rhodamine 6G, respectively. Due to the remarkable magnetic properties of Ferrites, a convenient recovery and reuse of the catalysts is possible after the photocatalytic tests. Based on the excellent catalytic performance of the nanocomposites under visible light and their ease of separation out of the solution after the catalytic reaction, the newly developed composite catalysts are considered very effective for wastewater treatment.