Abstract: Studies of materials' properties at high and ultrahigh pressures lead to discoveries of unique physical and chemical phenomena and a deeper understanding of matter. In high-pressure research, an achievable static pressure limit is imposed by the strength of available strong materials and design of high-pressure devices. Using a high-pressure and high-temperature technique, we synthesized optically transparent microballs of bulk nanocrystalline diamond, which were found to have an exceptional yield strength (similar to 460 GPa at a confining pressure of similar to 70 GPa) due to the unique microstructure of bulk nanocrystalline diamond. We used the nanodiamond balls in a double-stage diamond anvil cell high-pressure device that allowed us to generate static pressures beyond 1 TPa, as demonstrated by synchrotron x-ray diffraction. Outstanding mechanical properties (strain-dependent elasticity, very high hardness, and unprecedented yield strength) make the nanodiamond balls a unique device for ultrahigh static pressure generation. Structurally isotropic, homogeneous, and made of a low-Z material, they are promising in the field of x-ray optical applications.

Abstract: A novel heap leaching method was investigated for selective removal of chromium (Cr) and-vanadium (V) from ferrochromium (FeCr) and stainless steel (SS) slags. In particular, alkaline oxidative heap leaching was simulated on lab-scale by batch and column leaching tests. The results show a selective leaching of Cr (11-19%) and V (7.0-7.5%) after 64 days of column leaching, with a very low dissolution (<2.2% (FeCr slag) and <0.15% (SS slag)) of matrix elements (e.g. Al, Fe, Si, Mg, Ca), when NaOCl is applied as oxidation agent and NaOH as alkaline agent. Furthermore, the used leaching liquor is reactive for a longer period of time, indicating that circulation of leaching liquor could be possible. Finally, the experimental results were fed into a first-order model which predicts that Cr will continue to leach from the tested slags for 4-5 years at a chosen infiltration rate of 73,000 l/(y m(2)). (C) 2016 Elsevier B.V. All rights reserved.

Abstract: The conventional treatment of municipal wastewater by means of activated sludge is typically energy demanding. Here, the potential benefits of: (1) the optimization of mesophilic digestion; and (2) transitioning to thermophilic sludge digestion in three wastewater treatment plants (Tilburg-Noord, Land van Cuijk and Bath) in the Netherlands is evaluated, including a full-scale trial validation in Bath. In Tilburg-Noord, thermophilic sludge digestion covered the energy requirements of the plant (102%), whereas 111% of sludge operational treatment costs could be covered in Bath. Thermophilic sludge digestion also resulted in a strong increase in nutrient release. The potential for nutrient recovery was evaluated via: (1) stripping/absorption of ammonium; (2) autotrophic removal of ammonium via partial nitritation/anammox; and (3) struvite precipitation. This research shows that optimization of sludge digestion may lead to a strong increase in energy recovery, sludge treatment costs reduction, and the potential for advanced nutrient management in full-scale sewage treatment plants. (C) 2016 Elsevier Ltd. All rights reserved.

Abstract: The combination of several micro-XRF analysis modes is presented for the investigation of an illuminated parchment manuscript. With a commercial instrument, conventional micro-XRF spot analysis (0D) and mapping (2D) are performed, yielding detailed lateral elemental information. Depth resolution becomes accessible by mounting an additional polycapillary lens in front of an SDD detector. Quantitative confocal depth profiles (1D) are presented as well as the full separation of the front and the backside decorations with the help of fast 3D mappings of specific areas. Only through the use of these multidimensional modes can elemental information be assigned both to lateral and depth positions, making the analysis of such heterogeneous samples feasible.

Abstract: This study focused on a physical separator in the form of a screen to out-select nitrite oxidizing bacteria (NOB) for mainstream sewage treatment. This separation relied on the principle that the NOB prefer to grow in flocs, while anammox bacteria (AnAOB) reside in granules. Two types of screens (vacuum and vibrating) were tested for separating these fractions. The vibrating screen was preferred due to more moderate normal forces and additional tangential forces, better balancing retention efficiency of AnAOB granules (41% of the AnAOB activity) and washout of NOB (92% activity washout). This operation resulted in increased NOB out-selection (AerAOB/NOB ratio of 2.3) and a total nitrogen removal efficiency of 70% at influent COD/N ratio of 1.4. An effluent total nitrogen concentration <10 mg N/L was achieved using this novel approach combining biological selection with physical separation, opening up the path towards energy positive sewage treatment. (C) 2016 Elsevier Ltd. All rights reserved.

Abstract: The increasing production of nitrogen-containing fertilizers is crucial to meet the global food demand, yet high losses of reactive nitrogen associated with the food production/consumption chain progressively deteriorate the natural environment. Currently, mesophilic nitrogen-removing microbes eliminate nitrogen from wastewaters. Although thermophilic nitrifiers have been separately enriched from natural environments, no bioreactors are described that couple these processes for the treatment of nitrogen in hot wastewaters. Samples from composting facilities were used as inoculum for the batch-wise enrichment of thermophilic nitrifiers (350 days). Subsequently, the enrichments were transferred to a bioreactor to obtain a stable, high-rate nitrifying process (560 days). The community contained up to 17% ammonia-oxidizing archaea (AOAs) closely related to 'Candidatus Nitrososphaera gargensis', and 25% nitrite-oxidizing bacteria (NOBs) related to Nitrospira calida. Incorporation of C-13-derived bicarbonate into the respective characteristic membrane lipids during nitrification supported their activity as autotrophs. Specific activities up to 198 +/- 10 and 894 +/- 81 mg N g(-1) VSS per day for AOAs and NOBs were measured, where NOBs were 33% more sensitive to free ammonia. The NOBs were extremely sensitive to free nitrous acid, whereas the AOAs could only be inhibited by high nitrite concentrations, independent of the free nitrous acid concentration. The observed difference in product/substrate inhibition could facilitate the development of NOB inhibition strategies to achieve more cost-effective processes such as deammonification. This study describes the enrichment of autotrophic thermophilic nitrifiers from a nutrient-rich environment and the successful operation of a thermophilic nitrifying bioreactor for the first time, facilitating opportunities for thermophilic nitrogen removal biotechnology.

Abstract: The surface of the aerial parts of the plant, also termed the phyllosphere, is a selective habitat for microbes. The bacterial composition of the phyllosphere depends on host plant species, leaf characteristics, season, climate, and geographic location of the host plant. In this study, we investigated the effect of an urban environment on the bacterial composition of phyllosphere communities. We performed a passive biomonitoring experiment in which leaves were sampled from ivy (Hedera sp.), a common evergreen climber species, in urban and non-urban locations. Exposure to traffic-generated particulate matter was estimated using leaf biomagnetic analyses. The bacterial community composition was determined using 16S rRNA gene sequencing on the Illumina MiSeq. The phyllosphere microbial communities of ivy differed greatly between urban and non-urban locations, as we observed a shift in several of the dominant taxa: Beijerinckia and Methylocystaceae were most abundant in the non-urban phyllosphere, whereas Hymenobacter and Sphingomonadaceae were dominating the urban ivy phyllosphere. The richness, diversity and composition of the communities showed greater variability in the urban than in the non-urban locations, where traffic-generated PM was lower. Interestingly, the relative abundances of eight of the ten most dominant taxa correlated well with leaf magnetism, be it positive or negative. The results of this study indicate that an urban environment can greatly affect the local phyllosphere community composition. Although other urban-related factors cannot be ruled out, the relative abundance of most of the dominant taxa was significantly correlated with exposure to traffic-generated PM.

Abstract: Large river catchments with mixed land use capture pesticides from many sources, and degradable pesticides are converted during downstream transport. Unravelling the contribution of pesticide source and the effect of degradation processes is a challenge in such areas. However, insight and understanding of the sources is important for targeted managen-lent, especially when water is abstracted from the river for drinking water production. The river Meuse is such a case. A long-term monitoring data set was applied in a modelling approach for assessing the contribution of waste water treatment plants (WWTPs) and tributaries (sub-basins) to surface water contamination, and to evaluate the effect of decay on the downstream concentrations of glyphosate and AMPA at the point of drinking water abstraction. The results show that WWTPs are important contributors for glyphosate and AMPA in large river catchments with mixed land uses. In the studied area, the river Meuse in the Netherlands, the relative contribution of WWTP effluents is above 29% for glyphosate and around 12% for AMPA. Local industries are found to be potentially big contributors of AMPA. Glyphosate entering the river system is gradually converted to AMPA and other degradation-productions, which results in downstream loads that are considerably lower than the sum of all influxes. In summer when the travel time is longer due to lower discharge, the first order decay of glyphosate in the river Meuse is estimated to result in about 50% reduction of the downstream glyphosate concentrations over a river stretch of 250 km. The contribution of glyphosate decay to the observed AMPA concentrations ranges between 2% and 10%. Contributions are sensitive to seasonal variations in discharge that influence the concentrations through dilution and degradation. (C) 2016 Elsevier B.V. All rights reserved.

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: Ca8MgR(PO4)(7) = La, Pr, Nd, Sm-Lu, and Y) phosphates with a beta-Ca-3(PO4)(2) related structure were prepared by a standard solid-state method in air. Second-harmonic generation, differential scanning calorimetry, and dielectric measurements led to the conclusion that all Ca8MgR(PO4)(7) are centrosymmetric and go to another centrosymmetric phase in the course of a first-order antiferroelectric phase transition well above room temperature (RT). High-temperature electron diffraction showed that the symmetry changes from R (3) over barc to R (3) over barm during the phase transition. Structures of Ca8MgR(PO4)(7) at RT were refined by the Rietveld method in centrosymmetric space group R (3) over barc. Mg2+ cations occupy the M5 site; the occupancy of the M1 site by R3+ cations increases monotonically from 0.0389 for R = La to 0.1667 for R = Er-Lu, whereas the occupancy of the M3 site by R3+ cations decreases monotonically from 0.1278 for R = La to 0 for R = Er-Lu. In the case of R = Er-Lu, the M3 site is occupied only by Ca2+ cations. P1O(4) tetrahedra and cations at the M3 site are disordered in the R (3) over barc structure of Ca8MgEu(PO4)(7). Using synchrotron X-ray powder diffraction, we found that annealing conditions do not significantly affect the distribution of Ca2+ and Eu3+ cations between the structure positions of Ca8MgEu(PO4)(7). Luminescent properties of CasMgEu(PO4)(7) powder samples were investigated under near-ultraviolet (n-UV) light. Excitation spectra of CasMgEu(PO4)(7) show the strongest absorption at about 395 nm that matches with commercially available n-UV-emitting GaN-based LED chips. Emission spectra show an intense red emission due to the D-5(0) -> F-7(2) transition of Eu3+. (C) 2016 Elsevier B.V. All rights reserved.

Abstract: The distribution of mass, water-soluble inorganic salts and mineral elements of size-segregated aerosols (PM1, PM2.5-1 and PM10-2.5), precursor gaseous pollutants, black carbon, and nanoparticles (10-300 nm size range) at the Southern Bight of the North Sea has been studied. The concentrations of air pollutants peaked over shipping lanes, open-water anchorage areas and frequently navigated waters, due to the presence of mobile emission sources. A considerable decrease in air pollutant levels was seen when diverting from these marine areas towards remote or coastal banks. These findings showed the rapid dispersion of pollutants in the marine air. The nano-aerosol count, originating from ocean-going ships, peaked at lower average aerodynamic diameters (e.g., approximate to 28 nm) than those, observed from low displacement vessels (45-50 nm, e.g., for fishing boats). The average diameter of nano-PM depended also on weather conditions, e.g., it was higher (approximate to 50 nm) in air of higher humidity. (C) 2016 Elsevier Ltd. All rights reserved.

Abstract: Manure represents an exquisite mining opportunity for nutrient recovery (nitrogen and phosphorus), and for their reuse as renewable fertilisers. The ManureEcoMine proposes an integrated approach of technologies, operated in a pilot-scale installation treating swine manure (83.7%) and Ecofrit® (16.3%), a mix of vegetable residues. Thermophilic anaerobic digestion was performed for 150 days, the final organic loading rate was 4.6 kgCOD m−3 d−1, with a CH4 production of 1.4 Nm3 m−3 d−1. The digester was coupled to an ammonia side-stream stripping column and a scrubbing unit for free ammonia inhibition reduction in the digester and nitrogen recovery as ammonium sulphate. The stripped digestate was recirculated daily in the digester for 15 days (68% of the digester volume), increasing the gas production rate by 27%. Following a decanter centrifuge, the digestate liquid fraction was treated with an ultrafiltration membrane. The filtrate was fed into a struvite reactor, with a phosphorus recovery efficiency of 83% (as orthophosphate). Acidification of digestate could increment the soluble orthophosphate concentration up to 4 times, enhancing phosphorus enrichment in the liquid fraction and its recovery via struvite. A synergistic combination of manure processing steps was demonstrated to be technologically feasible to upgrade livestock waste into refined, concentrated fertilisers.

Abstract: A study has been conducted on the leaching of two fungicides, tebuconazole and cymoxanil, in a soil amended with spent mushroom substrate (SMS), with an evaluation of how different factors influence this process.The objective was based on the potential use of SMS as a biosorbent for immobilizing pesticides in vulnerable soils, and the need to know how it could affect the subsequent transport of these retained compounds. Breakthrough curves (BTCs) for C-14-fungicides, non-incubated and incubated over 30 days, were obtained in columns packed with an unamended soil (S), and this soil amended with SMS at rates of 5% (S + SMS5) and 50% (S + SMS50) under saturated and saturated-unsaturated flows. The highest leaching of tebuconazole (> 50% of the total C-14 added) was found in S when a saturated water flow was applied to the column, but the percentage of leached fungidde decreased when a saturated-unsaturated flow was applied in both SMS-amended soils. Also a significant decrease in teaching was observed for tebuconazole after incubation in the column, especially in S + SMS50 when both flows were applied. Furthermore, cymoxanil leaching was complete in S and S + SMS when a saturated flow was applied, and maximum peak concentrations were reached at 1 pore volume (PV), although BTCs showed peaks with lower concentrations in S + SMS. The amounts of cymoxanil retained only increased in S + SMS when a saturated-unsaturated flow was applied. A more relevant effect of SMS for reducing the leaching of fungidde was observed when cymoxanil was previously incubated in the column, although mineralization was enhanced in this case. These results are of interest for extending SMS application on the control of the leaching of fungicides with different physicochemical characteristics after different ageing times in the soil and water flow conditions applied. (C) 2017 Elsevier B.V. All rights reserved.

Abstract: Single-layer, large-scale two-dimensional material growth is still a challenge for their wide-range usage. Therefore, we carried out a comprehensive study of monolayer MoS2 growth by CVD investigating the influence of growth zone configuration and precursors ratio. We first compared the two commonly used approaches regarding the relative substrate and precursor positions, namely, horizontal and face-down configurations where facedown approach is found to be more favorable to obtain larger flakes under identical growth conditions. Secondly, we used different types of substrate holders to investigate the influence of the Mo and S vapor confinement on the resulting diffusion environment. We suggest that local changes of the S to Mo vapor ratio in the growth zone is a key factor for the change of shape, size and uniformity of the resulting MoS2 formations, which is also confirmed by performing depositions under different precursor ratios. Therefore, to obtain continuous monolayer films, the S to Mo vapor ratio is needed to be kept within a certain range throughout the substrate. As a conclusion, we obtained monolayer triangles with a side length of 90 mu m and circles with a diameter of 500 mu m and continuous films with an area of 85 0 mu m x 1 cm when the S-to-Mo vapor ratio is optimized. (C) 2017 The Japan Society of Applied Physics

Abstract: Several HNO3-based leaching approaches were tested and optimized to selectively recover Pb and other minor metals (Cu, Ni, Zn) from secondary lead smelter residues (i.e., slag and matte). Firstly, the leaching behaviors of Pb and the matrix element Fe were studied at atmospheric pressure in the temperature range 25-70 degrees C. These elements were present in both materials studied as sulfide and oxide phases. For the sulfur-rich matte residue, the Pb leaching increased from 63% to 69% upon increasing the HNO3 concentration from 0.2 M to 0.5 M. However, by adding Fe(III) as an oxidation agent, Pb leaching from the matte amounted to 90% at 25 degrees C. At a higher temperature, Pb leaching was reduced due to PbSO4 precipitation. In this process, Cu, Zn and Ni leaching was insignificant. For the slag residue, HNO3 could not leach Pb (0.03% Pb leached), while Fe leaching was 19.8% due to a galvanic effect. However, Pb leaching of the slag was 82% in the presence of additional Fe(III). Secondly, to enhance leaching of the other base metals (Cu, Zn and Ni) from the matte, roasting followed by water leaching and (microwave assisted or autoclave) pressurized leaching in 0.5 M HNO3 were applied. During roasting, the FeS phase converted to Fe2O3 above 500 degrees C, and PbS and Pb phases were transformed into insoluble PbSO4 above 400 degrees C. Cu, Ni and Zn leaching was drastically enhanced by a roasting step at 600 degrees C followed by leaching with 0.5 M HNO3 at 50 degrees C, or by pressurized HNO3 leaching above 130 degrees C, whereby Pb leaching almost ceased due to PbSO4 precipitation. During the roasting above 600 degrees C, or microwave assisted extraction (MAE) at 160 degrees C for 15 min, FeS was completely converted to iron oxides that can be used as raw material for pig iron production. Based on the results, the methods investigated can be combined as process steps of two possible routes for the selective recovery of valuable metals and the production of a clean source of Fe oxides from the secondary lead smelting residues studied. (C) 2017 Elsevier B.V. All rights reserved.