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This research specifically focused on the development of a novel methodology to reduce excess nitrate in drinking water utilizing zerovalent iron nanoparticles (nZVI)-stabilized radiation-grafted copolymer matrix. nZVI was synthesized by borohydrate reduction of FeCl3 and stabilized on acrylic acid (AAc)-grafted non-woven polyethylene/polypropylene (NWPE/PP-g-AAc) copolymer matrix, which was grafted using gamma radiation. The use of nZVI for environmental applications is challenging because of the formation of an oxide layer rapidly in the presence of oxygen. Therefore, radiation-grafted NWPE/PP synthetic fabric was used as the functional carrier to anchor nZVI and enhance its spreading and stability. The chemical reduction of nitrate by nZVI-adsorbed NWPE/PP-g-AAc (nZVI-Ads-NWP) fabric was examined in batch experiments at different pH values. At low pH values, the protective layers on nZVI particles can be readily dissolved, exposing the pure iron particles for efficient chemical reduction of nitrate. After about 24 h, at pH 3, almost 96% of nitrate was degraded, suggesting that this reduction process is an acid-driven, surface-mediated process. The nZVI-water interface has been characterized by the 1-pK Basic Stern Model (BSM). An Eley-Rideal like mechanism well described the nitrate reduction kinetics. In accordance with green technology, the newly synthesized nZVI-Ads-NWP has great potential for improving nitrate reduction processes required for the drinking water industry.

The aim of the present study was to investigate the detailed evolution of the SAz-1 smectite in 1 MKOH at 80[degrees]C at a solid/liquid ratio of 1/80. AFM observations indicated no change in crystal size or shape. XRD measurements at 40% relative humidity revealed changes in expandability of the smectite. The (001) reflection profile of smectite was modeled using a trial-and-error approach. The results indicate that with increasing run time, the number of non-expandable layers with zero or one water layer increases and that the coherent scattering domain size of the smectite decreases. IR spectroscopy of the reacted smectite suggests that there is no change from the initial clay products. The dehydroxylation temperature showed a slight decrease from 619 to 605[degrees]C. STA measurements demonstrated that the cis-vacant character of the octahedral sheet remained nearly unchanged throughout the experiment. Determination of the average layer charge showed a continuous increase from 0.32 to 0.42 eq/[(Si/Al).sub.4][O.sub.10], whereas the layer charge distribution indicated the appearance of high charged smectite layers with a charge of ~ 0.6 eq/[(Si/Al).sub.4] [O.sub.10] and the disappearance of the low charged layers. XPS and SEM measurements indicate an increase orAl in the smectite samples. Isotope data support the theory of an internal diffusion mechanism by gradual changes in [delta][sup.18]O values. From these data it appears that KOH solutions provoke a mineralogical change in the 2:1 layer of the smectite minerals that increases the layer charge by increasing the Al content. This mineralogical change does not involve dissolution/crystallization processes and then must show solid-state transformation of the clays at 80[degrees]C. Keywords: Smectite, illitization, solid-state transformation, KOH

X-ray absorption and X-ray photoelectron spectroscopy are used to study the structure of Ti atoms in NaAlH(sub 4) doped with TiCl(sub 3) or I(sub 13).6THF by the ball milling method. The results suggest that the reversible hydrogen capacity of the structure reduces with the increasing number of cycles and is directly related to the decreasing reaction rate.

In alloyed nanoparticles, synergistic electronic and/or geometric effects may enhance the catalytic properties compared to their monometallic counterparts. Herein, we address the synthesis of bimetallic Au/Cu nanoparticles with different compositions by wet chemical reduction in ionic liquids. The nanoparticles were successively supported on carbon. The ionic liquid could be recycled after synthesis. Annealing of the carbon‐supported NPs at 400 °C led to NPs of the ordered intermetallic L10 AuCu phase. The nanoparticle‐derived catalysts were characterized by X‐ray diffraction analysis, transmission electron microscopy, X‐ray photoelectron spectroscopy and optical emission spectroscopy with inductively coupled plasma. Oxidation of biomass‐derived furans is a prominent process for biomass transformation into value‐added chemicals. Herein, the oxidation of 5‐hydroxymethyl‐2‐furfural (HMF) to 2,5‐furandicarboxylic acid (FDCA) was chosen as a model reaction to evaluate the effect of Cu addition and intermetallic structure on the catalytic performance. Particularly Au/Cu nanoparticles with an Au/Cu ratio of 3 : 1 showed very high conversion to FDCA. [ABSTRACT FROM AUTHOR]

This article reports results from two distinct, originally unrelated studies that show unexpected behavior with respect to sodium sulfate solutions in contact with flat surfaces. On the one hand, we investigated immersion freezing of sulfate containing solutions (target salt was CaSO4 and Na2SO4 was used as one control) in the presence of flat sapphire‐0001 crystals using second‐harmonic generation (SHG) spectroscopy. Further control experiments were carried out with neat water and CaCl2. The SHG signals from CaSO4 and Na2SO4 solutions behave somewhat differently from those recorded for the two other cases, the neat water and CaCl2. The common pattern shows a decrease of the SHG signal with decreasing temperature down to about −15°C, whereupon the signal sharply drops, indicating freezing. With the Na2SO4 solution, although the signal initially follows closely the neat water curve, the trend increases sharply at about −10°C followed by a gradual decrease with further cooling. There is no plausible explanation for the distinct behavior of the Na2SO4 solution, and thermodynamic calculations do not suggest any precipitation of a sodium sulfate solid phase. At the end of the freeze–thaw cycle, the initial SHG for each system is retrieved, suggesting reversibility. On the other hand, in a separate investigation unrelated to the freezing study, it was repeatedly observed that sodium sulfate precipitates from solution on flat steel surfaces at room temperature. As in the freezing experiments, thermodynamic calculations for the bulk solution solubility of sodium sulfate indicate that precipitates should not be forming under the conditions of the studies. The crystals observed on the steel samples have snowflake shapes similar to one literature report. We conclude that Na2SO4 in the presence of flat surfaces shows unexpected behavior that should incite further detailed studies in the future to elucidate the phenomenon. [ABSTRACT FROM AUTHOR]

The solubility of 99Tc(IV) was investigated from undersaturation conditions in NaCl–Na2SO4 (0.3 M ≤ I ≤ 5.0 M), MgCl2–MgSO4 (I = 13.5 M) and CaCl2–CaSO4 (I = 13.5 M) systems with 0.001 M ≤ [SO42−]tot ≤ 1.0 M and 1 ≤ pHm ≤ 12 (with pHm = −log[H+], in molal units). Reducing conditions were set by either Sn(II) or Fe(0). Special efforts were dedicated to accurately characterize the correction factors Am required for the determination of pHm from the experimentally measured pH values in the mixed salt systems investigated, with pHm = pHexp + Am. The combination of (pe + pH m) measurements with Pourbaix diagrams of Tc suggests that technetium is present in its +IV redox state. This hypothesis is confirmed by XANES, which unambiguously shows the predominance of Tc(IV) both in the aqueous and solid phases of selected solubility samples. XRD and SEM–EDS support the amorphous character of the solid phase controlling the solubility of Tc(IV). EXAFS data confirm the predominance of TcO2(am, hyd) at pHm > 1.5, whereas the formation of a Tc(IV)–O–Cl solid phase is hinted at lower pHm values in concentrated NaCl–Na2SO4 systems with ≈5 M NaCl. Solubility data collected in sulfate-containing systems are generally in good agreement with previous solubility studies conducted in sulfate-free NaCl, MgCl2 and CaCl2 solutions of analogous ionic strength. Although the complexation of Tc(IV) with sulfate cannot be completely ruled out, these results strongly support that, if occurring, complexation must be weak and has no significant impact on the solubility of Tc(IV) in dilute up to highly saline media. Solubility upper-limits determined in this work can be used for source term estimations including the effect of sulfate in a variety of geochemical conditions relevant in the context of nuclear waste disposal. [ABSTRACT FROM AUTHOR]

Several countries consider hosting a deep geological repository for high-level nuclear waste (HLW) in salt rock. In the unexpected case of solution access to the emplacement caverns during the long-term evolution of such a repository, metallic containers will be exposed to highly saline brines. In this study, corrosion experiments under conditions expected to be representative of HLW disposal in salt rock have been performed with stainless steel, a material typically used to construct containers containing vitrified HLW. Experiments were performed in closed vessels under anoxic and highly saline conditions at 90 ∘ C. Polished stainless steel coupons were suspended in 5 mol L -1 NaCl or 3.4 mol L -1 MgCl 2 at their natural pH. At the end of the experiments (up to 294 d), vessels were cooled down to room temperature, pH and Eh were measured in situ, the ultra-centrifuged contacting brines were analyzed by (HR)ICP-MS (high-resolution inductively coupled plasma mass spectrometry) and the formed corrosion products were identified. In all corrosion experiments, pH m and Eh hardly changed with exposure time, and the nature of the salt had no significant effect. The overall corrosion rates were low, and the quantities of dissolved metal ions revealed the formation of only sparingly soluble corrosion products. The formation of a passivation layer mostly made of Cr(III) (hydr)oxide was evidenced, but no localized surface attack could be detected. The coupon corroded in 5 mol L -1 NaCl was embedded in resin and cross-cut for further analyses, using synchrotron-based techniques with a small beam footprint (X-Ray fluorescence (μ XRF), X-Ray diffraction (μ XRD), and X-ray absorption near-edge structure (μ XANES)). Element distribution maps revealed the presence of a very thin (<1 µm) layer of corrosion products, with regions enriched either in Cr or in Fe and Ni. X-ray diffractograms identified the presence of spinel-type compounds (Fe 3 O 4 and NiFe 2 O 4) and Cr 2 O 3 , which was corroborated by recording μ XANES at the Cr, Fe and Ni K-absorption edges. The additional presence of layered double hydroxides in addition to NiO and Ni(OH) 2 was also evidenced. Overall, results point to a corrosion layer having a duplex structure, with an inner layer mostly of chromium (hydr)oxides and an outer layer made of Fe- and Ni-based spinel compounds admixed with nickel (hydr)oxides. [ABSTRACT FROM AUTHOR]

Spheroidal graphite cast iron (GGG40/0.7040) is used as an overpack material for the reference Pollux 10 container, a prototype for the storage of fuel elements in different types of host rocks (Hassel et al., 2019). Corrosion processes are expected to be triggered after some decades, as the contacting bentonite, which is used as fill material, becomes soggy because of the decay of the fission heat generation and the intrusion of pore water as the temperature decreases under the condensation point (King and Padovani, 2011). The distinct electrochemical reactivities of the graphite, ferrite, pearlite, and cementite phases exposed by this material introduce local galvanic elements which influence the topographic evolution of degradation (Spence, 2005). The aim of this work is to elucidate the corrosion dynamics of active and passive areas by following the chemical evolution at the interface of cast iron–bentonite during the first stages after its saturation with geological pore water. Polarization experiments and electrochemical impedance spectroscopy were applied to monitor the corrosion process in a bentonite cell, where GGG40 steel is put into contact with a light compacted Wyoming bentonite slurry 1 : 10 w/w of bentonite to Opalinus Clay pore water (Fig. 1a). Experiments were performed at 30 and 50 ∘ C for longer than 3 months. The surface chemistry and morphological changes were investigated by local XPS, SEM-EDX, and TEM (X-ray photoelectron spectroscopy, scanning electron microscopy with energy dispersive X-ray, and transmission electron microscopy, respectively). These experiments were complemented with corrosion studies performed in pore water under different temperatures, hydrostatic pressures, and pH and with and without dissolved oxygen. The polarization curves indicate a constant corrosion rate of GGG40 steel in saturated bentonite after 30 d. SEM micrographs reveal a preferential dissolution of the ferrite phase around the graphite spheres and the ferrite lamellae contained in the pearlitic eutectic. A strong localized dissolution of ferrite along the graphite boundary can be also observed; this is a typical case of crevice corrosion caused by the unhindered access of oxygen to the graphitic cathodic areas (Wang et al., 2022). The surface chemical studies indicate the accumulation of iron oxides, which can be attributed to a hydrated magnetite and the formation of iron silicates (Zhang et al., 2021). TEM pictures of a cross-sectional lamella, including part of graphite sphere, show the formation of a silicate film covering the corroding surface with an irregular adherence (Fig. 1b). The initial relatively high corrosion rate of GGG40 steel can be attributed to the dissolution of the more active ferrite with the formation of poorly passivating iron oxides and silicates. The system is driven towards the dissolution of pearlite at more positive electrode potentials. The bentonite slurry limits the access of oxygen to the graphitic cathodic areas, reducing the corrosion rate by 1 order of magnitude in comparison with that in aerated pore water. A surface enrichment of cementite with superior passive properties and the neutralization of the local elements by approaching the corrosion potential of graphite (Kadowaki et al., 2019) is also expected. Thus, the consumption of oxygen and the transport limitation of the cathodic reaction by bentonite forecast a considerable reduction in the degradation of the container after a sacrificial corrosion phase. [ABSTRACT FROM AUTHOR]

Technetium-99 (99 Tc) is a long-lived fission product (2.13×105 years) of uranium-235 (235 U) and plutonium-239 (239 Pu) and, therefore, of great concern for the long-term safe management of nuclear waste. The migration of Tc in the environment is highly influenced by the redox conditions, since Tc may be present in various oxidation states. Depending on the chemical properties of environmentally relevant systems, Tc is expected to mainly occur as Tc(VII) and as Tc(IV) under oxidizing and reducing conditions, respectively. The anion pertechnetate (Tc(VII)O 4-) is known to barely interact with mineral surfaces; this, in turn, enhances its migration in groundwater and favors its entry into the biosphere. On the contrary, the formation of Tc(IV) limits the migration of Tc, since it forms a low soluble solid (TcO 2) and/or species, whose interaction with minerals is more favorable. In the last few decades Tc migration has been focused on the reduction of Tc(VII) to Tc(IV) by various reductants, such as Fe(II), Sn(II), or S(-II), which are either present in solution, taking part in mineral structures (Pearce et al., 2019), or metabolically induced by microbial cascades (Newsome et al., 2014). We have studied the immobilization of technetium (Tc) by various Fe(II)-containing phases, including Fe 2+ pre-sorbed on alumina nanoparticles (Mayordomo et al., 2020), Fe(II)-Al(III)-layered double hydroxide (Mayordomo et al., 2021), and Fe(II) sulfides (Rodríguez et al., 2020; Rodríguez et al., 2021). We have combined sorption experiments with microscopic and spectroscopic techniques (scanning electron microscopy, Raman microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, and X-ray absorption spectroscopy) to elucidate the mechanisms responsible for Tc(VII) reductive immobilization. Those works have been focused on binary systems (i.e., studies of the interaction of Tc with a given reductant). However, the environment is a complex system, where different components often depend on and modify each other. Thus, Tc migration is susceptible and varies, depending on environmental conditions, and should not be studied in an isolated manner. The young investigator group TecRad (HZDR, 2022), funded by the German Federal Ministry of Education and Research, aims at analyzing Tc chemistry from a wider perspective. Our goal is to study the biogeochemical behavior of Tc when it interacts with (i) microorganisms, (ii) metabolites, (iii) Fe(II) minerals, and (iv) Fe(II) minerals in presence of metabolites. An important part of this project deals with implementing new spectro-electrochemical methods to monitor the in situ the behavior of Tc in solution and at interfaces as a function of the redox potential. With these tools, we aspire to characterize the molecular structures of Tc species under a variable range of redox conditions to broaden the understanding of the chemical behavior of the pollutant. We aim at generating valuable thermodynamic data (complex formation constants, solubility constants of minerals, redox potentials, and Tc distribution coefficients) that will be used to implement a geochemical modeling able to explain Tc's environmental fate, even under different redox conditions. [ABSTRACT FROM AUTHOR]

Environmental and health hazards associated with the trace element selenium are mainly related to the presence of the highly mobile selenium oxyanions selenite and selenate (oxidation states IV and VI). In this study, we investigated the immobilization of dissolved selenite and selenate during the formation of magnetite in coprecipitation experiments based on the progressive oxidation of an alkaline, anoxic Fe2+ system (pH 9.2). Up to initial selenium concentrations of 10−3 mol L−1 (mass/volume ratio = 3.4 g L−1), distribution coefficient values (log Kd) of 3.7 to 5.1 L kg−1 demonstrate high retention of selenium oxyanions during the mineral formation process. This immobilization is due to the reduction of selenite or selenate, resulting in the precipitation of sparingly soluble selenium compounds. By X-ray diffraction analysis, these selenium compounds were identified as trigonal elemental selenium that formed in all coprecipitation products following magnetite formation. Time-resolved analysis of selenium speciation during magnetite formation and detailed spectroscopic analyses of the solid phases showed that selenium reduction occurred under anoxic conditions during the early phase of the coprecipitation process via interaction with iron(ii) hydroxide and green rust. Both minerals are the initial Fe(ii)-bearing precipitation products and represent the precursor phases of the later formed magnetite. Spectroscopic and electron microscopic analysis showed that this early selenium interaction leads to the formation of a nanoparticulate iron selenide phase [FeSe], which is oxidized and transformed into gray trigonal elemental selenium during the progressive oxidation of the aquatic system. Selenium is retained regardless of whether the oxidation of the unstable iron oxides leads to the formation of pure magnetite or other iron oxide phases, e.g. goethite. This reductive precipitation of selenium induced by interaction with metastable Fe(ii)-containing iron oxide minerals has the potential to influence the mobility of selenium oxyanions in contaminated environments, including the behavior of 79Se in the near-field of nuclear waste repositories. [ABSTRACT FROM AUTHOR]

The solubility and redox behavior of hydrous Pu(IV) oxide was comprehensively investigated by an experimental multi-method approach as a function of different redox conditions in 0.1 M NaCl solutions, allowing a detailed characterization of Pu(IV) and Pu(III) solubility and solid phase stability in these systems. Samples were prepared at ~3≤pHm≤~6 (pHm=–log m H + ) ${{\text{m}}_{{{\text{H}}^{\text{ + }}}}})$ and ~8≤pHm≤~13 at T=(22±2)°C under Ar atmosphere. No redox buffer was used in one set of samples, whereas mildly and strongly reducing redox conditions were buffered in two series with hydroquinone or SnCl2, respectively, resulting in (pe+pHm)=(9.5±1) and (2±1). XRD, XANES and EXAFS confirmed the predominance of Pu(IV) and the nanocrystalline character of the original, aged PuO2(ncr,hyd) solid phase used as a starting material. Rietveld analysis of the XRD data indicated an average crystal (domain) size of (4±1) nm with a mean cell parameter of (5.405±0.005) Å. The solubility constant of this solid phase was determined as log ∗ ​ K ° s , 0 $^ * K{^\circ _{{\text{s}},0}}$ =–(58.1±0.3) combining solubility data in acidic conditions and redox speciation by solvent extraction and CE–SF–ICP–MS. This value is in excellent agreement with the current thermodynamic selection in the NEA-TDB. Synchrotron-based in-situ XRD, XANES and EXAFS indicate that PuO2(ncr,hyd) is the solid phase controlling the solubility of Pu in hydroquinone buffered samples. Under these redox conditions and ~8≤pHm≤~13, the solubility of Pu is very low (~10−10.5 m) and pH-independent. This is consistent with the solubility equilibrium PuO2(am,hyd)+2H2O(l)⇔ Pu(OH)4(aq). Although in-situ XRD unequivocally shows the predominance of PuO2 in Sn(II)-buffered systems, XANES analyses indicate a significant contribution of Pu(III) (30±5%) in the solid phases controlling the solubility of Pu at (pe+pHm)=(2±1). For this system, EXAFS shows a systematic shortening of Pu–O and Pu–Pu distances compared to the starting Pu material and hydroquinone-buffered systems. The solubility of Pu remains very low (~10−10.5 m) at pHm>9, but shows a very large scattering (~10−9–10−10.5 m) at pHm=8. Experimental observations collected in Sn(II) buffered systems can be explained by the co-existence of both PuO2(ncr,hyd) and Pu(OH)3(am) solid phases, but also by assuming the formation of a sub-stoichiometric PuO2−x(s) phase. This extensive study provides robust upper limits for Pu solubility in alkaline, mildly to strongly reducing conditions relevant in the context of nuclear waste disposal. The potential role of Pu(III) in the solid phases controlling the solubility of Pu under these conditions is analysed and discussed in view of the current NEA-TDB thermodynamic selection, which supports the predominance of PuO2(am,hyd) and constrains the formation of Pu(OH)3(am) at pHm>8 outside the stability field of water. [ABSTRACT FROM AUTHOR]

The exceptional physico-chemical properties of ionic liquids are exploited for the synthesis and catalytic application of heterometallic nanoparticles. Pt/Sn-based nanoparticles with 2-3 nm diameter are synthesized by chemical reduction of the metal salt precursors in the ionic liquid (i.e., methyltrioctylammonium bis(trifluoromethylsulfonyl)imide) using triethylborohydride as reducing agent. Investigations by X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy suggest the formation of randomly alloyed Pt/Sn-based nanoparticles. The tin precursor and the platinum to tin ratio of the precursors are shown to influence the nature of the nanoparticles. The selective hydrogenation of cinnamaldehyde is used to probe the catalytic performance of the Pt/Sn nanoparticles, demonstrating the effect of tin alloying on the catalytic activity and selectivity to the α,β-unsaturated cinnamic alcohol. [ABSTRACT FROM AUTHOR]

In this article we introduce and compare three techniques for low-cost and rapid bonding of stereolithographically structured epoxy components to polydimethylsiloxane (PDMS). In short, we first create a polysiloxane layer on the epoxy surface via silane surface coupling and polymerization. Afterwards, the modified epoxy surface can be bonded to a PDMS component at room temperature using a handheld corona discharger, which is a commonly used low-cost technique for bonding two PDMS components. Using these methods bonds of desirable strength can be generated within half an hour. Depending on the epoxy resin, we found it necessary to modify the silanization procedure. Therefore, we provide a total of three different silanization techniques that allow bonding of a wide variety of stereolithographically structurable epoxy resins. The first technique is a UV-light induced silanization process which couples a silane that contains an epoxy-ring ((3-glycidoxypropyl)trimethoxysilane (GPTMS)). For surfaces that cannot be modified with this silane we use dimethoxydimethylsilane (DMDMS). This silane can either be coupled to the surface by a sol–gel process or UV-light induced polymerisation. The sol–gel process which is a heat induced surface modification technique results in high bond strengths. Because of the heat which triggers the sol–gel process, this technique is limited to epoxy polymers with high glass transition temperatures. For the majority of stereolithographically structured epoxy resins which typically have glass transition temperatures of around 60 °C the light-induced bonding technique is preferable. For all three techniques we performed DIN EN-conform tensile testing demonstrating maximum bond strengths of up to 350 kPa which is comparable with bond strengths reported for PDMS-to-PDMS bonds. For all bond methods, long-term stability as well as hydrolytic stability was assessed. [ABSTRACT FROM AUTHOR]

The interaction of lanthanides and trivalent actinides with borate in dilute to concentrated alkaline NaCl, MgCl2 and CaCl2 solutions was investigated at 22 ± 2 °C by a comprehensive series of solubility experiments with Nd(OH)3(am), and complemented with Cm(iii)–TRLFS studies (TRLFS: time resolved laser fluorescence spectroscopy) under analogous pH and ionic strength conditions. Although there was clear evidence of borate complexation in the pH range of 8.5 to 10, overall no significant increase in Nd(iii) solubility occurred in any of the investigated salt systems in the presence of [B]tot≤ 0.4 M, compared with analogous borate-free solutions. On the contrary, a significant decrease in Nd(iii) concentration was observed at pHc≤ 9 in NaCl and MgCl2 systems with [B]tot≥ 0.16 M (diluted salt systems) or [B]tot≥ 0.04 M (concentrated salt systems). This observation, together with a clear change in the slope of the solubility curve and the further confirmation by XPS analyses, indicates the transformation of Nd(OH)3(am) into a so far unknown Nd(iii)–borate solid phase with significantly lower solubility. Similar Nd(iii) concentrations in the aqueous phase are obtained in undersaturation solubility experiments conducted with a synthesized crystalline phase Nd[B9O13(OH)4](cr). TRLFS confirmed the formation of aqueous Cm(iii)–borate complexes in dilute to concentrated NaCl and MgCl2 systems at pHc = 8 and [B]tot≥ 0.04 M. Two different Cm(iii)–borate species are proposed based on the peak shift of the spectra, although the resulting fluorescence emission bands do not allow the definition of an unequivocal chemical model for this system. TRLFS also shows that no Cm(iii)–borate complexes form under hyperalkaline conditions (pHc = 12), due to the stronger competition posed by hydrolysis and the predominance of weakly coordinating B(OH)4− in the aqueous phase. These results show the impact of An(iii)–borate interactions on An(iii) speciation and highlight the hitherto unknown role of borate in the immobilization of trivalent actinides under repository-relevant conditions due to the formation of borate-bearing solid phases with significantly lower solubility than the corresponding hydroxides. [ABSTRACT FROM AUTHOR]

Materials matter in microfluidics. Since the introduction of soft lithography as a prototyping technique and polydimethylsiloxane (PDMS) as material of choice the microfluidics community has settled with using this material almost exclusively. However, for many applications PDMS is not an ideal material given its limited solvent resistance and hydrophobicity which makes it especially disadvantageous for certain cell-based assays. For these applications polystyrene (PS) would be a better choice. PS has been used in biology research and analytics for decades and numerous protocols have been developed and optimized for it. However, PS has not found widespread use in microfluidics mainly because, being a thermoplastic material, it is typically structured using industrial polymer replication techniques. This makes PS unsuitable for prototyping. In this paper, we introduce a new structuring method for PS which is compatible with soft lithography prototyping. We develop a liquid PS prepolymer which we term as “Liquid Polystyrene” (liqPS). liqPS is a viscous free-flowing liquid which can be cured by visible light exposure using soft replication templates, e.g., made from PDMS. Using liqPS prototyping microfluidic systems in PS is as easy as prototyping microfluidic systems in PDMS. We demonstrate that cured liqPS is (chemically and physically) identical to commercial PS. Comparative studies on mouse fibroblasts L929 showed that liqPS cannot be distinguished from commercial PS in such experiments. Researchers can develop and optimize microfluidic structures using liqPS and soft lithography. Once the device is to be commercialized it can be manufactured using scalable industrial polymer replication techniques in PS – the material is the same in both cases. Therefore, liqPS effectively closes the gap between “microfluidic prototyping” and “industrial microfluidics” by providing a common material. [ABSTRACT FROM AUTHOR]

The concentrations of magnesium (Mg) and calcium (Ca) in natural aqueous environments are controlled by sorption and dissolution–precipitation reactions. Ca binding in calcareous soils depends on the degree of solution saturation with respect to CaCO3. Mg may be bound in precipitating calcite. Here, we investigated Mg incorporation into calcite via the recrystallization of vaterite, which simulates a very low supersaturation in a wide range of Mg to Ca ratios and pH conditions. Increasing the Mg to Ca ratios (0.2 to 10) decreased the partition coefficient of Mg in calcite from 0.03 to 0.005. An approximate thermodynamic mixing parameter (Guggenheim a0 = 3.3 ± 0.2), that is valid for dilute systems was derived from the experiments at the lowest initial Mg to Ca ratio (i.e., 0.2). At elevated Mg to Ca ratios, aragonite was preferentially formed, indicating kinetic controls on Mg partitioning into Mg-calcite. Scanning electron microscopy (SEM-EDX) analyses indicated that Mg is not incorporated into aragonite. The thermodynamic mixing model suggests that at elevated Mg to Ca ratio (i.e., ≥1) Mg-calcite becomes unstable relative to pure aragonite. Finally, our results suggest that the abiotic incorporation of Mg into calcite is only effective for the removal of Mg from aqueous environments like calcareous soil solution, if the initial Mg to Ca ratio is already low. [ABSTRACT FROM AUTHOR]

Glass is one of the most important high-performance materials used for scientific research, in industry and in society, mainly owing to its unmatched optical transparency, outstanding mechanical, chemical and thermal resistance as well as its thermal and electrical insulating properties. However, glasses and especially high-purity glasses such as fused silica glass are notoriously difficult to shape, requiring high-temperature melting and casting processes for macroscopic objects or hazardous chemicals for microscopic features. These drawbacks have made glasses inaccessible to modern manufacturing technologies such as three-dimensional printing (3D printing). Using a casting nanocomposite, here we create transparent fused silica glass components using stereolithography 3D printers at resolutions of a few tens of micrometres. The process uses a photocurable silica nanocomposite that is 3D printed and converted to high-quality fused silica glass via heat treatment. The printed fused silica glass is non-porous, with the optical transparency of commercial fused silica glass, and has a smooth surface with a roughness of a few nanometres. By doping with metal salts, coloured glasses can be created. This work widens the choice of materials for 3D printing, enabling the creation of arbitrary macro- and microstructures in fused silica glass for many applications in both industry and academia. [ABSTRACT FROM AUTHOR]

Green rust (GR) as sodium sulphate form, NaFe(II)6Fe(III)3(OH)18(SO4)2 · 12H2O, is reacted with an aqueous solution of neptunyl ions (NpO2+) and the resulting Np(IV) solid phase is investigated at a nanometer scale by different transmission electron microscopy (TEM) techniques, including high-resolution TEM (HRTEM), high-angle annular dark-field scanning TEM (HAADF-STEM), energy-dispersive X-ray spectroscopy (EDXS), and electron energy-loss spectroscopy (EELS). The aim of the analyses is to achieve insight into the potential immobilization mechanism for Np(V) in the context of safety assessment of a nuclear-waste repository. The neptunium is found to be immobilized at the edge of the green rust platelets, in a rim composed of nanocrystallites about 2-3.5 nm in size. The EELS results and more particularly the HRTEM findings are consistent with NpO2 crystallizing in a fluorite-type structure. Furthermore, the Np-O4,5 edges recorded by EELS at the Np(IV) phase are presented, expanding the EELS-data set currently available in the literature for Np. [ABSTRACT FROM AUTHOR]