Determination of Cr(III) and Cr(VI) in water by wavelength‐dispersive X‐ray fluorescence spectrometry after preconcentration with an ion‐exchange resin disk

A rapid and simple method using an ion‐exchange resin disk combined with wavelength‐dispersive X‐ray fluorescence (WDXRF) spectrometry was developed for the determination of Cr(III) and Cr(VI) in water. A 100‐ml water sample was first adjusted to pH 3 with nitric acid and then passed through an anion‐exchange resin disk placed on top of a cation‐exchange resin disk at a flow rate of 1 ml min^?1 to separate Cr(III) and Cr(VI). Anionic Cr(VI) was preconcentrated on the upper anion‐exchange resin disk, whereas cationic Cr(III) was preconcentrated on the lower cation‐exchange resin disk. Each ion‐exchange resin disk was dried at 100 °C for 30 min in an electric oven and coated with a commercially available laminate film. The specimens were measured using a WDXRF spectrometer. The calibration curves of Cr(III) and Cr(VI) showed good linearity in the range 1–10 µg. The detection limits corresponding to three times the standard deviation (n = 5) of blank values were 0.17 µg for Cr(III) and 0.16 µg for Cr(VI). If a 1‐l water sample is used, these limits would be 0.17 and 0.16 µg l^?1, respectively. A spike test for 50 µg l^?1 Cr(III) and Cr(VI) in tap water and river water showed quantitative recoveries (94–114%), although this was not observed for mineral drinking water owing to the overlap of V Kβ with Cr Kα. The recovery after overlap correction was satisfactory (115%). Copyright © 2011 John Wiley & Sons, Ltd.     

Sonochemical reduction of Cr(VI) in air in the presence of organic additives: What are the involved mechanistic pathways?

The sonochemical (850 kHz) reduction of Cr(VI) (0.3 mM, pH 2, reactor open to air) was analyzed in the presence of different additives. The effects on Cr(VI) reduction efficiency of added formic acid (FA, 10 mM), citric acid (Cit, 2 mM), ethylenediaminetetraacetic acid (EDTA, 1 mM), methanol (MeOH, 0.1 M), ethanol (EtOH, 0.1 M), 2-propanol (2-PrOH, 0.1 M), tert-butanol (t-BuOH, 0.1 M), phenol (PhOH, 2 mM) and sodium lauryl sulfate (SLS, 1 mM) have been evaluated in comparison with the system in the absence of additives. Complete Cr(VI) reduction was obtained only when using EDTA (at 120 min) and Cit (at 180 min). Cr(III) complexes with these compounds or with their degradation products were detected as final products. For EDTA, Cit, t-BuOH, FA and SLS, the Cr(VI) decay could be adjusted to a zero-order kinetics; in the cases of MeOH, EtOH and 2-PrOH, there was a deviation from the zero-order kinetics. The Cr(VI) conversion increased in the order SLS (very low) < no additive ≅ MeOH ≅ EtOH ≅ 2-PrOH < FA < t-BuOH < PhOH < Cit < EDTA. The role of EDTA and Cit in stabilizing intermediate Cr(V) peroxo compounds and enhancing their direct transformation into different Cr(III) species is considered a major factor in the acceleration of Cr(VI) reduction processes. Mechanistic pathways are proposed.     

Adsorption of Cr(VI) from Aqueous Solutions Onto Raw and Acid-Activated Reşadiye and Hançılı Clays

ABSTRACT

The adsorption of Cr(VI) from aqueous solutions onto raw and acid-activated clays—namely, Re?adiye region clay (R, raw Re?adiye region clay; R-H₂SO₄, acid-activated with H₂SO₄ Re?adiye region clay; R-HCl, acid-activated with HCl Re?adiye region clay) and Hanç?l? region clay (H, raw Hanç?l? region clay; H-H₂SO₄, acid-activated with H₂SO₄ Hanç?l? region clay; H-HCl, acid-activated with HCl Hanç?l? region clay)—was studied in a batch system. For optimization of the Cr(VI) adsorption on raw clays and acid-activated clays, the effect of pH, temperature, initial Cr(VI) concentration, time, and adsorbent dosage were investigated. X-ray diffraction analyses of raw and acid-activated clays were used to determine the effects of acid-activating on the layer structure of the clays. The surface characterizations of clays and modified clays were performed by using FT-IR spectroscopy. The Langmuir and Freundlich adsorption models were employed to describe the equilibrium isotherms, and thus the isotherm constants were determined. The data obtained from our investigations were well described by the Langmuir model. The adsorption capacity of the adsorbents Re?adiye and Hanç?l? clays were found to be 0.0269, 0.0144, and 0.0170 mmol/g for H, H-HCl, and H-H₂SO₄ and 0.0356, 0.0276, and 0.0422 mmol/g for R, R-HCl, and R-H₂SO₄, respectively. The results show that the adsorption was strongly dependent on pH of the medium, initial Cr(VI) concentration and temperature. The removal of Cr(VI) reached saturation in about 120 min, and the adsorption process of Cr(VI) was observed as exothermic. A maximum removal of 73% was noted at 1.0 × 10^?4 M concentration of Cr(VI) in solution for H-HCl. Furthermore the enhancement of removal of Cr(VI) was observed from pH 3 to 4. The results are discussed to highlight the influence of acid activation on Cr(VI) adsorption characteristics of the clays.     

Characterization of water exposed plasma sprayed oxide coating materials using XPS

The surface compositions and oxidation states of non-exposed and water exposed plasma sprayed oxide coatings were studied using X-ray photoelectron spectroscopy (XPS). Coating materials were TiO₂, Al₂O₃ and Cr₂O₃ and their mixtures. Water exposures were performed for free standing coating disks at mild electrolyte (1 mmol NaCl solution) at pH 4, 7 and 9. The exposure time was two weeks.It was observed that pure plasma sprayed TiO₂ material was chemically stable over whole experiment pH range and only slight surface hydroxylation was observed for this material.In case of plasma sprayed Al₂O₃ materials the surface O/Al ratio increased considerably during water exposure especially at exposure pH 7. This was probably result of surface conversion to hydrous form. No surface oxidation state changes were observed for this material.The non-exposed Cr₂O₃ materials contained both Cr(III) and Cr(VI) oxides. The water exposures increased the surface oxygen and Cr(VI) contents at the expense of Cr(III). The most probable reason for that was the dissolution of surface Cr(VI) oxide phase during water exposures and the (re)adsorption of dissolved Cr(VI) species back to the surface.     

In situ synchrotron diffraction studies on the formation kinetics of jarosites

This paper reports the results of time‐resolved synchrotron powder diffraction experiments where jarosites with different K/H₃O, K/Na and Na/H₃O ratios were synthesized in situ at temperatures of 353, 368 and 393 K in order to observe the effect on kinetics and species produced. The Na/H₃O sample formed monoclinic jarosite at all three temperatures, whereas the K/H₃O and K/Na samples formed as rhombohedral jarosites at 353 K, and as mixtures of rhombohedral and monoclinic jarosites at the higher temperatures. The relative amount of the monoclinic phase increased with increase in temperature. Unit‐cell parameter changes with reaction time could be explained by changes in iron stoichiometry (samples become more stoichiometric with time) together with changes in K/H₃O and Na/H₃O ratios. The reaction kinetics have been fitted using a two‐stage Avrami model, with two different Avrami exponents corresponding to initial two‐dimensional growth followed by one‐dimensional diffusion‐controlled growth. Activation energies for the initial growth stage were calculated to be in the range 90–126 kJ mol^?1.     

Magnetic properties of hard magnetic (Fe,Cr)3Sn2 intermetallic compound

By high‐throughput screening Fe–Sn–Cr, (Fe,Cr)₃Sn₂ (Fe_53.5Cr_6.5Sn₄₀) with high potential as new hard magnetic compound is discovered. To produce the compound in large amounts a special procedure is needed. By quantitative microscopy and magnetometry promising intrinsic properties, J_s ～ 0.9 T, K₁ ～ 1.7 MJ/m³, T_C ～ 612 K, are found with K₁ increasing with temperature.

     

In vivo time‐resolved X‐ray fluorescence mapping measurements of Egeria densa immersed in Cr(VI) aqueous solution

In vivo time‐resolved Cr and Ca X‐ray fluorescence (XRF) mapping measurements were performed in a laboratory over a period of 69 days on a living common aquatic plant Egeria densa that was immersed in 5 mM K₂CrO₄ aqueous solution. The time and spatial resolution for each time‐resolved XRF map were ~1.6 days and 1 × 1 mm², respectively. The obtained XRF maps exhibited characteristic localized Cr and Ca areas where the XRF signals were especially strong (‘hot spots’), and this indicated the necessity of preliminary millimeter‐resolution surveying in XRF microscopy. Ca hot spots were detected prior to Cr(VI) immersion and nearly disappeared after immersion in deionized water for 2 weeks and the Cr(VI) solution for 1 week. After these immersions, a Cr hot spot was formed at approximately the same location of the missing Ca hot spot, which suggests that the original Ca‐accumulated regions were substituted for the isolation of Cr species when they were introduced. The sizes and intensity distributions of the Cr hot spots were sensitive to the Cr(VI) exposure approximately 1 week prior to each XRF measurement. This sensitivity suggests potential applications of E. densa as a Cr(VI) biomonitor in aquatic environments. Copyright © 2014 John Wiley & Sons, Ltd.     

Solid state reduction of chromium (VI) pollution for Al2O3–Cr metal ceramics application

Reduction of chromium (VI) from Na₂CrO₄ through aluminothermic reaction and fabrication of metal-ceramic materials from the reduction products have been investigated in this study. Na₂CrO₄ could be successfully reduced into micrometer-sized Cr particles in a flowing Ar atmosphere in presence of Al powder. The conversion ratio of Na₂CrO₄ to metallic Cr attained 96.16% efficiency. Al₂O₃–Cr metal-ceramic with different Cr content (5 wt%, 10 wt%, 15 wt%, 20 wt%) were further prepared from the reduction product Al₂O₃–Cr composite powder, and aluminum oxide nanopowder via pressure-less sintering. The phase composition, microstructure and mechanical properties of metal-ceramic composites were characterized to ensure the potential of the Al₂O₃–Cr composite powder to form ceramic materials. The highest relative density and bending strength can reach 93.4% and 205 MP, respectively. The results indicated that aluminothermic reduction of chromium (VI) for metal-ceramics application is a potential approach to remove chromium (VI) pollutant from the environment.     

The isothermal section of the Tb–Co–Cr ternary system at 873 K

The isothermal section of the phase diagram of the Tb–Co–Cr ternary system at 873?K was investigated by means of X-ray diffraction, metallography, and scanning electron microscopy equipped with energy dispersive X-ray spectroscopy. Ternary phases and their lattice parameters as a function of composition of solid solution were systematically studied. The existence of one ternary phase reported previously was confirmed. The ternary compound Tb(Co,?Cr)₁₂ crystallizes with ThMn₁₂-type structure, space group I4/mmm. The linear homogeneity range along the line of 7.69 at.% Tb in TbCo_{12? x} Cr _x was found to be about x?=?3.6–5.7, i.e., 27.7–43.8 at.% Cr. The lattice parameters are a?=?0.8326–0.8352?nm and c?=?0.4709–0.4740?nm. The maximum solid solubilities of Cr in Tb₂Co₁₇, TbCo₃, and TbCo₂ are about 20.0, 8.2, and 7.9 at.%, respectively.     

Surface characterisation of ethylene-propylene-diene rubber upon exposure to aqueous acidic solution

Two types of pure ethylene propylene diene rubbers were exposed to two different acids for varying period of time. Surface characterisation was carried out using X-ray photoelectron spectroscopy (XPS). Two EPDM rubbers selected for this study were comparable in co-monomer compositions but significantly different with respect to molar mass and the presence of long chain branching. Both rubbers contained 5-ethylidene-2-norbornene (ENB) as diene. Solution cast films of pure EPDM samples were exposed in two different acidic solutions, viz. chromosulphuric (Cr (VI)/H₂SO₄) and sulphuric acid (H₂SO₄) (20%, v/v) at ambient temperature from 1 to 12 weeks. XPS analysis indicated that several oxygenated species were formed on the surface of both rubbers after exposure. It was postulated from the XPS analyses that both aqueous acidic solutions attacked the olefinic double bonds (CC) of ENB. Furthermore, 20% Cr (VI)/H₂SO₄ also attacked the allylic carbon-hydrogen (CH) bonds of ENB resulting in more oxygenated species on the surface compared to 20% H₂SO₄ under identical conditions. Cr (VI) in the 20% Cr (VI)/H₂SO₄ was found to play an important role in alteration of surface chemistry. Studies using a model system consisting of EPDM mixed with Cr (VI) and Cr (III) salts revealed that the change of oxidation state from Cr (VI) to Cr (III) as a consequence of direct involvement of Cr (VI) in the chemical alteration of EPDM surfaces. Interestingly, the presence of long chain branching and molar mass did not significantly influence the chemical processes owing to the acid treatment.     

The specific heat of potassium holmium double tungstate

The results of measurements of thermal properties (specific heat) of potassium holmium double tungstate KHo(WO₄)₂ as a function of temperature (from 0.5 to 300?K) and magnetic field (up to 2?T) are presented. The total specific heat without the phonon and Schottky contributions is found to have the anomaly with maximum at T _SPT?～?5?K. This anomaly is likely related with the structural phase transition (SPT) caused by the cooperative Jahn–Teller effect. The increase of specific heat at very low temperatures and its shift towards high temperatures with increasing magnetic field are observed. The origin of this behaviour can be connected with possible magnetic phase transition induced by magnetic field.     

Metal–Organic Framework Supported Palladium Nanoparticles: Applications and Mechanisms

Heterogeneous palladium (Pd)‐based catalysts are extensively applied to improve the catalytic performance and/or expand the reaction scope in many catalytic processes, involving the cross‐coupling, hydrogenation, reduction, and oxidation reactions. Among them, metal–organic framework (MOF)‐supported Pd nanoparticles (Pd NPs) are becoming the most popular one for their excellent catalytic performance and reusable property. To motivate the development of this technology, the applications of MOF‐supported Pd NPs (Pd NPs/MOFs) in heterogeneous catalysis are critically summarized herein, including the hydrogenation reduction of nitro‐ and polyunsaturated compounds, synthesis of carbon–carbon (C? C) bonds compounds, chromium (Cr(VI)) reduction, dehalogenation, alcohol oxidation, CO₂ conversion, and CO oxidation. The influences of base, solvents, electron character of substitutes, and type of halogen on the catalytic performance are comprehensively discussed. Finally, the application prospects of Pd NPs/MOFs and existing shortcomings in the catalytic field are proposed.     

Dielectric properties of ferroelectric diisopropylammonium iodide

Temperature dependences of dielectric constant, amplitude of the third harmonic and heat capacity for the organic ferroelectric of diisopropylammonium iodide (C₆H₁₆NI) have been investigated. The measurements were carried out through heating and cooling cycles in the range of 300–400?K. It was found that upon the first heating, only one phase transition occurred without the presence of the ferroelectric phase. For samples preheated over 420?K, two phase transitions at 363 and 378?K appeared in the heating process, and the ferroelectric state was also observed between them. Upon cooling, the ferroelectric phase was detected in the range of lower 361?K and persisted up to room temperature.     

Magnetic characterization of Bi2FeMnO6 film grown on (100) SrTiO3 substrate

Single phase Bi₂FeMnO₆ films on (100) SrTiO₃ substrate were fabricated using a pulsed laser deposition method through optimization of the preparation conditions. The magnetic moment is 0.30μ_B at 5 K in the magnetic field of 1 T, indicating that B site cations of Fe and Mn are disordered in the sample. The zero‐field‐cooling (ZFC) and field‐cooling (FC) magnetization curves measured from 2 K to 400 K coincide at 360 K. This is consistent with the observation that hysteresis disappears at 360 K, revealing the antiferromagnetic transition at this temperature. A spin‐glass‐like behaviour was observed at low temperature (～100 K) with a cusp of 25 K. Mn shows multiple valence states in the film. It is possibly because Mn²⁺ and Mn⁴⁺ could decrease the Jahn–Teller effect from Mn³⁺ in the film which results in less lattice distortion. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

我国几种地带性土壤中磷素形态的研究

探明土壤磷素的存在形态,有助于揭示其在环境中的累积、迁移和转化过程及生物有效性。目前,在大尺度样带上开展土壤磷素形态空间变异规律的研究较少。本研究中,沿纬度方向采集了我国东部不同气候带分布的7种地带性林地土壤（包括寒温带的棕色针叶林土、中温带的暗棕壤、暖温带的棕壤、北亚热带的黄棕壤、中亚热带的黄壤、南亚热带的赤红壤和热带的砖红壤）,将化学浸提法与溶液磷-31核磁共振（31P NMR）波谱法相结合,分析了土壤中磷素形态以及与其他土壤性质之间的关系,以期为阐明土壤磷素形态的空间变异性及其驱动因素提供基础资料。结果表明：供试土壤中,全磷、有效磷、无机磷和有机磷的含量范围分别为179.8～825.2,2.41～15.3,92.6～351.2和14.7～474.4 mg·kg-1,其中活性、中等活性、中等稳定性和高稳定性有机磷组分的含量范围分别为1.38～30.9,8.63～213.7,3.01～32.2和1.73～199.2 mg·kg-1。根据溶液31P NMR波谱,鉴定出供试土壤中含有无机形态的磷素即正磷酸盐和焦磷酸盐,同时也鉴定出了磷酸单酯、磷酸二酯和膦酸盐等有机形态磷素的存在,其中磷酸单酯中又鉴定出了新-肌醇六磷酸、D-手性-肌醇六磷酸、RNA单核苷酸、α-磷酸甘油、肌-肌醇六磷酸、β-磷酸甘油和鲨-肌醇六磷酸,磷酸二酯中又鉴定出了DNA的存在;所有土壤中均未检测出多聚磷酸盐的存在,除棕色针叶林土和暗棕壤外的其他土壤中未检测出膦酸盐的存在,而赤红壤中未检测出DNA的存在;无机形态的磷素以正磷酸盐为主,而有机形态的磷素则以磷酸单酯为主。总体来看,无论化学浸提法还是溶液31P NMR波谱法,从寒温带的棕色针叶林土到热带的砖红壤,全磷、有效磷、无机磷、有机磷及其组分的含量均呈现下降趋势。溶液31P NMR波谱与化学浸提法鉴定的磷素形态之间存在相关关系,其中正磷酸盐与活性有机磷的关系最为密切,磷酸单酯和膦酸盐与中等活性有机磷的关系最为密切,而焦磷酸盐和磷酸二酯与中等稳定性有机磷的关系最为密切。与化学浸提法相比,溶液31P NMR波谱法能从详细的分子水平上揭示土壤磷素形态的空间变异规律。     

Spin‐dependent‐magnetoresistance control by regulation of heat treatment temperature for magnetite nano‐particle sinter

The control of spin‐dependent‐magnetoresistance by regulation of the heat treatment (HT) temperature for magnetite (Fe₃O₃) nano‐particle sinter (MNPS) has been studied. The average nano‐particle size in the MNPS is 30nm and the HT was carried out from 400°C to 800°C. The HT of the MNPS varies the coupling form between adjacent magnetite nano‐particles and the crystallinity of that. The measurements on electrical resistance (ER), magnetoresistance (MR) and magnetization were performed between 4K and 300K. The behavior of the ER and MR considerably changes at the HT temperature of ～600°C. Below ～600°C the ER indicates the variable‐range‐hopping conduction behavior and the MR shows the large intensity in a wide temperature region. Above ～600°C the ER shows the indication of the Verwey transition near 110K like a bulk single crystal and the MR designates the smaller intensity. We consider that below ～600°C the ER and MR are dominated by the grain‐boundary conduction and above ～600°C those are determined by the inter‐grain conduction. The magnetic field application to the grain‐boundary region is inferred to cause the large enhancement of the MR.     

Magnetic and optical properties of Zn1– x Fe x O ( x = 0.05 and 0.10) diluted magnetic semiconducting nanoparticles

We have investigated the magnetic and optical properties of chemically low temperature-synthesized Zn_{1– x} Fe _x O (x = 0.05 and 0.10) diluted magnetic semiconducting nanoparticles (～7 nm). Observed magnetic behaviour of x = 0.05 samples showed that the net magnetic interaction was antiferromagnetic-like, a feature established by Curie–Weiss fit, concave Arrott–Belov–Kouvel (ABK) plots with the absence of spontaneous magnetization even at 5 K and stretched exponential-type time-dependent magnetization behaviour. Optimization of the Fe(x) dopant concentration in Zn_{1– x} Fe _x O gave the most favourable room-temperature ferromagnetism for x = 0.10, as supported by finite coercive field (～94.4 Oe) and remanent magnetization (0.011 µ_B/Fe ion) from strong hysteretic magnetization vs. magnetic-field curves at room temperature. The Curie temperature of the x = 0.10 sample was estimated at ～388 K. The existence of a room-temperature ferromagnetic phase was further established by the convex nature of the ABK plots with finite spontaneous magnetization. The observed magnetic behaviour for different x values is best explained by a magnetic polaron model.     

Characterization of Cr‐doped Sb2Te3 films and their application to phase‐change memory

Phase‐change memory (PCM) is regarded as one of the most promising candidates for the next‐generation nonvolatile memory. Its storage medium, phase‐change material, has attracted continuous exploration. Along the traditional GeTe–Sb₂Te₃ tie line, the binary compound Sb₂Te₃ is a high‐speed phase‐change material matrix. However, the low crystallization temperature prevents its practical application in PCM. Here, Cr is doped into Sb₂Te₃, called Cr–Sb₂Te₃ (CST), to improve the thermal stability. We find that, with increase of the Cr concentration, grains are obviously refined. However, all the CST films exhibit a single hexagonal phase as Sb₂Te₃ without phase separation. Also, the Cr helps to inhibit oxidation of Sb atoms. For the selected film CST_10.5, the resistance ratio between amorphous and crystalline states is more than two orders of magnitude; the temperature for 10‐year data retention is 120.8 °C, which indicates better thermal stability than GST and pure Sb₂Te₃. PCM cells based on CST_10.5 present small threshold current/voltage (4 μA/0.67 V). In addition, the cell can be operated by a low SET/RESET voltage pulse (1.1 V/2.4 V) with 50 ns width. Thus, Cr–Sb₂Te₃ with suitable composition is a promising novel phase‐change material used for PCM with high speed and good thermal stability performances. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Chromium isotopes tracking the resurgence of hexavalent chromium contamination in a past-contaminated area in the Friuli Venezia Giulia Region,northern Italy

The origin of a resurgent hexavalent chromium contamination in groundwater from a phreatic aquifer in the Friuli Venezia Giulia Region plain was investigated by chromium isotopic systematics. The area underwent a severe Cr(VI) contamination by industrial effluents in 1997, when Cr(VI) concentration in groundwater reached 4500?µg/L. In subsequent years the contamination naturally attenuated, totally disappearing in 2003. A renewal of water contamination was observed in 2008, Cr(VI) reaching 1560?µg/L. The δ⁵³Cr value in groundwater and extracts from sediments was measured in 2009–2011, and it ranges between ?3.21 and +0.21‰ and between ?4.71 and +1.26‰, respectively. Due to the lack of geogenic Cr-sources, these data are interpreted as evidence of the subsequent oxidation through Mn-oxides of the Cr(III) hosted in the aquifer and originated by the reduction of the original industrial chromates. Cr(III) is characterized by negative δ⁵³Cr, starting from the δ⁵³Cr value around zero of Cr(VI) in industrial effluents. Oxidation liberates soluble Cr(VI) which is transported by groundwater and permeated soils. The complex Cr-isotopic vs. concentration distribution reflects both the new Cr(VI) reduction and dilution processes in the aquifer system. From an environmental point of view, the data raise concerns regarding the potential impact of past Cr(VI)-contamination.     

Giant magnetoresistance of MexMn1−x S (Me=Fe, Cr) sulfides

The structural, electrical, and magnetic properties, as well as the magnetoresistance of polycrystalline Me_xMn_1?x S (Me=Fe and Cr) sulfides were investigated in longitudinal magnetic fields of up to 50 kOe over the temperature range 4.2–300 K. The ferromagnetic compound Fe_xMn_1?x S (x=0.29) exhibits the giant magnetoresistance (GMR) effect with magnitude δ_H=?450% in a field of 30 kOe at 50 K. Antiferromagnetic Cr_xMn_1?x S (x=0.5) sulfide undergoes a transition to the GMR state δ_H～?25% in a field of 30 kOe at 4.2 K) in the region of antiferromagnet-ferromagnet transition (T _c ～66 K). A mechanism of the GMR in these compounds is discussed.