Unveiling the Structural Origins of Dynamic Diversity in Pd-Based Metallic Glasses.

The ß-relaxation is one of the major dynamic behaviors in metallic glasses (MGs) and exhibits diverse features. Despite decades of efforts, the understanding of its structural origin and contribution to the overall dynamics of MG systems is still unclear. Here two palladium-based Pd─Cu─P and Pd─Ni─P MGs are reported with distinct different ß-relaxation behaviors and reveal the structural origins for the difference using the advanced X-ray photon correlation spectroscopy and absorption fine structure techniques together with the first-principles calculations. The pronounced ß-relaxation and fast atomic dynamics in the Pd─Cu─P MG mainly come from the strong mobility of Cu atoms and their locally favored structures. In contrast, the motion of Ni atoms is constrained by P atoms in the Pd─Ni─P MG, leading to the weakened ß-relaxation peak and sluggish dynamics. The correlation of atomic dynamics with microscopic structures provides a way to understand the structural origins of different dynamic behaviors as well as the nature of aging in disordered materials.

Chlorine levels and species in fine and size resolved atmospheric particles by X-ray absorption near-edge structure spectroscopy analysis in Beijing, China.

An understanding of the species of chlorine is crucial in the metropolis-Beijing, which is suffering serious haze pollution with high frequency. Particulate Matters (PMs) with five different sizes were collected in Beijing from July 2009 to March 2016, and characterized non-destructively by X-ray absorption near edge structure spectroscopy. PM<0.2, PM0.2-0.5 and PM>2.5 contributed for the major PMs mass in spring and summer, PM0.5-1.0 and PM1.0-2.5 contributed for the major PMs mass in autumn and winter. The concentrations of the three chlorine species were in the order of inorganic chlorine (Clinorg) > aliphatic chlorine (Clali) > aromatic chlorine (Claro), indicating that Clinorg constituted the primary chlorine fraction and less toxic Clali constituted the primary total organic chlorine (Clali + Claro, abbreviated as Clorg) in the PMs in Beijing. In addition, these three chlorine species exhibited identical seasonal variation in PM2.5: winter > autumn > spring > summer. Wet precipitation is an important factor to result in the lower mass concentrations of these three chlorine species in summer. The temporal variations of both size resolved PM mass concentrations and chlorine species concentrations suggested that the air pollution prevention and control in Beijing has just won initial success.

[X-ray absorption spectroscopic evidence for the formation of Pb(II) inner-sphere adsorption complexes and precipitates at the alkaline soil-water interface].

Adsorption mechanisms of Pb on soil with high CaCO3 content were investigated by combined batch sorption and X-ray absorption fine structure (XAFS). Date from the batch equilibrium studies showed that Pb sorption was nonlinear and was well fitted to Langmiur isotherm. The XAFS data indicated that Pb could be adsorbed via the inner-sphere complex, the precipitation of calcium carbonate containing Pb (PbCaCO3), and outer-sphere Pb sorption complex. The formations of inner-sphere complexes and PbCaCO3 implied strong metal interactions with the surfaces the mechanistic reason for the affinity of Pb for CaCO3 as observed in macroscopic studies. At low metal concentration, 500 mg x L(-1) of initial Pb, radial distance of the first-shell Pb-O (R1) was 0.169 2 nm, however, at 1 000 mg x L(-1) of initial Pb, the R1 was 0.166 8 nm. These revealed that the percentage of inner-sphere complexes increased when the initial Pb was increased from 500 to 1 000 mg x L(-1).

[X-ray absorption fine structure (XAFS) study of the effects of pH on Pb(II) sorption by soil].

Combined batch sorption and in situ X-ray absorption fine structure (XAFS) provide direct assessment of the mechanisms for Pb(II) sorption at the soil-water interface under different pH conditions. The XAFS data indicated that the innersphere Pb sorption complex with ionic character (Pb4 (OH)4(4+)) dominated the Pb surface speciation, and the outer-sphere Pb sorption complex and the precipitation of calcium carbonate containing Pb(PbCaCO3) were also involved in the adsorption samples. Coordination number and radial distance of the first-shell Pb-O decreased from 0.172 7 to 0.166 6 nm and the percentage of inner-sphere complexes increased when the initial pH changed from 6.0 to 8.5, indicating that the mechanism of Pb(II) sorption by the soil was pH-dependent.

Difference of toxicity and accumulation of methylated and inorganic arsenic in arsenic-hyperaccumulating and -hypertolerant plants.

The arsenic (As) hyperaccumulators, Pteris vittata and Pteris cretica and an As-tolerant plant Boehmeria nivea, were selected to compare the toxicity, uptake, and transportation of inorganic arsenate (As(V)) and its methylated counterpart dimethylarsinic acid (DMA). The XANES method was used to elucidate the effect of As species transformation on As toxicity and accumulation characteristics. Significantly higher toxicity and lower accumulation of DMAthan inorganic As(V) was shown in the As hyperaccumulators and the As-tolerant plant. Reduction of As(V) was commonly found in the plants. Arsenic complexation with thiols, which have less mobility in plants and usually occur in As-tolerant plants, was also found in rhizoids of P. cretica. Plants with greater ability to form As-thiolate have lower ability for upward transport of As. Demethylation of DMA occurred in the three plants. The DMA component decreased from the rhizoids to the fronds in both hyperaccumulators, while this tendency is reverse in B. nivea.

Arsenic transformation and volatilization during incineration of the hyperaccumulator Pteris vittata L.

Safe incineration of harvested hyperaccumulators containing high content of heavy metals to avoid secondary environmental pollution is a problem for popularizing phytoremediation technology. The As volatilization behavior and its mechanism during incineration of Pteris vittata, an As-hyperaccumulator, was investigated. Incineration results reveal that 24% of total As accumulated by P. vittata (H-As) containing high As content (1170 mg/kg) is emitted at 800 degrees C, of which 62.5% of the total emitted As is volatilized below 400 degrees C. A study of the extended X-ray absorption fine structure (EXAFS) shows that part of As(III) was identified in the thermal decomposition residue of dried P. vittata (H-As), As2O5 + P. vittata (L-As) containing low As content (14.7 mg/kg), and As2O5 + charcoal (C) at 200 degrees C, suggesting that carbon originating from biomass incineration might catalyze As(V) reduction. This speculation was tested through thermogravimetric experiments, in which either C or P. vittata (L-As) markedly catalyzed the volatilization of pure As2O5 at low temperature. Therefore, the reduction of As(V) to As(III) is responsible for As volatilization during incineration of P. vittata below 400 degrees C. This study provides important insights into As behavior during incineration of As-hyperaccumulators, which is helpful to safely dispose harvested biomass with high As content.

XAFS studies and computational simulation of calixcrowns-caesium complexes in solution.

Caesium L(3)-edge XANES (X-ray absorption near-edge structure) and EXAFS (extended X-ray absorption fine structure) have been evaluated as means of probing the local structure and the interaction of caesium ions with BPC6 {1,3-alternate bis(2-propyloxy)calix[4]arenecrown-6}, BOC6 {1,3-alternate bis(octyloxy)calix[4]arenecrown-6} and BisC6 (1,3-alternate calix[4]arene bis-crown-6) in NPME (o-nitrophenyl methyl ether) or OA (n-octyl alcohol). The XANES results indicate that the molecular symmetry is enhanced as the caesium ions are embedded. The EXAFS spectra demonstrate that the coordination numbers (N) and average distances (R) from the central caesium ion to the O atoms are: for BPC6, N = 7.0, R = 3.22 Angstroms (in NPME), and N = 7.0, R = 3.23 Angstroms (in OA); for BOC6, N = 6.8, R = 3.28 Angstroms (in NPME), and N = 6.9, R = 3.27 Angstroms (in OA); for BisC6, N = 6.9, R = 3.21 Angstroms (in NPME). Density functional theory at the triple-zeta adding polarization basis set level was used to simulate the BPC6, BOC6 and BisC6 coordination with the caesium ions. Data show that the seven-oxygen-configuration average distances from the central caesium ion to the O atoms are R = 3.38 for BPC6, R = 3.40 for BisC6 and R = 3.39 for BOC6.

[EXAFS study on the stripping mechanism in N263/alkaline cyanide gold solution/sulfuric thiourea system].

Quaternary ammonium salt has strong affinity with gold in cyanide solutions, but it is not readily stripped. Stripping with acidic thiourea solutions and air sparging shows promise. There are some reports on the process of thiourea stripping, but little about its mechanism. In this paper, the stripping mechanism of N263/sulphuric thiourea/alkaline cyanide gold solution is studied by EXAFS. According to the experiments, sulphuric acid, thiourea and gold-thiourea complex can be extracted by N263 as a neutral molecule, and the stripping process can be described as following: (1) Sulphuric acid and thiourea are extracted by N263; (2) In organic phase, gold-cyanide complex is converted to gold-thiourea complex, which exists as Au[SC(NH2)2]2HSO4, and CN- forms HCN with acid at the same time; (3) HCN is removed by air sparging, and Au[SC(NH2)2]2HSO4 is distributed between organic phase and liquor phase, most of which transfers to liquor phase and is stripped.