Interference effects in the extraction of trace metals from estuarine waters

We have found that a commonly used complexation and solvent extraction technique (using mixed dithiocarbamates/Freon/HNO3) does not always extract Cd, Co, Cu and Ni from estuarine samples with the same efficiency as from Milli-Q water. For samples collected from the Derwent Estuary (Australia), the reduced extraction efficiency only occurred for unfiltered samples, but low extraction efficiencies were also observed for a (filtered) riverine certified reference material (SLRS-3) suggesting that the effect may be widespread. We have not been able to identify the reason for the low extraction efficiency and, although it is strongly correlated with the presence of high concentrations of suspended solids, dissolved organic matter and particulate iron, we have no experimental evidence to directly link any of these parameters to the effect. It is possible that similar effects may occur in other techniques which rely on a preconcentration step prior to analysis and that some literature values of heavy metals in estuarine waters may be low. We propose a modification of the standard complexation/solvent extraction method which overcomes these difficulties without adding significantly to the time taken for analyses.

Anodic Stripping Voltammetry at Bismuth-Coated and Uncoated Carbon Microdisk Electrodes:Application to Trace Metals Analysis in Flood Samples

This article reports on the performance of a bismuth-coated carbon microdisk electrode (BiFμE) for the determination of trace heavy metals by anodic stripping voltammetry (ASV). The BiFμE was prepared by electrodeposition of a metallic bismuth film onto the microdisk, by applying an in-situ electroplating procedure. To test the performance of the BiFμE, ASV measurements were performed on synthetic solutions containing Cd2+, Pb2+, and Cu2+ as target ions. The results indicated that cadmium and lead gave well-defined ASV peaks with no interference, and their quantitative determination could be carried out straightforwardly. In particular, linear calibration curves over the range 5.0 x 10-8-1.0 x 10-6M for both ions, and detection limits of 7.8 and 2.9 nM, for cadmium and lead, respectively, after applying a 60 sec preconcentration step, were obtained. The reproducibility was also satisfactory, the relative standard deviation (RSD) being within 2.5% for both ions. Copper, instead, gave an ASV response that. in most experimental conditions, overlapped with that of bismuth. This circumstance made the determination of copper at the BiFμE difficult. Since the latter element could be detected reliably at the uncoated carbon microdisk electrode (CμE), both BiFμE and CμE were employed, respectively, for the determination of lead and copper ions in drinking water, wine, and tomato sauce.

Sorption of metals on humic acid

The sorption on humic acid (HA) of metals from an aqueous solution containing Hg(II). Fe(III), Pb, Cu, Al, Ni, Cr(III), Cd, Zn, Co and Mn, was investigated with special emphasis on effects of pH, metal concentration and HA concentration. The sorption efficiency tended to increase with rise in pH, decrease in metal concentration and increase in HA concentration of the equilibrating solution. At pH 2.4. the order of sorption was: Hg Fe Pb Cu=Al Ni Cr=Zn=Cd=Co=Mn. At pH 3.7. the order was: Hg and Fe were always most readily removed, while Co and Mn were sorbed least readily. There were indications of competition for active sites (CO2H and phenolic OH groups) on the HA between the different metals. We were unable to find correlations between the affinities of the eleven metals to sorb on HA and their atomic weights, atomic numbers, valencies, and crystal and hydrated ionic radii. The sorption of the eleven metals on the HA could be described by the equation Full-size image (1K), where Y = % metal removed by HA; X = mgHA; and A and B are empirical constants

Heavy Metals in Soil and Crops of an Intensively Farmed Area: A Case Study in Yucheng City, Shandong Province, China

lThe study was supported by the Knowledge Innovation Foundation of the institute of Geographical Sciences and Natural Resource, Chinese Academy of Sciences (Grant No. 200906002) and Key Directional Project of Knowledge Innovation of Chinese Academy of Sciences (Grant No. KSCX2-YW-N-46-01). The authors would like to thank to Luke Driskell for his kind help and hard work on English language polishing of the article.

Effects of soil type on leaching and runoff transport of rare earth elements and phosphorous in laboratory experiments

Through leaching experiments and simulated rainfall experiments, characteristics of vertical leaching of exogenous rare earth elements (REEs) and phosphorus (P) and their losses with surface runoff during simulated rainfall in different types of soils (terra nera soil, cinnamon soil, red soil, loess soil, and purple soil) were investigated. Results of the leaching experiments showed that vertical transports of REEs and P were relatively low, with transport depths less than 6 cm. The vertical leaching rates of REEs and P in the different soils followed the order of purple soil > terra nera soil > red soil > cinnamon soil > loess soil. Results of the simulated rainfall experiments (83 mm h(-1)) revealed that more than 92% of REEs and P transported with soil particles in runoff. The loss rates of REEs and P in surface runoff in the different soil types were in the order of loess soil > terra nera soil > cinnamon soil > red soil > purple soil. The total amounts of losses of REEs and P in runoff were significantly correlated.

Interactions Between Exogenous Rare Earth Elements and Phosphorus Leaching in Packed Soil Columns

Through leaching experiments and simulated rainfall experiments, characteristics of vertical leaching of exogenous rare earth elements (REEs) and phosphorus (P) and their losses with surface runoff during simulated rainfall in different types of soils (terra nera soil, cinnamon soil, red soil, loess soil, and purple soil) were investigated. Results of the leaching experiments showed that vertical transports of REEs and P were relatively low, with transport depths less than 6 cm. The vertical leaching rates of REEs and P in the different soils followed the order of purple soil > terra nera soil > red soil > cinnamon soil > loess soil. Results of the simulated rainfall experiments (83 mm h(-1)) revealed that more than 92% of REEs and P transported with soil particles in runoff. The loss rates of REEs and P in surface runoff in the different soil types were in the order of loess soil > terra nera soil > cinnamon soil > red soil > purple soil. The total amounts of losses of REEs and P in runoff were significantly correlated.

Effects of rare earth on the structure and properties of Mg–6Zn–5Al–4Gd–1RE (RE = Ce or Y) alloys

The microstructures and mechanical properties of Mg-6Zn-5Al-4Gd-1RE (RE = Ce or Y) alloys were investigated. The addition of Ce or Y obviously refines the grain size for the Mg-6Zn-5Al-4Gd-based alloy, while the Y element has a better refining effect. The Ce and Y show different grain-refining mechanisms: Ce addition mostly promotes the growth of secondary dendrite, while Y addition mainly increases the heterogeneous nucleation sites.

Synthesis, Reactivity, and Characterization of Sodium and Rare-Earth Metal Complexes Bearing a Dianionic N-Aryloxo-Functionalized -Ketoiminate Ligand

The synthesis and reactivity of a series of sodium and rare-earth metal complexes stabilized by a dianionic N-aryloxo-functionalized beta-ketoiminate ligand were presented. The reaction of acetylacetone with 1 equiv of 2-amino-4-methylphenol in absolute ethanol gave the compound 4-(2-hydroxy-5-methylphenyl)imino-2-pentanone (LH2, 1) in high yield.

Rare-earth-metal mixed hydride/aryloxide complexes bearing mono(cyclopentadienyl) ligands. Synthesis, CO2 fixation, and catalysis on copolymerization of CO2 with cyclohexene oxide

Hydrogenolysis of mono(cyclopentadienyl)-ligated rare-earth-metal bis(alkyl) complexes Cp'Ln-(CH2SiMe3)2(THF) (Ln = Y (1a), Dy (1b), Lu (1c); Cp' = C5Me4SiMe3) with PhSiH3 afforded the mixed hydride/alkyl complexes [Cp'Ln(mu-H)(CH2SiMe3)(THF)](2) (Ln = Y (2a), Dy (2b), Lu (2c)). The overall structure of complexes 2a-c is a C-2-symmetric dimer containing a planar symmetric Ln(2)H(2) core at the center of the molecule. Deprotonation of ArOH (Ar = C6H2-Bu-t(2)-2,6-Me-4) by the metal alkyl group of 2a-c led to formation of the mixed hydride/aryloxide derivatives [Cp'Ln(mu-H)(OAr)](2) (Ln = Y (3a), Dy (3b), Lu (3c)), which adopt the dimeric structure through hydride bridges with trans-accommodated terminal aryloxide groups.

Properties of poly(sodium 4-styrenesulfonate)-ionic liquid composite film and its application in the determination of trace metals combined with bismuth film electrode

A new kind of bismuth film modified electrode to sensitively detect trace metal ions based on incorporating highly conductive ionic liquids 1-butyl-3-methyl-imidazolium hexafluorophosphate (BMIMPF6) in solid matrices at glassy carbon (GC) was investigated. Poly(sodium 4-styrenesulfonate) (PSS), silica, and Nafion were selected as the solid matrices. The electrochemical properties of the mixed films modified GC were evaluated. The electron transfer rate of Fe(CN)(6)(4-)/Fe(CN)(6)(3-) can be effectively improved at the PSS-BMIMPF6 modified GC.

Investigation of thermal expansion and compressibility of rare-earth orthovanadates using a dielectric chemical bond method

The chemical bond properties, lattice energies, linear expansion coefficients, and mechanical properties of ReVO4 (Re = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, Y) are investigated systematically by the dielectric chemical bond theory. The calculated results show that the covalencies of Re-O bonds are increasing slightly from La to Lu and that the covalencies of V-O bonds in crystals are decreasing slightly from La to Lu. The linear expansion coefficients decrease progressively from LaVO4 to LuVO4; on the contrary, the bulk moduli increase progressively. Our calculated results are in good agreement with some experimental values for linear expansion coefficients and bulk moduli.

Uniform Colloidal Alkaline Earth Metal Fluoride Nanocrystals: Nonhydrolytic Synthesis and Luminescence Properties

In this paper, we present a facile and general synthetic route to high-quality alkaline earth metal fluoride (AEF(2), AE = Ca, Sr, Ba) nanocrystals and CaF2:Tb3+ nanocrystals based on the thermal decomposition of corresponding trifluoroacetate precursors in hot oleylamine. X-ray diffraction, transmission electron microscopy, thermogravimetric and differential thermal analysis, Fourier transform infrared spectra, photoluminescence spectra, and kinetic decays were employed to characterize the samples. The use of single-source precursors plays an important role in the formation of high-quality AEF(2) nanocrystals, and the formation process is demonstrated in detail.

Alternating Copolymerization of Cyclohexene Oxide and Carbon Dioxide Catalyzed by Noncyclopentadienyl Rare-Earth Metal Bis(alkyl) Complexes

The syntheses of several dialkyl complexes based on rare-earth metal were described. Three beta-diimine compounds with varying N-aryl substituents (HL1 = (2-CH3O(C6H4))N=C(CH3)CH=C(CH3)NH(2-CH3O(C6H4)), HL2 = (2,4,6-(CH3)(3) (C6H2))N=C(CH3)CH=C(CH3)NH(2,4,6-(CH3)(3)(C6H2)), HL3 = PhN=C(CH3)CH(CH3) NHPh) were treated with Ln(CH2SiMe3)(3)(THF)(2) to give dialkyl complexes L(1)Ln (CH2SiMe3)(2) (Ln = Y (1a), Lu (1b), Sc (1c)), L(2)Ln(CH2SiMe3)(2)(THF) (Ln = Y (2a), Lu (2b)), and (LLu)-Lu-3(CH2SiMe3)(2)(THF) (3). All these complexes were applied to the copolymerization of cyclohexene oxide (CHO) and carbon dioxide as single-component catalysts.

Thiophene-NPN Ligand Supported Rare-Earth Metal Bis(alkyl) Complexes. Synthesis and Catalysis toward Highly trans-1,4 Selective Polymerization of Butadiene

A series of new rare-earth metal bis(alkyl) complexes [L(1-3)Ln(CH2SiMe3)(2)(THF)(n)] (L-1 = MeC4H2SCH2NC6H4(Ph)(2)P=NC6H2Me3-2,4,6: Ln = Sc, n = 1 (1a); Ln = Lu, n = 1 (1b); L-2 = MeC4H2SCH2NC6H4(Ph)(2)P=NC6H3Et2-2,6: Ln = Sc, n = 1 (2a); Ln = Lu, n = 1 (2b); Ln = Y, n = 1 (2c); L-3 = MeC4H2SCH2NC6H4(Ph)(2)P=(NC6H3Pr2)-Pr-i-2,6: Ln = Sc, n = 0 (3a)) and (LSc)-Sc-4(CH2SiMe3)(2()THF) (4a) (L-4 = C6H5CH2NC6H4(Ph)(2)P=NC6H3Et2-2,6) have been prepared by reaction of rare-earth metal tris(alkyl)s with the corresponding HL1-4 ligands via alkane elimination.