Heavy metal concentrations in soils from a remote oceanic island, Fernando de Noronha, Brazil

This paper examines the role of parent rock, pedogenetic processes and airborne pollution in heavy metal accumulation in soils from a remote oceanic island, Fernando de Noronha, Brazil. We studied five soil profiles developed from different volcanic rocks. Mineralogical composition and total concentrations of major and trace elements were determined in 43 samples. The obtained concentrations range for heavy metals were: Co: 26-261 ppm; Cu: 35-97 ppm; Cr: 350-1446 ppm; Ni: 114-691 ppm; Zn: 101-374 ppm; Hg: 2-150 ppb. The composition of soils is strongly affected by the geochemical character of the parent rock. Pedogenesis appears to be responsible for the accumulation of Zn, Co, and, to a lesser extent, of Ni and Cu, in the upper, Mn- and organic carbon-enriched horizons of the soil profiles. Pedogenic influence may also explain the relationship observed between Cr and the Fe. Hg is likely to have been added to the soil profile by long-range atmospheric transport. Its accumulation in the topsoil was further favoured by the formation of stable complexes with organic matter. Clay minerals do not appear to play an important role in the fixation of heavy metals.

Preparação de membranas de acetato de celulose organomodificadas para adsorção dos íons Cu(II), Cd(II), Mn(II) e Ni(II)

Cellulose acetate polymeric membranes had been prepared by a procedure of two steps, combining the method of phase inversion and the technique of hydrolysis-deposition. The first step was the preparation of the membrane, and together was organomodified with tetraethylortosilicate and 3-aminopropyltrietoxysilane. Parameters that exert influence in the complexation of the metallic ion, as pH, time of complexation, metal concentration, had been studied in laboratory using tests of metal removal. The membranes had presented resistance mechanics and reactivity to cations, being able to be an alternative for the removal, daily pay-concentration or in the study of the lability of metals complexed.

Spectroscopic characterization of schiff base-copper complexes immobilized in smectite clays

Herein, the immobilization of some Schiff base-copper(II) complexes in smectite clays is described as a strategy for the heterogenization of homogeneous catalysts. The obtained materials were characterized by spectroscopic techniques, mostly UV/Vis, EPR, XANES and luminescence spectroscopy. SWy-2 and synthetic Laponite clays were used for the immobilization of two different complexes that have previously shown catalytic activity in the dismutation of superoxide radicals, and disproportionation of hydrogen peroxide. The obtained results indicated the occurrence of an intriguing intramolecular redox process involving copper and the imine ligand at the surface of the clays. These studies are supported by computational calculations.

Oxidative DNA damage induced by S(IV) in the presence of Cu(II) and Cu(I) complexes

The DNA damage induced by S(IV) in the presence of some Cu(II) complexes in air saturated solution was investigated. The addition of S(IV) to an air saturated solution containing CuII GGA (GGA = glycylglycyl-L-alanine), CuII G3 (G3 = triglycine) or CuII G4 (G4 = tetraglycine) and Ni(II) traces, causes rapid formation of the respective Cu(III) complex, with simultaneous O2 uptake and S(IV) oxidation. SO3•- and HO• were detected by EPR-spin trapping experiments. The DNA strand breaks were attributed to the oxysulfur radicals formed. In the reduction of Cu(II)/BCA (BCA = 4,4' dicarboxy-2-2'-biquinoline) by S(IV), with CuI BCA complex formation, there is the possible formation of carbon centered radical of BCA or peroxyl radical (ROO•) capable of oxidizing DNA bases. The intensity of DNA damage in the presence of these Cu(II) complexes and S(IV) (10-300 µmol L-1) followed the order: CuII BCA ∼ CuII G4 ∼ Cu(II) (added as Cu(NO3)2) > CuII G3 ∼ CuII GGA. Specifically for CuII BCA the damage occurred even at lower S(IV) concentration (0.1 µmol L-1). For the Cu(II) complexes with glycylglycylhistidine, glycylhistidylglycine, glycylhistidyllysine and glycylglycyltyrosylarginine the Cu(III) formation and the DNA damage was not observed.

Utilização de pelos de animais silvestres para monitoramento ambiental de Cd, Cr, Cu, Fe, Mn, Pb e Zn

This study investigates the use of wild animal hair of C. brachyurus, C. thous and L. pardalis as biomonitors of trace metal at Parque Nacional das Emas, Brazil. Results reveal a strong correlation between Cd and Pb as well as Cu and Zn, which suggests a single source of emission. Most metals showed a lower or equal concentration than those obtained in previous studies. The research shows that monitoring may be performed only with Zn, Pb, Cd, and Cr because of statistical similarity and of a non-natural occurrence of large amounts of the material under analysis.

Electronic properties and hyperfine fields of nickel-related complexes in diamond

We carried out a first-principles investigation on the microscopic properties of nickel-related defect centers in diamond. Several configurations, involving substitutional and interstitial nickel impurities, have been considered either in isolated configurations or forming complexes with other defects, such as vacancies and boron and nitrogen dopants. The results, in terms of spin, symmetry, and hyperfine fields, were compared with the available experimental data on electrically active centers in synthetic diamond. Several microscopic models, previously proposed to explain those data, have been confirmed by this investigation, while some models could be discarded. We also provided insights into the microscopic structure of several of those centers.

Mn, Cu, and Zn abundances in barium stars and their correlations with neutron capture elements

Barium stars are optimal sites for studying the correlations between the neutron-capture elements and other species that may be depleted or enhanced, because they act as neutron seeds or poisons during the operation of the s-process. These data are necessary to help constrain the modeling of the neutron-capture paths and explain the s-process abundance curve of the solar system. Chemical abundances for a large number of barium stars with different degrees of s-process excesses, masses, metallicities, and evolutionary states are a crucial step towards this goal. We present abundances of Mn, Cu, Zn, and various light and heavy elements for a sample of barium and normal giant stars, and present correlations between abundances contributed to different degrees by the weak-s, mains, and r-processes of neutron capture, between Fe-peak elements and heavy elements. Data from the literature are also considered in order to better study the abundance pattern of peculiar stars. The stellar spectra were observed with FEROS/ESO. The stellar atmospheric parameters of the eight barium giant stars and six normal giants that we analyzed lie in the range 4300 < T(eff)/K < 5300, -0.7 < [Fe/H] <= 0.12 and 1.5 <= log g < 2.9. Carbon and nitrogen abundances were derived by spectral synthesis of the molecular bands of C(2), CH, and CN. For all other elements we used the atomic lines to perform the spectral synthesis. A very large scatter was found mainly for the Mn abundances when data from the literature were considered. We found that [Zn/Fe] correlates well with the heavy element excesses, its abundance clearly increasing as the heavy element excesses increase, a trend not shown by the [Cu/Fe] and [Mn/Fe] ratios. Also, the ratios involving Mn, Cu, and Zn and heavy elements usually show an increasing trend toward higher metallicities. Our results suggest that a larger fraction of the Zn synthesis than of Cu is owed to massive stars, and that the contribution of the main-s process to the synthesis of both elements is small. We also conclude that Mn is mostly synthesized by SN Ia, and that a non-negligible fraction of the synthesis of Mn, Cu, and Zn is owed to the weak s-process.

Mn dimers on graphene nanoribbons: An ab initio study

We show, using ab initio density functional theory calculations, that Mn dimers adsorbed on graphene nanoribbons (Mn(2)/GNRs) present a magnetic bistability, as does the isolated Mn dimer. Our total energy results indicate that Mn dimers lying along the edge sites of zigzag GNRs represent the most likely configuration. We find that similar to the isolated Mn(2) molecule, the antiferromagnetic coupling represents the ground state for Mn(2)/GNR, and the spin density configuration of the GNR does not play an important role on the net magnetic moment of Mn(2), which makes GNRs an ideal substrate for adsorption of these molecules. The ground state and the excited state configuration of the Mn dimer, viz., low-spin (LS) and high-spin (HS), are maintained in the face of changes in the spin density configuration of the substrate. Here we find that the Mn(2)/GNR systems exhibit a LS <-> HS binary behavior, which can be considered as a useful property in the development of nanomemories based upon metallic clusters. (C) 2011 American Institute of Physics. [doi:10.1063/1.3553849]

Mn-doped cubic BN as an atomiclike memory device: A density functional study

We investigate the electronic properties of Mn(B) substitutional doping in cubic boron nitride (BN), for different charge states, using density functional theory (DFT) calculations. We show that the neutral Mn has a nonmagnetic ground state (S=0). Upon charge injection, it is unambiguously shown that the Mn(B)(-) has a high-spin configuration with a strong, localized magnetic moment of 5 mu(Bohr). We developed a simple model, parameterized by the DFT results, that allows us to interpret the rules played by the crystal-field and exchange-correlation splitting in the magnetization process.

Quantum confinement effects on Mn-doped InAs nanocrystals: A first-principles study

We studied the effect of quantum confinement in Mn-doped InAs nanocrystals using theoretical methods. We observe that the stability of the impurities decreases with the size of the nanocrystals, making doping more difficult in small nanoparticles. Substitutional impurities are always more stable than interstitial ones, independent of the size of the nanocrystal. There is also a decrease in the energy difference between the high and low spin configurations, indicating that the critical temperature should decrease with the size of the nanoparticles, in agreement with experimental observations and in detriment to the development of functional spintronic devices with doped nanocrystals. Codoping with acceptors or saturating the nanocrystals with molecules that insert partially empty levels in the energy gap should be an efficient way to increase T(C).

Atomic scale characterization of Mn doped InAs/GaAs quantum dots

Several growth procedures for doping InAs/GaAs quantum dots (QDs) with manganese (Mn) have been investigated with cross-sectional scanning tunneling microscopy. It is found that expulsion of Mn out of the QDs and subsequent segregation makes it difficult to incorporate Mn in the QDs even at low growth temperatures of T=320 degrees C and high Mn fluxes. Mn atoms in and around QDs have been observed with strain and potential confinement changing the appearance of the Mn features.

Intermolecular energy transfer and photostability of luminescence-tuneable multicolour PMMA films doped with lanthanide-beta-diketonate complexes

It is reported in this work the preparation, characterisation and photoluminescence study of poly(methylmethacrylate) (PMMA) thin films co-doped with [Eu(tta)(3)(H(2)O)(2)] and [Tb(acac)(3)(H(2)O)(3)] complexes. Both the composition and excitation wavelength may be tailored to fine-tune the emission properties of these Ln(3+)-beta-diketonate doped polymer films, exhibiting green and red primary colours, as well as intermediate colours. In addition to the ligand-Ln(3+) intramolecular energy transfer, it is observed an unprecedented intermolecular energy transfer process from the (5)D(4) emitting level of the Tb(3+) ion to the excited triplet state T(1) of the tta ligand coordinated to the Eu(3+) ion. The PMMA polymer matrix acts as a co-sensitizer and enhances the overall luminescence intensity of the polymer films. Furthermore, it provides considerable UV protection for the luminescent species and improves the photostability of the doped system.

Effect of Mn concentration and atomic structure on the magnetic properties of Ge thin films

This work reports on the magnetic properties of Ge(100-x)Mn(x) (x=0-24 at. %) films prepared by cosputtering a Ge+Mn target and submitted to cumulative thermal annealing treatments up to 500 degrees C. Both as-deposited and annealed films were investigated by means of compositional analysis, Raman scattering spectroscopy, magnetic force microscopy, superconducting quantum interference device magnetometry, and electrical resistivity measurements. All as-deposited films (either pure or containing Mn) exhibit an amorphous structure, which changes to crystalline as the annealing treatments are performed at increasing temperatures. In fact, the magnetic properties of the present Ge(100-x)Mn(x) films are very sensitive to the Mn content and whether their atomic structure is amorphous or crystalline. More specifically: whereas the amorphous Ge(100-x)Mn(x) films (with high x) present a characteristic spin glass behavior at low temperature; after crystallization, the films (with moderate Mn contents) are ferromagnetic at room temperature. Moreover, the magnetic behavior of the films scales with their Mn concentration and tends to be more pronounced after crystallization. Finally, the semiconducting behavior of the films, experienced by previous optical studies, was confirmed through electrical measurements, which also indicate the dependence of the resistivity with the atomic composition of the films. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3520661]

3-Nitrophenol-4,4 '-bipyridyl N,N '-dioxide (2/1): a DFT study and CSD analysis of DPNO molecular complexes

The title 2:1 complex of 3-nitrophenol (MNP) and 4,4'-bipyridyl N, N'-dioxide (DPNO), 2C(6)H(5)NO(3)center dot C(10)H(8)N(2)O(2) or 2MNP center dot DPNO, crystallizes as a centrosymmetric three-component adduct with a dihedral angle of 59.40 (8)degrees between the planes of the benzene rings of MNP and DPNO (the DPNO moiety lies across a crystallographic inversion centre located at the mid-point of the C-C bond linking its aromatic rings). The complex owes its formation to O-H center dot center dot center dot O hydrogen bonds [O center dot center dot center dot O = 2.605 (3) angstrom]. Molecules are linked by intermolecular C-H center dot center dot center dot O and C-H center dot center dot center dot N interactions forming R(2)(1) (6) and R(2)(2) (10) rings, and R(6)(6) (34) and R(4)(4) (26) macro-rings, all of which are aligned along the [(1) over bar 01] direction, and R(2)(2) (10) and R(2)(1) (7) rings aligned along the [010] direction. The combination of chains of rings along the [(1) over bar 01] and [010] directions generates the three-dimensional structure. A total of 27 systems containing the DNPO molecule and forming molecular complexes of an organic nature were analysed and compared with the structural characteristics of the dioxide reported here. The N-O distance [1.325 (2) angstrom] depends not only on the interactions involving the O atom at the N-O group, but also on the structural ordering and additional three-dimensional interactions in the crystal structure. A density functional theory (DFT) optimized structure at the B3LYP/6-311G(d,p) level is compared with the molecular structure in the solid state.

Chemical and in vitro study of the potential of 3-(aryl)-2-sulfanylpropenoic acids and their Zn(II) complexes as protective agents against cadmium toxicity

The free H(2)xspa ligands [xspa = pspa, Clpspa, tspa or fspa where p = 3-(phenyl), Clp = 3-(2-chlorophenyl), t = 3-(2-thienyl), f = 3-(2-furyl) and spa = 2-sulfanylpropenoato], their Zn(II) complexes of formula [HQ](2)[Zn(xspa)(2)] (HQ=diisopropylammonium) and the Cd(II) equivalents were prepared and characterized by elemental analysis and by IR, Raman and NMR ((1)H, (13)C) spectroscopy. X-Ray studies of the crystal structures of [HQ](2)[Zn(pspa)(2)], [HQ](2)[Zn(Clpspa)2], [HQ](2)[Zn(tspa)(2)] and [HQ](2)[Zn(fspa)(2)] show that the zinc atom is coordinated to two O atoms and two S atoms of the ligands in a distorted tetrahedral ZnO(2)S(2) environment. In the structures of [HQ](2)[Cd(pspa)(2)] and [HQ](2)[Cd(Clpspa)(2)] the cadmium atom is coordinated to three S atoms and two carboxylato O atoms of the ligands in a distorted trigonal bipyramidal environment. The interchange of ligands between Zn( II) and Cd( II) was studied by (113)Cd NMR spectroscopy. The in vitro protective effect of H(2)xspa and their Zn( II) complexes against Cd toxicity was investigated using the human hepatocarcinoma HepG2 cell line and the pig renal proximal tubule LLC-PK1 cell line. The incorporation of Zn( II) was found to be relevant in the case of H(2)pspa, with an increase observed in the cell viability of the LCC-PK1 cells with respect to the value for the free ligand.