Deciphering the weathering processes using environmental mineralogy and geochemistry: Towards an integrated model of laterite and podzol genesis in the Upper Amazon Basin

This article reports major results from collaborative research between France and Brazil on soil and water systems, carried out in the Upper Amazon Basin. It reveals the weathering processes acting in the partly inundated, low elevation plateaus of the Basin, mostly covered by evergreen forest. Our findings are based on geochemical data and mineral spectroscopy that probe the crystal chemistry of Fe and Al in mineral phases (mainly kaolinite, Al- and Fe-(hydr)oxides) of tropical soils (laterites). These techniques reveal crystal alterations in mineral populations of different ages and changes of metal speciation associated with mineral or organic phases. These results provide an integrated model of soil formation and changes (from laterites to podzols) in distinct hydrological compartments of the Amazon landscapes and under altered water regimes. (C) 2010 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.

Complexos metálicos com o herbicida glifosato: revisão

We present studies involving metallic ions and the herbicide glyphosate. The metallic complexes of Cu(II), Zn(II), Mn(II), Ni(II), Cd(II), Pb(II), Cr(III), Fe(III), Co(III), ammonium, sodium, Ag(I), alkaline earth metals and of some lanthanides ions are described. The complexes are discussed in terms of their synthesis, identification, stability and structural properties, based on data from the current literature.

Spectrophotometric study of iron oxidation in the iron(II)/thiocyanate/acetone system and some analytical applications

The possibility of using thiocyanate to determine iron(II) and/or iron(III) in water-acetone mixture has been re-examined as part of a systematic and comparative study involving metallic complexes of pseudohalide ligands. Some parameters that affect the complete oxidation of the ferrous cations, their subsequent complexation and the system stability have been studied to optimize the experimental conditions. Our results show the viability and potentiality of this simply methodology as an alternative analytical procedure to determine iron cations with high sensitivity, precision and accuracy. Studies on the calibration, stability, precision, and effect of various different ions have been carried out by using absorbance values measured at 480 nm. The analytical curve for the total iron determination obeys Beer's law (r = 0.9993), showing a higher sensitivity (molar absorptivity of 2.10x10(4) L cm-1 mol-1) when compared with other traditional systems (ligands) or even with the "similar" azide ion [1.53x10(4) L cm-1 mol-1, for iron-III/azide complexes, in 70% (v/v) tetrahydrofuran/water, at 396 nm]. Under such optimized experimental conditions, it is possible to determine iron in the concentration range from 0.5 to 2 ppm (15-65% T for older equipments, quartz cells of 1.00 cm). Analytical applications have been tested for some different materials (iron ores), also including pharmaceutical products for anemia, and results were compared with atomic absorption determinations. Very good agreement was obtained with these two different techniques, showing the potential of the present experimental conditions for the total iron spectrophotometric determinations (errors < 5%). The possibility of iron speciation was made evident by using another specific and auxiliary method for iron(II) or (III).

Dihydrogen bonds: a study

Un pont de dihidrogen (dihydrogen bond,DHB) és un tipus de pont d'hidrogen atípic que s'estableix entre un hidrur metàl·lic i un donador de protons com un grup OH o NH. Els ponts de dihidrogen són claus en les característiques geomètriques i altres propietats de compostos que en presenten tan de molècules petites com el dímer de NH3BH3, com d'estructures superiors més complicades com complexes metàl·lics o sòlids. Poden ser útils aplicats a certes molècules o síntesis moleculars per a obtenir nous materials amb propietats o característiques fetes a mida. El treball d'aquesta tesi està orientat a millorar la comprensió dels ponts de dihidrogen, aprofundint en certs aspectes de la seva naturalesa atòmica/molecular utilitzant mètodes teòrics basats en la química física quàntica.

Efeito da complexação de metais aos antiinflamatórios na ação contra agentes oxidativos e radicais livres: ação do cetoprofeno

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Deciphering the weathering processes using environmental mineralogy and geochemistry: Towards an integrated model of laterite and podzol genesis in the Upper Amazon Basin

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Potencialidades analíticas do dietilditiofosfato de amônio em espectrometria de massas com plasma indutivamente acoplado empregando extração em fase sólida e sistemas de injeção em fluxo

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Podzolization as a deferralitization process: a study of an Acrisol-Podzol sequence derived from Palaeozoic sandstones in the northern upper Amazon Basin

Morphological, geochemical and mineralogical studies were carried out in a representative soil catena of the low-elevation plateaux of the upper Amazon Basin to interpret the steps and mechanisms involved in the podzolization of low-activity clay soils. The soils are derived from Palaeozoic sandstones. They consist of Hydromorphic Podzols under tree savannah in the depressions of the plateaux and predominantly of Acrisols covered by evergreen forest elsewhere.Incipient podzolization in the uppermost Acrisols is related to the formation of organic-rich A and Bhs horizons slightly depleted in fine-size particles by both mechanical particle transfer and weathering. Weathering of secondary minerals by organic acids and formation of organo-metallic complexes act simultaneously over short distances. Their vertical transfer is limited. Selective dissolution of aluminous goethite, then gibbsite and finally kaolinite favour the preferential cheluviation of first Fe and secondly Al. The relatively small amount of organo-metallic complexes produced is related to the quartzitic parent materials, and the predominance of Al over Fe in the spodic horizons is due to the importance of gibbsite in these low-activity clay soils.Morphologically well-expressed podzols occur in strongly iron-depleted topsoils of the depression. Mechanical transfer and weathering of gibbsite and kaolinite by organic acids is enhanced and leads to residual accumulation of sands. Organo-metallic complexes are translocated in strongly permeable sandy horizons and impregnate at depth the macro-voids of embedded soil and saprolite materials to form the spodic Bs and 2BCs horizons. Mechanical transfer of black particulate organic compounds devoid of metals has occurred later within the sandy horizons of the podzols. Their vertical transfer has formed well-differentiated A and Bh horizons. Their lateral removal by groundwater favours the development of an albic E horizon. In an open and waterlogged environment, the general trend is therefore towards the removal of all the metals that have initially accumulated as a response to the ferralitization process and have temporarily been sequestrated in organic complexes in previous stages of soil podzolization.

Desenvolvimento de filtros solares a partir de complexos metálicos de Zn2+ e/ou Ce3+ com quercetina para protetores solares

Pós-graduação em Química - IQ

Complexos de európio e /ou de zinco com ácido 3-piridinocarboxílico

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Hetero-metallic trinuclear nickel(II)–cadmium(II) complexes of a salicylaldimine ligand with thiocyanate, cyanate and azide ions: isolation of a pair of polymorphs with thiocyanate ion

Four new trinuclear hetero-metallic nickel(II)-cadmium(II) complexes [(NiL)(2)Cd(NCS)(2)] (1A and 1B), [(NiL)(2)Cd(NCO)(2)] (2) and [(NiL)(2)Cd(N-3)(2)] (3) have been synthesized using [NiL] as a so-called "ligand complex" (where H2L = N,N'-bis(salicylidene)-1,3-propanediamine) and structurally characterized. Crystal structure analyses reveal that all four complexes contain a trinuclear moiety in which two square planar [NiL] units are bonded to a central cadmium(II) ion through double phenoxido bridges. The Cd(II) is in a six-coordinate distorted octahedral environment being bonded additionally to two mutually cis nitrogen atoms of terminal thiocyanate (in 1A and 1B), cyanate (in 2) and azide (in 3). Complexes 1A and 1B have the same molecular formula but crystallize in very different monoclinic unit cells and can be considered as polymorphs. On the other hand, the two isoelectronic complexes 2 and 3 are indeed isomorphous and crystallize only in one form. Their conformation is similar to that observed in 1A.

Homo-and heteropolymetallic 3-(2-pyridyl)pyrazolate manganese and rhenium complexes

fac-[MBr(CO)(3)(pypzH)] (M = Mn, Re; pypzH = (3-(2-pyridyl) pyrazole) complexes are prepared from fac[ MBr(CO)(3)(NCMe)(2)] and pypzH. The result of their deprotonation depends on the metallic substrate: the rhenium complex affords cleanly the bimetallic compound [fac-{Re(CO)(3)(mu(2)-pypz)}] 2 (mu(2)-pypz = mu(2)-3-(2pyridyl-. 1N) pyrazolate-2. 1N), which was crystallographically characterized, whereas a similar manganese complex was not detected. When two equivalents of pyridylpyrazolate are used, polymetallic species [fac-M(CO) 3(mu(2)-pypz)(mu(3)-pypz) M'] (mu(3)-pypz = mu(3)-3-(2-pyridyl-kappa N-1) pyrazolate-1 kappa 2N, N: 2. 1N:; M = Mn, M' = Li, Na, K; M = Re, M' = Na) are obtained. The crystal structures of the manganese carbonylate complexes were determined. The lithium complex is a monomer containing one manganese and one lithium atom, whereas the sodium and potassium complexes are dimers and reveal an unprecedented coordination mode for the bridging 3-(2-pyridyl) pyrazolate ligand, where the nitrogen of the pyridyl fragment and the nitrogen-1 of pyrazolate are chelated to manganese atoms, and each nitrogen-2 of pyrazolate is coordinated to two alkaline atoms. The polymetallic carbonylate complexes are unstable in solution and evolve spontaneously to [fac-{Re(CO) 3(mu(2)-pypz)}](2) or to the trimetallic paramagnetic species [MnII(mu(2)-pypz) 2{fac-{MnI(CO) 3(mu(2)-pypz)}(2)}]. The related complex cis-[MnCl2(pypzH)(2)] was also synthesized and structurally characterized. The electrochemical behavior of the new homo-and heteropolymetallic 3-(2-pyridyl) pyrazolate complexes has been studied and details of their redox properties are reported.

Molybdenum – and tungsten(II) monometallic 3-(2-pyridyl)pyrazole and bimetallic 3-(2-pyridyl)pyrazolate complexes

Molybdenum and tungsten complexes containing the pypzH (3-(2-pyridyl)pyrazole) ligand as a chelating bidentate are prepared: [Mo(CO)(4)(pypzH)], cis-[MoBr(eta(3)-allyl)(CO)(2)(pypzH)], cis-[MoCl(eta(3)-methallyl)(CO)(2)(pypzH)], [MI2(CO)(3)(pypzH)] (M = Mo, W) from [Mo(CO)(4)(NBD)] or the adequate bis(acetonitrile) complexes. The deprotonation of the molybdenum allyl or methallyl complexes affords the bimetallic complexes [cis-{Mo(eta(3)-allyl)(CO)(2)(mu(2)-pypz)}](2) or [cis-{Mo(eta(3)-methallyl)(CO)(2)(mu(2)-pypz)}](2) (mu(2)-pypz = mu(2)-3-(2-pyridyl-kappa N-1) pyrazolate-2 kappa N-1). The allyl complex was subjected to an electrochemical study, which shows a marked connection between both metallic centres through the bridging pyridylpyrazolates.

Structures of ethylenediaminetetraacetato (3-) metal complexes. I complexes with Co, Mg and Cd metals

(I): Hexaaquacobalt(II) aqua[ethylenediaminetetraacetato(3-)]cobaltate(II) dihydrate, [Co(H2O)6][Co(C10H13N2O8)(H2O)]2.2H2O (Ibis): Hexaaquamagnesium(II) aqua[ethylenediaminetetraacetato(3-)]magnesiate(II) dihydrate, [Mg(H2O)6][Mg(C10H13N2O8)(H2O)]2.2H2O (II):Tetraaquabis{aqua[ethylenediaminetetraacetato(3-)]cadmium(II)-O-O'}Cadmium(II) tetrahydrate

Structures of ethylenediaminetetraacetato (3-) metal complexes. I complexes with Co, Mg and Cd metals

(I): Hexaaquacobalt(II) aqua[ethylenediaminetetraacetato(3-)]cobaltate(II) dihydrate, [Co(H2O)6][Co(C10H13N2O8)(H2O)]2.2H2O (Ibis): Hexaaquamagnesium(II) aqua[ethylenediaminetetraacetato(3-)]magnesiate(II) dihydrate, [Mg(H2O)6][Mg(C10H13N2O8)(H2O)]2.2H2O (II):Tetraaquabis{aqua[ethylenediaminetetraacetato(3-)]cadmium(II)-O-O'}Cadmium(II) tetrahydrate