Recovery and refining of manganese as by-product from hydrometallurgical processes

The consumption of manganese is increasing, but huge amounts of manganese still end up in waste in hydrometallurgical processes. The recovery of manganese from multi-metal solutions at low concentrations may not be economical. In addition, poor iron control typically prevents the production of high purity manganese. Separation of iron from manganese can be done with chemical precipitation or solvent extraction methods. Combined carbonate precipitation with air oxidation is a feasible method to separate iron and manganese due to the fast kinetics, good controllability and economical reagents. In addition the leaching of manganese carbonate is easier and less acid consuming than that of hydroxide or sulfide precipitates. Selective iron removal with great efficiency from MnSO4 solution is achieved by combined oxygen or air oxidation and CaCO3 precipitation at pH > 5.8 and at a redox potential of > 200 mV. In order to avoid gypsum formation, soda ash should be used instead of limestone. In such case, however, extra attention needs to be paid on the reagents mole ratios in order to avoid manganese coprecipitation. After iron removal, pure MnSO4 solution was obtained by solvent extraction using organophosphorus reagents, di-(2-ethylhexyl)phosphoric acid (D2EHPA) and bis(2,4,4- trimethylpentyl)phosphinic acid (CYANEX 272). The Mn/Ca and Mn/Mg selectivities can be increased by decreasing the temperature from the commonly used temperatures (40 –60oC) to 5oC. The extraction order of D2EHPA (Ca before Mn) at low temperature remains unchanged but the lowering of temperature causes an increase in viscosity and slower phase separation. Of these regents, CYANEX 272 is selective for Mn over Ca and, therefore, it would be the better choice if there is Ca present in solution. A three-stage Mn extraction followed by a two-stage scrubbing and two-stage sulfuric acid stripping is an effective method of producing a very pure MnSO4 intermediate solution for further processing. From the intermediate MnSO4 some special Mn- products for ion exchange applications were synthesized and studied. Three types of octahedrally coordinated manganese oxide materials as an alternative final product for manganese were chosen for synthesis: layer structured Nabirnessite, tunnel structured Mg-todorokite and K-kryptomelane. As an alternative source of pure MnSO4 intermediate, kryptomelane was synthesized by using a synthetic hydrometallurgical tailings. The results show that the studied OMS materials adsorb selectively Cu, Ni, Cd and K in the presence of Ca and Mg. It was also found that the exchange rates were reasonably high due to the small particle dimensions. Materials are stable in the studied conditions and their maximum Cu uptake capacity was 1.3 mmol/g. Competitive uptake of metals and acid was studied using equilibrium, batch kinetic and fixed-bed measurements. The experimental data was correlated with a dynamic model, which also accounts for the dissolution of the framework manganese. Manganese oxide micro-crystals were also bound onto silica to prepare a composite material having a particle size large enough to be used in column separation experiments. The MnOx/SiO2 ratio was found to affect significantly the properties of the composite. The higher the ratio, the lower is the specific surface area, the pore volume and the pore size. On the other hand, higher amount of silica binder gives composites better mechanical properties. Birnesite and todorokite can be aggregated successfully with colloidal silica at pH 4 and with MnO2/SiO2 weight ratio of 0.7. The best gelation and drying temperature was 110oC and sufficiently strong composites were obtained by additional heat-treatment at 250oC for 2 h. The results show that silica–supported MnO2 materials can be utilized to separate copper from nickel and cadmium. The behavior of the composites can be explained reasonably well with the presented model and the parameters estimated from the data of the unsupported oxides. The metal uptake capacities of the prepared materials were quite small. For example, the final copper loading was 0.14 mmol/gMnO2. According to the results the special MnO2 materials are potential for a specific environmental application to uptake harmful metal ions.

Environmental assessment and biomonitoring of the Twelve Mile Creek watershed, Niagara Peninsula, Ontario

In light of the heavy reliance of the people of the Niagara Peninsula on the T\\'elve Mile Creek (TMC) watershed for recreational activities and for municipal and industrial uses ( e.g., drinking water, shipping and discharge of effluents), it was deemed prudent to assess the envirol1tnental health of the system by analysing the sediments total and exchangeable metal, and TPH contents. The MOEE has set guidelines with limits for the protection and management of aquatic sediments, and the sediments from the headwaters of the TMC have total metal and TPH (subset of O&G) contents well below the lower provincial limits. Areas of environmental concern where total metal contents in sediments, either individually or collectively, exceed the guideline, are the south side of Lake Gibson, the Old WeIland Canal, a segment of TMC just south of the QEW and Martindale Pond. The total metal content of sediments does not in all instances identify areas of biological concern. Instead, it has been found that the exchangeable metal fraction of sediments is a better indicator of metal availability and thus potential accumulation in organisms. In some instances, the exchangeable metal fraction agrees with the total metal fraction defining areas of environmental concern, but it does vary from site to site reflecting the natural variability of the ambient environment. Overall, the exchangeable metal fraction of sediments appears to be a better indicator of anthropogenic pollution and ecosystem impact. A histochemical study of Anodon.ta sp., Elliptio sp. and zebra mussels (Dreissena polyn'101pha) was done in conjunction with passive biomonitoring of zebra and quagga mussels (Dreissena bugensis) from the Twelve Mile Creek watershed and Lake 51. Clair (Jeanette's Creek, Chatham, Ontario). The highest concentrations of divalent metals such as Cu, Ni, Cd, and Zn, and trivalent Al appear to accumulate in gill and kidney tissues. Metal contents of organ tissues in Anodonta sp. vary with size class. Organ metal content varies among size classes, thus requiring consideration of size in biomonitoring studies. Shucked zebra and quagga mussel tissues, exhibited similar size class to Al content trends. In addition they reflected the Al content trends of top (approximately 10 cm) most sediments in the Twelve Mile Creek watershed. Quagga mussels appear to have higher Al concentrations than zebra mussels, thus suggesting that quagga mussels may be better passive biomonitors of AI. Cd content in zebra mussel tissues, seemed to increase with size class trends. This was not demonstrated in the quagga mussel tissues. This suggests that Cd may be regulated by quagga mussels and not by zebra mussels, and that zebra mussels may be better passivebiomonitors of Cd than are quagga mussels. Zebra mussel, quagga mussel, Anodonta sp., and Elliptio sp. were used in a two part, active (translocated) biomonitoring study of the Twelve Mile Creek watershed. There was no statistical difference in death rates between zebra and quagga mussels after 65 days of biomonitoring. However there does appear to be a difference of death rates between sites. Unfortunately the data base did not permit us to differentiate between sites. Relative to Port Colborne Harbour (Port Colborne, Ontario), the Twelve Mile Creek watershed appears to be elevated in bioavailable AI. An area near the terminus of the Twelve Mile Creek appears to be an area of environmental concern since mussels seemed to have accumulated relatively large concentrations of Cd, Zn, and Pb. In addition to possible metal loading from a nearby outfalls, or possible upstream outfalls, road salt runoff from storm sewers may have contributed to metal accumulation through cation exchanges processes. Similar trends in cumulative quagga mussel metal concentrations during the two time periods (65 and 159 days), suggest that quagga mussels may reach equilibrium within 65 days of translocation. Differences in bioaccumulated metal concentrations of the two dreissenid species demonstrate that active biomonitoring studies must use a variety of organisms to adequately assess the environmental situation of specific waterways and/or bodies.

Propuesta para la utilización del ordenador como recurso tecnológico en la enseñanza de la Micología.

Desarrolla un programa educativo de Micología con Hypercard, en los anexos se dispone de la estructura y formato de las pantallas del mismo, pero no existe ningún disquete ni CD-ROM que contenga el programa desarrollado en el documento de innovación

Proyecto de innovación de estrategias didácticas para potenciar y crear valores y actitudes con el alumnado de secundaria a través del ámbito de la comunicación.

Premios Nacionales de Innovación Educativa del CIDE 2006. El ejemplar con R. 161230 no tiene CD. El ejemplar con R. 161092 no tiene resumen ni CD

Differential/combined effect of water contamination with cadmium and nickel on tissues of rats

The contamination of water by metal compounds is a worldwide environmental problem. Concentrations of metals are widely related to biochemical values which are used in disease diagnosis due to environmental toxicity. The acute combined effects of cadmium and nickel on biochemical parameters were determined and compared with those of Cd2+ or Ni2+ alone in rats. Male adult rats were given drinking solutions of CdCl2 [Cd(II) cation, 100 mg/liter] or NiSO4 [Ni(II) cation, 100 mg/liter]. For the combined treatment, the animals (Ni+Cd) received both Ni(II)) cation (100 mg/liter) and Cd(II) cation (100 mg/liter). Nickel treatment induced increased alanine transaminase (ALT) activity and hepatotoxicity, but not renal injury. In contrast, cadmium exposure produced hepatic, renal and myocardial damage, characterized by increased creatinine, total and direct bilirubin concentrations and increased ALT and lactate dehydrogenase (LDH) activities. The combined effect Ni-Cd is less toxic than cadmium alone, suggesting antagonism between these toxicants. The toxicity of nickel and cadmium, alone and in combination, decreased Cu-Zn superoxide dismutase (SOD) activity and increased lipoperoxide formation. (C) 1998 Elsevier B.V. Ltd. All rights reserved.

Lability of heavy metal species in aquatic humic substances characterized by ion exchange with cellulose phosphate

Labile metal species in aquatic humic substances (HSs) were characterized by ion exchange on cellulose phosphate (CellPhos) by applying an optimized batch procedure. The HSs investigated were pre-extracted from humic-rich waters by ultrafiltration and a resin XAD 8 procedure. The HS-metal species studied were formed by complexation with Cd(II), Ni(II), Cu(II), Mn(II) and Pb(II) as a function of time and the ratio ions to HSs. The kinetics and reaction order of this exchange process were studied. At the beginning (<3 min), the labile metal fractions are separated relatively quickly. After 3 min, the separation of the metal ions proceeds with uniform half-lives of about 12-14 min, revealing rather slow first-order kinetics. The metal exchange between HSs and CellPhos exhibited the following order of metal lability with the studied HSs: Cu > Pb > Mn > Ni > Cd. The required metal determinations were carried out by atomic absorption spectrometry.

Desempenho de reator anaeróbio de fluxo ascendente alimentado com lodo de estação de tratamento de água e esgoto sanitário

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Fitodisponibilidade de metais utilizando ácidos orgânicos após sucessiva aplicação de resíduos no solo

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

Valutazione del contributo emissivo in condizioni non-stazionarie alle emissioni totali di una stufa a pellet domestica

The aim of this work is to evaluate the emissions of the main pollutants of a pellet stove, by trying to simulate the real use in domestic operations. All the operating phases of this system were considered: ignition, partial load, increase in power, and nominal load. In each phase, quantity and type of some pollutants in emissions were determined: the main pollutant gases (CO, NOx, SO2, H2S and volatile organic compounds (VOCs)), total dust (PM) and its content of polycyclic aromatic hydrocarbons (PAHs), regulated heavy metals (Ni, Cd, As and Pb), main soluble ions and Total Carbon (TC). Results show that emission factors of TSP, CO, and of the main determined pollutants (TC, Cd and PAHs) are higher during ignition phase. In particular, this phase prevalently contributes to PAHs emissions. During increase in power phase, gas and particulate emissions do not appreciably differ from nominal load ones; nevertheless, PAH emission factors are higher than steady state ones, but lower than ignition phase. Moreover, during not-steady state phases, PAH mixture is more toxic than during steady state phases. In conclusion, this study allowed to go deeper in pellet stove environmental impact, by pointing out how the different operating conditions can modify the emissions. These are different from certificated data, which are based exclusively on measurements in steady state conditions.

Concentrations of suspended matter and heavy metals in melted ice- and snow water from the Barents Sea

In September-October 1998, during Cruise 14 of R/V Akademik Fedorov to the Barents Sea, in the region of 82° N between the Spitsbergen and Novaya Zemlya archipelagos samples of snow and ice were collected within four polygons. By means of atomic absorption with an electothermal atomizer (onboard the ship) in filtered (dissolved form) and unfiltered (sum of dissolved and particulate forms) samples of snow melt and ice melt concentrations of Fe, Mn, Cu, Cr, Ni, Co, Pb, and Cd were determined in order to estimate level of potential contamination of snow and ice with these metals. Excluding data on Ni, Cd (and probably Cu) in ice that were regarded to be unsatisfactory because of probable contamination of the ice samples during drilling concentrations of all the elements in snow and ice of the northern part of the Barents Sea appeared to be close to their background values or below. An attempt to identify the main sources of metal supply to snow from the atmosphere by comparison of ratios of metal particulate form to total content in snow of the Barents Sea and the same ratios in snow samples from clean regions of Finland and from contaminated areas of the Kola Peninsula showed that aerosols in the area of the expedition were supplied into the Barents Sea atmosphere from different sources, both natural and anthropogenic.

Efeito residual da aplicação de biosólido na cultura do milho.

EFEITO RESIDUAL DA APLICAÇÃO DE BIOSÓLIDO NA CULTURA DO MILHO. MA039 Fernanda Ardilha dos Santos1; Fernanda Gonçalves Serrenho1; Germana Breves Rona1; Sarai de Alcantara1; Daniel Vidal Perez2; Wagner Bettiol3 ; Waldemore Moriconi3, fernanda.ardilha@oi.com.br (1) Instituto de Química, UFRJ, (2) Embrapa Solos, RJ, (3) Embrapa Meio Ambiente (INTRODUÇÃO) A operação de uma Estação de Tratamento de Esgoto visa diminuir a carga poluente que seria lançada nos corpos receptores. Porém um novo problema é gerado: a disposição do lodo de esgoto, ou biossólido. Uma opção seria a disposição em aterro sanitário, que agrava ainda mais o problema de manejo do lixo urbano. Uma alternativa razoável seria a sua utilização como condicionador de solo e/ou fertilizantes, já que o biossólido promove a reciclagem de matéria orgânica e nutrientes. Entretanto, metais pesados são facilmente encontrados na composição de um biossólido. A utilização desse material para fins agrícolas pode causar alterações nos teores desses metais e na sua dispersão, tanto na fase sólida quanto na líquida do solo, com conseqüências ainda pouco conhecidas para nossas condições. O objetivo deste trabalho é estudar o impacto causado pelo uso agrícola do biossólido, de origem doméstica/industrial, nos teores e na evolução dos elementos Mn, Zn, Cu, Ni, Cd e Cr. (METODOLOGIA) A área experimental situou-se em Jaguariúna (SP), em Latossolo Vermelho Distroférrico (textura argilosa). O delineamento experimental escolhido foi o de fatorial (2 x 6) em blocos ao acaso, com 3 repetições, em que um tratamento correspondeu a uma dose aplicada, antes do plantio de milho, do lodo de esgoto. Os tratamentos estudados constaram de uma Testemunha Absoluta, Testemunha convencional (NPK), 1, 2, 4 e 8 vezes a dose de lodo de esgoto, calculada com base na adubação de N, requerida pela cultura do milho. O outro tratamento se refere ao tipo de lodo de esgoto utilizado, que foi fornecido pela SABESP, a saber: Barueri (Industrial) e de Franca (Doméstico), em SP. A amostragem ocorreu em novembro de 2004,2005,2006 e 2007 sendo a profundidade de coleta de 0-20cm. A técnica de extração seqüencial utilizada foi a descrita por Wasserman et al. (2005). As determinações analíticas dos metais estudados foram realizadas por ICP-OES(PE OPTIMA 3000). (RESULTADOS) Para o Zn, com o aumento da dose aplicada, observa-se um aumento significativo na concentração das fases 1e 2 e em menor grau na fase 5. Para o Cu observa-se um aumento na concentração de todas as frações em função do aumento da dose aplicada de lodo sendo a fase 5 desprezível. Nota-se que, apesar da tendência do Cu formar complexos com a matéria orgânica, é a fase 2 a mais representativa, sendo que a fase 1 apresenta alguma importância nas doses mais elevadas. O Cr sofreu um aumento na concentração total com o aumento da dose de lodo aplicada, apresentando um incremento nas concentrações de todas as fases exceto a fase 5. Todas as concentrações totais dos elementos estudados aumentaram em função do aumento das doses de lodo aplicadas. Vale ressaltar que o ano de 2003 foi o último onde houve aplicação do biossólido. Portanto, a amostragem feita em 2006 já se refere a um estudo de atenuação natural. Ademais, os resultados são relativos a aplicação do lodo de Barueri já que este apresenta concentrações metálicas mais elevadas e o comportamento dos elementos são semelhantes para distintoas fontes de lodo. (CONCLUSÃO) As concentrações nas fases aumentaram em função do aumento da concentração de lodo utilizada. As fases 1 e 2 apresentam importância neste sentido sendo este um motivo de grande preocupação, por serem frações biodisponíveis, podendo agravar seriamente, os riscos de contaminação pelos metais em questão. No entanto, as concentrações encontradas são bem menores que aquelas recomendadas pela CONAMA no375/2006 . Isto indica que a utilização do lodo oriundo das ETES na agricultura é uma solução bastante viável para sua disposição final, sendo uma prática já adotada em vários países (Ludivice et al, 2000). Agradecimentos: CNPq, FAPERJ, FUJB, EMBRAPA

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.

Metal separation from mixed types of batteries using selective precipitation and liquid-liquid extraction techniques

The purpose of this paper is to study metal separation from a sample composed of a mixture of the main types of spent household batteries, using a hydrometallurgical route, comparing selective precipitation and liquid-liquid extraction separation techniques. The preparation of the solution consisted of: grinding the waste of mixed batteries, reduction and volatile metals elimination using electric furnace and acid leaching. From this solution two different routes were studied: selective precipitation with sodium hydroxide and liquid-liquid extraction using Cyanex 272 [bis(2,4,4-trimethylpentyl) phosphoric acid] as extracting agent. The best results were obtained from liquid-liquid extraction in which Zn had a 99% extraction rate at pH 2.5. More than 95% Fe was extracted at pH 7.0, the same pH at which more than 90% Ce was extracted. About 88% Mn, Cr and Co was extracted at this pH. At pH 3.0, more than 85% Ni was extracted, and at pH 3.5 more than 80% of Cd and La was extracted. (C) 2010 Elsevier Ltd. All rights reserved.

Synthesis, structure and electrochemical behaviour of Na, Mg-II, Mn-II, Cd-II and Ni-II complexes of 3-(2-carboxyphenylhydrazone)pentane-2,4-dione

Mononuclear manganese(II) [Mn(kappa O-HL)(2)(CH3OH)(4)] (4), nickel(II) [Ni(kappa O-2, kappa N-L)(H2O)(3)] (5), cadmium(II) [Cd(kappa O-2-HL)(2)(CH3OH)(3)] (7), tetranuclear zinc(II) [Zn-4(mu-OH)(2)(1 kappa O:2 kappa O-HL)(4)(kappa O-HL)(2)(H2O)(4)] (6) and polynuclear aqua sodium(I) [Na(H2O)(2)(mu-H2O)(2)](n)(HL)(n) (2) and magnesium(II) [Mg(OH)(H2O)(mu-H2O)(2)](n)(-HL)(n) (3) complexes were synthesized using 3-(2-carboxyphenyl-hydrazone)pentane-2,4-dione (H2L, 1) as a ligand precursor. The complexes were characterized by single crystal X-ray diffraction, elemental analysis, IR, H-1 and C-13 NMR (for 2, 3, 6 and 7) spectroscopies. Mono- or dianionic deprotonated derivatives of H2L display different coordination modes and lead to topologies and nuclearities of the complexes depending on metal ions and conditions used for the syntheses. Extensive intermolecular H-bonds form supramolecular arrangements in 1D chains (4 and 6), 1D chains of the organic anion and 2D networks of the metal-aqua aggregates (2 and 3), 2D networks (7) or even 3D frameworks (5). Electrochemical studies, by cyclic voltammetry and controlled potential electrolysis, show ligand centred redox processes as corroborated by theoretical DFT calculations in terms of LUMO and HOMO compositions. (C) 2012 Elsevier Ltd. All rights reserved.

Survey of trace elements (Al, As, Cd, Cr, Co, Hg, Mn, Ni, Pb, Se, and Si) in retail samples of flavoured and bottled waters

Concentrations of eleven trace elements (Al, As, Cd, Cr, Co, Hg, Mn, Ni, Pb, Se, and Si) were measured in 39 (natural and flavoured) water samples. Determinations were performed using graphite furnace electrothermetry for almost all elements (Al, As, Cd, Cr, Co, Mn, Ni, Pb, and Si). For Se determination hydride generation was used, and cold vapour generation for Hg. These techniques were coupled to atomic absorption spectrophotometry. The trace element content of still or sparkling natural waters changed from brand to brand. Significant differences between natural still and natural sparkling waters (p<0.001) were only apparent for Mn. The Mann–Whitney U-test was used to search for significant differences between flavoured and natural waters. The concentration of each element was compared with the presence of flavours, preservatives, acidifying agents, fruit juice and/or sweeteners, according to the labelled composition. It was shown that flavoured waters generally increase the trace element content. The addition of preservatives and acidifying regulators had a significant influence on Mn, Co, As and Si contents (p<0.05). Fruit juice can also be correlated to the increase of Co and As. Sweeteners did not provide any significant difference in Mn, Co, Se and Si content.