Extraction and separation of heavy rare earth (III) with Extraction Resin containing di(2,4,4-trimethyl pentyl) phosphinic acid (Cyanex 272)

Extraction resins, of the type of;levextrel, (which is a collective term for styrene/divinylbenzene based copolymers of predominantly macroporous structure that contain a selective extractant) are important for the recovery and separation of metal ions, as they combine features of solvent extraction and ion exchange resins. This paper presents the results of the adsorption of heavy rare earth ions (Ho(III), Er(III), Tm(III), Yb(III), Lu(III) and Y(III)) from hydrochloric acid solutions at 0.2 mol/L ionic strength and 50 degrees C by the extraction resin containing di (2,4,4-trimethyl pentyl) phosphinic acid (Cyanex 272) and the chromatographic separation of (Er(III), Tm(III) and Yb(III)). Technological separation products, with purity and yield of Tm2O3 >99.97%, >80%, Er2O3 >99.9%, >94% and Yb2O3 >99.8%, >80% respectively, have been obtained from a feed having the composition Tm2O3 60%, Er2O3 10%, and Yb2O3 3%, the others 27%. The distribution coefficients, extraction equilibrium constants and separation factors have been determined as a function of acidity, loading of the resin and rare earths, flow rates and column ratios. The resolutions and efficiencies of separation of Er/Tm/Yb each other have been calculated. The stoichiometry of the extraction of rare earth ions has been suggested as well.

Catalysis of copper-containing transition metal hydrotalcite-like compounds in the phenol hydroxylation with hydrogen peroxide

Hydrotalcite-like compounds containing carbonate ion as the interlayer anion were prepared by coprecipitation under low supersaturation condition by mixing an aqueous solution of metal nitrates with an aqueous solutions of NaOH and Na2CO3, at room temperature, maintaining pH = 8-10 with vigorous stirring, Following the mixing, the resulting heavy slurry was aged at 353 K for 18 h with vigorous stirring, The precipitate was then filtered, washed several times with hot distilled water and dried in air at 353 K overnight, In this way, CuMI AlCO3-HTLcs and M-I AlCO3-HTLcs were synthesized and characterized by means of XRD and IR, The catalysis of the above mentioned HTLcs were investigated in the phenol hydroxylation with H2O2. The results indicated that all of the copper-containing HTLcs had a higher catalytic activity in the reaction, However, those catalysts that did not contain copper had no catalytic activity in this reaction, This means that copper was the active center in the phenol hydroxylation. Meanwhile, the mechanism was also proposed, which could be used to explain the main reason for higher activity for CuCuAlCO3-HTLcs in the phenol hydroxylation and the effect of Mg2+, Zn2+, Co2+, Ni2+ on activity of CuMI AlCO3-HTLcs.

Variation characteristics and ecological risk of heavy metals in the south Yellow Sea surface sediments

Eight cruises were conducted on the south Yellow Sea (SYS) from 1998 to 2005. Variations and the potential ecological risk of heavy metals were studied using the survey data collected during October 2003. The metal content (except for As) was high in the central area where the fine grain size sediments were dominant, and low inshore area where more coarse sediments were present. This suggested that grain size was important in determining distributions of heavy metals. In some local areas, other influencing factors, such as organic content, sedimentation rate, burial efficiency and metal's existing form were discussed. The annual averages of metals showed a stable trend with appreciable fluctuations in 8 years. Using potential ecological risk index (E (RI)) to evaluate the integrated pollution effect of heavy metals, 38.7% of the investigated area was in a moderate degree of contamination, while 77.8% was under moderate ecological risk. However, no distinct correlation was found between E (RI) and plankton biomass. In conclusion, the sediment quality of SYS was good, and the ecological risk was low in general.

Uso agrícola de composto de lixo: estudo da transferência de metal pesado no sistema solo-cana-de-açúcar.

Este estudo buscou avaliar uma solução agronômica para a destinação do lixo urbano com a utilização de sua compostagem na adubação da cana-de-açúcar. A utilização de composto de lixo (CL) altera a dinâmica de matéria orgânica do solo, tendo um impacto sobre seus processos físicos, químicos, mineralógicos e biológicos, podendo ser benéfica, pois constitui uma importante fonte de nutrientes, mas pode também causar problemas, em médio e longo ´prazos por conter metais pesados, que podem contaminar os solos e até entrar na cadeia alimentar.

Uso agrícola de composto de lixo: efeito do tempo de incubação solo/resíduo na disponibilidade de metal pesado.

O uso agrícola dos compostos de lixo (CL) urbano constitui a alternativa de maior visibilidade técnico-científica-econômica, pois estes são fontes de nutrientes e de matéria orgânica. Entretanto, é importante esclarecer que o uso do CL deve ser regulamentado, disciplinado e orientado tecnicamente por protocolos que definam a sua disposição final prevista em legislação, pois estes materiais podem conter metais pesados, que podem acumular-se nos alimentos e serem ingeridos pelo homem. Dentro desse contexto o trabalho buscou supror a deficiência de conhecimento relativo ao tempo que os metais pesados (Cádmio - Cd, Crômio - Cr, Cobalto- Co, Níquel - Ni e Chumbo - Pb), permanecem disponíveis nos solos após a adição do CL. A estração foi feita pelo método Mehlich-1, quando adicionado o CL incubado em cinco tipos de solos (Latossolo Vermelho-Amarelo, Podzólico Vermelho-Amarelo, Brunizem, planossolo e TerraRoxa Estruturada) de duas profundidades (0-20 e 20-40 cm), utilizando-se quatro doses de CL (0, 25, 50 e 100 t ha -1, em base úmida) e quatro períodos de incubação: 16, 32, 64 e 150 dias. A maioria dos metais pesados teve sua disponibilidade reduzida nos primeiros tempos de incubalção, sendo esse efeito dependente da textura, pH e teor de matéria orgânica do solo. Os dados relativos aos teores totais de metais pesados evidenciaram que o uso continuado de composto de lixo, principalmente nas doses mais elevadas, e em especial para o Cd, pode resultar riscos de contaminação do ambiente pelo efeito cumulativo.

An Imperial Legacy? An Exploration of the environmental impact of ancient metal mining and smelting in southern Jordan

Pyatt, B. Gilmore, G. Grattan, J. Hunt, C. McLaren, S. An imperial legacy? An exploration of the environmental impact of ancient metal mining and smelting in southern Jordan. Journal of Archaeological Science. 2000. 27 pp 771-778

Characterization of carbonated tricalcium silicate and its sorption capacity for heavy metals: A micron-scale composite adsorbent of active silicate gel and calcite

Adsorption-based processes are widely used in the treatment of dilute metal-bearing wastewaters. The development of versatile, low-cost adsorbents is the subject of continuing interest. This paper examines the preparation, characterization and performance of a micro-scale composite adsorbent composed of silica gel (15.9 w/w%), calcium silicate hydrate gel (8.2 w/w%) and calcite (75.9 w/w%), produced by the accelerated carbonation of tricalcium silicate (C(3)S, Ca(3)SiO(5)). The Ca/Si ratio of calcium silicate hydrate gel (C-S-H) was determined at 0.12 (DTA/TG), 0.17 ((29)Si solid-state MAS/NMR) and 0.18 (SEM/EDS). The metals-retention capacity for selected Cu(II), Pb(II), Zn(II) and Cr(III) was determined by batch and column sorption experiments utilizing nitrate solutions. The effects of metal ion concentration, pH and contact time on binding ability was investigated by kinetic and equilibrium adsorption isotherm studies. The adsorption capacity for Pb(II), Cr(III), Zn(II) and Cu(II) was found to be 94.4 mg/g, 83.0 mg/g, 52.1 mg/g and 31.4 mg/g, respectively. It is concluded that the composite adsorbent has considerable potential for the treatment of industrial wastewater containing heavy metals.

Quantitative Cytochemical Effects Of 3 Metal-Ions On A Lysosomal Hydrolase Of A Hydroid

The quantitative effects of Cu8+, Cd2+ and Hg2+ on the cytochemical staining reaction for lysosomal N-acetyl-/?-D-glucosaminidase have been determined and related to the inhibitory effects of the metals on colonial growth rate in the experimentally cultured hydroid Campanularia flexuosa. Cytochemical threshold concentrations are comparable to known environmental levels and are about one order of magnitude lower than those obtained by measuring colony growth rates. Pretreatment of colonies with Cuz+ gave no indication of tolerance adaptation, although there is evidence of the cumulative toxicity of Cu2+ and the possible sequestration of this metal in endodermal cell lysosomes. There is also an indication that the Cu2+ may exert its toxic effect by decreasing the stability of the lysosomal membranes, thus increasing the level of free glucosaminidase activity.

Marine micro and macro algal species as biosorbents for heavy metals

This paper reviews some practical aspects of the application of algal biomass for the biosorption of heavy metals from wastewater. The ability of different algal species to remove metals varies with algal group and morphology, with the speciation of specific metals and their competition with others in wastewater, and with environmental or process factors. The scattered literature on the uptake of heavy metals by both living and dead algal biomass - both macroalgae and immobilized microalgae - has been reviewed, and the uptake capacity and efficiency of different species, as well as what is known about the mechanisms of biosorption, are presented. Data on metal uptake have commonly been fitted to equilibrium models, such as the Langmuir and Freundlich isotherm models, and the parameters of these models permit the uptake capacity of different algal species under different process conditions to be compared. Higher uptake capacities have been found for brown algae than for red and green algae. Kelps and fucoids are the most important groups of algae used for biosorption of heavy metals, probably because of their abundant cell wall polysacchrides and extracellular polymers. Another important practical aspect is the possibility of re-using algal biomass in several adsorption/desorption cycles (up to 10 have been used with Sargassum spp), and the influence of morphology and environmental conditions on the re-usability of algal tissue is also considered.

Sulfur-tolerant NOx storage traps: an infrared and thermodynamic study of the reactions of alkali and alkaline-earth metal sulfates

The sulfur tolerance of a barium-containing NOx storage/reduction trap was investigated using infrared analysis. It was confirmed that barium carbonate could be replaced by barium sulfate by reaction with low concentrations of sulfur dioxide (50 ppm) in the presence of large concentrations of carbon dioxide (10%) at temperatures up to 700 degreesC. These sulfates could at least be partially removed by switching to hydrogen-rich conditions at elevated temperatures. Thermodynamic calculations were used to evaluate the effects of gas composition and temperature on the various reactions of barium sulfate and carbonate under oxidizing and reducing conditions. These calculations clearly showed that if, under a hydrogen-rich atmosphere, carbon dioxide is included as a reactant and barium carbonate as a product then barium sulfate can be removed by reaction with carbon dioxide at a much lower temperature than is possible by decomposition to barium oxide. It was also found that if hydrogen sulfide was included as a product of decomposition of barium sulfate instead of sulfur dioxide then the temperature of reaction could be significantly lowered. Similar calculations were conducted using a selection of other alkaline-earth and alkali metals. In this case calculations were simulated in a gas mixture containing carbon monoxide, hydrogen and carbon dioxide with partial pressures similar to those encountered in real exhausts during switches to rich conditions. The results indicated that there are metals such as lithium and strontium with less stable sulfates than barium, which may also possess sufficient NOx storage capacity to give sulfur-tolerant NOx traps.

The mechanistic basis of interactions between mycorrhizal associations and toxic metal cations

Mycorrhizal associations, including ericoid, arbuscular and ecto-mycorrhizas, are found colonising highly metal contaminated soils. How do mycorrhizal fungi achieve metal resistance, and does this metal resistance confer enhanced metal resistance to plant symbionts? These are the questions explored in this review by considering the mechanistic basis of mycorrhizal adaptation to metal cations. Recent molecular and physiological studies are discussed. The review reappraises what constitutes metal resistance in the context of mycorrhizal associations and sets out the constitutive and adaptive mechanisms available for mycorrhizas to adapt to contaminated sites. The only direct evidence of mycorrhizal adaptation to metal cation pollutants is the exudation of organic acids to alter pollutant availability in the rhizosphere. This is not to say that other mechanism of adaptation do not exist, but conclusive evidence of adaptive mechanisms of tolerance are lacking. For constitutive mechanisms of resistance, there is much more evidence, and mycorrhizas possess the same constitutive mechanisms for dealing with metal contaminants as other organisms. Rhizosphere chemistry is critical to understanding the interactions of mycorrhizas with polluted soils. Soil pH, mineral weathering, pollutant precipitation with plant excreted organic acids all may have a key role in constitutive and adaptive tolerance of mycorrhizal associations present on contaminated sites. The responses of mycorrhizal fungi to toxic metal cations are diverse. This, linked to the fact that mycorrhizal diversity is normally high, even on highly contaminated sites, suggests that this diversity may have a significant role in colonisation of contaminated sites by mycorrhizas. That is, the environment selects for the fungal community that can best cope with the environment, so having diverse physiological attributes will enable colonisation of a wide range of metal contaminated micro-habitats.

Intelligent potentiostat for identification of heavy metals in situ

This article presents a low-cost portable electrochemical instrument capable of on-site identification of heavy metals. The instrument acquires metal-specific voltage and current signals by the application of differential pulse anodic stripping voltammetry. This technique enhances the analytical current and rejects the background current, resulting in a higher signal-to-noise ratio for a better detection limit. The identification of heavy metals is based on an intelligent machine-based method using a multilayer perceptron neural network consisting of three layers of neurons. The neural network is implemented using a 16 bit microcontroller. The system is developed for use in the field in order to avoid expensive and time-consuming procedures and can be used in a variety of situations to help environmental assessment and control. 

Adaptation of Cladocerans in metal-polluted heterogeneous environments

No presente trabalho o cladócero Daphnia longispina foi utilizado como organismo modelo para a avaliação dos efeitos ecológicos da adaptação a ambientes contaminados por metais. Foram amostradas populações naturais de D. longispina num local sujeito à contaminação por metais e num local próximo, de referência, ambos localizados no sistema aquático na área envolvente à mina abandonada de São Domingos. Várias linhagens clonais de ambas as populações foram mantidas em laboratório, sob condições controladas, para a execução dos testes. Um dos testes realizados permitiu estudar e quantificar as diferenças na tolerância letal entre as linhagens clonadas de ambas as populações e também avaliar os custos associados. Utilizando vinte linhagens clonais de D. longispina das duas populações verificou-se que apenas clones sensíveis ao cobre estavam presentes na população de referência e clones resistentes ao cobre estavam presentes na população do local contaminado. Os custos associados à tolerância foram ilustrados pela determinação de taxas alimentares mais baixas para a população tolerante quando comparadas com as da população de referência. Outro dos testes realizados permitiu comparar as respostas de clones de populações de ambos os locais – contaminado e referência – à exposição a concentrações sub-letais do metal cobre. A tolerância evidenciada anteriormente ao nível letal foi confirmada ao nível sub-letal, com o clone proveniente da população do local contaminado evidenciando uma maior tolerância ao cobre quando comparado com os restantes clones, para todos os parâmetros analisados (taxas alimentares, consumo de oxigénio, crescimento e reprodução). Os efeitos da aclimatação ao cobre ao longo de várias gerações foram também avaliados num clone de D. longispina. Os resultados evidenciaram a existência de uma adaptação fisiológica ao cobre ao longo das várias gerações que, no entanto, apenas aumentou marginalmente a tolerância a níveis de cobre letais. Para além disso, observou-se também uma grande variação nas respostas do clone de D. longispina estudado, não só entre concentrações de cobre mas também entre gerações. Os resultados obtidos nos vários estudos realizados com linhagens clonais de ambas as populações de D. longispina reforçam a importância de integrar a temática do desenvolvimento de tolerância à poluição aquando da avaliação dos riscos ambientais e ecológicos de compostos químicos, como os metais, no meio ambiente.

Bio-removal of toxic metals by metal resistant anaerobic bacteria: molecular characterization and performance studies

Tese de dout., Ciências Biotecnológicas (Biotecnologia Ambiental), Faculdade de Ciências e Tecnologia, Univ. do Algarve, 2010

Assessment of heavy metals in the surroundings of coal-fired power plant

This paper aims to survey metal concentrations in soils in the vicinity of a coal-firedpower plant located in southwest of Portugal. Two annual sampling campaigns were carried out to measure a hypothetical soil contamination around the coal plant. The sampling area was divided into two subareas, both centered in the emission source, delimited by two concentric circles with radius of 6 km and 20 km. About 40 samplings points were defined in the influence area. Metals measurements were performed with a portable analytical X-ray dispersive energy fluorescence spectrometer identifying about 20 different elements in each sampling point. The most relevant elements measured included As, Cu, Fe, Hg, Pb, Ti and Zn in both sampling areas. Considering the results obtained in the first sampling campaign, arsenic is predominantly higher within the 6-20 km sampling area. The second sampling campaign showed that both sampling areas presented relatively similar metal concentrations except for Fe, Mn, Sr and Zn which concentration is higher within the 6-20 km sampling area. Also, As, Fe, Mn and Ti concentrations decreased significantly from the first to the second sampling campaign and their concentration were predominately higher in the NE-E and E-SE directions.