This thesis concerns the development of new types of solvent extractants for use in the hydrometallurgical recovery of base metals, and addresses the ligand design features which are needed to control the strength, transport efficiency and selectivity of these extractants. Chapter 1 provides background on the development of extractive metallurgy, e.g. pyrometallurgy and hydrometallurgy, and introduces the history, basic terminology and various processes and reagents involved. Solvent extraction as a hydrometallurgical technique to achieve the recovery of base metals is discussed in most detail. The design criteria of extractants are highlighted as the focus of the whole thesis. Chapter 2 investigates the potential of salicylaldehyde hydrazones as cation exchange extractants for hydrometallurgical recovery of copper, and studies substituent effects, e.g. electronic, steric and particularly “buttressing” of ligand-ligand hydrogen bonding, on the strength and efficacy of the extractants. A series of 3-substituted (X) and N-substituted salicylaldehyde hydrazones has been developed. Solvent extraction experiments show that the 3-substitution can increase the distribution coefficient of the methylhydrazone for copper extraction by more than three orders of magnitudes along the series (X) Me < OMe ≤ H < Br < NO2. Both the phenol acidity and intermolecular hydrogen bonding are significantly influenced by the 3-substituent as judged by a systematic NMR study on the solution speciation of the free ligands. Electron-withdrawing groups which also act as hydrogen bond acceptors (X = NO2 or Br) are particularly effective in enhancing the strength of the methylhydrazones. Compared to the commercially applied salicylaldoximes, the hydrazones are weaker extractants, and the strength varies in the order: oximes > methylhydrazones > phenylhydrazones. This order probably arises from a combination of variations in the phenol acidities and the strength of the hydrogen bonding motifs, which are also probed in the free ligands using NMR techniques. Chapter 3 considers reagents capable of extracting metal salts and deals with the development of polytopic salicylaldimine ligands bearing pendant tertiary amine groups for the hydrometallurgical recovery of zinc chloride. These extractants show extremely high transport efficiency of metal salts with more than two moles of ZnCl2 loaded per mole of ligand, and high chloride over sulfate selectivity in solvent extraction experiments. The unusual multiple loading suggests the extraction of chlorozincate as anion species, which is supported by the elemental analysis and ESI MS spectra of the formed complexes. The zinc chloride dependent extraction and stripping experiments further indicate that the extraction process is controlled by the Cl- activities in the aqueous solutions. 1H NMR studies show that two different complexes are successively formed in solution as the ligand to zinc stoichiometry is increased to 1L : 2ZnCl2, with the first formed by extracting the zinc cation at low ZnCl2 concentrations and the second likely resulting from the further extraction of chlorozincate at high ZnCl2 concentrations. An extraction mechanism is proposed in which a tritopic assembly [ZnLCl2] forms by binding the Zn2+ cation with the N2O2 2- site of the “salen” type ligands and two Cl- anions with the protonated pendant amine groups and then a ditopic assembly [ZnL(ZnCl4)] forms by extracting the [ZnCl4]2- anion when the reagent is contacted with high tenor ZnCl2 feed. The possible formation of tritopic assemblies [ZnL(ZnCl3)2] accounts for Zn-loadings higher than 200%. The ligand design features such as the benefits of combining cation and anion binding sites in the same molecule are indicated by comparing the polytopic ligands with a series of dual host pairs of the salen ligand and hydrophobic amines. The polytopic ligands show potential for industrial application as ZnCl2 extractants. Finally chapter 4 focuses on the anion binding and selectivity involving simple anions and chlorometallates in solvent extraction by the polytopic ligands discussed in chapter 3 and their metal complexes. A novel and reliable method for chloride analysis in the presence of complexing metal cations has been developed using excess silver(I) to precipitate chloride and then analyze the silver content by ICP-OES technique. Multiple loadings of chloride are achieved by the polytopic ligands, which confirms the uptake of metal salt as ZnCl2, and is desirable for excellent material balances in hydrometallurgical processes. The anion binding of the copper-only complex [Cu(L-2H)] supports the proposed extraction mechanism by indicating that one mole of zinc is extracted in the likely form of chlorozincate anions when the cation binding site is occupied by Cu2+. The polytopic ligands and their copper-only complexes [Cu(L-2H)] show the same anion selectivity following the order [ZnCl4]2- > Cl- > SO4 2-, which can be explained by the hydration energies of these anions. Extractions from ZnCl2, ZnSO4, Zn(NO3)2 or mixed feed solutions indicate that the zinc transport efficiency is also dependent on the nature of counter anions.

This work seeks to compare various Acetone-Butanol-Ethanol (ABE) fermentation extraction chemicals on an economic and environmental basis. The chemicals considered are: decane, a decane/oleyl alcohol blend, decanol, a decanol/oleyl alcohol blend, 2-ethyl-hexanol, hexanol, mesitylene, and oleyl alcohol. To facilitate comparison a pure-distillation base case was also considered. The aforementioned extractants are a mix of both toxic and non-toxic extractants. Non-toxic extractants can be used directly in fermentation reactors, improving overall fermentation yield by removal of toxic butanol. The extractants were modelled in Aspen Plus V8.8 and separation trains were designed to take advantage of extractant properties. The separation section of the plant was then integrated with upstream and downstream units to determine the Minimum Butanol Selling Prices (MBSP) for second generation extractive ABE fermentation. Upstream processes include biomass (switchgrass) solids processing, biomass pre-treatment/saccharification and fermentation while downstream processes include utility generation and wastewater treatment. The cost of CO2 equivalent emissions avoided (CCA) was used as a metric to compare environmental impact of each process as compared to gasoline. The economic best and environmental best extractant is shown to be 2-ethyl-hexanol with a MBSP of $1.58/L and a CCA of $471.57/tonne CO2 equivalent emissions avoided. Wastewater treatment, which is often ignored in other works, was found to makeup over 30% of total installed capital cost for all extractants. / Thesis / Master of Applied Science (MASc)

Chalcopyrite ore forms the significant fraction of copper deposits in the earth crust. However, it is also the most difficult to treat using conventional ferric leaching methods. Smelting and electro-refining are currently the methods used in treating chalcopyrite concentrate obtained from froth flotation. Due to the ever increasing environmental requirements on smelters by the Environmental Protection Agency, new smelters are scarce in the United States. The scarcity of smelters has led to the urgent need to find a novel leaching method for the abundant chalcopyrite deposits in the USA and the rest of the world. This chapter(one) of the dissertation, therefore, investigated the leaching of chalcopyrite ore at pH 2 using a newly discovered oxidant (peroxodisulfate). Our results show that chalcopyrite leaching using peroxodisulfate follows a surface reaction shrinking core model. The activation energy of chalcopyrite leaching using peroxodisulfate ion was calculated as 41.1 kJ mol⁻¹. We also report that the leaching of chalcopyrite ore is affected by particle size and that stirring hurts leaching of chalcopyrite. Additionally, we found that peroxodisulfate can produce from sulfuric ions electrochemically. Hydrogen peroxide, permanganate, peroxodisulfate and ferric ions are all strong oxidants that have been researched in production pregnant leach solution (PLS) from chalcopyrite ore leaching. Because, solvent extraction is the next step in the recovery of copper from pregnant leach solutions (PLS). The questions, therefore, arises as to the fate of the organic extractant used in solvent extraction coming in contact with strong oxidant residual in the PLS. In chapter two of the dissertation, we studied the effect of strong oxidant residual in PLS on the degradation of organic extractants during solvent extraction of copper. Exposed organic extractants were analyzed using interfacial tension(IFT), Fourier Transform Infrared (FTIR) spectroscopy and CG LS. The results obtained from IFT and FTIR analysis, show no effect on the organic extractants exposed to sunlight and PLS containing the residual strong oxidant. Finally in chapter 3, the dissertation exams alternative water source for the flotation of chalcopyrite. Mineral flotation is a water-intensive process in mining. In order to sustain mining operations such flotation, which rely heavily on water, chapter 3 of the dissertation looks at using alternative water sources (in this case reclaimed wastewater) in the flotation of chalcopyrite ores; this effort is to limit the mining industries dependence on fresh ground water particularly in the Southwest of United States where water is a scarce commodity. The research studied the effect of reclaimed waste water on chalcopyrite flotation via contact angle and surface energy measurements. Furthermore, atomic force microscopy (AFM) and flotation tests were used to supplement the findings from contact angle and surface studies. We conclude here that the contact angle of a pure chalcopyrite surface was determined to be 75.6 degrees. We also found that pure chalcopyrite mineral surface is slightly polar with surface energies γCuFeS2^(LW) = 41.4 mJ/m² (apolar), γCuFeS2^(AB) = 2.9 mJ/m² (polar). The high value of the surface energy indicates pure chalcopyrite surface is slightly hydrophobic.

A fitodisponibilidade de metais pesados em solos tratados com biossólido está relacionada com o processo de solubilização destes metais presentes, predominantemente, na fase sólida do resíduo. A formação de complexos solúveis entre metais e ácidos orgânicos liberados na rizosfera por plantas e microorganismos parece ter um importante papel na solubilização e, consequentemente, na fitodisponibilidade dos metais pesados. Ainda não foi estabelecido um método de extração eficiente para estimar teores fitodisponíveis destes metais, provavelmente por que os extratores geralmente utilizados não simulam reações que ocorrem próximas às raízes. O presente estudo foi realizado com o objetivo de determinar a composição de ácidos orgânicos na rizosfera de algumas espécies vegetais cultivadas na presença de biossólidos, estudar o potencial de dissolução de metais pesados originários de biossólidos por estes ácidos orgânicos e testar a viabilidade do uso de soluções de ácidos orgânicos como extratores de metais pesados fitodisponíveis. Braquiária, eucalipto, cana de açúcar e milho foram cultivadas em areia ou areia tratada com biossólido. Análises cromatográficas foram realizadas em amostras coletadas do sistema hidropônico utilizado, identificando-se os ácidos acético, cítrico, lático e oxálico, respectivamente nas porcentagens de 43,21; 31,13; 20,41 e 5,25 calculadas em relação ao total de ácidos determinado. Os teores de ácido acético, lático e oxálico no extrato correlacionaram com os teores de Cd, Cu, Ni e Zn na parte aérea das espécies vegetais estudadas. O teor de ácido cítrico não correlacionou com nenhum dos metais estudados. Considerando-se a somatória dos teores dos ácidos estudados obteve-se correlação com o teor de metais pesados nas plantas, evidenciando o efeito destes ácidos na fitodisponibilidade dos metais. O estudo de cinética foi realizado utilizando-se solução dos ácidos acético, cítrico, lático e oxálico, preparada de modo a se obter concentração final igual a 0,05 e 0,10 mol L -1 . A extração foi feita segundo o método do equilíbrio de batch. A solução de ácidos orgânicos de concentração 0,10 mol L -1 extraiu maiores quantidades dos metais. A cinética de solubilização apresentou duas fases: uma inicial com rápida liberação dos metais, seguida de outra mais lenta tendendo ao equilíbrio. As constantes de velocidade mais altas foram observadas para Ni e Zn, seguidos de Cu, Cr e Pb. Os valores para o reservatório lábil não ultrapassaram 15% do total de metais presentes. A porcentagem referente ao reservatório lábil do metal em relação ao total presente obedeceu a ordem: Zn > Cu @ Ni > Cr @ Pb. Um método de extração de teores fitodisponíveis de metais pesados em solos tratados com biossólidos foi desenvolvido, sendo a solução extratora utilizada composta pelos ácidos acético, cítrico, lático e oxálico em concentrações de 1,00; 0,72; 0,49 e 0,12 mol L -1 , respectivamente. Amostras de terra e plantas provenientes de 3 experimentos de campo que apresentavam tipo de solo, espécie vegetal cultivada e origem do biossólido diferentes foram utilizadas para testar o método. As correlações entre os teores de Cu, Ni, Pb e Zn removidos pela solução de ácidos orgânicos e os teores destes metais no tecido vegetal foram significativas (1 %). / Heavy metals phytoavailability in soils treated with biosolid is directly related with the solubilization process of these metals, which are predominantly present at the solid phase of the residue. Soluble complex formation between metals and organic acids liberated into the rhizosphere by plants and microorganisms, seems to have an important role at the solubilization, and consequently, at the heavy metals phytoavailability. It was not yet established an efficient extraction method to estimate phytoavailable concentrations of heavy metals, probably because the extractors generally used do not simulate the reactions that occurs close to the roots. The present study was done with the purpose of determining the composition of organic acids at rhizosphere of some vegetal species cultivated on the presence of biosolid, to study solubilization potential of heavy metals originated from the residue by these organic acids, and to test viability of using organic acids solution as extractors of phytoavailable heavy metals. Marandu grass, eucalyptus, sugar cane and corn were cultivated in sand or sand treated with biossolid. Cromatographic analyzes were done in solutions samples collected from the hydroponics system used, identifying the acetic, citric, lactic and oxalic acids, in the percentages 43.21, 31.13, 20.41 and 5.25 respectively, calculated in relation to the determined total. Concentrations of acetic, lactic, and oxalic acids within the collected extract, significantly correlated with the concentrations of Cd, Cu, Ni and Zn with the shoot of the studied vegetal species. Citric acid concentration did not correlated with any of the studied metals. Considering the concentration sum of the studied acids, it was achieved a correlation with Cd, Cr, Cu, Ni e Zn concentration in the shoot of the plants, what makes evident the effect of these metals at heavy metal phyoavailability. The kinetics study of solubilization reaction of Cd, Cu, Cr, Ni, Pb and Zn in soils treated with biosolid was done using a solution of acetic, citric, lactic, and oxalic acids, prepared in such a way that a final concentration of 0,05 e 0,10 mol L -1 was obtained. The extraction was done following the batch equilibrium method. The solution of organic acids with a concentration of 0,10 mol L -1 extracted more quantities of Cu, Cr, Ni and Zn than the 0,05 mol L -1 solution. The solubilization kinetics presented two phases: an initial one with fast liberation of metals, followed by a slower one tending for equilibrium. The higher velocity constants were observed for Ni and Zn, followed by Cu, Cr and Pb. The values calculated for the labile pool did not exceeded 15% of the present metals total. The percentage concerned to this pool related to the total, followed the order: Zn > Cu @ Ni > Cr @ Pb. An extraction method of heavy metals phytoavailable in soil treated with biosolid was developed, and the extractor solution used was composed by acetic, citric, lactic, and oxalic acids in concentrations of 1,00; 0,72; 0,49 and 0,12 mol L -1 , respectively. Samples of soils and plants from 3 (three) field experiments, which presented different type of soil, cultivated vegetal specie, and biosolid origin, were used to test the method. Correlation between Cu, Ni, Pb and Zn concentration removed by the solution of organic acids, and the concentration of these metals within the vegetal tissue were significant (1 %).

A determinação de elementos tóxicos em solo é uma importante ferramenta para monitorar a poluição ambiental. O cádmio é um elemento potencialmente tóxico às plantas, aos animais superiores e ao homem, podendo estar presente no ambiente, natural ou antropicamente, em condição de causar toxicidade. Pouco se conhece sobre o comportamento desse cátion nos solos tropicais muito intemperizados, e que apresentam atributos diferentes daqueles de regiões temperadas onde a maioria dos estudos têm sido conduzidos. Esse trabalho teve como objetivos verificar: a) a extratabilidade do cádmio nas amostras de solos naturais com extratores químicos convencionais como o DTPA-TEA pH 7,3, o Mehlich 3 e o CaCl2 0,01 mol L -1 relacionando-a com os diversos atributos dos solos, b) a potencialidade de extração do Cd pelo uso de soluções de ácidos orgânicos de baixo peso molecular (acético, cítrico e oxálico) que foi comparada com os extratores convencionais e c) a extratabilidade do cádmio em amostras de solos provenientes de regiõescontaminadas usando-se os mesmos extratores convencionais e orgânicos. As relações solo:solução utilizadas foram para Mehlich 3, DTPA-TEA pH 7,3, CaCl2 0,01 mol L -1 , ácido acético 57 mmol L -1 , ácido cítrico 2,1 mmol L -1 e ácido oxálico 10,4 mmol L -1 , respectivamente, as seguintes: 2,5:25; 10:20; 1:10; 10:20; 10:20 e 10:20 (g/ml). Foram feitas análises de regressão simples obtendo-se correlação negativa significativa (r = 0,73) entre o Cd extraído pelo DTPA-TEA pH 7,3 e o teor de argila dos solos naturais, entre o extrator e o teor de ferro livre (r = 0,65) e entre o extrator e o pH em KCl 1 mol L -1 (r = 0,47). Análises de regressão múltipla também foram feitas obtendo-se correlação negativa significativa (R 2 = 0,528) entre o DTPA-TEA pH 7,3 e o teor de argila. O extrator DTPA-TEA pH 7,3 foi o que apresentou diferença significativa e maior extratabilidade de Cd em solos naturais. As soluções de CaCl2 0,01 mol L -1 e os ácidos orgânicos extraíram pequena quantidade de Cd dos solos naturais. Para as amostras de solos contaminados a solução de ácido acético foi a que mostrou maior potencialidade de extração do elemento. / The determination of toxic elements in the soil is an important tool for monitoring environmental pollution. Cadmium is an element potentially toxic to the plants, superior animals and man. Not too much is known about of this cation the behaviour in the very weathered tropical soils which present different attributes from the areas where most of the studies has ben conducted. The objectives of this paper was to verify: a) the extractability of cadmium in natural and contaminated soil samples with the addition of chemical extractants DTPA-TEA pH 7,3, MEHLICH 3 and CaCl2 0,01 mol L -1 and relate the amount extracted with different soil attributes, b) the extractability potential of three low-molecular- weight organic acids (acetic, citric and oxalic acids) and compare to the conventional extractants and c) the extratibility of cadmium in soil samples from polluted areas with the same conventional and organic extractants. The> soil:solution ratios used for Mehlich 3, DTPA-TEA pH 7,3, CaCl2 0,01 mol L -1 , acetic acid 57 mmol L -1 , citric acid 2,1 mmol L -1 and oxalic acid 10,4 mmol L -1 , were respectively, the following: 2,5:25; 10:20; 1:10; 10:20; 10:20 and 10:20 (m/v). Simple linear regression analysis showed negative correlations (r = -0,73) just for DTPA-TEA pH 7,3 extractable Cd and soil clay content, and free Fe content (r = -0,65) and pH in KCl solution (r = -0,47). Multiple regression analysis was also performed and a significant negative correlations (R 2 = 0,528) obtained just for DTPA-TEA pH 7,3 extractable cadmium and soil clay content. The DTPA-TEA pH 7,3 extractant presented the highest results for Cd extratability in natural soils. The CaCl2 0,01 mol L -1 and organic acids solutions extracted very low amount of Cd in natural soils, almost always near the detection limit of the equipament. For contaminated soil samples the acetic acid solution presented the biggest extraction potential for Cd.

Em solos tratados com lodo de esgoto, a concentração de metais pesados em solução é baixa e a cinética de dissolução é lenta. Com isso, as reações de complexação que ocorrem na rizosfera passam a ser importantes para a fitodisponibilidade destes metais. Estudos recentes demonstraram que ácidos orgânicos liberados por raízes, como acético, cítrico, láctico, oxálico e tartárico, são importantes agentes complexantes e, conseqüentemente, fitodisponibilizadores de metais pesados. Soluções de ácidos acético, cítrico, lático, oxálico e tartárico, nas concentrações: 0,4; 0,6; 0,8 e 1,00 mol L-1 foram utilizadas para extrair Cd, Cu, Cr, Ni, Zn e Pb de amostras de um LATOSSOLO VERMELHO AMARELO Distrófico (LVAd) e de um LATOSSOLO VERMELHO Eutroférrico (LVef) tratados com doses de 0, 40 e 80 Mg ha-1 de lodo de esgoto. Nas mesmas amostras foram cultivadas plantas de arroz, pelo método de Neubauer. Os teores de metais pesados nas plantas, colhidas 18 dias após a germinação, foram correlacionados com os teores extraídos pelas diferentes soluções dos ácidos orgânicos. Os resultados mostraram que a fitodisponibilidade de Cu e Zn pode ser estimada por todos os ácidos estudados e em todas as concentrações. Os ácidos lático e tartárico, em concentrações de 0,4 até 1 mol L-1, apresentaram potencial para estimar a disponibilidade Ni, e o ácido oxálico, em todas as concentrações, para Cr. Com aplicação de doses de lodo de esgoto de até 80 Mg ha-1 (base seca) não é prevista a disponibilidade de Cd e Pb, por isso não foi possível avaliar a eficiência dos ácidos orgânicos na previsão da fitodisponibilidade desses elementos. / In soils treated with sewage sludge, heavy metals concentration in solution is low and solubilization kinetics is slow. So, soluble complex formation that occurs in the rhizosphere became to be important in plant availability of these metals. Recent studies showed that organic acids released by roots, like acetic, citric, lactic, oxalic and tartaric acids, are important agents of solubilization and consequently can change heavy metals availability. Solution of acetic, citric, lactic, oxalic and tartaric acids in concentrations: 0.4, 0.6, 0.8, and 1.0 mol L-1 were used to extract Cd, Cu, Cr, Ni, Pb and Zn of soil samples treated with sewage sludge, in levels of 0, 40 and 80 Mg ha-1. Soils samples were also used in a Neubauer essay with rice as test plant. Heavy metals concentrations in the plants harvested 18 days after the germination were correlated with metals quantities removed from the different organic acid solutions. The results showed that Cu and Zn plant availability can be evaluated with all tested acids in all tested concentrations. Lactic and tartaric acids, 0.4 to 1.0 mol L-1, can be used to evaluate availability of Ni and oxalic acid, in all concentrations, can be a Cr extractant. . In the treatment receiving 80 Mg ha-1 of sewage sludge the Cd and Pb were not available as a result it was not possible to determine the organic acids efficiency to evaluate the bioavailability of these elements.

A determinação de elementos tóxicos em solo é uma importante ferramenta para monitorar a poluição ambiental. O cádmio é um elemento potencialmente tóxico às plantas, aos animais superiores e ao homem, podendo estar presente no ambiente, natural ou antropicamente, em condição de causar toxicidade. Pouco se conhece sobre o comportamento desse cátion nos solos tropicais muito intemperizados, e que apresentam atributos diferentes daqueles de regiões temperadas onde a maioria dos estudos têm sido conduzidos. Esse trabalho teve como objetivos verificar: a) a extratabilidade do cádmio nas amostras de solos naturais com extratores químicos convencionais como o DTPA-TEA pH 7,3, o Mehlich 3 e o CaCl2 0,01 mol L -1 relacionando-a com os diversos atributos dos solos, b) a potencialidade de extração do Cd pelo uso de soluções de ácidos orgânicos de baixo peso molecular (acético, cítrico e oxálico) que foi comparada com os extratores convencionais e c) a extratabilidade do cádmio em amostras de solos provenientes de regiõescontaminadas usando-se os mesmos extratores convencionais e orgânicos. As relações solo:solução utilizadas foram para Mehlich 3, DTPA-TEA pH 7,3, CaCl2 0,01 mol L -1 , ácido acético 57 mmol L -1 , ácido cítrico 2,1 mmol L -1 e ácido oxálico 10,4 mmol L -1 , respectivamente, as seguintes: 2,5:25; 10:20; 1:10; 10:20; 10:20 e 10:20 (g/ml). Foram feitas análises de regressão simples obtendo-se correlação negativa significativa (r = 0,73) entre o Cd extraído pelo DTPA-TEA pH 7,3 e o teor de argila dos solos naturais, entre o extrator e o teor de ferro livre (r = 0,65) e entre o extrator e o pH em KCl 1 mol L -1 (r = 0,47). Análises de regressão múltipla também foram feitas obtendo-se correlação negativa significativa (R 2 = 0,528) entre o DTPA-TEA pH 7,3 e o teor de argila. O extrator DTPA-TEA pH 7,3 foi o que apresentou diferença significativa e maior extratabilidade de Cd em solos naturais. As soluções de CaCl2 0,01 mol L -1 e os ácidos orgânicos extraíram pequena quantidade de Cd dos solos naturais. Para as amostras de solos contaminados a solução de ácido acético foi a que mostrou maior potencialidade de extração do elemento. / The determination of toxic elements in the soil is an important tool for monitoring environmental pollution. Cadmium is an element potentially toxic to the plants, superior animals and man. Not too much is known about of this cation the behaviour in the very weathered tropical soils which present different attributes from the areas where most of the studies has ben conducted. The objectives of this paper was to verify: a) the extractability of cadmium in natural and contaminated soil samples with the addition of chemical extractants DTPA-TEA pH 7,3, MEHLICH 3 and CaCl2 0,01 mol L -1 and relate the amount extracted with different soil attributes, b) the extractability potential of three low-molecular- weight organic acids (acetic, citric and oxalic acids) and compare to the conventional extractants and c) the extratibility of cadmium in soil samples from polluted areas with the same conventional and organic extractants. The> soil:solution ratios used for Mehlich 3, DTPA-TEA pH 7,3, CaCl2 0,01 mol L -1 , acetic acid 57 mmol L -1 , citric acid 2,1 mmol L -1 and oxalic acid 10,4 mmol L -1 , were respectively, the following: 2,5:25; 10:20; 1:10; 10:20; 10:20 and 10:20 (m/v). Simple linear regression analysis showed negative correlations (r = -0,73) just for DTPA-TEA pH 7,3 extractable Cd and soil clay content, and free Fe content (r = -0,65) and pH in KCl solution (r = -0,47). Multiple regression analysis was also performed and a significant negative correlations (R 2 = 0,528) obtained just for DTPA-TEA pH 7,3 extractable cadmium and soil clay content. The DTPA-TEA pH 7,3 extractant presented the highest results for Cd extratability in natural soils. The CaCl2 0,01 mol L -1 and organic acids solutions extracted very low amount of Cd in natural soils, almost always near the detection limit of the equipament. For contaminated soil samples the acetic acid solution presented the biggest extraction potential for Cd.

A fitodisponibilidade de metais pesados em solos tratados com biossólido está relacionada com o processo de solubilização destes metais presentes, predominantemente, na fase sólida do resíduo. A formação de complexos solúveis entre metais e ácidos orgânicos liberados na rizosfera por plantas e microorganismos parece ter um importante papel na solubilização e, consequentemente, na fitodisponibilidade dos metais pesados. Ainda não foi estabelecido um método de extração eficiente para estimar teores fitodisponíveis destes metais, provavelmente por que os extratores geralmente utilizados não simulam reações que ocorrem próximas às raízes. O presente estudo foi realizado com o objetivo de determinar a composição de ácidos orgânicos na rizosfera de algumas espécies vegetais cultivadas na presença de biossólidos, estudar o potencial de dissolução de metais pesados originários de biossólidos por estes ácidos orgânicos e testar a viabilidade do uso de soluções de ácidos orgânicos como extratores de metais pesados fitodisponíveis. Braquiária, eucalipto, cana de açúcar e milho foram cultivadas em areia ou areia tratada com biossólido. Análises cromatográficas foram realizadas em amostras coletadas do sistema hidropônico utilizado, identificando-se os ácidos acético, cítrico, lático e oxálico, respectivamente nas porcentagens de 43,21; 31,13; 20,41 e 5,25 calculadas em relação ao total de ácidos determinado. Os teores de ácido acético, lático e oxálico no extrato correlacionaram com os teores de Cd, Cu, Ni e Zn na parte aérea das espécies vegetais estudadas. O teor de ácido cítrico não correlacionou com nenhum dos metais estudados. Considerando-se a somatória dos teores dos ácidos estudados obteve-se correlação com o teor de metais pesados nas plantas, evidenciando o efeito destes ácidos na fitodisponibilidade dos metais. O estudo de cinética foi realizado utilizando-se solução dos ácidos acético, cítrico, lático e oxálico, preparada de modo a se obter concentração final igual a 0,05 e 0,10 mol L -1 . A extração foi feita segundo o método do equilíbrio de batch. A solução de ácidos orgânicos de concentração 0,10 mol L -1 extraiu maiores quantidades dos metais. A cinética de solubilização apresentou duas fases: uma inicial com rápida liberação dos metais, seguida de outra mais lenta tendendo ao equilíbrio. As constantes de velocidade mais altas foram observadas para Ni e Zn, seguidos de Cu, Cr e Pb. Os valores para o reservatório lábil não ultrapassaram 15% do total de metais presentes. A porcentagem referente ao reservatório lábil do metal em relação ao total presente obedeceu a ordem: Zn > Cu @ Ni > Cr @ Pb. Um método de extração de teores fitodisponíveis de metais pesados em solos tratados com biossólidos foi desenvolvido, sendo a solução extratora utilizada composta pelos ácidos acético, cítrico, lático e oxálico em concentrações de 1,00; 0,72; 0,49 e 0,12 mol L -1 , respectivamente. Amostras de terra e plantas provenientes de 3 experimentos de campo que apresentavam tipo de solo, espécie vegetal cultivada e origem do biossólido diferentes foram utilizadas para testar o método. As correlações entre os teores de Cu, Ni, Pb e Zn removidos pela solução de ácidos orgânicos e os teores destes metais no tecido vegetal foram significativas (1 %). / Heavy metals phytoavailability in soils treated with biosolid is directly related with the solubilization process of these metals, which are predominantly present at the solid phase of the residue. Soluble complex formation between metals and organic acids liberated into the rhizosphere by plants and microorganisms, seems to have an important role at the solubilization, and consequently, at the heavy metals phytoavailability. It was not yet established an efficient extraction method to estimate phytoavailable concentrations of heavy metals, probably because the extractors generally used do not simulate the reactions that occurs close to the roots. The present study was done with the purpose of determining the composition of organic acids at rhizosphere of some vegetal species cultivated on the presence of biosolid, to study solubilization potential of heavy metals originated from the residue by these organic acids, and to test viability of using organic acids solution as extractors of phytoavailable heavy metals. Marandu grass, eucalyptus, sugar cane and corn were cultivated in sand or sand treated with biossolid. Cromatographic analyzes were done in solutions samples collected from the hydroponics system used, identifying the acetic, citric, lactic and oxalic acids, in the percentages 43.21, 31.13, 20.41 and 5.25 respectively, calculated in relation to the determined total. Concentrations of acetic, lactic, and oxalic acids within the collected extract, significantly correlated with the concentrations of Cd, Cu, Ni and Zn with the shoot of the studied vegetal species. Citric acid concentration did not correlated with any of the studied metals. Considering the concentration sum of the studied acids, it was achieved a correlation with Cd, Cr, Cu, Ni e Zn concentration in the shoot of the plants, what makes evident the effect of these metals at heavy metal phyoavailability. The kinetics study of solubilization reaction of Cd, Cu, Cr, Ni, Pb and Zn in soils treated with biosolid was done using a solution of acetic, citric, lactic, and oxalic acids, prepared in such a way that a final concentration of 0,05 e 0,10 mol L -1 was obtained. The extraction was done following the batch equilibrium method. The solution of organic acids with a concentration of 0,10 mol L -1 extracted more quantities of Cu, Cr, Ni and Zn than the 0,05 mol L -1 solution. The solubilization kinetics presented two phases: an initial one with fast liberation of metals, followed by a slower one tending for equilibrium. The higher velocity constants were observed for Ni and Zn, followed by Cu, Cr and Pb. The values calculated for the labile pool did not exceeded 15% of the present metals total. The percentage concerned to this pool related to the total, followed the order: Zn > Cu @ Ni > Cr @ Pb. An extraction method of heavy metals phytoavailable in soil treated with biosolid was developed, and the extractor solution used was composed by acetic, citric, lactic, and oxalic acids in concentrations of 1,00; 0,72; 0,49 and 0,12 mol L -1 , respectively. Samples of soils and plants from 3 (three) field experiments, which presented different type of soil, cultivated vegetal specie, and biosolid origin, were used to test the method. Correlation between Cu, Ni, Pb and Zn concentration removed by the solution of organic acids, and the concentration of these metals within the vegetal tissue were significant (1 %).

Em solos tratados com lodo de esgoto, a concentração de metais pesados em solução é baixa e a cinética de dissolução é lenta. Com isso, as reações de complexação que ocorrem na rizosfera passam a ser importantes para a fitodisponibilidade destes metais. Estudos recentes demonstraram que ácidos orgânicos liberados por raízes, como acético, cítrico, láctico, oxálico e tartárico, são importantes agentes complexantes e, conseqüentemente, fitodisponibilizadores de metais pesados. Soluções de ácidos acético, cítrico, lático, oxálico e tartárico, nas concentrações: 0,4; 0,6; 0,8 e 1,00 mol L-1 foram utilizadas para extrair Cd, Cu, Cr, Ni, Zn e Pb de amostras de um LATOSSOLO VERMELHO AMARELO Distrófico (LVAd) e de um LATOSSOLO VERMELHO Eutroférrico (LVef) tratados com doses de 0, 40 e 80 Mg ha-1 de lodo de esgoto. Nas mesmas amostras foram cultivadas plantas de arroz, pelo método de Neubauer. Os teores de metais pesados nas plantas, colhidas 18 dias após a germinação, foram correlacionados com os teores extraídos pelas diferentes soluções dos ácidos orgânicos. Os resultados mostraram que a fitodisponibilidade de Cu e Zn pode ser estimada por todos os ácidos estudados e em todas as concentrações. Os ácidos lático e tartárico, em concentrações de 0,4 até 1 mol L-1, apresentaram potencial para estimar a disponibilidade Ni, e o ácido oxálico, em todas as concentrações, para Cr. Com aplicação de doses de lodo de esgoto de até 80 Mg ha-1 (base seca) não é prevista a disponibilidade de Cd e Pb, por isso não foi possível avaliar a eficiência dos ácidos orgânicos na previsão da fitodisponibilidade desses elementos. / In soils treated with sewage sludge, heavy metals concentration in solution is low and solubilization kinetics is slow. So, soluble complex formation that occurs in the rhizosphere became to be important in plant availability of these metals. Recent studies showed that organic acids released by roots, like acetic, citric, lactic, oxalic and tartaric acids, are important agents of solubilization and consequently can change heavy metals availability. Solution of acetic, citric, lactic, oxalic and tartaric acids in concentrations: 0.4, 0.6, 0.8, and 1.0 mol L-1 were used to extract Cd, Cu, Cr, Ni, Pb and Zn of soil samples treated with sewage sludge, in levels of 0, 40 and 80 Mg ha-1. Soils samples were also used in a Neubauer essay with rice as test plant. Heavy metals concentrations in the plants harvested 18 days after the germination were correlated with metals quantities removed from the different organic acid solutions. The results showed that Cu and Zn plant availability can be evaluated with all tested acids in all tested concentrations. Lactic and tartaric acids, 0.4 to 1.0 mol L-1, can be used to evaluate availability of Ni and oxalic acid, in all concentrations, can be a Cr extractant. . In the treatment receiving 80 Mg ha-1 of sewage sludge the Cd and Pb were not available as a result it was not possible to determine the organic acids efficiency to evaluate the bioavailability of these elements.

An innovative sampling technique employing extractant impregnated membranes is presented for the selective sorption and stabilization of specific oxidation states of chromium. Polymer-based selective ion traps employing the extractants tricaprylmethylammonium chloride (Aliquat-336) and di-(2-ethylhexyl) phosphoric acid (DEHPA) were used for the selective removal and enrichment of the anionic forms of Cr(VI) and cationic forms of Cr(III), respectively. Results show Aliquat-336 and DEHPA effectively remove Cr(VI) and Cr(III) from aqueous solutions. Extraction efficiency is independent of source concentration from 1-50 ppm but is dependent upon time, pH of the source, ionic strength, extractant concentration, composition of source phase, and choice of stripping agent and stripping agent concentration. Optimum conditions for Cr(VI) and Cr(III) were determined to be 1 v/v% Aliquat-336 and 30 v/v% DEHPA; an extraction time of at least 3-5 days; source phase pH between 3-5; and 1 M NaOH/ 0.5 M HNO3 as stripping agent for Cr(VI) and Cr(III) species, respectively. Batch extraction efficiencies of 97 +/- 3 % were obtained for the optimal conditions. Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) was used for total chromium determination. UV-VIS spectrometry was used for Cr(VI) determination. Scanning Electron Microscopy revealed the physical structure of the polymeric supports and subsequent impregnation was evidenced by the SEM images. X-ray photoelectron spectroscopic results provided the elemental composition of the Versapor-450 membrane to be 71. 5% C, 7.0% O, 9.5% Cl and 12.0% N. The Whatman PP membrane was and 100.0 % C. Elemental composition of 1 v/v% Aliquat-336 on Versapor-450 and Whatman PP membrane was 92.3% C, 0.8% O, 3.6% N, and 3.3% Cl and 94.3% C, 3.3% N, and 2.4% Cl, respectively. Elemental composition of 30 v/v% DEHPA on Versapor-450 and Whatman PP membranes were 78.8% C, 3.4% P, 17.8% O and 76.3% C, 19.3% O, 4.4% P, respectively. Column studies under simulated groundwater conditions utilizing the extractant impregnated membranes showed no statistical difference in Cr(VI) recoveries from those obtained in batch experiments. Cr(III) extraction revealed a statistical difference in analyte recovery vs. batch experiments. This is attributed to the lowered pH and cationic interferences present in simulated groundwater. / Ph. D.