Active sulphide mine tailings impoundments as sources of contaminated drainage: controlling factors, methods of characterisation and geochemical constraints for mitigation

Low quality mine drainage from tailings facilities persists as one of the most significant global environmental concerns related to sulphide mining. Due to the large variation in geological and environmental conditions at mine sites, universal approaches to the management of mine drainage are not always applicable. Instead, site-specific knowledge of the geochemical behaviour of waste materials is required for the design and closure of the facilities. In this thesis, tailings-derived water contamination and factors causing the pollution were investigated in two coeval active sulphide mine sites in Finland: the Hitura Ni mine and the Luikonlahti Cu-Zn-Co-Ni mine and talc processing plant. A hydrogeochemical study was performed to characterise the tailingsderived water pollution at Hitura. Geochemical changes in the Hitura tailings were evaluated with a detailed mineralogical and geochemical investigation (solid-phase speciation, acid mine drainage potential, pore water chemistry) and using a spatial assessment to identify the mechanisms of water contamination. A similar spatial investigation, applying selective extractions, was carried out in the Luikonlahti tailings area for comparative purposes (Hitura low-sulphide tailings vs. Luikonlahti sulphide-rich tailings). At both sites, hydrogeochemistry of tailings seepage waters was further characterised to examine the net results of the processes observed within the impoundments and to identify constraints for water treatment. At Luikonlahti, annual and seasonal variation in effluent quality was evaluated based on a four-year monitoring period. Observations pertinent to future assessment and mine drainage prevention from existing and future tailings facilities were presented based on the results. A combination of hydrogeochemical approaches provided a means to delineate the tailings-derived neutral mine drainage at Hitura. Tailings effluents with elevated Ni, SO₄ ^2- and Fe content had dispersed to the surrounding aquifer through a levelled-out esker and underneath the seepage collection ditches. In future mines, this could be avoided with additional basal liners in tailings impoundments where the permeability of the underlying Quaternary deposits is inadequate, and with sufficiently deep ditches. Based on the studies, extensive sulphide oxidation with subsequent metal release may already initiate during active tailings disposal. The intensity and onset of oxidation depended on e.g. the Fe sulphide content of the tailings, water saturation level, and time of exposure of fresh sulphide grains. Continuous disposal decreased sulphide weathering in the surface of low-sulphide tailings, but oxidation initiated if they were left uncovered after disposal ceased. In the sulphide-rich tailings, delayed burial of the unsaturated tailings had resulted in thick oxidized layers, despite the continuous operation. Sulphide weathering and contaminant release occurred also in the border zones. Based on the results, the prevention of sulphide oxidation should already be considered in the planning of tailings disposal, taking into account the border zones. Moreover, even lowsulphide tailings should be covered without delay after active disposal ceases. The quality of tailings effluents showed wide variation within a single impoundment and between the two different types of tailings facilities assessed. The affecting factors included source materials, the intensity of weathering of tailings and embankment materials along the seepage flow path, inputs from the process waters, the water retention time in tailings, and climatic seasonality. In addition, modifications to the tailings impoundment may markedly change the effluent quality. The wide variation in the tailings effluent quality poses challenges for treatment design. The final decision on water management requires quantification of the spatial and seasonal fluctuation at the site, taking into account changes resulting from the eventual closure of the impoundment. Overall, comprehensive hydrogeochemical mapping was deemed essential in the identification of critical contaminants and their sources at mine sites. Mineralogical analysis, selective extractions, and pore water analysis were a good combination of methods for studying the weathering of tailings and in evaluating metal mobility from the facilities. Selective extractions with visual observations and pH measurements of tailings solids were, nevertheless, adequate in describing the spatial distribution of sulphide oxidation in tailings impoundments. Seepage water chemistry provided additional data on geochemical processes in tailings and was necessary for defining constraints for water treatment.

Estudo multivariado de solos urbanos da cidade de Teresina

The concentrations of Cu, Pb, Zn, Cr, Ni, Al, Mn and Fe were measured by atomic absorption spectrometry, of 19 topsoil samples collected in the Teresina city urban area to discriminate natural and anthropic contributions and identify possible sources of pollution. The average concentrations of Cu, Zn, Pb and Cr of the urban soils were 6.11, 8.56, 32.12 and 7,17 mg/kg-1, respectively. Statistical analysis techniques, such as principal component analysis (PCA) and hierarchical cluster analysis (HCA), were used to analyze the data. Mn, Ni and Cr levels were interpreted as natural contributions, whereas Pb, Zn and, in part, Cu were accounted for mainly by anthropic activities. High Pb levels were observed in the ancient avenues.

Análise estatística e optimização de perfis de redução termoprogramada (TPR)

The effect of operational variables and their interaction in TPR profiles was studied using a fractional factorial experimental design. The heating rate and the reducing agent concentration were found to be the most important variables determining the resolution and sensitivity of the technique. They showed opposite effects. Therefore, they should be manipulated preferentially in order to obtain optimized TPR profiles. The effect of sample particle size was also investigated. The tests were carried out within a Cu/Zn/Al2O3 catalyst used for the water-gas shift reaction that presented two distinct species of Cu2+ in TPR profiles.

Retenção de metais pesados em micélio de fungos micorrízicos arbusculares

This work evaluated the kinetics as well as the retention capacity of Cu, Zn, Cd, and Pb by arbuscular mycorrhizal fungi (AMF) mycelium. The metal retention is a fast process with Cu being retained 3, 30, and 60 times faster than Zn, Cd, and Pb, respectively. Metal retention capacity varied amongst the different tested AMF species and decreased in the following order: Cu>Zn>>Cd>Pb. The Glomus clarum mycelium showed the highest retention capacity for Cu, Cd and Pb, whereas Zn was mostly retained by Gigaspora gigantea mycelium. The simultaneous application of all tested metals in solution decreased Cu and Zn retention by AMF mycelium. The high retention capacity of Cu and Zn by mycelium of G. clarum and G. gigantea suggests a promising use of these isolates in phytoremediation.

Caracterização dos níveis de elementos químicos em solo, submetido a diferentes sistemas de uso e manejo, utilizando espectrometria de fluorescência de raios-x por energia dispersiva (EDXRF)

This study aimed to evaluate the chemical elements levels in soil, submitted to different management systems and use by the Energy Dispersive X-Ray Fluorescence Spectrometry - EDXRF. The systems were T1 - agro forestry (SAF), T2 - Native Field (CN), T3 - Native Forest (NM), T4 - Tillage Forest (PF); T5 - conventional tillage system (SPC) and T6 - System tillage (NT). Samples were collected at 0-10 and 10-20 cm, dried and ground for analysis in EDX-720. The soil showed no difference in the average concentrations of chemical elements analyzed in the profiles, but the systems presented different concentrations of metal elements, and T3 had the highest K, Ca and Zn at 0-10 cm and higher contents of K, Ca, Cu, Zn and Mn in the layer of 10-20 cm.

Desenvolvimento de microcélula eletroquímica para estudos de microrregiões

The construction and optimization of a device that can be applied to electrochemical studies in flat micro regions are described. This was developed as an attempt to study small regions of metallic samples, whose properties may differ completely from its macroscopic behavior and for studies in highly resistive medium. Some results were obtained for individual grains of polycrystalline samples, welded regions, pure copper, platinum, glassy carbon, single crystals of Cu-Zn-Al alloy, and steel in biodiesel without electrolyte intentionally added. The device showed to be useful for the proposed purpose, allowing to be automated and has potential possibilities of other applications.

Synthesis, characterization and thermal behaviour on solid pyruvates of some bivalent metal ions

Solid state M-L compounds, were M stands for bivalent Mn, Fe, Co, Ni, Cu, Zn and L is pyruvate, have been synthesized. Thermogravimetry and derivative thermogravimetry (TG/DTG), differential scanning calorimetry (DSC), X-Ray powder diffractometry, infrared spectroscopy, elemental analysis, and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, ligand denticity, and thermal decomposition of the isolated compounds.

Conteúdo e exportação de micronutrientes em acácia-negra (Acacia Mearnsii De Wild.) procedência batemans bay (Austrália)

O objetivo do presente trabalho foi estimar o conteúdo e a exportação de micronutrientes (Mn, B, Cu, Zn e Fe) e o Na nos diferentes componentes de árvores de um povoamento de acácia-negra (Acacia mearnsii De Wild.), procedência australiana Batemans Bay, com 2,4 anos de idade, em Butiá-RS (Brasil). A biomassa total estimada foi de 36.155 kg/ha, apresentando distribuição de 46,0, 20,0, 19,5, 12,0 e 3,0%, na madeira do lenho, nas folhas, nos galhos vivos, na casca e nos galhos mortos, respectivamente. A proporção de micronutrientes acumulados na biomassa dos componentes da árvore foram 43,76% nas folhas, 26,94% na madeira do tronco, 19,56% nos galhos vivos, 7,21% na casca e 2,54% nos galhos mortos. A quantidade estimada de micronutrientes contidos na biomassa acima do solo foi 10,4 kg/ha, acumulados da seguinte forma: Na (58,84%), Fe (21,79%), Zn (9,16%), B (4,09%), Mn (4,59%) e Cu (1,54%). A casca e a madeira do lenho acumulou Na (21,47%), Fe (6,71%), Mn (2,11%), Zn (1,66%), B (1,58%) e Cu (0,63%). A copa (folhas e galhos vivos e mortos) acumularam Na (37,36%), Fe (15,07%), Zn (7,49%), B (2,53%), Mn (2,48%) e Cu (0,91%). A exploração intensiva de áreas com a procedência Batemans Bay gera suspeitas de possíveis ocorrências de deficiências nutricionais de Na nas rotações futuras, tornando necessário o emprego de fertilizantes para manter a produtividade do sítio.

Eficiência do uso de micronutrientes e sódio em três procedências de acácia-negra (Acacia mearnsii De Wild.)

Objetivou-se avaliar a eficiência nutricional de micronutrientes (Mn, B, Cu, Zn e Fe) e Na nos diferentes componentes das árvores de três procedências de acácia-negra (Acacia mearnsii), com 2,4 anos de idade, plantadas em Butiá-RS (Brasil). As procedências selecionadas foram Lake George, Bodalla e Batemans Bay. Constatou-se grande variação na eficiência nutricional entre as procedências. A Lake George, além de acumular maior biomassa total, foi também a mais eficiente na utilização dos nutrientes na produção de biomassa total das árvores. No entanto, a Bodalla mostrou ser a procedência mais eficiente no uso dos nutrientes para produção de biomassa da casca e da madeira.

Avaliação da utilização de composto orgânico produzido a partir dos resíduos de fábrica de celulose quanto aos níveis de organoclorados e metais

Lodos gerados em Estações de Tratamento de Efluentes de fábricas de celulose kraft branqueada podem conter metais pesados e compostos organoclorados mesmo para fábricas que possuam sequências de branqueamento ECF (livres de cloro elementar), devido à presença de dióxido de cloro. Neste trabalho, buscou-se avaliar o potencial de absorção de metais pesados e compostos organoclorados (PCDD e PCDF) por Brassica juncea, utilizando como substrato o composto orgânico constituído por lodo biológico de uma Estação de Tratamento de Efluentes por lodos ativados misturado com cascas de eucalipto de uma fábrica de celulose brasileira. As plantas de Brassica juncea foram cultivadas em vasos de 0,63 dm³ em casa de vegetação, durante 73 dias. Os seguintes parâmetros foram monitorados no substrato e nas plantas: Fe, Mn, Pb, Ni, Cu, Zn, Cr, Cl-, carbono orgânico total e AOX (compostos organo-halogenados adsorvíveis). Os níveis de metais pesados presentes no solo após a aplicação do composto ficaram dentro de faixas permissíveis da legislação brasileira para aplicação de composto orgânico para uso agrícola. Traços de PCDD e PCDF foram encontrados no substrato em concentrações menores do que 0,5 ng I-TEQ/kg (ppt). Tais valores ficaram abaixo de 17 ng I-TEQ/kg, considerado o limite mais exigente de qualidade de compostos adotados na Alemanha e no Canadá.

Caracterização e biodigestão anaeróbia dos dejetos de caprinos

Quantificar e caracterizar os dejetos gerados por cabras Saanen em quatro categorias de idade e alimentadas com três dietas e na seqüência, e promover a biodigestão anaeróbia dos dejetos constituíram os objetivos deste trabalho. Para a produção de dejetos, foram utilizadas 36 cabras Saanen, com idades entre 2 e 4 (C1), 4 e 8 (C2), 8 e 12 (C3) e acima de 12 meses (C4), alimentadas com as dietas 1 (D1: 80% volumoso (Vol) e 20% concentrado (Con)); 2 (D2: 60% Vol e 40% Con) e 3 (D3: 40% Vol e 20% Con). Foram quantificadas as produções diárias de fezes e urina e seus teores em N, P, K, Ca, Mg, Na, Fe, Cu, Zn e Mn. Com a mistura das fezes e urina de todas as categorias, separadas segundo as dietas, foram abastecidos biodigestores batelada, com capacidade para 4 L de substrato em fermentação. A C1 apresentou menor (P<0,05) excreção de fezes (164,1 g de MS (massa seca)/animal por dia) e o menor consumo de alimento (362,2g MS (massa seca)/animal por dia). As maiores concentrações de N, P, K, Ca, Mg e K ocorreram nas fezes e urina geradas por cabras da C4 e alimentadas pela D3. O substrato preparado com dejetos oriundos da D3 apresentou 45% de redução nos teores de sólidos voláteis (SV). Os substratos preparados com dejetos obtidos de animais alimentados com a D3 produziram mais biogás (P<0,01) por kg de sólidos totais e SV adicionados.

Eficiência de utilização de água e nutrientes em plantas de feijão-de-corda irrigadas com água salina em diferentes estádios de desenvolvimento

O objetivo deste trabalho foi investigar os efeitos do uso de água salina em diferentes estádios de desenvolvimento de plantas de feijão-de-corda sobre a eficiência de utilização de água e de nutrientes. O experimento foi conduzido no campo e obedeceu ao delineamento em blocos ao acaso, com cinco tratamentos e cinco repetições. Os tratamentos empregados foram: T1 - água de poço com condutividade elétrica (CEa) de 0,8 dS m-1 durante todo o ciclo; T2 - água salina (CEa de 5,0 dS m-1) durante todo o ciclo; T3, T4 e T5 - água salina de 0 a 22 dias após o plantio (DAP), de 23 a 42 DAP e de 43 a 62 DAP, respectivamente. As plantas dos tratamentos T3, T4 e T5 foram irrigadas com água de poço nas demais fases do ciclo. Aos 8; 23; 43 e 63 DAP, as plantas foram colhidas e determinaram-se a matéria seca total e de grãos, a eficiência no uso da água, considerando a produção de matéria seca total (EUA P) e a produção de grãos (EUA GR), e a eficiência de utilização de nutrientes (K, Ca, N, P, Fe, Cu, Zn e Mn). A aplicação de água salina durante todo o ciclo (T2) reduziu a EUA P e a EUA GR, enquanto a aplicação de água na fase inicial do ciclo (T3) reduziu a EUA GR e a eficiência de utilização da maioria dos nutrientes. Por outro lado, a irrigação com água salina dos 23 aos 42 DAP (T4) e dos 43 aos 62 DAP (T5) não afetou as eficiências nos usos de água e de nutrientes.

Spatial variability of yield and other parameters associated with pear trees

In the last few years, precision agriculture has become commonly used with many crops, particularly cereals, and there is also interest in precision horticulture. Pear is a seasonal fruit and well appreciated by Brazilian people, although it is mostly imported. Brazilian farmers are nowadays trying to increase pear production. Thus, this research aimed at mapping the yield of pear trees in order to study the spatial variability of yield as well as its comparison with spatial variability of soil and plant attributes. The experimental field had 146 pear trees, variety 'Pêra d'água', distributed on a 1.24 ha. Four harvests were performed according to the fruit ripening and from each tree; only the ripe fruits were harvested. In each harvest, all the fruits were weighed and the total yield was obtained based on the sum of each harvest. The soil attributes analyzed were P, K, Ca, Mg, pH in CaCl2, C, Cu, Zn, Fe, Mn and base saturation, and the plant attributes were fruit length, diameter and yield. Yield had low correlation with soil and plant attributes. An index of spatial variability was suggested in this study and helped in classifying levels of spatial dependence of the various soil and plant attributes: very low (fruit length); low (P, fruit diameter), medium (Mg, pH, Cu, Zn, Fe), high (Ca, K, base saturation and yield), and very high (Mn and C).

Nutrient loss in composting of agroindustrial residues

The management of composting may influence the characteristics of the produced compounds. The experiment used three frequencies of plowing, combined with the conditions: with and without coverage of the composting patio, with and without the use of commercial inoculant, resulting in 12 furrows, installed on the Experimental Center of Agricultural Engineering (NEEA), of the STATE UNIVERSITY OF WEST PARANÁ (UNIOESTE), Campus of Cascavel city - state of Paraná (PR), in Brazil. The waste and quantities used in kg were: corn cob (7.5); hatchery residue (5); floater sludge (31); ash (1); wheat cleaning residue (120); wheat pre-cleaning residue (120); corn peel (7.5); solid fraction of wash trucks used to transport chickens (2); solid fraction of pig manure (1) and coal (5), totaling 300kg of natural matter. The aim of this study was to evaluate the influence of plowings, patio coverage and inoculation in losses of N, P, K, Ca, Mg, Na, Cu, Zn, Mn, Fe. The furrows plowed three times a week in the first month showed significant higher losses of N (p<0.05). The coverage of the composting patio influenced significantly the losses of N, K, Mg and Na (p<0.05). The produced compounds had a high agronomic value in relation to macro and micronutrients. It is recommended the use of patio coverage and plowing twice a week in the first month and once a week in the subsequent months for a compound with higher concentrations of nutrients.

Pedological characterization and land use and occupation: influences on water quality in a watershed located in the zona da mata (MG)

In order to verify the influence of class and use and occupation of land on water quality, it was performed the characterization and analyzes of land use and monitoring of seven springs inserted in a watershed located in the rural of Viçosa city - Minas Gerais (MG) state, in Brazil. Through soil analyzes, carried out in five different profiles, it was possible to identify three distinct pedological classes: Argisol, Cambisol and Latosol. Furthermore, the concentrations of Fe, Mn, Cu, Zn, Cr, Cd, Pb and Ni were identified in each of the horizons in the considered profiles. Water samples were collected and analyzed monthly, over eight months, twenty two parameters of water quality. Comparing the results of each survey, it was possible to identify a relation between water quality and land use in the round of the springs, considering color, BOD, DO, E. coli and Mn as the most affected parameters, influenced mainly by soil characteristics and the presence of a large percentage of pasture in the study area.