Barytes (the naturally occurring BaSO4) is used as the standard densification agent in drilling fluids world-wide. It increases the density of the drilling fluids for control of formation pressures. It has been highlighted as a major source of toxic heavy metals input in the oil and gas industry. Large scale use in the offshore oil well drilling operations and subsequent discharges of spent drilling fluids containing barytes to the marine environment have raised concerns regarding the potential for bioaccumulation in marine biota of the toxic heavy metals and the possible human health risks. Various analytical and biological aspects of barytes regarding chemistry, analytical methodology, toxicity and heavy metal bioavailability have been thoroughly investigated in this study. Electron probe microanalysis (EPMA) confirms the presence of a number of minerals including barite, galena, anglesite, pyrite, sphalerite, zincite, quartz, barium feldspar, hematite, anhydrite, orthoclase, silicates, mixed minerals in barytes. Quantitative strontium and calcium as part of the crystal lattice whereas other trace heavy metals occur as associated minerals. Image analysis shows that the bulk of barium in barytes corresponds to the mineral barite (BaSO4), however, a small quantity of barium was found to be associated with silicon which confirmed the presence of barium feldspar. The presence of toxic heavy metals such as Cu, Ni, V, Co, Cr, Cd, Bi, Ti, Hg, Te, Sn, Sb, As etc. in barytes is likely to be as inclusions or substitutions in sulphide minerals associated with barite. Mineralogical studies suggest that barytes is not the traditionally inert BaSO4 but, rather, a potentially toxic substance due to its associated toxic heavy metal impurities. Comparative studies on the performance of chemical dissolution procedures such as sodium carbonate fusion, aqua regia digestion, aqua regia /HF digestion and a non-destructive technique, X-ray fluorescence spectrometry shows that sodium carbonate fusion procedure is the best method for the determination of barium in different types of barytes. DTPA and EDTA extractibilities for barium at pHs 12.6 and 10.8 respectively (25oC) were found to be low even though predictions based on thermodynamic data had suggested that BaSO4 should be soluble.

M. Tech. (Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology| / The co-existence of organic acids and toxic heavy metals in natural water creates harmful effects on human, plants and animals. Therefore, it is necessary to treat organic acids and toxic heavy metal contaminated wastewater prior to its discharge to the environment. The aim of this study was to apply co-treatment of industrial wastewater containing citric acid and toxic heavy metals in single and binary systems using photocatalysis process. The hydrothermal method was used to synthesise dandelion-like TiO2 structures. Modifications of the dandelion-like TiO2 by deposition of gold nanoparticles and immobilisation on calcium alginate were done using deposition precipitation and one-step encapsulation methods, respectively. Dandelion-like TiO2 and dandelion-like TiO2 immobilised on calcium alginate (Alg/TiO2) were used as photocatalysts for Cr(VI), Hg(II) and citric acid removal from water. The results showed that the production of dandelion-like TiO2 structures strongly depends on the reaction time and synthesis temperature as key process parameters. The characterisation of the dandelion-like TiO2 by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) and Brunauer-Emmett-Teller (BET) revealed the crystal structure, morphology, chemical composition and surface area. It was found that the efficiency of photocatalytic process depends on the type of pollutants, initial pH of the solution, photocatalyst dosage, contact time, substrate initial concentration, UV wavelength and light intensity. The reduction efficiency of Cr(VI) ion and citric acid increased with decreasing the initial pH values and initial concentration. On the other hand, Hg(II) reduction efficiency increased with increasing the initial pH values and initial concentration. In a binary system, the reduction of Cr(VI) and Hg(II) was found to be faster than in the single and ternary systems. The relationship of the chemical reaction rate of Cr(VI), Hg(II) and citric acid were expressed by the pseudo-first-order kinetic equation. Addition of ferric ions to Cr(VI)-citric acid complex and Hg(II)-citric acid complex enhanced the reduction of Cr(VI) and Hg(II), a complete reduction was accomplished within 30 and 60 minutes (min) of irradiation time, respectively. The reduction efficiency of both Cr(VI) and Hg(II) in the presence of citric acid in a solution was still significant after four times of Alg/TiO2 reuse. These results indicated that the UV/TiO2 photocatalysis process can be considered as a suitable method to reach a complete reduction of Cr(VI) and Hg(II) in the presence of citric acid in a solution.

Pollution from industrial sources, such as leather tanneries, jewelry factories, car batteries, and construction refuse, has been linked to increased concentrations of toxic heavy metals in rivers in Costa Rica. This study focused on the concentrations of arsenic, cadmium, chromium, copper, nickel, and lead in sediment and water in Rio Baru, Costa Rica, which has not been previously studied. The concentrations in Rio Baru were compared to two controls and the Environmental Protection Agency toxicity limits to determine pollution levels. Inductively coupled plasma mass spectrometry was utilized to determine the concentrations of heavy metals in water and sediment samples from Rio Baru, Terciopelo, and Rio Tarcoles. Watershed analysis for Rio Baru was expected to reveal mostly agricultural sources of contaminants. Rio Baru was predicted to have levels of inorganic heavy metals between Rio Tarcoles and Terciopelo, with Tarcoles containing the highest levels. As, Cr, and Ni in Rio Baru were between unpolluted levels in Terciopelo and polluted levels in Rio Tarcoles, but Rio Baru had lower concentrations of Cu and Pb than both Rio Tarcoles and Terciopelo. Analysis of watersheds determined that Rio Baru’s watershed contained intermediate ratios of human development and agricultural sources of pollution. Further comparisons of watershed size with total dissolved sediment levels found a positive linear relationship, indicating a portion of differences in heavy metal concentrations were due to watershed sizes. Concentrations of heavy metals in Rio Baru’s water were below toxic limits for drinking water and placed Rio Baru within “good” sediment levels for As, Cd, Cr, Ni, and Pb. As geochemistry and proximity to industrial sources was not accounted for in methodology, further research would be necessary for determination of natural concentrations of heavy metals in Rio Baru.

Pouco se conhece sobre a origem das matérias primas utilizadas na fabricação de micronutrientes. Muitos fertilizantes podem conter em sua matéria prima nutrientes em formas indisponíveis para as plantas que limitam a produção. Fontes secundárias de origem industrial vêem sendo utilizadas para fabricação de fertilizantes no Brasil há muito tempo, somente a poucos anos a legislações e órgãos ambientais tem questionado a origem destas matérias primas quanto a contaminação por metais pesados tóxicos e sua eficiência agronômica como fonte de micronutrientes. Neste sentido foi desenvolvido estudo a fim de obter informações básicas dos materiais secundários como origem, composição elementar, composição mineralógica, disponibilidade de metais pesados tóxicos em extratores ácidos (Agua Régia, 3050B, HCl) disponibilidade de Zn e Cu em extratores solúveis (AC 2% e CNA) efeitos da aplicação de onze materiais secundários em plantas de arroz em dois cultivos, divididos em nove fontes fornecedoras exclusivamente de zinco com composições mineralógicas diversas; fontes binárias contendo diferentes concentrações de zinco e cobre em cinco doses (0; 6; 9; 12; 18 kg ha-1 Zn) e três materiais secundários fontes de cobre contendo concentrações variadas de cobre em cinco doses (0;1,5;3,0;4,5 e 6,0 kg.ha-1 Cu) avaliando a eficiência em fornecer nutrientes e potencial de contaminação do solo e planta. Conclui-se que materiais secundários tem grande variabilidade quanto à composição mineralógica e elementar, mesmo quando originados em processos similares. O método AC 2% é ineficiente para materiais com concentração de zinco superior a 59% e para matrizes com alta concentração de silicatos. As formas de Pb identificadas nos materiais secundários interferem na quantificação do elemento nos extratores utilizados; o método oficial 3050B subestima a concentração de Pb dependendo de sua matriz. A eficiência agronômica das fontes de Zn foi semelhante ou superior a fonte padrão no primeiro cultivo. A matriz das fontes Cinza de Zn I e Escória de Latão II apresentaram menor efeito residual e eficiência agronômica inferior à fonte padrão no segundo cultivo. As fontes binárias foram eficientes em disponibilizar cobre e zinco ao solo e planta em relação a suas respectivas misturas pró analise no primeiro cultivo de arroz. A fonte Escória de Latão III apresentou efeito residual inferior em relação a sua mistura pró analise na avaliação do IEA, para cobre e zinco, no segundo cultivo de arroz. Houve correlação significativa entre acumulo de nutrientes e os extratores CNA para o nutriente Cu e AC 2% para o nutriente Zn na fonte Escória de Latão III. A fonte Minério de Cu apresentou baixo desempenho em todos os parâmetros avaliados no primeiro cultivo, IER 17% e IEA -65%. Nos dois cultivos avaliados nenhum dos materiais influenciou os teores de metais pesados tóxicos nos no solo e planta. O extrator CNA não apresentou correlação significativa com o conteúdo de cobre acumulado na planta de arroz em dois cultivos. / Little is known about the origin of the raw materials used in manufacturing of micronutrients. Many fertilizers may contain in their raw materials, nutrients in unavailable forms to plants that limit production. Secondary sources of industrial origin see being used for the manufacture of fertilizers in Brazil long ago, only a few years legislation and environmental agencies have questioned the source of these raw materials for contamination by toxic heavy metals and their agronomic efficiency as a source of micronutrients. In this sense the study was designed to obtain basic information of secondary materials like elemental composition, mineralogical composition, availability of toxic heavy metals in different acid extractors (Aqua Regia, 3050B, HCl) availability of Cu and Zn in soluble extractors (AC 2% and CNA) effects of eleven secondary materials on rice in two consecutive crops, divided into nine zinc sources, with different mineralogical compositions, binary sources containing different concentrations of zinc and copper in five different doses (0, 6, 9, 12, 18 kg ha-1 Zn) and three secondary materials, source of copper in five doses (0, 1.5 , 3.0, 4.5 and 6.0 kg ha-1 Cu) evaluating efficiency in delivering nutrients and potential contamination of soil and plant. It\'s possible to conclude that secondary materials have great variability regarding the mineralogical and elemental composition, even when originated in similar processes. The AC 2% method is inefficient for materials with higher zinc concentration (>59%) and for matrices with high silicate. The various Pb related forms founded interfere with the quantification in the different used extractants; the official method 3050B underestimates the concentration of Pb depending on the matrix. The agronomic efficiency of Zn sources was similar to or greater than the default font in the first crop evaluation. The Zinc Ash I and Slag Brass II sources had reduced residual effect and lower AEI in the second crop of rice. The binary sources were effective in delivering copper and zinc to soil and plant in relation to their respective pro analyse mixtures in the first crop evaluation. Slag Brass III had lower residual effect in relation to its pro analysis mixture in the evaluation of the AEI, for copper and zinc, in the second crop of rice. Significant correlation between nutrients accumulation and the CNA extractors for Cu and AC 2% for Zn nutrient was observed in Slag Brass III. Cu Ore obtained poor performance in all parameters evaluated for the first crop, relative efficiency index 17% and agronomic efficiency index -65%. In both experiments evaluated any of the materials influence the levels of toxic heavy metals in the soil and plants. The CNA extractor did not correlate significantly with the content of copper accumulated in the rice plant two crops.

Pouco se conhece sobre a origem dos materiais utilizados na fabricação de micronutrientes. Muitos fertilizantes podem conter em sua matéria prima nutrientes em formas indisponíveis para as plantas. Este fato pode limitar a produção, pois, até 2007 a legislação não contemplava parâmetros de solubilidade mínima e concentração máxima de metais pesados tóxicos. Atualmente estes parâmetros presumem que a solubilidade mínima de 60% nos extratores, ácido cítrico e citrato neutro de amônio para zinco e cobre respectivamente e a extração de metais pesados tóxicos pelo método 3050B da Agência de Proteção Ambiental Americana (EPA) são suficientes em garantir fertilizantes eficientes e de baixo impacto ambiental.Fontes secundárias de origem industrial vêem sendo utilizadas para fabricação de fertilizantes no Brasil há muitos anos. Recentemente, o mistério da agricultura e órgãos ambientais tem questionado a origem destas matérias primas como possível fonte de contaminação por metais pesados tóxicos e também sua eficiência como fonte de micronutrientes. A indústria por outro lado declara que o uso destes materiais é uma questão favorável ao ambiente, pois permite uso de materiais que seriam descartados. Outra alegação são os altos preços das matérias primas autorizadas para uso, e há escassez de minerais disponíveis. Nesse sentido foram instalados experimentos com dois materiais secundários, A e B, de origem industrial com concentrações variadas de Zn e Cu. As fontes foram caracterizadas desde sua origem, avaliando-se processos, mineralogia por difração de raios X, concentrações de nutrientes e metais pesados tóxicos por fluorescência de raios X e determinação nos extratores HF, HCl concentrado, água-régia, 3050B, ácido cítrico 20g.L-1, citrato neutro de amônio (1:1). Após a caracterização conduziu-se experimento com a cultura do arroz, em casa de vegetação, para verificar os efeitos da aplicação destas fontes nas doses de (0;2,5;5;10;15 kg.ha-1 Zn) em um Latossolo Vermelho distroférrico. A análise dos difratogramas de raios X dos materiais secundários A e B mostraram diferenças quanto à cristalinidade, sendo este fenômeno melhor compreendido com os maiores teores de silício no material B obtidos na fluorescência de raios X. A cristalinidade das amostras traduziu-se em diferença entre os teores obtidos pelo diferentes extratores. Embora o material B ser agronomicamente ineficiente (IEA=49%), foi o único a ter as garantias mínimas de 60% de Cu e Zn atingidas e concentrações baixas de metais pesados tóxicos. Por outro lado, o material A apresentou desempenho agronômico satisfatório (IEA=94%) mas não atingiu solubilidade mínima em ácido cítrico 2% para Zn e cítrato neutro de amônio (1:1) para Cu, porem, apresentou maiores teores de metais pesados tóxicos, principalmente chumbo. Diante do exposto sugere-se que as matérias primas tenham sua origem caracterizada e rastreada nos fertilizantes, as extrações sejam realizadas em função da origem do material e que os níveis de metais pesados tóxicos sejam mais limitantes. / The origin of materials used in the manufacture of micronutrients is unexplored. Many fertilizers can contain nutrients in the raw material into unavailable forms to plants. This fact can limit the production because the legislation, until 2007, did not include parameters of minimum solubility and maximum concentration of toxic heavy metals. After that, these parameters assume that the minimum solubility of 60% in the extractors, citric acid, neutral ammonium citrate for zinc and copper respectively and the extraction of toxic heavy metals by the 3050B method of the U.S. Environmental Protection Agency (EPA) are enough to ensure efficient fertilizer and low environmental impact. Secondary materials from industrial have been used for the manufacture of fertilizers in Brazil for many years. Recently, the ministry of agriculture and environmental agencies have been questioned the origin of raw materials as possible source of contamination with toxic heavy metals and also its efficiency as a source of micronutrients. On the other hand, the industry, states that the use of these materials can be environmentally friendly because it allows using these materials that would be discarded. Moreover, the raw materials that are authorized for use are very expensive and there is scarcity of available minerals. Experiments in this direction have been realized with two secondary materials from industry, A and B, with several concentrations of Zn and Cu. The sources have been characterized since its origin, evaluating processes, mineralogy by x-ray diffraction, concentrations of nutrients and toxic heavy metals by x-ray fluorescence and analyzed by different extractants (HF, concentrated HCl, aqua regia, 3050B, 20 g L-1 citric acid, neutral ammonium citrate (1:1)) determined by flame spectrometry coupled plasma (ICP - MS). After characterization, greenhouse experiment was conducted with rice crop to check the effects of applying these sources at rates of (0, 2.5, 5, 10, Zn 15 kg ha-1) in an Oxisol. The analysis of X-ray diffraction patterns of secondary materials A and B showed differences in the crystallinity, this phenomenon was better understood with higher levels of silicon in material B, obtained by X-ray fluorescence analyzes. The crystallinity of the samples resulted in differences between the levels obtained by different extractants. Although material B be agronomically inefficient (AE=49%), was the only one with the minimum guarantees of 60% for Zn and Cu and low concentrations of toxic heavy metals. On the other hand, the material A had good agronomic performance (AE=94%) but did not reach minimum solubility in 2% citric acid for Zn and neutral ammonium citrate (1:1) for Cu. However, the levels of toxic heavy metals, mainly lead, were highest. To conclude, we suggest that the origins of raw materials needs to be characterized and traced in fertilizers, the extractions should be realized according to the origin of the material and the levels of toxic heavy metals should be more limitants.

Pouco se conhece sobre a origem das matérias primas utilizadas na fabricação de micronutrientes. Muitos fertilizantes podem conter em sua matéria prima nutrientes em formas indisponíveis para as plantas que limitam a produção. Fontes secundárias de origem industrial vêem sendo utilizadas para fabricação de fertilizantes no Brasil há muito tempo, somente a poucos anos a legislações e órgãos ambientais tem questionado a origem destas matérias primas quanto a contaminação por metais pesados tóxicos e sua eficiência agronômica como fonte de micronutrientes. Neste sentido foi desenvolvido estudo a fim de obter informações básicas dos materiais secundários como origem, composição elementar, composição mineralógica, disponibilidade de metais pesados tóxicos em extratores ácidos (Agua Régia, 3050B, HCl) disponibilidade de Zn e Cu em extratores solúveis (AC 2% e CNA) efeitos da aplicação de onze materiais secundários em plantas de arroz em dois cultivos, divididos em nove fontes fornecedoras exclusivamente de zinco com composições mineralógicas diversas; fontes binárias contendo diferentes concentrações de zinco e cobre em cinco doses (0; 6; 9; 12; 18 kg ha-1 Zn) e três materiais secundários fontes de cobre contendo concentrações variadas de cobre em cinco doses (0;1,5;3,0;4,5 e 6,0 kg.ha-1 Cu) avaliando a eficiência em fornecer nutrientes e potencial de contaminação do solo e planta. Conclui-se que materiais secundários tem grande variabilidade quanto à composição mineralógica e elementar, mesmo quando originados em processos similares. O método AC 2% é ineficiente para materiais com concentração de zinco superior a 59% e para matrizes com alta concentração de silicatos. As formas de Pb identificadas nos materiais secundários interferem na quantificação do elemento nos extratores utilizados; o método oficial 3050B subestima a concentração de Pb dependendo de sua matriz. A eficiência agronômica das fontes de Zn foi semelhante ou superior a fonte padrão no primeiro cultivo. A matriz das fontes Cinza de Zn I e Escória de Latão II apresentaram menor efeito residual e eficiência agronômica inferior à fonte padrão no segundo cultivo. As fontes binárias foram eficientes em disponibilizar cobre e zinco ao solo e planta em relação a suas respectivas misturas pró analise no primeiro cultivo de arroz. A fonte Escória de Latão III apresentou efeito residual inferior em relação a sua mistura pró analise na avaliação do IEA, para cobre e zinco, no segundo cultivo de arroz. Houve correlação significativa entre acumulo de nutrientes e os extratores CNA para o nutriente Cu e AC 2% para o nutriente Zn na fonte Escória de Latão III. A fonte Minério de Cu apresentou baixo desempenho em todos os parâmetros avaliados no primeiro cultivo, IER 17% e IEA -65%. Nos dois cultivos avaliados nenhum dos materiais influenciou os teores de metais pesados tóxicos nos no solo e planta. O extrator CNA não apresentou correlação significativa com o conteúdo de cobre acumulado na planta de arroz em dois cultivos. / Little is known about the origin of the raw materials used in manufacturing of micronutrients. Many fertilizers may contain in their raw materials, nutrients in unavailable forms to plants that limit production. Secondary sources of industrial origin see being used for the manufacture of fertilizers in Brazil long ago, only a few years legislation and environmental agencies have questioned the source of these raw materials for contamination by toxic heavy metals and their agronomic efficiency as a source of micronutrients. In this sense the study was designed to obtain basic information of secondary materials like elemental composition, mineralogical composition, availability of toxic heavy metals in different acid extractors (Aqua Regia, 3050B, HCl) availability of Cu and Zn in soluble extractors (AC 2% and CNA) effects of eleven secondary materials on rice in two consecutive crops, divided into nine zinc sources, with different mineralogical compositions, binary sources containing different concentrations of zinc and copper in five different doses (0, 6, 9, 12, 18 kg ha-1 Zn) and three secondary materials, source of copper in five doses (0, 1.5 , 3.0, 4.5 and 6.0 kg ha-1 Cu) evaluating efficiency in delivering nutrients and potential contamination of soil and plant. It\'s possible to conclude that secondary materials have great variability regarding the mineralogical and elemental composition, even when originated in similar processes. The AC 2% method is inefficient for materials with higher zinc concentration (>59%) and for matrices with high silicate. The various Pb related forms founded interfere with the quantification in the different used extractants; the official method 3050B underestimates the concentration of Pb depending on the matrix. The agronomic efficiency of Zn sources was similar to or greater than the default font in the first crop evaluation. The Zinc Ash I and Slag Brass II sources had reduced residual effect and lower AEI in the second crop of rice. The binary sources were effective in delivering copper and zinc to soil and plant in relation to their respective pro analyse mixtures in the first crop evaluation. Slag Brass III had lower residual effect in relation to its pro analysis mixture in the evaluation of the AEI, for copper and zinc, in the second crop of rice. Significant correlation between nutrients accumulation and the CNA extractors for Cu and AC 2% for Zn nutrient was observed in Slag Brass III. Cu Ore obtained poor performance in all parameters evaluated for the first crop, relative efficiency index 17% and agronomic efficiency index -65%. In both experiments evaluated any of the materials influence the levels of toxic heavy metals in the soil and plants. The CNA extractor did not correlate significantly with the content of copper accumulated in the rice plant two crops.

Made available in DSpace on 2017-07-10T17:48:12Z (GMT). No. of bitstreams: 1 Lucas_Wachholz.pdf: 1452353 bytes, checksum: 74f234ce97c8cd31a35f5b2a4fe9dc32 (MD5) Previous issue date: 2016-03-18 / Fundação Araucária / This study aimed to evaluate the use of golden mussels contaminated with levels of Pb and Cd as a source of Ca replacing limestone in diets for broilers from 14 to 42 days and its effect on performance, blood parameters, digestibility metals and bone quality. two similar experiments were carried out where they were used 60 broilers, males 14-42 days of age were housed in cages of four Pb contamination levels (71.33; 147.55; 223.78 and 300.00 mg kg-1) or Cd (6.94; 14.55; 22.40 and 30.00 mg kg-1) and five replications. The golden mussel was added to the diet as a source of calcium in total replacement of limestone. At 42 days of age were weighed birds for performance evaluation and blood samples were collected for determination of serum parameters and after we carried out the slaughter and collection of tissues for analysis of concentrations of metals and collecting the bones to perform the evaluations of bone quality parameters. In the study of Pb can be seen that the increase in the Pb concentrations in the mussel increases the digestibility and metabolism of metal and causes an increase in production by the liver AST. Pb levels mussel above 214.11 mg kg-1 impair bone strength and flexibility. And experiment with Cd concentrations above 20 mg kg-1 of Cd from the golden mussel are sufficient to cause the maximum values of Cd contamination in animals. The use of concentrations of up to 22.40 mg kg-1 of Cd in the mussel flour for the pectoralis major muscle and 6.94 mg kg-1 in the case of liver provide Cd concentrations that can be used in human food, but for the other tissues evaluated the concentration of 6.94 mg kg-1 brings in Cd concentrations above the permitted. The increase in the concentrations of Cd causes increased production of bilirubin in bile, metabolism and increases the digestibility of Cd and serum concentrations of Ca. AST production by the liver and bone flexibility are increased by Cd levels mussel flour / O presente estudo objetivou avaliar a utilização de mexilhão dourado contaminado com níveis de Pb e Cd como fonte de Ca em substituição ao calcário calcítico em dietas para frangos de corte dos 14 aos 42 dias de idade e seus efeitos sobre desempenho, parâmetros sanguíneos, digestibilidade de metais e qualidade óssea. Foram realizados dois experimentos semelhantes onde foram utilizados 60 frangos de corte, machos de 14 a 42 dias de idade, alojados em gaiolas, com quatro níveis de contaminação de Pb (71,33; 147,55; 223,78 e 300,00 mg kg-1) ou Cd (6,94; 14,55; 22,40 e 30,00 mg kg-1) e cinco repetições. O mexilhão dourado foi adicionado à dieta como fonte de cálcio em substituição total ao calcário calcítico. Aos 42 dias de idade, foram pesadas as aves para avaliação do desempenho e foram coletadas amostras de sangue para determinação dos parâmetros séricos e após foi realizado o abate e coleta dos tecidos para análise das concentrações dos metais e a coleta dos ossos para realizar as avaliações dos parâmetros de qualidade óssea. No estudo com Pb, pode-se observar que o aumento nas concentrações de Pb no mexilhão eleva a digestibilidade e metabolismo deste metal e provoca aumento na produção de AST pelo fígado. Níveis de Pb no mexilhão dourado acima de 214,11 mg kg-1 prejudicam a resistência e a flexibilidade óssea. E no experimento com Cd as concentrações acima de 20 mg kg-1 de Cd presentes no mexilhão dourado são suficientes para provocar os valores máximos de contaminação por Cd nos animais. A utilização de concentrações de até 22,40 mg kg-1 de Cd na farinha de mexilhão dourado para o músculo Pectoralis major e de 6,94 mg kg-1 no caso do fígado proporcionam concentrações de Cd que podem ser utilizadas na alimentação humana, porém para os demais tecidos avaliados a concentração de 6,94 mg kg-1 acarreta em concentrações de Cd acima das permitidas. A elevação nas concentrações de Cd provoca aumento na produção de bilirrubina pela bile, aumenta a metabolização e digestibilidade de Cd e as concentrações séricas de Ca. A produção de AST pelo fígado e flexibilidade óssea são aumentados pelas concentrações de Cd na farinha de mexilhão

The rivers, lakes and seas are the major water sources for the animal and plant kingdom in this earth. In recent times, the usage and wastage of water have been increasing due to the uncontrolled population growth. In addition to that, the rapid industrialization over the years has led to the gradual depletion of the natural resources like water, soil and air. Some of these industries discharge contaminants like organic products and inorganic (or) toxic heavy metals without treatment into the environment, leading to its degradation. Zinc is the 24th most abundant element present in the earth crust, amounting 75 ppm (0.0075%). The concentration of zinc present in the soil and seawater is about 64 ppm and 30 ppb respectively (Emsley, 2001). Generally, the zinc is found with the base metals such as copper and lead and it has less affinity with oxides and strong affinity with sulphides. Sphalerite, a zinc sulphide ore, is majorly containing 60-62% of zinc. The other sources of zinc from the minerals are smithsonite, hemimorphite, quartzite, and hydro zincate. The major sources of zinc contamination arise from several industrial activities such as mining, coal, waste combustion and steel and iron processing. Drinking water also contains certain amounts of Zn, which may be higher when it is stored in metal tanks. The acute toxicity arises from the ingestion of excessive amounts of zinc salts, either accidentally or as dietary supplement. Vomiting, nausea and stomach cramps usually occur after the consumption of more than 500 mg of zinc sulfate. In addition to that, the higher amounts of zinc affect gastrointestinal tract, liver, bone and prostate glands. Finally, Zn can interrupt the activity in soils, as it negatively influences the activity of microorganisms and earthworms, thus retarding the breakdown of organic matter. To combat this problem, techniques such as chemical precipitation, ion exchange, reverse osmosis, etc. are adopted, but these processes result in a huge amount of secondary sludge formation, inefficient removal of metals and are not cost effective. In recent times, an innovative, eco-friendly, cost-effective method has been introduced to treat the toxic heavy metals namely bioremediation. ―Bioremediation‖ is a process of removal of organic or inorganic contaminants by using bacteria, fungi, algae and its metabolites In this research work, the potential of four bacterial strains of the Pseudomonas sp. such as P.putida, P.alcaligenes, P.aeruginosa and P.fluorescens and the extracellular proteins secreted by these four species for the bio-sorption of zinc has been investigated through batch experiments. The mechanisms of interaction between the zinc ion and the bacterial biomass as well as with the extracellular proteins have been elucidated. Additionally, a carbon paste electrode has been modified by using Pseudomonas sp. and its metabolites to develop biosensors for zinc and the lower limit of detection of zinc in aqueous solution has been determined. The major objectives of this research work are specified below: • To study the potential of Pseudomonas sp. such as P.putida, P.alcaligenes, P.aeruginosa and P.fluorescens for the bio sorption of zinc, in batch systems. • To determine the speciation of zinc with respect to pH in the growth medium and the maximum inhibitory effect of zinc on the growth of the four chosen Pseudomonas sp. • To isolate and characterize the extracellular proteins from the four Pseudomonas sp. such as P.putida, P.alcaligenes, P.aeruginosa and P.fluorescens. • To study the biosorption of zinc by extracellular proteins secreted by the Pseudomonas sp. • To elucidate the mechanisms involved in the biosorption of zinc at the microbe- metal interface and protein-metal ion interface for all the four systems by different characterization studies such as zeta potential, FTIR analysis and EDAX analysis. • To develop a biomass modified CPE using bacterial cells and extracellular protein to detect the concentration of zinc in aqueous solutions adopting voltammetric techniques. The significant results obtained from this research work are summarized as follows: The initial studies were concentrated on the bio sorption of zinc by using four Pseudomonas species such as P.putida, P.alcaligenes, P.aeruginosa and P.fluorescens. The various factors affecting the bio sorption of zinc by these species were investigated by varying the contact time (10-80 min), pH (2-5±0.2), biomass concentration of the four species in the range of 108- 1011 cells / mL, and the initial zinc concentration from 5 mg/L to 80 mg/L respectively, keeping other parameters such as temperature and agitation speed constant in all the experiments. From the results obtained, the maximum percentage of biosorption achieved by the P.putida, P.alcaligenes, P.aeruginosa and P.fluorescens was found to be 60%, 93%, 70% and 65% respectively for 25 mg/L at pH 5±0.2. The equilibrium time taken by the four species to achieve maximum biosorption was about 10 min and the biosorption kinetics adhered to pseudo-second order reaction and the rate constants were determined for different concentrations of zinc. The biosorption isotherm followed both the Langmuir and Freundlich isotherm models. The Gibbs free energy (ΔG) values determined from the Langmuir isotherm model for all the four systems were found to be -26, -32, -30 and -28 kJ /mole respectively. The Gibbs free energy values indicate that the biosorption of zinc ions onto the bacterial surface is a chemi-sorption process involving co-ordination, complexation or chelation. The characterization studies, namely zeta potential, FTIR analysis and SEM-EDX were also carried out on the bacterial cells before and after interaction with zinc. These studies also provide evidence in support of the complexation of zinc with the functional groups on the bacterial cell surface apart from electrostatic interaction. In the second part of the investigation, the inhibitory effect of zinc on the growth of four Pseudomonas sp. was investigated by varying the concentration of zinc from 50 mg/L to 1000 mg/L and the stability of zinc was analysed with respect to pH (2-12) with different concentrations from 50 - 1700 mg/L. It was found that in the absence of zinc the time taken to reach the exponential phase and the specific growth were almost the same for all the four systems. However, in the presence of zinc ions, the growth of the four Pseudomonas sp. was suppressed beyond 50mg/L of zinc. A control study on the stability of zinc in Luria broth medium showed that zinc was highly stable up to 200 mg/L from pH 2-8. However, the stability of zinc in the growth medium decreased beyond that concentration Additionally, studies on the biosorption of zinc were performed using extracellular proteins isolated from the four Pseudomonas sp. The amount of protein was estimated by the Bradford protein assay method at 594 nm. The biosorption experiments were carried out by varying the protein concentration from 50 to 1000µg/mL and the zinc concentration from 50-1000 mg/L and keeping other parameters fixed, namely such as pH at 5±0.2, reaction time of 20 min, temperature at 30±0.2 and the speed of rotation of 200 rpm. It was found that the maximum percentage of zinc biosorbed by the proteins isolated from P.putida was found to be 91% at 500µg/mL of protein concentration and from the other three species, it was found to be about 60% of biosorption at the same protein concentration. The biosorption isotherms of zinc for extracellular protein adhered to the Giles H1 type for all the four systems. The maximum amount of zinc biosorbed by the protein isolated from P.putida, P.alcaligenes, P.aeruginosa and P.fluorescens was found to be 35.6, 19,18.3 and 10 mg/µg respectively and the Gibbs free energy values were found to be -32, -22,-22 and -23 kJ/mole. The mechanisms involved in protein-zinc interaction were elucidated using FTIR analysis and EDX analysis. The FTIR analysis revealed, that the zinc ions were complexed with carboxylic and amine functional groups. Further, the potential of P.putida, P.alcaligenes, P.aeruginosa and P.fluorescens and their extracellular proteins of P.putida as biosensors for detecting zinc ions in aqueous solutions, using electrochemical methods such as, Cyclic Voltammetry and Differential pulse anodic stripping voltammetry, was assessed. The developed carbon paste electrode coated by the biomass showed an approximately 3-fold increase in the sensing of Zn2+ ion in comparison with the bare electrode. The lower limit of detection of the biosensor for zinc ions by Cyclic voltammetry was found to be 10-6 M, and in case of DPASV the lower limit of detection was about 10-7M. The lower limit of detection of the protein modified biosensor for zinc ions by cyclic voltammetry was found to be 10-7M and in the case of DPASV method the lower limit of detection was found to be 10-9 M.

Pouco se conhece sobre a origem dos materiais utilizados na fabricação de micronutrientes. Muitos fertilizantes podem conter em sua matéria prima nutrientes em formas indisponíveis para as plantas. Este fato pode limitar a produção, pois, até 2007 a legislação não contemplava parâmetros de solubilidade mínima e concentração máxima de metais pesados tóxicos. Atualmente estes parâmetros presumem que a solubilidade mínima de 60% nos extratores, ácido cítrico e citrato neutro de amônio para zinco e cobre respectivamente e a extração de metais pesados tóxicos pelo método 3050B da Agência de Proteção Ambiental Americana (EPA) são suficientes em garantir fertilizantes eficientes e de baixo impacto ambiental.Fontes secundárias de origem industrial vêem sendo utilizadas para fabricação de fertilizantes no Brasil há muitos anos. Recentemente, o mistério da agricultura e órgãos ambientais tem questionado a origem destas matérias primas como possível fonte de contaminação por metais pesados tóxicos e também sua eficiência como fonte de micronutrientes. A indústria por outro lado declara que o uso destes materiais é uma questão favorável ao ambiente, pois permite uso de materiais que seriam descartados. Outra alegação são os altos preços das matérias primas autorizadas para uso, e há escassez de minerais disponíveis. Nesse sentido foram instalados experimentos com dois materiais secundários, A e B, de origem industrial com concentrações variadas de Zn e Cu. As fontes foram caracterizadas desde sua origem, avaliando-se processos, mineralogia por difração de raios X, concentrações de nutrientes e metais pesados tóxicos por fluorescência de raios X e determinação nos extratores HF, HCl concentrado, água-régia, 3050B, ácido cítrico 20g.L-1, citrato neutro de amônio (1:1). Após a caracterização conduziu-se experimento com a cultura do arroz, em casa de vegetação, para verificar os efeitos da aplicação destas fontes nas doses de (0;2,5;5;10;15 kg.ha-1 Zn) em um Latossolo Vermelho distroférrico. A análise dos difratogramas de raios X dos materiais secundários A e B mostraram diferenças quanto à cristalinidade, sendo este fenômeno melhor compreendido com os maiores teores de silício no material B obtidos na fluorescência de raios X. A cristalinidade das amostras traduziu-se em diferença entre os teores obtidos pelo diferentes extratores. Embora o material B ser agronomicamente ineficiente (IEA=49%), foi o único a ter as garantias mínimas de 60% de Cu e Zn atingidas e concentrações baixas de metais pesados tóxicos. Por outro lado, o material A apresentou desempenho agronômico satisfatório (IEA=94%) mas não atingiu solubilidade mínima em ácido cítrico 2% para Zn e cítrato neutro de amônio (1:1) para Cu, porem, apresentou maiores teores de metais pesados tóxicos, principalmente chumbo. Diante do exposto sugere-se que as matérias primas tenham sua origem caracterizada e rastreada nos fertilizantes, as extrações sejam realizadas em função da origem do material e que os níveis de metais pesados tóxicos sejam mais limitantes. / The origin of materials used in the manufacture of micronutrients is unexplored. Many fertilizers can contain nutrients in the raw material into unavailable forms to plants. This fact can limit the production because the legislation, until 2007, did not include parameters of minimum solubility and maximum concentration of toxic heavy metals. After that, these parameters assume that the minimum solubility of 60% in the extractors, citric acid, neutral ammonium citrate for zinc and copper respectively and the extraction of toxic heavy metals by the 3050B method of the U.S. Environmental Protection Agency (EPA) are enough to ensure efficient fertilizer and low environmental impact. Secondary materials from industrial have been used for the manufacture of fertilizers in Brazil for many years. Recently, the ministry of agriculture and environmental agencies have been questioned the origin of raw materials as possible source of contamination with toxic heavy metals and also its efficiency as a source of micronutrients. On the other hand, the industry, states that the use of these materials can be environmentally friendly because it allows using these materials that would be discarded. Moreover, the raw materials that are authorized for use are very expensive and there is scarcity of available minerals. Experiments in this direction have been realized with two secondary materials from industry, A and B, with several concentrations of Zn and Cu. The sources have been characterized since its origin, evaluating processes, mineralogy by x-ray diffraction, concentrations of nutrients and toxic heavy metals by x-ray fluorescence and analyzed by different extractants (HF, concentrated HCl, aqua regia, 3050B, 20 g L-1 citric acid, neutral ammonium citrate (1:1)) determined by flame spectrometry coupled plasma (ICP - MS). After characterization, greenhouse experiment was conducted with rice crop to check the effects of applying these sources at rates of (0, 2.5, 5, 10, Zn 15 kg ha-1) in an Oxisol. The analysis of X-ray diffraction patterns of secondary materials A and B showed differences in the crystallinity, this phenomenon was better understood with higher levels of silicon in material B, obtained by X-ray fluorescence analyzes. The crystallinity of the samples resulted in differences between the levels obtained by different extractants. Although material B be agronomically inefficient (AE=49%), was the only one with the minimum guarantees of 60% for Zn and Cu and low concentrations of toxic heavy metals. On the other hand, the material A had good agronomic performance (AE=94%) but did not reach minimum solubility in 2% citric acid for Zn and neutral ammonium citrate (1:1) for Cu. However, the levels of toxic heavy metals, mainly lead, were highest. To conclude, we suggest that the origins of raw materials needs to be characterized and traced in fertilizers, the extractions should be realized according to the origin of the material and the levels of toxic heavy metals should be more limitants.