Per- and polyfluoroalkyl substances (PFAS) are a large group of anthropogenic compounds with unique properties, including chemical inertness, resistance to many degradation processes and amphiphilic structure. This makes them useful in a range of applications, but also very persistent and bioaccumulative in nature, where PFAS have been linked to adverse health effects in both animals and humans. There are regulations for PFAS, including the REACH regulation and Stockholm Convention, but for now PFAS are monitored individually. This poses a problem since many regulated, long-chain PFAS today are being replaced with unregulated, short-chain homologues with similar hazardous properties.For water remediation of PFAS, a popular and effective sorption technique for their removal is activated carbon (AC), with its close to 100% sorption efficiency. This study focuses on the efficiency of more sustainable materials like bark, steel slag and biochar to sorb eleven different PFAS (PFAS-11) from contaminated water. In this work, contaminated water passed through different constellations of sorbent materials by flow-through experiments, underwent solid-phase extraction (SPE) using a weak anion-exchange (WAX) adsorbent for sample clean-up, and was lastly prepared for analysis using an ultra-performance liquid chromatograph (UPLC) coupled to a quadrupole tandem mass spectrometer (MS/MS).For the different sorbent constellations tested, perfluorooctane sulfonic acid (PFOS) was removed to the highest degree, with an average removal of 70%. When studying the sum of PFAS-11 between the tested sorption constellations, the bark tests sorbed around 20%, the steel slag combinations sorbed between 30-40% and biochar sorbed 43% of the initial PFAS-11 concentration (1 750 ng/L) in the contaminated water. None of these materials achieved an efficient enough sorption to go below the Swedish PFAS-11 drinking water limit value of 90 ng/L, so the results are for the time being suggested more as complementary, low-cost sorption techniques. Further research is recommended to extensively be able to implement more sustainable sorbents with higher sorbing efficiencies.

No description available.

This study addresses the critical environmental issue of elevated nitrate levels in water bodies, primarily due to excessive use of nitrogenous fertilizers and improper waste disposal. It focuses on reducing nitrate concentrations in polluted water to permissible levels through the effectiveness of hybrid materials in nitrate adsorption. We synthesized nine amino-functionalized adsorbents using grafting and sol-gel techniques. Batch adsorption tests confirmed the high nitrate adsorption capacities of these adsorbents, with sol-gel materials showing the highest efficiency due to their abundant amino group contents. Among these, the surfactant-free, sol-gel adsorbent was the most effective, combining ease of synthesis with cost-efficiency. Our study of temperature dependence revealed optimal nitrate removal at ambient conditions and decreased capacity at higher temperatures. These adsorbents remained highly efficient over five adsorption/regeneration cycles. This research significantly advances efficient nitrate removal methods, presenting a promising approach for environmental remediation.

A study was conducted on sol-gel synthesis of an adsorbent (phosphotungstic acid embedded in silica gel, H-PTA/SiO­2) of radioactive cesium. A novelty of this work is covalent bonding of PTA to the surface of solid support that prevents leaching from the surface of the material. The sample was granulated with a binder, aluminium oxide (γ-Al2O3). Solid-state NMR and FT-IR spectroscopy were used to confirm the presence of Keggin units of PTA in the bound materials. Thermal analysis of H-PTA/SiO­2 - γ-Al2O3 (50 %) showed that the water content in the bound material was appreciably lower than in the pure adsorbent. Quantitative determination of surface acidity of porous materials is an important analytical problem in characterization of the adsorbents. This problem was solved by reversed titration after saturation of the materials by anhydrous solution of pyridine. Batch and column adsorption tests showed that the adsorbent demonstrated high adsorption capacities towards cesium.

Este trabalho teve como objetivo principal a utilização de duas variantes da técnica analítica de fluorescência de raios X, dispersiva em energia - EDXRF e reflexão total TXRF, na determinação de Pb em amostras de águas superficiais e subterrâneas, e em sedimentos em suspensão e de fundo. Cinco amostras de cada matriz foram coletadas em uma área contaminada, nas proximidades da desativada fábrica de baterias Indústria Acumuladores Ajax Ltda., localizada no km 229 da rodovia Jaú-Ipaussu, em Bauru, SP. As variantes EDXRF com pré-concentração com APDC e medida direta por TXRF mostraram resultados satisfatórios na determinação de Pb em soluções-padrão e amostra certificada de água natural SRM1640, produzida pelo NIST, obtendo-se concentrações compatíveis com os valores esperados. A primeira técnica resultou em limite de detecção da ordem de 0,70 mg L-1, com tempo de análise de 300 s, melhor que a segunda técnica (4,46 mg L-1), em 200 s. Estas duas variantes também foram utilizadas para outros elementos químicos, como o Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn e Br, onde a EDXRF mostrou também melhores limites de detecção para todos os elementos. Para Ni, Cu e Zn, importantes na indústria de baterias, foram encontrados os limites de 0,34 - 0,27 e 0,24 mg L-1, respectivamente, enquanto que por TXRF foram encontrados os valores ao redor de 1 mg L-1. Na validação destas duas metodologias para análise de água, a EDXRF mostrou resultados mais próximos aos valores esperados, enquanto que por TXRF foram superestimados na maioria das vezes, com exceção para As, Se e Pb. Este erro foi devido a uma interferência espectral ocasionada provavelmente pela presença dos elementos Ti ao Zn nos componentes metálicos do arranjo experimental, ausentes no suporte refletor de quartzo, colimador do detector ou solução do padrão interno. Sem a eliminação dessa interferência, os resultados obtidos por TXRF para estes elementos, com exceção para As, Se e Pb, só podem ser utilizados como qualitativos. Para análise de sedimentos em suspensão foi utilizada a técnica de EDXRF, assumindo a amostra como filme fino, atingindo limite de detecção da ordem de 2 mg g-1 para Pb, enquanto que para o Cu e Zn o limite de detecção foi da ordem de 5 mg g-1, em 300 s. Para sedimento de fundo foi utilizada a mesma técnica, mas admitindo a amostra como espessa, corrigindo-se o efeito matriz através do fator de absorção, validando-a pela análise de amostras certificadas de sedimento (SRM1646a/NIST) e solo (SRM2711/NIST). O limite de detecção para Pb ficou em torno de 2 mg g-1, e para outros elementos os limites foram de 3,07 mg g-1 para Ni, 2,12 mg g-1 para Cu e 1,50 mg g-1 para Zn, em 500 s. Com base nos valores máximos permitidos para Pb, estabelecidos pela Portaria 1469/00 e Resolução 20/1986 CONAMA, duas amostras de água mostraram-se contaminadas pelos resultados obtidos pela variante EDXRF, e quatro pelos resultados da TXRF. Para os outros elementos, apesar da interferência na TXRF, por esta técnica uma amostra de água ultrapassou o limite permissível para Cu e todas as cinco para Zn, e pela EDXRF uma amostra para Ni e Cu em água, e três para Zn. Na legislação brasileira não há limite máximo permitido para Pb e outros elementos em solos e sedimentos, e portanto foram adotados os limites TEL (Threshold Effect Level, nível limiar do efeito) e PEL (Probable Effect Level, nível provável do efeito), utilizados pela Agência Ambiental Canadense. As amostras de sedimento em suspensão mostraram concentrações de Pb menores que o limite de detecção, e das cinco amostras de sedimento de fundo, uma amostra apresentou valor acima do limite TEL, e outra, coletada num ponto bem ao lado da fábrica, acima do limite PEL. Para os outros elementos Ni, Cu e Zn, nenhuma das amostras de sedimento em suspensão ou de fundo não ultrapassaram os limites TEL. / This study had as main objective the use of two variants of the analytical technique of X-ray fluorescence, energy dispersive - EDXRF and total reflection - TXRF, for the determination of Pb in superficial and underground water and in suspended and bottom sediment samples. Five samples of each matrix were collected in a contaminated area near the closed battery plant, Indústria de Acumuladores Ajax Ltd., located on km 229 of the Jaú-Ipaussu highway, near the city of Bauru in São Paulo State, Brazil. The two variants – EDXRF with preconcentration with APDC and TXRF direct measurement – had shown satisfactory results in the determination of Pb in standard solutions and certified natural water sample SRM1640/NIST, obtaining compatible concentrations with the expected values. The first technique resulted in a 0.70 mg L-1 limit of detention, with 300 s analysis time, and the second one 4.46 mg L-1 in 200 s. These two variants were also used for other chemical elements, such as Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn and Br. EDXRF also showed better limits of detection for all the elements. For Ni, Cu and Zn, important in the industry of batteries, the limits of 0.34, 0.27 and 0.24 mg L-1, respectively, were found, while with TXRF the values of around 1 mg L-1 were achieved. In the validation of these two methodologies for water analysis, the EDXRF showed results nearer to the expected values, while with TXRF the results were overestimated most of the times, with the exceptions of As, Se and Pb. This error was due to a spectral interference caused probably by the presence of the elements Ti to Zn in the metallic parts of the experimental arrangement, absent in the quartz reflecting support, detector collimator or internal standard solution. Without the elimination of this interference, the results for TXRF for these elements, with the exceptions of As, Se and Pb, can only be used as qualitative results. For analysis of suspended sediments, the EDXRF technique was used, assuming the sample as thin film, the limit of detection of around 2 mg g-1 for Pb was reached, while that for Cu and Zn was around 5 mg g-1, in 300 s. For bottom sediments the same technique was used, but admitting the sample as thick, the matrix effect through the absorption factor was corrected, validating it for the analysis of certified samples of sediment (SRM1646a/NIST) and soil (SRM2711/NIST). The limit of detention for Pb was around 2 mg g-1 and for other elements the limits were 3.07, 2.12 and 1.50 mg g-1 for Ni, Cu and Zn, respectively, in 500 s. On the basis of the Brazilian allowed maximum values for Pb, established by Decree 1469/00 and Resolution 20/1986 CONAMA, two water samples were shown to be contaminated by the results gotten with variant EDXRF, and four by the results of TXRF. For the other elements from the TXRF results (despite the interference) one water sample exceeded the permissible limit for Cu and all the five for Zn, and for the EDXRF results one sample for Ni and Cu and three for Zn. In the Brazilian legislation there is no maximum limit allowed for Pb and other elements in soils and sediments; therefore, TEL (Threshold Effect Level) and PEL (Probable Effect Level) limits from the Canadian Environment Agency were adopted. The suspended sediment samples showed Pb concentrations lesser than the limit of detection. From the five bottom sediment samples, one sample presented a value above the TEL limit, and another one, collected in a point very close to the plant, above the PEL limit. For the other elements, Ni, Cu and Zn, none of the suspended or bottom sediment samples exceeded the TEL limits.

Groundwater is a major and sometimes lone source of drinking water worldwide. The chemical composition of groundwater is a combined product of the composition of water that enters the aquifer and its reaction with various minerals present in the soil and rock mass, which alter the water composition with time and space. Some important factors influencing groundwater quality are (1) physiochemical characteristics o the rocks through which the water circulates; (2) geology of the location; (3) climate of the area; (4) role of microorganisms, which includes oxidative and reductive biodegradation of organic matter; (5)chemical, physical, and mineralogical characteristics of the overburden soils through which the rainwater percolates; and (6) human intrusion affecting the hydrological cycle and degradation in water quality through utilization of water for agricultural and industrial activities. By far the most serious naturally occurring groundwater-quality problem in India derives from high fluoride, arsenic and iron concentrations which are dissolved from the bedrocks by geochemical processes. Presence of excess fluoride in groundwater is identified as a naturally occurring health hazard by the World Health Organization (WHO). Prolonged ingestion of fluoride beyond certain permissible limit leads to ffluorosis, one of the common water-related diseases recognized by the WHO and the United Nations Children's Fund (UNICEF). Endemic fluorosis is now known to be global in scope, occurring on all continents and affecting many millions of people. According to estimates made in the early 1980s, around 260 million people in 30 countries worldwide were drinking water with more than 1 ppm of fluoride. The ultimate source of fluoride in water, soil or biosphere is associated with its distribution in rocks and its dispersion in groundwater. The three most important minerals of fluoride are fluorite (CaF2), cryolite (Na3AlF6) and fluorapatite (Ca5(PO4)3F); cryolite is a rare mineral where as by far the largest amount of fluorine in the earth's crust is in the form of fluorapatite (about 3.5% by weight of fluorine) which is processed almost exclusively for its phosphate content. Fluoride substitutes readily in hydroxyl positions in late-formed minerals in igneous rocks, and in primary minerals especially micas (such as biotites) and amphiboles (such as hornblende). The most important controlling factors influencing fluoride presence in groundwater include: distribution of easily weathered fluoride-bearing minerals, the accessibility of circulating water to these minerals, pH of the percolating water, calcium content of the leaching water, temperature of the percolating water and the soil, exchangeable ions in the percolating water, extent of fresh water exchange in an aquifer, evaporation and evapotranspiration, complexing of fluoride ions with other ions, presence of CO2 and other chemicals in draining water and residence time of the percolating water in soil. High fluoride levels are observed in the groundwater in 19 states of the country. Fluorite, apatite, rock phosphate, phosphorites, phosphatic nodules and topaz are major fluoride bearing minerals in India with varying levels of fluoride content. There are three major fluoride bearing areas in India :1) Gujarat-Rajasthan in the north-west and 2) Chandidongri-Raipur in central India 3) Tamil Nadu-Andhra Pradesh in the south; besides other areas in Karnataka, Bihar, Punjab and in the North-west Himalayas. The total mineral reserves of fluorite, rock phosphate and apatite in the country are estimated at 11.6, 71 and 2.82 million tonnes respectively. The distribution of areas with excess fluoride in groundwater concurs with that of fluorine-bearing minerals. Further high fluoride concentrations are observed from arid and semi arid regions of the country and the areas with advanced stage of groundwater development. An estimated 62 million people, including 6 million children suffer from fluorosis in India because of consuming fluoride-contaminated water. Endemic fluorosis is found to practically exist only in the villages due to lack of piped water supply. The Indian Drinking Water Standard specifies the desirable and permissible limits for fluoride in drinking water as 1.0 and 1.5ppm respectively. De-fluoridation of groundwater is the only alternative to prevent fluorosis in the absence of alternate water source especially for immediate and/or interim relief. De-fluoridation of drinking water in India is usually achieved by the Nalgonda technique or activated alumina process. The Nalgonda method involves addition of aluminum salts (aluminium sulphate and/or aluminium chloride), lime and bleaching powder to water, followed by rapid mixing, flocculation, sedimentation, filtration and disinfection. Only aluminum salt is responsible for removal of fluoride from water .Fluoride removal is achieved in a combination of complexation with polyhydroxy aluminium species and adsorption on polymeric alumino hydroxides (floc). Activated alumina(Al2O3) was proposed for de-fluoridation of water for domestic use in 1930’s and since then it has become one of the most advocated de-fluoridation methods. Activated alumina is a semi crystalline porous inorganic adsorbent and an excellent medium for fluoride removal. When the source water passes through the packed column of activated alumina, fluoride (and other components in the water) is removed via exchange reaction with surface hydroxides on alumina; this mechanism is generally called adsorption although ligand exchange is a more appropriate term for the highly specific surface reactions involved. The fluoride removal capacity of alumina is highly sensitive to pH, the optimum being about pH5.5-6. Significant reduction in fluoride removal by activated alumina is also observed in presence of sulfate and silicate ions. The column needs periodic regeneration once break point(where the effluent concentration is, for example, 2ppm at normal saturation) is reached. For regeneration, the medium is backwashed for 5-10 min and then subjected to two step regeneration with base (NaOH) followed by acid(H2SO4). A major cause for concern with the Nalgonda method is the possibility of formation of residual aluminum and soluble aluminum fluoride complexes in the treated water and a potential breach of the 0.2ppm Indian drinking water standard for aluminium. Concerns with the activated alumina filter method are that the process is pH dependent, with an optimum (pH) working range of 5-6. Further, the activated alumina column requires periodic recharge using caustic soda and acid solutions to rejuvenate the fluoride retention capacity of the column. After 3-4 regenerations the medium has to be replaced. If the pH is not readjusted to normal following the regeneration process, there is a possibility that the aluminum concentration in the treated water may exceed the 0.2ppm standard. Due to the aforementioned drawbacks of the currentde-fluoridation technologies in India that chiefly rely on aluminum based compounds, magnesia(magnesium oxide, MgO) is selected to develop an alternate sustainable de-fluoridation method. The potential of MgO for de-fluoridation has been examined owing to its very limited solubility(6.2mg/L), non-toxicity and excellent fluoride retention capacity. A review of the previous studies on fluoride removal using MgO reveals that the relevant information is essentially scattered. Though studies demonstrated the fluoride removing ability of MgO and brought into focus certain aspects of the fluoride removal mechanism and change in water quality upon MgO addition, vital issues necessary for efficient design and successful field implementation of the de-fluoridation processusing MgO were not addressed. The significant limitations in the earlier works include: influence of process variables(such as MgO dosage, initial fluoride concentration, contact time, temperature, initial solution pH, presence of co-ions and ionic strength) on fluoride retention characteristics (such as removal rate, equilibrium time, capacity) of MgO were not systematically determined, optimum operating parameters/conditions (such as MgO dosage, stirring and settling time) for effective de-fluoridation process applicable to a wide range of groundwater chemical composition and fluoride concentrations were not defined, mechanism of fluoride retention by MgO was not fully understood, issue of lowering the pH of MgO treated water within potable water limits was not comprehensively addressed, safe disposal methods of fluoride bearing sludge were not explored. Failure to address the above issues has impeded the adoption of the MgO treatment method for fluoride removal from water. Scope of the study Present study aims to develop a new sustainable de-fluoridation method, applicable to a wide range of groundwater chemical compositions and fluoride concentrations, based on co-precipitation/precipitation-sedimentation-filtration processes using light MgO. Efforts are made to implement the method at domestic level in a rural area with incidence of high fluoride concentration in groundwater and to understand the status and geochemistry of fluoride contamination in the area. The main objectives of the study include: To determine the fluoride retention characteristics of MgO viz.,rate, equilibrium time and capacity of fluoride retention. To examine the influence of process variables on fluoride retention characteristics of MgO and to determine the optimum operating parameters for effective de-fluoridation process. To understand the mechanism and rate limiting step of MgO de-fluoridation process. To propose methods and specifications to lower the pH of MgO treated water within permissible limits to ensure its potability. To design a simple to use, single-stage domestic de-fluoridation unit. To propose procedures for implementation of the new de-fluoridation method in field. To evaluate the efficiency of the new de-fluoridation method as a useful remedial measure in the fluoride affected areas. To understand the geochemical factors governing the quality of the fluoride rich groundwater and to ascertain the status and geochemistry of fluoride contamination in the area where felid implementation of de-fluoridation method is planned. To characterize the fluoride bearing sludge and propose methods for safe disposal and reuse of fluoride bearing sludge. Organization of the thesis Chapter1 presents an overview of the various aspects of excess fluoride presence in groundwater, remedial measures, and emphasizes the need for a new sustainable de-fluoridation method and defines the scope of present study. Chapter 2 performs a detailed investigation to determine the fluoride retention characteristics of MgO under the influence of various process variables at transient and equilibrium conditions using batch studies. The process variables that have been considered are, contact time, initial fluoride concentration, dosage of MgO, temperature, initial pH, presence of co-ions and ionic strength. Studies to determine the optimum operating parameters for efficient de-fluoridation and to understand some basics of reaction mechanisms involved are also part of this chapter. Chapter 3 examines the true nature of the reaction mechanism between fluoride ions and MgO in aqueous media and the rate-limiting step of the de-fluoridation process by investigating the hydration process of MgO and its influence/relation on fluoride removal. Chapter 4 addresses issues that will assist applying the MgO treatment method for fluoride removal in field such as 1)methods and specifications for lowering the pH of the MgO treated water within permissible limits, 2)design of a simple to use, single-stage de-fluoridation unit, and 3)characterization of the resultant fluoride bearing sludge. Chapter 5 performs a detailed investigation to evaluate the efficiency of the new de-fluoridation method in laboratory and field, and to understand the origin and the geochemicall mechanisms driving the groundwater fluorine enrichment in the area where field implementation of the de-fluoridation unit was planned. Chapter 6 explores an environmentally safe route for the disposal and re-use of fluoride bearing sludge in soil based building materials such as, stabilized soil blocks (produced by cement stabilization of densely compacted soil mass) which are alternative to burnt bricks. Chapter 7 summarizes the major results, observations and contributions from the study.

Este trabalho teve como objetivo principal a utilização de duas variantes da técnica analítica de fluorescência de raios X, dispersiva em energia - EDXRF e reflexão total TXRF, na determinação de Pb em amostras de águas superficiais e subterrâneas, e em sedimentos em suspensão e de fundo. Cinco amostras de cada matriz foram coletadas em uma área contaminada, nas proximidades da desativada fábrica de baterias Indústria Acumuladores Ajax Ltda., localizada no km 229 da rodovia Jaú-Ipaussu, em Bauru, SP. As variantes EDXRF com pré-concentração com APDC e medida direta por TXRF mostraram resultados satisfatórios na determinação de Pb em soluções-padrão e amostra certificada de água natural SRM1640, produzida pelo NIST, obtendo-se concentrações compatíveis com os valores esperados. A primeira técnica resultou em limite de detecção da ordem de 0,70 mg L-1, com tempo de análise de 300 s, melhor que a segunda técnica (4,46 mg L-1), em 200 s. Estas duas variantes também foram utilizadas para outros elementos químicos, como o Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn e Br, onde a EDXRF mostrou também melhores limites de detecção para todos os elementos. Para Ni, Cu e Zn, importantes na indústria de baterias, foram encontrados os limites de 0,34 - 0,27 e 0,24 mg L-1, respectivamente, enquanto que por TXRF foram encontrados os valores ao redor de 1 mg L-1. Na validação destas duas metodologias para análise de água, a EDXRF mostrou resultados mais próximos aos valores esperados, enquanto que por TXRF foram superestimados na maioria das vezes, com exceção para As, Se e Pb. Este erro foi devido a uma interferência espectral ocasionada provavelmente pela presença dos elementos Ti ao Zn nos componentes metálicos do arranjo experimental, ausentes no suporte refletor de quartzo, colimador do detector ou solução do padrão interno. Sem a eliminação dessa interferência, os resultados obtidos por TXRF para estes elementos, com exceção para As, Se e Pb, só podem ser utilizados como qualitativos. Para análise de sedimentos em suspensão foi utilizada a técnica de EDXRF, assumindo a amostra como filme fino, atingindo limite de detecção da ordem de 2 mg g-1 para Pb, enquanto que para o Cu e Zn o limite de detecção foi da ordem de 5 mg g-1, em 300 s. Para sedimento de fundo foi utilizada a mesma técnica, mas admitindo a amostra como espessa, corrigindo-se o efeito matriz através do fator de absorção, validando-a pela análise de amostras certificadas de sedimento (SRM1646a/NIST) e solo (SRM2711/NIST). O limite de detecção para Pb ficou em torno de 2 mg g-1, e para outros elementos os limites foram de 3,07 mg g-1 para Ni, 2,12 mg g-1 para Cu e 1,50 mg g-1 para Zn, em 500 s. Com base nos valores máximos permitidos para Pb, estabelecidos pela Portaria 1469/00 e Resolução 20/1986 CONAMA, duas amostras de água mostraram-se contaminadas pelos resultados obtidos pela variante EDXRF, e quatro pelos resultados da TXRF. Para os outros elementos, apesar da interferência na TXRF, por esta técnica uma amostra de água ultrapassou o limite permissível para Cu e todas as cinco para Zn, e pela EDXRF uma amostra para Ni e Cu em água, e três para Zn. Na legislação brasileira não há limite máximo permitido para Pb e outros elementos em solos e sedimentos, e portanto foram adotados os limites TEL (Threshold Effect Level, nível limiar do efeito) e PEL (Probable Effect Level, nível provável do efeito), utilizados pela Agência Ambiental Canadense. As amostras de sedimento em suspensão mostraram concentrações de Pb menores que o limite de detecção, e das cinco amostras de sedimento de fundo, uma amostra apresentou valor acima do limite TEL, e outra, coletada num ponto bem ao lado da fábrica, acima do limite PEL. Para os outros elementos Ni, Cu e Zn, nenhuma das amostras de sedimento em suspensão ou de fundo não ultrapassaram os limites TEL. / This study had as main objective the use of two variants of the analytical technique of X-ray fluorescence, energy dispersive - EDXRF and total reflection - TXRF, for the determination of Pb in superficial and underground water and in suspended and bottom sediment samples. Five samples of each matrix were collected in a contaminated area near the closed battery plant, Indústria de Acumuladores Ajax Ltd., located on km 229 of the Jaú-Ipaussu highway, near the city of Bauru in São Paulo State, Brazil. The two variants – EDXRF with preconcentration with APDC and TXRF direct measurement – had shown satisfactory results in the determination of Pb in standard solutions and certified natural water sample SRM1640/NIST, obtaining compatible concentrations with the expected values. The first technique resulted in a 0.70 mg L-1 limit of detention, with 300 s analysis time, and the second one 4.46 mg L-1 in 200 s. These two variants were also used for other chemical elements, such as Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn and Br. EDXRF also showed better limits of detection for all the elements. For Ni, Cu and Zn, important in the industry of batteries, the limits of 0.34, 0.27 and 0.24 mg L-1, respectively, were found, while with TXRF the values of around 1 mg L-1 were achieved. In the validation of these two methodologies for water analysis, the EDXRF showed results nearer to the expected values, while with TXRF the results were overestimated most of the times, with the exceptions of As, Se and Pb. This error was due to a spectral interference caused probably by the presence of the elements Ti to Zn in the metallic parts of the experimental arrangement, absent in the quartz reflecting support, detector collimator or internal standard solution. Without the elimination of this interference, the results for TXRF for these elements, with the exceptions of As, Se and Pb, can only be used as qualitative results. For analysis of suspended sediments, the EDXRF technique was used, assuming the sample as thin film, the limit of detection of around 2 mg g-1 for Pb was reached, while that for Cu and Zn was around 5 mg g-1, in 300 s. For bottom sediments the same technique was used, but admitting the sample as thick, the matrix effect through the absorption factor was corrected, validating it for the analysis of certified samples of sediment (SRM1646a/NIST) and soil (SRM2711/NIST). The limit of detention for Pb was around 2 mg g-1 and for other elements the limits were 3.07, 2.12 and 1.50 mg g-1 for Ni, Cu and Zn, respectively, in 500 s. On the basis of the Brazilian allowed maximum values for Pb, established by Decree 1469/00 and Resolution 20/1986 CONAMA, two water samples were shown to be contaminated by the results gotten with variant EDXRF, and four by the results of TXRF. For the other elements from the TXRF results (despite the interference) one water sample exceeded the permissible limit for Cu and all the five for Zn, and for the EDXRF results one sample for Ni and Cu and three for Zn. In the Brazilian legislation there is no maximum limit allowed for Pb and other elements in soils and sediments; therefore, TEL (Threshold Effect Level) and PEL (Probable Effect Level) limits from the Canadian Environment Agency were adopted. The suspended sediment samples showed Pb concentrations lesser than the limit of detection. From the five bottom sediment samples, one sample presented a value above the TEL limit, and another one, collected in a point very close to the plant, above the PEL limit. For the other elements, Ni, Cu and Zn, none of the suspended or bottom sediment samples exceeded the TEL limits.

M. Tech. (Department of Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / This work investigates the possible use of chitosan beads and polyaniline grafted chitosan beads (PGCB) for the adsorption of copper ions from copper contaminated water. For this purpose chitosan flakes were converted to chitosan beads. However, a variable from a number of reaction variables (aniline concentration, chitosan concentration, temperature, acid concentration, reaction time and initiator concentration) was varied while others was kept constant, in an attempt to determine the best conditions for grafting of polyaniline onto chitosan beads. Percentage (%) grafting and % efficiency were key parameters used to determine such conditions. The chitosan beads and PGCB were characterized using physical techniques such as Fourier transformed infra red (FTIR), X-ray diffraction (XRD), and scanning electron microscope (SEM). The beads were used as an adsorbent for copper ions removal. The effect of pH on the removal rate of copper (II) by PGCB was investigated on by varying the pH values from pH 3 to 8 at an initial concentration of 40 mg/l. The effect of contact time, initial concentration and temperature was also investigated. The Langmuir and Freundlich model were used to describe adsorption isotherms for chitosan beads and PGCB, with correlation coefficient (R2) as the determining factor of best fit model. The thermodynamics of adsorption of copper (II) onto PGCB was described by parameters such as standard Gibb’s free energy change (ΔGo), standard enthalpy change (ΔHo), and standard entropy change (ΔSo) while the pseudo first-order and pseudo second-order kinetic model was used to describe kinetic data for the PGCB, with R2 and chi- square test (  2) as the determinant factor of best fit model. From the desorption studies, the effect of eluants (HCl and HNO3) and contact time on percentage desorption of PGCB loaded copper (II) ion was investigated upon. In determining the reusability of the PGCB loaded copper (II) ion, three cycles of adsorption/desorption studies was carried out. The results obtained from determining the best conditions for grafting polyaniline onto chitosan beads revealed the following grafting conditions; [Aniline] 0.1 g/l, [temperature] 35oC, [chitosan] 0.45 g/l, [HCl] 0.4 g/l, [(NH4)2S2O8] 0.35 g/l, and [time] 1 h. These conditions were applied in the grafting of polyaniline onto chitosan beads. FTIR analysis showed increase intensity in the grafted beads which provided evidence of grafting, XRD measurement showed a decrease in crystallinity in the PGCB as against the partial crystalline nature of chitosan. In SEM analysis, evidence of grafting was revealed by the closed gap between the polysaccharide particles in the PGCB. From the investigation carried out on the effect of pH on the percentage removal of Cu(II) ions by PGCB, the optimal pH value was found to be pH 5 with a percentage removal of 100% and this value was used for all adsorption experiment. Also from the investigation performed on the effect of contact time and initial concentration, it was observed that there was a sharp increase in the amount of Cu(II) ions adsorbed by PGCB up until contact time of 30 min and thereafter, it increases gradually. From the experiment carried out on the effect of temperature on adsorption capacity, there was an increase in adsorption capacity with increase in temperature. Moreover, at temperatures of 25oC, 35 oC and 45oC the Langmuir model gave the best fit for the chitosan beads having R2 values that are equal and greater than 0.942 in contrast to Freundlich having R2 values that is equal and greater than 0.932. The maximum adsorption capacity (Qm) from Langmuir model at these temperatures were 30.3 mg/g, 47.6 mg/g and 52.6 mg/g respectively. Also, the Langmuir model gave the best fit for the PGCB having R2 values that are equal and greater than 0.956 in contrast to Freundlich model with R2 values that is equal and greater than 0.935. The Qm from Langmuir model at these temperatures were 80.3 mg/g, 90.9 mg/g and 100 mg/g respectively. The values of Qm for PGCB appears to be significantly higher when compared to that of chitosan beads and this makes PGCB a better adsorbent than chitosan beads. From the thermodynamic studies carried out on PGCB, the values of ΔGo were negative and this denotes that the adsorption of copper ions onto PGCB is favorable and spontaneous, the positive value of ΔHo shows the adsorption process is endothermic and the positive value of ΔSo illustrate increased randomness at the solid-liquid interface during the adsorption process. Also, from the kinetic studies carried out on the PGCB, the pseudo second-order kinetic model best described the kinetic data having R2 values that are equal and greater than 0.994 in contrast to the pseudo first-order kinetic model with R2 values that is equal and greater than 0.913. The  2 values for the pseudo first-order and pseudo second-order kinetic model were similar; however, there was a large difference for qe between the calculated (qeCal) values of the first-order kinetic model and experimental (qeExp) values. In the case of the pseudo second-order model, the calculated qe values agree very well with the experimental data. Desorption of the metal ions from PGCB was efficient. 0.5 M HCl was successfully used in desorbing the beads loaded with copper ions and a percentage desorption of 97.1% was achieved at contact time of 180 min. PGCB were successfully re-used for adsorption/desorption studies were a Qm of 83.3 mg/g, 83.3 mg/g and 76.9 mg/g was achieved in the first, second and third cycle respectively.

A combinação do teste de Ames e métodos seletivos de extração para os principais grupos de compostos responsáveis pela atividade genotóxica em amostras ambientais tem sido muito utilizada. O objetivo foi validar o uso do Blue rayon como alternativa para extração de compostos presentes em águas brutas e tratadas. Foram realizados experimentos comparativos entre o Blue rayon e XAD-4 com amostras fortificadas e amostras reais. Dois mananciais, um contaminado com compostos policíclicos e outro não, foram estudados. As amostras foram extraídas com resina XAD4, e com Blue rayon, este último seletivo para compostos policíclicos. Os extratos foram testados com as linhagens de Salmonella typhimurium TA98 e TA100 na presença e ausência de mistura S9. O Blue rayon foi menos eficiente na detecção da mutagenicidade total das amostras quando comparado com a XAD-4. Porém foi capaz de distinguir a mutagenicidade já presente na água bruta daquela gerada durante o tratamento. / The combination of the Ames test and selective extraction methodologies has been successfully used to indicate the possible classes of organic contaminants in environmental samples. The aim of this study was to validate the use of Blue rayon as an alternative extraction method to detect compounds in raw and treated waters. Two different water bodies were evaluated and in one of the sites, raw waters were known to be contaminated with polycyclic compounds. Experiments comparing the Blue rayon technique with XAD-4 resin were done in environmental and spiked samples. The extracts were tested for mutagenicity with Salmonella typhimurium strains TA98 and TA100, with and without metabolic activation. Blue rayon was less efficient in detecting the overall mutagenicity of the samples analyzed in comparison with XAD-4. It was able though to distinguish the mutagenicity due to the contaminants in raw from the ones generated by water treatment.

A combinação do teste de Ames e métodos seletivos de extração para os principais grupos de compostos responsáveis pela atividade genotóxica em amostras ambientais tem sido muito utilizada. O objetivo foi validar o uso do Blue rayon como alternativa para extração de compostos presentes em águas brutas e tratadas. Foram realizados experimentos comparativos entre o Blue rayon e XAD-4 com amostras fortificadas e amostras reais. Dois mananciais, um contaminado com compostos policíclicos e outro não, foram estudados. As amostras foram extraídas com resina XAD4, e com Blue rayon, este último seletivo para compostos policíclicos. Os extratos foram testados com as linhagens de Salmonella typhimurium TA98 e TA100 na presença e ausência de mistura S9. O Blue rayon foi menos eficiente na detecção da mutagenicidade total das amostras quando comparado com a XAD-4. Porém foi capaz de distinguir a mutagenicidade já presente na água bruta daquela gerada durante o tratamento. / The combination of the Ames test and selective extraction methodologies has been successfully used to indicate the possible classes of organic contaminants in environmental samples. The aim of this study was to validate the use of Blue rayon as an alternative extraction method to detect compounds in raw and treated waters. Two different water bodies were evaluated and in one of the sites, raw waters were known to be contaminated with polycyclic compounds. Experiments comparing the Blue rayon technique with XAD-4 resin were done in environmental and spiked samples. The extracts were tested for mutagenicity with Salmonella typhimurium strains TA98 and TA100, with and without metabolic activation. Blue rayon was less efficient in detecting the overall mutagenicity of the samples analyzed in comparison with XAD-4. It was able though to distinguish the mutagenicity due to the contaminants in raw from the ones generated by water treatment.