A preocupação com o desenvolvimento sustentável tem levado a indústria e os órgãos controladores do meio ambiente a reavaliarem o emprego em larga escala de procedimentos industriais que, embora eficientes, são prejudiciais à saúde humana e ao meio ambiente. Em concordância com estas novas tendências, as indústrias de tratamento de superfícies de metais e instituições de pesquisa têm empregado grandes esforços no sentido de encontrar substitutos eficientes para procedimentos de proteção contra a corrosão que contenham íons de cromo hexavalente, os quais são muito eficientes, mas apresentam o inconveniente de não serem ambientalmente corretos devido ao caráter cancerígeno e poluente do íon Cr(VI) já reconhecido por diversas agências de proteção ambiental. Com a finalidade de aumentar a proteção contra a corrosão, em linhas industriais contínuas de eletrogalvanização por eletrodeposição, as peças produzidas são protegidas por uma camada de passivação obtida em banho de conversão contendo sais de Cr(VI) e, na maioria dos casos, não passa pelo processo de enxágue após sua produção. Neste trabalho o comportamento de corrosão do aço eletrogalvanizado protegido com camadas de passivação obtidas a partir de banhos de conversão contendo sais de Cr(III) e Co(II) ou uma emulsão de um copolímero de etileno, sem enxágue, foi avaliado por técnicas eletroquímicas, especificamente, acompanhamento do potencial de circuito aberto, curvas de polarização potenciodinâmica anódicas e catódicas, e espectroscopia de impedância eletroquímica (EIS), em soluções com diferentes concentrações de NaCl. Adicionalmente foi avaliado o comportamento de corrosão por ensaios em câmara de névoa salina, realizados de acordo com a norma ASTM B117-11. Como referência, os resultados foram comparados com aqueles apresentados por amostras protegidas por camada de passivação produzida a partir de banho contendo íons de Cr(VI). Para melhor compreender a influência da microestrutura sobre o mecanismo de corrosão, as amostras foram caracterizadas por microscopia eletrônica de varredura antes e após imersão nos diferentes eletrólitos. A análise microestrutural foi complementada por ensaios de difração de raios-X. 7 Os resultados dos ensaios eletroquímicos realizados após tempos curtos de imersão mostraram melhor desempenho para as amostras protegidas com a camada de passivação produzida a partir de banho contendo íons Cr(VI). Entretanto os ensaios de EIS após tempos mais longos de imersão nos diferentes eletrólitos ensaio, bem como os ensaios de névoa, evidenciaram que as amostras protegidas com a camada passiva obtida a partir do banho contendo íons de Cr(III) e Co(II) podem apresentar desempenho semelhante àquelas protegidas com camada de conversão de Cr(VI). Para esta condição, a análise microestrutural e o ajuste dos diagramas de EIS com circuitos equivalentes indicaram um papel importante dos produtos de corrosão no comportamento anticorrosivo das amostras protegidas com a camada de passivação de Cr(III) e Co(II). Em nenhuma das condições estudadas as amostras protegidas com o copolímero de etileno apresentaram desempenhos comparáveis aos das outras duas camadas de passivação estudadas. / Recent concerns with sustainable development have led industries and environment regulatory agencies to reassess the use at large scale of industrial procedures that, although efficient, are harmful to human health and the environment. In accordance with these new tendencies, surface treatment industries and research institutes have expended great efforts to find efficient substitutes for corrosion protection procedures that employ hexavalent chromium ions (Cr(VI)). They are very effective but have the drawback of not being environmentally friendly due to the carcinogenic and pollutant properties of Cr(VI) ions, already recognized by several environmental protection agencies. Aiming to increase the corrosion protection, in industrial continuous lines of galvanizing by electroplating, the parts produced are protected with a passivation layer obtained from a conversion bath containing Cr(VI). These parts are not rinsed after the final production step. In this work the corrosion behavior of electroplated galvanized steel protected with passivation layers from conversion baths containing Cr(III) and Co(II) ions or an ethylene copolymer emulsion was evaluated by means of electrochemical techniques, specifically, open circuit potential measurements, anodic and cathodic potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS). The tests were performed in sodium chloride solutions of different concentrations. Additionally, the corrosion behavior was evaluated by salt spray tests performed according the ASTM B117-11 standard. For reference, the results were compared with those presented by samples protected by passivation layers produced from conversion baths containing Cr (VI) ions. Aiming to better understand the influence of microstructure on the corrosion mechanism, the samples were characterized by scanning electron microscopy before and after immersion in the different electrolytes. Microstructure analysis was complemented by X-ray diffraction. The results of electrochemical tests performed after short immersion times showed better corrosion performance for samples protected with the passivation layer produced from conversion baths containing Cr(VI) ions. However, the EIS tests performed after longer immersion times in the different electrolytes, as well as the 9 salt spray tests, showed that samples protected with the passive layer obtained from the bath containing Cr (III) and Co (II) ions may present similar performance to those protected with the Cr (VI) conversion layer. The microstructural analysis and fitting of the EIS diagrams with equivalent circuits indicated an important role of corrosion products in the anti-corrosive performance of the samples protected with the passivation layer of Cr (III) and Co (II). In the studied conditions, the samples protected with the ethylene copolymer did not showed comparable performance to the other two passivation layers investigated in the present study.

Made available in DSpace on 2015-09-25T12:23:36Z (GMT). No. of bitstreams: 1 SALOMAO_DE_ANDRADE_PASCOAL.pdf: 1571379 bytes, checksum: 8dcb3d302822615da27bf933016a3cef (MD5) Previous issue date: 2006-02-23 / The industry is a section of the contemporary society with great pollutant potential of the environment, especially of the aquatic ecosystems. The tanning industries are big producing of dejections with significant amounts of organic matter and of chrome. The conventional processes of treatment applied those dejections, not always they possess good effectiveness. Actuality, the Advanced Oxidation Processes represent an excellent alternative of tertiary treatment. In the present study, the application of the heterogeneous photocatalysis was evaluated, being used a photocatalyst (TiO2) immobilized, in the tertiary treatment of synthetic liquid effluents representative of tanning industries. It was aimed at to remove Cr(VI) and organic matter. The photocatalytic reactor was of the type Fixed Bed of Fine Film, built with a plate of glass arrayed for the fixation of TiO2. It was adopted as radiation sources, the sun and lamps issuing of UV radiation (l= 250 nm). The smallest values of removal effectiveness for Cr(VI) they were of 62% and 51% and of DOC they were from 60% and 53% to the experiments done with radiation UV originating from of the sun and of lamps, respectively. The results of the parameters related to the reduction phases and oxidation of the heterogeneous photocatalysis, they showed that the exhibition in the sun, he/she has effectiveness of larger relative removal than the exhibition to UV lamps. The data of relative removal of Cr(VI) and of DOC and the constants kinetics of these parameters, they indicated that the adopted experimental configurations optimized the phase of reduction of the heterogeneous photocatalysis. / A indústria é um setor da sociedade contemporânea com grande potencial poluidor do meio ambiente, especialmente dos ecossistemas aquáticos. As indústrias de curtume são grandes produtoras de dejetos com significativas quantidades de material orgânico e de cromo. Os processos convencionais de tratamento aplicados a esses dejetos, nem sempre possuem boa eficácia. Atualmente, os Processos Oxidativos Avançados representam uma excelente alternativa de tratamento terciário. No presente estudo, avaliou-se a aplicação da fotocatálise heterogênea, usando-se um fotocatalisador (TiO2) imobilizado, no tratamento final de efluentes líquidos sintéticos representativos de indústrias de curtume. Objetivou-se remover Cr(VI) e matéria orgânica. O fotorreator foi do tipo Leito Fixo de Filme Fino, construído com uma placa de vidro jateado para a fixação do TiO2. Adotou-se como fontes de radiação, o sol e lâmpadas germicidas emissoras de radiação UV (l= 250 nm). Os menores valores de eficácia de remoção para Cr(VI) foram de 62% e 51% e de DQO foram de 60% e 53% para os experimentos feitos com radiação UV oriundas do sol e de lâmpadas, respectivamente. Os resultados dos parâmetros relacionados às fases de redução e oxidação da fotocatálise heterogênea, mostraram que a exposição ao sol, tem eficácia de remoção relativa maior do que a exposição à lâmpadas UV. Os dados de remoção relativa de Cr(VI) e de DQO e as constantes cinéticas destes parâmetros, indicaram que as configurações experimentais adotadas otimizaram a fase de redução da fotocatálise heterogênea.

The production of ferrochrome (FeCr) from chromite ore is a reducing process, whereby the Cr(III) and Fe(II) in the ore are reduced to metallic chromium (Cr) and iron (Fe) in the final product. FeCr is mostly used for the production of stainless steel, which is a vital alloy in modern society. It is, however, impossible to exclude oxygen completely from all the high temperature steps during the production process and very small amounts of Cr(VI) are therefore formed, although not intended. The formed Cr(VI) is mostly associated with the off-gas of the high temperature processes, which are cleaned before it is released into the atmosphere by means of venturi scrubbers or bag filter systems. Certain Cr(VI) species are regarded as carcinogenic, with specifically airborne exposure to these Cr(VI) species being associated with cancer of the respiratory system. FeCr smelter facilities generate three main types of waste materials, i.e. slag, venturi sludge and bag filter dust (BFD). Most of the Cr in the waste materials consists mostly of Cr(III). However, BFD generated during the cleaning of the off-gas of open/semi-closed furnaces, could contain more significant levels of Cr(VI) than the slag and sludge. The aim of this study was to determine the solubility of different Cr(VI) species present in BFDs. This would allow that the Cr(VI) in BFD is categorised as water soluble Cr(VI), sparingly soluble and insoluble Cr(VI). These solubility categories can then be related to groups of Cr(VI) compounds, therefore taking the first step in better characterisation of Cr(VI) present in BFD. Four different BFD samples from FeCr producers in South Africa were characterised in detail. Analytical methods such as scanning electron microscope (SEM), SEM with energy-dispersive X-ray spectroscopy (SEM-EDS), particle size analysis, trace metal analysis with inductively coupled plasma with a mass spectrometer detector (ICP-MS) and Cr(VI) analysis with ion chromatography (IC) were utilised in order to characterise and categorise the samples. The results indicated that more Cr(VI) leached with an increase in pH. This was in contrast with the trend for most heavy metals. This was also an indication that not only soluble, but also sparingly- and insoluble Cr(VI) compounds occur in the BFD samples evaluated. Further analysis showed that approximately one third of the Cr(VI) species was insoluble and the remainder consisted of sparingly insoluble and soluble Cr(VI) compounds. The most significant finding was that the current leaching procedures applied by FeCr producers, prior to the chemical reduction of Cr(VI), do not effectively extract the sparingly water insoluble compounds. This results in Cr(VI) leaching from waste facilities at later stages, even if seemingly effective Cr(VI) treatment was applied. Therefore, it should be considered as an extremely important future perspective to develop economically feasible Cr(VI) extraction procedures that will ensure complete extraction of sparing water soluble Cr(VI) compounds together with the water soluble fraction, prior to chemical reduction of Cr(VI) and subsequent storage of the residue on a waste facility. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2015

The production of ferrochrome (FeCr) from chromite ore is a reducing process, whereby the Cr(III) and Fe(II) in the ore are reduced to metallic chromium (Cr) and iron (Fe) in the final product. FeCr is mostly used for the production of stainless steel, which is a vital alloy in modern society. It is, however, impossible to exclude oxygen completely from all the high temperature steps during the production process and very small amounts of Cr(VI) are therefore formed, although not intended. The formed Cr(VI) is mostly associated with the off-gas of the high temperature processes, which are cleaned before it is released into the atmosphere by means of venturi scrubbers or bag filter systems. Certain Cr(VI) species are regarded as carcinogenic, with specifically airborne exposure to these Cr(VI) species being associated with cancer of the respiratory system. FeCr smelter facilities generate three main types of waste materials, i.e. slag, venturi sludge and bag filter dust (BFD). Most of the Cr in the waste materials consists mostly of Cr(III). However, BFD generated during the cleaning of the off-gas of open/semi-closed furnaces, could contain more significant levels of Cr(VI) than the slag and sludge. The aim of this study was to determine the solubility of different Cr(VI) species present in BFDs. This would allow that the Cr(VI) in BFD is categorised as water soluble Cr(VI), sparingly soluble and insoluble Cr(VI). These solubility categories can then be related to groups of Cr(VI) compounds, therefore taking the first step in better characterisation of Cr(VI) present in BFD. Four different BFD samples from FeCr producers in South Africa were characterised in detail. Analytical methods such as scanning electron microscope (SEM), SEM with energy-dispersive X-ray spectroscopy (SEM-EDS), particle size analysis, trace metal analysis with inductively coupled plasma with a mass spectrometer detector (ICP-MS) and Cr(VI) analysis with ion chromatography (IC) were utilised in order to characterise and categorise the samples. The results indicated that more Cr(VI) leached with an increase in pH. This was in contrast with the trend for most heavy metals. This was also an indication that not only soluble, but also sparingly- and insoluble Cr(VI) compounds occur in the BFD samples evaluated. Further analysis showed that approximately one third of the Cr(VI) species was insoluble and the remainder consisted of sparingly insoluble and soluble Cr(VI) compounds. The most significant finding was that the current leaching procedures applied by FeCr producers, prior to the chemical reduction of Cr(VI), do not effectively extract the sparingly water insoluble compounds. This results in Cr(VI) leaching from waste facilities at later stages, even if seemingly effective Cr(VI) treatment was applied. Therefore, it should be considered as an extremely important future perspective to develop economically feasible Cr(VI) extraction procedures that will ensure complete extraction of sparing water soluble Cr(VI) compounds together with the water soluble fraction, prior to chemical reduction of Cr(VI) and subsequent storage of the residue on a waste facility. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2015

No description available.

The USEPA Maximum Contaminant Level (MCL) for Total Chromium in drinking water is 100 μg/L. Total chromium includes both trivalent chromium (Cr(III), a trace nutrient) and hexavalent chromium (Cr(VI), a probable human carcinogen). The State of California set a Cr(VI)-specific MCL of 10 μg/L in 2014, and USEPA is considering a new federal MCL for Cr(VI). This would have a significant impact on drinking water systems across the US, with estimated annual cost of compliance between $0.6 to 5.1 billion per year. While Cr(VI) is the species of concern for health effects, water utilities must also consider Cr(III) since it can be oxidized to Cr(VI) by various chemicals. This oxidation has been documented for commonly used disinfectants. However, past studies were conducted with higher levels of chromium (e.g., 20 to 500 μg/L) and it is unknown if the reactions proceed at the same rate and extent at the lower concentrations relevant to most water treatment plants (< 10 μg/L). This project, funded by the Water Research Foundation, systematically evaluated the extent of oxidation of Cr(III) by drinking water oxidants under conditions relevant to drinking water utilities. Five oxidants (chlorine, monochloramine, chlorine dioxide, potassium permanganate, and ozone) were tested. Two doses were used for each chemical with their respective reaction times reflecting the typical application of the chemical in treatment. Three different water qualities were evaluated, each at pH 5.5, 7, and 9, and at two different temperatures (5 and 16 °C). Chlorine consistently oxidized an average of 80% of the available Cr(III), with the majority of the oxidation happening within the first 7 hours. Monochloramine did not significantly oxidize Cr(III) at any of the conditions tested. Chlorine dioxide was an effective oxidant at pH 7, with complete oxidation occurring in 6 hours, but was less effective at pH 5.5 and 9. Potassium permanganate achieved complete oxidation in 4 hours at each pH, with pH 7 experiencing the fastest oxidation. Ozone oxidized all available Cr(III) within minutes at all pH values. Quantifying the Cr(III) oxidation as a result of using these oxidants provides understanding of potential Cr(VI) addition into drinking water.

Water pollution, especially caused due to the indiscriminate release of heavy metals as a result of anthropogenic activities is a major concern worldwide. Chromium, a heavy metal, regardless of its commercial importance has found to be a potent water pollutant. Chromium generally exist as hexavalent (Cr(VI)) and trivalent (Cr(III)) chromium in the environment. Cr(VI) is ascertained to be more toxic compared to Cr(III) and the former is identified as a carcinogen by the World Health Organisation (WHO). Some of the conventional methods currently available for chromium pollution mitigation are not cost effective and most importantly lead to secondary pollution in the form of sludge. Bioremediation is a promising alternative technique which is also ecofriendly. The bioremediation process utilises biological materials such as microorganisms and agricultural byproducts. Biosorption is a bioremediation process that is a surface related phenomenon involving adsorption of contaminant chromium ions onto the binding sites of the biosorbents. In addition to the efforts made to the remediation of chromium, continuous monitoring of chromium contaminant level in polluted water bodies becomes imperative. The present research study encompasses findings related to bioremediation and detection of chromium ions using bacterial cells. The first part of the dissertation involves studies pertaining to the bioremediation of chromium ions using different bacterial strains as biosorbent. For the study, bacterial strains procured from a microbial culture collection bank as well as those isolated from chromium polluted water samples collected from an industrial site were assessed for their ability to remediate chromium. The next aim of the study was to elucidate the mechanisms involved in the bioremediation of chromium ions by the bacterial cells for which the different characterisation methods such as, Fourier Transform Infrared (FTIR) spectroscopy, Energy Dispersive Spectroscopy (EDS), X-ray Photoelectron Spectroscopy (XPS) and zeta potential measurements which enabled to throw light on the reactions occurring at the bacterial cell surface-chromium solution interface. The later part of the study examines the capability of the bacterial strains used in the bioremediation studies as sensors for the detection of Cr(VI) and Cr(III) ions by adopting electroanalytical techniques, such as, Cyclic Voltammetry (CV) and Cathodic Stripping Voltammetry (CSV), wherein a microbe-modified Carbon Paste Electrode (CPE) was used as the working electrode in a typical three electrode electrochemical cell with Saturated Calomel Electrode (SCE) and platinum wire used as the reference and auxiliary electrodes respectively. The key objectives of the present study are as follows: (i) To study the bioremediation of Cr(VI) and Cr(III) ions present in aqueous solutions using two bacterial strains procured from a microbial culture collection bank as biosorbents. The bacterial strains used were Corynebacterium paurometabolum (Cp), a Gram positive bacterium and Citrobacter freundii (Cf), a Gram negative bacterium. The various factors affecting the biosorption process are to be investigated. (ii) To isolate and identify bacterial strains from water samples collected from chromium contaminated mining site in Sukinda, Odisha, India, by adopting appropriate microbiological and molecular biological procedures. (iii) To study the various factors affecting bioremediation of Cr(VI) using the mine isolates (Chromobacterium sp. (Cb) and Sphingopyxis sp. (Sp)) both Gram negative, as biosorbents. (iv) To elucidate the mechanisms adopted by the chosen bacterial cells in the bioremediation of chromium. (v) To develop an electrochemical-microbial sensor by modifying the Carbon Paste Electrode (CPE) using the bacterial strains for the detection of Cr(VI) and Cr(III) ions present in aqueous solutions. (vi) To determine the capability of the developed sensor in the detection of Cr ions in mine water samples collected from Sukinda chromite mine in Odisha, India. (vii) To elucidate the mechanisms occurring at the bio-modified electrode–solution interface. A compendious description of the findings from the present work is given below: The capability of two bacterial strains procured from a microbial culture collection bank (MTCC), Corynebacterium paurometabolum (Gram positive bacterium) and Citrobacter freundii (Gram negative bacterium) as biosorbents for Cr (VI) and Cr(III) ions was assessed. Further, it became of interest to translate the studies related to bioremediation to an industrial situation. For this, bacterial strains were isolated from chromium contaminated water samples collected from surface water of Sukinda chromite mine in Odisha, India. Based on detailed microbiological and molecular biological protocols, two strains of bacteria were identified and characterised as Chromobacterium sp. and Sphingopyxis sp. The bioremediation efficiency of the strains was evaluated taking into consideration the various factors such as effect of contact time of bacterial cells with the chromium ions, pH of the chromium ion solution, biomass loading and initial chromium ion concentration. The Cr(VI) biosorption efficiency obtained for C. freundii was found to be about 59 %, followed by Sphingopyxis sp. and C. paurometabolum ≈ Chromobacterium sp. in the range of 50 % to 55 %. Subsequent to interaction of the bacterial cells with the Cr(VI) solution, the residual chromium was found to be in the form of Cr(III) ions. Hence, complete bioremediation of Cr(VI) could be achieved in terms of both biosorption and bioreduction processes using all the bacterial strains. It was found that the bioreduction process occurring in conjunction with the biosorption process resulted in nil concentration of Cr(VI) ions in the bulk solution. Similarly, studies related to bioremediation of Cr(III) using C. paurometabolum and C. freundii bacterial strains were also performed with higher biosorption efficiency achieved for the former, 50 % compared to 30 % obtained for C. freundii bacterial cells. The bioremediation of Cr(III) ions by the bacterial cells is achieved by the biosorption process. Biosorption of Cr ions by all the bacterial strains were found to follow a typical Langmuirian behaviour. The bioremediation process by the bacterial strains was also evaluated using suitable kinetic models and the results indicated that the bioremediation of Cr(VI) and Cr(III) by C. paurometabolum and C. freundii respectively followed pseudo first order kinetics, while the bioremediation of Cr(VI) by C. freundii, Chromobacterium sp. and Sphingopyxis sp. followed pseudo second order kinetics. It becomes of importance to ascertain the mechanisms of bioremediation of chromium ions by the bacterial cells and for this, different characterisation methods were adopted that helped in deducing the reactions occurring at the bacterial cell surface-chromium solution interface. The involvement of chemical forces in the bioremediation process was corroborated by the achievement of only partial desorption of chromium ions from the biosorbed bacterial cells. This was further confirmed by the Gibbs free energy (∆G) values, which were found to be in the range of -25 to -30 kJ/mol. FTIR spectral studies provided evidence in support of the key functional groups present on the bacterial cell surface such as, –OH, -COOH and –NH, which facilitated the binding with chromium. The EDS data for chromium biosorbed bacterial cells showed peaks corresponding to chromium, thereby confirming the binding of chromium by the bacterial cells. The redox state of chromium bound on the bacterial cell surface was determined with the help of XPS analysis. In the Cr2p XPS spectra obtained for the bacterial cells interacted with Cr(VI), it was interesting to observe a peak corresponding to Cr(III) in addition to Cr(VI), unequivocally indicating that the Cr(III) formed via bioreduction was not only released into the bulk solution but also got biosorbed on the bacterial cell surface. Apparent shifts in the binding energy values for the bacterial cells interacted with chromium were observed in the spectra recorded corresponding to C1s, O1s, N1s, P2p and S2p as compared to the spectra obtained for the bacterial cells alone. This attests to the fact that the functional groups corresponding to the elements mentioned are involved in chemical interaction with the chromium ions or are involved in the donation of electrons to bring about reduction of Cr(VI) to the less toxic Cr(III). The variation in the charge of the bacterial cell surface before and after interaction with chromium ions was monitored by performing zeta potential measurements as a function of pH. The surface charge of the bacterial cells alone was found to be negative over a wide range of pH. Subsequent to interaction of the bacterial cells with the negatively charged oxyanions of Cr(VI) ions, the surface charge was observed to be less electronegative, which further confirmed the binding of the positively charged Cr(III) ions formed via bioreduction on the bacterial cell surface. Similar results were also observed in the case when cells were allowed to interact with Cr(III) ions. The shifts in the iso-electric point for bacterial cells interacted with chromium ions further testified to the involvement of chemical binding forces in the bioremediation process. The findings obtained from the different characterisation methods enabled in understanding the reactions that are occurring at the bacterial cell surface-Cr solution interface. Initially, biosorption via electrostatic interaction of negatively charged oxyanions of Cr(VI) with the positively charged amino groups present on the bacterial cell surface takes place. Subsequent to the biosorption of Cr(VI) ions, the adjacent electron donating functional groups containing ligands present on the bacterial cell surface reduce Cr(VI) to Cr(III) via the reactions shown below: Bioreduction involving –OH group Bioreduction involving –SH group It can be seen that, the reactions involving bioreduction of Cr(VI) in the form of chromate oxyanion to Cr(III) involving hydroxyl and thiol group present on the bacterial cell surface result in the formation of intermediates, chromate-oxy and chromate-thio ester respectively. These intermediates facilitate the transfer of electrons from oxygen/sulphur donor centers to Cr(VI) acceptor molecule, thereby resulting in the reduction of Cr(VI) to Cr(III). The Cr(III) ions thus formed are then either released into the bulk solution or get complexed with the binding groups present on the bacterial cell surface. The next objective was to explore the potential of bacterial strains as sensors for the detection of Cr(VI) and Cr(III) ions. The chromium ions were detected using CV and CSV, both of which are electroanalytical techniques. For this, CPE was coated with the bacterial strains, C. paurometabolum, C. freundii, Chromobacterium sp. and Sphingopyxis sp., and the modified electrode was used as the working electrode in a typical three electrode electrochemical cell. These biosensors developed using each of the aforementioned strains resulted in a ~ 2 to 2.5 fold improved performance compared to the bare CPE for the detection of Cr(VI) ions, due to the binding ability of the various functional groups present on the bacterial cell surface. The lower limit of detection (LLOD) obtained for Cr(VI) and Cr(III) ions using CV technique was found to be 1x10-4 M and 5x10-4 M respectively. The LLOD was further improved to 1x10-9 M and 1x10-7 M for Cr(VI) and Cr(III) respectively using CSV. From the voltammograms obtained, it was postulated that the different functional groups present on the bacterial cell surface facilitate the detection of the chromium ions. Additionally, the developed microbial sensors were also found to be capable of detecting Cr(VI) ions in mine water samples collected from Sukinda chromite mine Odisha, India. In summary, the mechanisms of bioremediation of toxic Cr(VI) ions have been delineated as comprising of both biosorption and bioreduction processes. The residual Cr(VI) concentration subsequent to the treatment of the Cr(VI) aqueous solution with the bacterial cells was found to be nil, which meets the regulatory limit of 0.05 mg L-1 put forward by the US-Environmental Protection Agency (EPA) for a safe effluent discharge. Moreover, it has also been demonstrated that the chosen bacterial strains could be used as sensors for the detection of upto nanomolar concentration of Cr(VI) ions, under optimum conditions.

Heavy metals are released into the environment either by natural processes or by anthropogenic activities. Industries such as leather tanning, textiles, metallurgical, electroplating and mining activities discharge the chromium along with other heavy metals, which causes water pollution and environmental degradation. There are many conventional methods to overcome this problem such as chemical precipitation, ion exchange, reverse osmosis, etc but, these methods have certain drawbacks like generation of secondary sludge, inefficient removal of metal ions of low concentration, high cost etc. To overcome these limitations by conventional methods, an environmental friendly method, namely bioremediation has been adopted. Bioremediation uses microorganisms, biodegradable industrial wastes, or plants to mitigate this problem. In this investigation, bacterial strains have been isolated from the soil and water samples collected from a chromite mine in Karnataka. The capability of these bacterial strains have been assessed to remediate Cr (VI) in batch experiments in order to achieve the prescribed standards of regulatory agencies, and to elucidate the mechanisms of bioremediation of Cr (VI). Additionally, using these bacterial strains, biosensors have been developed to detect Cr (VI) ions in the solution by electroanalytical techniques. The major objectives of this research investigation are: a) Isolation, characterization and identification of bacterial strains from water and soil samples obtained from a chromite mine in Karnataka. b) To study the ability of three isolated bacterial strains namely Arthrobacter sp, Exiguobacterium sp. and Micrococcus sp. to remediate Cr (VI) during growth in media, amended with different concentrations of Cr (VI) c) Delineation of the probable mechanisms of bioremediation of Cr (VI) by three bacterial strains with the aid of proteomic and metabolomic studies d) Optimization of factors influencing the bioremoval of Cr (VI) using the isolated bacterial strains as biosorbents in batch experiments. c) Elucidation of mechanisms of bioremoval of Cr (VI) at the microbe – metal interface for all three bacterial strains, adopting characterization techniques like FTIR, XPS, SEM – EDS and zeta potential measurements. d) Micrococcus sp. was chosen for the fabrication of biomodified carbon paste electrode (CPE) to sense the Cr (VI) ions using voltammetric techniques, namely cyclic voltammetry (CV) and differential pulse cathodic stripping voltammetry (DPCSV). The salient findings of this research work are highlighted as follows: Firstly, bioremediation experiments were carried out using the bacterial strains isolated from soil and water samples collected from the chromite mines of Mysore Minerals Limited, Hassan district, Karnataka, India. Initially, the characterisation of the isolated bacterial strains were carried out with respect to their biochemical aspects, antibiotic susceptibility, morphology using scanning electron microscopy and cell wall nature by Gram’s staining. The identification of the three isolated bacterial strains were accomplished by 16S rRNA method and the three bacterial strains have been identified as Arthrobacter sp., Exiguobacterium sp. and Micrococcus sp.. The experiments were conducted to assess the potential of the isolated bacterial strains namely, Arthrobacter sp., Exiguobacterium sp. and Micrococcus sp., for the remediation at two different concentrations of 10 mg/L and 30 mg/L of Cr (VI) ions, during cell growth i.e. using metabolically active cells of bacteria. It was found that the three bacterial strains could bioreduce toxic Cr (VI) to the less toxic Cr (III) form, by 95% to 99%, within a time span of 12 h to 120 h. In the experiment with sulphate as the competitive ion in the growing mode of the bacterial strains Arthrobacter sp., Exiguobacterium sp. and Micrococcus sp., the percentage bioreduction of Cr (VI) to Cr (III) was not hampered. Scanning electron microscopic studies on the bacterial cells of Arthrobacter sp., Exiguobacterium sp. and Micrococcus sp., before and after interaction with Cr (VI) showed the morphological changes after interaction with Cr (VI), as an adaptive strategy to counter the toxic effect of Cr (VI). Further, to elucidate the mechanisms of bioreduction of Cr (VI) to Cr (III) by the three bacterial strains, the proteins and metabolites were isolated from the pristine bacterial cells and Cr (VI) interacted bacterial cells. The proteins were isolated from different parts of the cells and assessed for the differential expression of proteins under Cr (VI) stress. It was found that, seven differentially expressed protein bands were observed on SDS PAGE profile of Arthrobacter sp. interacted with Cr (VI), from the soluble protein isolated from the crude extract, devoid of cell membrane. A single band of differentially expressed protein was observed in the extracellular secretion in Exiguobacterium sp. and in the case of Micrococcus sp. four differentially expressed proteins were observed in the membrane fraction of proteins. The mass spectrometry data of the differentially expressed proteins were used to identify the probable protein candidates using MASCOT search in NCBIr database. It was found that some of these proteins were a class of transport proteins and a few belong to the reactive oxygen species scavengers. These findings suggested that the bioreduction of Cr (VI) to Cr (III) involved the efflux mechanism and ROS scavenger production, to resist the toxicity of Cr (VI). The metabolite concentration profile was studied for the all three bacterial cells in the absence and presence of Cr (VI) using NMR spectroscopy. The results of this study showed an increase and decrease in the concentration of various metabolite components after interaction with Cr (VI), and this was observed in all the three bacterial strains. Some of the metabolites identified using Chenomx 8.1 metabolite library, were found to be osmoprotectants like betaine, proline etc, which combat the stress of Cr (VI). Therefore, the overall bioremediation of Cr (VI) by metabolically active bacterial cells is through bioreduction of toxic Cr (VI) to the less toxic Cr (III) form and the resistance mechanisms to overcome the toxic effect of Cr (VI) is by the efflux mechanism, production of osmoprotectants and expression of ROS scavengers. In the third part of investigation, the bioremoval of Cr (VI) ions in batch experiments using metabolically inactive cells as biosorbents, for all the three bacterial strains, were studied. The bioremediation efficiency of each bacterial strain was evaluated, considering the various parameters like effect of contact time of bacterial cells with the Cr (VI) ions, pH of Cr ion solution, biomass loading and initial concentration of Cr (VI) ion. The Cr (VI) biosorption efficiency obtained for the bacterial strains Arthrobacter sp., Exiguobacterium sp. and Micrococcus sp. was found to be 93 %, 85 % and 100 % respectively. Apart from the biosorption of Cr (VI) by bacterial cells, the residual Cr was found to be in the form of Cr (III) ions. Therefore, complete bioremoval of Cr (VI) ions could be achieved as a combined process of biosorption and bioreduction, for all three bacterial strains, meeting the acceptable limits prescribed for Cr (VI) ion for drinking water, by regulatory agencies i.e. 0.05 mg/L of Cr (VI) ions. The biosorption of Cr ions by all the three bacterial strains were found to follow a typical Langmurian behaviour. The bioremediation process by the bacterial strains was also evaluated using suitable kinetic models and the results indicated that the bioremoval of Cr (VI) by Arthrobacter sp., Exiguobacterium sp. and Micrococcus sp. followed pseudo second order kinetics. The next aim was to ascertain the mechanism of bioremoval of Cr (VI) ions by the metabolically inactive cells. For this, different characterisation techniques were adopted that aided in the elucidation of reactions occurring at the interface of bacterial cell surface and Cr solution. The nature of interacting forces in bioremoval process was found out by desorption studies, and it was observed that only partial desorption of Cr ions was achieved from the biosorbed bacterial cells. This was further confirmed, by calculation of Gibbs free energy and the values were found to be in the range of – 25 to -32 kJ/mol, thus indicating that the process of bioremoval of Cr (VI) ions by the bacterial cells, is by chemisorption process. The variation in the charge of the bacterial cell surface, before and after interaction with chromium ions, was studied by performing zeta potential measurements as a function of pH. The surface charge of the bacterial cells alone was found to be negatively charged over a wide range of pH. Subsequent to interaction of the bacterial cells with the negatively charged oxyanions of Cr (VI) ions, the surface charge was observed to be less electronegative, which further confirmed the binding of the positively charged Cr (III) ions, formed via bioreduction on the bacterial cell surface. FTIR spectral studies revealed the functional groups involved, in bioremoval of Cr ions, present on bacterial cell surface. The functional group facilitating the bioremoval of Cr ions are –NH, -COOH and phosphate. EDS studies confirmed the Cr peak for the bacterial cells interacted with Cr ions. The oxidation state of Cr ion bound to the bacterial cell surface was determined with the help of XPS analysis. It was interesting to observe the Cr (III) peaks along with their Cr (VI) peaks. These studies provided evidence in support of the bioreduction of Cr (VI) to Cr (III) and biosorption of bioreduced Cr (III) ions onto the surface of bacterial cells, apart from the fraction present in bulk solution. The next objective was to assess the potential of Micrococcus sp. as sensor for the detection of Cr (VI) ions, using electroanalytical techniques such as, cyclic voltammetery (CV) and differential pulse cathodic stripping voltammetry (DPCSV). For this, Carbon Paste Electrode (CPE) was coated with the bacterial strain namely, Micrococcus sp and the modified electrode was used as the working electrode in a three electrode system. The developed biomodified electrode showed an approximately 3-fold increase in the sensing of Cr (VI) ion in comparison with the unmodified electrode CPE, which is attributed to the binding of Cr (VI) ions to functional groups present on the bacterial cell surface. The lower limit of detection obtained for Cr (VI) ions using CV was found to be 1 x10-4 M. The lower limit of detection was improved to 1 x 10-9 M of Cr (VI) using DPCSV.

In South Africa, the ferrochromium industry produces approximately 100,000 t bag house filter dust and slurry, while the stainless steel industry produces 24,000 t of dust annually [17,39]. The toxic substances in these wastes potentially pose a threat to the environment and human health, especially Cr (VI) due to its toxic, carcinogenic, highly soluble and strongly oxidizing properties. Therefore, the existence and treatment of wastes from stainless steel and ferrochrome production remain a challenge and an issue of concern. The increase of environmental legislation globally and the trend towards sustainable development are drives for alternatives to landfill. In the present thesis, the characteristics, formation mechanisms, leachability and stabilisation of the Cr (VI)-containing electric furnace dust and filter cake were investigated using various techniques such as XRD, XRF, TG/DTA, XPS, SEM-EDS, FT-IR, Raman spectrometer and UV/Vis spectrometer. The electric furnace dust and filter cake are very fine particles. Stainless steel dust forms by the entrainment of charge materials, evaporation or volatilisation of elements and ejection of slag and metal by spitting or the bursting of gas bubbles. It was found that ferrochrome dust is formed by the ejection of slag and metals droplets from the electrode hole, the entrainment of charge materials, vaporisation as well as the formation and precipitation of compounds from vaporised species in the off-gas duct. Filter cake contains crystal phases (CaF2 and CaSO4 ) and metal rich amorphous phases. It is formed due to super saturation and precipitation. Leaching experiments on the wastes showed that Cr (VI) rapidly leaches out by distilled water. Bricks were produced by mixing wastes (stainless steel plant dust, ferrochrome dust and filter cake) and clay. The optimum sinter parameter was found to be 1100oC and 5 hours for a 50wt% SPD-50wt% AS mixture in the brick. The leachability of Cr(VI) is strongly influenced by the mass%CaO/mass%SiO2 ratio and alkali metal oxides content in the wastes. The emission factors from the stabilised wastes (SPD, FCD1, FCD2 and FC) are similar to those reported for the cement industry. Semi-dynamic leaching tests indicated that the predominant leaching mechanisms of chromium species are initial surface wash-off followed by matrix diffusion. / Thesis (PhD (Metallurgical Engineering))--University of Pretoria, 2007. / Materials Science and Metallurgical Engineering / unrestricted

M. Tech (Department of Chemistry, Faculty of Applied and Computer Sciences) Vaal University of Technology. / Macadamia activated carbon (MAC) was impregnated with different concentrations of nitric acid and heated under reflux to improve the structural characteristics of the adsorbent for both considerable reduction and enhanced removal of Cr(VI). The chemical oxidation of ACs increased the surface oxygenated functional groups. Adsorption of Cr(VI) was carried out by varying parameters such as contact time, pH, concentration, and adsorbent dosage. The optimum operating conditions for the adsorption of Cr(VI) were pH 1, contact time 240 min, adsorbent dosage 10.67 g/L and Cr(VI) concentration 100 mg/L. The results showed that the Macadamia–based AC could be used efficiently for the treatment of chromium-containing solutions as a low-cost alternative compared to commercial AC and other adsorbent reported. The results showed that treated MAC performed better than untreated MAC, signifying the effect of secondary treatment on the enhanced removal of pollutants. Comparable to the application of ACs is the development of imprinting technologies for selective metal ion remediation in environmental samples. The combination of ion imprinting effects and functionalized carbon adsorbents produce materials which effectively remove and selectively recognize the target analyte. Macadamia activated carbon (MAC) was chemically pre-treated with nitric acid to generate carboxyl groups on the surface. The carboxylated MAC was then reacted with triethylenetetramine, N,N’-diisopropylcarbodiimide and CrCl3.6H2O to produce MACN20-imprinted sorbents (MACN20-IIP). MACN20-non imprinted (MACN20-NIP) counterparts were prepared, but Cr3+ was excluded in the synthesis. Alteration of surface structural characteristics and characterization of prepared adsorbents as confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, elemental analysis, Brunauer–Emmett–Teller and scanning electron microscopy. MACN20-IIP and MACN20-NIP adsorbents were evaluated for their Cr3+ uptake from aqueous solution in batch format. Maximum conditions were achieved at pH 5, 50 mg/L Cr(III) initial concentration and 33.33 g/L of adsorbent dosage. Presence of co-ions slightly diminished the removal of Cr(III) by MAC-IIP adsorbents. Application of the MACN20-IIP and MACN20-NIP on spiked acid mine drainage artificial sample led to collapse in the removal efficiency of MACN20-NIP while MACN20-IIP still showed good removal efficiencies. These results demonstrated that surface imprinting led to better adsorption rates and capacity. The data was better described by the Freundlich multilayer adsorption and pseudo-second order kinetic rate model. The combination of both the carbon sorbent and the surface-mediated IIPs effectively improved total chromium remediation in aqueous systems.