No description available.

In order to identify hexavalent chromium (Cr6) sources, behavior, and treatability, this thesis has profiled Cr6 in seven full-scale drinking water treatment plants and six distribution systems. Bench-scale jar tests assessed the treatment efficacy of coagulation and developed strategies to remove ultra-low level (0.01- 1.0 ~tg/L) Cr6. All water sources measured in this project contained dissolved Cr6 greater than or equal to the California Public Health Goal (0.02 ~g/L Cr6). The investigated coagulation plants did not remove Cr6; in fact, four of the seven treatment plants inadvertently added Cr6 to the treated waters. Thirteen types of drinking water treatment chemicals were evaluated as a potential non-water source of chromium. Amongst these, only iron-based coagulants contained trace levels of chromium sufficient to account for the observed increases at the full-scale plants. Other discussed non-water sources include leaching of chromium-bearing infrastructure or oxidation of Cr3. One of the treatment systems showed chlorine oxidized Cr3 to Cr6 and raised the finished concentration, in less than seven hours. One suggested improvement strategy was to use ferrous iron to reduce and remove Cr6 during coagulation. Bench-scale tests showed ferrous iron and a cationic polymer improved removal of both Cr6 and Total Cr. Chlorine interfered with that reduction. The full-scale test of this reduction-coupled coagulation treatment successfully decreased the finished Cr6 concentration when 40% ferrous iron was used and the point of chlorination was moved downstream from the coagulation process.

No description available.

Hexavalent Chromium (Cr(VI) induces malignant cell transformation in normal bronchial epithelial (BEAS-2B) cells. Cr(VI)-transformed cells exhibit increased level of antioxidants, are resistant to apoptosis, and are tumorigenic. RNAseq analysis in Cr(VI)-transformed cells showed that expression of transcripts associated with mitochondrial oxidative phosphorylation is reduced, and the expression of transcripts associated with pentose phosphate pathway, glycolysis, and glutaminolysis are increased. Sirtuin-3 (SIRT3) regulates mitochondrial adaptive response to stress, such as metabolic reprogramming and antioxidant defense mechanisms. SIRT3 was upregulated and it positively regulated mitochondrial oxidative phosphorylation in Cr(VI)-transformed cells. Our results suggests that SIRT3 plays an important role in mitophagy deficiency of Cr(VI)-transformed cells. Furthermore, SIRT3 knockdown suppressed cell proliferation and tumorigenesis of Cr(VI)-transformed cells. Nrf2 is a transcription factor that regulates oxidative stress response. This study investigated the role of Nrf2 in regulating metabolic reprogramming in Cr(VI)-transformed cells. We observed that in Cr(VI)-transformed cells p-AMPKthr172 was increased, when compared to normal BEAS-2B cells. Additionally, Nrf2 knockdown reduced p-AMPKthr172. Our results suggest that Nrf2 regulated glycolytic shift via AMPK regulation of PFK1/PFK2 pathway. Furthermore, our results showed that Nrf2 constitutive activation in Cr(VI-transformed cells increased cell proliferation and tumorigenesis. Overall this dissertation demonstrated that Cr(VI)-transformed cells undergo metabolic reprogramming. We demonstrated that Nrf2 constitutive activation plays decisive role on metabolic reprogramming induction, and SIRT3 activation contributing to increased cancer cell proliferation and tumorigenesis.

In order to assess the benefit or toxicity of chromium in dietary supplements, trivalent chromium and hexavalent chromium must be measured and verified with mass balance (sum of both species equaling total chromium). This is necessary because dietary supplements report trivalent chromium, an essential trace element, as an ingredient, but hexavalent chromium, a toxic carcinogen, may also be present. Because trivalent chromium is stable in acidic conditions and hexavalent chromium in alkaline conditions, interconversions between species occur and increase the difficulty of quantification. Therefore, EPA Method 3060A was first performed to extract hexavalent chromium. Then, EPA Method 3052 was performed on the residue to digest the remaining trivalent chromium. Speciated Isotope Dilution Mass Spectrometry (SIDMS) with Ion-Exchange Chromatography-Inductively Coupled Plasma-Mass Spectrometry (IC-ICP-MS) was used to account for interconversions as well as determination of trivalent and hexavalent chromium concentrations in the studied samples. Mass balance indicated that the analyzed supplements contained hexavalent chromium ranging from 0 to 16% of the total chromium content. / Bayer School of Natural and Environmental Sciences / Environmental Science and Management (ESM) / MS / Thesis

In order to assess the benefit or toxicity of chromium in dietary supplements, trivalent chromium and hexavalent chromium must be measured and verified with mass balance (sum of both species equaling total chromium). This is necessary because dietary supplements report trivalent chromium, an essential trace element, as an ingredient, but hexavalent chromium, a toxic carcinogen, may also be present. Because trivalent chromium is stable in acidic conditions and hexavalent chromium in alkaline conditions, interconversions between species occur and increase the difficulty of quantification. Therefore, EPA Method 3060A was first performed to extract hexavalent chromium. Then, EPA Method 3052 was performed on the residue to digest the remaining trivalent chromium. Speciated Isotope Dilution Mass Spectrometry (SIDMS) with Ion-Exchange Chromatography-Inductively Coupled Plasma-Mass Spectrometry (IC-ICP-MS) was used to account for interconversions as well as determination of trivalent and hexavalent chromium concentrations in the studied samples. Mass balance indicated that the analyzed supplements contained hexavalent chromium ranging from 0 to 16% of the total chromium content. / Bayer School of Natural and Environmental Sciences; / Environmental Science and Management (ESM) / MS; / Thesis;

Orientador: Meuris Gurgel Carlos da Silva / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-23T11:03:55Z (GMT). No. of bitstreams: 1 Bertagnolli_Caroline_D.pdf: 3477463 bytes, checksum: df8d9fab006a696fa5d027c25e848099 (MD5) Previous issue date: 2013 / Resumo: O cromo é um dos metais pesados que causa mais danos à saúde e ao meio ambiente. É utilizado em uma grande variedade de processos industriais podendo provocar contaminação dos recursos hídricos devido ao descarte de resíduos industriais. Neste trabalho a bioadsorção de cromo total e trivalente pela alga marinha Sargassum filipendula, pelo alginato extraído dessa alga e pelo resíduo da extração, assim como a bioadsorção das espécies de cromo por uma amostra de alginato comercial, foram estudados por meio de ensaios em sistema de batelada e em coluna. Os experimentos envolveram preparo e caracterização dos bioadsorventes, o estudo cinético e de equilíbrio, além de testes em sistema contínuo. Os bioadsorventes foram caracterizados antes e após a bioadsorção por microscopia eletrônica de varredura e o cromo presente no bioadsorvente foi mapeado. As técnicas de espectroscopia na região do infravermelho e espectroscopia de fotoelétrons excitados por raios-X foram utilizadas para compreensão dos mecanismos de ligação cromo+adsorvente e para avaliar o estado de oxidação do cromo adsorvido. O processo de extração do alginato a partir da alga brasileira foi estudado e os produtos da extração caracterizados. Os resultados mostraram capacidades máximas de adsorção obtidas pelo ajuste de Langmuir entre 0,411 e 2,493 mmol/g, com destaque para o resíduo da extração do alginato que se mostrou como uma boa alternativa de bioadsorvente, pois apresentou capacidade de adsorção máxima próxima à da alga e superior à dos alginatos para ambas as espécies de cromo, possibilitando o reaproveitamento de um rejeito do processo e comercialização do alginato extraído. Observou-se a ocorrência de diferentes mecanismos de adsorção simultaneamente, com formação de complexos de ambas as espécies de cromo com grupos sulfônico, amino e carboxila do adsorvente e a contribuição de mecanismos de troca iônica. No estudo da adsorção do cromo hexavalente foi verificada sua redução a cromo trivalente na superfície do adsorvente / Abstract: Chromium is one of the heavy metals that pose the greatest damages to health and to the environment. It is used in a great range of industrial processes, and it might even generate the contamination of water resources due to the disposal of industrial residues. In this study, hexavalent and trivalent chromium biosorption by Sargassum filipendula, alginate extracted from this seaweed, extraction residue and a commercial alginate were studied by means of batch and fixed-bed column. The experiments involved preparation and characterization of biosorbents, kinetic and equilibrium studies. The biosorbents were characterized before and after the biosorption process by scanning electron microscopy and the chromium present in the biosorbent has been mapped. The X-ray photoelectron spectroscopy and infrared spectroscopy have been used to evaluate the chromium oxidation state and the biosorbent group to which the metal is bound after the biosorption process. The process of alginate extraction from Brazilian seaweed has been studied and the extraction products characterized. The results showed the maximum adsorption capacities by Langmuir adjustment between 0.411 and 2.493 mmol/g and the alginate extraction residue as an alternative bioadsorbent. The residue has adsorption capacity near to seaweed and better than the alginates for both chromium species. Different mechanisms were observed for the adsorption of different chromium species as complexation of chromium with sulfonic, amino and carboxyl groups of the adsorbent and ion exchange mechanisms. In the adsorption of hexavalent chromium was verified reduction to trivalent chromium at the surface of the adsorbent / Doutorado / Engenharia de Processos / Doutora em Engenharia Quimica

O homem cada vez mais interfere e contamina o meio ambiente. Acidentes envolvendo o derramamento de substâncias químicas no solo tem sido cada vez mais frequente, gerando preocupação aos órgãos ambientais, visto que essa contaminação promove riscos à saúde humana, o que torna necessário intervenções que impulsionam o aprimoramento de técnicas de remediação. Dentre essas técnicas, a utilização de nanopartículas, em especial as nanopartículas de ferro de valência zero, têm se destacado para uso em remediação devido ao baixo custo de produção, elevada reatividade para contaminantes orgânicos e inorgânicos e baixa toxicidade. Para contaminantes inorgânicos não se tem definidas as melhores relações de nano ferro em relação ao contaminante e também o comportamento no solo. Dessa forma o objetivo do trabalho foi avaliar o transporte e a aplicação de nanopartículas de ferro para remediação de um solo residual argiloso, contaminado com cromo hexavalente. O trabalho foi dividido em três fases, em que na primeira foi avaliado a melhor concentração, tipo de nano ferro e determinação do parâmetro de filtração através do uso do ensaio em coluna de parede flexível com corpos de prova indeformados. Na segunda fase, a partir dos resultados da primeira, foram realizados ensaios de remediação do solo contaminado em bancada para se definir as melhores relações entre o nano ferro e o contaminante. E na terceira fase foram realizados ensaios com corpos de prova deformados e contaminados (800mg/Kg de Cr(VI)), para se avaliar a influência da pressão de injeção na eficiência do processo de redução do Cr (VI) Para realização dos ensaios de coluna, foi utilizado um solo residual argiloso, moldando-se corpos de prova de 5 cm de diâmetro e 5 cm de altura, utilizados na fase 1 e 3. Para avaliação do transporte e determinação do parâmetro de mobilidade de filtração foram utilizados 3 tipos de nanopartículas de ferro com e sem estabilizantes, nas concentrações de (1g/L, 4g/L, 7g/L e 10g/L), avaliando mudança na condutividade hidráulica do solo e concentração retida no meio. O parâmetro de filtração foi determinado utilizando-se o modelo analítico proposto por Reddy et al., (2014). Os resultados demonstram que as nanopartículas apresentam uma alta reatividade, porém baixa mobilidade para concentrações mais elevadas, tendo influência também o uso de estabilizantes. Os melhores valores obtidos nesta fase foram para concentrações de 1g/L e 4g/L, tanto para a mobilidade, quanto para a mudança na condutividade do meio O parâmetro de filtração, variou de 10-3s-1, para o nano ferro com surfactante e 10-2s-1, para o nano ferro sem surfactante. Para a remediação do cromo hexavalente se observou uma eficiência de 87% para a relação de 1000mg de Fe° para 23 mg de Cr(VI). Utilizando 4g/L na referida relação agente redutor e contaminante, em coluna se observou que maiores valores de pressão aumentam a eficiência da redução, porém acabam favorecendo a colmatação dos vazios do solo pelas nanopartículas. Utilizando uma pressão de 100Kpa, se obteve um valor de redução máximo próximo de 50%, muito menor que aqueles em bancada. Assim o uso de nanopartículas de ferro é eficiente para remediação de um solo argiloso contaminado com cromo (VI) ex situ, pois o contato do contaminante com o agente redutor se torna mais fácil pela melhor homogeneização do solo. As nanopartículas com surfactante apresentam melhor movimentação no solo e menor valor de filtração, sendo indicado o uso de uma concentração de até 4 g/L para não alterar as características naturais do meio. / The human being is constantly interfering and contaminating the environment. Accidents evolving the spill of chemical and toxic substances in the soil has been more frequently nowadays. This topic became a concern to the environmental regulation departments around the world, since this contaminations promote risks to the human health. In this way the necessity for improvements in the remediation techniques is required. Among the techniques, the use of nanoparticles zero valent iron has being highlight for use in remediation process due it's low cost for production, low toxicity and high reactivity for organic and inorganic contaminants. For inorganic contaminants the best nanoiron/contaminant ration and also the behavior in the soil have not been defined. Thus, the objective of this work was to evaluate the transport and the application of iron nanoparticles for the remediation of residual clay soil contaminated with hexavalent chromium The work is divided in three phases: The first evaluated the best concentration, type of nanoiron and determination of the filtration parameter through the use of the flexible wall column test with undeformed specimens. In the second phase, from the results of the first phase remediation tests were carried out on the contaminated soil in the workbench to define the best relations between the nanoiron and the contaminant. In the third phase, tests with deformed and contaminated test specimens (800 mg / kg Cr (VI)) were carried out to evaluate the influence of the injection pressure on the Cr (VI) reduction efficiency. To perform the column tests, a residual clay soil was used, molding test pieces 5 cm in diameter and 5 cm in height, used in phase 1 and 3. For evaluation of the transport and determination of the parameter of mobility of filtration (1 g / L, 4 g / L, 7 g / L and 10 g / L) were used, evaluating changes in soil hydraulic conductivity and the concentration retained in the system. The filtration parameter was determined using the analytical model proposed by Reddy et al., (2014).The results demonstrate that the nanoparticles have a high reactivity, but low mobility at higher concentrations, and also the use of stabilizers. The best values obtained in this phase were for concentrations of 1g/L and 4 g/L, both for mobility and for the change in conductivity of the system The filtration parameter ranged from 10-3s-1, for the nanoiron with surfactant and 10-2s-1, to the nanoiron without surfactant. For the remediation of the hexavalent chromium, an efficiency of 87% was observed for the ratio of 1000mg Fe ° to 23mg Cr (VI). By using 4g / L in the referred reducing agent and contaminant ratio, it was observed in column that higher pressure values increase the reduction efficiency, but they end up favoring the filling of the voids of the soil by the nanoparticles. Using a pressure of 100Kpa, a maximum reduction value of around 50% was obtained, much lower than those in bench. Thus, the use of iron nanoparticles is efficient for the remediation of a clay soil contaminated with chromium (VI) in deformed samples, since the contact of the contaminant with the reducing agent is made easier by better homogenization of the soil. The nanoparticles with surfactant present better a better movement in the soil and a lower filtration value, being indicated the use of a concentration of up to 4 g/l in order not to alter the natural characteristics of the system.

Avaliação ambiental, biológica e médica foram realizadas em 17 cromadores de 9 galvânicas do Estado de São Paulo, sendo cinco de cromo decorativo e quatro de cromo duro. O ar do ambiente de trabalho foi coletado individual e estacionariamente durante a semana de trabalho. Amostras de urina dos cromadores, foram coletadas no início e final do período de trabalho, encontrando-se uma correlação entre cromo urinário final e cromo no ar de 0,5. Usou-se a Absorção Atômica com Forno de Grafite GFAAS para determinar-se a concentração de cromo no ar ( Cr-ar) e cromo urinário ( Cr-U). O cromo hexavalente Cr (VI) foi extraído dos filtros de membrana de PVC com porosidade 5 µm com o tampão ácido acético/acetato de sódio, com a complexação do Cr (VI) feita por APDC. O complexo foi extraído com MIK. O limite de detecção foi de 1,1 µg/L. O Cr-U foi analisado diretamente por GFAAS com o limite de detecção 0,50 µg/L utilizando-se como modificador de matriz, nitrato de magnésio hexahidratado. Sem o modificador de matriz o limite de detecção foi de 0,14 µg/L. As concentrações de Cr (VI) no ar nas galvânicas de cromo decorativo variaram de 0,3 a 64,6 µg/m3 e nas de cromo duro variaram de 4,1 a 72,8 µg/m3 , mostrando a inadequação de alguns sistemas de exaustão. 60% dos cromadores das galvânicas de cromo duro tinham o septo nasal perfurado e todos os cromadores avaliados clinicamente tinham alterações nas vias aéreas superiores. O Cr-Uf que é utilizado como indicador biológico para compostos solúveis de cromo hexavalente, em muitos casos seus valores deram menores que o Cr-Ui, necessitando-se de estudos mais aprofundados quanto a esse aspecto, para evitar que o trabalhador possa ser prejudicado com resultados nem sempre condizentes com sua exposição. / Environmental, biological and medical evaluations was made in 17th workers of 9 chrome plating plants of the State of Sao Paulo, being 5 of decorative chrome plating and 4 of hard chrome plating. Environmental air samples were individual and stationarily collected during are week. Worker\'s urine samples were collected in the starting and in the end of the working period and it was obtained a correlation of 0,5 between the final urine chromium content and chromium air content. Graphite Furnace Atomic Absorption Spectrometry GFAAS was used for the determination of the chromium levels in the air (Cr-air) and in the urine(Cr-U). The Cr (VI) was extrated of the PVC membrane filters with an acetic acid/sodium acetate buffer and the Cr (VI) was isolated with APDC/MIBK. The detection limit obtained was 1,1 µg/L. The Cr-U was analised directly by GFAAS and the detection limit obtained was 0,50 µg/L, using magnesium Nitrate as matrix modifier and 0,14 µg/L without matrix modifier. The Cr (VI) concentration in the air was in the range of 0,3 to 64,6 µg/m3 in the decorative chrome plating and of 4,1 to 72,8 µg/m3 in the hard chrome plating, showing that the exhaust systems were inadequate. 60% of the workers of the hard chrome plating had perforation in the nasal cartilage and alI workers clinically evaluated presented alterations in the upper respiratory airway. The Cr-Uf that is used as biological indicator for the Cr(VI) soluble compounds, in many cases presented lower levels that the Cr-Ui showing that it is necessary more studies about this subject. In order to present inadequated results concerning the worker\'s exposition.

abstract: Mineral weathering and industrial activities cause elevated concentration of hexavalent chromium (Cr(VI)) in groundwater, and this poses potential health concern (>10 ppb) to southwestern USA. The conversion of Cr(VI) to Cr(III) – a fairly soluble and non-toxic form at typical pH of groundwater is an effective method to control the mobility and carcinogenic effects of Cr(VI). In-situ chemical reduction using SnCl2 was investigated to initiate this redox process using jar testing with buffered ultrapure water and native Arizona groundwater spiked with varying Cr(VI) concentrations. Cr(VI) transformation by SnCl2 is super rapid (<60 seconds) and depends upon the molar dosage of Sn(II) to Cr(VI). Cr(VI) removal improved significantly at higher pH while was independent on Cr(VI) initial concentration and dissolved oxygen (DO) level. Co-existing oxyanions (As and W) competed with Cr(VI) for SnCl2 oxidation and adsorption sites of formed precipitates, thus resulted in lower Cr(VI) removal in the challenge water. SnCl2 reagent grade and commercial grade behaved similarly when freshly prepared, but the reducing strength of the commercial product decreased by 50% over a week after exposing to atmosphere. Equilibrium modeling with Visual MINTEQ suggested redox potential < 400 mV to reach Cr(VI) treatment goal of 10 ppb. Kinetics of Cr(VI) reduction was simulated via the rate expression: r=-k[H+]-0.25[Sn2+]0.5[Cr2O72-]3 with k = 0.146 uM-2.25s-1, which correlated consistently with experimental data under different pH and SnCl2 doses. These results proved SnCl2 reductive treatment is a simple and highly effective method to treat Cr(VI) in groundwater. / Dissertation/Thesis / Masters Thesis Civil, Environmental and Sustainable Engineering 2019