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.

Biological remediation of Cr(VI) contaminated soil and groundwater is an emerging field. In this study, the in situ bioremediation technology for treating Cr(VI) contaminated groundwater aquifers was evaluated using a laboratory microcosm system. The study was conducted using columns with five equally spaced intermediate sampling ports along the length to facilitate finite difference modelling of the Cr(VI) concentration profile within the column. Cr(VI) concentration was continuously measured in the influent, in five equally spaced intermediate ports within the column and in the effluent port. The change or the shift in microbial community within the inoculated column was also monitored due to exposure to toxic conditions after seven weeks of operation using the 16S rRNA genotype fingerprinting method. The effect of introducing a natural carbon source (sawdust) in inoculated columns in comparison with the performance of sterile controls under various loading conditions was also evaluated. Near complete Cr(VI) removal was achieved in an inoculated carbon source reactor, whereas only 69.5% of Cr(VI) removal was achieved in an inoculated column without an added carbon source after 4 days of operation at 20 mg/L. In a sterile control reactor less than 2% of Cr(VI) was removed after 4 days of operation at 20 mg/L. Experimental cores demonstrated a successful Cr(VI) reduction process in the simulated microbial barrier system that was evaluated internally. The model that simulates Cr(VI) removal and transport in the subsoil environment was developed. The Cr(VI) mass balance model across the reactor that accounts for the flow characteristics and biological removal mechanism successfully captured the trends of Cr(VI) response profiles under quasi-steady state conditions for different loading conditions. This study demonstrate the potential of applying effective Cr(VI) reducers in the reactive barrier systems to contain or attenuate the spread of Cr(VI) contaminant in groundwater aquifer systems. The finite difference model developed in this study to evaluate the behaviour of Cr(VI) in the reactor could contribute towards improved designs of future in situ bioremediation systems that can be implemented for remediation of Cr(VI) on site. / Dissertation (MSc)--University of Pretoria, 2011. / Chemical Engineering / unrestricted

Chromium exists largely in two oxidation states, namely hexavalent chromium (Cr(VI)) which is carcinogenic, mutagenic to living organisms including humans and trivalent chromium (Cr(III)) which is known to be 1000 times less toxic than Cr(VI). It is therefore desirable in most cases to reduce Cr(VI) to Cr(III). Various studies have been conducted on the Cr(VI) reduction process either in situ or ex situ. However in situ bioremediation using permeable reactive barrier system appears as a potential and attractive technology compared to other in situ technologies. This study was conducted to evaluate the reduction of Cr(VI) to Cr(III) in the short term and regeneration of the biological reactive barrier to achieve continuous long term operation. It was observed from the study that the chromium hydroxide Cr(OH)3(s) precipitated and thus affected the porosity and hydraulic conductivity of the barrier system. It was therefore proposed to implement a regeneration process involving remobilization of precipitated Cr(OH)3 using a dilute acid (0.1% HCl) and recover Cr(III) by electrokinetics. Lowering the pH in the reactor introduced harsh conditions which necessitated the evaluation of a possible culture shift during the regeneration phase. Microbial culture composition during bioremediation and after soil washing was evaluated using a 16S rRNA finger printing method. The microbial barrier was initially inoculated with indigenous bacterial species from dried sludge. The results presented in the phylogenic tree diagrams confirm that, after microbial barrier system operation, the well-known Cr(VI) reducers Bacillus mycoides, Lysinibacillus fusiformis and Micrococcus lylae were the predominant species in the microbial community of the barrier. The microbial barrier system successfully achieved near complete removal of Cr(VI), whereby approximately 75% Cr(VI) removal was achieved within 63 days of operation. The formation of Cr(OH)3(s) was observed in the second week of operation. After 4 weeks of operating the mesocosm under soil washing with 0.1% HCl and electrokinetics remediation with a DC voltage of 50-150 V an increase in total chromium (73%) was observed suggesting that the trapped chromium species in the mesocosm was effectively remobilized with the assumption that Cr(III) had attached to the cathode forming a white-yellow precipitate layer around the cathode. Additionally more than 95% Cr(VI) was transformed to lower toxicity Cr(III) during electrokinetics and soil washing remediation. However, one of the limitations of electrokinetics is near anode focusing effect whereby a layer of precipitate is formed around the anode that lead to the reduction of efficiency of the technology. / Dissertation (MSc)--University of Pretoria, 2014. / lk2014 / Chemical Engineering / MSc / Unrestricted

M. Tech (Department of Chemistry, Faculty of Applied and Computer Sciences) Vaal University of Technology. / Agricultural waste such as Macadamia nutshells are currently receiving more attention for removal of hexavalent chromium (Cr(VI)). However, they have low adsorption capabilities when used in their raw form. In this study, the efficiency of using Macadamia nutshell powder modified with different concentrations of hydrogen peroxide, grafted with 1,5’-diphenylcarbizide (DPC) for the removal of hexavalent chromium from aqueous solution was explored. The effects of various parameters controlling adsorption of Cr(VI) onto Macadamia adsorbents such as initial concentration, contact time, adsorbent concentration and pH were investigated. The optimal operating parameters for Macadamia nutshells treated with hydrogen peroxide (MHP) adsorbents were determined to be 75 mg/L, 3 h, 0.1 g and pH 1. The optimal operating parameters for Macadamia nutshells treated with hydrogen peroxide and grafted with 1,5’-diphenylcarbizide (MHPD) were determined to be 150 mg/L, 1 h, 0.1 g and pH 3. Fourier transform infrared (FTIR) spectroscopy of the adsorbents revealed that treated MHP showed amino groups attached to the adsorbents. Thermogravimetric analysis (TGA) revealed that the grafted material lowered the thermal stability from 180◦C to 300◦C due to volatile nature of DPC. The surface of the MHPD materials was rough due to grafting. The results showed that the 1,5’-diphenylcarbazide treatment improved the removal efficiency of Cr(VI).

This study was designed to accomplish two primary objectives: (1) to compare two test methods commonly used to evaluate toxicity of inhaled air pollutants, and (2) to observe the response as measured by each of the methods, of pulmonary alveolar macrophages exposed to 2μg hexavalent chromium. The firs t method evaluated featured use of intratracheal injections to simulate live inhalation exposures, and the second required exposure of macrophages cultured on petri plates. Pulmonary alveolar macrophages harvested from Long Evans rats were used. The two cell function parameters measured in the evaluations were chemiluminescence and oxygen consumption (which was determined for cells at rest and during phagocytosis). These two tests have been shown to be sensitive indicators of macrophage damage. Results of CL output and oxygen consumption revealed the two methods were significantly different. Evaluation of macrophages from live animals treated with CrO3 or CaCrO4showed no differences between their respective untreated controls as determined by measurement of their chemiluminescence production or of oxygen consumption rates. Alveolar macrophages that were cultured in media during treatment with the same two forms of hexavalent chromium showed statistically significant differences from untreated controls. These comparisons indicate that choices of investigative toxicological models influence interpretation of data recorded.

No description available.

La détection sensible et sélective des métaux lourds, en particulier les métaux detransition, est d’une grande importance pour la santé publique ainsi que pour la surveillancede l’environnement. Les méthodes actuelles de référence, de par leur non portabilité, limitentla possibilité de disposer de mesures à haute résolution spatiale et temporelle. Lesmicrocapteurs optiques offrent un moyen attrayant et pratique pour surmonter ces limitationsde coût global et de temps d’analyse, en permettant la mesure en temps réel sur site.Pour démontrer ce potentiel, ces travaux de thèse sont orientés sur la détermination duchrome hexavalent Cr(VI) en solution à l’aide d’une réaction colorimétrique avec le 1,5-diphénylcarbazide (DPC), permettant de créer un complexe présentant un maximumd’absorption dans le domaine du visible. Ces travaux s’inscrivent dans la volonté dedévelopper un véritable laboratoire sur puce, intégrant la fonction fluidique parélectromouillage sur diélectrique pour créer la réaction colorimétrique, ainsi que la fonctionde mesure par intégration d’un capteur optique dédié à la mesure d’absorption dans desmicrovolumes (< μL). Pour la mesure d'absorption sur de si faibles volumes, l'utilisation demicrorésonateurs vise à augmenter de façon importante le chemin optique effectif et ainsi lasensibilité du capteur.Nous décrivons nos travaux sur la conception, la fabrication de la plateformemicrofluidique digitale ainsi que du résonateur optique en anneaux à des dimensionssubmicroniques par photolithographie par projection. Les matériaux polymères sontprivilégiés pour une intégration totale bas coût à terme, ainsi qu’un substrat verre, dont lespropriétés sont particulièrement adaptées aux applications optiques dans le domaine duvisible. / The selective and sensitive detection of heavy metals, such as transition metals, is ofparamount importance for health and safety an environmental monitoring. Current referencemethods, due to their lack of portability, are limiting factors to obtain high-resolution spatialand temporal data. Optical sensors offer an attractive and convenient way to overcome theselimitations of cost and time per analysis by offering real time, on-site measurementcapabilities.In order to demonstrate this potential, this thesis is focused on the detection and quantificationof hexavalent chromium Cr(VI) in water samples by a colorimetric reaction based on areaction with the 1,5-diphenylcarbazide (DPC), that produces a complex possessing anabsorption maximum in the visible range. This works endorse the goal of creating a true labon-chip, integrating both the fluidic function based on ElectroWetting on Dielectric (EWOD)to create the colorimetric reaction, and the sensing function based on the integration of anoptical sensor able to measure absorption variations in micro-volumes (< μL). In order toobtain sufficient sensitivity on such small volumes, optical microring resonators are used inthis work, due to their ability to enhance the effective optical path length by constructiveinterferences.This thesis describes the conception and fabrication of the EWOD microfluidic platform, aswell as the conception, simulation and fabrication of submicronic microring resonators usingstepper lithography. Polymer materials and glass substrates are selected, due to their greatoptical properties in the visible range, their compatibility with the EWOD platform, and theirintegrability at a reasonable cost.

Submitted by Erika Demachki (erikademachki@gmail.com) on 2017-01-10T17:07:20Z No. of bitstreams: 2 Dissertação - Glalber Luiz da Rocha Ferreira - 2016.pdf: 1694646 bytes, checksum: 0edfdeae06383f7209358539abe161f7 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2017-01-11T09:54:35Z (GMT) No. of bitstreams: 2 Dissertação - Glalber Luiz da Rocha Ferreira - 2016.pdf: 1694646 bytes, checksum: 0edfdeae06383f7209358539abe161f7 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-01-11T09:54:35Z (GMT). No. of bitstreams: 2 Dissertação - Glalber Luiz da Rocha Ferreira - 2016.pdf: 1694646 bytes, checksum: 0edfdeae06383f7209358539abe161f7 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2016-08-29 / Fundação de Amparo à Pesquisa do Estado de Goiás - FAPEG / The existing techniques for removing heavy metals are expensive and are often not effective. Thus the application arises from biosorbents, an emerging technology that needs to be studied and explored, in order to promote better environmental and human life quality. The study craved verify removal capacity in synthetic aqueous solutions of ions Cr (VI) at concentrations of 10, 25, 50, 75, 100, 125 and 150 mg/L by biosorption by use of active and inactive fungal biomass Pleurotus ostreatus. In the use of the active biosorbent, kinetic studies revealed that in 336 hours was achieved 100% of its saturation capacity at concentrations of 10 and 25 mg/L of Cr (VI), achieving total removal of Cr (VI) in the order of 250 times over the recommended limit for industrial effluents in CONAMA Resolution nº 430/2011, and 360 hours biomass reached its maximum capacity of saturation, reaching values of 98,18% and 96,84%, in concentrations of 50 and 75 mg/L of Cr (VI), respectively. Observing the concentrations of 100% removal was confirmed by analysis of the total EAA chromium values of 141,66 mg/g and 133,55 mg/g biomass respectively. The analysis revealed the micrographs by SEM and TEM we observed at the cellular composition of biomass the presence of bacterial cells associated with the fungus, which on analysis was not possible to know where the metal was in adsorbed, it is better to point out that it was possible to detect content chromium from the cellular structure of the biomass. In the use of the idle biosorbent, kinetic studies showed that 6, 10 and 12 minutes it was reaching 100% of its saturation capacity at concentrations of 10, 25 and 50 mg/L of Cr (VI), respectively, achieving total removal Cr (VI) in the order of 500 times over the recommended limit for industrial effluents in CONAMA Resolution No. 430/2011, and in 22 minutes biomass reached its maximum capacity of saturation, reaching values of 73,21% and 55,13% at concentrations of 75 and 100 mg/L of Cr (VI), respectively. The Langmuir model was the one that best fit the experimental data biosorbent P. ostreatus, when evaluating the separation factor (RL), responding to values between zero and 1. Now, considering the values of the coefficient of determination (R2), the Freundlich model fit better due to present higher values in relation to the Langmuir model. / As técnicas existentes de remoção de metais pesados são caras e muitas vezes não são eficientes. Dessa forma surge a aplicação de biossorventes, uma tecnologia emergente que precisa ser estudada e explorada, com o objetivo de promover melhor qualidade ambiental e da vida humana. O estudo almejou verificar a capacidade de remoção em soluções aquosas sintéticas de íons Cr(VI) nas concentrações de 10, 25, 50, 75, 100, 125 e 150 mg/L, através da biossorção pela utilização da biomassa fúngica ativa e inativa de Pleurotus ostreatus. Na utilização do biossorvente ativo, os estudos cinéticos revelaram que em 336 horas foi alcançado 100% de sua capacidade de saturação nas concentrações de 10 e 25 mg/L de Cr(VI), alcançando uma remoção total de Cr(VI) na ordem de 250 vezes em relação ao limite preconizado para efluentes industriais na Resolução do CONAMA nº 430/2011, e em 360 horas a biomassa atingiu sua capacidade máxima de saturação, atingindo valores de 98,18% e 96,84%, nas concentrações de 50 e 75 mg/L de Cr(VI), respectivamente. Observando as concentrações de 100% de remoção, foi confirmando através da análise de EAA valores de crômio total de 141,66 mg/g e 133,55 mg/g de biomassa, respectivamente. Na análise revelada pelas microfotografias por MEV e MET foi possível verificar junto a composição celular da biomassa a presença de células bacterianas associadas ao fungo, que em análise não foi possível saber onde o metal se encontrava adsorvido, mais vale salientar que foi possível detectar conteúdo de crômio junto a estrutura celular da biomassa. Na utilização do biossorvente inativo, os estudos cinéticos revelaram que em 6, 10 e 12 minutos foi alcançando 100% de sua capacidade de saturação nas concentrações de 10, 25 e 50 mg/L de Cr(VI), respectivamente, alcançando uma remoção total de Cr(VI) na ordem de 500 vezes em relação ao limite preconizado para efluentes industriais na Resolução do CONAMA nº 430/2011, e em 22 minutos a biomassa atingiu sua capacidade máxima de saturação, atingindo valores de 73,21% e 55,13%, nas concentrações de 75 e 100 mg/L de Cr(VI), respectivamente. O modelo de Langmuir foi o que se melhor ajustou aos dados experimentais do biossorvente P. ostreatus, quando avaliando o fator de separação (RL), respondendo a valores entre zero e 1. Agora, considerando os valores do coeficiente de determinação (R2), o modelo de Freundlich se ajustou melhor, devido apresentar valores maiores em relação ao modelo de Langmuir.

Hexavalent chromium, Cr(VI), is an established human carcinogen that is a worldwide environmental health concern. It is well understood that reactive oxygen species, genomic instability, and DNA damage repair deficiency are important contributors to Cr(VI)-induced carcinogenesis. After decades of research some cancer hallmarks remain understudied for the mechanism of Cr(VI) carcinogenesis. Dysregulated cellular energetics have been established as a hallmark of cancer. Energy pathways that become dysregulated in cancer include mitochondrial respiration, lipogenesis, pentose phosphate pathway, one carbon metabolism, and increased anaerobic glycolysis in the presence of oxygen or ‘Warburg effect’. To investigate metabolism changes in Cr(VI) carcinogenesis, we exposed human lung epithelial cells (BEAS-2B cells) to Cr(VI) for six months and isolated a colony from soft agar. To confirm the results in the BEAS-2B cells, we used two other sets of Cr(VI)-transformed cells, human lung epithelial cells (BEP2D cells) and human lung fibroblasts (WTHBF-6 cells). We found increased lipogenesis related protein expressions including: ATP citrate lyase (ACLY), acetyl-CoA carboxylase 1 (ACC1), and fatty acid synthase (FASN) in Cr(VI)-transformed cells as compared to passage-matched control cells. We also observed increased palmitic acid levels, confirming that Cr(VI)-transformed cells were making more lipids. Cr(VI)-transformed BEAS-2B cells had decreased colony formation in soft agar and decreased cell growth when treated with a FASN inhibitor (C75). ACLY, ACC1, and FASN protein expressions were also increased in chromate-induced lung tumors in human tissue samples. We also observed that Cr(VI)-transformed human lung cells (BEAS-2B, BEP2D, and WTHBF-6 cells) had no major changes in their mitochondrial respiration as measured by the Seahorse Analyzer when compared to their passage-matched control cells. Conversely, xenograft tumor-derived cells had mitochondrial respiratory dysfunction. Interestingly, we also found that Cr(VI)-transformed human lung cells (BEAS-2B, BEP2D, and WTHBF-6 cells) had no major changes in their glycolytic function as measured by the Seahorse Analyzer when compared to their passage-matched control cells. Similarly, these cells did not have changes in glycolytic enzymes or extracellular L-lactate levels. Moreover, xenograft tumor-derived cells showed no changes in glycolytic endpoints or L-lactate levels. This indicates these cells did not undergo the ‘Warburg effect’. These data demonstrate that increased lipogenesis is important to Cr(VI)-induced lung carcinogenesis and are consistent with the cancer literature which reports that increased lipogenesis proteins occur during carcinogenesis. Additionally, our results indicate mitochondrial respiratory dysfunction is likely a result of the tumor microenvironment and a later step during Cr(VI) carcinogenesis. Lastly, we observed the ‘Warburg effect’ is not required for Cr(VI)-induced carcinogenesis in vitro. However, it remains to be shown if the ‘Warburg effect’ is still a consequence or contributing factor for tumorigenesis. Future studies are needed to investigate other metabolic pathways in Cr(VI)-induced carcinogenesis. In conclusion, some metabolism pathways are important to Cr(VI)-induced carcinogenesis, while others appear not to be.

<p>The RoHS Directive was introduced in order to restrict hazardous substances in Electrical and Electronic Equipment, EEE. It currently restricts the use of six hazardous substances/compounds; cadmium, lead, mercury, hexavalent chromium, PBB, and PBDE. The RoHS Directive currently includes category 1-7 and 10 in the categories of EEE listed in Annex 1A to the WEEE-Directive (Waste of EEE). The aim with the report is to investigate and elucidate prospects and obstacles to increase the scope of RoHS. This report mainly considers the inclusion of product categories 8 (Medical Devices) and 9 (Monitoring and Control Instruments). </p><p>In order to fulfil the aim eight questions were formulated, that shall be answered in the report. In order to find the knowledge of and attitude towards RoHS of manufacturers, retailers, and importers of products falling under category 8 and 9, a questionnaire was sent to 80 companies, of which 25 answered. The answers showed that many of the companies did not know of RoHS before the questionnaire was sent out. The majority did not consider that their product category needed a longer time period to find alternatives for the applications where any of the in RoHS restricted substances were used, compared with the other categories in annex 1A to WEEE. Of the companies that answered on the questionnaire the majority had less than 50 employees. The companies in the study had limited knowledge of the contents of their products, they bought the function rather than the contents. </p><p>One important conclusion in this report is that only a few of the companies in category 8 and 9 are likely to keep using non compliant components for a long time if they use standard electronic equipment irrespective if they intend to readjust their production according to the RoHS Directive or not. The reason is that most subcontractors will be forced by the customers, mainly the larger ones, to readjust their production. They certainly will not keep two production lines. A paradox problem that can arise for small and medium sized companies, the majority of those answering the questionnaire were, is to get access to compliant components before the RoHS Directive is put into force. These companies order such small batches that it is unrealistic to order them from the original manufacturer, who usually is located in Asia. The small and medium sized companies usually buy their components from middlemen/grossists in Europe and Sweden. These grossist in many cases have large stocks with non-compliant components that they want to sell out before RoHS Directive is put into force from the 1st July 2006. </p><p>The RoHS Directive has been critized for restricting lead, but different studies show that the alternatives to e.g. Lead gives only slightly worse results, which by way of introduction can be expected from a new technology compared with an old, more investigated. The work with the report has also revealed a lack in communication and cooperation not only between the different stakeholders in electronic industry: retailers, importers, manufacturers and subcontractors, but also between industry, customers and authorities. The RoHS Directive may improve the communication and cooperation between these different actors.</p>