Precipitation of Gold, Silver, and Copper from Cyanide Solutions on Activated Charcoal.

Charcoal has been known for a considerable length of time to have the property of recovering gold, silver, and copper from cyanide solutions of these metals. Quantita­tive data that may shed light on the mechanism of the re­moval of these metals is very limited except that char­coal in a form known as activated has the power to abstract gold and silver in considerable quantities from the above solutions.

Experimental and Calculated Spectra of π-Stacked Mild Charge-Transfer Complexes: Jet-Cooled Perylene·(Tetrachloroethene) n , n = 1,2

The S0 ↔ S1 spectra of the mild charge-transfer (CT) complexes perylene·tetrachloroethene (P·4ClE) and perylene·(tetrachloroethene)2 (P·(4ClE)2) are investigated by two-color resonant two-photon ionization (2C-R2PI) and dispersed fluorescence spectroscopy in supersonic jets. The S0 → S1 vibrationless transitions of P·4ClE and P·(4ClE)2 are shifted by δν = −451 and −858 cm–1 relative to perylene, translating to excited-state dissociation energy increases of 5.4 and 10.3 kJ/mol, respectively. The red shift is ∼30% larger than that of perylene·trans-1,2-dichloroethene; therefore, the increase in chlorination increases the excited-state stabilization and CT character of the interaction, but the electronic excitation remains largely confined to the perylene moiety. The 2C-R2PI and fluorescence spectra of P·4ClE exhibit strong progressions in the perylene intramolecular twist (1au) vibration (42 cm–1 in S0 and 55 cm–1 in S1), signaling that perylene deforms along its twist coordinate upon electronic excitation. The intermolecular stretching (Tz) and internal rotation (Rc) vibrations are weak; therefore, the P·4ClE intermolecular potential energy surface (IPES) changes little during the S0 ↔ S1 transition. The minimum-energy structures and inter- and intramolecular vibrational frequencies of P·4ClE and P·(4ClE)2 are calculated with the dispersion-corrected density functional theory (DFT) methods B97-D3, ωB97X-D, M06, and M06-2X and the spin-consistent-scaled (SCS) variant of the approximate second-order coupled-cluster method, SCS-CC2. All methods predict the global minima to be π-stacked centered coplanar structures with the long axis of tetrachloroethene rotated by τ ≈ 60° relative to the perylene long axis. The calculated binding energies are in the range of −D0 = 28–35 kJ/mol. A second minimum is predicted with τ ≈ 25°, with ∼1 kJ/mol smaller binding energy. Although both monomers are achiral, both the P·4ClE and P·(4ClE)2 complexes are chiral. The best agreement for adiabatic excitation energies and vibrational frequencies is observed for the ωB97X-D and M06-2X DFT methods.

(Table 1) Concentrations of neutral and phenolic organohalogen compounds in adipose tissue, blood, brain and liver of polar bears (Ursus maritimus) from East Greenland

The tissue-specific composition of sum classes of brominated and chlorinated contaminants and metabolic/degradation byproducts was determined in adult male and female polar bears from East Greenland. Significantly (p < 0.05) higher concentrations of SUM-PCBs, various other organochlorines such as SUM-CHL, p,p'-DDE, SUM-CBz, SUM-HCHs, octachlorostyrene (OCS),SUM-mirex, dieldrin, the flame retardants SUM-PBDEs, and total-(R)-hexabromocyclododecane (HBCD), SUM-methylsulfonyl (MeSO2)-PCBs and 3-MeSO2-p,p'-DDE, were found in the adipose and liver tissues relative to whole blood and brain. In contrast, SUM-hydroxyl (OH)-PCB, 4-OH-heptachlorostyrene and SUM-OH-PBDE concentrations were significantly highest (p < 0.05) in whole blood, whereas the highest concentrations of SUM-OH-PBBs were found in the adipose tissue. Based on the total concentrations of all organohalogens in all three tissues and blood, the combined body burden was estimated to be 1.34 ± 0.12 g, where >91% of this amount was accounted for by the adipose tissue alone, followed by the liver, whole blood, and brain. These results show that factors such as protein association and lipid solubility appear to be differentially influencing the toxicokinetics, in terms of tissue composition/localization and burden, of organohalogen classes with respect to chemical structure and properties such as the type of halogenation (e.g., chlorination or bromination), and the presence or absence of additional phenyl group substituents (e.g., MeO and OH groups). The tissue- and blood-specific accumulation (or retention) among organohalogen classes indicates that exposure and any potential contaminant-mediated effects in these polar bears are likely tissue or blood specific.

Investigación sobre tratamientos de aguas seguros en emergencias

Esta Tesis Doctoral tiene como principal objetivo el obtener una cadena de tratamientos seguros de aguas seriados que nos permita asegurar la calidad de las aguas para consumo humano en caso de emergencias, de tal forma que se minimicen los efectos de acciones hostiles, como sabotajes o actos terroristas, desastres naturales, etc y buscar soluciones adecuadas para garantizar en este caso la salud. Las plantas de tratamientos de aguas existentes comercialmente no aseguran dicha calidad y la documentación sobre el tema presenta vacíos de conocimiento, contradicciones entre resultados de investigaciones o insostenibilidad de conclusiones de las mismas. Estas carencias nos permiten determinar los aspectos a tratar durante la investigación. Por ello, este objetivo se concretó en tres acciones: Investigar sobre rendimientos de plantas convencionales en eliminación de microorganismos y productos tóxicos y peligrosos. Introducir mejoras que garanticen el rendimiento de las plantas convencionales. Investigar sobre la conveniencia de complementar las instalaciones existentes buscando seguridad y garantía sanitaria. Y se desarrollaron tres líneas de investigación: LI 1 “Inorgánicos”: Investigación sobre la eliminación de los metales boro, cobre y molibdeno mediante procesos de intercambio iónico y de coagulaciónfloculación- decantación. LI 2 “Compuestos Orgánicos Volátiles”: Investigación sobre la eliminación de los compuestos orgánicos 1,1 dicloroetano, 1,2 dicloroetano, clorobenceno, 1,3 dicloropropeno y hexacloro 1,3 butadieno mediante procesos de carbón activo granular y de oxidación avanzada. LI 3 “Plantas portátiles”: Investigación sobre plantas existentes portátiles para verificar su rendimiento teórico y proponer mejoras. Estas líneas de investigación se desarrollaron tanto en el nivel teórico como en el empírico, bien sea en laboratorio como en campo. A lo largo del documento se demuestra que las principales fuentes de contaminación, salvo la degradación de yacimientos naturales, proceden de la actividad humana (efluentes industriales y agrícolas, aguas residuales y actividades beligerantes) que provocan un amplio espectro de enfermedades por lo que dificultan tanto la definición de la fuente como la anticipada detección de la enfermedad. Las principales conclusiones que se obtuvieron están relacionadas con el rendimiento de eliminación de los parámetros tras la aplicación de los procesos y plantas de tratamiento de aguas anteriormente reseñadas. Sin embargo, el verdadero elemento designador de originalidad de esta Tesis Doctoral, tal como se ha reseñado arriba, radica en la definición de un sistema seriado de procesos de tratamiento de aguas que asegura la calidad en caso de emergencia. Éste se define en el siguiente orden: pretratamiento, oxidación, coagulación-floculación-decantación, filtración por arena, intercambio iónico, carbón activo granular, microfiltración, radiación UV, ósmosis inversa, radiación UV y cloración final. The main objective of this Thesis is to obtain a chain of stepwise safe water treatments that allow us to ensure the quality of water for human consumption in case of emergencies, so that the effects of hostile actions, such as sabotage or terrorism, natural disasters, etc. and seek appropriate solutions in this case to ensure health. The existing commercial water treatment plants do not ensure quality, and the documentation on the subject presents knowledge gaps or contradictions. These gaps allow us to determine the issues to be discussed during the investigation. Therefore, this objective was manifested in three actions: Researching yields in commercial plants and microorganisms, or toxic and dangerous products removal. Improvements to ensure the performance of conventional plants. Inquire about the advisability of implementing existing facilities for safety and health guarantee. And three lines of research are developed: LI 1 “Inorganic elements”: Research removing metals iron, copper and molybdenum by ion exchange processes and coagulation-flocculation-decantation. LI 2 “Volatile Organic Compounds”: Research removing organic compounds 1,1 dichloroethane, 1,2 dichloroethane, chlorobenzene, 1,3-dichloropropene and 1,3-butadiene hexachloro through processes of granular activated carbon and advanced oxidation. LI 3 “Compact Water Treatment Plants”: Research on existing packaged plants to verify theoretical performance and suggest improvements. These lines of research are developed both theoretically and empirically, both in the laboratory and in the field. Throughout the document, it is evident that the main sources of pollution, other than the degradation of natural deposits, come from human activity (industrial and agricultural effluents, sewage and belligerent activities) which cause a broad spectrum of diseases which hamper both the definition of the source and the early detection of the disease. The main conclusions drawn are related to both the removal efficiency parameters after application of processes and treatment plants outlined above water. However, the real designator of originality of this thesis, such as outlined above, lies in the definition of a serial system water treatment processes assuring quality in case of emergency. This is defined in the following order: pretreatment, oxidation, coagulation-flocculation-sedimentation, sand filtration, ion exchange, granular activated carbon, microfiltration, UV radiation, reverse osmosis, UV radiation and final chlorination.

Replacement of the proximal heme thiolate ligand in chloroperoxidase with a histidine residue

Chloroperoxidase is a versatile heme enzyme which can cross over the catalytic boundaries of other oxidative hemoproteins and perform multiple functions. Chloroperoxidase, in addition to catalyzing classical peroxidative reactions, also acts as a P450 cytochrome and a potent catalase. The multiple functions of chloroperoxidase must be derived from its unique active site structure. Chloroperoxidase possesses a proximal cysteine thiolate heme iron ligand analogous to the P450 cytochromes; however, unlike the P450 enzymes, chloroperoxidase possesses a very polar environment distal to its heme prosthetic group and contains a glutamic acid residue in close proximity to the heme iron. The presence of a thiolate ligand in chloroperoxidase has long been thought to play an essential role in its chlorination and epoxidation activities; however, the research reported in this paper proves that hypothesis to be invalid. To explore the role of Cys-29, the amino acid residue supplying the thiolate ligand in chloroperoxidase, Cys-29 has been replaced with a histidine residue. Mutant clones of the chloroperoxidase genome have been expressed in a Caldariomyces fumago expression system by using gene replacement rather than gene insertion technology. C. fumago produces wild-type chloroperoxidase, thus requiring gene replacement of the wild type by the mutant gene. To the best of our knowledge, this is the first time that gene replacement has been reported for this type of fungus. The recombinant histidine mutants retain most of their chlorination, peroxidation, epoxidation, and catalase activities. These results downplay the importance of a thiolate ligand in chloroperoxidase and suggest that the distal environment of the heme active site plays the major role in maintaining the diverse activities of this enzyme.

Remoção de atividade estrogênica do hormônio 17β-Estradiol em processos de oxidação de águas para abastecimento

Muitos oxidantes químicos reativos acarretam na ruptura de estruturas moleculares complexas de vários tipos de compostos orgânicos decompondo-as em estruturas mais simples e propiciando condições melhores para uma efetiva ação de micro-organismos na degradação biológica. A presença de hormônios, entre eles o 17β-estradiol, em estações de tratamento de esgoto e em águas subterrâneas e superficiais mostra a necessidade de uma avaliação dos processos de tratamento convencionais. O objetivo deste trabalho foi a análise e remoção de hormônios através de técnicas de cloração e ozonização de amostras reais de águas de saída de filtro de estações de tratamento de água (ETAs), operadas pelo Serviço Autônomo de Água e Esgoto (SAAE) de São Carlos (ETA Centro), que capta águas dos ribeirão Feijão e córrego Espraiado e pela Sociedade de Abastecimento de Água e Saneamento S/A (SANASA) de Campinas (ETAs 3 e 4), que capta águas do rio Atibaia. Foram realizados ensaios contaminando-se as amostras com 17β-estradiol, que é o hormônio natural mais presente no meio ambiente, em concentração de 6.000 ng L-1, submetendo-se tratamento com dosagens em torno de 0,5 e 2,0 mg L-1 desses oxidantes, em tempos de contato de, respectivamente, 10 e 30 min. As amostras submetidas à contaminação e tratamento e as de controle (sem contaminação e tratamento) foram analisadas através da remoção do 17β-estradiol com a verificação da atividade estrogênica das amostras por ensaios de Sistema de Expressão de Estrogênio Induzida por Levedura Bioluminescente (BLYES), que apresentou-se como uma ferramenta simples. Os resultados apresentados neste trabalho demonstram que a oxidação por ozônio se mostrou mais eficiente do que aquela por cloro para a remoção da atividade estrogênica causada, única e exclusivamente, pelo 17β-estradiol para uma dosagem inicial desse hormônio relativamente alta (6.000 ng L-1). Todavia, em todos os ensaios a concentração final da atividade estrogênica permaneceu acima do limite de quantificação desses hormônio, indicando que a remoção não foi completa, mesmo em condições favoráveis, isto é, matriz limpa, com padrões de potabilidade para os parâmetros físico-químicos.

Ocorrência e caracterização de Giardia e Cryptosporidium em águas captadas para abastecimento público no município de Cajamar-SP e avaliação do risco

Introdução: O risco à saúde humana ocasionado pela contaminação biológica de águas captadas para abastecimento público é realçado pela ocorrência de surtos de doenças associadas aos protozoários Giardia e Cryptosporidium, que possuem baixas doses infecciosas e alta capacidade de sobrevivência no ambiente, além de serem capazes de resistir ao processo tradicional de desinfecção da água (cloração). Partindo-se da hipótese de que há um risco elevado de infecção por estes protozoários pela ingestão de água tratada por métodos convencionais e que fazem uso de mananciais superficiais impactados por contaminação biológica, resultando num possível incremento da incidência de diarréias, este estudo se propôs a verificar a ocorrência destes protozoários em águas captadas para abastecimento público no município de Cajamar-SP, caracterizar sua patogenicidade e avaliar o risco associado ao seu consumo através da água tratada. Métodos: Foram coletadas 48 amostras do ribeirão dos Cristais no ponto de captação da estação de tratamento de água, semanalmente, durante 12 meses (de 16/05/2013 a 21/05/2014). A detecção e a análise da concentração dos protozoários foram realizadas de acordo com Método 1623.1 da United States Environmental Protection Agency e a extração e caracterização dos espécies/genótipos de Giardia e Cryptosporidium foi realizada através metodologias moleculares e seqüenciamento. O risco de infecção pela ingestão de cistos de Giardia e oocistos de Cryptosporidium presentes na água tratada foi calculado usando a ferramenta da Avaliação Quantitativa do Risco Microbiológico, a partir dos dados de concentração dos patógenos obtidos pelo Método 1623.1, eficiência de remoção dos (oo)cistos durante o processo convencional de tratamento da água, modelo dose-resposta e taxa de ingestão diária de água para indivíduos menores de 5 anos e maiores de 21 anos. Resultados: Cistos de Giardia foram detectados em 83,3% das amostras (40/48), com concentrações variando desde o limite de detecção (<0,1) até 8,6 cistos/L. Oocistos de Cryptosporidium foram etectados em 37,5% das amostras (18/48), com concentrações variando desde o limite de detecção (<0,1) até 2 oocistos/L. As espécies/genótipos encontrados (Giardia intestinalis A e B e Cryptosporidium parvum e hominis) são característicos de contaminação antrópica e são frequentemente identificados em estudos epidemiológicos como responsáveis por surtos. A estimativa do risco anual de infecção por Giardia foi de 3,3x10-3 (IC95% 4,6x10-3) para crianças e de 11,5x10-3 (IC95% 13,3x10-3) para adultos, enquanto o risco por Cryptosporidium foi de 1,1x10-3 (IC95% 1,7x10-3) para crianças e de 3,9x10-3 (IC95% 5,0x10-3) para adultos. O incremento da incidência de diarréias foi observado no cenário de estudo após um acidente que resultou em transbordamento de esgotos não tratados no manancial, coincidindo com o aumento na detecção de (oo)cistos. Conclusão: Os resultados evidenciaram que a vulnerabilidade do ribeirão dos Cristais a contaminações biológicas pode culminar em um risco elevado de infecção e adoecimento por Giardia e Cryptosporidium através da ingestão de água tratada. Portanto, o caso é preocupante, tanto do ponto de vista do tratamento e abastecimento de água potável, quanto da degradação e contaminação do manancial, evidenciando a necessidade de se estabelecer medidas de intervenção direcionadas a promover a qualidade da água e garantir sua segurança

Reduction of haloacetonitriles and haloacetones in natural waters using ceramic nanofiltration membranes

Póster presentado en 19th International Congress of Chemical and Process Engineering, Prague, Czech Republic August 28th-September 1st, 2010.

A continuous electrolytic process for the production of beryllium metal /

The continuous production of beryllium metal by low-temperature fused salt electrolysis into a continuously circulating mercury cathode has been demonstrated. The product is amenable to direct hot pressing or to powder preparation by distilling off the mercury. The production of pure beryllium chloride in good yield by direct chlorination of beryllium oxide has also been demonstrated.

Nitrogen trichloride as a chlorinating agent : the action of nitrogen trichloride on ethyl bromide /

Typescript.

Genotoxicity investigation of chlorinated degradation products of a cyanobacterial toxin, cylindrospermopsin

Cylindrospermopsin (CYN), a potent cyanobacterial hepatotoxin produced by Cylindrospermopsis raciborskii and other cyanobacteria, is regularly found in water supplies in many parts of the world and has been associated with the intoxication of humans and livestock.Water treatment via chlorination can degrade the toxin effectively but result in the production of several byproducts. In this study, male and female Balb/c mice were injected via the intraperitoneal (IP) route with a single dose of 10 mg/kg 5-chlorouracil and 10 mg/kg 5-chloro-6-hydroxymethyluracil; these two compounds are the predicted chlorinated degradation products of CYN.DNA was isolated from the mouse livers and examined for strand breakage by alkaline gel electrophoresis (pH 12). The median molecular length (MML) of the DNA distributed in the gel was determined by estimating the midpoint of the DNA size distribution by densitometry. The toxicity of 5-chlorouracil (as measured by DNA strand breakage) was significantly influenced by time from dosing. There was no significant difference in MML between mice dosed with 5-chloro-6-hydroxymethyluracil and the controls. In another experiment, mice were dosed with 0, 0.1, 1, 10 and 100 mg/kg body weight 5-chlorouracil and 0, 0.1, 1, 10 and 20 mg/kg 5-chloro-6-hydroxymethyluracil via IP injection. The heart, liver, kidney, lung and spleen were removed, fixed and examined under electron microscopy. Liver was the main target organ. The EM results revealed marked distortion on the nuclear membrane of liver cells in mice dosed with 1.0 mg/kg 5-chlorouracil or 10 mg/kg 5-chloro-6-hydroxymethyluracil, or higher.

Preliminary investigations into oxidation of paralytic shellfish poisons (saxitoxins and derivatives) in drinking water by chlorine

The fresh water cyanobacterium Anabaena circinalis produces saxitoxin (STX) and several other toxins with similar basic structural skeleton. Collectively, these toxins are known as Paralytic Shellfish Poisons or PSPs. These toxins are water soluble and can escape into the water body after cell lysis. The presence of these toxins in drinking water is a serious threat to human health. The present work has shown that Paralytic Shellfish Poisons (PSPs) in drinking water can be removed by chlorination at high pH (>9.0), provided a residual of 0.5 mg/L of free chlorine is present after 30 minutes of contact time.

Protein oxidation:role in signalling and detection by mass spectrometry

Proteins can undergo a wide variety of oxidative post-translational modifications (oxPTM); while reversible modifications are thought to be relevant in physiological processes, non-reversible oxPTM may contribute to pathological situations and disease. The oxidant is also important in determining the type of oxPTM, such as oxidation, chlorination or nitration. The best characterized oxPTMs involved in signalling modulation are partial oxidations of cysteine to disulfide, glutathionylated or sulfenic acid forms that can be reversed by thiol reductants. Proline hydroxylation in HIF signalling is also quite well characterized, and there is increasing evidence that specific oxidations of methionine and tyrosine may have some biological roles. For some proteins regulated by cysteine oxidation, the residues and molecular mechanism involved have been extensively studied and are well understood, such as the protein tyrosine phosphatase PTP1B and MAP3 kinase ASK1, as well as transcription factor complex Keap1-Nrf2. The advances in understanding of the role oxPTMs in signalling have been facilitated by advances in analytical technology, in particular tandem mass spectrometry techniques. Combinations of peptide sequencing by collisionally induced dissociation and precursor ion scanning or neutral loss to select for specific oxPTMs have proved very useful for identifying oxidatively modified proteins and mapping the sites of oxidation. The development of specific labelling and enrichment procedures for S-nitrosylation or disulfide formation has proved invaluable, and there is ongoing work to establish analogous methods for detection of nitrotyrosine and other modifications.

Redox signalling and detection of protein oxidation by mass spectrometry

It is now recognised that redox control of proteins plays an important role in many signalling pathways both in health and disease. Proteins can undergo a wide variety of oxidative post-translational modifications (oxPTM); while the reversible modifications are thought to be most important in physiological processes, non-reversible oxPTM may contribute to pathological situations and disease. The oxidant is also important in determining the type of oxPTM (chlorination, nitration, etc.), and the susceptibilities of residues vary depending on their structural location. The best characterized oxPTMs involved in signalling modulation are partial oxidations of cysteine to the disulfide, glutathionylated or sulfenic acid forms, but there is increasing evidence that specific oxidations of methionine and tyrosine may have some biological roles. Well understood examples of oxidative regulation include protein tyrosine phosphatases, e.g. PTP1B/C, and members of the MAPK pathways such as MEKK1 and ASK1. Transcription factors such as NFkB and Nrf-2 are also regulated by redox-active cysteines. Improved methods for analysing specific oxPTMs in biological samples are critical for understanding the physiological and pathological roles of these changes, and tandem or MS3 mass spectrometry techniques interfaced with nano-LC separation are being now used. MS3 fragmentation markers for a variety of oxidized residues including tyrosine, tryptophan and proline have been identified, and a precursor ion scanning method that allows the selective identification of these oxPTMs in complex samples has been developed. Such advances in technology offer potential for biomarker development, disease diagnosis and understanding pathology.

Protein oxidative modifications:new mass spectrometry approaches to detection in biological samples

In inflammatory diseases, release of oxidants leads to oxidative damage to proteins. The precise nature of oxidative damage to individual proteins depends on the oxidant involved. Chlorination and nitration are markers of modification by the myeloperoxidase-H2O2-Cl- system and nitric oxide-derived oxidants, respectively. Although these modifications can be detected by western blotting, currently no reliable method exists to identify the specific sites damage to individual proteins in complex mixtures such as clinical samples. We are developing novel LCMS2 and precursor ion scanning methods to address this. LC-MS2 allows separation of peptides and detection of mass changes in oxidized residues on fragmentation of the peptides. We have identified indicative fragment ions for chlorotyrosine, nitrotyrosine, hydroxytyrosine and hydroxytryptophan. A nano-LC/MS3 method involving the dissociation of immonium ions to give specific fragments for the oxidized residues has been developed to overcome the problem of false positives from ions isobaric to these immonium ions that exist in unmodified peptides. The approach has proved able to identify precise protein modifications in individual proteins and mixtures of proteins. An alternative methodology involves multiple reaction monitoring for precursors and fragment ions are specific to oxidized and chlorinated proteins, and this has been tested with human serum albumin. Our ultimate aim is to apply this methodology to the detection of oxidative post-translational modifications in clinical samples for disease diagnosis, monitoring the outcomes of therapy, and improved understanding of disease biochemistry.