Estudio de la movilidad que presenta el diésel en un suelo contaminado empleando surfactantes

La contaminación de suelos con hidrocarburos de petróleo en México es un problema que se ha vuelto muy común en nuestros días, debido principalmente a derrames, así como a las actividades propias de la industria petrolera. Algunos suelos contaminados, principalmente en el sureste de México, contienen concentraciones de hidrocarburos hasta de 450,000 mg/kg. Por dichas razones, una de las preocupaciones de las autoridades ambientales es el desarrollo de tecnologías eficientes y económicamente factibles que permitan la eliminación de este tipo de contaminantes. El saneamiento del sitio se puede lograr a través de diversos procedimientos, como son la aplicación de métodos físicos, químicos y biológicos (o combinaciones de ellas). La elección de un método depende de la naturaleza del contaminante, su estado físico, concentración, tipo de suelo, espacio físico disponible, tiempo destinado para su tratamiento, así como de los recursos económicos disponibles. Previa a la aplicación de la tecnología es necesario la realización de un diagnóstico de la contaminación del suelo, con el fin de conocer el tipo, concentración y distribución de los contaminantes presentes, así como el volumen de suelo a tratar, las condiciones climáticas de la zona, y características físicas del lugar (vías de acceso y servicios, entre otros). En la presente tesis, el empleo de surfactantes, se ha propuesto como una técnica para incrementar la movilidad de contaminantes orgánicos hidrofóbicos (HOCs) como hidrocarburos totales del petróleo (HTPs), bifenilos policlorados (PCBs), Benceno, Tolueno, Xilenos, explosivos, clorofenoles, pesticidas, entre otros, y así facilitar su degradación. Los surfactantes debido a que reducen la tensión superficial del agua, son moléculas formadas por grupos polares hidrofílicos y largas cadenas carbonadas hidrofóbicas. Sus grupos polares forman puentes hidrógeno con las moléculas de agua, mientras que las cadenas carbonadas se asocian a los hidrocarburos debido a interacciones hidrofóbicas que estos presentan. En soluciones acuosas, los surfactantes forman estructuras esféricas organizadas llamadas micelas. La solubilización de los contaminantes se lleva a cabo solamente cuando se forma la fase micelar, la cual se obtiene cuando la concentración del surfactante es superior a la concentración micelar crítica (CMC), es decir, arriba de la concentración de la cual el monómero se comienza a auto-agregar. La eficiencia de desorción de diésel por un surfactante depende de su naturaleza, de la dosis empleada, de la hidrofobicidad del contaminante, de la interacción surfactante-suelo y del tiempo de contacto surfactante-suelo. Sin embargo, la mejor eficiencia de desorción no está siempre relacionada con la mejor eficiencia de movilidad o solubilidad, debido principalmente a que el empleo de una alta concentración de surfactante puede inhibir la movilización. De acuerdo con información proporcionada por la Procuraduría Federal de Protección al Ambiente (PROFEPA), a la fecha no se ha llevado a cabo en México ninguna restauración de sitios específicamente contaminados con diésel, la técnica de lavado de suelos. Por lo anterior existe la necesidad de emplear la técnica de lavado de suelos ex situ. Específicamente en el suelo extraído de la ex refinería 18 de marzo ubicada en el Distrito Federal México y empleando una solución de surfactantes con agua desionizada, la cual consiste ponerlos en contacto con el suelo contaminado con diésel por medio de columnas de lavado cilíndricas, para lograr la remoción del contaminante. Se emplearon como surfactantes el lauril sulfato de sodio, lauril éter sulfato de sodio y Glucopon AV-100 a diferentes concentraciones de 0.5 a 4.0 [g/L], lográndose obtener una eficiencia del 80 % con este último surfactante. El lavado de suelos contaminados con diésel empleado surfactantes, es una tecnología que requiere que se profundice en el estudio de algunas variables como son el tipo de surfactante, concentración, tiempo de lavado, fenómenos de difusión, desorción, propiedades termodinámicas, entre otros. Los cuales determinarán el éxito o fracaso de la técnica empleada. Nowadays, soil pollution with oil in Mexico is a very common issue due mainly to both oil spill and oil activities. For example, mainly in the southeast area of Mexico, polluted soil contains high concentrations of hydrocarbons, up to 450,000 mg/kg. For these reasons, enviromental authorities have the concern in developing economically feasible and efficient technology that allow the elimination of these type of contaminants. The sanitation in sites can be achieved through several procedures such as physical, chemical and biological methods (or a combination among them). The choice of a method depends on the nature and physical state of the contaminant, the concentration, type of soil, physical space available, time consumption and financial resources. Before any technological application, a diagnostic of the polluted soil is necessary in order to know the type, concentration and distribution of contaminants as well as the soil volume, climatic conditions and physical features of the place (access routes and services, among others). In this thesis, surfactants has been proposed as a technique to increase the mobility of hydrophobic-organic contaminants (HOCs), e.g. total hydrocarbons of petroleum, polychlorinated biphenyls, benzene, toluene, xylenes, explosives, chlorophenols, pesticides, among others, and, hence, to facilitate degradation. Since surfactants reduce the water surface tension, they are molecules comprised of hydrophilic polar groups and long-hydrophobic carbon chains. Surfactant’s polar groups form hydrogen bonding with water molecules while carbon chains, i.e. hydrocarbon chains, have hydrophobic interactios. In aqueous solutions, surfactants form self-organised spherical structures called micelles. The solubilisation of contaminants is carried out only when the micellar phase is formed. This is obtained when the surfactant concentration is higher than the crítical micelle concentration (CMC), i.e. above the concentration where the surfactant monomer begins to self-aggregate. The diesel efficiency desorption by surfactants depends on their nature, the dose use, the contaminant hydrophobicity, the surfactant-soil interaction and the contact time with surfactant soil. However, the best desorption is not always related with the best either mobility or solubility efficiency since high concentration of surfactant can inhibit mobilisation. According to information of the Federal Bureau of Environmental Protection (PROFEPA), up today, there is not any restauration of diesel-polluted sites using the washing-soil technique. Due to the above, there exist the necessity of employing the waching-soil technique ex situ. More specifically, a sample soil from the oil-refinery of “18 de marzo” in Mexico city was extracted and a surfactant solution with deionised water was put in contact with the diesel contaminated soil by means of cylindrical waching columns in order to remove the contaminant. The surfactants employed in this work were sodium lauryl sulfate, sodium lauryl ether sulfate and Glucopon AV-100 at different concentrations of 0.5 to 4 [g/L], obtaining a efficiency of 80 % with this last surfactant. The washing of diesel-polluted soil using surfactants is a technology which requires a deeper study of some variables such as the type of surfactant, concentration, washing time, difusión phenomena, desorption, thermodynamic properties, among others. These parameters determine the succes or failure of the employed technique.

Nitrosative stress: Metabolic pathway involving the flavohemoglobin

Nitric oxide (NO) biology has focused on the tightly regulated enzymatic mechanism that transforms l-arginine into a family of molecules, which serve both signaling and defense functions. However, very little is known of the pathways that metabolize these molecules or turn off the signals. The paradigm is well exemplified in bacteria where S-nitrosothiols (SNO)—compounds identified with antimicrobial activities of NO synthase—elicit responses that mediate bacterial resistance by unknown mechanisms. Here we show that Escherichia coli possess both constitutive and inducible elements for SNO metabolism. Constitutive enzyme(s) cleave SNO to NO whereas bacterial hemoglobin, a widely distributed flavohemoglobin of poorly understood function, is central to the inducible response. Remarkably, the protein has evolved a novel heme-detoxification mechanism for NO. Specifically, the heme serves a dioxygenase function that produces mainly nitrate. These studies thus provide new insights into SNO and NO metabolism and identify enzymes with reactions that were thought to occur only by chemical means. Our results also emphasize that the reactions of SNO and NO with hemoglobins are evolutionary conserved, but have been adapted for cell-specific function.

The 9-cis-epoxycarotenoid cleavage reaction is the key regulatory step of abscisic acid biosynthesis in water-stressed bean

Abscisic acid (ABA), a cleavage product of carotenoids, is involved in stress responses in plants. A well known response of plants to water stress is accumulation of ABA, which is caused by de novo synthesis. The limiting step of ABA biosynthesis in plants is presumably the cleavage of 9-cis-epoxycarotenoids, the first committed step of ABA biosynthesis. This step generates the C15 intermediate xanthoxin and C25-apocarotenoids. A cDNA, PvNCED1, was cloned from wilted bean (Phaseolus vulgaris L.) leaves. The 2,398-bp full-length PvNCED1 has an ORF of 615 aa and encodes a 68-kDa protein. The PvNCED1 protein is imported into chloroplasts, where it is associated with the thylakoids. The recombinant protein PvNCED1 catalyzes the cleavage of 9-cis-violaxanthin and 9′-cis-neoxanthin, so that the enzyme is referred to as 9-cis-epoxycarotenoid dioxygenase. When detached bean leaves were water stressed, ABA accumulation was preceded by large increases in PvNCED1 mRNA and protein levels. Conversely, rehydration of stressed leaves caused a rapid decrease in PvNCED1 mRNA, protein, and ABA levels. In bean roots, a similar correlation among PvNCED1 mRNA, protein, and ABA levels was observed. However, the ABA content was much less than in leaves, presumably because of the much smaller carotenoid precursor pool in roots than in leaves. At 7°C, PvNCED1 mRNA and ABA were slowly induced by water stress, but, at 2°C, neither accumulated. The results provide evidence that drought-induced ABA biosynthesis is regulated by the 9-cis-epoxycarotenoid cleavage reaction and that this reaction takes place in the thylakoids, where the carotenoid substrate is located.

The University of Minnesota Biocatalysis/Biodegradation Database: emphasizing enzymes

The University of Minnesota Biocatalysis/Biodegradation Database (UM-BBD, http://umbbd.ahc.umn.edu/) provides curated information on microbial catabolic enzymes and their organization into metabolic pathways. Currently, it contains information on over 400 enzymes. In the last year the enzyme page was enhanced to contain more internal and external links; it also displays the different metabolic pathways in which each enzyme participates. In collaboration with the Nomenclature Commission of the International Union of Biochemistry and Molecular Biology, 35 UM-BBD enzymes were assigned complete EC codes during 2000. Bacterial oxygenases are heavily represented in the UM-BBD; they are known to have broad substrate specificity. A compilation of known reactions of naphthalene and toluene dioxygenases were recently added to the UM-BBD; 73 and 108 were listed respectively. In 2000 the UM-BBD is mirrored by two prestigious groups: the European Bioinformatics Institute and KEGG (the Kyoto Encyclopedia of Genes and Genomes). Collaborations with other groups are being developed. The increased emphasis on UM-BBD enzymes is important for predicting novel metabolic pathways that might exist in nature or could be engineered. It also is important for current efforts in microbial genome annotation.

Fungal metabolic model for human type I hereditary tyrosinaemia.

Type I hereditary tyrosinaemia (HT1) is a severe human inborn disease resulting from loss of fumaryl-acetoacetate hydrolase (Fah). Homozygous disruption of the gene encoding Fah in mice causes neonatal lethality, seriously limiting use of this animal as a model. We report here that fahA, the gene encoding Fah in the fungus Aspergillus nidulans, encodes a polypeptide showing 47.1% identity to its human homologue, fahA disruption results in secretion of succinylacetone (a diagnostic compound for human type I tyrosinaemia) and phenylalanine toxicity. We have isolated spontaneous suppressor mutations preventing this toxicity, presumably representing loss-of-function mutations in genes acting upstream of fahA in the phenylalanine catabolic pathway. Analysis of a class of these mutations demonstrates that loss of homogentisate dioxygenase (leading to alkaptonuria in humans) prevents the effects of a Fah deficiency. Our results strongly suggest human homogentisate dioxygenase as a target for HT1 therapy and illustrate the usefulness of this fungus as an alternative to animal models for certain aspects of human metabolic diseases.

Cloning of an organic solvent-resistance gene in Escherichia coli: the unexpected role of alkylhydroperoxide reductase.

Although bacterial strain able to grow in the presence of organic solvents have been isolated, little is known about the mechanism of their resistance. In the present study, 1,2,3,4-tetrahydronaphthalene (tetralin), a solvent with potential applications in industrial biocatalysis, was used to select a resistant mutant of Escherichia coli. The resultant mutant strain was tested for resistance to a wide range of solvents of varying hydrophobicities and was found to be resistant not only to tetralin itself but also to cyclohexane, propylbenzene, and 1,2-dihydronaphthalene. A recombinant library from mutant DNA was used to clone the resistance gene. The sequence of the cloned locus was determined and found to match the sequence of the previously described alkylhydroperoxide reductase operon ahpCF. The mutation was localized to a substitution of valine for glycine at position 142 in the coding region of ahpC, which is the gene encoding the catalytic subunit of the enzyme. The ahpC mutant was found to have an activity that was three times that of the wild type in reducing tetralin hydroperoxide to 1,2,3,4-tetrahydro-1-naphthol. We conclude that the toxicity of such solvents as tetralin is caused by the formation of toxic hydroperoxides in the cell. The ahpC mutation increases the activity of the enzyme toward hydrophobic hydroperoxides, thereby conferring resistance. The ahpC mutant was sensitive to the more hydrophilic solvents xylene and toluene, suggesting that there are additional mechanisms of solvent toxicity. Mutants resistant to a mixture of xylene and tetralin were isolated from the ahpC mutant but not from the wild-type strain.

Desenvolvimento e validação de métodos bioanalíticos para o monitoramento dos produtos das vias metabólicas do triptofano em linhagem celular de glioma humano

O metabolismo do triptofano (Trp) se dá pela via das quinureninas (QUIN), pela via serotoninérgica (SER) e pela via das aminas traço. A primeira gera QUIN e uma variedade de outros metabólitos secundários. Quando conduzida pela enzima indolamina 2,3 dioxigenase (IDO) contribui para os fenômenos de tolerância e imune escape de células tumorais; e quando conduzida pela triptofano 2,3 dioxigenase (TDO) no fígado, participa na síntese da niacina e NAD. A via SER leva à formação do neurotransmissor serotonina (SER), que pode gerar o hormônio melatonina (MEL), respectivamente e outros metabólitos biologicamente ativos. Outra via menos estudada, a via das aminas traço, produz produtos neuroativos. Dada a abrangência e importância das rotas metabólicas do Trp, nós desenvolvemos e validamos uma metodologia bioanalítica robusta, seletiva e sensível por cromatografia líquida de alta eficiência (HPLC), acoplado espectrometria de massas (MS) para a determinação simultânea do Trp e seus 15 metabólitos. Para tanto, escolhemos para a avaliação das três vias, linhagens de glioma humano. A escolha por este tipo celular deveu-se ao grande interesse de estudos de metabolismo de Trp em células tumorais, no qual células de glioma tem sido modelo. Nos ensaios com as células de glioma acompanhamos os efeitos de um indutor e inibidores da primeira etapa de metabolização do Trp pela via das quinureninas, ou seja, IFN-γ (indutor da IDO), 1-metiltriptofano (1-MT; inibidor competitivo da IDO) e 680C91 (inibidor seletivo da TDO). Pudemos observar o impacto que a indução ou a inibição do primeiro passo teve sobre os metabólitos subsequentes e as diferenças no metabolismo das duas linhagens estudadas, A172 e T98G. A linhagem T98G só tem atividade de IDO, enquanto que a A172 tem tanto atividade IDO quanto TDO. A indução por IFN-γ mostrou que essa citocina não só atua na formação da via QUIN, mas possui um impacto modesto nas demais rotas. Observamos também que a inibição do 1-MT mostrou seu impacto nos metabólitos invdividualmente, do que a simples relação Trp-QUIN. Contudo, nosso resultados nos permitiu mostrar pela primeira vez a descrição completa dessas vias, em especial nessas linhagens celulares, podendo supor estratégias terapêuticas nessas rotas que estão relacionadas a progressão ou não tumoral.

Stabilisation of low softening point petroleum pitch fibres by HNO3

This paper deals with the stabilisation of low softening point pitch fibres obtained from petroleum pitches using HNO3 as oxidising agent. This method presents some advantages compared with conventional methods: pitches with low softening point (SP) can be used to prepare carbon fibres (CF), the stabilisation time has been reduced, the CF yields are similar to those obtained after general methods of stabilisation, and the initial treatments to increase SP when low SP pitches are used to prepare CF, are avoided. The parent pitches were characterised by different techniques such as diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), elemental analysis and solvent extraction with toluene and quinoline. The interaction between HNO3 and the pitch fibres, as well as the changes occurring during the heat treatment, have been followed by DRIFTS.

BETA Zeolite Thin Films Supported on Honeycomb Monoliths with Tunable Properties as Hydrocarbon Traps under Cold-Start Conditions

A high percentage of hydrocarbon (HC) emissions from gasoline vehicles occur during the cold-start period. Among the alternatives proposed to reduce these HC emissions, the use of zeolites before the three-way catalyst (TWC) is thought to be very effective. Zeolites are the preferred adsorbents for this application; however, to avoid high pressure drops, supported zeolites are needed. In this work, two coating methods (dip-coating and in situ crystallization) are optimized to prepare BETA zeolite thin films supported on honeycomb monoliths with tunable properties. The important effect of the density of the thin film in the final performance as a HC trap is demonstrated. A highly effective HC trap is prepared showing 100 % toluene retention, accomplishing the desired performance as a HC trap, desorbing propene at temperatures close to 300 °C, and remaining stable after cycling. The use of this material before the TWC is very promising, and works towards achieving the sustainability and environmental protection goals.

Glyoxylic Acid versus Ethyl Glyoxylate for the Aqueous Enantio­selective Synthesis of α-Hydroxy-γ-Keto Acids and Esters by the N-Tosyl-(S a)-binam-l-prolinamide-Organocatalyzed Aldol Reaction

N-Tosyl-(S a)-binam-l-prolinamide is an efficient catalyst for the aqueous aldol reaction between ketones and glyoxylic acid, as the monohydrate or as an aqueous solution, or a 50% toluene solution of ethyl glyoxylate. These reactions led to the formation of chiral α-hydroxy-γ-keto carboxylic acids and esters in high levels of diastereo- and enantioselectivities (up to 97% ee), providing mainly anti aldol products. Only cyclopentanone and cyclohexane-1,4-dione afforded an almost 1:1 mixture of the syn/anti-diastereoisomers; however, the reaction between 4-phenylcyclohexanone and ethyl glyoxylate gave the corresponding syn,syn-product as the major diastereoisomer.

Insights into the Active Species of Nanoparticle-Functionalized Hierarchical Zeolites in Alkylation Reactions

Supported iron oxide nanoparticles have been incorporated onto hierarchical zeolites by microwave-assisted impregnation and mechanochemical grinding. Nanoparticle-functionalised porous zeolites were characterised by a number of analytical techniques such as XRD, N2 physisorption, TEM, and surface acidity measurements. The catalytic activities of the synthesised nanomaterials were investigated in an alkylation reaction. The results pointed to different species with varying acidity and accessibility in the materials, which provided essentially different catalytic activities in the alkylation of toluene with benzyl chloride under microwave irradiation, selected as the test reaction.

Ethanol dehydration via azeotropic distillation with gasoline fractions as entrainers: A pilot-scale study of the manufacture of an ethanol–hydrocarbon fuel blend

We establish experimentally and through simulations the economic and technical viability of dehydrating ethanol by means of azeotropic distillation, using a hydrocarbon as entrainer. The purpose of this is to manufacture a ready-to-use ethanol–hydrocarbon fuel blend. In order to demonstrate the feasibility of this proposition, we have tested an azeotropic water–ethanol feed mixture, using a hydrocarbon as entrainer, in a semi pilot-plant scale distillation column. Four different hydrocarbons (hexane, cyclohexane, isooctane, and toluene) that are representative of the hydrocarbons present in ordinary gasoline have been tested. Each of these hydrocarbons was tested separately in experiments under conditions of constant feed rate and variable reboiler heat duty. The experimentally obtained results are compared with results calculated by a simulator. Finally, the proposed and traditional ethanol dehydration processes are compared to ascertain the advantages of the former over the latter.

Ethanol dehydration via azeotropic distillation with gasoline fraction mixtures as entrainers: A pilot-scale study with industrially produced bioethanol and naphta

Various hydrocarbons (n-hexane, cyclohexane, toluene, isooctane) and mixtures of them (binary, ternary or quaternary), as well as two different types of industrially produced naphtha (one obtained by direct distillation and the other from a catalytic cracking process), have been tested as candidate entrainers to dehydrate ethanol. The tests were carried out in an azeotropic distillation column on a semi pilot plant. The results show that it is possible to dehydrate bioethanol using naphtha as entrainer, obtaining as a result a fuel blend with negligible water content and ready for immediate use in motor vehicles.

Bifunctional primary amine 2-aminobenzimidazole organocatalyst anchored to trans-cyclohexane-1,2-diamine in enantioselective conjugate additions of aldehydes

Bifunctional chiral primary amine 8 containing an (S,S)-trans-cyclohexane-1,2-diamine scaffold and a 2-benzimidazole unit is used as a general organocatalyst for the Michael addition of α,α-branched aldehydes to nitroalkenes and maleimides. The reactions take place, with 20 mol % of catalyst in dichloromethane at rt for nitroalkenes and with 15 mol % catalyst loading in toluene at 10 °C for maleimides, in good yields and enantioselectivities. DFT calculations demonstrate the bifunctional character of this organocatalyst activating the aldehyde by enamine formation and the Michael acceptor by double hydrogen bonding.

Concentrations and isotopic compositions of low molecular weight hydrocarbons in hydrothermal fluids from ODP Field, Middle Valley, northern Juan de Fuca Ridge

The presence of sedimentary organic matter blanketing midocean ridge crests has a potentially strong impact on metal transport in hydrothermal vent fluids. To constrain the role of organic matter in metal mobility during hydrothermal sediment alteration, we reacted organic-rich diatomaceous ooze from Guaymas Basin, Gulf of California, and organic-poor hemipelagic mud from Middle Valley, northern Juan de Fuca Ridge, with seawater and a Na-Ca-K-Cl fluid of seawater chlorinity, at 275° to 400°C, 350 to 500 bars, and initial fluid: sediment mass ratios ranging from 1.6 to 9.8. Reaction of these fluids with both sediment types released CO2 and high concentrations of ore-forming metals (Fe, Mn, Zn, Pb) to solution. Relatively low concentrations of Cu were observed in solution and likely reflect the reducing conditions that resulted from the presence of sedimentary organic matter. Both the concentrations of CO2 and dissolved metals were lower in fluids reacted with Middle Valley sediment compared with aqueous concentrations in fluids reacted with Guaymas Basin sediment. During alteration of both sediment types, metal concentrations varied strongly as a function of temperature, increasing by up to an order of magnitude over the 75°C range of each experiment. Major element fluid chemistry and observed alteration assemblages suggest that during hydrothermal alteration of organic-lean sediment from Middle Valley a feldspar-quartz-illite mineral assemblage buffered in situ pH. In contrast, data from the experimental alteration of organic-rich Guaymas Basin sediment suggest that a calcite-plagioclase-quartz assemblage regulated in situ pH. Fluid speciation calculations suggest that in situ pH during Guaymas Basin sediment alteration was lower than during alteration of Middle Valley sediment and accounts for the substantially greater metal mobility at a given temperature and pressure during the former experiment. Comparison of our results with the results of basalt alteration experiments indicate that except for Cu, hydrothermal sediment alteration results in equal or greater concentrations of ore-forming metals at a given temperature and pressure. Accordingly, the presence of ore-forming metals in fluids currently venting from sediment-covered hydrothermal systems at concentrations substantially lower than in fluids from bare-rock systems may reflect chemical reequilibration during subsurface cooling within the sediment pile.