Gloria Restrepo

Application of excitation–emission fluorescence matrices and UV/Vis absorption to monitoring the photocatalytic degradation of commercial humic acid

This study reports the use of excitation-emission matrix (EEM) fluorescence and UV/Vis spectroscopy to monitor the changes in the composition and reactivity of Aldrich humic acids (Aldrich HA) as a model compound for natural organic matter (NOM) during photocatalytic degradation. Degussa P-25 titanium dioxide (TiO(2)) and a solar UV-light simulator (a batch reactor) were used. The photocatalysis shifted the fluorescence maxima of EEMs of Aldrich HA toward shorter wavelengths, which implied that the photocatalytic degradation of commercial Aldrich HA caused the breakdown of high molecular weight components and the formation of lower molecular weight fractions. In addition, the fluorescence intensity of fulvic- and humic-like Aldrich HA presented a strong correlation with dissolved organic carbon (DOC), specific UV absorbance (SUVA) parameters, trihalomethane formation potential (THMFP), and organically bound halogens absorbable on activated carbon formation potential (AOXFP). Fluorescence spectroscopy was shown to be a powerful tool for monitoring of the photocatalytic degradation of HA.

Magnetron-sputtered Ag surfaces. New evidence for the nature of the ag ions intervening in bacterial inactivation.

DC-magnetron sputtering with an Ag target on textile surfaces produced Ag particles with sizes approximately 4.7 nm (+/-15%). Sputtering for 15 s led to Ag layers of 15-20 nm. The threshold sputtering time precluding airborne bacterial growth was about 60 s. In this case, the coating was approximately 40-50 nm thick and the cotton Ag loading was 0.0026 wt %. The Ag particle size did not vary significantly with sputtering time between 15 and 600 s. Only coatings above this thickness lead to bacterial inactivation. Ag/Pt targets with sputtering times<60 s did not increase the bactericide performance of the Ag cotton samples with respect to sputtering from an Ag target alone, as expected from the position of Pt respect to Ag in the electrochemical series (Galvanic effect). The Ag cotton deposition led to very thin metallic semitransparent gray color coatings. X-ray of the Ag cotton suggested the presence of amorphous and crystalline Ag species. By X-ray photoelectron spectroscopy (XPS), it was found that the amount of oxidized silver species on the cotton was similar for sputtering times of 60 and 600 s, but the total amount of Ag deposited was almost two times higher after 600 s sputtering. This suggests that the positive silver-ions were located mainly at the silver interface. The type of silver ions produced using the Ag/Pt sputtering was determined to be very similar at 15, 60, and 600 s with the silver ions produced with the Ag target. This explains the lack of an increased inhibitory effect of Pt during the inactivation of airborne bacteria when present in the Pt/Ag target with respect to the Ag target, because in both cases similar silver ionic species were found.

Evaluation of natural organic matter changes from Lake Hohloh by three-dimensional excitation–emission matrix fluorescence spectroscopy during TiO2/UV process

This study shows the changes of natural organic matter (NOM) from Lake Hohloh, (Black Forest, Germany) during heterogeneous photocatalysis with TiO2 (TiO2/UV). The effect of pH on the adsorption of NOM onto TiO2 in the dark and TiO2/UV degradation of NOM was followed using three-dimensional excitation-emission matrix (EEM) fluorescence. At pH values between 4 and 9, the NOM was adsorbed onto TiO2 in the dark with a greater decrease in the fluorescence intensity and in the spectral shapes, especially under acidic pH conditions. However, at pHxa0=xa010 there was not adsorption on NOM which led to a negligible changes the fluorescence intensity. A significant high linear correlation was observed between the DOC adsorption onto TiO2 and the maximum fluorescence intensity. Additionally, the NOM adsorption onto TiO2 and its TiO2/UV degradation shifted the fluorescence maxima toward shorter wavelengths in the EEM contour plots, with a decrease in aromaticity. These changes were accompanied by a substantial decrease in the organically bound halogens adsorbable on activated carbon (AOXFP) and the trihalomethane formation potential (THMFP). Thus, the decrease in maximum fluorescence intensity can be used as an indicator of AOXFP and TTHMFP removal efficiency. Therefore, fluorescence spectroscopy is a robust analytical technique for evaluate TiO2/UV removal of NOM.

Study of pH effects on the evolution of properties of brown-water natural organic matter as revealed by size-exclusion chromatography during photocatalytic degradation

This study shows the effect of pH on the photocatalytic degradation of natural organic matter (NOM). The experiments were carried out in batch reactor (a solar UV-light simulator) with Degussa P-25 titanium dioxide (TiO2). The NOM degradation was followed by size-exclusion chromatography for dissolved organic carbon (DOC), ultraviolet absorption and fluorescence-detection (SEC-DOC, SEC-UV254 and SEC-Fl254/450). Changes in pH values affected the adsorption of NOM onto TiO2, but did not affect the photodegradation sequence of NOM. For high or low pH values, the degradation of the NOM preferentially removed the larger molecular size fraction in comparison to the middle and small molecular size fractions, resulting in the relative increase of these smaller fractions. This sequence of NOM degradation leads to the evolution of the formation potential for disinfection by-products (DBPs). Specifically, the trihalomethanes and halogenated organic compounds formation potential (THMF and AOXFP) decreased steadily.

Innovative UVC Light (185 nm) and Radio-Frequency-Plasma Pretreatment of Nylon Surfaces at Atmospheric Pressure and Their Implications in Photocatalytic Processes

Innovative pretreatment by UVC light (185 nm) and by radio-frequency (RF) plasma at atmospheric pressure to functionalize the Nylon surface, increasing its bondability toward TiO(2), is reported in this study. In the case of UVC light pretreatment in air, the molar absorption coefficient of O(2)/N(2) at 185 nm is very low and the air in the chamber absorbs very little light from the UVC source before reaching the Nylon sample. Nylon fabrics under RF plasma were also functionalized at atmospheric pressure because of the marked heating effect introduced in the Nylon by the RF plasma. This effect leads to intermolecular bond breaking and oxygenated surface groups in the topmost Nylon layers. Both pretreatments enhanced significantly the photocatalytic discoloration of the red-wine stain in Nylon-TiO(2) compared with samples without pretreatment. The UVC and RF methods in the absence of vacuum imply a considerable cost reduction to functionalize textile surfaces, suggesting a potential industrial application. Red-wine-stain discoloration under simulated sunlight was monitored quantitatively by diffuse-reflectance spectroscopy and by CO(2) evolution. X-ray photoelectron spectroscopy (XPS) was used to monitor the changes of the C, N, and S species on the Nylon topmost layers during the discoloration process. Significant changes in the XPS spectra of Ti 2p peaks were observed during discoloration of the wine spots. Wine stains attenuated the signal of the Ti 2p (458.4 eV) peak in the Nylon-TiO(2)-stained wine sample at time zero (from now on, the time before the discoloration process). Furthermore, a decrease of the wine-related O 1s signal at 529.7 eV and N 1s signal at 399.5 eV was observed during the discoloration process, indicating an efficient catalytic decomposition of the wine pigment on Nylon-TiO(2). X-ray diffraction detected the formation of anatase on the Nylon fibers. High-resolution transmission electron microscopy shows the formation of anatase particles with sizes between 8 and 20 nm.

Evaluations of the TiO2/simulated solar UV degradations of XAD fractions of natural organic matter from a bog lake using size-exclusion chromatography.

This work reports on the changes in compositions of humic acids (HAs) and fulvic acids (FAs) during photocatalytic degradation. The HAs and FAs were obtained from the XAD-resin fractionation of natural-organic matter (NOM) from a bog lake (Lake Hohloh, Black Forest, Germany). Degussa P-25 titanium dioxide (TiO2) in a suspension and a solar UV simulator (batch reactor) were used in the experiments. The photocatalytic degradation of the HAs and FAs were monitored using size-exclusion chromatography (SEC) equipped with dissolved organic carbon (DOC) and ultraviolet (UV254) detection (SEC-DOC and SEC-UV254) and UV-Vis spectrophotometry. The evolutions of the photocatalytic degradations of the HA and FA fractions were selective. The photocatalytic degradation started with the degradations of high molecular weight compounds with relatively high UV254 absorbances in the HA and FA fractions to yield low molecular weight compounds showing less specific UV254 absorbances. Observance of the same tendency for the original NOM from Lake Hohloh indicates that these XAD-fractions still having complex compound mixtures. However, the larger molecular weight fractions of the FAs showed higher preferential adsorptions onto TiO2, which caused their faster degradation rates. Furthermore, FAs showed a greater reduction of the total THM formation potential (TTHMFP) and the organic halogen compounds adsorbable on activated carbon formation potential (AOXFP), in comparison with the HAs.

Soporte de Nuevas Películas de TiO2 y TiO2/SiO2 sobre Gránulos de Poliéster para Aplicación en Fotocatálisis

Peliculas de TiO2 o TiO2/SiO2 fueron soportadas sobre granulos de poliester usando mecanismos de difusion y posterior tratamiento termico a 100oC. Se emplearon dos clases de geles. El primero fue preparado usando diferentes cantidades de TiO2, cloruro de metileno y silicona liquida. El segundo fue obtenido por medio del metodo sol-gel, empleado para producir una matriz de silice a partir de la hidrolisis el tetraetilo ortosilicato, en un medio organico de 2-propanol, en el cual se disperso el fotocatalizador. Los precursores de cada sistema fueron agregados en diferentes relaciones para determinar su influencia en la estabilidad, propiedades y fotoactividad de las peliculas. La actividad fotocatalitica fue evaluada en la fotodegradacion de metanol en fase gaseosa. Los resultados muestran la produccion de materiales con alta resistencia, funcionalidad y actividad asi como una fuerte relacion entre la actividad fotocatalitica con las propiedades fisicoquimicas.

Composición Elemental y Fuentes de Origen de Partículas Respirables (PM10) y Partículas Suspendidas Totales (PST) en el Área Urbana de la Ciudad de Riohacha, Colombia

This research evaluated the concentration, elemental composition and sources of origin of particle PM10 and TSP. Fifteen chemical elements (As, Cd, Ca, Zn, Cu, Cr, Co, Fe, Mg, Mn, Ni, Pb, K, Na and V) were determined using atomic absorption spectrometry. Levels of PM10 (19.4 and 51 µg/m3) and TSP (27.6 and 53.7 µg/m3) did not exceed international standards. The enrichment factor (EF) showed that the soil tracer elements are associated with TSP particles while elements of anthropogenic origin are associated with PM 10 particles. Zn, Cu and Co, showed strong enrichment in PM10 and TSP in the two stations, concluding that are elements of anthropogenic origin. For the group of soil trace elements: Na, As, Pb and Ni, showed a moderate enrichment. The results showed that elements such as Mg, Mn, V and K originated from the natural process of soil.

Diseño y Evaluación Energética de dos Circuitos de Molienda y Clasificación para un Clinker de Cemento a Escala Piloto

Resumen Se presentan los resultados del diseno y evaluacion de dos sistemas de molienda en circuito cerrado, para un clasificador tipo ciclon neumatico y uno tipo harnero vibratorio. Se comparan las eficiencias energeticas bajo similares condiciones de granulometrias a la entrada del molino, conservando el mismo tamano de corte en el clasificador. El material se caracterizo mediante: fluorescencia de rayos X, area superficial por el metodo Brunauer-Emmet-Teller y analisis granulometrico por tamizado. Los resultados indican que la velocidad de giro del molino no tiene significancia estadistica sobre la eficiencia mecanica de molienda. A partir de un analisis de superficies de respuestas se determino que el ciclon favorece la eficiencia (valor optimo 30%) comparado con el harnero (valor optimo 18%). Los modelos encontrados para la determinacion de la eficiencia mecanica del sistema molino-ciclon y molino-harnero, muestran correlaciones del 85 y 83 % respectivamente.

Síntesis de poli ácido láctico y poli ricinoleato empleando calentamiento por microondas y su utilización en la producción de termoplasticos de poliuretano

In this paper we report on the synthesis of thermoplastic polyurethane (TPU) using oligomers synthesized from DL Lactic acid and ricinoleic acid. These polyols were obtained from renewable sources by polycondensation of monomers without catalysts. The effect of microwaves on the reactions was evaluated, where non-thermal effects were found to lower the activation energy and increase the rate constant in a third-order kinetics. The monitoring and characterization of intermediate products was done by quantification of acid value by titration (ASTM D4662 - 03) and hydroxyl number (ASTM D4274 - 05). Thermoplastics obtained are characterized by the following tests: tensile strength and elongation percentage (ASTM D882-97), analysis of differential scanning calorimetry (DSC), infrared spectroscopy (IR) and atomic force microscopy (AFM). TPU was obtained with a percentage of 50% soft segments, all have segmented morphology and segregation of phases. The formulations with poly(DL lactic acid) and Methylene diphenyl diisocyanate (MDI) have the highest stiffness and glass transition temperature (Tg).