Photodegradation of ciprofloxacin adsorbed in the intracrystalline space of montmorillonite.

Although photolysis of antibiotics in aqueous solution was widely studied for a better understanding of their photolytic behavior in aqueous phase, the knowledge about photodegradation of antibiotics adsorbed on solid surfaces is still very limited. In this study, photodegradation of ciprofloxacin (CIP), a fluoroquinolone antibiotic, adsorbed in the intracrystalline space of montmorillonite (MMT) was examined using a xenon light source (300 W, λ > 320 nm). The gradual decrease of basal spacing of MMT from 1.66 to 1.46 nm with irradiation confirmed CIP decomposition in the intracrystalline space under simulated solar irradiation. Nearly 70 percent of adsorbed CIP was degraded after 5 h irradiation, and the reaction followed the first-order kinetics with a rate constant roughly 3 times than that in aqueous solution, indicating more efficient photodegradation of CIP after being adsorbed in the intracrystalline space of MMT. Spectroscopic analysis revealed that direct photolysis was the main photolytic mechanism. The hydroxyl radical induced by irradiated MMT might play an important role. The major photoproducts were identified with liquid chromatography-tandem mass spectrometry, and the main degradation pathways were proposed. The results demonstrated that the photoproduct distribution and degradation pathways of CIP adsorbed in the intracrystalline space differed from those in aqueous solution.

Water radiolysis in exchanged-montmorillonites: the H2 production mechanisms.

The radiolysis of water confined in montmorillonites is studied as a function of the composition of the montmorillonite, the nature of the exchangeable cation, and the relative humidity by following the H2 production under electron irradiation. It is shown that the main factor influencing this H2 production is the water amount in the interlayer space. The effect of the exchangeable cation is linked to its hydration enthalpy. When the water amount is high enough to get a basal distance higher than 1.3 nm, then a total energy transfer from the montmorillonite sheets to the interlayer space occurs, and the H2 production measured is very similar to the one obtained in bulk water. For a basal distance smaller than 1.3 nm, the H2 production increases with the relative humidity and thus with the water amount. Lastly, electron paramagnetic resonance measurements evidence the formation of a new defect induced by ionizing radiation. It consists of a hydrogen radical (H2 precursor) trapped in the structure. This implies that structural hydroxyl bonds can be broken under irradiation, potentially accounting for the observed H2 production.

Ultrasound irradiation combined with hydraulic cleaning on fouled polyethersulfone and polyvinylidene fluoride membranes.

In this study, an ultrasonic irradiation technique was utilized to mitigate the fouling of polyethersulfone (PES) and polyvinylidene fluoride (PVDF) membranes. The use of ultrasound at 20 kHz was applied to a dead-end microfiltration cell in order to mitigate fouling caused by the presence of colloidal bentonite particles. The effect of ultrasonic power and pulse duration on the permeate flux recovery was examined. Measurements indicate that an increase in ultrasonic power and longer pulse duration results to a higher permeate flux recovery. In order to reduce power consumption, a low to high power shift (LHPS) and pulsation method, were investigated. Methods of cleaning such as ultrasonic irradiation, ultrasonic cleaning with forward flushing and ultrasonic cleaning with backwashing were utilized and their cleaning efficiencies were examined. The cleaning performance was assessed using the clean water flux method and scanning electron microscope analysis of the cleaned membranes. Results showed that LHPS and pulsation method both improve the permeate flux recovery but were not able to attain the 93.97 and 74.88% flux recovery for PES and PVDF that was achieved by constant-15 W ultrasonic cleaning. In addition, forward flushing and backwashing may enhance the performance of ultrasonic cleaning at 9 W but could become disadvantageous at 15 W.

Synthesis of silver/montmorillonite nanocomposites using γ-irradiation.

Silver nanoparticles (Ag-NPs) were synthesized into the interlamellar space of montmorillonite (MMT) by using the γ-irradiation technique in the absence of any reducing agent or heat treatment. Silver nitrate and γ-irradiation were used as the silver precursor and physical reducing agent in MMT as a solid support. The MMT was suspended in the aqueous AgNO(3) solution, and after the absorption of silver ions, Ag(+) was reduced using the γ-irradiation technique. The properties of Ag/MMT nanocomposites and the diameters of Ag-NPs were studied as a function of γ-irradiation doses. The interlamellar space limited particle growth (d-spacing [d(s)] = 1.24-1.42 nm); powder X-ray diffraction and transmission electron microscopy (TEM) measurements showed the production of face-centered cubic Ag-NPs with a mean diameter of about 21.57-30.63 nm. Scanning electron microscopy images indicated that there were structure changes between the initial MMT and Ag/MMT nanocomposites under the increased doses of γ-irradiation. Furthermore, energy dispersive X-ray fluorescence spectra for the MMT and Ag/ MMT nanocomposites confirmed the presence of elemental compounds in MMT and Ag-NPs. The results from ultraviolet-visible spectroscopy and TEM demonstrated that increasing the γ-irradiation dose enhanced the concentration of Ag-NPs. In addition, the particle size of the Ag-NPs gradually increased from 1 to 20 kGy. When the γ-irradiation dose increased from 20 to 40 kGy, the particle diameters decreased suddenly as a result of the induced fragmentation of Ag-NPs. Thus, Fourier transform infrared spectroscopy suggested that the interactions between Ag-NPs with the surface of MMT were weak due to the presence of van der Waals interactions. The synthesized Ag/MMT suspension was found to be stable over a long period of time (ie, more than 3 months) without any sign of precipitation.

Ultrasound promoted selective synthesis of 2-aryl-5,6-dihydro-4H-1,3-oxazines catalyzed by K-10 and KSF montmorillonite clays: a practical procedure under mild and solvent-free conditions.

Montmorillonite K-10 and KSF were found to be highly efficient, environmentally friendly and recyclable heterogeneous catalysts for the selective synthesis of a variety of 2-aryl-5,6-dihydro-4H-1,3-oxazines from arylnitriles and 3-amino-1-propanol under ultrasound irradiation. This new methodology provides excellent yields in short reaction times (10-25 min). The reaction work-up is very simple and the catalysts can be easily separated from the reaction mixture and reused several times in subsequent reactions. This catalytic system also exhibits excellent chemoselectivity in the synthesis of mono-oxazines from dinitriles.

Sonocatalytic oxidation of olefins catalyzed by heteropolyanion-montmorillonite nanocomposite.

A Keggin-type heteropolyanion compound (HPO) was doped within the montmorillonite (MMT) structure by impregnation method. The synthesized catalyst was characterized by FT-IR, XRD, UV-vis, CV, SEM and elemental analysis. Based on chemical adsorption between HPO, and hydroxyl surface groups, HPOs nanoparticles were successfully located on the MMT. Moreover, the obtained nanocomposite was found as an efficient catalyst for oxidation of hydrocarbons under reflux and ultrasonic irradiation conditions.

Thermal stability of the thermoluminescence trap structure of bentonite.

This work reports about the thermal stability of the blue thermoluminescence (TL) of a well-characterised natural bentonite from Almeria (Spain). The main interest of this clay, mainly composed of montmorillonite, is because of its application in the field of high-level radioactive waste (HLW) repository in deep-lying rocks. As observed in other aluminosilicates, bentonite exhibits a very complex structure of the emission spectra based on a wide broad maximum peaked at approximately 265 degrees C that can be associated to physico-chemical processes such as dehydroxylation processes, consecutive breaking linking of bonds, formation of hydrolysed ions and redox reactions. The thermal stability tests performed at different temperatures confirm a continuum in the distribution of traps. Hence, the glow curve analysis methods commonly used for synthetic materials based on single discrete traps cannot be applied for this material and the kinetic parameters were fitted assuming an exponential distribution of trapped electrons.

Thermoluminescence response of calcic bentonite subjected to conditions of high nuclear waste underground storage.

Bentonite is regarded as a backfilling material for underground storage facilities of highly radioactive nuclear waste built on granite formations. In these facilities, bentonite will be subjected to a gradient of temperature and dose rate, achieving a very high integrated dose and, therefore, changes in its structure and physical properties may take place. Two experiments to discriminate between the thermal and the irradiation effect were performed. In the first (named BIC 2A), samples were subjected to temperature while in the second (named BIC-2B) the combined effect of temperature and irradiation was studied. The experimental conditions were: a thermal gradient between 130 degrees C and 90 degrees C, a maximum dose rate of 3.5 kGy.h(-1) and a gradient of the integrated dose between 1.75 MGy and 10 MGy. Both experiments lasted a total of 124 days. An irradiation source of 60Co with an activity close to 300,000 Ci, and bentonite samples of 200 mm in length and 50 mm in diameter were used. After the experiment, the samples were ground and two fractions were obtained: a fine fraction (<2 microm) enriched in montmorillonite clay mineral and a coarse fraction (>80 microm). The results are described of thermoluminescence analyses on the two fractions obtained which showed that the coarse fraction can be 100 times more sensitive to radiation than the fine fraction. On the other hand, the heated and irradiated samples showed a thermoluminescence response around 50 times greater than the samples that were only heated. In addition to this, the temperature and dose rate conditions are relevant parameters in the generation and stabilisation of radiation induced defects. Finally, the response of samples heated and irradiated for two months was quite similar to that obtained on samples heated and irradiated for four months, indicating a saturation phenomenon.

The radiolysis and radioracemization of amino acids on clays.

L-Leucine and its hydrochloride salt have been deposited on the clay minerals kaolin and bentonite, and the amino acid/clay preparations have been irradiated in a 3000 Ci60Co gamma-ray source for radiation dosages that achieved 2-89% radiolysis of the leucine. The undecomposed leucine was thereupon recovered and both percent radiolysis and percent radioracemization were determined. Similar studies were made using solid L-leucine and its hydrochloride, and L-leucine in 0.1 M aqueous solution. It has been found that radiolysis and radio-racemization in these and the previously studied leucine systems follow pseudo-first-order rate laws, and the corresponding specific rate constants are evaluated and compared. Leucine and its hydrochloride salt proved to be the most stable to both radiolysis and radioracemization, followed by leucine and its HCl salt on kaolin, followed by leucine and its HCl salt on bentonite, with leucine (and its HCl and Na salts) in aqueous solution being least stable to both radiolysis and (except for the HCl salt) radioracemization. Implications of these observations as regards the Vester-Ulbricht mechanism for the origin of optical activity are discussed.