TG, FT-IR and NMR characterization of n-C16H34 contaminated alumina and silica after mechanochemical treatment.

This paper deals with the application of mechanochemistry to model systems composed of alumina or silica artificially contaminated with n-C16H34. The mechanochemical treatment was carried out by means of a ring mill for times ranging from 10 to 40h. Thermogravimetry and infrared and nuclear magnetic resonance spectroscopies were used for the characterization of the mechanochemical products. The results have indicated that, in the case of alumina, almost all the contaminant n-C16H34 undergoes a complex oxidative reaction path whose end products are strongly held on the surface. These end products are most likely made of crosslinked, partially oxidized hydrocarbon chains bond to the solid surface via COO(-) groups. In the case of silica, the hydrocarbon undergoes a different, equally complex reaction path, but to a lower extent. In this case the end products are most probably carbonylic compounds and graphitic carbon. Then, for both solid matrices, the mechanochemical treatment promotes significant modification of the chemical nature of the polluting hydrocarbon with end products much more difficult to remove from the surface. As the systems studied are models of sites contaminated by aliphatic hydrocarbon, the results are worthy of consideration in relation to the mobility of the contaminants in the environment.

Adsorption of chlorophenol, chloroaniline and methylene blue on fuel oil fly ash.

Fuel oil fly ash has been tested as low-cost carbon-based adsorbent of 2-chlorophenol (CP), 2-chloroaniline (CA) and methylene blue (MB) from aqueous solutions. In all the cases the adsorption was found to be of cooperative type. Different adsorption capacities were found for the three organics. Specifically, it was highest for 2-chlorophenol, reaching about 70 mg g(-1), and quite lower in the other two cases, that is about 47 and 36 mg g(-1) for methylene blue and 2-chloroaniline, respectively. Varying the initial pH and adding KCl were found to have different effects on the adsorption of the three organics. In particular, the presence of other ions had no effect on the adsorption of methylene blue, adverse effect in the case of 2-chlorophenol and enhancing effect in the case of 2-chloroaniline.

Characterization of raw and stabilized waste in relation to toxic metals mobility in realistic landfilling scenarios.

Toxic metal release in simple leaching tests has been studied in this paper to assess waste behaviour in realistic landfilling scenarios. The waste is a galvanic sludge, raw or cement stabilized. Six different leachants were taken into account: distilled water, CO2-saturated solution, Olsen solution, Mehlich No. 3 solution, acid or alkaline soil circulating solution. Dynamic leaching tests of different duration were used for raw and stabilized waste. The results have shown that, with the exception of Mehlich No. 3 solution, when the waste comes into contact with waters of composition similar to that of the solutions studied, the potential environmental contamination should not be of concern.

Recycling of Pre-Washed Municipal Solid Waste Incinerator Fly Ash in the Manufacturing of Low Temperature Setting Geopolymer Materials.

In this work, three samples of municipal solid waste incinerators fly ash (MSWI-FA) have been stabilized in systems containing coal fly ash to create geopolymers through a polycondensation reaction. Monolithic products have been obtained with both MSWI fly ash as received and after the partial removal of chloride and sulfate by water washing. The polycondensation products have been characterized qualitatively by means of Fourier transform infrared spectroscopy, X-ray diffraction and scanning electron microscopy and quantitatively, through the determination of the volume of reacted water and silicate. Furthermore, the heavy metals and chloride releases together with the physico-mechanical properties have been evaluated on the hardened products. In conclusion, considering the technological and environmental performances of the obtained geopolymers, they could be suitable for many non-structural applications, such as backfilling of abandoned quarries, decorative materials or brick fireplaces, hearths, patios, etc.

Mechanochemistry of ibuprofen pharmaceutical.

In this paper mechanochemistry has been studied in view of possible application to detoxification of expired pharmaceuticals. The experiments have been carried out with a commercial medication containing ibuprofen ((RS)-2-(4-(2-methylpropyl)phenyl)propanoic acid) which has been submitted to prolonged milling up to 40h. When Al(OH)(3) is used as co-reagent, the first degradation step induced by the mechanochemical treatment is an acid-base reaction with the ibuprofen carboxylic acid group. The subsequent degradation follows a complex pathway leading to 1-(4-isobutylphenyl)ethanone, 1-isobutyl-4-vinylbenzene and 2-(4-(3-methylbutan-2-yl)phenyl)propan-1-ol after 10h milling and, in addition, 1-(4-acetylphenyl)-2-methylpropan-1-one, 1-(4-(1-hydroxy-2-methylpropyl)phenyl)ethanone and 1-(4-(2-hydroxy-2-methylpropyl)phenyl)ethanone after 40h milling. The degradation reaction path and products have been identified by means of FT-IR spectroscopy, thin layer chromatography, NMR spectroscopy, mass spectroscopy and elemental analysis. The observed ibuprofen decarboxylation makes the drug simultaneously lose both its pharmaceutical activity and toxicity.

Cadmium adsorption by coal combustion ashes-based sorbents--relationship between sorbent properties and adsorption capacity.

A very interesting possibility of coal combustion ashes reutilization is their use as adsorbent materials, that can also take advantage from proper beneficiation techniques. In this work, adsorption of cadmium from aqueous solutions was taken into consideration, with the emphasis on the intertwining among waste properties, beneficiation treatments, properties of the beneficiated materials and adsorption capacity. The characterization of three solid materials used as cadmium sorbents (as-received ash, ash sieved through a 25 µm-size sieve and demineralized ash) was carried out by chemical analysis, infrared spectroscopy, laser granulometry and mercury porosimetry. Cadmium adsorption thermodynamic and kinetic tests were conducted at room temperature, and test solutions were analyzed by atomic absorption spectrophotometry. Maximum specific adsorption capacities resulted in the range 0.5-4.3 mg g(-1). Different existing models were critically considered to find out an interpretation of the controlling mechanism for adsorption kinetics. In particular, it was observed that for lower surface coverage the adsorption rate is governed by a linear driving force while, once surface coverage becomes significant, mechanisms such as the intraparticle micropore diffusion may come into play. Moreover, it was shown that both external fluid-to-particle mass transfer and macropore diffusion hardly affect the adsorption process, which was instead regulated by intraparticle micropore diffusion: characteristic times for this process ranged from 4.1 to 6.1d, and were fully consistent with the experimentally observed equilibrium times. Results were discussed in terms of the relationship among properties of beneficiated materials and cadmium adsorption capacity. Results shed light on interesting correlations among solid properties, cadmium capture rate and maximum cadmium uptake.