In this study, we describe the statistical analysis of the usage profile of the European population to seven cosmetic products. The aim of the study was to construct a reliable model of exposure of the European population from use of the selected products: body lotion, shampoo, deodorant spray, deodorant non-spray, facial moisturiser, lipstick and toothpaste.The first step in this process was to gather reliable data on consumer usage patterns of the products. These data were sourced from a combination of market information databases and a controlled product use study by the trade association Colipa. The market information study contained a large number of subjects, in total 44,100 households and 18,057 habitual users (males and females) of the studied products, in five European countries.The data sets were then combined to generate a realistic distribution of frequency of use of each product, combined with distribution of the amount of product used at each occasion using the CREMe software. A Monte Carlo method was used to combine the data sets. This resulted in a new model of European exposure to cosmetic products being constructed.

The Monte Carlo computational system for stochastic modelling of dietary exposure to food chemicals and nutrients is presented. This system was developed through a European Commission-funded research project. It is accessible as a Web-based application service. The system allows and supports very significant complexity in the data sets used as the model input, but provides a simple, general purpose, linear kernel for model evaluation. Specific features of the system include the ability to enter (arbitrarily) complex mathematical or probabilistic expressions at each and every input data field, automatic bootstrapping on subjects and on subject food intake diaries, and custom kernels to apply brand information such as market share and loyalty to the calculation of food and chemical intake.

The microstructure of an iron oxide based high temperature water-gas shift (WGS) catalyst has been studied by X-ray diffraction (XRD), high resolution electron microscopy (HREM), high spatial resolution energy dispersive X-ray analysis (STEM-EDX) and X-ray photoelectron spectroscopy (XPS). The iron oxide contains a chromia additive that structurally stabilises the catalyst. Chemical microanalysis indicates that the chromia forms a solid solution within the magnetite Fe3O4 lattice and that no discrete chromia phases are formed. The level of Cr dissolution varies greatly at the intergranular level. XPS and STEM-EDX studies suggest that the activated catalyst is surface enriched in chromia. On the basis of these results a model for the stabilising effect is proposed in which the enriched surface shell encapsulates each catalyst grain and, being more thermodynamically stable than the iron-rich core, reduces ion diffusion and sintering effects. A Cu dopant is often added to the Fe3O4/Cr2O3 catalyst to promote its activity. Chemical microanalysis shows that this dopant also exists in solid solution. Furthermore, STEM-EDX and XPS analyses indicate that the catalyst grains also exhibit a strong surface enrichment in the Cu species. Analysis of aged ex-reactor specimens suggest that deactivation occurs as a result of eventual sintering, with a substantial increase in grain-size relative to the fresh catalyst. The Cu dopant is also demonstrated to have a propensity to segregate as CuO on the surface of the catalyst grains in aged specimens.

During the transformation of a phenol–phenylacetate mixture over a HBEA zeolite (Si/Al=10), carried out in a batch reactor at 160°C in sulfolane or in dodecane solvents, a rapid initial decrease in the formation of hydroxyacetophenones is observed. The compositions of the reaction mixture, of the organic material recovered in methylene chloride by a direct soxhlet treatment and of the compounds retained in the zeolite pores (`coke') were compared after 2 h and 24 h reaction. `Coke' is mainly constituted of phenol and hydroxyacetophenones and of a small amount of heavy secondary reaction products: bisphenol A and acylated derivatives, hydroxy or acetoxy phenylbenzoate, hydroxy or acetoxydypnone, 2 methyl coumarine and 4 methyl chromone, and of sulfolane but not of dodecane. Only a very small quantity of phenylacetate is found. The rate of hydroxyacetophenone formation depends on the order of introduction of the reactants. It is shown that the rapid initial deactivation is not due to the heavy reaction products but to the limitations by phenols (reactant and products) of the access of phenylacetate to the inner acid sites.

The liquid phase acetylation over a HBEA zeolite (Si/Al=10) of anisole with acetic anhydride in equimolar amounts was carried out in a batch reactor at 60°C. p-Methoxyacetophenone is selectively and rapidly formed on the fresh catalyst. However, a rapid deactivation occurs which could be attributed to a large extent to the pronounced inhibiting effect that p-methoxyacetophenone has on the acetylation. In a flow reactor and at a higher temperature (90°C), the catalyst deactivation is much slower particularly when an anisole rich mixture (anisole/acetic anhydride molar ratio of 5) is used as a reactant. Catalyst samples were recovered after various times on stream and the organic material which was retained in significant amounts on the zeolite was analysed by GC and GC/MS. The major part of this material, which consists of p-methoxyacetophenone, can be recovered by soxhlet extraction in methylene chloride. Due to its high polarity, this reaction product is strongly retained in the large mesopore volume of the HBEA zeolite. The minor part can only be recovered after dissolution of the zeolite in a hydrofluoric acid solution. It consists mainly of di- and triacetylated anisole entrapped in the zeolite micropores. As shown by nitrogen adsorption, these compounds cause pore blockage. The latter is responsible for part of the catalyst deactivation, the other part being due to p-methoxyacetophenone located in the mesopores. The use of an excess of anisole enhances catalyst stability as it limits both the retention of p-methoxyacetophenone and the formation of the polyacetylated anisoles.

A kinetic study of the acylation of phenol with phenyl acetate was carried out in liquid phase at 160 degrees C over HBEA zeolite samples, sulfolane or dodecane being used as solvents. The initial rates of hydroxyacetophenone (HAP) production were similar in both solvents. However the catalyst deactivation was faster in dodecane, most likely because of the faster formation of heavy reaction products such as bisphenol A derivatives. Moreover, sulfolane had a very positive effect on p-HAP formation and a negative one on o-HAP formation. To explain these observations as well as the influence of phenol and phenyl acetate concentrations on the rates of o- and p-HAP formation it is proposed that sulfolane plays two independent roles in phenol acylation : solvation of acylium ions intermediates and competition with phenyl acetate and phenol for adsorption on the acid sites. Donor substituents of phenyl acetate have a positive effect on the rate of anisole acylation, provided however there are no diffusion limitations in the zeolite pores.

2-(2-Hydroxyethyl)-pyridine was dehydrated to 2-vinyl-pyridine in liquid phase over solid acid catalysts, with very high selectivity and fairly good reaction rate at relatively low reaction temperature (160 degrees C). The catalytic activity is well correlated with the presence on the catalyst surface of medium to weak Bronsted acid sites. The analysis of "coke" left behind onto the catalyst and the effect of partial poisoning of catalytic activity by CO2 indicate that the reaction takes place through two mechanisms, involving either a Bronsted acid site or a couple of acid-base sites.

Vanadium oxide catalysts supported on titanium oxide have been tested as catalysts for the selective oxidation of butan-2-ol to methylethylketone by hydrogen peroxide at 90°C with a mixture of acetone and water as solvent. A range of catalyst preparation methods were used including wet impregnation and grafting and a number of unsupported oxides were also tested. The main side product observed was acetic acid, probably derived from oxidation of the enol form of methylethylketone. The selectivity of alcohol utilization was always better than the corresponding value for oxidant utilization for all catalysts studied and at all conversion levels. None of the catalysts tested were stable to leaching in the reaction environment. A steady state vanadium concentration became established in the reaction medium a short time after the reaction started. An attempt was made to differentiate between the contribution to the observed catalysis by the homogeneous and heterogeneous forms of vanadium present in the reactor. No correlation was observed between the amount of dissolved vanadium species and the catalytic activity, but there was a correlation between the activity and the total amount of vanadium species present. In addition, the selectivity improved as the dispersion of the vanadium oxide on the surface of the titania increased.

A series of materials featuring copper oxide and/or vanadium oxide supported on titanium oxide, aluminium oxide or a composite alumina-titania carrier were tested for suitability as sorbents/catalysts for the simultaneous removal of SO2 and NOx from flue gases. Sulphur dioxide sorption at 300°C was associated with the formation of copper sulphate and some aluminium sulphate, the latter via a bridging Cu-SO4-Al surface species. Only part of the sorption capacity could be regenerated by reduction in hydrogen at 450°C. Selective catalytic reduction of nitric oxide by ammonia over CuO/TiO2, CuO/Al2O3-TiO2 and CuO/Al2O3 was lessened following exposure of the catalysts to SO2 and this feature was assigned to competition for ammonia between nitric oxide and surface sulphate species, the latter involving formation of (NH4)2SO4. Vanadia supported on a composite support featuring 20 wt.-% alumina, balance titania, was as active as V/TiO2 for nitric oxide reduction by ammonia and the Al2O3 component rendered the catalyst resistant to SO2 poisoning because sulphate formed on vanadia could be transferred to Al2O3 where it did not interfere with the activity. Catalysts with copper and vanadium oxides supported on alumina-titania were not resistant to SO2 poisoning during selective catalytic reduction of nitric oxide because the copper component attracted too much SO2 onto the support, thus exceeding the protective capacity of the alumina component.