No abstract

The aim of this work is to estimate background concentrations of organometallic compounds, such as tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), triphenyltin (TPhT), diphenyltin (DPhT), monophenyltin (MPhT), methylmercury (MeHg), inorganic mercury (iHg) and diethyllead (Et2Pb) in the aquatic environment at the French national scale. Both water and sediment samples were collected all over the country, resulting in 152 water samples and 123 sediment samples collected at 181 sampling points. Three types of surface water bodies were investigated: rivers (140 sites), lakes (19 sites) and coastal water (42 sites), spread along the 11 French river basins. The choice of sites was made on the basis of previous investigation results and the following target criteria: reference, urban sites, agricultural and industrial areas. The analytical method was properly validated for both matrices prior to analysis, resulting in low limits of quantification (LOQ), good precision and linearity in agreement with the Water Framework Directive demands. The results were first evaluated as a function of their river basins, type of surrounding pressure and water bodies. Later, background concentrations at the French national scale were established for both water and sediment matrices, as well as their threshold, i.e., the concentration that distinguishes background from anomalies or contaminations. Background concentrations in water are ranging between <0.04-0.14 ng Hg. L(-1) for MeHg, <0.14-2.10 ng Hg. L(-1) for iHg, <1.0-8.43 ng Pb. L(-1) for Et2Pb and 0.49-151 ng Sn. L(-1), <0.08-3.04 ng Sn. L(-1) and <0.08-0.25 ng Sn. L(-1) for MBT, DBT and TBT, respectively. For sediments, background concentrations were set as <0.09-1.11 ng Hg. g(-1) for MeHg, <0.06-24.3 ng Pb. g(-1) for Et2Pb and <1.4-13.4 ng Sn. g(-1), <0.82-8.54 ng Sn. g(-1), <0.25-1.16 ng Sn. g(-1) and <0.08-0.61 ng Sn. g(-1) for MBT, DBT, TBT and DPhT, respectively. TBT occurs in higher concentrations than the available environmental protection values in 24 and 38 sampling sites for both water and sediment samples, respectively. Other phenyltins (MPhT and TPhT) did not occur above their LOQ and therefore no background was possible to establish. Throughout this work, which is the first assessment of background concentrations for organometallic compounds at the French national level ever being published, it was possible to conclude that over the last 10-20 years organotin concentrations in French river basins have decreased while MeHg concentration remained stable.

Infant formula developed by manufacturers requires a rigorous control of composition, particularly those elements added routinely in an attempt to mimic the mineral composition of human milk. A total of 97 different types of powdered infant formulae (preterm, adapted starter, adapted follow-up, toddler, specialised and soy based formulae) commercially available in Spain were studied. It is noteworthy great differences in mineral (Ca, P, Mg) and trace element (Zn, Fe, Cu, Mn) contents found between analysed and listed in label information. The development of a fast, simple and direct slurry method for the determination of these essential micronutrients in infant formula by inductively coupled plasma optical emission spectrometry (ICP OES) and flame atomic absorption spectrometry (FAAS) was performed in order to help in quality control tasks. Infant formula samples were solubilised using different amounts of several different solvents. An addition of 250 L of a solution 10 % tetramethylammonium hydroxide and 25 % ammonium hydroxide were required for the accurate quantification of Ca and P, Mg, Zn, Fe, Cu and Mn, respectively. The standard reference material 1549 non-fat milk powder was solubilised to compare the validity of assayed methodology following slurry nebulisation and traditional microwave-assisted acid digestion method. Good agreement of the analytical results by both ICP OES and FAAS, with the certified values was obtained. Method performance parameters (accuracy, precision and methodological detection limits) were determined for studied elements to check the quality and usefulness of the optimised slurry method. The analytical procedure was applied successfully to the analysis of a representative group of infant formulae. Levels of analysed elements were graphically represented, showing an acceptable comparability between slurry and acid-mineralisation method set by linear correlation coefficients and slopes close to the unit. The described simple and slurry method is appropriate, as an attractive alternative, for routine control analysis of added essential elements in infant formulae regardless of predominant protein type used in manufacture.