The potential of asymmetric flow field-flow fractionation hyphenated to multiple detectors for the quantification and size estimation of silica nanoparticles in a food matrix.

This work represents a first systematic approach to the size-based elemental quantification and size estimation of metal(loid) oxide nanoparticles such as silica (SiO2) in a real food matrix using asymmetric flow field-flow fractionation coupled online with inductively coupled plasma mass spectrometry (ICP-MS) and multi-angle light scattering (MALS) and offline with transmission electron microscopy (TEM) with energy-dispersive X-ray analysis (EDAX). Coffee creamer was selected as the model sample since it is known to contain silica as well as metal oxides such as titania at the milligramme per kilogramme levels. Optimisation of sample preparation conditions such as matrix-to-solvent ratio, defatting with organic solvents and sonication time that may affect nanoparticle size and size distribution in suspensions was investigated. Special attention was paid to the selection of conditions that minimise particle transformation during sample preparation and analysis. The coffee creamer matrix components were found to stabilise food grade SiO2 particles in comparison with water suspensions whilst no significant effect of defatting using hexane was found. The use of sample preparation procedures that mimic food cooking in real life was also investigated regarding their effect on particle size and particle size distribution of silica nanoparticles in the investigated food matrix; no significant effect of the water temperature ranging from ambient temperature to 60 °C was observed. Field-flow fractionation coupled to inductively coupled plasma-mass spectrometry (FFF-ICP-MS) analysis of extracts of both unspiked coffee creamer and coffee creamer spiked with food grade silicon dioxide, using different approaches for size estimation, enabled determination of SiO2 size-based speciation. Element-specific detection by ICP-MS and post-FFF calibration with elemental calibration standards was used to determine the elemental composition of size fractions separated online by FFF. Quantitative data on mass balance is provided for the size-based speciation of the investigated inorganic nano-objects in the complex matrix. The combination of FFF with offline fractionation by filtration and with detection by ICP-MS and TEM/EDAX has been proven essential to provide reliable information of nanoparticle size in the complex food matrix.

Tributyltin and triphenyltin uptake by lettuce.

This paper provides quantitative information on the transfer of TBT (tributyltin) and TPhT (triphenyltin) from sludged soil to cultivated lettuce. The effect of their initial concentrations in the soil (varying from 20 to 50 microg(Sn)kg(-1) for each triorganotin), sludge amount (between 1% and 9%), and cultivation duration (32-54 days) was evaluated by means of experimental designs. The impact of the cultivation temperature at 13 degrees C and 19 degrees C on organotin fate in the soil/plant system was also considered. The final concentration of a given organotin in the plant roots was found to depend directly on its initial concentration in the soil. A total of (85+/-15)% of initial TBT in the soil was still present at the end of the experiments, regardless of the cultivation duration. Consequently, TBT appeared to be taken up by lettuce continually. A total of (75+/-5)% of TPhT was found to be degraded in the soil at 54 days. So, this compound could have been taken up by the plant at the beginning of the cultivation. Sludge amount seemed to have a negative effect on TPhT concentration in a plant at 32 days. This could be due to the quantitative TPhT sorption onto the sludge, observed just after spiking. Organotin plant uptake appeared to be more important at 19 degrees C than at 13 degrees C. TBT and TPhT were mainly accumulated in the roots, and up to 2% and 10% of TPhT and TBT, respectively, were translocated to the shoots. Despite TPhT degradation, products in large amounts were present in the soil and were not significantly taken up by the plant. They possibly remained immobilized on solid phases of the sludged soil.

Kinetic degradation processes of butyl- and phenyltins in soils.

The degradation of organotin compounds (OTC) in agricultural and forest soils is studied in sandy soil samples. Individual experiments involving the three butyl- and the three phenyltins were carried out during 90 d in controlled conditions (darkness, 28 degrees C, aerobic conditions, 13% moisture) and with spiking concentration representative of environmental levels (20-50 micrg(Sn) kg(-1)). After the validation of first-order degradation kinetic model, mechanisms involved throughout the study were considered. Degradation pathways are proposed for butyl- and phenyltins and discussed according to literature data. The degradation of mono- (MBT, MPhT), di-organotins (DBT, DPhT) and TBT is clearly identified as a single successive loss of an organic group whereas TPhT is directly degraded to MPhT. The half-life times were dependent on their substitution degree, ranging from 24 (TPhT) to 220 (MBT) d. The less substituted the OTC is, the more persistent it is. In the range 4.3-5.7, pH does not seem to influence OTC degradation under the present operating conditions. Finally this study shows the significant persistence in soil samples in our experimental conditions for most of studied organotins and highlights the potential impact on soil quality.

Analytical advances in butyl-, phenyl- and octyltin speciation analysis in soil by GC-PFPD.

The development and validation of a method for organotin analysis in soils, including butyl-, phenyl- and octyl-tins, are described in this study. The influence of pretreatment step based on sample lyophilization was first studied. Different solid-liquid extraction techniques including mechanical stirring (MSAE), accelerated solvent (ASE), microwave (MAE) and ultrasound (UAE), were compared. MSAE gave the best recoveries and repeatability and was thus chosen for OTC extraction from soils. Then, ethylation/extraction step before GC-PFPD analysis was investigated and the best derivatisation conditions were assessed in order to achieve a simple, non-expensive and reliable routine procedure. Finally, the robustness of the method was tested by the analysis of several soils with different organic matter content allowing the validation of developed protocol. The method appears to be reliable and accurate for the OTC determination in a broad range of soils.

Evaluation of a combined fractionation and speciation approach for study of size-based distribution of organotin species on environmental colloids.

Results relating to the first original application of an analytical approach combining asymmetric flow field-flow fractionation (As-Fl-FFF) with multi-detection and chemical speciation for determination of organotins in a landfill leachate sample are presented. The speciation analysis involved off-line head-space solid-phase microextraction (HS-SPME)-gas chromatography with pulsed-flame photometric detection (GC-PFPD) performed after three consecutive collections of five different fractions of interest from the As-Fl-FFF system and cross-flow part (assumed to be representative of the <10 kDa phase). After 0.45 microm filtration and without preconcentration before fractionation and speciation analysis, limits of detection (LOD) were 4-45 ng (Sn) L(-1) in the sample, with relative standard deviations (RSD) of 3-23%. The As-Fl-FFF fractionation of this sample enables characterization of two distinct populations-organic-rich and inorganic colloids with gyration radius up to 120 nm. Total Sn and mono and dibutyltins (MBT and DBT) appear to be distributed over the whole colloidal phase. Tributyl, monomethyl, monooctyl, and diphenyltins (TBT, MMT, MOcT, and DPhT) were also detected. Quantitative speciation analysis performed on the two colloidal populations and in the <10 kDa phase revealed concentrations from 130 +/- 10 (MMT) to 560 +/- 50 ng (Sn) L(-1) (DPhT).

Organotin speciation in French brandies and wines by solid-phase microextraction and gas chromatography--pulsed flame photometric detection.

An analytical method devoted to organotin compounds (OTC) determination in brandy and wine was developed. It is based on solid-phase microextraction (SPME) of ethylated organotins. The following operating factors were examined: SPME mode/nature of fibre coating, sample volume/dilution, and sampling time. The optimisation work led to dilute the sample in an aqueous buffer (1/11, v/v ratio) in order to satisfactorily decrease the matrix effects due to competitive sorption of non-OTC species onto/into fibre coating. The optimised operating conditions consist of polydimethylsiloxane (PDMS) coated fibre used in headspace mode for 30 min. In wines, the limits of detection (LOD) and quantification (LOQ) ranged from 1 to 40 and 3 to 80 ng(Sn)L(-1) respectively, according to the species. The analytical validation was made by evaluating the accuracy of OTC determination in spiked samples with various concentrations over the whole calibration range, i.e. from LOQ to 1000 ng(Sn)L(-1). Recovery was around 80-110% and precision (relative standard deviation, RSD) was between 12% and 25%. Despite the presence of two chromatographic peaks corresponding to sulphur compounds during brandy analysis, the selectivity of the method is adequate. The analysis confirmed the analytical performances and applicability of the method to wine and brandy samples. The obtained results emphasise the contamination of brandy and wine by organotins, the storage in plastic container seeming to be confirmed as the main OTC source.