Comparison of three labeled silica nanoparticles used as tracers in transport experiments in porous media. Part I: syntheses and characterizations.

The synthesis and the characterization of three kinds of labeled silica nanoparticles were performed. Three different labeling strategies were investigated: fluorescent organic molecule (FITC) embedded in silica matrix, heavy metal core (Ag(0)) and radioactive core ((110m)Ag) surrounded by a silica shell. The main properties and the suitability of each kind of labeled nanoparticle in terms of size, surface properties, stability, detection limits, and cost were determined and compared regarding its use for transport studies. Fluorescent labeling was found the most convenient and the cheapest, but the best detection limits were reached with chemical (Ag(0)) and radio-labeled ((110m)Ag) nanoparticles, which also allowed nondestructive quantifications. This work showed that the choice of labeled nanoparticles as surrogates of natural colloids or manufactured nanoparticles strongly depends on the experimental conditions, especially the concentration and amount required, the composition of the effluent, and the timescale of the experiment.

Foliar exposure of the crop Lactuca sativa to silver nanoparticles: evidence for internalization and changes in Ag speciation.

The impact of engineered nanomaterials on plants, which act as a major point of entry of contaminants into trophic chains, is little documented. The foliar pathway is even less known than the soil-root pathway. However, significant inputs of nanoparticles (NPs) on plant foliage may be expected due to deposition of atmospheric particles or application of NP-containing pesticides. The uptake of Ag-NPs in the crop species Lactuca sativa after foliar exposure and their possible biotransformation and phytotoxic effects were studied. In addition to chemical analyses and ecotoxicological tests, micro X-ray fluorescence, micro X-ray absorption spectroscopy, time of flight secondary ion mass spectrometry and electron microscopy were used to localize and determine the speciation of Ag at sub-micrometer resolution. Although no sign of phytotoxicity was observed, Ag was effectively trapped on lettuce leaves and a thorough washing did not decrease Ag content significantly. We provide first evidence for the entrapment of Ag-NPs by the cuticle and penetration in the leaf tissue through stomata, for the diffusion of Ag in leaf tissues, and oxidation of Ag-NPs and complexation of Ag(+) by thiol-containing molecules. Such type of information is crucial for better assessing the risk associated to Ag-NP containing products.

Comparison of three labeled silica nanoparticles used as tracers in transport experiments in porous media. Part II: transport experiments and modeling.

Three types of labeled silica nanoparticles were used in transport experiments in saturated sand. The goal of this study was to evaluate both the efficiency of labeling techniques (fluorescence (FITC), metal (Ag(0) core) and radioactivity ((110m)Ag(0) core)) in realistic transport conditions and the reactive transport of silica nanocolloids of variable size and concentration in porous media. Experimental results obtained under contrasted experimental conditions revealed that deposition in sand is controlled by nanoparticles size and ionic strength of the solution. A mathematical model is proposed to quantitatively describe colloid transport. Fluorescent labeling is widely used to study fate of colloids in soils but was the less sensitive one. Ag(0) labeling with ICP-MS detection was found to be very sensitive to measure deposition profiles. Radiolabeled ((110m)Ag(0)) nanoparticles permitted in situ detection. Results obtained with radiolabeled nanoparticles are wholly original and might be used for improving the modeling of deposition and release dynamics.

Reactive transport of 85Sr in a chernobyl sand column: static and dynamic experiments and modeling.

The effects of nonlinear sorption and competition with major cations present in the soil solution on radioactive strontium transport in an eolian sand were examined. Three laboratory techniques were used to identify and quantify the chemical and hydrodynamic processes involved in strontium transport: batch experiments, stirred flow-through reactor experiments and saturated laboratory columns. The major goal was to compare the results obtained under static and dynamic conditions and to describe in a deterministic manner the predominant processes involved in radioactive strontium transport in such systems. Experiments under dynamic conditions, namely flow-through reactor and column experiments, were in very good agreement even though the solid/liquid ratio was very different. The experimental data obtained from the flow-through reactor study pointed to a nonlinear, instantaneous and reversible sorption process. Miscible displacement experiments were conducted to demonstrate the competition between stable and radioactive strontium and to quantify its effect on the 85Sr retardation factor. The results were modeled using the PHREEQC computer code. A suitable cation-exchange model was used to describe the solute/soil reaction. The model successfully described the results of the entire set of miscible displacement experiments using the same set of parameter values for the reaction calculations. The column study revealed that the stable Sr aqueous concentration was the most sensitive variable of the model, and that the initial state of the sand/solution system had also to be controlled to explain and describe the measured retardation factor of radioactive strontium. From these observations, propositions can be made to explain the discrepancies observed between some data obtained from static (batches) and dynamic (reactor and column) experiments. Desorbed antecedent species (stable Sr) are removed from the column or reactor in the flow system but continue to compete for sorption sites in the batch system. Batch experiments are simple and fast, and provide a very useful means of multiplying data. However, interpretation becomes difficult when different species compete for sorption sites in the soil/solution system. A combination of batches, flow-through reactor and column experiments, coupled with hydrogeochemical modeling, would seem to offer a very powerful tool for identifying and quantifying the predominant processes on a cubic decimeter scale (dm3) and for providing a range of radioactive strontium retardation factor as a function of the geochemistry of the soil/solution system.