Separation of nanoparticles from polydisperse environmental samples: comparative study of filtration, sedimentation, and coiled tube field-flow fractionation.

Nanoparticles (NPs) in the environment have a potential risk for human health and the ecosystem due to their ubiquity, specific characteristics, and properties (extreme mobility in the environment, abilities to accumulate of toxic elements and penetrate into living organisms). There is still a gap in studies on the chemical composition of natural NPs. The main reason is the difficulty to recover NPs, which may represent only one-thousandth or less of the bulk environmental sample, for further dimensional and quantitative characterization. In the present study, a methodology for the recovery of the nanoparticle fraction from polydisperse environmental samples was developed taking as example volcanic ashes from different regions of the world. For the first time, three separation methods, namely, filtration through a 0.45-µm membrane, sedimentation, and coiled tube field-flow fractionation (CTFFF), were comparatively studied. The separated fractions were characterized by laser diffraction and scanning electron microscopy and then analyzed by inductively coupled plasma atomic emission and mass spectrometry. It has been shown that all three methods provide the separation of NPs less than 400 nm from the bulk material. However, the fraction separated by sedimentation also contained a population (5% in mass) of submicron particles (~ 400-900 nm). The filtration resulted in low recovery of NPs. The determination of most trace elements was then impossible; the concentration of elements was under the limit of detection of the analytical instrument. The sedimentation and CTFFF made it possible to determine quantifiable concentrations for both major and trace elements in separated fractions. However, the sedimentation took 48 h while CTFFF enabled the fractionation time to be decreased down to 2 h. Hence, CTFFF looked to be the most promising method for the separation of NPs followed by their quantitative elemental analysis.

Design and Cellular Fate of Bioinspired Au-Ag Nanoshells@Hybrid Silica Nanoparticles.

Silica-coated gold-silver alloy nanoshells were obtained via a bioinspired approach using gelatin and poly-l-lysine (PLL) as biotemplates for the interfacial condensation of sodium silicate solutions. X-ray photoelectron spectroscopy was used as an efficient tool for the in-depth and complete characterization of the chemical features of nanoparticles during the whole synthetic process. Cytotoxicity assays using HaCaT cells evidenced the detrimental effect of the gelatin nanocoating and significant induction of late apoptosis after silicification. In contrast, PLL-modified nanoparticles had less biological impact that was further improved by the silica layer, and uptake rates of up to 50% of those of the initial particles could be achieved. These results are discussed considering the effect of nanosurface confinement of the biopolymers on their chemical and biological reactivity.

Determination of total and electrolabile copper in agricultural soil by using disposable modified-carbon screen-printed electrodes.

The objective of the study is to evaluate modified-carbon screen-printed working electrodes (SPE) combined with square wave anodic stripping voltammetry (SWASV) to determine electrolabile and total copper in soils with the perspective to assess the environmental hazard resulting from copper anthropogenic contamination. The voltammetric method was investigated using a mineralized certified reference soil such that it can be assumed that the copper was totally under electrolabile form in the solution of mineralized soil. In optimal conditions, a copper recovery of 97% and a relative standard deviation (RSD) of 9% were found. The limits of detection and quantification for copper were 0.4 and 1.3 µg L(-1), respectively. Finally, the method was applied on soil leachates, which allowed evaluating the cupric transfer from the soil to the leachates and quantifying the electrolabile copper part in leachates.

Centrifugal ultrafiltration preconcentration for studying the colloidal phase of a uranium-containing soil suspension.

The objective of this work was to explore centrifugal ultrafiltration (UF) to separate and / or preconcentrate natural colloidal particles for their characterization. A soil suspension obtained by batch leaching was used as a laboratory reference sample. It was preconcentrated with concentration factors (CF) varying from 10 to 450. The dimensional analysis of the colloidal phase was carried out by Asymmetric Flow Field-Flow Fractionation (AF4)-multidetection. The colloidal masses were estimated by mass balance of the initial suspension, its concentrates and filtrates. The size-dependent distribution (expressed in gyration radius) and total colloidal mass (especially recovery), as well as chemical composition and concentration (including species partitioning between dissolved and colloidal phases) were determined to assess the effects of UF preconcentration on colloidal particles. The gyration radius of the colloidal particles recovered in these concentrated suspensions ranged from about 20 nm to over 150 nm. Neither de-agglomeration nor agglomeration was observed. However, only (64 ± 4) % (CF = 10) of the colloidal particles initially in the soil suspension were found in the recovered concentrated suspensions, and this percentage decreased as CF increased. The filter membrane trapped all other particles, mainly the larger ones. Whatever the CF, the centrifugal UF did not appear to change the dissolved-colloidal partitioning of certain species (Al, organic carbon); whereas it led to an enrichment of the colloidal phase for others (Fe, U). The enrichment rate was specific to each species (15% for Fe; 100% for U). By fitting the observed trends (i.e. conservation, depletion or enrichment of the colloidal phase in the concentrate) as a function of CF, the colloidal concentrations (total and species) were assessed without bias. This methodology offers a new perspective for determining physicochemical speciation in natural waters, with a methodology applicable for environmental survey or site remediation studies.

Platinum group elements contamination in soils: Review of the current state.

Platinum group elements (PGE: Ru, Rh, Pd, Os Ir, Pt) are rare metals with low abundance in the continental crust. The elements of the palladium subgroup of PGE (PPGE: Pt, Pd, Rh) have been exploited more and more over the last thirty years for their physicochemical properties such as high melting point, high resistance to corrosion, mechanical strength and ductility. This led to emerging environmental contamination in different media such as air, road dust, soil, sediment, vegetation, and snow. The aim of this review is to summarize the available data on soil contamination by PPGE and its potential environmental impact. In this paper, the environmental issue of PPGE is discussed with regard to their anthropogenic emission and fate, which includes speciation, possible transformations into bioavailable forms and toxicity. Soil contamination by PPGE is described taking into account urban and non-urban areas. The analytical determination process is also discussed.

Characterization of volcanic ash nanoparticles and study of their fate in aqueous medium by asymmetric flow field-flow fractionation-multi-detection.

Dimensional and elemental characterization of environmental nanoparticles is a challenging task that requires the use of a set of complementary analytical methods. Asymmetric flow field-flow fractionation coupled with UV-Vis, multi-angle laser light scattering and ICP-MS detection was applied to study the nanoparticle fraction of a volcanic ash sample, in a Milli-Q water suspension at pH 6.8. It has been shown that the separated by sedimentation nanoparticle fraction of the Klyuchevskoy volcano ash suspension contains 3 polydisperse populations for which size ranges (expressed in gyration radius, rG), hydrodynamic behaviours (evaluated via shape index) and elemental compositions are different. These 3 populations did not dissolve over the 72-h study but aggregated and settled out differently. Thus, the population of particles with gyration radii <140 nm (P1), which contained 6% Al2O3 and represented approximately 20% by mass of the nanoparticle fraction, remained in suspension without observable aggregation. The populations P2 and P3, which represented 67% and 13% by mass in the initial suspension, covered the rG range 25-250 nm and contained 17% and 15% Al2O3, respectively. Over time, populations P2 and P3 aggregated and their concentration in suspension at 72 h decreased by approximately 40% compared with the initial suspension. The decrease of these nanoparticle populations occurred either from the beginning of the temporal monitoring (P2) or after 30 h (P3). Aggregation generated a new population (P4) in suspension with rG up to 300 nm and mostly consisting of P2. This population represented only up to 6 to 7% of the nanoparticle fraction and decreased beyond 50 h. As a result, the trace elements present in the nanoparticle fraction and monitored (Cu and La) were also no longer found in the suspension. The results obtained can offer additional insights into the fate of volcanic ash nanoparticles in the environment.

Nanoanalytics: history, concepts, and specificities.

This article deals with analytical chemistry devoted to nano-objects. A short review presents nano-objects, their singularity in relation to their dimensions, genesis, and possible transformations. The term nano-object is then explained. Nano-object characterization activities are considered and a definition of nanoanalytics is proposed. Parameters and properties for describing nano-objects on an individual scale and on the scale of a population are also presented. They enable the specificities of analytical activities to be highlighted in terms of multi-criteria description strategies and observation scale. Special attention is given to analytical methods, their dimensioning and validation.

Gold and silver quantification from gold-silver nanoshells in HaCaT cells.

A method to determine total gold (Au) and/or silver (Ag) elemental concentrations from gold nanoparticles, Au-Ag nanoshells (NS) and silica coated Au-Ag nanoshells was developed, evaluated and validated. Samples were mineralized in a mixture of concentrated aqua regia and hydrofluoric acid at 65 °C for 4 h. Mineralized solutions were diluted and standard solutions were prepared in aqua regia 5%. ICP-MS analysis was performed with or without the use of a reaction cell (CRC). For the determination of elemental concentrations of nanopowders and test suspensions, the average recovery was 99 ±â€¯2% and 101 ±â€¯2% for gold and silver respectively. The repeatability was evaluated by the Relative Standard Deviation (RSD). The overall analytical RSD was ≤4% (n = 3) and the RSD associated to ICP-MS analysis was ≤2% (n = 10). The limits of detection were 0.005 and 0.002 µg(element) L-1 (analyzed solution), and the limits of quantitation 0.017 and 0.005 µg(element) L-1 (analyzed solution), for 197Au and 109Ag respectively. The Ag/Au mass ratios of the NS in the different samples considered were all equal to (0.93 ±â€¯0.04). From this information, the average thickness of gold and silver layers in the nanoshells was deduced, being 7.5 ±â€¯0.5 and 23 ±â€¯3 nm respectively. Finally, the developed method was successfully applied to in vitro studies to evaluate NS cellular uptake in HaCaT keratinocyte cells confirming the method robustness toward biological medium. Experiments in cell culture medium gave coherent concentrations, 70-100% of uncoated or silica-coated NS being recovered, distributed between the culture medium and the cells (internalized). The analytical repeatability (over the whole procedure, or that of the ICP-MS analysis only) remains in the same order of magnitude as in test suspensions. Minimum concentrations less than or equal to 1 µg(element) g-1(suspension) were determined with the same accuracy.

Characterization of polymer-coated CdSe/ZnS quantum dots and investigation of their behaviour in soil solution at relevant concentration by asymmetric flow field-flow fractionation - multi angle light scattering - inductively coupled plasma - mass spectrometry.

A careful separation, identification and characterization of polymer-coated quantum dots (P-QDs) in complex media such as soil solution is the key point to understand their behaviour and to accurately predict their fate in the environment. In the present study, a synthesized CdSe/ZnS core/shell P-QDs suspension, proved to be stable for at least six months, was investigated with respect to P-QDs dimension, structure and elemental composition. Separation of P-QDs and size distribution determination were carried out by Asymmetric Flow Field-Flow Fractionation (AF4) - Multi Angle Light Scattering (MALS). AF4 and MALS were coupled to Inductively Coupled Plasma-Mass Spectrometry (ICPMS) as a selective and sensitive technique for the detection and the characterization of metallic and metalloid analytes. The exploration of element-specific data obtained by ICPMS after AF4 separation enabled the signal to be deconvoluted reliably. Thus, 3 classes of size populations were identified from the whole population of P-QDs. Additionally, a soil solution and a mix of P-QDs suspension with soil solution were characterized by the same method. This strategy enabled the P-QD population, which interacted with the soil solution, to be determined, this interaction leading either to an aggregation or dissolution of the P-QDs. Reproducibility and recovery of the size distributions and element concentrations were examined for each sample. Complementarily, Dynamic Light Scattering (DLS) and Scanning Transmission Electron Microscopy (STEM) were used jointly with AF4-MALS-ICPMS in order to demonstrate all potentialities of this coupling technique.

Quantification of titanium from TiO2 particles in biological tissue.

This study presents the development of a strategy for the quantification of titanium from titanium dioxide polydisperse particles (TiO2) in dry biological tissue. Calf liver was chosen as laboratory testing material. The challenge was to (i) obtain a complete mineralization of the solid material (biological tissue and TiO2) and (ii) ensure the accuracy of the determined concentrations with a sufficient sensitivity. Mineralization was performed using a mixture of concentrated nitric and hydrofluoric acids. Atomic mass spectrometry associated with light-scattering technique was used to control the physical state (dissolved and particle forms) of titanium and reliably estimate the total titanium concentration in calf liver. The monitoring of (46)Ti and (49)Ti, operating in helium collision/reaction cell mode, and using external calibration with internal standard addition, allowed the quantification of Ti while removing isobaric interferences. The limit of detection and quantification were 0.7 and 2.3µg (Ti)g(-1) (tissue) respectively. The mean analytical recovery over the whole procedure was (103±6)% in a range of concentrations from LOD to 200µg(Ti)g(-1) (tissue).