Séparation, détection et caractérisation de nanoparticules manufacturées dans des eaux naturelles et usées avec la chromatographie hydrodynamique et de multiples détecteurs

L’utilisation accrue des nanomatériaux manufacturés (NM) fait en sorte que les différents acteurs de réglementation se questionnent de plus en plus par rapport à leur destin et leurs impacts sur les écosystèmes et la santé humaine suite à leur rejet dans l’environnement. Le développement de techniques analytiques permettant de détecter et de caractériser les NM en matrice environnementale est impératif étant donné la nécessité d’évaluer le risque relié à ces polluants émergents. Une des approches de plus en plus favorisée est d’utiliser une technique chromatographique et un ou plusieurs détecteurs sensibles dans les buts de réduire les effets de matrice, d’identifier des nanoparticules (NP) selon leurs temps de rétention et de les quantifier à des concentrations représentatives de la réalité environnementale. Une technique analytique utilisant la chromatographie hydrodynamique (HDC) et des détecteurs en ligne ou hors ligne (détecteurs de diffusion statique ou dynamique de la lumière, spectromètre de masse par torche à plasma en mode particule unique (SP-ICPMS), l’ultracentrifugation analytique) a donc été développée. Le couplage de la colonne HDC avec ces détecteurs a permis de caractériser des NP standards et l’optimisation des conditions de séparation de ces nanoparticules de polystyrène, d’or et d’argent a permis de confirmer que les NP y sont bel et bien séparées seulement selon leur taille, tel que la théorie le prédit. De plus, l’utilisation de la colonne HDC couplée au SP-ICPMS a permis de séparer un mélange de nanoparticules d’argent (nAg) et de les détecter à des concentrations représentatives de celles rencontrées dans l’environnement, soit de l’ordre du μg L-1 au ng L-1. Par exemple, dans un échantillon d’eau usée (effluent), un mélange de nAg de 80 et de 40 nm a été séparé et les nAg ont été détectées à l’aide du SP-ICPMS connecté à la colonne HDC (temps de rétention de 25.2 et 25.6 minutes et diamètres déterminés de 71.4 nm et 52.0 nm). Finalement, pour plusieurs échantillons environnementaux auxquels aucun ajout de nanoparticules n’a été fait, les analyses HDC-SP-ICPMS effectuées ont permis de déterminer qu’ils ne contenaient initialement pas de nAg.

Synthesis of ZnO nanoparticles by hydrothermal method

Stable, OH free zinc oxide (ZnO) nanoparticles were synthesized by hydrothermal method by varying the growth temperature and concentration of the precursors. The formation of ZnO nanoparticles were confirmed by x-ray diffraction (XRD), transmission electron microscopy (TEM) and selected area electron diffraction (SAED) studies. The average particle size have been found to be about 7-24 nm and the compositional analysis is done with inductively coupled plasma atomic emission spectroscopy (ICP-AES). Diffuse reflectance spectroscopy (DRS) results shows that the band gap of ZnO nanoparticles is blue shifted with decrease in particle size. Photoluminescence properties of ZnO nanoparticles at room temperature were studied and the green photoluminescent emission from ZnO nanoparticles can originate from the oxygen vacancy or ZnO interstitial related defects.

Impact of zinc substitution on the structural and magnetic properties of chemically derived nanosized manganese zinc mixed ferrites

Mn1-xZnxFe2O4 nanoparticles (x=0-1) were synthesized by wet chemical co-precipitation techniques. X-ray diffraction, transmission electron microscopy and high-resolution transmission electron microscopy were effectively utilized to investigate the different structural parameters. The elemental analysis was conducted using energy-dispersive spectrum and inductively coupled plasma analysis. The magnetic properties such as magnetization and coercivity were measured using vibrating sample magnetometer. The observed magnetization values of the nanoparticles were found to be lower compared to the bulk counterpart. The magnetization showed a gradual decrease with zinc substitution except for a small increase from x=0.2 to 0.3. The Curie temperature was found to be enhanced in the case of ferrites in the nanoregime. The variation in lattice constant, reduced magnetization values, variation of magnetization with zinc substitution, the presence of a net magnetic moment for the zinc ferrite and the enhancement in Curie temperature in Mn1-xZnxFe2O4 all provide evidence to the existence of a metastable cation distribution together with possible surface effects at the nanoregime.

Template-Assisted Synthesis and Characterization of Passivated Nickel Nanoparticles

Potential applications of nickel nanoparticles demand the synthesis of self-protected nickel nanoparticles by different synthesis techniques. A novel and simple technique for the synthesis of self-protected nickel nanoparticles is realized by the inter-matrix synthesis of nickel nanoparticles by cation exchange reduction in two types of resins. Two different polymer templates namely strongly acidic cation exchange resins and weakly acidic cation exchange resins provided with cation exchange sites which can anchor metal cations by the ion exchange process are used. The nickel ions which are held at the cation exchange sites by ion fixation can be subsequently reduced to metal nanoparticles by using sodium borohydride as the reducing agent. The composites are cycled repeating the loading reduction cycle involved in the synthesis procedure. X-Ray Diffraction, Scanning Electron Microscopy, Transmission Electron microscopy, Energy Dispersive Spectrum, and Inductively Coupled Plasma Analysis are effectively utilized to investigate the different structural characteristics of the nanocomposites. The hysteresis loop parameters namely saturation magnetization and coercivity are measured using Vibrating Sample Magnetometer. The thermomagnetization study is also conducted to evaluate the Curie temperature values of the composites. The effect of cycling on the structural and magnetic characteristics of the two composites are dealt in detail. A comparison between the different characteristics of the two nanocomposites is also provided

Rice husk ash – A valuable reinforcement for high density polyethylene

This paper presents the results of a study on the use of rice husk ash (RHA) for property modification of high density polyethylene (HDPE). Rice husk is a waste product of the rice processing industry. It is used widely as a fuel which results in large quantities of RHA. Here, the characterization of RHA has been done with the help of X-ray diffraction (XRD), Inductively Coupled Plasma Atomic Emission Spectroscopy (ICPAES), light scattering based particle size analysis, Fourier transform infrared spectroscopy (FTIR) and Scanning Electron Microscope (SEM). Most reports suggest that RHA when blended directly with polymers without polar groups does not improve the properties of the polymer substantially. In this study RHA is blended with HDPE in the presence of a compatibilizer. The compatibilized HDPE-RHA blend has a tensile strength about 18% higher than that of virgin HDPE. The elongation-at-break is also higher for the compatibilized blend. TGA studies reveal that uncompatibilized as well as compatibilized HDPERHA composites have excellent thermal stability. The results prove that RHA is a valuable reinforcing material for HDPE and the environmental pollution arising from RHA can be eliminated in a profitable way by this technique.

High Density Single Crystalline GaN Nanodot Arrays Fabricated Using Template-Assisted Selective Growth

High density, uniform GaN nanodot arrays with controllable size have been synthesized by using template-assisted selective growth. The GaN nanodots with average diameter 40nm, 80nm and 120nm were selectively grown by metalorganic chemical vapor deposition (MOCVD) on a nano-patterned SiO2/GaN template. The nanoporous SiO2 on GaN surface was created by inductively coupled plasma etching (ICP) using anodic aluminum oxide (AAO) template as a mask. This selective regrowth results in highly crystalline GaN nanodots confirmed by high resolution transmission electron microscopy. The narrow size distribution and uniform spatial position of the nanoscale dots offer potential advantages over self-assembled dots grown by the Stranski–Krastanow mode.

Compositional data analysis in archaeometry

We shall call an n × p data matrix fully-compositional if the rows sum to a constant, and sub-compositional if the variables are a subset of a fully-compositional data set1. Such data occur widely in archaeometry, where it is common to determine the chemical composition of ceramic, glass, metal or other artefacts using techniques such as neutron activation analysis (NAA), inductively coupled plasma spectroscopy (ICPS), X-ray fluorescence analysis (XRF) etc. Interest often centres on whether there are distinct chemical groups within the data and whether, for example, these can be associated with different origins or manufacturing technologies

Elemental analysis of New Zealand Nephrite Jade (pounamu) for forensic purposes

Pounamu (NZ jade), or nephrite, is a protected mineral in its natural form following the transfer of ownership back to Ngai Tahu under the Ngai Tahu (Pounamu Vesting) Act 1997. Any theft of nephrite is prosecutable under the Crimes Act 1961. Scientific evidence is essential in cases where origin is disputed. A robust method for discrimination of this material through the use of elemental analysis and compositional data analysis is required. Initial studies have characterised the variability within a given nephrite source. This has included investigation of both in situ outcrops and alluvial material. Methods for the discrimination of two geographically close nephrite sources are being developed. Key Words: forensic, jade, nephrite, laser ablation, inductively coupled plasma mass spectrometry, multivariate analysis, elemental analysis, compositional data analysis

Characterization and identification of mixed-metal phosphates in soils: the application, of Raman spectroscopy

The development of protocols for the identification of metal phosphates in phosphate-treated, metal-contaminated soils is a necessary yet problematical step in the validation of remediation schemes involving immobilization of metals as phosphate phases. The potential for Raman spectroscopy to be applied to the identification of these phosphates in soils has yet to be fully explored. With this in mind, a range of synthetic mixed-metal hydroxylapatites has been characterized and added to soils at known concentrations for analysis using both bulk X-ray powder diffraction (XRD) and Raman spectroscopy. Mixed-metal hydroxylapatites in the binary series Ca-Cd, Ca-Pb, Ca-Sr and Cd-Pb synthesized in the presence of acetate and carbonate ions, were characterized using a range of analytical techniques including XRD, analytical scanning electron microscopy (SEM), infrared spectroscopy (IR), inductively coupled plasma-atomic emission spectrometry (ICP-AES) and Raman spectroscopy. Only the Ca-Cd series displays complete solid solution, although under the synthesis conditions of this study the Cd-5(PO4)(3)OH end member could not be synthesized as a pure phase. Within the Ca-Cd series the cell parameters, IR active modes and Raman active bands vary linearly as a function of Cd content. X-ray diffraction and extended X-ray absorption fine structure spectroscopy (EXAFS) suggest that the Cd is distributed across both the Ca(1) and Ca(2) sites, even at low Cd concentrations. In order to explore the likely detection limits for mixed-metal phosphates in soils for XRD and Raman spectroscopy, soils doped with mixed-metal hydroxylapatites at concentrations of 5, 1 and 0.5 wt.% were then studied. X-ray diffraction could not confirm unambiguously the presence or identity of mixed-metal phosphates in soils at concentrations below 5 wt.%. Raman spectroscopy proved a far more sensitive method for the identification of mixed-metal hydroxylapatites in soils, which could positively identify the presence of such phases in soils at all the dopant concentrations used in this study. Moreover, Raman spectroscopy could also provide an accurate assessment of the degree of chemical substitution in the hydroxylapatites even when present in soils at concentrations as low as 0.1%.

A dendrochemical study of Pinus sylvestris from Siljansfors Experimental Forest, central Sweden

Inductively coupled plasma mass spectrometry (ICP-MS) was used to investigate changes in trace element concentration in two high resolution sequences of tree rings from central Sweden. Individual annual growth increments from 18002002 to 1930-2002 were sampled from two Scots pine (Pinus sylvestris) trees from the Siljansfors Experimental Forest. The aims of the study were: to test the viability of conventional solution induction ICP-MS as a technique for investigating the multi-elemental chemistry of long tree ring sequences at annual resolution, and, to test this specifically with a view to detecting changes in elemental concentrations of Swedish tree rings contemporary with the major (and relatively proximal) Icelandic eruption of Askja (1875). It was found that despite a time consuming sample preparation process, it was possible to use conventional ICP-MS for multi-elemental analysis of a long sequence of tree rings at annual resolution. Although promising data were produced, no truly conclusive concentration anomaly could be detected in the sequence to indicate the impact of the Askja eruption on environmental chemistry. Overall findings underlined the complexity of the tree/environment interaction and the cautious approach to data interpretation essential for any dendrochemical study. (c) 2006 Elsevier Ltd. All rights reserved.

Record of natural and anthropogenic changes in reef environments (Barbados West Indies) using laser ablation ICP-MS and sclerochronology on coral cores

Coral growth rate can be affected by environmental parameters such as seawater temperature, depth, and light intensity. The natural reef environment is also disturbed by human influences such as anthropogenic pollutants, which in Barbados are released close to the reefs. Here we describe a relatively new method of assessing the history of pollution and explain how these effects have influenced the coral communities off the west coast of Barbados. We evaluate the relative impact of both anthropogenic pollutants and natural stresses. Sclerochronology documents framework and skeletal growth rate and records pollution history (recorded as reduced growth) for a suite of sampled Montastraea annularis coral cores. X-radiography shows annual growth band patterns of the corals extending back over several decades and indicates significantly lower growth rate in polluted sites. Results using laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) on the whole sample (aragonite, organic matter, trapped particulate matter, etc.), have shown contrasting concentrations of the trace elements (Cu, Sn, Zn, and Pb) between corals at different locations and within a single coral. Deepwater corals 7 km apart, record different levels of Pb and Sn, suggesting that a current transported the metal pollution in the water. In addition, the 1995 hurricanes are associated with anomalous values for Sn and Cu from most sites. These are believed to result from dispersion of nearshore polluted water. We compared the concentrations of trace elements in the coral growth of particular years to those in the relevant contemporaneous seawater. Mean values for the concentration factor in the coral, relative to the water, ranged from 10 for Cu and Ni to 2.4 and 0.7 for Cd and Zn, respectively. Although the uncertainties are large (60-80%), the coral record enabled us to demonstrate the possibility of calculating a history of seawater pollution for these elements from the 1940s to 1997. Our values were much higher than those obtained from analysis of carefully cleaned coral aragonite; they demonstrate the incorporation of more contamination including that from particulate material as well as dissolved metals.

Cloning, expression, and characterization of human cytosolic aminopeptidase P: a single manganese(II)-dependent enzyme

The mammalian bradykinin-degrading enzyme aminopeptidase P (AP-P; E. C. 3.4.11.9) is a metal-dependent enzyme and is a member of the peptidase clan MG. AP-P exists as membrane-bound and cytosolic forms, which represent distinct gene products. A partially truncated clone encoding the cytosolic form was obtained from a human pancreatic cDNA library and the 5' region containing the initiating Met was obtained by 5' rapid accumulation of cDNA ends (RACE). The open reading frame encodes a protein of 623 amino acids with a calculated molecular mass of 69,886 Da. The full-length cDNA with a C-terminal hexahistidine tag was expressed in Escherichia coli and COS-1 cells and migrated on SDS-PAGE with a molecular mass of 71 kDa. The expressed cytosolic AP-P hydrolyzed the X-Pro bond of bradykinin and substance P but did not hydrolyze Gly-Pro-hydroxyPro. Hydrolysis of bradykinin was inhibited by 1,10-phenanthroline and by the specific inhibitor of the membrane-bound form of mammalian AP-P, apstatin. Inductively coupled plasma atomic emission spectroscopy of AP-P expressed in E. coli revealed the presence of 1 mol of manganese/mol of protein and insignificant amounts of cobalt, iron, and zinc. The enzymatic activity of AP-P was promoted in the presence of Mn(II), and this activation was increased further by the addition of glutathione. The only other metal ion to cause slight activation of the enzyme was Co(II), with Ca(II), Cu(II), Mg(II), Ni(II), and Zn(II) all being inhibitory. Removal of the metal ion from the protein was achieved by treatment with 1,10-phenanthroline. The metal-free enzyme was reactivated by the addition of Mn(II) and, partially, by Fe(II). Neither Co(II) nor Zn(II) reactivated the metal-free enzyme. On the basis of these data we propose that human cytosolic AP-P is a single metal ion-dependent enzyme and that manganese is most likely the metal ion used in vivo.

Distribution of calcium (Ca) and magnesium (Mg) in the leaves of Brassica rapa under varying exogenous Ca and Mg supply

Background and Aims Leafy vegetable Brassica crops are an important source of dietary calcium (Ca) and magnesium (Mg) and represent potential targets for increasing leaf Ca and Mg concentrations through agronomy or breeding. Although the internal distribution of Ca and Mg within leaves affects the accumulation of these elements, such data are not available for Brassica. The aim of this study was to characterize the internal distribution of Ca and Mg in the leaves of a vegetable Brassica and to determine the effects of altered exogenous Ca and Mg supply on this distribution. Methods Brassica rapa ssp. trilocularis ‘R-o-18’ was grown at four different Ca:Mg treatments for 21 d in a controlled environment. Concentrations of Ca and Mg were determined in fully expanded leaves using inductively coupled plasma-mass spectrometry (ICP-MS). Internal distributions of Ca and Mg were determined in transverse leaf sections at the base and apex of leaves using energy-dispersive X-ray spectroscopy (EDS) with cryo-scanning electron microscopy (cryo-SEM). Key Results Leaf Ca and Mg concentrations were greatest in palisade and spongy mesophyll cells, respectively, although this was dependent on exogenous supply. Calcium accumulation in palisade mesophyll cells was enhanced slightly under high Mg supply; in contrast, Mg accumulation in spongy mesophyll cells was not affected by Ca supply. Conclusions The results are consistent with Arabidopsis thaliana and other Brassicaceae, providing phenotypic evidence that conserved mechanisms regulate leaf Ca and Mg distribution at a cellular scale. The future study of Arabidopsis gene orthologues in mutants of this reference B. rapa genotype will improve our understanding of Ca and Mg homeostasis in plants and may provide a model-to-crop translation pathway for targeted breeding.

Biomineralisation by earthworms: an investigation into the stability and distribution of amorphous calcium carbonate

Background Many biominerals form from amorphous calcium carbonate (ACC), but this phase is highly unstable when synthesised in its pure form inorganically. Several species of earthworm secrete calcium carbonate granules which contain highly stable ACC. We analysed the milky fluid from which granules form and solid granules for amino acid (by liquid chromatography) and functional group (by Fourier transform infrared (FTIR) spectroscopy) compositions. Granule elemental composition was determined using inductively coupled plasma-optical emission spectroscopy (ICP-OES) and electron microprobe analysis (EMPA). Mass of ACC present in solid granules was quantified using FTIR and compared to granule elemental and amino acid compositions. Bulk analysis of granules was of powdered bulk material. Spatially resolved analysis was of thin sections of granules using synchrotron-based μ-FTIR and EMPA electron microprobe analysis. Results The milky fluid from which granules form is amino acid-rich (≤ 136 ± 3 nmol mg−1 (n = 3; ± std dev) per individual amino acid); the CaCO3 phase present is ACC. Even four years after production, granules contain ACC. No correlation exists between mass of ACC present and granule elemental composition. Granule amino acid concentrations correlate well with ACC content (r ≥ 0.7, p ≤ 0.05) consistent with a role for amino acids (or the proteins they make up) in ACC stabilisation. Intra-granule variation in ACC (RSD = 16%) and amino acid concentration (RSD = 22–35%) was high for granules produced by the same earthworm. Maps of ACC distribution produced using synchrotron-based μ-FTIR mapping of granule thin sections and the relative intensity of the ν2: ν4 peak ratio, cluster analysis and component regression using ACC and calcite standards showed similar spatial distributions of likely ACC-rich and calcite-rich areas. We could not identify organic peaks in the μ-FTIR spectra and thus could not determine whether ACC-rich domains also had relatively high amino acid concentrations. No correlation exists between ACC distribution and elemental concentrations determined by EMPA. Conclusions ACC present in earthworm CaCO3 granules is highly stable. Our results suggest a role for amino acids (or proteins) in this stability. We see no evidence for stabilisation of ACC by incorporation of inorganic components.

Study of environmental burden of lead in children using teeth as bioindicator

The south region of Sao Paulo city hosts the Guarapiranga dam, responsible for water supply to 25% of the city population. Their surroundings have been subject to intense and irregular occupation by people from very low socioeconomics classes. Measurements undertaken on sediment and particulate materials in the dam revealed concentrations of lead. copper, zinc and cadmium above internationally accepted limits. Epidemiological and toxicological studies undertaken by the World Health Organization in individuals exhibiting lead concentrations in blood, near or below the maximum recommended (10 mu g dl(-1)), surprisingly revealed that toxic effects are more intense in individuals belonging to low socioeconomics classes. Motivated by these facts, we aimed at the investigation of chronic incorporation of lead. as well as the use of our BIOKINETICS code, which is based on an accepted ICRP biokinetics model for lead, in order to extrapolate the results from teeth to other organs. The focus of our data taking was children from poor families, living in a small, restrict and allegedly contaminated area in Sao Paulo city. Thus, a total of 74 human teeth were collected. The average concentration of lead in teeth of children 5 to 10 years old was determined by means of a high-resolution inductively coupled plasma mass spectrometer (ICP-MS). For standardization of the measurements, an animal bone certified material (H-Animal Bone), from the International Atomic Energy Agency, was analyzed. The amount of lead in children living in the surroundings of the dam, was approximately 40% higher than those from the control region, and the average lead concentration was equal to 1.3 mu g g(-1) approximately. Grouping the results in terms of gender, tooth type and condition, it was concluded that a carious molar of boys is a much more efficient contamination pathway for lead, resulting in concentrations 70% higher than in the control region. We also inferred the average concentrations of lead in other organs of these children, by making use of our BIOKINETIC code. (C) 2008 Elsevier Ltd. All rights reserved.