Inter-laboratory comparison of ED-XRF/PIXE analytical techniques in the elemental analysis of filter-deposited multi-elemental certified reference materials representative of ambient particulate matter.

The quantification of the elemental concentration of ambient particulate matter is a challenging task because the observed elemental loadings are not well above the detection limit for most analytical techniques. Although non-destructive nuclear techniques are widely used for the chemical characterization of ambient aerosol, only one multi-element standard reference filter material that mimics ambient aerosol composition has become recently available in the market. To ensure accuracy, reliability and comparability of instruments performance, multiple reference materials with different elemental mass loadings are necessary. In this study, an intercomparison exercise was performed to evaluate the measurement uncertainty and instruments performance using multi-element dust standard reference samples deposited on PTFE filters. The filter samples, produced by means of dust dispersion, were tested in terms of homogeneity, reproducibility and long-term stability (≈40 months). Eight laboratories participated in the exercise. The evaluation of the results reported by the participants was performed by using two sets of reference values: a) the concentrations reported by the Expert Laboratory, b) the robust average concentrations reported by all participants. Most of the reported on the certificate of analysis elements were efficiently detected in the sample loadings prepared as representative for atmospheric samples by the Expert Laboratory. The average absolute relative difference between the reported and the reference values ranged between 0.1% (Ti) and 33.7% (Cr) (CRM-2584). The participants efficiently detected most of the elements except from the elements with atomic number lower than 16 (i.e. P, Al, Mg). The average absolute percentage difference between the participants results and the assigned value as derived by the expert laboratory was 17.5 ± 18.1% (CRM-2583; Cr, Pb excluded) and 16.7 ± 16.7% (CRM-2584; Cr, P excluded). The average "relative robust standard deviation" of the results reported by all participants was 25.1% (CRM-2583) and 22.8% (CRM-2584).

CuO/PMMA Polymer Nanocomposites as Novel Resist Materials for E-Beam Lithography.

Polymer nanocomposites have emerged as a new powerful class of materials because of their versatility, adaptability and wide applicability to a variety of fields. In this work, a facile and cost-effective method to develop poly(methyl methacrylate) (PMMA)-based polymer nanocomposites with copper oxide (CuO) nanofillers is presented. The study concentrates on finding an appropriate methodology to realize CuO/PMMA nanocomposites that could be used as resist materials for e-beam lithography (EBL) with the intention of being integrated into nanodevices. The CuO nanofillers were synthesized via a low-cost chemical synthesis, while several loadings, spin coating conditions and two solvents (acetone and methyl ethyl ketone) were explored and assessed with regards to their effect on producing CuO/PMMA nanocomposites. The nanocomposite films were patterned with EBL and contrast curve data and resolution analysis were used to evaluate their performance and suitability as a resist material. Micro-X-ray fluorescence spectroscopy (µ-XRF) complemented with XRF measurements via a handheld instrument (hh-XRF) was additionally employed as an alternative rapid and non-destructive technique in order to investigate the uniform dispersion of the nanofillers within the polymer matrix and to assist in the selection of the optimum preparation conditions. This study revealed that it is possible to produce low-cost CuO/PMMA nanocomposites as a novel resist material without resorting to complicated preparation techniques.

Direct non-destructive total reflection X-ray fluorescence elemental determinations in zirconium alloy samples.

The development of a direct non-destructive synchrotron-radiation-based total reflection X-ray fluorescence (TXRF) analytical methodology for elemental determinations in zirconium alloy samples is reported for the first time. Discs, of diameter 30 mm and about 1.6 mm thickness, of the zirconium alloys Zr-2.5%Nb and Zircalloy-4 were cut from plates of these alloys and mirror polished. These specimens were presented for TXRF measurements directly after polishing and cleaning. The TXRF measurements were made at the XRF beamline at Elettra synchrotron light source, Trieste, Italy, at two different excitation energies, 1.9 keV and 14 keV, for the determinations of low- and high-Z elements, respectively. The developed analytical methodology involves two complementary quantification schemes, i.e. using either the fundamental parameter method or relative sensitivity based method, allowing quantification of fifteen minor and trace elements with respect to Zr with very good precision and accuracy. In order to countercheck the TXRF analytical results, some samples were analyzed using the DC arc carrier distillation atomic emission spectrometry technique also, which shows an excellent agreement with the results of the TXRF-based methodology developed in this work. The present work resulted in a non-destructive TXRF elemental characterization methodology of metal and alloy samples avoiding the cumbersome dissolution and matrix separation which are normally required in other techniques and traditional methods of TXRF determination. In addition, the production of analytical waste could also be avoided to a large extent. Although the work was carried out for specific applications in the nuclear industry, it is equally suitable for other such samples in different industrial applications.

Localization, ligand environment, bioavailability and toxicity of mercury in Boletus spp. and Scutiger pes-caprae mushrooms.

This study provides information on mercury (Hg) localization, speciation and ligand environment in edible mushrooms: Boletus edulis, B. aereus and Scutiger pes-caprae collected at non-polluted and Hg polluted sites, by LA-ICP-MS, SR-µ-XRF and Hg L3-edge XANES and EXAFS. Mushrooms (especially young ones) collected at Hg polluted sites can contain more than 100 µg Hg g-1 of dry mass. Imaging of the element distribution shows that Hg accumulates mainly in the spore-forming part (hymenium) of the cap. Removal of hymenium before consumption can eliminate more than 50% of accumulated Hg. Mercury is mainly coordinated to di-thiols (43-82%), followed by di-selenols (13-35%) and tetra-thiols (12-20%). Mercury bioavailability, as determined by feeding the mushrooms to Spanish slugs (known metal bioindicators owing to accumulation of metals in their digestive gland), ranged from 4% (S. pes-caprae) to 30% (B. aereus), and decreased with increasing selenium (Se) levels in the mushrooms. Elevated Hg levels in mushrooms fed to the slugs induced toxic effects, but these effects were counteracted with increasing Se concentrations in the mushrooms, pointing to a protective role of Se against Hg toxicity through HgSe complexation. Nevertheless, consumption of the studied mushroom species from Hg polluted sites should be avoided.

An IAEA multi-technique X-ray spectrometry endstation at Elettra Sincrotrone Trieste: benchmarking results and interdisciplinary applications.

The International Atomic Energy Agency (IAEA) jointly with the Elettra Sincrotrone Trieste (EST) operates a multipurpose X-ray spectrometry endstation at the X-ray Fluorescence beamline (10.1L). The facility has been available to external users since the beginning of 2015 through the peer-review process of EST. Using this collaboration framework, the IAEA supports and promotes synchrotron-radiation-based research and training activities for various research groups from the IAEA Member States, especially those who have limited previous experience and resources to access a synchrotron radiation facility. This paper aims to provide a broad overview about various analytical capabilities, intrinsic features and performance figures of the IAEA X-ray spectrometry endstation through the measured results. The IAEA-EST endstation works with monochromatic X-rays in the energy range 3.7-14 keV for the Elettra storage ring operating at 2.0 or 2.4 GeV electron energy. It offers a combination of different advanced analytical probes, e.g. X-ray reflectivity, X-ray absorption fine-structure measurements, grazing-incidence X-ray fluorescence measurements, using different excitation and detection geometries, and thereby supports a comprehensive characterization for different kinds of nanostructured and bulk materials.

Synthesis, characterization and in vivo evaluation of a magnetic cisplatin delivery nanosystem based on PMAA-graft-PEG copolymers.

The development of anticancer drug delivery systems which retain or enhance the cytotoxic properties of the drug to tumorous tissues, while reducing toxicity to other organs is of key importance. We investigated different poly(methacrylic acid)-g-poly(ethyleneglycol methacrylate) polymers as in situ coating agents for magnetite nanocrystallites. The obtained magnetic nano-assemblies were in turn thoroughly characterized for their structural, colloidal and physicochemical properties (drug loading capacity/release, magnetic field triggered drug release, cell uptake and localization) in order to select the best performing system. With the focus on in vivo validation of such magnetic drug delivery systems for first time, we selected cisplatin as the drug, since it is a potent anticancer agent which exhibits serious side effects due to lack of selectivity. In addition, cisplatin would offer facile determination of the metal content in the animal tissues for biodistribution studies. Alongside post-mortem Pt determination in the tissues, the biodistribution of the drug nanocarriers was also monitored in real time with PET-CT (positron emission tomography/computed tomography) with and without the presence of magnetic field gradients; using a novel chelator-free method, the nanoparticles were radiolabeled with 68Ga without having to alter their structure with chemical modifications for conjugation of radiochelators. The ability to be radiolabeled in such a straightforward but very robust way, along with their measured high MRI response, renders them attractive for dual imaging, which is an important functionality for translational investigations. Their anticancer properties were evaluated in vitro and in vivo, in a cisplatin resistant HT-29 human colon adenocarcinoma model, with and without the presence of magnetic field gradients. Enhanced anticancer efficacy and reduced toxicity was recorded for the cisplatin-loaded nanocarriers in comparison to the free cisplatin, particularly when a magnetic field gradient was applied at the tumor site. Post mortem and real-time tissue distribution studies did not reveal increased cisplatin concentration in the tumor site, suggesting that the enhanced anticancer efficacy of the cisplatin-loaded nanocarriers is driven by mechanisms other than increased cisplatin accumulation in the tumors.

New insights into the chemical and isotopic composition of human-body biominerals. I: Cholesterol gallstones from England and Greece.

We have analyzed gallstones from four patients of Europe and particularly from England (including samples from a mother and a daughter) and Greece. According to the XRD, FTIR, NMR and laser micro-Raman results the studied materials correspond to typical cholesterol monohydrate (ChM). The micro-morphology of cholesterol microcrystals was investigated by means of SEM-EDS. The XRF results revealed that Ca is the dominant non-organic metal in all gallstones (up to ∼1.95wt.%) together with Fe, Cu, Pb and Ni (up to ~19ppm for each metal). Gallstones from England contain additional Mn (up to ~87ppm) and Zn (up to ∼6ppm) while the sample of the mother contains negligible Zn and Mn, compared to that of her daughter, but significant As (~4.5ppm). All cholesterol gallstones examined are well enriched in potentially toxic metals (Pb, as well as Ni in one case) and metalloids (As also in one case) as compared to the global average. The position of Zn, which is a characteristic biometal, in the structure of cholesterol, was investigated by molecular simulation using the Accelrys Materials Studio(®) software. On the basis of IRMS results, all gallstones examined exhibit a very light δ(13)C signature (average δ(13)C ~-24‰ PDB). Gamma-ray spectrometry measurements indicate the presence of (214)Pb and (214)Bi natural radionuclides due to the (238)U series as well as an additional amount of (40)K.

Secondary fluorescence enhancement in confocal X-ray microscopy analysis.

In the present work, the influence of the secondary fluorescence enhancement in confocal X-ray microscopy analysis is studied when stratified type of materials are examined. Through a proper mathematical formalism, an exact global theoretical model is presented which accounts for the secondary fluorescence enhancement when either particle (3D-Micro particle induced X-ray emission) or photon (3D-Micro X-ray fluorescence) microbeams are used in the excitation channel. The contribution of the secondary fluorescence effect to the confocal X-ray intensity profiles was calculated for some typical representative cases. In addition, the influence of several experimental parameters was examined in terms of their influence in the absolute intensity and shape of the secondary fluorescence intensity profile.