Intra-source provenance study on Monte Arci (Sardinia) obsidian by pXRF: Role of the data acquisition and analysis tools.

In this work, a detailed study of Monte Arci obsidian sub-sources using the increasingly accessible technique of pXRF is presented based upon a large dataset of 68 geological samples, for the development of X-ray fluorescence-based analytical standardless procedure. In addition, a non-conventional (for obsidian provenance study) direct application of multivariate analysis on XRF spectra (continuous variables), rather than absolute concentrations or intensity ratios (discrete variables) is proposed. Results from different softwares and data analysis approaches (bi-/trivariate versus multivariate) were compared. In a blind test, the bi-/trivariate approach led to the correct assignment for the main SA, SB, and SC sub-sources, taking into account averaged values of intensity ratios with their standard deviation obtained from three independent measurements. A high intra-source variability for the SB subgroups was detected (almost 13% of error in the assignment, 9 samples out of 68). A non-conventional application of multivariate analysis was carried out directly on the XRF spectra and correct assignments were obtained for SA, SB1, SC groups, while 71% of the SB2 samples were correctly identified. The non-destructive analysis on 14 archaeological samples from Su Carroppu (Carbonia, southwestern Sardinia) rockshelter and from the Middle Neolithic (MN) 422 structure of the open-air dwelling site at Cuccuru is Arrius (Cabras, central-western Sardinia) permitted to test the method and hypothesise their provenance. The comparison with visual characterization or previous analyses by Particle Induced X-Ray Emission (PIXE) permitted to verify the correct provenance assignment of all artifacts for the bi-/trivariate method, and for 12/14 samples in the case of the multivariate one. The standardless analytical approach proposed in this work can represent a more general method exploitable for other obsidian sources, other glassy materials, besides other materials of archaeological interest.

Hard-Soft Core-Shell Architecture Formation from Cubic Cobalt Ferrite Nanoparticles.

Cubic bi-magnetic hard-soft core-shell nanoarchitectures were prepared starting from cobalt ferrite nanoparticles, prevalently with cubic shape, as seeds to grow a manganese ferrite shell. The combined use of direct (nanoscale chemical mapping via STEM-EDX) and indirect (DC magnetometry) tools was adopted to verify the formation of the heterostructures at the nanoscale and bulk level, respectively. The results showed the obtainment of core-shell NPs (CoFe2O4@MnFe2O4) with a thin shell (heterogenous nucleation). In addition, manganese ferrite was found to homogeneously nucleate to form a secondary nanoparticle population (homogenous nucleation). This study shed light on the competitive formation mechanism of homogenous and heterogenous nucleation, suggesting the existence of a critical size, beyond which, phase separation occurs and seeds are no longer available in the reaction medium for heterogenous nucleation. These findings may allow one to tailor the synthesis process in order to achieve better control of the materials' features affecting the magnetic behaviour, and consequently, the performances as heat mediators or components for data storage devices.

Size dependence of the surface spin disorder and surface anisotropy constant in ferrite nanoparticles.

The magnetic properties of nanoscale magnets are greatly influenced by surface anisotropy. So far, its quantification is based on the examination of the blocking temperature shift within a series of nanoparticles of varying sizes. In this scenario, the surface anisotropy is assumed to be a particle size-independent quantity. However, there is no solid experimental proof to support this simplified picture. On the contrary, our work unravels the size-dependent magnetic morphology and surface anisotropy in highly uniform magnetic nanoparticles using small-angle polarized neutron scattering. We observed that the surface anisotropy constant does not depend on the nanoparticle's size in the range of 3-9 nm. Furthermore, our results demonstrate that the surface spins are less prone to polarization with increasing nanoparticle size. Our study thus proves the size dependence of the surface spin disorder and the surface anisotropy constant in fine nanomagnets. These findings open new routes in materials based on a controlled surface spin disorder, which is essential for future applications of nanomagnets in biomedicine and magnonics.

Germination and early seedling development of Helichrysum microphyllum Cambess. subsp. tyrrhenicum Bacch., Brullo & Giusso in the presence of arsenates and arsenites.

Arsenate, As(V), and arsenite, As(III), are the most available arsenicals present in the soil solutions, in particular in mine polluted substrates, and cause several symptoms of toxicity in plants (like inhibition of seed germination and reduction of seedling development). For these reasons, seeds germination studies are essential for the design of phytoremediation activities of mine sites. Seed germination and seedling development of Helichrysum microphyllum subsp. tyrrhenicum, were evaluated at 15 °C using various concentrations of As(V) and As(III) (0-500 mg/L and 0-200 mg/L, respectively). Seeds were harvested (I) into a mine dump contaminated in As, (II) nearby this site, and (III) faraway the As contaminated area and without mine activities. Seed germination, cotyledons emergence, and seedling mortality were evaluated for 90 days. As(V) and As(III) acted differently, showing a much higher toxicity when arsenite was added than arsenate. The taxon was able to germinate, develop cotyledons, and survive under all arsenate concentrations, whereas arsenite acted on these steps already at 2.5 mg/L. Moreover, a linear decrease in cotyledons emergence was assessed with the increase of both arsenicals' concentrations, as well as a linear decrease of seedling survival under arsenite. The taxon showed great adaptability to As pollution, giving an important contribution in phytoremediation of mining sites.

Effect of different molecular coatings on the heating properties of maghemite nanoparticles.

In this work, the effect of different molecular coatings on the alternating magnetic field-induced heating properties of 15 nm maghemite nanoparticles (NPs) in water dispersions was studied at different frequencies (159-782 kHz) and field amplitudes (100-400 G). The original hydrophobic oleate coating was replaced with dimercaptosuccinic acid (DMSA) or polyethylene glycol trimethoxysilane (PEGTMS), while cetrimonium bromide (CTAB) or stearic acid-poloxamer 188 (SA-P188) was intercalated or encapsulated, respectively, to transfer the dispersions into water. Surface modification, based on intercalation processes, induced clustering phenomena with the formation of spherical-like assemblies (CTAB and SA-P188), while ligand-exchange strategies kept the particles isolated. The clustering phenomenon has detrimental effects on the heating performances compared with isolated systems, in line with the reduction of Brown relaxation times. Furthermore, broader comprehension of the heating phenomenon in this dynamic system is obtained by following the evolution of SPA and ILP with time and temperature beyond the initial stage.

As(III, V) Uptake from Nanostructured Iron Oxides and Oxyhydroxides: The Complex Interplay between Sorbent Surface Chemistry and Arsenic Equilibria.

Iron oxides/oxyhydroxides, namely maghemite, iron oxide-silica composite, akaganeite, and ferrihydrite, are studied for AsV and AsIII removal from water in the pH range 2-8. All sorbents were characterized for their structural, morphological, textural, and surface charge properties. The same experimental conditions for the batch tests permitted a direct comparison among the sorbents, particularly between the oxyhydroxides, known to be among the most promising As-removers but hardly compared in the literature. The tests revealed akaganeite to perform better in the whole pH range for AsV (max 89 mg g-1 at pH0 3) but to be also efficient toward AsIII (max 91 mg g-1 at pH0 3-8), for which the best sorbent was ferrihydrite (max 144 mg g-1 at pH0 8). Moreover, the study of the sorbents' surface chemistry under contact with arsenic and arsenic-free solutions allowed the understanding of its role in the arsenic uptake through electrophoretic light scattering and pH measurements. Indeed, the sorbent's ability to modify the starting pH was a crucial step in determining the removal of performances. The AsV initial concentration, contact time, ionic strength, and presence of competitors were also studied for akaganeite, the most promising remover, at pH0 3 and 8 to deepen the uptake mechanism.

Nanoscaled Metal-Organic Frameworks: Challenges Towards Biomedical Applications.

Achieving metal-organic frameworks (MOFs) in the form of nanoparticles (NanoMOFs) represents a recent challenge due to the possibility to combine the intrinsic porosity of these materials with the nanometric dimension, a fundamental requirement for strategic biomedical applications. In this outlook we envision the current/future opportunities of the NanoMOFs in the field of biomedicine, with particular emphasis on (i) biocompatible MOFs composition; (ii) MOFs miniaturization and (iii) nanoMOFs applications.

On the synthesis of bi-magnetic manganese ferrite-based core-shell nanoparticles.

Multifunctional nano-heterostructures (NHSs) with controlled morphology are cardinal in many applications, but the understanding of the nanoscale colloidal chemistry is yet to be fulfilled. The stability of the involved crystalline phases in different solvents at mid- and high-temperatures and reaction kinetics considerably affect the nucleation and growth of the materials and their final architecture. The formation mechanism of manganese ferrite-based core-shell NHSs is herein investigated. The effects of the core size (8, 10, and 11 nm), the shell nature (cobalt ferrite and spinel iron oxide) and the polarity of the solvent (toluene and octanol) on the dissolution phenomena of manganese ferrite are also studied. Noteworthily, the combined use of bulk (powder X-ray diffraction, 57Fe Mössbauer spectroscopy, and DC magnetometry) and nanoscale techniques (HRTEM and STEM-EDX) provides new insights into the manganese ferrite dissolution phenomena, the colloidal stability in an organic environment, and the critical size below which dissolution is complete. Moreover, the dissolved manganese and iron ions react further, leading to an inverted core-shell in the mother liquor solution, paving the way to novel synthetic pathways in nanocrystal design. The MnFe2O4@CoFe2O4 core-shell heterostructures were also employed as heat mediators, exploiting the magnetic coupling between a hard (CoFe2O4) and a soft phase (MnFe2O4).

Meso- and macroporous silica-based arsenic adsorbents: effect of pore size, nature of the active phase, and silicon release.

Arsenic pollution in ground and drinking water is a major problem worldwide due to the natural abundance of arsenic by dissolution from ground sediment or mining activities from anthropogenic activities. To overcome this issue, iron oxides as low-cost and non-toxic materials, have been widely studied as efficient adsorbents for arsenic removal, including when dispersed within porous silica supports. In this study, two head-to-head comparisons were developed to highlight the As(v)-adsorptive ability of meso- and macrostructured silica-based adsorbents. First, the role of the textural properties of a meso-(SBA15) and macrostructured (MOSF) silica support in affecting the structural-morphological features and the adsorption capacity of the active phase (Fe2O3) have been studied. Secondly, a comparison of the arsenic removal ability of inorganic (Fe2O3) and organic (amino groups) active phases was carried out on SBA15. Finally, since silica supports are commonly proposed for both environmental and biomedical applications as active phase carriers, we have investigated secondary silicon and iron pollution. The batch tests at different pH revealed better performance from both Fe2O3-composites at pH 3. The values of q m of 7.9 mg g-1 (53 mg gact -1) and 5.5 mg g-1 (37 mg gact -1) were obtained for SBA15 and MOSF, respectively (gact stands for mass of the active phase). The results suggest that mesostructured materials are more suitable for dispersing active phases as adsorbents for water treatment, due to the obtainment of very small Fe2O3 NPs (about 5 nm). Besides studying the influence of the pore size of SBA15 and MOSF on the adsorption process, the impact of the functionalization was analyzed on SBA15 as the most promising sample for As(v)-removal. The amino-functionalized SBA15 adsorbent (3-aminopropyltriethoxysilane, APTES) exhibited a q m of 12.4 mg g-1 and faster kinetics. Furthermore, issues associated with the release of iron and silicon during the sorption process, causing secondary pollution, were evaluated and critically discussed.

Self-Limitations of Heat Release in Coupled Core-Shell Spinel Ferrite Nanoparticles: Frequency, Time, and Temperature Dependencies.

We explored a series of highly uniform magnetic nanoparticles (MNPs) with a core-shell nanoarchitecture prepared by an efficient solvothermal approach. In our study, we focused on the water dispersion of MNPs based on two different CoFe2O4 core sizes and the chemical nature of the shell (MnFe2O4 and spinel iron oxide). We performed an uncommon systematic investigation of the time and temperature evolution of the adiabatic heat release at different frequencies of the alternating magnetic field (AMF). Our systematic study elucidates the nontrivial variations in the heating efficiency of core-shell MNPs concerning their structural, magnetic, and morphological properties. In addition, we identified anomalies in the temperature and frequency dependencies of the specific power absorption (SPA). We conclude that after the initial heating phase, the heat release is governed by the competition of the Brown and Néel mechanism. In addition, we demonstrated that a rational parameter sufficiently mirroring the heating ability is the mean magnetic moment per MNP. Our study, thus, paves the road to fine control of the AMF-induced heating by MNPs with fine-tuned structural, chemical, and magnetic parameters. Importantly, we claim that the nontrivial variations of the SPA with the temperature must be considered, e.g., in the emerging concept of MF-assisted catalysis, where the temperature profile influences the undergoing chemical reactions.

Coupled hard-soft spinel ferrite-based core-shell nanoarchitectures: magnetic properties and heating abilities.

Bi-magnetic core-shell spinel ferrite-based nanoparticles with different CoFe2O4 core size, chemical nature of the shell (MnFe2O4 and spinel iron oxide), and shell thickness were prepared using an efficient solvothermal approach to exploit the magnetic coupling between a hard and a soft ferrimagnetic phase for magnetic heat induction. The magnetic behavior, together with morphology, stoichiometry, cation distribution, and spin canting, were investigated to identify the key parameters affecting the heat release. General trends in the heating abilities, as a function of the core size, the nature and the thickness of the shell, were hypothesized based on this systematic fundamental study and confirmed by experiments conducted on the water-based ferrofluids.

Defect-assisted synthesis of magneto-plasmonic silver-spinel ferrite heterostructures in a flower-like architecture.

Artificial nano-heterostructures (NHs) with controlled morphology, obtained by combining two or more components in several possible architectures, make them suitable for a wide range of applications. Here, we propose an oleate-based solvothermal approach to design silver-spinel ferrite flower-like NHs. Small oleate-coated silver nanoparticles were used as seeds for the growth of magnetic spinel ferrite (cobalt ferrite and spinel iron oxide) nanodomains on their surface. With the aim of producing homogeneous flower-like heterostructures, a careful study of the effect of the concentration of precursors, the reaction temperature, the presence of water, and the chemical nature of the spinel ferrite was carried out. The magnetic and optical properties of the NHs were also investigated. A heterogeneous growth of the spinel ferrite phase on the silver nanoparticles, through a possible defect-assisted mechanism, was suggested in the light of the high concentration of stacking faults (intrinsic and twins) in the silver seeds, revealed by Rietveld refinement of powder X-ray diffraction patterns and High-Resolution electron microscopy.

Nanostructured spinel cobalt ferrites: Fe and Co chemical state, cation distribution and size effects by X-ray photoelectron spectroscopy.

Nanostructured spinel cobalt ferrite samples having crystallite size ranging between 5.6 and 14.1 nm were characterized by X-ray photoelectron spectroscopy and X-ray induced Auger electron spectroscopy in order to determine the chemical state of the elements, the iron/cobalt ratio and the cation distribution within tetrahedral and octahedral sites. The presence of size-dependent trends in the binding energy of the main photoelectron peaks and in the kinetic energy of the X-ray induced O KLL signal was also investigated. The results showed that iron is present as FeIII and cobalt is present as CoII. The iron/cobalt ratio determined by XPS ranges between 1.8 and 1.9 and it is in very good agreement, within experimental uncertainty, with the expected 2 : 1 ratio. The percentage of Fe in octahedral sites ranges between 62% and 64% for all samples. The kinetic energy of the O KLL signals increases with crystallite size. These results are explained in terms of changes in the ionicity of the metal-oxygen bonds. The results of this investigation highlight how the XPS technique represents a powerful tool to investigate the composition, the chemical state and inversion degree of cobalt spinel ferrites, contributing to the comprehension of their properties.

Spinel Ferrite Core-Shell Nanostructures by a Versatile Solvothermal Seed-Mediated Growth Approach and Study of Their Nanointerfaces.

An easy, low-cost, repeatable seed-mediated growth approach in solvothermal condition has been proposed to synthesize bimagnetic spinel ferrite core-shell heterostructures in the 10-20 nm particle size range. Cobalt ferrite and manganese ferrite nanoparticles (CoFe2O4 and MnFe2O4) have been coated with isostructural spinel ferrites like maghemite/magnetite, MnFe2O4, and CoFe2O4 with similar cell parameters to create different heterostructures. The conventional study of the structure, morphology, and composition has been combined with advanced techniques in order to achieve details on the interface at the nanoscale level. Clear evidence of the heterostructure formation have been obtained (i) indirectly by comparing the 57Fe Mössbauer spectra of the core-shell samples and an ad hoc mechanical mixture and (ii) directly by mapping the nanoparticles' chemical composition by electron energy loss spectroscopy (EELS) and energy-dispersive X-ray spectroscopy (EDX) in the scanning transmission electron microscopy mode (STEM). In addition, chemical-sensitive electron tomography in STEM-EDX mode has been applied in order to obtain detailed 3D images with a sub-nanometer spatial resolution.