Evaluation of novel biomass-derived materials as binding layers for determining labile mercury in water by diffusive gradient in thin-films technique.

In this work, several binding gels were successfully prepared in Diffusive Gradient in Thin-film (DGT) that targeted the inclusion of novel biomass-derived materials for the determination of the labile fraction of mercury (Hg) in water. First, five biomass-derived materials were tested and the descending order as a function of the average percentage of Hg removal in solution was feathers > biochar > cork > canola meal > rice husk. The best two materials were treated and pulverized into powder to be embedded in a hydrogel; and so, feathers were pyrolyzed preserving the sulfur contained in their keratin structure (FBC), and biochar (BC) was modified and pyrolyzed with sublimated sulfur (SBC) to increase the Hg sorption sites in its structure.

Simple and reliable determination of Zn and some additional elements in seminal plasma samples by using total reflection X-ray fluorescence spectroscopy.

Trace elements are essential for the normal spermatogenesis of mammals and play a critical role in sperm quality and pathological processes e.g. inflammation.

Pehuén (Araucaria araucana) seed residues are a valuable source of natural antioxidants with nutraceutical, chemoprotective and metal corrosion-inhibiting properties.

In the last decade, green chemistry has been attracting great interest in many contexts, including, among others, natural antioxidants. However, only a few works deal with natural residue extracts and biowaste, which could be an efficient, economical and environmentally friendly source for the production of useful compounds. In this study, we look for antioxidant activity in Araucaria araucana seeds, an iconic pine species of the Argentine and Chilean Patagonia commonly known as "pehuén".

Cellulose mini-membranes modified with TiO for separation, determination, and speciation of arsenates and selenites.

Sorptive and selective mini-membranes based on TiO directly synthesized onto cellulose filters (TiO@cellulose) have been developed. The in situ synthesis of TiO@cellulose applied is simple and economically advantageous. The obtained membranes can be useful for (1) separating arsenic(V) and selenium(IV) from other ions and organic matter, (2) speciation of arsenic and selenium, and (3) determining ulratraces of these ions in water samples.

Interaction of silver nanoparticles with mediterranean agricultural soils: Lab-controlled adsorption and desorption studies.

The production of silver nanoparticles (AgNPs) has increased tremendously during recent years due to their antibacterial and physicochemical properties. As a consequence, these particles are released inevitably into the environment, with soil being the main sink of disposal. Soil interactions have an effect on AgNP mobility, transport and bioavailability.

Determination of gold leaf thickness using X-ray fluorescence spectrometry: Accuracy comparison using analytical methodology and Monte Carlo simulations.

In this work, we compared the accuracy of gold leaves thickness determination using X-ray Fluorescence (XRF) setups for different X-ray excitation sources. The sources used consisted on: a) direct Bremsstrahlung from an Amptek Mini-X X-ray tube with Rh target, b) partially monochromatized radiation of the same X-ray tube using combination of Al and Ag filters and, c) monochromatic radiation using secondary target, in a portable setup with triaxial geometry. The performance of the used setups was compared using model samples made with gold foil standard reference materials of known thicknesses (1, 2 and 2.

Comprehensive analysis of renal arsenic accumulation using images based on X-ray fluorescence at the tissue, cellular, and subcellular levels.

Exposure to arsenic (As) through drinking water results in accumulation of As and its methylated metabolites in several organs, promoting adverse health effects, particularly potential development of cancer. Arsenic toxicity is a serious global health concern since over 200 million people are chronically exposed worldwide. Abundant biochemical and epidemiological evidence indicates that the kidney is an important site of uptake and accumulation of As, and mitochondrial damage plays a crucial role in arsenic toxicity.

Critical evaluation of the use of total reflection X-ray fluorescence spectrometry for the analysis of whole blood samples: application to patients with thyroid gland diseases.

Multielemental analysis of whole blood can provide significant information for the evaluation of nutritional status and diagnosis of certain diseases as well as for the assessment of exposure to potentially toxic metals. However, the quantification of multiple elements in whole blood is not easy partly because of the wide variation in element concentrations (from ng L to g L) and the complex matrix. The aim of this work was to develop a fast, sustainable, and reliable analytical method, in combination with low-power TXRF, for multielemental analysis of blood samples.

Determination and speciation of ultratrace arsenic and chromium species using aluminium oxide supported on graphene oxide.

Alumina supported on graphene oxide (AlO/GO) nanocomposite as new nanosorbent in dispersive micro-solid phase extraction (DMSPE) for As(V) and Cr(III) preconcentration is described. The crucial issue of the study is synthesis of novel nanocomposite suitable for sorption of selected species of arsenic and chromium. AlO/GO demonstrates selectivity toward arsenates in the presence of arsenites at pH 5 and chromium(III) ions in the presence of chromate anions at pH 6.

Ceria nanoparticles deposited on graphene nanosheets for adsorption of copper(II) and lead(II) ions and of anionic species of arsenic and selenium.

A nanocomposite prepared from graphene nanosheets and cerium nanoparticles (G/CeO) was applied to the extraction of Se(IV), As(V), As(III), Cu(II) and Pb(II). The structure of G/CeO was investigated by scanning electron microscopy, X-ray diffraction and Raman spectroscopy. The optimal pH values for extraction are 4.

Usefulness of a Dual Macro- and Micro-Energy-Dispersive X-Ray Fluorescence Spectrometer to Develop Quantitative Methodologies for Historic Mortar and Related Materials Characterization.

Wavelength dispersive X-ray fluorescence (WD-XRF) spectrometry has been widely used for elemental quantification of mortars and cements. In this kind of instrument, samples are usually prepared as pellets or fused beads and the whole volume of sample is measured at once. In this work, the usefulness of a dual energy dispersive X-ray fluorescence spectrometer (ED-XRF), working at two lateral resolutions (1 mm and 25 μm) for macro and microanalysis respectively, to develop quantitative methods for the elemental characterization of mortars and concretes is demonstrated.

Holocene geochemical footprint from Semi-arid alpine wetlands in southern Spain.

Here we provide the geochemical dataset that our research group has collected after 10 years of investigation in the Sierra Nevada National Park in southern Spain. These data come from Holocene sedimentary records from four alpine sites (ranging from ∼2500 to ∼3000 masl): two peatlands and two shallow lakes. Different kinds of organic and inorganic analyses have been conducted.

Graphene Oxide Decorated with Cerium(IV) Oxide in Determination of Ultratrace Metal Ions and Speciation of Selenium.

Graphene oxide decorated with cerium(IV) oxide (GO/CeO) was synthesized and applied in adsorption of several metal ions such as As(III), As(V), Se(IV), Cu(II), and Pb(II) from aqueous samples. The important feature of GO/CeO nanocomposite is also its selectivity toward selenite in the presence of selenate. The structure of GO/CeO has been proven by microscopic and spectroscopic techniques.

Atmospheric dust deposition on soils around an abandoned fluorite mine (Hammam Zriba, NE Tunisia).

The present study focuses on the eolian dispersion and dust deposition, of major and trace elements in soils in a semi-arid climate, around an old fluorite (CaF) and barite (BaSO) mine, located in Hammam Zriba in Northern Tunisia. Ore deposits from this site contain a high amount of metal sulphides constituting heavy metal pollution in the surrounding environment. Samples of waste from the surface of mine tailings and agricultural topsoil samples in the vicinity of the mine were collected.

Development of X-ray Fluorescence Quantitative Methodologies To Analyze Aqueous and Acid Extracts from Building Materials Belonging to Cultural Heritage.

Energy dispersive X-ray fluorescence spectrometry (ED-XRF) is widely used in art and cultural heritage for direct measurements and elemental quantification of solid samples. However, in the literature there are not works dealing with the quantitative application of ED-XRF to liquid extracts coming from samples belonging to cultural heritage. In this work, a novel methodology based on the use of ED-XRF spectrometry after thin film deposition on special sample retainers and a subsequent evaporation was developed to quantify light elements (Z ≤ 20) in aqueous extracts and heavy elements (Z > 20) in acid extracts, coming from materials and degradation products belonging to built heritage (mortars, black crusts, and calcium carbonate formations).

Immunotoxicological effects of arsenic bioaccumulation on spatial metallomics and cellular enzyme response in the spleen of male Wistar rats after oral intake.

Arsenic (As) is a worldwide environmental contaminant, which compromises immunity and causes various associated disorders. To further investigate its immunotoxicity, male Wistar rats were exposed to 100ppm of sodium arsenite (inorganic AsIII) in drinking water for 2 months. Given that metals are significant immune regulators, their content and distribution were analysed in spleen tissues, to then evaluate subsequent changes of redox enzyme responses in spleen parenchyma cells (splenocytes).

Bromine and bromide content in soils: Analytical approach from total reflection X-ray fluorescence spectrometry.

Monitoring total bromine and bromide concentrations in soils is significant in many environmental studies. Thus fast analytical methodologies that entail simple sample preparation and low-cost analyses are desired. In the present work, the possibilities and drawbacks of low-power total reflection X-ray fluorescence spectrometry (TXRF) for the determination of total bromine and bromide contents in soils were evaluated.

Green approach for ultratrace determination of divalent metal ions and arsenic species using total-reflection X-ray fluorescence spectrometry and mercapto-modified graphene oxide nanosheets as a novel adsorbent.

A new method based on dispersive microsolid phase extraction (DMSPE) and total-reflection X-ray fluorescence spectrometry (TXRF) is proposed for multielemental ultratrace determination of heavy metal ions and arsenic species. In the developed methodology, the crucial issue is a novel adsorbent synthesized by grafting 3-mercaptopropyl trimethoxysilane on a graphene oxide (GO) surface. Mercapto-modified graphene oxide (GO-SH) can be applied in quantitative adsorption of cobalt, nickel, copper, cadmium, and lead ions.

Total reflection X-ray spectrometry (TXRF) for trace elements assessment in edible clams.

The present contribution presents a preliminary investigation of the chemical composition with respect to major, minor, trace, and ultratrace elements in several clam species that are frequently used for human consumption in Portuguese markets and worldwide. In order to use a simple and rapid analytical methodology for clam analysis, energy dispersive X-ray fluorescence (EDXRF) spectrometry and total reflection X-ray fluorescence (TXRF) spectrometry were selected as analytical techniques. The analytical capabilities of TXRF spectrometry were evaluated for the determination of minor and trace elements in commercial edible clams.

Liquid phase microextraction strategies combined with total reflection X-ray spectrometry for the determination of low amounts of inorganic antimony species in waters.

In the present study, and taking into account the microanalytical capability of total reflection X-ray spectrometry (TXRF), we explored the possibilities of hollow fibre liquid-phase microextraction (HF-LPME) and dispersive liquid-liquid microextraction (DLLME) combined with TXRF for the determination of low amounts of inorganic Sb species in waters. For each of the LPME configurations aforementioned, experimental parameters affecting Sb extraction but specially the proper sample preparation process (deposition volume on the reflective carrier and drying mode) and measurement conditions for subsequent TXRF analysis have been carefully evaluated. The best analytical strategy for the determination of Sb(III) and Sb(V) in the low μg L(-1) range was found to be the application of the DLLME mode before TXRF analysis.

Dispersive micro solid-phase extraction using multiwalled carbon nanotubes for simultaneous determination of trace metal ions by energy-dispersive X-ray fluorescence spectrometry.

A methodology based on dispersive micro solid-phase extraction (DMSPE) using multiwalled carbon nanotubes (MWCNTs) as solid sorbent prior to measurement with energy-dispersive X-ray fluorescence (EDXRF) spectrometry is proposed. The procedure consists of chelating of nickel, cobalt, copper, and lead ions with ammonium pyrrolidinedithiocarbamate (APDC) and posterior adsorption of metal chelates on MWCNTs (1 mg) dispersed in the aqueous samples (100 mL). DMSPE promotes immediate interaction between the metal chelates and MWCNTs and shortens time of sample preparation in comparison with classical solid-phase extraction.

High-energy polarized-beam energy-dispersive X-ray fluorescence analysis combined with activated thin layers for cadmium determination at trace levels in complex environmental liquid samples.

In this paper, we describe a new method for trace level Cd determination in complex environmental liquid samples. Thin layers activated with the extractant Aliquat 336 were prepared either by direct impregnation of commercial polymeric supports or by physical inclusion in a cellulose triacetate matrix, and both were effectively used to collect Cd present at low concentration in different aqueous matrixes. Quantitation of Cd contained in the thin layers was performed by high-energy polarized-beam energy-dispersive X-ray fluorescence.