Frederico Garcia Pinto

Sample Preparation for Determination of Rare Earth Elements in Geological Samples by ICP-MS: A Critical Review

The presence of rare earth elements (REE) in geological materials provides important information about the formation and the geochemical processes that rocks undergo. Therefore, there is a constant necessity for accurate data and reliable and fast analytical methods. However, the low concentrations of these elements typically found in rocks require quantification by sufficiently sensitive techniques, such as Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The preparation of these samples to the introduction in ICP-MS is a critical part of the process. Traditional wet dissolution methods, such as acid digestion or alkaline fusion followed by dissolution are mostly employed. The acid digestion requires a mixture of strong acids due to the presence of low soluble constituents common in rock samples, such as silicates or clays. The alkaline fusion is fast and efficient, but the dissolution of the melted material results in solutions with a high amount of total dissolved solids (TDS), which can be a problem due to the possibility of deposition in parts of the ICP-MS. Other instrumental approaches have been spread rapidly, as the coupling of a laser ablation accessory or an electrothermal vaporizer to the ICP-MS, as they can allow the direct sample introduction, or at least with minimum preparation. This paper presents a review of sample preparation methods, aimed at the quantification of rare earth elements by ICP-MS and focusing on works published in the last decade.

Ozone treatment for pesticide removal from carrots: Optimization by response surface methodology

The present study aimed to optimize ozone (O3) treatments, as gas and dissolved in water, to remove difenoconazole and linuron in carrots. We employed a central composite design to study three variables governing the efficacy of treatments: O3 concentration, temperature and treatment time. The temperature did not influence the efficacy of treatments. The removal percentage of pesticides increases with increases in ozone concentration and the time of treatment. O3 application promoted the removal of more than 80% of pesticides when the roots were exposed for approximately 120min at 5 and 10mgL-1, respectively, in treatments with O3 as gas and dissolved in water. After storage, pesticide removal was higher than 98% for difenoconazole and 95% for linuron. The degradation products from the pesticides resulting from treatment were monitored, but none were found. This is the first report demonstrating the removal of difenoconazole and linuron from carrots by ozone.

Native defects as sources of optical transitions in MgAl2O4 spinel

The outstanding physical and chemical properties of the magnesium aluminate (MgAl2O4) spinel makes it an important material for novel technological applications. Considering that a presence of native defects can promote important changes in those properties, in this work we present a study of the structural, electronic and thermodynamic properties of the MgAl2O4 spinel. The calculated formation energy for isolated defects, such as the vacancies of magnesium (V Mg), aluminum (V Al) and oxygen (V O), oxygen interstitial (Oi), magnesium and aluminum antisites (MgAl, AlMg), as well as some complex defects (V O + Oi, V O + AlMg, V O + MgAl, MgAl + AlMg) in the most stable charge states are shown. Through experimental data, we obtained that complex defects centers, such as V O , V O + Oi, V O + AlMg and VO + MgAl at different charge states are good candidates for the observed optical transitions at 4.75, 5.3, and 6.4 eV. Our findings were obtained from ab initio electronic structure calculations performed by using density functional theory. The Perdew–Burke–Ernzerhof generalized gradient approximation was used for the exchange-correlation potential. Furthermore, a modified Becke-Johnson exchange potential (GGA-mBJ) correction to the exchange potential were used to obtain a suitable value for the band gap energy, 7.40 eV, in accordance with the experimental one of 7.8 eV.

Removal of Sodium Dodecylbenzenesulphonate and Cetyltrimethylammonium Bromide Using a Carbon Composite Derived from Modified Zn–Al-Layered Double Hydroxide

We describe the synthesis of a composite carbon derived from zinc–aluminium-layered double hydroxides. The material was characterized by powder X-ray diffraction, Fourier transform infrared/attenuated total reflectance spectroscopy, thermogravimetric analysis–differential scanning calorimetry–mass spectrometry, measurement of BET specific surface area, zeta-potential analysis and scanning electron microscopy. The resulting material was used for adsorption studies with an anionic surfactant, sodium dodecylbenzenesulphonate, and a cationic surfactant, cetyltrimethylammonium bromide, as adsorbates. The adsorption of the surfactants was well described by the typical Langmuir pattern. An investigation of the influence of initial pH of a medium on surfactant adsorption showed that high pH values decrease the adsorption capacity of the adsorbent. The adsorption processes were exothermic. The results also showed that the adsorption of the two surfactants was chemical and that the kinetic models were best described by a pseudo-second-order model.

A flow injection procedure using Layered Double Hydroxide for on line pre-concentration of fluoride

This work showed a flow system designed with solenoid valves for preconcentration of fluoride using SPADNS method in water samples. The analyte was preconcentrated in a mini-column coated with Layered Double Hydroxides (LDH) used as adsorbent. Then, the fluoride ions were eluted with 0.5molL-1 sodium hydroxide and determined by spectrophotometry. The variables that affect the system such adsorbent mass, type of eluent, solutions flow rate, reagent concentration and pH effect were critically evaluated. Under optimized conditions, the detection limit, coefficient of variation, linear range and preconcentration factor were estimated at 15µgL-1 (99.7% confidence level), 0.8% (500µgL-1, n = 10), 50-500µgL-1 and 10, respectively. The accuracy of the method was evaluated by analysis of ALPHA APS 1076 (Simulated Rain Water) certified material, the values were not significantly different at a 95% level of confidence. The method was applied for fluoride determination in water samples and the levels found were below the maximum values established by Brazilian environmental and health legislations.