Visceral fat increase and signals of inflammation in adipose tissue after administration of titanium dioxide nanoparticles in mice.

Titanium dioxide nanoparticles (TiO2 NP) are present in several daily use products, and the risks associated with their bioaccumulation must be stablished. Thus, an evaluation of several toxicological-related effects was conducted after intraperitoneal injection of TiO2 NPs in mice. Mice were divided into two groups, which received 2 mg kg-1 day-1 of TiO2 NPs or vehicle saline. Assessments of body and organ weight as well as biochemical, hematological, and histopathological analyses were performed in order to evaluate adverse effects. The results showed that treatment resulted in an increased visceral and abdominal fat deposition, as well as a mononuclear inflammatory infiltrates in the abdominal fat tissue. The TiO2 NPs induced significant decrease in the weight gain and splenomegaly. Additionally, TiO2 NP-treated mice showed altered hematological parameters and significant liver injuries, which were characterized by histopathological and biochemical changes. Our results also indicated that TiO2 NPs were absorbed and significantly accumulated in the spleen, liver, and kidney. These results showed the ability of TiO2 NPs to infiltrate different organs and to induce inflammation and liver and spleen damage with visceral fat accumulation. The data obtained are useful for the governmental authorities to legislate and implement regulations concerning the use and the production of this kind of material that might be hazardous to the living beings, as well as to the environment.

Assessment of the Halogen Content of Brazilian Inhalable Particulate Matter (PM10) Using High Resolution Molecular Absorption Spectrometry and Electrothermal Vaporization Inductively Coupled Plasma Mass Spectrometry, with Direct Solid Sample Analysis.

Halogens in the atmosphere play an important role in climate change and also represent a potential health hazard. However, quantification of halogens is not a trivial task, and methods that require minimum sample preparation are interesting alternatives. Hence, the aim of this work was to evaluate the feasibility of direct solid sample analysis using high-resolution continuum source molecular absorption spectrometry (HR-CS MAS) for F determination and electrothermal vaporization-inductively coupled plasma mass spectrometry (ETV-ICP-MS) for simultaneous Cl, Br, and I determination in airborne inhalable particulate matter (PM10) collected in the metropolitan area of Aracaju, Sergipe, Brazil. Analysis using HR-CS MAS was accomplished by monitoring the CaF molecule, which was generated at high temperatures in the graphite furnace after the addition of Ca. Analysis using ETV-ICP-MS was carried out using Ca as chemical modifier/aerosol carrier in order to avoid losses of Cl, Br, and I during the pyrolysis step, with concomitant use of Pd as a permanent modifier. The direct analysis approach resulted in LODs that were proven adequate for halogen determination in PM10, using either standard addition calibration or calibration against a certified reference material. The method allowed the quantification of the halogens in 14 PM10 samples collected in a northeastern coastal city in Brazil. The results demonstrated variations of halogen content according to meteorological conditions, particularly related to rainfall, humidity, and sunlight irradiation.

Bromine isotope ratio measurements in seawater by multi-collector inductively coupled plasma-mass spectrometry with a conventional sample introduction system.

A simple and accurate methodology for Br isotope ratio measurements in seawater by multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS) with pneumatic nebulization for sample introduction was developed. The Br(+) signals could be measured interference-free at high mass resolution. Memory effects for Br were counteracted using 5 mmol L(-1) of NH4OH in sample, standard, and wash solutions. The major cation load of seawater was removed via cation exchange chromatography using Dowex 50WX8 resin. Subsequent Br preconcentration was accomplished via evaporation of the sample solution at 90 °C, which did not induce Br losses or isotope fractionation. Mass discrimination was corrected for by external correction using a Cl-matched standard measured in a sample-standard bracketing approach, although Sr, Ge, and Se were also tested as potential internal standards for internal correction for mass discrimination. The δ(81)Br (versus standard mean ocean bromide (SMOB)) values thus obtained for the NaBr isotopic reference material NIST SRM 977 and for IRMM BCR-403 seawater certified reference material are in agreement with literature values. For NIST SRM 977, the (81)Br/(79)Br ratio (0.97291) was determined with a precision ≤0.08‰ relative standard deviation (RSD).

Graphene oxide functionalized with N-methyl-d-glucamine as a novel sorbent for boron removal from produced and formation waters.

This work describes the synthesis of a novel material based on graphene oxide (GO) for the selective removal of boron in an aqueous medium. The material was obtained by functionalizing graphene oxide with N-methyl-d-glucamine (NMDG). This material, named NMDG@GO, was successfully characterized using Fourier-transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, thermogravimetric analysis, atomic force microscopy, and elemental analysis. The adsorption process was studied from a kinetic perspective using pseudo-first-order and pseudo-second-order models, with the pseudo-second-order model presenting a better fit. The adsorption process was studied using Langmuir and Freundlich isotherms, with the Freundlich model providing a better fit and an r2 value of 0.9368. This result indicates that the adsorption process occurred in multilayers, considering a heterogeneous distribution of adsorption sites. The levels of the factor's adsorbent mass, pH, and time were optimized using a central composite design, with the optimal values achieved at 120 mg of material, pH = 2.0, and an agitation time of 40 min. Under these optimized conditions, it was possible to remove 22 to 35% of the boron present in saline waters from oil production (production and formation waters) using the developed adsorbent.

Direct solid sample analysis using synchronous fluorescence spectroscopy coupled with chemometric tools for the geographical discrimination of coffee samples.

This work aims the study chemometric methods for the classification of the origin of coffee samples. Samples of finely pulverized coffee grains were analyzed by synchronous molecular fluorescence spectroscopy to carry out the classification. The spectral data of the samples were obtained in triplicate in two offsets: 10 nm (with emission wavelengths from 240 nm to 600 nm) and 40 nm (from 240 nm to 560 nm), all with 1 nm resolution. Different strategies were performed using the spectra obtained with the offsets of 10 nm and 40 nm and fused data at mid-level (10 nm + 40 nm). The performances of linear and nonlinear methods were compared, the best results were obtained from the raw data from the fusion at low-level of the 10 nm and 40 nm offset spectra with the Pareto optimization criterion.

Multivariate optimization of microwave-assisted digestion methods for Cu and Sn determination in antifouling paints using inductively coupled plasma optical emission spectrometry.

Antifouling paints containing Cu, Zn, organotins, and many organic booster biocides may be found in ships and watercraft hulls to avoid the fouling of marine organisms. This type of paint can be harmful to the environment, therefore, the monitoring of toxic elements and compounds in antifouling paints are of great importance to access its quality and potential toxicity to the environment. Hence, this work describes the development of microwave-assisted digestion methods for the determination of Cu and Sn in antifouling paints by inductively coupled plasma optical emission spectrometry (ICP OES). The factors: sample mass and solutions of HNO3, HF, and HCl were optimized using the central composite design (CCD). Dry ashing with a muffle furnace and laser ablation-ICP-MS were used for methodological comparison with the microwave digestion-assisted ICP-OES methods. All the mixtures of acids allowed efficient extraction of the analytes; however, the one that stood out was the use of HF, HNO3, and H2O2.

Presence of other rare earth metals in gadolinium-based contrast agents.

Gadolinium-based contrast agents (GBCA) are widely used to enhance tissue contrast during magnetic resonance imaging (MRI) procedures. However, free Gadolinium (Gd) is undesirable as a drug substance, due to its high toxicity. Consequently, a coordinating ligand is required to keep it in solution and to increase tolerance. In order to achieve an adequate performance, GBCA must be administered in relatively large amounts. Chelate amounts are around 13-20 g and for Gd alone, this may amount to 3.3 g. Taking into account the route of administration, impurities in GBCA may be significant. Gadolinium occurs in nature along with 16 other elements known collectively as rare earth metals (RE), which are found throughout the earth's crust in minerals such as monazite. Gadolinium oxide corresponds to 0.7-4.0% of the RE present in minerals, and the sum concentration of RE in minerals is around 4%. Rare earth metals are difficult to separate, as the chemical and physical properties of one RE are significantly similar to those of others. In this study, the presence of other RE in GBCA formulations was investigated. Different lots of Magnevist®, Viewgam®, OptiMARK®, Omniscan®, Dotarem®, and Gadovist® were analyzed. Inductively-coupled plasma mass spectrometry and atomic absorption spectrometry were used for RE determination. Procedure optimization included sample decomposition and method validation for element determination. The results showed that Sc, Y, La, Ce, Pr, Nd, Eu, Tb, Tm, Dy, Ho, and Er were present in the 22 samples analyzed. Terbium, Thulium, Europium, and Lanthanum were, on average, found in the highest amounts, which were 0.42 mg/L, 0.17 mg/L, 0.17 mg/L, and 0.16 mg/L, respectively. These results could be attributed to the similarity among Europium, Gadolinium, and Terbium. They are in sequence in the periodic table and therefore present very close ionic radii, restricting their separation. Considering the sum of all RE, Viewgam® was the most contaminated formulation (mean of 2.16 mg/L) and Magnevist® the least (mean of 0.64 mg/L). Although the RE are chemically similar, the other RE do not perform as Gd as a contrast agent; therefore, their presence in formulations may be a matter of concern.

Changes in organic acids, polyphenolic and elemental composition of rosé sparkling wines treated with mannoproteins during over-lees aging.

The effect of mannoproteins on the evolution of rosé sparkling wines during over-lees aging was investigated on the basis of the chemical characterization of polyphenols, organic acids, macro- and microelements using a combined analytical approach. Variations on these constituents were assessed using Raman and near-infrared spectroscopy. During the biological aging, caffeic acid, catechin, gallic acid and malvidin-3-O-glucoside were the most abundant polyphenolics in the rosé wines. The phenolic compound tyrosol, a fermentation derivative, was found at concentrations up to 98.07 mg L-1. The addition of mannoproteins significantly affected the concentrations of organic acids and individual polyphenolic compounds, particularly trans-resveratrol, quercetin, catechin, p-coumaric and hydroxybenzoic acids that showed increased concentrations over time. The positive effects of mannoproteins were mainly observed at the end of the biological aging. The mineral composition remained stable, while potassium was the most abundant mineral in all wines. The observed changes involving these constituents may offer new insights on their behavior during wine aging and on the bioactive and nutritional quality of rosé sparkling wines.

Determination of fluorine in copper concentrate via high-resolution graphite furnace molecular absorption spectrometry and direct solid sample analysis - Comparison of three target molecules.

The chemical composition of complex inorganic materials, such as copper concentrate, may influence the economics of their further processing because most smelters, and particularly the producers of high-purity electrolyte copper, have strict limitations for the permissible concentration of impurities. These components might be harmful to the quality of the products, impair the production process and be hazardous to the environment. The goal of the present work is the development of a method for the determination of fluorine in copper concentrate using high-resolution graphite furnace molecular absorption spectrometry and direct solid sample analysis. The molecular absorption of the diatomic molecule CaF was measured at 606.440nm. The molecule CaF was generated by the addition of 200µg Ca as the molecule-forming reagent; the optimized pyrolysis and vaporization temperatures were 900°C and 2400°C, respectively. The characteristic mass and limit of detection were 0.5ng and 3ng, respectively. Calibration curves were established using aqueous standard solutions containing the major components Cu, Fe, S and the minor component Ag in optimized concentrations. The accuracy of the method was verified using certified reference materials. Fourteen copper concentrate samples from Chile and Australia were analyzed to confirm the applicability of the method to real samples; the concentration of fluorine ranged from 34 to 5676mgkg-1. The samples were also analyzed independently at Analytik Jena by different operators, using the same equipment, but different target molecules, InF and GaF, and different operating conditions; but with a few exceptions, the results agreed quite well. The results obtained at Analytik Jena using the GaF molecule and our results obtained with CaF, with one exception, were also in agreement with the values informed by the supplier of the samples, which were obtained using ion selective electrode potentiometry after alkaline fusion. A comparison will also be made for the three target molecules and the three independently developed methods for the determination of fluorine, although all three methods used direct solid sample analysis.

Simultaneous determination of bromine and chlorine in coal using electrothermal vaporization inductively coupled plasma mass spectrometry and direct solid sample analysis.

A new method for the direct analysis of coal using electrothermal vaporization inductively coupled plasma mass spectrometry and direct solid sample analysis was developed, aiming at the determination of Br and Cl. The procedure does not require any significant sample pretreatment and allows simultaneous determination of both elements to be carried out, requiring small mass aliquots of sample (about 0.5 mg). All operating parameters, including carrier gas flow-rate and RF power, were optimized for maximum sensitivity. The use of modifiers/aerosol carriers (Pd, Pd+Al and Pd+Ca) was evaluated, and the mixture of Pd and Ca was chosen, allowing pyrolysis and vaporization temperatures of 700°C and 1900°C, respectively. Chlorine was accurately determined using calibration against solid standards, whereas Br could also be determined using calibration against aqueous standard solutions. The limits of quantification were 0.03 µg g(-1) for Br and 7 µg g(-1) for Cl, and no spectral interferences were observed.