Tentative identification of phytochelatins, their derivatives, and Cd-phytochelatin complexes in Ocimum basilicum L. roots by Paper Spray Mass Spectrometry.

An unprecedented and direct PS-MS (paper spray ionization mass spectrometry) method was proposed for the detection of native peptides, that is, glutathiones (GSHs), homoglutathiones (hGSHs), and phytochelatins (PCs), in basil (Ocimum basilicum L.) roots before and after cadmium exposure. The roots were submitted to cold maceration followed by sonication with formic acid as the extractor solvent for sample preparation. PS-MS was used to analyze such extracts in the positive mode, and the results allowed for the detection of several GSHs, hGSHs, and PCs. Some of these PCs were not distinguished in the control samples, that is, basil roots not exposed to cadmium. Other PCs were noticed in both types of roots, uncontaminated and cadmium-contaminated, but the intensities were higher in the former samples. Moreover, long-time exposure to cadmium stimulated the formation of some of these PCs and their cadmium complexes. The results, therefore, provided some crucial insights into the defense mechanism of plants against an external stress condition due to exposure to a toxic heavy metal. The present study represents a promising alternative to investigate other crucial physiological processes in plants submitted to assorted stress conditions.

The impact of lipid degradation on fingerprint quality on fired firearm cartridges.

The recovery of identifiable fingerprints from fired cartridge cases is challenging. Therefore, the characterization of chemical modifications and their effects on fingerprint integrity post-firing is essential. In this study, the primary fingerprint lipids, including myristic acid, pentadecanoic acid, palmitoleic acid, palmitic acid, stearic acid, squalene, and cholesterol in fired and unfired cartridges, were extracted with acetonitrile, followed by derivatization using N,O-Bis(trimethylsilyl)trifluoroacetamide with 1% trimethylchlorosilane (BSTFA/1%TMCS). Squalane was used as the internal standard, and all quantifications were performed using gas chromatography coupled with mass spectrometry using a triple-quadrupole mass filter. All lipids identified in the unfired cartridges were also detected in the fired cartridges, and statistical analysis using Student's t-test and F tests was performed with a 95% confidence level. The concentration of lipids in the unfired cartridges was found to be similar to that detected in the fired cartridges, except for squalene, the recovery of which was 28% lower in the fired cartridges.

Ionomic responses of hydroponic-grown basil (Ocimum basilicum L.) to cadmium long-time exposure.

The ionomic response of basil leaves, stems, and roots to Cd2+ was evaluated in seedlings grown in a hydroponic system for 15 days. Ions were quantified by the inductively coupled plasma-mass spectrometry (ICP-MS). Cd accumulated mainly in roots, while Be, Li, Ca, Mg, and Sr in leaves, and K and Mn in stems. Compared to the control group, basil seedlings treated with Cd2+ accumulated higher Ca, Cu, Mn, Sr, and Zn contents in roots, even when exposed at low levels. Pearson positive correlations between Cd and essential and nonessential elements were mostly observed in leaves and roots (P < 0.05). On the other hand, negative correlations were observed mainly in stems with all elements except Ba, Li, Sr, and Zn. Principal component analysis showed an ionomic discrimination between leaves, stems, and roots, with Cd strongly correlated to Zn, Cu, and Sr.

Analysis of Diglycolic Acid after Mass Poisoning by Diethylene Glycol.

In December 2019, unusual cases of acute renal failure with neurological changes were observed in the State of Minas Gerais, Brazil. Criminal investigations indicated cases of intoxication after consumption of beers contaminated with diethylene glycol (DEG). The elimination of DEG by the body is fast, but its metabolite, diglycolic acid (DA), may persist for a long time. To assess the level of intoxicated victims who consumed the contaminated beers, qualitative and quantitative methods were developed to determine DA in biological matrices by gas chromatography coupled to a mass spectrometer (GC-MS) and gas chromatography coupled to a mass spectrometer with triple-quadrupole mass filter (GC-MS-MS), respectively. The validated qualitative method presents good selectivity and limit of detection of 1 µg/mL (whole blood, urine, vitreous humor and cerebrospinal fluid) and 5 µg/g (liver and kidney), respectively. A quantitative method for whole blood presented satisfactory performance to determine DA. Twelve victims presented positive results for DA in whole blood, with concentrations ranging from 2 to 108 µg/mL. The toxicology laboratory of the Institute of Forensic Medicine of Minas Gerais was the first governmental agency to identify DA in whole blood, vitreous humor, cerebrospinal fluid, kidney and urine in victims affected by this contaminant. The results of this study legally supported the prohibition of the continued consumption of the beer and avoided further intoxications. Our results showed, for real cases of human intoxication, that DA can still be detected in alternative matrices, even when non-detectable in blood, demonstrating the importance of collecting different kinds of samples for a proper investigation.

Interactions between As and Se upon long exposure time and effects on nutrients translocation in golden flaxseed seedlings.

Se is a beneficial nutrient for some plant species, while As is considered a toxic element, even at low concentrations. This study investigated the interaction between As and Se on golden flaxseed (Linum usitatissimum L.) seedlings to better understand the extent of Se in the mitigation of As uptake and translocation. In addition, co-exposure experiments allowed to determine how As and Se affected absorption and distribution of the essential micronutrients Fe, Zn and Mn. Seedlings were cultivated in a 10 % v v-1 Hoagland solution supplemented with AsV, SeIV, SeVI or AsV + SeIV at different concentrations. SeVI presented the highest toxicity and translocation factor. The toxicity of AsV was attenuated by SeIV, which stimulated As uptake and translocation. SeIV reduced As accumulation, establishing a tolerance mechanism. Only a high concentration of As (200 µmol L-1) led to leaf chlorosis or seedling death, independently of co-exposure with Se species. Co-exposure also altered the uptake of Fe, Zn and Mn, without affecting As translocation from roots to shoot. In general, the interaction of As with Se was beneficial for golden flaxseed seedlings, when compared to the effects of As solely.

Inductively coupled plasma mass spectrometry and standard dilution analysis applied to concentrated acids.

This work describes a procedure using the recently proposed standard dilution analysis (SDA) calibration method for the determination of As, Cr and Ni in concentrated HNO3 and HCl by inductively coupled plasma tandem mass spectrometry (ICP-MS/MS). Because of the low contaminant levels, and consequently low limits of detection required for these reagents (commonly used in trace element analysis and the semiconductor industry), samples were minimally diluted. The analysis of concentrated acids can result in matrix/transport effects, which may compromise accuracy in ICP-MS determinations. High-chlorine content samples are also challenging for As and Cr determination due to the formation of polyatomic species such as 40Ar35Cl+ and 35Cl16OH+, which overlap the only As isotope, 75As+, and the main Cr isotope, 52Cr+, respectively. The combination of SDA and ICP-MS/MS was evaluated to overcome matrix, transport and spectral interferences in order to increase accuracy, precision and sample throughput. The performance of SDA was compared with the traditional methods of external standard calibration (EC), internal standardization (IS), and standard additions (SA). The limits of detection for SDA were calculated as 6, 10, and 30ngL-1 for As, Cr, and Ni, respectively. Recoveries for spike experiments using the new method were in the 90-114% range for all analytes. The procedure described here provides similar or even better analytical performance in comparison with EC, IS and SA.

Identification of metal-binding to proteins in seed samples using RF-HPLC-UV, GFAAS and MALDI-TOF-MS.

An extraction procedure using Tris-HCl buffer solution was employed in order to extract water-soluble proteins from seed samples of oat, wheat and soybean. Initially, the total protein concentration was determined by the Bradford method in each solution, after the extraction procedure. The soybean sample showed a higher concentration of total protein compared to the others. The protein extracts obtained were separated by reverse-phase chromatography (RP-HPLC-UV). The protein fractions were collected and analyzed by graphite furnace atomic absorption spectrometry (GFAAS) and matrix-assisted laser desorption/ionization (MALDI-TOF-MS) for determination of Cu, Fe, Mn and Zn and identification of proteins, respectively. The combination of techniques such as RP-HPLC-UV, GFAAS and MALDI-TOF-MS allowed the identification of several proteins bound to metals present in the seed samples.

Production of activated carbon from biodiesel solid residues: An alternative for hazardous metal sorption from aqueous solution.

In this study, the potential for the sorption of Pb(2+) and Cd(2+) from aqueous solutions using HNO3-treated activated carbon (TAC) obtained from radish press cake (Raphanus sativus L.), a solid residue from biodiesel production, was investigated. Activated carbon (AC) was obtained by physical activation with CO2(g). Chemical modification with HNO3 was employed to increase the sorption capability of the AC. The sorption of Pb(2+) and Cd(2+) was studied in monometallic systems in equilibrium with different metal-ion concentrations (10-400 mg L(-1)). The experimental sorption equilibrium data were fit to the Langmuir and Freundlich isotherm models. The maximum sorption capacity (qmax) obtained for AC from the Langmuir isotherm was 45.5 mg g(-1) for Cd(2+) and 250 mg g(-1) for Pb(2+). Moreover, TAC presented qmax of 166.7 mg g(-1) (1.48 mmol g(-1)) for Cd(2+) and 500.0 mg g(-1) (2.41 mmol g(-1)) for Pb(2+)showing the effect of chemical modification. Sorption-desorption studies showed that the interaction between metals and TAC is reversible and this sorbent can be reused for several consecutive cycles. Furthermore, the sorption of Cd(2+) and Pb(2+) by TAC was not affected by the presence of competing ions. The experimental data obtained in this study indicated that this solid residue is viable for the production of sorbents that remove metals, such as cadmium and lead, from wastewaters and thereby contribute to the sustainable development of the production of biodiesel.

Efficient removal of Cd2+ from aqueous solutions using by-product of biodiesel production.

In this study, chemically modified radish cake, a by-product of biodiesel production, was used to remove Cd(2+) from aqueous solutions. The chemical modification was carried out by treating the radish cake with citric acid (CRC), NaOH (NRC) or the combination of citric acid and NaOH (CNRC). The sorbents were characterized by elemental analysis, surface area analysis, infrared spectroscopy (FTIR), potentiometric titration (PT), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), and thermogravimetric analysis (TGA). The effect of the chemical treatment and contact time on cadmium sorption was evaluated. The equilibrium data were analyzed using Freundlich and Langmuir models. The maximum sorption capacity obtained by the Langmuir isotherm was 58.5mg/g and 64.10mg/g for the CRC, and CNRC sorbents, respectively. Complete desorption of Cd(2+) was achieved using 0.1 mol/L HNO(3). The results obtained demonstrate that chemically modified radish cake has potential as a sorbent for Cd(2+) removal from aqueous solutions.

A critical evaluation of digestion procedures for coffee samples using diluted nitric acid in closed vessels for inductively coupled plasma optical emission spectrometry.

The efficiency of diluted nitric acid solutions for digesting regular coffee samples was evaluated employing two closed vessel procedures: one was based on microwave-assisted heating and the other was based on conductive heating using pressurized Parr bomb. The efficiency of digestion was evaluated by determining residual carbon content (RCC) and residual acidity. The digestion was effective using both procedures, i.e. there were no solid residues after the decomposition reactions when using up to 3.5 mol L(-1) nitric acid solutions. It was demonstrated that the digestion procedures are critically dependent on reactions occurring in liquid and gas phase and that the formation of NO and its conversion to NO2 by O2 exerts a major effect in the oxidation of organic matter. These processes are more effective in closed vessels heated by microwave radiation due to the greater volume of these flasks and the temperature gradient that exists during the first step of the digestion process. The proposed model for the digestion processes in diluted nitric acid solution is corroborated by data about consumption of acid during the digestion and by measuring the pressure during the whole process.

Determination of ethanol and specific gravity in gasoline by distillation curves and multivariate analysis.

The partial least-squares regression method (PLS) was employed to predict the amount of ethanol and specific gravity in automotive gasoline using distillation curves (ASTM-D86). Additionally, a comparison was made between regression coefficients of all the algorithms, after selecting the number of latent variables. The low values obtained for RMSEC and RMSEP, associated with high accuracy when compared to the standard methodologies (NBR-13992, ASTM-D4052 and D1298) showed that PLS was efficient to determine the ethanol content and specific gravity in gasoline, since the model contains samples of different gasoline compositions, thus reflecting the variety of fuel in the Brazilian market. In addition, the proposed method is low cost, time reducing and easy to implement, as it utilizes the results of a routine assay carried out to evaluate the quality of automotive fuel.

Multi-element determination in acid-digested soy protein formulations by inductively coupled plasma-optical emission spectrometry.

The concentrations of major (Ca, K, Mg, Na and P) and trace elements (Al, Cu and Fe) in soy protein formulations sold in Bahia (Brazil) were determined by inductively coupled plasma-optical emission spectrometry (ICP-OES). Liquid and powdered soy protein formulation samples, both whole and light, were digested using a conventional heating program on a hot-plate. The powdered samples were prepared according to the label instructions for human consumption. A 5.0-ml aliquot of the soy protein emulsion was transferred to a borosilicate Erlenmeyer and concentrated nitric and sulfuric acid added. After a digestion time of approximately 50 min, hydrogen peroxide was added and heating continued to give a final volume of approximately 5 ml; the colorless digests were then made up to 15.0 ml with deionised water. Residual acid content was determined by acid-base titration. Good agreement between measured and certified values for all analytes in a non-fat milk powder (NIST SRM 1549) indicated that the method was suitable for major and trace elements determination in soy protein formulations.

A new procedure for bovine milk digestion in a focused microwave oven: gradual sample addition to pre-heated acid.

Milk samples can be efficiently digested using a focused microwave oven, however the conventional procedure of addition of concentrated acids to the liquid sample leads to digestates with elevated acidity and residual carbon concentrations. In this work a focused microwave oven was applied for acid digestion of bovine milk samples using a conventional and an alternative procedure based on gradual sample addition to hot and concentrated acids. A two-level 2(3) full factorial design experiment with eight runs was carried out to evaluate the optimum experimental conditions for reducing both the residual carbon and the final acidity of digestates. The three studied parameters were: temperature of the digestion medium for sample addition, addition of sulfuric acid before the sample or during the first step, and number of aliquots of the sample gradually added. The best conditions were attained by adding small aliquots of milk (ten-fold a volume of 0.5ml added during 5.0min) to a digestion mixture containing 3.0ml nitric acid plus 1.0ml sulfuric acid heated at 105 degrees C. It was demonstrated that the digestion efficiency of the alternative procedure was better than the conventional procedure, i.e. 98 and 80%, respectively. The alternative procedure was applied for determination of Ba, Ca, Cu, K, Mg, Na, P, and Zn in whole and non-fat bovine milk. The accuracy was proved using two certified reference materials (whole and non-fat milk powder).

Comparison of heating extraction procedures for Al, Ca, Mg, and Mn in tea samples.

A focused-microwave-assisted procedure was adopted for the extraction of Al, Ca, Mg, and Mn in tea leaves. The efficiency of extraction was evaluated using diluted acids and a water-soluble alkaline tertiary-amines solution. The extraction procedure was implemented in 5 min. A conventional hot-plate digestion procedure was employed for a comparison. A colorless digest was obtained for all tea samples and the total contents determined for each analyte were employed for estimating the efficiency of extraction. Tea infusions were also prepared. Subsequent determinations of Al, Ca, Mg, and Mn were carried out using flame atomic absorption spectrophotometry (FAAS) and inductively coupled plasma optical emission spectrometry (ICP-OES). In most cases, quantitative, or at least semi-quantitative, extractions were attained for Ca, Mg, and Mn. Lower recoveries were attained to Al, which seems to be related to compounds that bind this element in the sample matrix. Large variations in the trace-element composition of teas were observed; these results are discussed with reference to both extraction media and type of tea.