Diethylene glycol is an extremely toxic substance to humans. Recently, cases of beer contamination in Brazil have raised awareness of the need for developing simple screening methods to evaluate this type of compound. This research developed a liquid-liquid extraction with low-temperature partitioning technique to determine diethylene glycol in beer via gas chromatography. Employing a flame-ionization detector simplifies the method, lowers its cost and therefore, it can be used as screening step to assess the possibility of contamination. A gas chromatograph coupled to a mass spectrometer would be used only for a confirmatory analysis. The optimized method was validated for the main figures of merit, and it proved to be adequate, with good values of recovery rate (94-106%), limit of detection (3.0 mg L-1), and quantification (10.0 mg L-1). Accuracy, in terms of repeatability and intermediate accuracy, showed variation coefficients lower than or equal to 20%. This method was applied to 28 samples of beers marketed in Brazil, and diethylene glycol was found above the limit of detection in three of them (10.7%). These results were confirmed by a gas chromatograph coupled to a mass spectrometer, which showed the reliability of the screening method for determining diethylene glycol in beer samples.

In the present work five acetylene derivatives (1-5), including three unknowns (1, 3 and 4), were isolated from seeds of Porcelia macrocarpa (Annonaceae). The structures of isolated compounds were determined as docos-13-yn-21-enoic acid (1), 3-hydroxy-4-methylene-2-(eicos-11’-yn-19’-enyl)but-2-enolide (2), 3-hydroxy-4-methylene-2-(octadec-9’-yn-17’-enyl)but-2-enolide (3), 3-hydroxy-4-methylene-2-(hexadec-7’-yn-15’-enyl)but-2-enolide (4), and (2S,3R,4R)-3-hydroxy-4-methyl-2-(eicos-11’-yn-19’-enyl)butanolide (5) by analysis of nuclear magnetic resonance (NMR) and electrospray ionization high-resolution mass spectrometry (ESI-HRMS) data. Moreover, all isolated compounds demonstrated selectivity towards intracellular amastigotes of Leishmania (L.) infantum, especially 2-4 with 50% inhibitory concentration (IC50) values of 9.2, 10.4 and 11.0 µM, respectively, indicating superior activity of that determined to positive control miltefosine (IC50 of 17.8 µM). Furthermore, these compounds showed higher selectivity index (SI) in comparison with miltefosine. Since related acetylene fatty acid 1 displayed reduced antiparasitic potential (IC50 of 48.5 µM), the obtained results suggested that the γ-lactone plays an important role in the antileishmanial activity. However, 2-4 exhibited cytotoxicity to mammalian NCTC cells (CC50 ca. 80 µM), which could be a result of the presence of a conjugated carbonyl system in the lactone ring, since 5, the only acetogenin that presents the saturated ring, lacked mammalian cytotoxicity (CC50 > 200 µM).

The liquid-liquid extraction with low-temperature partitioning technique (LLE/LTP) was miniaturized to determine the pesticides chlorpyrifos, bifenthrin, λ-cyhalothrin, and deltamethrin in a biological matrix, by gas chromatography. The method was proposed for fetal-bovine serum samples (500 μL), by using a full factorial design (23) with one center point. The evaluated factors included the volume of water added to the sample (1000 μL), volume of extraction solvent (500 μL) and stirring time (60 s) – a cleanup step was not necessary. The method was validated for the main figures of merit. The results indicated that the LLE/LTP/GC/ECD miniaturized method was efficient in extracting pesticides from blood-serum samples (75 to 115%). It showed both selectivity and sensitiveness, with limits of quantification (LOQ) ranging from 8 at 17 μg L-1;. Once validated, the method was applied to blood-serum samples of rural workers from a city in the Brazilian state of Minas Gerais. In that case, the presence of chlorpyrifos was detected in two of the samples.

Birnessite type manganese oxide (δ-MnO2) was synthesized for use in degradation of the cationic dye methylene blue in aqueous solution. The material was characterized using infrared spectroscopy, X-ray diffraction, and Brunauer-Emmett-Teller (BET) surface area calculations. The removal of the dye from aqueous solutions was evaluated considering the effects of the following variables: pH, manganese oxide concentration, contact time, and temperature. UV-Vis spectroscopy analyses indicated achievement of 99 and 95% removal of methylene blue (7 mg L-1) at pH 2.0 and 4.0, respectively, after 120 min of contact with the birnessite (100 mg L-1). At higher pH of 6.0 and 8.0, removals of around 99 and 80%, respectively, were obtained after a longer time of 1860 min. Analyses of total organic carbon (TOC) revealed that 80% reduction of organic matter was obtained at pH 4.0. The method of multivariate curve resolution-alternating least squares (MCR-ALS) was used together with UV-Vis spectroscopy to evaluate the removal process, confirming the degradation of methylene blue. Thionine (λmax = 601 nm) was identified as one of the byproducts of N-demethylation of methylene blue. The results indicated that the degradation process started with N-demethylations of the methylene blue molecule.

Silver nanoparticles (AgNPs) stabilized with glutathione (GSH) were used as nanosensors for the determination of fluoroquinolones such as ciprofloxacin (CIP), norfloxacin (NOR) and enrofloxacin (ENRO) in aqueous systems. The AgNPs were stabilized with GSH (Ag-GSH NPs), whereas the decrease of the surface plasmon resonance (SPR) band at 400 nm and the bathochromic shift of the absorption band were monitored. The method was validated and the analytical performance was verified. The results were satisfactory, with recoveries between 83.7 and 110% in almost all the experimental conditions and the repeatability and intermediate accuracy of less than 20%. The limits of detection were 0.397, 0.437 and 0.398 µmol L-1, and the limits of quantification were 1.203, 1.323 and 1.205 µmol L-1 for ciprofloxacin, norfloxacin and enrofloxacin, respectively. The method was selective in a group of drugs and applied in the determination of fluoroquinolones in potable water samples.

Clomazone exhibits high water solubility, low sorption in soil colloids, and therefore can leach and contaminate deep layers of soil profile and groundwater. In this work, the effect of the incorporation of sugarcane bagasse biochar in leaching and bioavailability of clomazone in red latosol was evaluated. Soil samples amended with 1% (m/m) biochar were placed in different depths (0-1, 0-2.5 and 0-5 cm) on the top of polyvinyl chloride (PVC) columns filled with soil. Clomazone-based herbicide was applied, and rainfall was simulated on top of the columns. A validated chromatographic method, together with a greenhouse bioassay, were used to quantify and to evaluate the mobility and availability of clomazone along the columns. The incorporation of sugarcane bagasse biochar in the superficial layers at the column tops increased herbicide sorption, reduced its leaching and bioavailability in soil and scaled down the environmental risk of clomazone avoiding contamination of underground aquifer reservoirs.

Two types of manganese oxide were investigated for the removal/degradation of Orange G (OG) dye in aqueous solution. One manganese oxide (pyrolusite) was obtained commercially and the other (birnessite) was prepared according to the polyol method by means of the oxidation of MnII hydroxide by H2O2. Both materials were characterized by X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), and nitrogen adsorption/desorption at 77 K. The effects of agitation time, pH, and MnO2 dose on the degradation of OG by the birnessite and pyrolusite were evaluated. Approximately 90 and 99% decoloration of OG (10 mg L-1) was obtained after 30 min of stirring with 0.20 g L-1 of birnessite or pyrolusite, respectively. The decoloration and increased intensity of absorbance bands in the UV-visible spectrum were indicative of a degradation process that followed pseudo-first order kinetics. The findings demonstrated the high efficiency of different types of manganese oxides for removal of this organic pollutant from waters.

ABSTRACT Kinetic studies of sulfentrazone herbicide dechlorination by Fe/Ni nanoparticles were performed in the presence of different electrolytes such as: Cl-, SO42-, NO3-, Cu2+, Na+ and Zn2+. In the presence of Cl- and SO42- the reaction occurred efficiently, reaching approximately 100% of dechlorination after 30 minutes of reaction. In the presence of NO3- and Cu2+ ions the sulfentrazone dechlorination was significantly inhibited, because these ions tend to compete with the substrate for the electrons donated by Fe0. In the presence of Na+ ions, the dechlorination efficiency remained approximately 100%, however, this electrolyte provided an increase on the reaction rate, due to the increase of the ionic strength in the system. The Zn2+ ions has no influence on the dechlorination efficiency, but the reaction rate was reduced due to the formation of a protective layer formed by the sorption of Zn2+ ions on the surface of the nanoparticles.

Abstract Biochar is a carbonaceous material that has excellent potential as a fertilizer and soil conditioner. However, there is a lack of information concerning the effects of the amount and particle size of this pyrogenic material on the soil sorption capacity. In this work, evaluation was made of changes in clomazone (CMZ) sorption in a Red Latosol following soil conditioning using different percentages (0.25, 0.5, and 1% w/w) of sugarcane biochar in three particle sizes (<106, 106-508, and 508-610 µm). The conditioned soils presented apparent sorption coefficients (Kd) up to 1300 times higher than that of pure soil, besides changes in the behavior of CMZ sorption. The biochar particle size and percentage influenced sorption of the herbicide as well as its retention in the amended soil during desorption processes. Both sorption and desorption Freundlich constants were linearly correlated with the external surface area of the biochar present in the soil.

The removal of the beta-lactam antibiotics (ceftriaxone and cefadroxil) through zero-valent copper nanoparticle (nZVC) was studied in this work. Excellent removal degrees (> 85%) were obtained for both analytes in only 20 min of reaction. Studies were performed in both oxic and anoxic conditions, and in the presence of t-butyl alcohol (TBA), an inhibitor of radicals. The results did not show significant changes. Therefore, the hydroxyl radicals are not the main species responsible for the removal. Total organic carbon cefadroxil analysis indicated a removal of 57% after 180 min of reaction. Studies involving Cu+ indicated that probably these are the principal species responsible for the removal of antibiotics. Kinetic studies have shown that two-phase reaction occurred in the antibiotics removal process and both phases followed pseudo-first order kinetic model. The first mechanism is related to the antibiotics degradation by Cu+ species and the second mechanism is related to the antibiotics adsorption by hydroxides/oxides of Cu2+ species.

A new method has been developed to determine trace levels of organophosphorus pesticide parathion-methyl in water samples by using dispersive liquid-liquid microextraction (DLLME), followed by gas chromatograph coupled with electron capture detector (GC/ECD) analysis. The optimized and validated method showed high extraction recovery (101.1%), high enrichment factor (57.3), low limits of detection and quantification, 0.083 and 0.250 µg L-1, respectively. The established DLLME-GC/ECD method has been successfully applied for the evaluation of the photodegradation of the parathion-methyl by UV254nm radiation in different conditions of pH and temperature. The parathion-methyl photodegradation at pH 3 and 35 °C achieved > 99.5% after 120 min of exposition. For this condition, it was observed the kinetic rate of 0.0515 min-1, the quantum yield of 1.22 × 10-5 mol Einstein-1 and a half-life time of 13.46 min. All experimental conditions tested proved to be strongly influenced by pH and temperature. The application of the optimized process in distilled and drinking water spiked with parathion-methyl provided residues of this pesticide at levels below the maximum permitted by Brazilian legislation, which is 9.0 µg L-1.

Improper disposal of electronic waste in the environment facilitates migration of heavy metals, especially lead, into the soil and can contribute to the bioavailability of this species. Based on a simplex-centroid mixture experimental design, small-scale tests were performed for incubation of printed circuit boards (PCBs) in mixtures containing organic matter (OM), kaolinite (KA) and iron oxides (IO) to verify lead migration. Regression equations were acquired and were adjusted to the obtained responses. Results showed high total content of Pb, ranging from 400 to 4000 mg kg-1, depending on the mixture and incubation time. Mobility and/or bioavailability of lead in the mixtures were evaluated by a three-step sequential extraction. The bioavailability factor (BF) was obtained from the ratio of the sum of exchangeable fraction (F1) and the organically bound fraction (F2) by F1, F2 and the residual fraction (F3) and the values of bioavailability factor for Pb, the heavy metal considered of greatest environmental concern in this study, ranged between 0.16 and 0.52.

Various greener microextraction procedures have been proposed with low limits of detection to control of pesticides present in the environment, including the low-density solvent dispersive liquid‑liquid microextraction (LDS/DLLME) technique. The addition of electrolytes is important in order to induce the salting-out effect. Thus, it is possible to use the Hofmeister series and the Voet lyotropic number to study the effect of different ions on pesticide extraction in LDS/DLLME technique. Different anions were tested and a strong correlation was observed between the lyotropic number of the anion and the recovered volume of extraction solvent. The lyotropic numbers of the anions were successfully compared with the chromatographic peak areas normalized by the recovered solvent volumes, and similar empirical cubic relationships were obtained for all the pyrethroids evaluated. In the extraction of the organophosphorous pesticides, chlorpyrifos presented similarity with the pyrethroids, while correlation was observed between methyl parathion and profenofos.

A new method for the extraction of pesticide residues from soil was developed, optimized, validated and applied to real samples. The technique consisted of combining single-drop microextraction and solid-liquid extraction with low temperature partitioning (SLE/LTP-SDME) followed by analysis using gas chromatography with electron capture detection (GC/ECD). This method was used to determine the presence of alachlor, methyl parathion, trifluralin, endrin, lindane, dieldrin and dichloro-diphenyl-trichloroethane (4,4’-DDT) in soil samples. Recoveries ranging from 67.2 to 122.5% were achieved, coefficients of variation (repeatability) were lower than 22.4% and limits of detection ranged from 0.18 to 0.59 µg kg-1. Recovery from soils fortified with different concentrations of the pesticides ranged from 61.5 to 123.5%. The new method combines the primary advantages of the two techniques: purification of the sample using SLE/LTP and preconcentration using SDME. The new method also enables the determination of low volatility compounds without requiring the sample to be heated.

Due to uncontrolled use of pesticides and disregard for harvest intervals, some pesticide residue is present in various foods. Treatments using ozone as an alternative for food decontamination have been studied in recent years due to ozone’s high oxidation potential even at low concentrations. The present work aimed to evaluate chlorothalonil removal from table grapes by the immersion of fruit in distilled water continuously bubbled with ozone gas. This strategy allowed the removal of 60% of chlorothalonil from table grapes (pulp and skin), regardless of ozone concentration. Ozone treatment of table grapes at a gas concentration of 3 mg L−1 changed most of the quality parameters evaluated. Treatment at 2 mg L−1 maintained the fruit quality for a longer storage period compared to the untreated control table grapes.