The dielectric barrier discharge ionization detector (BID) is one of the most modern detectors commercially available for gas chromatography (GC). Its technology based on the sample ionization through the energy released from the helium plasma generation process gives it the ability to act as a universal detector and a greater response to various types of compounds compared to the well-established flame ionization detector (FID). In this study, polycyclic aromatic hydrocarbons (PAHs), organophosphates (OPPs) and organochlorines pesticides (OCPs) were investigated. The parameters that could explain the performance of the BID and FID detectors were: structural factors, ionization energy (IE) and energy of the highest occupied molecular orbital (EHOMO), which were obtained by density functional theory (DFT). The relative (BID/FID) responses to PAHs and pesticides were about 1.8 and 3.0 times greater than FID, respectively. Less structural dependence of the BID signal compared to the FID signal was observed. Among the parameters calculated by DFT, the IE was the one that most seemed to have influenced the response of the two detectors studied. The theoretical data proved to be quite consistent to explain the trends observed experimentally, especially to the BID.

NaA ZEOLITE SYNTHESIZED OVER FIBERGLASS AS A STRATEGY FOR OPTIMIZING HARD WATER SOFTENING. Zeolite NaA has been successfully synthesized over glass fiber surface previously activated by alkaline treatment. By varying the time of the treatment and the amount of silica and alumina precursors used in the reaction mixture, a sample with higher zeolite concentration could be obtained. This material was evaluated for water softening process as an alternative substitute for the use of the zeolite in its powder form, in which several drawbacks related to recovery and reuse limit its application. Water softening experiments, carried out in a continuous flow system, with a column containing the glass fiber-zeolite NaA, showed high performance in decreasing the Ca2+ ions, with complete removal achieved for 20 mL of simulated hard water (Ca2+ 100.0 mg L-1) by using 200 mg of the sample in form of column (10 mm diameter × 300 mm high). The sample maintained this performance in a wide range of pH (3.0-9.0), and also presented a feasible regenerability, with no decrease in its performance during the first four cycles of use, reaching 87.3% of efficiency over the tenth cycle.

Metabolomics, together with analytical methods and chemometric tools, point to new paths for selecting species that are resistant to pests and diseases. In this work, the forage palm species' metabolomic profile was investigated, and the relation between the chemical composition and resistance to Dactylopius opuntiae (carmine cochineal). The study was performed in cladodes of different non-susceptible cultivars (Nopalea cochenillifera (L.) Salm-Dyck, Opuntia stricta (Haw.), Nopalea cochenillifera and susceptible cultivar (Opuntia ficus-indica (L.) Mill.)). Metabolic profile showed 28 metabolites detected in the four species. From these total, 18 metabolites were annotated using UPLC-QTOF-MSE (ultra-performance liquid chromatography coupled with an electrospray ionization quadrupole time-of-flight mass spectrometry operating in MSE mode). By comparing the chemical profiles of non-susceptible and susceptible species through the application of chemometric tools, it was possible to obtain biomarkers (quercetin-3-O-2',6'-dirhamnosylglucoside, quercetin rhamnosyl dihexoside, and isorhamnetin-3-sophoroside-7-rhamnoside) that may be associated with resistance to carmine cochineal. Metabolomics based on UPLC-QTOF-MSE and chemometric allowed to establish the biomarkers knowledge of the resistance present in forage palm species. These results contribute to developing the initial understanding of flavonoids' role in the defense mechanisms of cactaceans and can be useful for application in breeding programs; it can increase the chances of success in creating new varieties of plants not susceptible to carmine cochineal.

This work focuses on the validation and application of solid phase extraction followed by high-performance liquid chromatography (SPE-HPLC) analysis of important endocrine disruptors compounds (EDC) from different classes in highly complex wastewater matrix. The endocrine disruptors investigated included three different categories: pharmaceuticals (sulfamethoxazole (SMZ), trimethoprim (TMP) and diclofenac (DCF)), hormones (estrone (E1), 17α-ethinylestradiol (EE2) and 17β-estradiol (E2)) and plastic materials (bisphenol A (BPA)). The method involves pre-concentration by SPE using Strata-X extraction cartridges followed by HPLC coupled with diode array detector (DAD). As the assumption of homoscedasticity was met for analytical data, ordinary linear regression procedure was applied to the data. The method was considered validated for 7 EDC after consistent evaluation of the key analytical parameters. Recoveries were ranged from 52.3 to 179.6%. Limits of quantification were in the range 6.0-0.4 µg L−1. The described method was applied to evaluate the occurrence and removal efficiency of EDC in two biological sewage treatment plants (STPs). The influent mean concentrations of E1, E2 and EE2 hormones were 79.54; 175.09 and 102.19 µg L−1, respectively, while for SMZ, TMP, DCF and BPA were 215.17; 187.01; 218.97 and 87.12 µg L−1 for STP A, respectively. The efficiencies for the removal of EDCs ranged from 0 to 79.4%.

Agroindustrial residues, such as leaves of fruit plants, can be sources of bioactive molecules, thus adding value to co-products that are rarely explored in agroindustry. In this context, this study aimed to look into the phytochemical profiles in detail and to explore the antitumor potential of S. tuberosa and S. mombin leaves. We observed that, S. tuberosa leaf extract was cytotoxic in both tumor and healthy cells. S. mombin extracts selectively inhibited cell proliferation in the tumor cell line for prostate cancer (PC3) and did not significantly affect healthy cells. The metabolic profiles of the extracts were evaluated by gas chromatography coupled with mass spectrometry and twenty-three metabolites were identified. The correlation of metabolic profiles with cytotoxic tests indicated possible chemical markers that may be responsible for the inhibition of cell proliferation. This study revealed that the unexplored co-products in agroindustry may have great therapeutic potential, and therefore should be screened for biologically active compounds.

Coprecipitation is one of the most practical methods used to synthesize ferrite nanoparticles. Fine characteristics of these materials can be improved by means of a series of modifications in the synthesis method. In this paper we present a study of influence of glycerol as structure directing and stabilizing agent in the synthesis of zinc ferrite nanoparticle, exploring its chelating capacity and oxidation. The studied materials include two series of zinc ferrite samples and its precursors obtained with or without glycerol throughout different stages during the synthesis process. The structural and morphological characteristics were evaluated by means of different techniques such as X-ray diffraction, Fourier transformed infrared spectroscopy, scanning and transmission electron microscopy and thermal analysis. The oxidation of glycerol was determined by high-performance liquid chromatograph. The obtained results demonstrate that zinc ferrite crystals synthesized in the presence of glycerol are initially bigger than those synthesized in absence of it, but according to the oxidation process they tend to decrease giving rise to intermediate phases. Interestingly, these samples grow back during more advanced stages and become structurally better organized, compared to the series of samples produced in absence of glycerol. These results indicate that glycerol is capable to modify the synthesis route of zinc ferrite nanoparticles via coprecipitation, acting directly over the size and morphology of the crystals.

The mesoporous material Al-Mobil Composition of Matter No. 41 (Al-MCM-41) was successfully obtained from kaolin, a low cost raw material, by means of hydrothermal route. The process of synthesis of Al-MCM-41 was based on calcination of kaolin, dealumination by acid treatment, hydrothermal synthesis in alkaline medium and surfactant extraction. The characterization of the obtained mesoporous material was carried out by techniques such as: X-ray diffraction, infrared vibrational spectroscopy, 29Si and 27Al solid state nuclear magnetic resonance, scanning electron microscopy, transmission electron microscopy and N2 adsorption-desorption. The X-ray diffraction at low angles allowed the determination of the cell parameter, which was 4.02 nm. The analyses of scanning and transmission electron microscopy revealed important morphological properties of the synthesized material. N2 adsorption/desorption showed a Brunauer-Emmett-Teller (BET) specific surface area of 1,303 m2 g-1, pore volume of 1.23 cm3 g-1 and average diameter of 2.45 nm. The mesoporous material presented a maximum adsorption capacity of 316 mg g-1 for the cationic dye methylene blue (MB) in a concentration typical of industrial effluents, which makes it a potential adsorbent for MB removal from wastewaters.

A method based on QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction and gas chromatography-mass spectrometry (GC-MS) detection was described for the pesticides dichlorvos, disulfoton, ethoprophos, parathion methyl, fenchlorphos, chlorpyrifos, azinphos methyl and prothiofos in sapodilla. For all compounds studies, it was observed a strong matrix effect showing the need to use matrix matched calibration strategy. Method was validated, and good linearity (R > 0.99) was obtained for all pesticides studied with limits of detection (LODs) and quantification (LOQs) ranging from 0.01 to 0.06 mg kg-1 and 0.03 to 0.2 mg kg-1, respectively. Recovery studies were performed at different levels (0.08, 0.10, 0.14, 0.20, 0.35 and 1.17 mg kg-1) and showed good results (between 70 and 120% with relative standard deviation (RSD) < 20%). A statistical test was applied to the coefficients of the analytical curves obtained in the sapodilla matrix. Analyses of commercial samples showed chlorpyrifos were detected in about 70 and 33% for fruit and pulps samples, respectively. It should be noted that chlorpyrifos is not permitted in sapodilla crops by ANVISA and EC guidelines.

Perfumes are products mainly consisting of ethyl alcohol, water and fragrance. These fragrances are responsible for characterizing the pleasant and unique odor of each perfume. Among the fragrances, we highlight a group of fragrances which can cause contact allergy, leading to dermatitis. Brazilian and the European law state that when these concentrations of allergenic fragrances exceed the limit of 0.01% for non-rinse products and 0.001% for products with rinsing, the manufacturer is obliged to discriminate on its label their presence. This work aims to quantify allergic fragrances in original and Brazilian perfume using solid-phase microextraction and analyze by gas chromatography-mass detector.

This paper investigates a strategy as a quality control parameter, using standard surrogate and determination of a relation factor for determination of parathion-methyl, chlorpyriphos and cypermethrin pesticides in environmental aqueous matrices with distinct characteristics (river water, estuarine, seawater and weir water), using the technique of solid phase microextraction gas chromatography with flame ionization detector (SPME-GC-FID). Pesticides were very susceptible to matrix effects promoted by environmental samples. The salinity and the organic matter seem to have been the main sources of interference in the method. For chlorpyriphos, in middle and high levels, the values of relation factor (Rf) for estuarines, seawater and weir matrices were statistically similar. For cypermethrin, the statistical equality occurred in estuarine matrices in medium and high levels of concentration. That indicates proportional behavior between the pesticide and the surrogate recovery, suggesting that a single value of Rf can be used as correction factor recovery for any of these matrices.

<p>An efficient, fast and cost-effective method for detecting adulteration in perfumes by UV spectroscopy and multivariate analysis is proposed. Classification of perfumes, either as original or fake, was accomplished with the spectroscopic data using chemometric techniques such as principal component analysis (PCA), soft independent modeling of class analogy (SIMCA) and linear discriminant analysis (LDA).</p>

<p>Pesticides are used mostly in rural areas for agriculture, but urban pest control, public health campaigns, and household and veterinary products can also be important sources of these contaminants. This aim of this study was to estimate household pesticide contamination in sediments of two urban estuaries due to pest control: Cocó and Ceará rivers located in the metropolitan area of Fortaleza, Ceará, Brazil. Cypermethrin and malathion were found in both rivers. Cypermethrin levels had the same magnitudes as other studied urban areas and were highest in the estuary, while malathion was similar in both fluvial and estuarine zones.</p>

Analysis of essential oil from fresh leaves of Capraria biflora allowed identification of fourteen essential oil constituents among which thirteen are sesquiterpene compounds, and α-humulene (43.0%) the major constituent. The essential oil was tested for larvicidal activity against Aedes aegypti showing good activity, with LC50 73.39 µg/mL (2.27 g/mL). Chromatographic studies of extracts from roots and stems allowed the isolation of five compounds: naphthoquinone biflorin, sesquiterpene caprariolide B, the steroid β-sitosterol, the carbohydrate D-mannitol and iridoid myopochlorin first reported in the species C. biflora. The structures of compounds were characterized by spectroscopic data, IR, MS, NMR13C, NMR¹H, NOE, HSQC and HMBC.

Neste estudo, métodos multirresíduos usando extração em fase sólida (SPE) e microextração em fase sólida (SPME) são comparados na determinação de pesticidas em amostras aquosas. Parâmetros como tipo de fibras e espessura, solvente de eluição, volume da amostra, tempo de equilíbrio, coeficiente de partição e solubilidade foram investigados. Resultados satisfatórios foram obtidos para a análise de pesticidas usando cartuchos C18 e acetato de etila como eluente, com taxas de recuperação entre 75-107%. As melhores condições para SPME foram com uma fibra PDMS 100 µm de espessura, volume de amostra de 40 mL, e tempo de equilíbrio de 45 min. O método SPME é o mais adequado para a análise de pesticidas em água, devido à sua rapidez e simplicidade e ao não uso de solventes. Os limites de detecção e quantificação são inferiores aos limites de concentração máximos estabelecidos pelas autoridades brasileiras, sendo portanto aceitável.

In this study, multiresidue method using solid phase extraction (SPE) and solid phase microextraction (SPME) are compared in the determination of pesticides in aqueous samples. Parameters such as fiber type and thickness, elution solvent, sample volume, equilibration time, partition coefficient and solubility were investigated. Satisfactory results were obtained for the analysis of pesticides using C18 cartridges and ethyl acetate as eluent, whith recovery rates between 75-107%. The best conditions for SPME fiber were PDMS with a 100 µm thick, sample volume of 40 mL, and reaction time was 45 min. SPME method is most suitable for the analysis of pesticides in water, due to its speed and simplicity and solvent-free. The limits of detection and quantification are below the maximum concentration limits established by Brazilian authorities and therefore acceptable.

The present study deals with phenol adsorption on chitin and chitosan and removal of contaminants from wastewater of a petroleum refinery. The adsorption kinetic data were best fitted to first- and second-order models for chitosan and chitin, respectively. The results of adsorption isotherms showed Langmuir model more appropriately described than a Freundlich model for both adsorbents. The adsorption capacity was 1.96 and 1.26 mg/g for chitin and chitosan, respectively. Maximum removal of phenol was about 70-80% (flow rate: 1.5 mL/min, bed height: 18.5 cm, and 30 mg/L of phenol. Wastewater treatment with chitin in a fixed-bed system showed reductions of about 52 and 92% for COD and oil and greases, and for chitosan 65 and 67%, respectively. The results show improvement of the effluent quality after treatment with chitin and chitosan.