Degradation of xanthene-based dyes by photoactivated persulfate: experimental and computational studies.

Dyes are naked-eye detectable even at low concentration levels and can cause environmental damage when released into aquatic effluents; therefore, methods for removing the residual color from the aquatic media are always a current issue. In this paper, degradation of three xanthene dyes, Rhodamine B, Eosin Y, and Sodium Fluorescein, using photoactivated persulfate was evaluated at pH 3.0 and 11.0. The dyes' degradation followed a pseudo-first-order reaction. Although the solution is completely decolorized in 40 min at pH 3.0, achieving 75% mineralization requires a longer reaction time of 180 min. Furthermore, GC-MS analyses indicate that degradation products are mainly low-molecular weight acids, CO2 and H2O. Experiments carried out in dark and under UV irradiation showed substantial contribution of radical (SO4•- and HO•) and non-radical pathways to dye degradation in both pH. Additionally, to get more insights into the degradation pathways, HOMO-LUMO energy gaps of the dyes were calculated by DFT using MPW1PW91/MidiXo level of theory and, in general, the lower the bandgap, the faster the degradation. Fukui functions revealed that the preferential sites to radical attack were the xanthene or the benzoate portion depending on the pH, wherein attack to the xanthene ring provided better kinetic and mineralization results.

Chemometric tools applied to optimize a fast solid-phase microextraction method for analysis of polycyclic aromatic hydrocarbons in produced water.

Chemometric tools are powerful strategies to efficiently optimize many processes. These tools were employed to optimize a fast-solid phase microextraction procedure, which was used for the analysis of polycyclic aromatic hydrocarbons (PAHs) in oil-based produced water using a Headspace-Solid Phase Microextraction technique (HS-SPME/GC-MS). This optimization was achieved with a 24 factorial design approach, where the final conditions for this extraction procedure were 10 µg L-1, 1 h, 92 °C (at headspace), and 0.62 mol L-1 for PAHs concentration, fiber exposition to headspace, temperature, and NaCl concentration, respectively. The limit of detection (LOD) in this protocol ranged from 0.2 to 41.4 ng L-1, while recovery values from 67.65 to 113.10%. Besides that, relative standard deviation (RSD) were lower than 8.39% considering high molecular weight compounds. Moreover, the proposed methodology in this work does not require any previous treatment of the sample and allows to quantify a higher number of PAHs. Notably, naphthalene was the major PAHs compound quantified in all samples of the produced water at 99.99 µg L-1. Altogether, these results supported this methodology as a suitable analytical strategy for fast determination of PAHs in produced water from oil-based industry.

Statistical evaluation of analytical curves for quantification of pesticides in bananas.

The aim of this paper is to statistically validate the analytical curves of a chromatography method to identify and quantify azoxystrobin, difenoconazole and propiconazole residues in banana pulp, using QuEChERS and GC-SQ/MS. A matrix-matched calibration was used and analytical curves were estimated by weighted least squares regression (WLS), confirming heteroscedasticity for all compounds. Statistical tests were performed to confirm the quality adjustment of the proposed linear model. The correlation coefficient for azoxystrobin, difenoconazole and propiconazole were, respectively, 0.9985, 0.9966 and 0.9997 (concentration range: 0.05 and 2.0 mg kg-1). The limits of detection and quantification were, respectively, between 0.007 and 0.066 mg kg-1, and between 0.022 and 0.199 mg kg-1, below the maximum limits stipulated by Brazilian, American, and European legislation. Only difenoconazole had an insignificant matrix effect (6.8%). Thus, the weighted least squares method is shown to be a safe linear regression model, providing greater reliability of the results.

A socio-environmental perspective on pesticide use and food production.

Pesticides are part of a large group of organic compounds with different physicochemical characteristics, designed to control and prevent pests in various crops and plantations, improving productivity. This works provides a perspective on pesticide use in current agriculture with the aim of identifying the influence of pesticides on food production and their impact on the environment. Therefore, it is necessary to highlight the importance of determining pesticide residues in food, aiming to ensure food safety, since these compounds can represent risks to human health and the environment. The effects of pesticides on humans range from headaches, nausea and skin and eye irritation to chronic problems such as cancer and neurological disorders, and extend to other non-target organisms such as birds, fish and bees, contaminating water, soil, and plants, as opposed to the benefits of increased production, consequently other measures for pesticide consumption need to be evaluate to ensure human health, food safety and environmental protection. It is important to note that chromatographic techniques and mass spectrometry assist in the determination of pesticide residues and evaluate the quality of the food that reaches the consumer, and together with the Maximum Residue Limits (MRLs), established by the legislation of each country, these instrumentation act to control the exposure of population to pesticides. Although the MRL is used as a parameter for food quality, the global differences in pesticide legislation do not guarantee the consumer safety. In this sense, a brief analysis of MRL inefficiency is also present in this paper.

Reactive Adsorption of Parabens on Synthesized Micro- and Mesoporous Silica from Coal Fly Ash: pH Effect on the Modification Process.

Parabens are widely used as preservatives in food, pharmaceutical, and cosmetic products. These compounds are known for their estrogen agonist activity. This research investigates the synthesis of micro- and mesoporous silica from coal fly ash at different pH values (13, 11, 9, and 7) as well as its use as an adsorbent for the removal of parabens. The materials were characterized, and X-ray fluorescence (XRF) analysis revealed that the fly ash acid treatment reduced the presence of aluminum, iron, and calcium oxides and also that silica synthesized at lower pH values (7 and 9) showed a higher SiO2 content. X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses revealed microporous silica formation for silica synthesized at pH 13 and mesoporous silica at pH 7, 9, and 11. Adsorption tests were performed with materials, and FA-AT7 showed a higher adsorption capacity. The effect of factors (A) adsorbent mass, (B) initial paraben concentration, and (C) agitation rate on the adsorption process was studied for the FA-AT7 adsorbent using a factorial experimental design. Standardized Pareto charts revealed a negative effect of factor A, positive effect of factor B, and negative interaction effects of factors A-B for all studied parabens. Isotherms and multicomponent kinetic studies were performed. A linear type-III isotherm was obtained, and adsorption equilibrium was reached at approximately 10 min.

Evaluating the presence of pesticides in bananas: An integrative review.

INTRODUCTION: Pesticides are organic compounds widely used in modern agriculture, being relevant for helping plantations and increasing food production. The banana, a fruit with oriental origin, stands out for being widely produced in tropical and subtropical regions which, like other matrices, is susceptible to pest action. This review aims to evaluate the presence of pesticides in bananas according to Brazilian, European and Codex legislation. METHODS: Four databases, ScienceDirect, SciELO, PubMed and Springer, were used to find relevant articles in the literature addressing methods for the determination of pesticide residues in bananas using the terms "banana", "chromatography", "pesticides" and "determination". The search stages included reading abstracts and titles, reading the full text, extracting data and analyzing data from eligible articles. The search was restricted to original research articles published in English from 2008 to 2018. RESULTS: 404 articles were found from the initial research, with only 15 studies being considered eligible for this review. Mass spectrometry is the most widely used detection technique. 5 articles were seen to use a multiresidue method to analyze only bananas (pulp), and from these, only 2 studies used methods to analyze the pulp and peel. The articles analyzed 172 samples, with 59.3% of these being conducted in Europe, 32.5% being conducted in Asia and only 8.1% in South America. A total of 79.1%, 32.4% and 42.6% of samples were unsatisfactory according to the Brazilian, European and Codex legislation, respectively, with these samples being contaminated with pesticide residues. CONCLUSION: This review presents the scarcity of articles aimed at identifying pesticide residues in bananas and the urgency of checking the quality of the fruit that reaches the population. The MRLs allowed by different legislations have clear divergences that do not ensure the lowest concentration values that guarantee consumer safety.

Efficiency of ESI and APCI ionization sources in LC-MS/MS systems for analysis of 22 pesticide residues in food matrix.

The intensive use of pesticides has led to the need to optimize analytical methodologies for the control of residues in food. The present study aims to compare the efficiency of different ion sources (Eletrospray Ionization-ESI and Atmospheric Pressure Chemical Ionization - APCI) in LC-MS/MS systems, when analysing 22 pesticides in a cabbage matrix. The method performance was evaluated during a validation study. Organophosphates, triazoles, pyrethroids and triazines compounds showed good linearity in the range 0.5-200 µg.Kg-1. Statistical tests were used to evaluate linearity. LOQm values varied from 0.50 to 1.0 µg.Kg-1 to the ESI source, and 1.0-2.0 µg.Kg-1 for the APCI source. Matrix effect was more intense when using the APCI source. Accuracy and precision were evaluated at three levels of concentration (2; 20 and 100 µg Kg-1). Most of the compounds presented recovery between 70 and 120%. ESI-LC-MS/MS system showed greater efficiency in multiresidue analysis in the cabbage matrix.

Effect of ozonization in degradation of trifluralin residues in aqueous and food matrices.

This study investigates the oxidation of trifluralin residues during ozonation in aqueous and food matrices (tomato). Domestic ozonation equipment with average production of 23.9 mg O3 L-1 h-1 was used in the tests. Modern chromatographic systems (SPME-GC-IT/MS/MS and QuEChERS-GC-IT/MS/MS) were applied for extraction and detection of trifluralin residue in fortified samples of ultrapure water, tap water, superficial water and tomato fruit. The samples were submitted to the ozonation process during 0, 5, 10 and 20 min. Treatment at 5 min was able to degrade 71.5% of herbicide trifluralin in surface water. The removal (%) in ultrapure water reached 83.4% after 20 min of ozonation. The degradation of trifluralin in fortified tomato samples (0.025-0.1 mg kg-1) were conducted with ozonation at 20 min, and it ranged from 84.4 to 92.7%. After treatment, levels of trifluralin in tomato remained within the established MRLs to EU, USEPA and ANVISA (Brazil). The data provided evidence that ozone is effective for removing trace trifluralin from water and foods.

Estimated Levels of Environmental Contamination and Health Risk Assessment for Herbicides and Insecticides in Surface Water of Ceará, Brazil.

Methodology using solid phase extraction and high performance liquid chromatography (SPE-C18/HPLC-DAD) was applied to pesticide determinations in ten water reservoirs in the semidarid region of northeastern Brazil. The validated method was suitable for determination of herbicides and insecticide in surface water. The recovery efficiency of atrazine, methyl-parathion and simazine was approximately 70%. The method also showed good linearity and selectivity with correlation coefficients (R) greater than 0.99. The limits of detection were below the maximum residue limits (MRLs) established by government agencies. Studied reservoirs showed presence of atrazine at mean levels from 7.0 to 15.0 µg/L. Simazine and methyl parathion were not detected during the period. The atrazine levels measured from this semiarid region are of the same magnitude as those found in regions with moderate to high agricultural activity. According to detected atrazine concentrations, the annual health risk to humans was insignificant. However, the control of herbicides is important to maintain the quality of water in the reservoirs of Ceará, Brazil.

Chemometric characterization of alembic and industrial sugar cane spirits from cape verde and ceará, Brazil.

Sugar cane spirits are some of the most popular alcoholic beverages consumed in Cape Verde. The sugar cane spirit industry in Cape Verde is based mainly on archaic practices that operate without supervision and without efficient control of the production process. The objective of this work was to evaluate samples of industrial and alembic sugar cane spirits from Cape Verde and Ceará, Brazil using principal component analysis. Thirty-two samples of spirits were analyzed, twenty from regions of the islands of Cape Verde and twelve from Ceará, Brazil. Of the samples obtained from Ceará, Brazil seven are alembic and five are industrial spirits. The components analyzed in these studies included the following: volatile organic compounds (n-propanol, isobutanol, isoamylic, higher alcohols, alcoholic grade, acetaldehyde, acetic acid, acetate); copper; and sulfates.