Greener production of a starch-based nanohybrid material (core-shell) for the simultaneous extraction of persistent organic pollutants in shrimp samples.

Here, a novel nanohybrid material (Ag@CD@ANS) based on oat starch was produced, characterized, and applied to extract persistent organic pollutants in a shrimp sample. By the characterization experiments, Ag@CD@ANS was successfully synthesized. The functionalization of the material by 1,2-naphthoquinone-4-sulphonic acid (ANS) was confirmed using the infrared technique and CHN elemental analysis. The isotherm study showed that the material has a high adsorption capacity for the pesticides of interest (flutriafol, atrazine, heptachlor, DDT and bifenthrin) allowing their extraction from shrimp samples. The optimal condition for extraction was obtained using multivariate analysis. The nature of the elution solvent (hexane, methanol, acetonitrile) and the mass ratio between sample:adsorbent (1:1; 1:5 and 1:10) were the evaluated factors for extraction using Ag@CD@ANS and commercial adsorbents (neutral alumina, octadecyl, silica gel). From the multivariate analysis, it was observed that the optimal condition for pesticide extraction using Ag@CD@ANS was reached, using a 1:5 ratio (sample:adsorbent) and acetonitrile (10 mL) as elution solvent. For the commercial adsorbents, the optimal condition for pesticide extraction was reached, using a 1:3 ratio (sample:adsorbent), acetonitrile (10 mL) and neutral alumina as commercial adsorbent. Ag@CD@ANS efficiency was compared with an optimal commercial adsorbent (neutral alumina). No significant difference (p < 0.05) between neutral alumina and Ag@CD@ANS was observed. Recoveries ranging from 75 to 105 % with coefficients of variation ≤ 15 % (n = 3) were obtained using neutral alumina while using Ag@CD@ANS, recoveries ranging from 73 to 102 %, with coefficient of variation ≤ 13 % (n = 3) were obtained for the target pesticides. Limits of detection ranging from 0.5 to 1.0 µg Kg-1 and limits of quantification ranging from 1.6 to 3.3 µg Kg-1 were reached. The results demonstrated that Ag@CD@ANS can alternatively be used as a support for the extraction of persistent organic pollutants, having the advantage of being reusable for up to three cycles.

The efficacy of washing strategies in the elimination of fungicide residues and the alterations on the quality of bell peppers.

Food safety problems caused by pesticide residues in vegetables have become a top issue to raise public concern. In this study, bell peppers were grown in an experimental field and sprayed with two systemic (azoxystrobin and difenoconazole) and one contact (chlorothalonil) fungicides. Ozone (ozonated water and water continuously bubble with ozone) or conventional domestic (washing with distilled water, detergent, acetic acid, sodium bicarbonate, and sodium hypochlorite solutions) procedures were investigated to identify the most effective way to remove fungicide residues in bell peppers. The residues in the fruits and the washing solutions were determined by solid-liquid extraction with a low-temperature partition (SLE/LTP) and liquid-liquid extraction with a low-temperature partition (LLE/LTP), respectively, and analyzed by gas chromatography. Water continuously bubbled with ozone a concentration of 3 mg L-1 was the most efficient treatment with removal of fungicides residues ranging from 67% to 87%. However, similar treatment at a lower concentration (1 mg L-1) did not only efficiently removed fungicide residues (between 53% and 75%) but also preserving the quality of the fruit along a storage time of 13 days. Among the conventional solutions, sodium bicarbonate at 5% showed good efficiency removing between 60% and 81% of the fungicide residues from bell peppers, affecting the color quality of the fruit. Overall, the most affected physicochemical parameters in bell peppers after the treatments were weight loss, color, and vitamin C content.

Building robust models for identification of adulteration in olive oil using FT-NIR, PLS-DA and variable selection.

Being a product with a high market value, olive oil undergoes adulterations. Therefore, studies that make the verification of the authenticity of olive oil more efficient are necessary. The aim of this study was to develop a robust model using FT-NIR and PLS-DA to discriminate extra virgin olive oil samples and build individual models to differentiate adulterated extra virgin olive oil samples. The best PLS-DA-OPS classification model for olive oils showed specificity (Spe) and accuracy (Acc) values higher than 99.7% and 99.9%. For the classification of adulterants, PLS-DA-OPS models presented values of Spe at 96.0% and Acc above 95.5% for varieties. For the blend, the best PLS-DA-GA model presented Acc and Spe values greater than 98.2% and 98.8%. Reliable and robust models have been built, allowing differentiation from seven adulterants to genuine extra virgin olive oils.

Headspace Solid-Phase Microextraction: Validation of the Method and Determination of Allyl Isothiocyanate Persistence in Cowpea Beans.

Essential oils are widely recognized as an efficient and safe alternative for controlling pests in foods. However, a few studies have determined the persistence of these compounds in stored grains. The present study optimized and validated a fast and effective method for extraction and quantification of allyl isothiocyanate (AITC-the main component of mustard essential oil) residue in cowpea beans. It also investigated the persistence of this substance in the grains. The proposed method employs headspace solid-phase microextraction (HS-SPME) and gas chromatography with a flame ionization detector (GC/FID). For optimizing it, a central composite design (CCD) was used, where the best conditions for the extraction of the AITC were achieved using 15 min fiber exposure at 30 °C. The performance of the method was assessed by studying selectivity, linearity, limits of detection (LOD) and quantification (LOQ), precision, and accuracy. The LOD and LOQ for AITC were 0.11 and 0.33 µg kg-1, respectively. The determination coefficient (R 2) was above 0.99. The relative recovery rate ranged from 108.2 to 114.8%, with an interday coefficient of variation below 9%. After 36 h, no residue was detected in the samples, demonstrating that the AITC has low persistence and can be safely used as a bioinsecticide for grains.

Eugenol diffusion coefficient and its potential to control Sitophilus zeamais in rice.

Given the insecticidal potential of eugenol as a fumigant, this work aimed to determine the diffusion coefficient of eugenol emanating from a pure standard solution (99%), as well as from clove essential oil (Eugenia caryophillata Thunb. (Myrtaceae)) through rice grain; to chemically analyse the volatile composition of commercially available eugenol and clove essential oil; and to evaluate the mortality of Sitophilus zeamais Motschulsky (Coleoptera: curculionidae) after exposure to eugenol inside a test chamber filled with rice. The solid phase microextraction method of extracting and quantifying eugenol by gas chromatography presented a good analytical response for the quantification of the analyte. There was no significant difference between the diffusion coefficient of eugenol diffusing from pure eugenol or from clove essential oil. The diffusion coefficient of eugenol through rice with the conditions herein adopted is 1.09 × 10-3 cm2 s-1. The characterization of clove essential oil confirmed the presence of eugenol as its major component (74.25%). A difference was observed in the composition of the distinct phases evaluated. The exposure of adult S. zeamais to diffused eugenol from pure eugenol over seven days resulted in significantly higher mortality rates (~37%) than eugenol diffused from clove essential oil (~11%). No differences in mortality rates were observed in individuals placed at different positions inside the test chamber during eugenol fumigation.

GIS applied to agriclimatological zoning and agrotoxin residue monitoring in tomatoes: A case study in Espírito Santo state, Brazil.

Searches related to global warming have provided important insights into the response of terrestrial ecosystems, but few have examined the impacts on agricultural crops, particularly those associated with the monitoring of agrotoxin residues. In this context, the agriclimatological zoning is an important tool in the planning and consolidation of crops and should be considered in any initiative that involves such planning. This tool is particularly important in the analysis of agrotoxin residues and may be applied by the Program Analysis of Agrotoxin Residues in Food (PARA) created by the National Health Vigilance Agency of Brazil (ANVISA), which enables greater food security and contributes to the improvement of human health. The aim of this study was to elaborate the current and future agriclimatological zoning for the tomato crop, relating it with the monitoring of samples collected by PARA in Espírito Santo State, Brazil. The results indicate that a temperature increase of 5 °C creates a decrease in apt areas from 37.3% to 4.3%, for a total reduction of 33 percentage points (-88.5%). It is noted that of the 41 producing municipalities, only 26 have apt areas greater than 50%, highlighting the municipalities with apt areas greater than 90%, represented by Mantenópolis (100%), Guaçuí (98.5%), São José do Calçado (97.8%), Irupi (94.4%), Santa Teresa (92.3%), and Marechal Floriano (91.4%). The veracity of agriclimatological zoning is proved by a Kendall rank correlation coefficient of 0.876, indicating that the distribution of the variables of apt areas and productivity are similar at the significance level of 0.05 with a confidence interval 95%. After validation of the agriclimatological zoning for the tomato crop, it is recommended that the PARA should monitor 36 municipalities rather than the current 18, representing an increase of 100%. The methodology can be adjusted to agricultural crops of other countries.