Multiresidue determination of pesticides in crop plants by the quick, easy, cheap, effective, rugged, and safe method and ultra-high-performance liquid chromatography tandem mass spectrometry using a calibration based on a single level standard addition in the sample.

In this study, a QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method, optimized by a 23 full factorial design, was developed for the determination of 72 pesticides in plant parts of carrot, corn, melon, rice, soy, silage, tobacco, cassava, lettuce and wheat by ultra-high-performance liquid chromatographic tandem mass spectrometry (UHPLC-MS/MS). Considering the complexity of these matrices and the need of use calibration in matrix, a new calibration approach based on single level standard addition in the sample (SLSAS) was proposed in this work and compared with the matrix-matched calibration (MMC), the procedural standard calibration (PSC) and the diluted standard addition calibration (DSAC). All approaches presented satisfactory validation parameters with recoveries from 70 to 120% and relative standard deviations≤20%. SLSAS was the most practical from the evaluated approaches and proved to be an effective way of calibration. Method limit of detection were between 4.8 and 48µgkg-1 and limit of quantification were from 16 to 160µgkg-1. Method application to different kinds of plants found residues of 20 pesticides that were quantified with z-scores values≤2 in comparison with other calibration approaches. The proposed QuEChERS method combined with UHPLC-MS/MS analysis and using an easy and effective calibration procedure presented satisfactory results for pesticide residues determination in different crop plants and is a good alternative for routine analysis.

Quantitative Multiclass Pesticide Residue Analysis in Apple, Pear, and Grape by Modified QuEChERS and Liquid Chromatography Coupled to High-Resolution Mass Spectrometry.

Most of the analytical methods currently applied in food control laboratories are focused on the determination of target compounds using LC coupled to tandem MS, which is an effective technique, but low-resolution MS is limited. Thus, a method for determination of pesticide multiresidues in fruits (pear, apple, and grape) using a modified quick, easy, cheap, effective, rugged, and safe method and LC coupled to quadrupole time-of-flight (Q-TOF) MS was developed and validated. The proposed method showed good linearity (r2 > 0.99) from 1 to 100 µg/L. Recoveries for blank samples spiked at 0.01, 0.04, and 0.10 mg/kg were between 66 and 122%, with RSDs <28%. Respective LOQs for apple, pear, and grape matrixes were 0.01 mg/kg for 112, 120, and 118 compounds, and 0.04 mg/kg for 22, 12, and 17 compounds, and average mass accuracy error was 3.2 ppm. LC with Q-TOF MS detection using protonated molecular ion and/or adducts and mass accuracy provided reliability for the method. The proposed method is effective for pesticide residue determination in apple, pear, and grape samples, proving that high-resolution MS using full scan mode can be a powerful and reliable technique for quantification purposes, being adequate for application in the surveillance of maximum residue limits set by different legislations.

Effect of diphenyl diselenide diet supplementation on oxidative stress biomarkers in two species of freshwater fish exposed to the insecticide fipronil.

The ability of diphenyl diselenide [(PhSe)2] to attenuate oxidative damage was evaluated in the liver, gills, brain, and muscle of carp (Cyprinus carpio) and silver catfish (Rhamdia quelen) experimentally exposed to fipronil (FPN). Initially, the fish were fed a diet without (PhSe)2 or a diet containing 3.0 mg/kg of (PhSe)2 for 60 days. After the 60-day period, the fish were exposed to 0.65 µg/L of FPN for 192 h. The results showed that carp exposed to FPN and not fed with (PhSe)2 exhibited acetylcholinesterase (AChE) inhibition in brain and muscle, and increased thiobarbituric acid-reactive substance (TBARS) in liver, gills, and brain. Furthermore, FPN decreased nonprotein thiols (NPSH) and δ-aminolevulinate dehydratase (δ-ALA-D) in carp liver and gills, and increased plasma glucose and protein levels. In silver catfish, FPN inhibited AChE and increased TBARS levels in muscle. In addition, glutathione S-transferase (GST) decreased in liver and muscle, and plasma glucose was increased. (PhSe)2 reversed some of these effects. It prevented the increase in TBARS levels in liver, gills, and brain in carp and in silver catfish muscle, and reversed the increase in plasma glucose levels in both species. Additionally, (PhSe)2 increased the NPSH levels in carp and silver catfish that had decreased in response to FPN exposure. However, (PhSe)2 was not effective in reversing the AChE inhibition in brain and muscle or the δ-ALA-D decrease in carp liver. Thus, (PhSe)2 protects tissues of both species of fish, mainly by preventing or counteracting the effects of FPN, on TBARS levels, antioxidants, and present anti-hyperglycemic property.

Twenty years' pediatric chronic peritoneal dialysis in Uruguay: patient and technique survival.

In this study we analyze the impact of the patient's socioeconomic status (SES) and the distance from the patient's home to the dialysis center (DPH-DC), classified as < or =300 km or >300 km, on the patient and technique survival of 59 patients starting chronic peritoneal dialysis (CPD) between May 1983 and January 2004 at a single center in Uruguay. SES was established using Graffar's method. Mean duration of CPD was 38.1+/-26.0 months. Mean age at the start of CPD was 8.4+/-5.2 years. Overall patient and technique survival at 5 years were 86.4% and 77.9%, respectively. Twenty (33.8%) patients were transferred to hemodialysis. Eight (13.5%) patients died. The incidence of peritonitis was one episode every 9.1 months. There was no statistically significant difference in patient and technique survival between the patients in the low and high SES groups (p=0.72 and 0.99, respectively), and between those in the two DPH-DC groups, (p=0.22 and p=0.99, respectively). Logistic regression analysis confirmed low SES and DPH-DC >300 km are not predictors of patient death (p=0.79 and p=0.09, respectively) or technical failure (p=0.35 and p=0.15, respectively). No SES- and DPH-DC-related statistically significant differences were found in patient and technique survival.