Simultaneous determination and dietary risk assessment of clethodim and its metabolites in different fruits and vegetables.

Clethodim is one of the most widely used herbicides in agriculture and, after field application, is metabolised to several metabolites. The potential toxicological negative effects of these compounds are poorly understood. Thus, recently, within the risk assessment framework, the European Food Safety Authority (EFSA) proposed to include the minor metabolites in the definition of clethodim residue. In this work, an easy to use and reliable UHPLC method coupled with a triple quadrupole MS/MS was developed and validated for the detection and quantification of the herbicide clethodim and related metabolites clethodim sulphone, clethodim sulphoxide, metabolites M17R and M18R in apple, grape, olive and rice. The five analytes were extracted by using a modified QuEChERS procedure, while the active ingredients were determined in multiple reaction monitoring (MRM) ion-switching mode. The proposed method showed calibration curve linearity with r2 ≥ 0.990 for all active ingredients (a.is.) both in solvent and matrix extracts. Limits of quantitation (LOQ) of the five compounds ranged from 9.44 µg/kg for M17R in olive extract to 11.01 µg/kg for clethodim in apple extract. Recoveries values ranged from 86% to 119% at two concentration levels (LOQ and 10xLOQ), while the intraday and interday precisions of the method were both below 10% in all cases. The method was successfully used for the quantification of the five a.is. in different food matrices. Furthermore, chronic dietary risk was investigated using a hazard quotients (HQ) method based on European dietary habits. The chronic dietary exposure risk quotients ranged from 1.0 × 10-5 (lower bound scenario) to 2.7 × 10-4 (upper bound scenario) which were significantly lower than 1. Data obtained indicate that the dietary exposure risks were acceptable for clethodim and its major and minor metabolites applied in apple, table grape, rice and table olive.

Dissipation behavior, residues distribution and dietary risk assessment of tembotrione and its metabolite in maize via QuEChERS using HPLC-MS/MS technique.

The dissipation and residues of tembotrione in corn field application were investigated using liquid chromatography tandem mass spectrometry (LC-MS/MS) method. The average recoveries of tembotrione in maize, corncob, and straw were in the ranges of 98-107% with relative standard deviations (RSDs ≤9.3%), respectively. The recoveries of M5 was in the ranges of 90-108% in all three matrices of maize, with RSDs were 3.3-12.8%. The LODs for tembotrione and M5 in maize were 0.85 µg/L and 1.0 µg/L, 0.84 µg/L and 0.43 µg/L in corncob, 0.94 µg/L and 1.5 µg/L in straw, respectively. The LOQs of the method in maize grain, corncob and straw were 0.01, 0.01 and 0.05 mg/kg for both analytes, respectively. The dissipation of tembotrione in straw was in compliance with the first-order dynamic equation, with half-lives of 1.18-1.23 days at Beijing and Heilongjiang. Total residue of tembotrione in maize grain and corncob matrix were both below 0.02 mg/kg, lower than the max residue limit (MRL) recommended by european food safety authority (EFSA). Risk quotients (RQs) of this pesticide was assessed via comparing national estimated daily intake with acceptable daily intake. The dietary intake risk of tembotrione residue in maize was very low for all groups of Chinese residents. These data could provide scientific data and strategies and facilitate Chinese government to establish the MRLs of tembotrione.

The Combined Influence of Air Pollution and Home Learning Environment on Early Cognitive Skills in Children.

Cognitive skills are one component of school readiness that reflect a child's neurodevelopment and are influenced by environmental and social factors. Most studies assess the impact of these factors individually, without taking into consideration the complex interactions of multiple factors. The objective of this study was to examine the joint association of markers of environmental pollution and of social factors on early cognitive skills in an urban cohort of children. For this, we chose isophorone in ambient air as a marker of industrial air pollution. Low quality home learning environments was chosen as a marker of the social factors contributing to cognitive development. Using a subpopulation from the Early Childhood Longitudinal Study, Birth Cohort (N = 4050), isophorone exposure was assigned using the 2002 National Air Toxics Assessment. Home learning environment was assessed with a modified version of the Home Observation for Measurement of the Environment (HOME) Inventory, and standardized math assessment scores were used as a measure of early cognitive skills. Multiple linear regression was used to estimate the effect of both exposures on math scores. After adjustment for confounders, children living in areas with ambient isophorone in the upper quintile of exposure (>0.49 ng/m³) had math scores that were 1.63 points lower than their less exposed peers [95% CI: -2.91, -0.34], and children with lower HOME scores (at or below 9 out of 12) had math scores that were 1.20 points lower than children with better HOME scores [95% CI: -2.30, -0.10]. In adjusted models accounting for identified confounders and both exposures of interest, both high isophorone exposure and low HOME score remained independently associated with math scores [-1.48, 95% CI: -2.79, -0.18; -1.05, 95% CI: -2.15, 0.05, respectively]. There was no statistical evidence of interaction between the two exposures, although children with both higher isophorone exposure and a low HOME score had a decrement in math scale score beyond the additive effect of each exposure. This was primarily observed among male children. These findings suggest that aspects of both the physical and social environments are independently associated with children's early cognitive skills. Future research aiming to improve children's early cognitive skills and subsequent school readiness should address both domains.

Persistence assessment of cyclohexyl- and norbornyl-derived ketones and their degradation products in different OECD screening tests.

The persistence of synthetic cyclohexyl- and norbornyl-derived ketones was assessed by using OECD 301F and 301D biodegradation tests. While cyclohexyl-derived ketones either reached or came close to the pass level (60%) after 60 d, the corresponding norbornyl derivatives yielded significantly less biodegradation (<40%). By analyzing extracts at 60 d, the key degradation products of four norbornyl derivatives were identified. Consistently, 2-bicyclo[2.2.1]heptane carboxylic acid was found as a principal degradation product with minor quantities of bicyclo[2.2.1]heptan-2-one and 2-bicyclo[2.2.1]heptane acetic acid. When the three degradation products were re-synthesized and tested individually for biodegradability, the former two were found to be ultimately biodegradable after 60 d in OECD 301D tests, thus proving non-persistence. Similarly, 2-bicyclo[2.2.1]heptane acetic acid was found to be degraded significantly, albeit with long lag phases exceeding 60 d in the case of freshwater inoculum, then ultimately reaching the pass level. On the other hand, norbornyl ketones were still only partially biodegradable in the same test. We conclude that despite the potential for ultimate biodegradation of norbornyl-derived ketones, current screening tests yield an incomplete picture of their biodegradability, particularly when applying strict OECD criteria. The appearance of long lag phases when re-testing norbornyl ketone degradation products underlines the importance of extending tests to well beyond 28 and even 60 d in the case of freshwater inocula.

Quantitative assessment of the contribution of high resolution mass spectrometric analysis to the reliability of compound confirmation.

Applications of high resolution mass spectrometry (HRMS) in food safety and residue analysis have increased remarkably over the last few years. The high resolution detection of ions reportedly enhances the assay selectivity but quantitative assessment of HRMS contribution to the assay selectivity has not yet been undertaken. We devised a method to assess the impact of instrument resolution on the probability that a spectral assignment to a given compound was made in error. The method allows for evaluating the quality of a spectral assignment based on resolution and the number of fragmentation stages. It thus provides a firm basis for comparing analytical methods performed on very different mass spectrometric instrumental platforms as well as in the context of the current regulatory framework.

Non-targeted multi-component analytical surveillance of plastic food contact materials: Identification of substances not included in EU positive lists and their risk assessment.

A procedure used by the Norwegian Food Safety Authority for surveillance of contaminants from plastic food contact materials (polyolefin drinking bottles, water boilers, polyamide cooking utensils and plastic multi-layer materials) is described. It is based on gas chromatographic-mass spectrometric (GC/MS) analysis of food simulants exposed to plastic materials. Most migrants were substances not-intentionally added to the plastic (degradation products, impurities) or originated from non-plastic components, such as printing inks, adhesives, not-listed additives, solvents and coatings. Hence, the majority of the identified migrants were regulated by the general statements in the EU Framework Regulation, which neither specify limits nor requirements regarding risk assessment, rather than by specific migration controls. Risk assessment has been carried out for selected non-authorized substances. The analysis and the management of these substances and materials with respect to safety represents a challenge to the food authorities.