Occurrence of Glyphosate and Other Polar Pesticides in Honey from Lombardy and Emilia-Romagna Regions in Italy: Three-Year Monitoring Results.

Intensive agricultural practices, such as pesticides use, may negatively affect bee health and hive products. Glyphosate is one of the most widely used polar pesticides applied in crops for weed control. In this study, honey samples, collected from beekeeping farms located in the Lombardy and Emilia-Romagna regions in Italy in the framework of regional monitoring plans activated from 2020 to 2022, were analyzed for the presence of residues of polar pesticides. The analytical method based on ion chromatography coupled to high-resolution mass spectrometry was applied to quantify glyphosate, glufosinate, ethephon, fosetyl aluminum, and their related metabolites. Residues of glyphosate were detected in around 28% of analyzed honey samples. Observations on the distribution of the honey-production-site locations suggest that honey samples originating from the provinces within the Lombardy region, where the agricultural sector is highly developed, were more affected by glyphosate contamination than the samples collected from the areas with low agricultural activity, where no glyphosate residues were detected over the three years of the monitoring program.

Safety Evaluation and Probabilistic Health Risk Assessment of Cow Milk Produced in Northern Italy According to Dioxins and PCBs Contamination Levels.

Contamination levels of dioxins and polychlorinated biphenyls (PCBs) were monitored over 2018-2021 in 214 bovine milk samples from farms located in two regions in northern Italy (Lombardy and Emilia-Romagna). The average concentrations of the sum of dioxins and dioxin-like PCBs (0.78 ± 0.55 pg TEQ/g fat) and six non-dioxin-like PCBs (6.55 ± 2.24 ng/g fat) were largely below the maximum, and action limits established at European level, confirming a decreasing trend observed both locally and across Europe in recent years. The impact of contamination levels on chronic dietary exposure of the Italian population to dioxins and PCBs was found to be highly variable based on the type of cow milk (skimmed, semi-skimmed, or whole-fat milk) and the population age group considered. Indeed, a first-tier screening of the potential exposure via determinist methods allowed for the identification of the youngest population as the group with the worst risk profile. The refinement of exposure assessment via Monte Carlo probabilistic methods suggested that, at the less pessimistic middle-bound simulation scenario, infants, toddlers, and children consuming whole cow milk may be exposed to dioxins and PCBs levels above the toxicological reference values with a probability of 76, 56, and 22%, respectively.

The influence of different production systems on dioxin and PCB levels in chicken eggs from Emilia-Romagna and Lombardy regions (Italy) over 2017-2019 and consequent dietary exposure assessment.

Hen eggs from farms with different production systems (organic, free range, barn, and in cage) sited in two regions of Italy (Emilia-Romagna and Lombardy) were collected from 2017 to 2019 to monitor the levels of 17 polychlorinated dibenzo-p-dioxin/dibenzofurans (PCDD/Fs), 12 dioxin-like polychlorinated biphenyls (dl-PCBs) and the 6 non-dioxin-like polychlorinated biphenyl indicators (ndl-PCBs). Average concentrations of PCDD/Fs (0.21 pg WHO(2005)-TEQ/g fat), PCDD/Fs + dl-PCBs (0.43 pg WHO(2005)-TEQ/g fat) and ndl-PCBs (6.41 ng/g fat) were below the maximum limits established at European level in eggs, but significantly higher amounts of PCDD/Fs and PCDD/Fs + dl-PCBs were found in eggs from free-range housing system compared to barn, cage, and organic ones. The potential dietary intake of the monitored contaminants by Italian population age groups through the consumption of locally produced eggs was also evaluated. Exposure levels to PCDD/Fs plus dl-PCBs were below the tolerable weekly intake (TWI) of 2 pg WHO(2005)-TEQ/kg bw/week recently set by the European Food Safety Authority (EFSA). However, the younger population was found to be more vulnerable than other age groups to exposure to these contaminants. Specifically, the preferential consumption of free-range eggs by infants, toddlers, and children contributed more than 30% to the TWI. The results confirm the need to continuously monitor the levels of chemical contaminants in the environment and provide a reminder of the importance of targeted intervention measures aimed to reduce their occurrence in food and feed, firstly by improving the management practices on egg-producing farms.

Glyphosate and other highly polar pesticides in fruit, vegetables and honey using ion chromatography coupled with high resolution mass spectrometry: Method validation and its applicability in an official laboratory.

An analytical method, using ion chromatography coupled to high resolution mass spectrometry was developed and validated to quantify glyphosate, glufosinate, ethephon, fosetyl aluminium and their related metabolites. This method allows multiresidue analysis of 11 highly polar molecules in a single chromatographic run, without derivatization step, using acidified water with low level of acetonitrile as extraction solvent. Three different matrices that are representative of commodity group were studied and validated: one fruit (grapes), one cereal (wheat) and honey, according to the criteria established by SANTE/12682/2019 taking into account maximum residue limits indicated by Regulation (EC) No. 396/2005, confirming that the procedure was selective, repeatable and robust. Matrix effect was studied and linearity was evaluated comparing analytical response differences between solvent standard solutions and matrix-matched calibration curve. Due to the relevant matrix effect observed, the use of response factor (RF) approach to quantify analytical batch was evaluated, using isotopically labelled internal standardisation. The in-depth study, validation results and several proficiency tests, used to verify procedure performance, demonstrated that the method is fit for purpose to routine analysis in an official laboratory. Moreover, it allows surveillance activities in fruits and vegetables control, as indicated by European Community, furthermore monitoring presence of polar pesticides, at low level, in some particular food as honey that could become environmental pollution indicator.

PCDD/Fs, DL-PCBs, and NDL-PCBs in Dairy Cows: Carryover in Milk from a Controlled Feeding Study.

A feeding study was carried out to investigate the kinetics in cow milk of the 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), the 12 dioxin-like polychlorinated biphenyls (DL-PCBs), and the 6 non-dioxin-like PCBs (NDL-PCBs) regulated by the European (EU) legislation. A fortified ration (ΣPCDD/Fs and DL-PCBs: 24.68 ng TEQ/day/cow; ΣNDL-PCBs: 163.99 µg/day/cow) was given to the animals for 49 days, followed by 42 days on clean feed. EU maximum limit for TEQPCDD/F+DL-PCB was exceeded in milk after 1 week of exposure, while for ΣNDL-PCBs, after 5 weeks. Milk compliance was restored after 1 week on clean feed, but to return to the basal TEQPCDD/F+DL-PCB it took 42 days. At the end of the study, ΣNDL-PCBs had not yet reached the basal level. The carryover rate of ΣNDL-PCBs was 25.4%, while the carryover rate of TEQPCDD/F+DL-PCB was 36.9%. The latter was mainly affected by the 12 congeners contributing most to the toxic equivalent (TEQ) level, explaining the fast overcome of the maximum limit in milk.