Detection of 130 pesticide residues in red berries from the North of Morocco: LC-ESI-MS/MS analysis and health risk assessment

Abstract

Red berries are one of the most cultivated crops due to their high nutritional and antioxidant values. However, various pests can attack these fruits, which compels the use of pesticides known for their persistence in these products, causing a risk of food contamination. Hence, this study aims to validate the detection methodology and quantification of 130 pesticides in 177 samples consisting of strawberry (60), raspberry (87), and blueberry (30) using high-performance liquid chromatography-tandem mass spectrometry (LC MS/MS) analysis. Moreover, a risk assessment was carried out to simulate the dietary exposure to the identified pesticides. The methodology was validated with excellent linearity (R 2 >0.99) in the studied range of 0.001 to 0.2 mg/kg. Detection and quantification limits (LOD, LOQ) varied between 0.0001 to 0.02 mg/kg and 0.0004 to 0.07 mg/kg, respectively. Recovery rates (73.22% and 108.50%), relative standard deviation (RSD<20%), and limited matrix effect (ME) confirmed methodology reliability on red berry samples. Out of 177 samples, 87% showed the presence of one or multiple residues, with raspberries showing the highest prevalence (52.6%), followed by strawberries (31.17%), and then blueberries (16.23%). As for the pesticides, difenoconazole was the most frequently detected fungicide (41.81%), followed by fludioxonil (28.81%), and cyprodinil (22.60%), while spinetoram (10.17%) was the most detected insecticide. Moreover, one sample (0.56%) exceeded the Moroccan maximum residue limits (MRLs), whereas 11 samples (6.21%) exceeded the European Union (EU) MRLs. An evaluation dietary risk assessment was carried out using a Monte Carlo approach to estimate the chronic (ADI%) and acute (ARfD%) exposure to the detected pesticide residues. Results showed that chronic risk values ranged from 4.52% to 0.0015%, whereas acute risk values ranged from 5.36% to 0.0082%. Overall, all values were below 100%, indicating a low sanitary risk for the adult consumer population. The pesticides that presented the highest contribution for chronic and acute risk, respectively, were formetanate and pyraclostrobin. Overall, despite the occurrence of pesticide residues, dietary exposure levels indicated a low risk for adult consumers, highlighting the importance of LC-MS/MS-based monitoring in food safety control.