State Institution «Kundiiev Institute of Occupational Health of the National Academy of Medical Sciences of Ukraine», Kyiv, Ukraine
Introduction. In Ukraine, the system of state registration of pesticides and agrochemicals requires comprehensive field tests with a mandatory assessment of the working conditions during their use and the occupational risk associated with exposure to pesticides based on hygienic monitoring (measuring pesticide concentrations in air and soil) and passive dosimetry (studying contamination of the operator's skin surface and overalls).
The aim of the research – to analyze the current state of the methodology and summarize our own experience in studying the exposure of operators to pesticides to substantiate safe conditions for their use in agriculture.
Materials and methods of the research. High-performance liquid chromatography (HPLC) and gas-liquid chromatography (GLC), as well, as HPLC and GLC with mass spectrometric (MS) detection (HPLC-MMS/MS, GLC-MS) in accordance with international requirements SANTE/2020/12830, Rev.2 14. February 2023. The QuEChERS sample preparation methodology in combination with GC and HPLC methods was used to determine trace amounts of pesticides in soil. The following equipment (software) was used: liquid chromatographs "LC 240" (with "TOTALCHROM" program) "PERKIN-ELMER", USA and "LC-20XR" (with "LabSolutions" program), “SHIMADZU”, Japan, gas chromatographs "CRYSTALUX-4000M" (with "NETCHROM" program) and "Clarus 600 GC" (with "TURBOCHROM" program, mass spectra database "NIST-11") "PERKIN-ELMER", USA.
Results. Chromatographic studies showed that in some instances the results of passive dosimetry (determination of contamination of the operator's skin surface and overalls) indicate the presence of exposure to pesticides even when the air pollution in the work area is below the limits of its quantification by GC and/or HPLC methods.
Conclusion. The results of combining hygienic monitoring with passive dosimetry allowed not only to evaluate the technologies of using different types of pesticides (fungicides, herbicides, insecticides, etc.), but also to calculate the absorbed dose when they enter the body by inhalation and percutaneous routes, to determine the degree of risk for workers, and, therefore, to develop appropriate hygienic regulations for the safe entry of workers into pesticide-treated areas ("exit times" for manual and mechanized work) and recommendations, i.e. to substantiate safe conditions for the use of pesticides in agriculture.
Key words: pesticides application, hygienic monitoring, high-performance liquid chromatography, gas-liquid chromatography, passive dosimetry, exposure, operators
References
1. [List of pesticides and agrochemicals that are allowed for use in Ukraine]. Official publication. Kyiv: Ministry of Environmental Protection and Natural
Resources of Ukraine, Univest Media; 2023. 1024 p. Ukrainian. Available from: https://eco.gov.ua/registers/perelik-pesticidiv-i-agrohimikativ-dozvolenih-dlyavikoristannya.
2. The Application of the GLP Principles to Field Studies. – OECD Series on Principles of GLP and Compliance Monitoring. Number 6 (Revised). ENV/JM/MONO (99) 22. [Internet] 1999 [cited 2023 Sep 20]. Available from: https://portail-qualite.public.lu/damassets/fr/publications/prestataires-services/bonnespratiques-laboratoire/rapports-application/bpl-6/bpl-6-en.pdf.
3. EFSA (European Food Safety Authority). Guidance on the assessment of exposure of operators, workers, residents and bystanders in risk assessment for plant
protection products. EFSA Journal. 2014;12(10):3874. DOI: https://doi.org/10.2903/j.efsa.2014.3874.
4. SANTE/2020/12830, Rev.2. Guidance Document on Pesticide Analytical Methods for Risk Assessment and Post-approval Control and Monitoring Purposes1 Supersedes Guidance Documents SANCO/3029/992 and SANCO/825/00. [Internet] 2023 Feb [cited 2023Sep 20. Available from: https://food.ec.europa.eu/document/download/d8f2d86294ea-412d-a0ddc037e41898b2_en?filename=pesticides_mrl_guidelines_2020-12830.pdf.
5. European Commission Directorate General Health and Consumer Protection. SANCO/3030/99 rev. 5 (22 March 2019). Technical Active Substance and Plant protection products: Guidance for generating and reporting methods of analysis in support of pre- and post-registration data requirements for Annex (Section 4) of Regulation (EU) No. 283/2013 and Annex (Section 5) of Regulation (EU) No. 284/2013. Available from: https://food.ec.europa.eu/system/files/2019-03/pesticides_ppp_appproc_guide_physchem-ana_3030.pdf
6. Anastassiades M, Lehotay SJ, Stajnbaher D, Schenck FJ. Fast and Easy Multiresidue Method Employing Acetonitile Extraction / Partitioning and "Dispersive Solid-Phase Extraction" for the Determination of Pesticide Residues in Produce. J. AOAC Int. 2003;86:412-31. DOI: https://doi.org/10.1093/jaoac/86.2.412.
7. EN 15662:2019 Foods of plant origin – Multimethod for the determination of pesticide residues using GC- and LC-based analysis following acetonitrile extraction/partitioning and clean-up by dispersive SPE – Modular QuEChERS-method. Available from: https://www.en-standard.eu/une-en-15662-2019-foods-of-plant-origin-multimethod-for-the-determination-of-pesticide-residues-using-gc-and-lc-basedanalysis-following-acetonitrile-extraction-partitioningand-clean-up-by-dispersive-spe-modular-quechersmethod.
8. Yastrub TO, Baranov YuS, Demchenko VF, Zayets ER. [Toxicological and hygienic assessment of the combined preparation based on S-metolachlor and terbuthylazine and determination of residual amounts of pesticides in soil, grain and oil crops using QuEChERS sample preparation]. Ukrainian Journal of Occupational Health. 2022;3:204-15. DOI: https://doi.org/10.33573/ujoh2022. Ukrainian.