Email this article Methodical approaches to scale-up measurement of glyphosate concentration using HPLC-FLD
- Authors: Fedorova N.E.1, Ivchenkova A.A.1, Stepanova N.A.1, Dobrev S.D.1
-
Affiliations:
- FBES «Federal Scientific Center of Hygiene named after F.F. Erisman» of Federal service for Surveillance on Consumer Rights Protection and Human Wellbeing
- Issue: No 6 (2022)
- Pages: 395-402
- Section: Research methods
- Published: 27.12.2022
- URL: https://rjpbr.com/0869-7922/article/view/641469
- DOI: https://doi.org/10.47470/0869-7922-2022-30-6-395-402
- ID: 641469
Cite item
Full Text
Abstract
Introduction. Traditionally, the hygienic assessment of working conditions when using glyphosate preparations, an extremely popular herbicide in the world, is based on the use of thin layer chromatography. In this paper, alternative approaches are considered. On the basis of experimental data, the conditions for the analysis of glyphosate content in air by high performance liquid chromatography were optimized.
Material and methods. All work with glyphosate solutions was carried out in polypropylene vessels. Sampling from the air medium was carried out on a medium filtration filter (“blue ribbon”). Subsequent extraction was carried out with water. The measurements were performed by high performance liquid chromatography with a fluorimetric detector at an excitation wavelength of 270 nm and an emission wavelength of 313 nm. To transfer glyphosate to a molecule with fluorimetric properties after derivatization of glyphosate in an alkaline medium using 9-fluorenylmethyl chloroformate by heating and washing off the excess of the reagent with toluene. A C18 reverse phase column was used; ammonium acetate with the addition of acetic acid and acetonitrile were used as eluents.
Results. Approbation of the developed technique was carried out on real samples taken during ground treatment of fallow fields and lands of industrial territories with glyphosate preparations. The detected levels of glyphosate did not exceed the lower limit of quantitative determination: 0.5 mg/m3 in the air of the working area and 0.025 mg/m3 in the atmospheric air (with maximum allowable concentrations of 1.0 and 0.1 mg/m3, respectively).
Limitations. The study considers a limited number of chromatographic columns. The study is performed on 25 model samples of the air of the working area and atmospheric air.
Conclusion. Based on the results of the work performed, methodological instructions “Measurement of glyphosate concentrations in the air by high-performance liquid chromatography” were formed and sent for metrological certification in the approved manner.
Compliance with ethical standards: no provision of the conclusion of the Biomedical Ethics Committee or other documents is required.
Author contribution:
Fedorova N.E., Dobrev S.D. — the concept and design of the study;
Stepanova N.A. — collection and processing of the material, statistical analysis;
Ivchenkova A.A. — collection and processing of the material, statistical analysis, writing the text, editing.
All co-authors — approval of the final version of the article, responsibility for the integrity of all parts of the article.
Conflict of interests. The authors declare no conflict of interest.
Funding. The study had no sponsorship.
Received: April 15, 2022 / Accepted: December 12, 2022 / Published: December 30, 2022
About the authors
Nataliya Evgen'evna Fedorova
FBES «Federal Scientific Center of Hygiene named after F.F. Erisman» of Federal service for Surveillance on Consumer Rights Protection and Human Wellbeing
Author for correspondence.
Email: fedorovane@fferisman.ru
ORCID iD: 0000-0001-8278-6382
Доктор биологических наук, главный научный сотрудник отдела аналитических методов контроля ФБУН «Федеральный научный центр гигиены им. Ф.Ф. Эрисмана» Роспотребнадзора, 1410014, г. Мытищи Московской области.
e-mail: fedorovane@fferisman.ru
Russian FederationAnastasiya Aleksandrovna Ivchenkova
FBES «Federal Scientific Center of Hygiene named after F.F. Erisman» of Federal service for Surveillance on Consumer Rights Protection and Human Wellbeing
Email: ivchenkovaaa@fferisman.ru
ORCID iD: 0000-0003-1342-1536
Researcher, FBES «Federal Scientific Center of Hygiene named after F.F. Erisman» of Federal service for Surveillance on Consumer Rights Protection and Human Wellbeing, 141014, Mytishchi, Moscow region, Russian Federation.
e-mail: ivchenkovaaa@fferisman.ru
Russian FederationNataliya Andreevna Stepanova
FBES «Federal Scientific Center of Hygiene named after F.F. Erisman» of Federal service for Surveillance on Consumer Rights Protection and Human Wellbeing
Email: stepanovana@fferisman.ru
ORCID iD: 0000-0001-9188-4881
Ведущий специалист отдела аналитических методов контроля ФБУН «Федеральный научный центр гигиены им. Ф.Ф. Эрисмана» Роспотребнадзора, 1410014, г. Мытищи Московской области.
e-mail: stepanovana@fferisman.ru
Russian FederationSvetoslav Dobrev Dobrev
FBES «Federal Scientific Center of Hygiene named after F.F. Erisman» of Federal service for Surveillance on Consumer Rights Protection and Human Wellbeing
Email: dobrevsd@fferisman.ru
ORCID iD: 0000-0001-9152-1239
Ведущий специалист отдела аналитических методов контроля ФБУН «Федеральный научный центр гигиены им. Ф.Ф. Эрисмана» Роспотребнадзора, 1410014, г. Мытищи Московской области.
e-mail: dobrevsd@fferisman.ru
Russian FederationReferences
- International Programme on Chemical Safety. Environmental Health Criteria 159: Glyphosate. WHO, Geneva: 1994: 113.
- Melo K.G., Nucci D.G., Trape A.Z. Brief review analytical methods for the determination of glyphosate. MedCrave Online Journal of Toxicology. 2018; 4(1): 39–42. https://doi.org/10.15406/mojt.2018.04.00088
- Collection: Guidelines for the determination of trace amounts of pesticides in food, feed and the environment [Sbornik: Metodicheskie ukazaniya po opredeleniyu mikrokolichestv pesticidov v produkta pitaniya, kormax i vneshnej srede]. Moscow: 1991; Chast` 18(1): 15–22. (in Russian)
- Royer T., Beguin S., Tabet J.C., Hulot S., Reding M.A., Communal P.Y. Determination of glyphosate and aminomethylphosphonic acid residues in water by gas chromatography tandem mass spectrometry with ion exchange resin after purification and derivatization. Application on vegetable Matrixes. Journal of Analytical Chemistry. 2000; 72(16): 3826–32. https://doi.org/10.1021/ac000041d
- Collection of guidelines: Determination of residual amounts of pesticides in food products, agricultural raw materials and environmental objects (MUC 4.1.2048 – 4.1.2061-06) [Sbornik metodicheskix ukazanij: Opredelenie ostatochny`x kolichestv pesticidov v pishhevy`x produktax, sel`skoxozyajstvennom sy`r`e i ob``ektax okruzhayushhej sredy` (MUK 4.1.2048 – 4.1.2061-06)]. Moscow: Federal’nyj centr gigieny i epidemiologii Rospotrebnadzora; 2009: 17–27. (in Russian)
- Tereza C.P.G. Catrinck, Amanda Dias, Maria Clara S. Aguiar, Flaviano O. Silverio, Paulo H. FidencioI, Gevany P. Pinho. A Simple and Efficient Method for derivatization of glyphosate and AMPA Using 9–Fluorenylmethyl chloroformate and spectrophotometric Analysis. Journal of the Brazil Chemical Society. 2014; 25(7): 1194–9. https://doi.org/10.5935/0103-5053.20140096
- Botta F., Laviso G., Couturier G., Alliot F., Moreau-Guigon E., Fauchon N. et al. Transfer of glyphosate and AMPA its degradate to surfacewaters through urban sewerage systems. Chemosphere. 2009; 77(1): 133–9. https://doi.org/10.1016/j.chemosphere.2009.05.008
- Sancho J.V., Hernandez M., Lopez F.J., Hogendoorn E.A., Dijkman E. Rapid determination of glufosinate, glyphosate and aminomethylphosphonic acid in environmental water samples using labeling and Fluorogenic precolun column liquid chromatography coupled. Journal of Chromatography. 1996; 1737: 75–83. https://doi.org/10.1016/0021-9673(96)00071-4
- Barcelo D., Mallat E. Analysis and study of degradation of glyphosate and aminomethylphosphonic acid in natural waters by means of ion–exchange polymeric and solid– phase extraction columns Followed by ion chromatography post–column derivatization with fluorescence detection. Journal of Chromatography. 1998; 823(2): 129–36. https://doi.org/10.1016/S0021-9673(98)00362-8
- MUC 4.1.2550-09. Determination of residual amounts of glyphosate in rapeseed seeds and oil by high performance liquid chromatography [MUK 4.1.2550-09. Opredelenie ostatochny`x kolichestv glifosata v semenax i masle rapsa metodom vy`sokoe`ffektivnoj zhidkostnoj xromatografii]. Metodicheskie ukazaniya. Мoscow: Federal’nyj centr gigieny i epidemiologii Rospotrebnadzora; 2009. (in Russian)
- Collection of guidelines: Determination of residual amounts of chemicals in environmental objects, atmospheric air, air of the working area and agricultural products (MUC 4.1.1960, 4.1.1961, 4.1.1963 – 4.1.1980-05) [Sbornik metodicheskix ukazanij: Opredelenie ostatochny`x kolichestv ximicheskix veshhestv v ob``ektax okruzhayushhej sredy`, atmosfernom vozduxe, vozduxe rabochej zony` i sel`skoxozyajstvennoj produkcii (MUK 4.1.1960, 4.1.1961, 4.1.1963 – 4.1.1980-05)]. Moscow: Federal’nyj centr gigieny i epidemiologii Rospotrebnadzora; 2007: 169–80. (in Russian)
- MUC 4.1.3513-17. Determination of residual amounts of glyphosate in the green mass of plants, grain and straw of cereal crops, pea grain, corn grain, sunflower seeds, rapeseed, flax, soybeans, vegetable oil, fruits and juice of pome fruits and stone fruits, berries and grape juice by a highly effective method liquid chromatography. Methodical instructions [MUK 4.1.3513-17. Opredelenie ostatochny`x kolichestv glifosata v zelenoj masse rastenij, zerne i solome zernovy`x kolosovy`x kul`tur, zerne goroxa, zerne kukuruzy`, semenax podsolnechnika, rapsa, l`na, bobax soi, rastitel`nom masle, plodax i soke plodovy`x semechkovy`x i plodovy`x kostochkovy`x, yagodax i soke vinograda metodom vy`sokoe`ffektivnoj zhidkostnoj xromatografii. Metodicheskie ukazaniya]. Moscow: Federal`naya sluzhba po nadzoru v sfere zashhity` prav potrebitelej i blagopoluchiya cheloveka; 2018. (in Russian)
- SanPin 1.2.3685–21. Hygienic standards and requirements for ensuring the safety and (or) harmlessness of environmental factors to humans. Sanitary and epidemiological rules and regulations (approved by the resolution of the Chief State Doctor of the Russian Federation of 28.01.2021; No. 2. [SanPiN 1.2.3685–21. Gigienicheskie normativy` i trebovaniya k obespecheniyu bezopasnosti i (ili) bezvrednosti dlya cheloveka faktorov sredy` obitaniya. Sanitarno-e`pidemiologicheskie pravila i normativy` (utv. Postanovleniem Glavnogo gosudarstvennogo vracha RF ot 28.01.2021 No. 2. (in Russian)
- Jamilu Garba, Abd Wahid Samsuri, Radziah Othman, Muhammad Saiful Ahmad Hamdani. Simplified method for derivatization of extractable glyphosate and aminomethylphosphonic acid and their determination by high performance liquid chromatography. Environmental Research and Technology. 2018; 1(2): 19–30.
- List of measurements related to the sphere of state regulation of ensuring the uniformity of measurements, approved by resolution of the Government of the Russian Federation of 16.11.2020 N 1847 “On approval of the list of measurements related to the sphere of state regulation of ensuring the uniformity of measurements.”[Perechen` izmerenij, otnosyashhixsya k sfere gosudarstvennogo regulirovaniya obespecheniya edinstva izmerenij, utverzhdenny`x postanovleniem Pravitel`stva RF ot 16.11.2020 No. 1847 “Ob utverzhdenii perechnya izmerenij, otnosyashhixsya k sfere gosudarstvennogo regulirovaniya obespecheniya edinstva izmerenij”]. (in Russian)
Supplementary files
