Abstract
This paper illustrates the non-target impact of imidacloprid (IM) residues on the grape global metabolome and biomarker identification with high-resolution mass spectrometry. IM was applied at the recommended dose (SD), and ten times SD (10 RD). The global metabolome analysis revealed that 21 metabolites were up- and down-regulated with IM SD treatment. In 10 RD, 9 metabolites were upregulated, and 28 were downregulated. Pathway enrichment analysis revealed the primary and secondary pathway disruption in grapes. Berry quality was affected with decrease in flavonoids by 32.97% in 10 RD; phenols were reduced by 53.93 in SD, 50.8% in 10 RD. The non-target and target study revealed the degradation of IM in grapes to desnitro-IM and IM-urea which were identified as a potential biomarker for IM residues in grapes, which would benefit the authentication of organic product. Overall, imidacloprid showed a significant impact on the grape metabolome and quality.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Data availability
Data associated with the manuscript will be available on request.
Abbreviations
- IM:
-
Imidacloprid
- SD:
-
Recommended dose
- DD:
-
Double of recommended dose
- 10 RD:
-
10 Times recommended dose
- BLQ:
-
Below limit of quantitation
- MRL:
-
Maximum residue level
- HRMS:
-
High-resolution mass spectrometry
- PCA:
-
Principal component analysis
- OPLS-DA:
-
Orthogonal projections to latent structure discriminant analysis
References
Andrew James C, Strand Stuart E (2009) Phytoremediation of small organic contaminants using transgenic plants. Curr Opin Biotechnol 20(2):237–241
Blondel C, Khelalfa F, Reynaud S, Fauvelle F, Raveton M (2016) Effect of organochlorine pesticides exposure on the maize root metabolome assessed using high-resolution magic-angle spinning 1H NMR spectroscopy. Environ Pollut 214:539–548. https://doi.org/10.1016/j.envpol.2016.04.057
Bourgin M, Violleau F, Debrauwer L, Albet J (2011) Ozonation of imidacloprid in aqueous solutions: reaction monitoring and identification of degradation products. J Hazard Mater 190(1–3):60–68. https://doi.org/10.1016/j.jhazmat.2011.02.065
Brennan J, Hackett R, McCabe T, Grant J, Fortune R, Forristal P (2014) The effect of tillage system and residue management on grain yield and nitrogen use efficiency in winter wheat in a cool Atlantic climate. Eur J Agron 54(61):69. https://doi.org/10.1016/j.eja.2013.11.009
EH Chang S Jeong YY Hur SW Koh IM Choi 2015 Changes of volatile compounds in Vitis labrusca ‘Doonuri’ grapes during stages of fruit development and in wine Horticult Environ Biotechnol 56 137 44 https://doi.org/10.1007/s13580-015-0068-3
Chauhan SS, Agrawal S, Srivastava AN (2013) Effect of imidacloprid insecticide residue on biochemical parameters in potatoes and its estimation by HPLC. Asian J. Pharm. Clin. Res 6(3):114–117 (https://innovareacademics.in/journals/index.php/ajpcr/article/view/291)
Cheng X, Chen K-X, Jiang N-D, Wang L, Jiang H-Y, Zhao Y-X, Dai Z-L, Dai Y-J (2022) Nitroreduction of imidacloprid by the actinomycete Gordonia alkanivorans and the stability and acute toxicity of the nitroso metabolite. Chemosphere 291:132885. https://doi.org/10.1016/j.chemosphere.2021.132885
Chun OK, Kim DO, Moon HY, Kang HG, Lee CY (2003) Contribution of individual polyphenolics to total antioxidant capacity of plums. J Agric Food Chem 51(25):7240–7245. https://doi.org/10.1021/jf0343579
Coats J. Pesticide degradation mechanisms and environmental activation 1991. http://lib.dr.iastate.edu/ent_pubs/379.
Davies C, Boss P, Geros H, Lecourieux F, Delrot S (2012) Source/sink relationships and molecular biology of sugar accumulation in grape berries. Biochem Grape Berry 44:66. https://doi.org/10.2174/978160805360511201010044
Deng Y, Lu S (2017) Biosynthesis and regulation of phenylpropanoids in plants. Crit Rev Plant Sci 36(4):257–290. https://doi.org/10.1080/07352689.2017.1402852
P Deore S Hingmire D Shinde A Pudale T Shabeer K Banerjee R Thosar S Saha 2021 Field bio-efficacy and residue dynamics of the fungicide polyoxin D zinc salt 5% SC in grape (Vitis vinifera) Int J Bio-Resource Stress Manag 12 6 603 610 https://doi.org/10.23910/1.2021.2455
Deore P, Shabeer TA, Upadhyay A, Sharma AK, Devarumath R, Kale R (2023) Non-target impact of imidacloprid residues on wine aroma characteristics assessed by GC×GC-TOF/MS analysis and its residual transformation in vinification by UHPLC-Orbitrap-MS analysis. Microchem J 109834.
Drappier J, Thibon C, Rabot A, Geny-Denis L (2019) Relationship between wine composition and temperature: impact on Bordeaux wine typicity in the context of global warming. Crit Rev Food Sci Nutr 59(1):14–30. https://doi.org/10.1080/10408398.2017.1355776
Duan S, Wu Y, Fu R, Wang L, Chen Y, Xu W, Zhang C, Ma C, Shi J, Wang S (2019) Comparative metabolic profiling of grape skin tissue along grapevine berry developmental stages reveals systematic influences of root restriction on skin metabolome. Int J Mol Sci 20(3):534. https://doi.org/10.3390/ijms20030534
El-Sobki AE, Saad AM, El-Saadony MT, El-Tahan AM, Taha AE, Aljuaid BS, El-Shehawi AM, Salem RE (2021) Fluctuation in amino acids content in Triticum aestivum L. cultivars as an indicator on the impact of post-emergence herbicides in controlling weeds. Saudi J Biol Sci 28(11):6332–6338. https://doi.org/10.1016/j.sjbs.2021.06.097
Gloria MBA, Vieira SM (2007) Technological and toxicological significance of bioactive amines in grapes and wines. Food 1(2):258
Gregan SM (2019) A study of amino acid metabolism in grape berries (Vitis vinifera L. Sauvignon blanc): a thesis submitted in partial fulfilment of the requirements for the degree of Doctor of Philosophy in Biochemistry at Lincoln University. Lincoln University.
Gur L, Cohen Y, Frenkel O, Schweitzer R, Shlisel M, Reuveni M (2022) Mixtures of macro and micronutrients control grape powdery mildew and alter berry metabolites. Plants 11(7):978. https://doi.org/10.3390/plants11070978
Jacyna J, Kordalewska M, Markuszewski MJ (2019) Design of Experiments in metabolomics-related studies: an overview. J Pharm Biomed Anal 5(164):598–606
Jaleel CA, Ragupathi G, Panneerselvam R (2008) Biochemical alterations in white yam (Dioscorea rotundata Poir.) under triazole fungicides: impacts on tuber quality. Czech Journal of Food Science 26(4):297–307. https://doi.org/10.17221/1117-CJFS
Laura A, Moreno-Escamilla JO, Rodrigo-García J, Alvarez-Parrilla E (2019) Phenolic compounds. In Postharvest physiology and biochemistry of fruits and vegetables Elsevier pp 253–271.
Lee J, Durst RW, Wrolstad RE, Eisele T, Giusti MM, Hach J, Hofsommer H, Koswig S, Krueger DA, Kupina S, Martin SK, Martinsen BK, Miller TC, Paquette F, Ryabkova A, Skrede G, Trenn U, Wightman JD (2005) Determination of total monomeric anthocyanin pigment content of fruit juices, beverages, natural colorants, and wines by the pH differential method collaborative study. J AOAC Int 88(5):1269–1278. https://doi.org/10.1093/jaoac/88.5.1269
Liu W, Zheng W, Ma Y, Liu KK (2006) Sorption and degradation of imidacloprid in soil and water. J Environ Sci Health B 41(5):623–634. https://doi.org/10.1080/03601230600701775
Lu Feng Fan, Jin Tong Liu, Nan Zhang, Zhao Jie Chen, Hong Yang (2020) Ospal as a key salicylic acid synthetic component is a critical factor involved in mediation of isoproturon degradation in a paddy crop J Clean Prod 262:121476.
Mahdavi V, Farimani MM, Fathi F, Ghassempour A (2015) A targeted metabolomics approach toward understanding metabolic variations in rice under pesticide stress. Anal Biochem 478:65–72. https://doi.org/10.1016/j.ab.2015.02.021
Mohapatra S, Ahuja AK, Sharma D, Deepa M, Prakash GS, Kumar S (2011) Residue study of imidacloprid in grapes (Vitis vinifera L.) and soil. Qual Assur Safety Crops Foods 3(1):24–27. https://doi.org/10.1111/j.1757-837X.2010.00084.x
Nantia A, Manfo F, Sonchieu J, Choumessi A, Bopuwouo R, Kakwang I, Lum D, Kenfack A (2017) Effect of agrochemicals use on total phenolic compounds and flavonoid content in aromatic fresh herbs from Santa (Cameroon). Acad J Agricult Res 5(2):18–27. https://doi.org/10.15413/ajar.2017.0207
Ospina M, Baker S, Bishop-Serafim A, Morales-Agudelo P, Calafat A (2020) Identification of biomarkers of neonicotinoid insecticides for human exposure assessment using biomonitoring. In ISEE Conference Abstracts 2020 https://doi.org/10.1289/isee.2020.virtual.P-0783.
Panche A, Chandra S, Ad D, Harke S (2015) Alzheimer’s and current therapeutics: a review. Asian J Pharm Clin Res 8(3):14–19 (https://innovareacademics.in/journals/index.php/ajpcr/article/view/5196)
Pereira SI, Figueiredo PI, Barros AS, Dias MC, Santos C, Duarte IF, Gil AM (2014) Changes in the metabolome of lettuce leaves due to exposure to mancozeb pesticide. Food Chem 154:291–298. https://doi.org/10.1016/j.foodchem.2014.01.019
Reddy BK, Bhuvaneswari K, Sadhineni M (2022) Dissipation dynamics and risk assessment of imidacloprid in grape berries using LC-MS for food safety. Int J Environ Clim Change 12(12):1458–67. https://doi.org/10.9734/ijecc/2022/v12i121586
Ribereau-Gayon P, Glories Y, Maujean A, Dubourdieu D (2021) Handbook of Enology 2: The chemistry of wine stabilization and treatments John Wiley & Sons
Salem MA, Perez de Souza L, Serag A, Fernie AR, Farag MA, Ezzat SM, Alseekh S (2020) Metabolomics in the context of plant natural products research from sample preparation to metabolite analysis. Metabolites 10(1):37
SANTE (2021) SANTE/11312/2021. Analytical quality control and method validation procedures for pesticide residues analysis in food and feed. https://www.eurlpesticides.eu/userfiles/file/EurlALL/SANTE_11312_2021.pdf
Schoning R, Schmuck R (2003) Analytical determination of imidacloprid and relevant metabolite residues by LC MS/MS. Bull Insectol 56:41–50
Schusterova D, Hajslova J, Kocourek V, Pulkrabova J (2021) Pesticide residues and their metabolites in grapes and wines from conventional and organic farming system. Foods 10(2):307. https://doi.org/10.3390/foods10020307
Shabeer TPA, Jadhav M, Girame R, Hingmire S, Bhongale A, Pudale A, Banerjee K (2017) Targeted screening and safety evaluation of 276 agrochemical residues in raisins using buffered ethyl acetate extraction and liquid chromatography–tandem mass spectrometry analysis. Chemosphere 184:1036–1042. https://doi.org/10.1016/j.chemosphere.2017.06.086
Shabeer TP, Rushali G, Sandip H, Manjusha J, Prachi J (2020) Residue dissipation, evaluation of processing factor and safety assessment of hexythiazox and bifenazate residues during drying of grape to raisin. Environ Sci Pollut Res 27:41816–41823. https://doi.org/10.1007/s11356-020-10169-5
Shabeer TP, Ghotgalkar P, Ekatpure S, Bhanbhane V, Pardeshi A, Deore P (2023) Assessment of degradation mechanism of imidacloprid residues in grape rhizosphere soil by UHPLC-Orbitrap™-MS and its residual impact on soil enzyme activity. Environ Sci Pollut Res 13:1–2. https://doi.org/10.1007/s11356-023-31285-y
Shakir SK, Irfan S, Akhtar B, Rehman SU, Daud MK, Taimur N, Azizullah A (2018) Pesticide-induced oxidative stress and antioxidant responses in tomato (Solanum lycopersicum) seedlings. Ecotoxicology 27:919–935. https://doi.org/10.1007/s10646-018-1916-6
Sheets LP (2010) Imidacloprid a neonicotinoid insecticide In: Hayes handbook of pesticide toxicology 2055–2064, Academic Press.
Singleton VL, Rossi JA (1965) Colorimetry of total phenolics with phosphomolybdic-phosphotungstic acid reagents. Am J Enol Viticult 16(3):144–158 (https://www.ajevonline.org/content/16/3/144)
Somasundaram L, Joel R Coats (1991) Pesticide transformation products in the environmen
Stines A, Grubb J, Gockowiak H, Henschke PA, Høj P, Van Heeswijck R (2000) Proline and arginine accumulation in developing berries of Vitis vinifera L. in Australian vineyards: influence of vine cultivar, berry maturity and tissue type. Aust J Grape Wine Res 6(2):150–158. https://doi.org/10.1111/j.1755-0238.2000.tb00174.x
Thurman EM, Ferrer I, Zavitsanos P, Zweigenbaum JA (2013) Identification of imidacloprid metabolites in onion (Allium cepa L.) using high-resolution mass spectrometry and accurate mass tools. Rapid Commun Mass Spectr 27(17):1891–1903. https://doi.org/10.1002/rcm.6637
Vogt T (2010) Phenylpropanoid biosynthesis. Mol Plant 3(1):2–20. https://doi.org/10.1093/mp/ssp106
Xiao JF, Zhou B, Ressom HW (2012) Metabolite identification and quantitation in LC-MS/MS-based metabolomics. TrAC, Trends Anal Chem 32:1–4. https://doi.org/10.1016/j.trac.2011.08.009
Zein AL, Valluru G, Georghiou PE (2012) Recent asymmetric syntheses of tetrahydroisoquinolines using “named” and some other newer methods. In: Atta ur R Studies in Natural Products Chemistry. Elsevier 53–80.
Zhang Y, Huang L, Liu L, Cao X, Sun C, Lin X (2022) Metabolic disturbance in lettuce (Lactuca sativa) plants triggered by imidacloprid and fenvalerate. Sci Total Environ 802:149764. https://doi.org/10.1016/j.scitotenv.2021.149764
Zhang Jing Jing, Jiang Yan Xu, Feng Fan Lu, She Feng Jin, Hong Yang (2017) Detoxification of atrazine by low molecular weight thiols in alfalfa (Medicago sativa) Chem Res Toxicol 30(10): 1835–1846. .
Zhao Z-M, Shang X-F, Lawoe RK, Liu Y-Q, Zhou R et al (2019) Anti-phytopathogenic activity and the possible mechanisms of action of isoquinoline alkaloid sanguinarine. Pestic Biochem Physiol 159:51–58. https://doi.org/10.1016/j.pestbp.2019.05.015
Author information
Authors and Affiliations
Contributions
Execution of experiment, statistical evaluation, and preliminary draft preparation: Pushpa Deore. Conceptualisation, methodology, design, and final manuscript: Ahammed Shabeer T. P. Final manuscript review: Anuradha Upadhyay and Rachayya Devarumath. All authors read and approved the final manuscript.
Corresponding author
Ethics declarations
Ethical approval
The authors confirm that:
• The manuscript has not submitted to more than one journal (Journal of Environmental Science and Pollution research) for simultaneous consideration.
• The submitted work is original and not have been published elsewhere in any form or language (partially or in full).
• Results are presented clearly, honestly, and without fabrication, falsification, or inappropriate data manipulation.
• No data, text, or theories by others are presented as if they were the author’s own (‘plagiarism’). Proper acknowledgements to other works are given.
Human and animal rights
The work does not include any human participants and/or animals.
Informed consent
Not applicable.
Consent to participate
Not applicable.
Consent for publication
Not applicable.
Competing interests
The authors declare no competing interests.
Additional information
Responsible Editor: Ester Heath
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Deore, P., Thekkumpurath, A.S., Upadhyay, A. et al. Non-target influence of imidacloprid residues on grape global metabolome and berry quality with the identification of metabolite biomarkers. Environ Sci Pollut Res 31, 15770–15787 (2024). https://doi.org/10.1007/s11356-024-32134-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-024-32134-2