{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,7]],"date-time":"2026-06-07T12:46:21Z","timestamp":1780836381222,"version":"3.54.1"},"reference-count":36,"publisher":"MDPI AG","issue":"15","license":[{"start":{"date-parts":[[2023,7,28]],"date-time":"2023-07-28T00:00:00Z","timestamp":1690502400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"National Natural Science Foundation of China","award":["32160656"],"award-info":[{"award-number":["32160656"]}]},{"name":"National Natural Science Foundation of China","award":["[2021] Yiban059"],"award-info":[{"award-number":["[2021] Yiban059"]}]},{"name":"National Natural Science Foundation of China","award":["GCC [2022]023-1"],"award-info":[{"award-number":["GCC [2022]023-1"]}]},{"name":"National Natural Science Foundation of China","award":["(2019) 09"],"award-info":[{"award-number":["(2019) 09"]}]},{"name":"Project of Application and Industrialization of Scientific-technological Achievement of Guizhou Province","award":["32160656"],"award-info":[{"award-number":["32160656"]}]},{"name":"Project of Application and Industrialization of Scientific-technological Achievement of Guizhou Province","award":["[2021] Yiban059"],"award-info":[{"award-number":["[2021] Yiban059"]}]},{"name":"Project of Application and Industrialization of Scientific-technological Achievement of Guizhou Province","award":["GCC [2022]023-1"],"award-info":[{"award-number":["GCC [2022]023-1"]}]},{"name":"Project of Application and Industrialization of Scientific-technological Achievement of Guizhou Province","award":["(2019) 09"],"award-info":[{"award-number":["(2019) 09"]}]},{"name":"Hundred Level Innovative Talent Foundation of Guizhou","award":["32160656"],"award-info":[{"award-number":["32160656"]}]},{"name":"Hundred Level Innovative Talent Foundation of Guizhou","award":["[2021] Yiban059"],"award-info":[{"award-number":["[2021] Yiban059"]}]},{"name":"Hundred Level Innovative Talent Foundation of Guizhou","award":["GCC [2022]023-1"],"award-info":[{"award-number":["GCC [2022]023-1"]}]},{"name":"Hundred Level Innovative Talent Foundation of Guizhou","award":["(2019) 09"],"award-info":[{"award-number":["(2019) 09"]}]},{"name":"Cultivation Program of Guizhou University","award":["32160656"],"award-info":[{"award-number":["32160656"]}]},{"name":"Cultivation Program of Guizhou University","award":["[2021] Yiban059"],"award-info":[{"award-number":["[2021] Yiban059"]}]},{"name":"Cultivation Program of Guizhou University","award":["GCC [2022]023-1"],"award-info":[{"award-number":["GCC [2022]023-1"]}]},{"name":"Cultivation Program of Guizhou University","award":["(2019) 09"],"award-info":[{"award-number":["(2019) 09"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Foods"],"abstract":"<jats:p>3,4-dichloroaniline (3,4-DCA) and 3,5-dichloroaniline (3,5-DCA) are, respectively, the primary metabolites deriving from the breakdown of phenylurea herbicides and dicarboximide fungicides in both soils and plants, whose residues in vegetable products have a heightened concern considering their higher health risks to humans and greater toxicity than the parent compounds in the environment. In this study, a sensitive high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS\/MS) method was developed for the simultaneous determination of 3,4-DCA and 3,5-DCA residues in chive products based on the optimization of HPLC-MS\/MS chromatographic and mass-spectrometric conditions using the standard substances and the modified QuEChERS preparation technique. The preparation efficiency of 3,4-DCA and 3,5-DCA from chive samples showed that acetonitrile was the best extractant. The combination of the purification agent graphite carbon black + primary secondary amine and the eluting agent acetonitrile + toluene (4:1, v\/v) had a satisfactory purification effect. The linear correlation coefficients (R2) were more than 0.996 with the six concentration range of 0.001\u20131.000 mg\/L for 3,4-DCA and 3,5-DCA. The limit of detection and limit of quantitation of this method was 0.6 and 2.0 \u00b5g\/kg for 3,4-DCA, as well as 1.0 and 3.0 \u00b5g\/kg for 3,5-DCA, respectively. The matrix effect range of 3,4-DCA and 3,5-DCA in chive tissues was from \u22129.0% to \u22122.6% and from \u22124.4% to 2.3%, respectively. The fortified recovery of 3,4-DCA and 3,5-DCA in chive samples at four spiked levels of 0.001\u20131.000 mg\/kg was 75.3\u201386.0% and 78.2\u201398.1%, with the relative standard deviation of 2.1\u20138.5% and 1.4\u201311.9%, respectively. The limit of detection (LOD) and limit of quantification (LOQ) of the method were 0.6, 2.0, and 1.0, 3.03 for 4-DCA and 3,5-DCA, respectively. This study highlights that the analytical method established here can efficiently and sensitively detect residues of 3,4-DCA and 3,5-DCA residues for monitoring chive products. The method was successfully applied to 60 batches of actual vegetable samples from different regions.<\/jats:p>","DOI":"10.3390\/foods12152875","type":"journal-article","created":{"date-parts":[[2023,7,31]],"date-time":"2023-07-31T01:39:32Z","timestamp":1690767572000},"page":"2875","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":9,"title":["Development of Simultaneous Determination Method of Pesticide High Toxic Metabolite 3,4-Dichloroaniline and 3,5 Dichloroaniline in Chives Using HPLC-MS\/MS"],"prefix":"10.3390","volume":"12","author":[{"given":"Yibo","family":"Dong","sequence":"first","affiliation":[{"name":"Institute of Crop Protection, Guizhou University, Guiyang 550025, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2547-7556","authenticated-orcid":false,"given":"Xiaolong","family":"Yao","sequence":"additional","affiliation":[{"name":"Institute of Crop Protection, Guizhou University, Guiyang 550025, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wanping","family":"Zhang","sequence":"additional","affiliation":[{"name":"Institute of Vegetable Research, Guizhou University, Guiyang 550025, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaomao","family":"Wu","sequence":"additional","affiliation":[{"name":"Institute of Crop Protection, Guizhou University, Guiyang 550025, China"},{"name":"Institute of Vegetable Research, Guizhou University, Guiyang 550025, China"},{"name":"Provincial Key Laboratory for Agricultural Pest Management in Mountainous Region, Guizhou University, Guiyang 550025, China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2023,7,28]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1291","DOI":"10.2298\/JSC091219103S","article-title":"Toxicity of Five Anilines to Crustaceans, Protozoa and Bacteria","volume":"75","author":"Mortimer","year":"2010","journal-title":"J. Serb. Chem. Soc."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"120606","DOI":"10.1016\/j.jhazmat.2019.04.089","article-title":"Removal of dimethachlon from soils using immobilized cells and enzymes of a novel potential degrader Providencia stuartii JD","volume":"378","author":"Zhang","year":"2019","journal-title":"J. Hazard. Mater."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"749","DOI":"10.1016\/j.scitotenv.2019.07.087","article-title":"Improvement of Pesticide Removal in Contaminated Media Using Aqueous Extracts from Contaminated Biopurification Systems","volume":"691","author":"Romero","year":"2019","journal-title":"Sci. Total Environ."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"97","DOI":"10.1016\/j.chemosphere.2007.10.006","article-title":"Pesticides Removal in the Process of Drinking Water Production","volume":"71","author":"Ormad","year":"2008","journal-title":"Chemosphere"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"304","DOI":"10.1016\/j.scitotenv.2016.02.019","article-title":"The Metabolite 3,4,3\u2032,4\u2032-Tetrachloroazobenzene (TCAB) Exerts a Higher Ecotoxicity than the Parent Compounds 3,4-Dichloroaniline (3,4-DCA) and Propanil","volume":"551\u2013552","author":"Xiao","year":"2016","journal-title":"Sci. Total Environ."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"129887","DOI":"10.1016\/j.jhazmat.2022.129887","article-title":"N-Acetylation of Toxic Aromatic Amines by Fungi: Strain Screening, Cytotoxicity and Genotoxicity Evaluation, and Application in Bioremediation of 3,4-Dichloroaniline","volume":"441","author":"Rodrigues","year":"2023","journal-title":"J. Hazard. Mater."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"260","DOI":"10.1080\/10934529.2017.1394701","article-title":"State of the Art of the Environmental Behaviour and Removal Techniques of the Endocrine Disruptor 3,4-Dichloroaniline","volume":"53","author":"Tasca","year":"2018","journal-title":"J. Environ. Sci. Health Part A"},{"key":"ref_8","doi-asserted-by":"crossref","unstructured":"Schiwy, S., Herber, A.-K., Hollert, H., and Brinkmann, M. (2020). New Insights into the Toxicokinetics of 3,4-Dichloroaniline in Early Life Stages of Zebrafish (Danio Rerio). Toxics, 8.","DOI":"10.3390\/toxics8010016"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"5949","DOI":"10.1039\/C6AY01298A","article-title":"Development and Validation of a Fast and Simple HPLC Method for the Simultaneous Determination of Aniline and Its Degradation Products in Wastewater","volume":"8","author":"Boulahlib","year":"2016","journal-title":"Anal. Methods"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"367","DOI":"10.1016\/j.marpolbul.2016.02.037","article-title":"Antifouling Paint Booster Biocides (Irgarol 1051 and Diuron) in Marinas and Ports of Bushehr, Persian Gulf","volume":"105","author":"Saleh","year":"2016","journal-title":"Mar. Pollut. Bull."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"149","DOI":"10.1002\/(SICI)1098-2256(1998)13:2<149::AID-TOX6>3.0.CO;2-7","article-title":"Acute Toxicity of Chlorinated Organic Chemicals to the Embryos and Larvae of the Marine WormPlatynereis Dumerilii (Polychaeta: Nereidae)","volume":"13","author":"Hutchinson","year":"1998","journal-title":"Environ. Toxicol. Water Qual."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"2975","DOI":"10.1016\/S0045-6535(98)00338-5","article-title":"Microalgal Ecotoxicity Test with 3,4-Dichloroaniline","volume":"37","author":"Tyrawska","year":"1998","journal-title":"Chemosphere"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"149","DOI":"10.1016\/S1382-6689(02)00004-2","article-title":"Interspecies Sensitivity in the Aquatic Toxicity of Aromatic Amines","volume":"11","author":"Ramos","year":"2002","journal-title":"Environ. Toxicol. Phar."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"1132","DOI":"10.1016\/j.chemosphere.2012.09.021","article-title":"Developmental Toxicity of 3,4-Dichloroaniline on Rare Minnow (Gobiocypris Rarus) Embryos and Larvae","volume":"90","author":"Zhu","year":"2013","journal-title":"Chemosphere"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"33","DOI":"10.1007\/BF00025817","article-title":"Ecotoxicological Studies with the Freshwater Rotifer Brachionus Calyciflorus II. An Assessment of the Chronic Toxicity of Lindane and 3,4-Dichloroaniline Using Life Tables","volume":"255\u2013256","author":"Ferrando","year":"1993","journal-title":"Hydrobiologia"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"193","DOI":"10.1007\/s00244-001-0010-9","article-title":"The Juvenile Growth Rate of Daphnia: A Short-Term Alternative to Measuring the Per Capita Rate of Increase in Ecotoxicology?","volume":"42","author":"Lampert","year":"2002","journal-title":"Arch. Environ. Contam. Toxicol."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"453","DOI":"10.1016\/S0045-6535(99)00223-4","article-title":"Determination of Presence of Fungicides by Their Common Metabolite, 3,5-DCA, in Compost","volume":"41","author":"Vanni","year":"2000","journal-title":"Chemosphere"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"271","DOI":"10.1016\/j.foodchem.2017.01.062","article-title":"Role of Structural Barriers in the in Vitro Bioaccessibility of Anthocyanins in Comparison with Carotenoids","volume":"227","author":"Carrillo","year":"2017","journal-title":"Food Chem."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"1505","DOI":"10.1002\/rcm.6598","article-title":"Ultraviolet Degradation of Procymidone\u2014Structural Characterization by Gas Chromatography Coupled with Mass Spectrometry and Potential Toxicity of Photoproducts Using in Silico Tests: UV Degradation of Procymidone","volume":"27","author":"Rifai","year":"2013","journal-title":"Rapid Commun. Mass Spectrom."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"163","DOI":"10.1016\/j.envres.2018.10.018","article-title":"Evaluation of Potential Carcinogenicity of Organic Chemicals in Synthetic Turf Crumb Rubber","volume":"169","author":"Perkins","year":"2019","journal-title":"Environ. Res."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"207","DOI":"10.1016\/0378-4274(95)03249-K","article-title":"3,5-Dichloroaniline Toxicity in Fischer 344 Rats Pretreated with Inhibitors and Inducers of Cytochrome P450","volume":"78","author":"Valentovic","year":"1995","journal-title":"Toxicol. Lett."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"129577","DOI":"10.1016\/j.chemosphere.2021.129577","article-title":"Toxicity Effects of Procymidone, Iprodione and Their Metabolite of 3,5-Dichloroaniline to Zebrafish","volume":"272","author":"Lai","year":"2021","journal-title":"Chemosphere"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"e01536-18","DOI":"10.1128\/AEM.01536-18","article-title":"Blame It on the Metabolite: 3,5-Dichloroaniline Rather than the Parent Compound Is Responsible for the Decreasing Diversity and Function of Soil Microorganisms","volume":"84","author":"Vasileiadis","year":"2018","journal-title":"Appl. Environ. Microbiol."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"1852","DOI":"10.1021\/acs.jafc.2c06648","article-title":"Identification and Quantification of Dimethachlon Degradation Products in Soils and Their Effects on Soil Enzyme Activities","volume":"71","author":"Li","year":"2023","journal-title":"J. Agric. Food Chem."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"215","DOI":"10.1016\/S0378-4347(01)00078-0","article-title":"Determination of Dichloroanilines in Human Urine by GC\u2013MS, GC\u2013MS\u2013MS, and GC\u2013ECD as Markers of Low-Level Pesticide Exposure","volume":"755","author":"Wittke","year":"2001","journal-title":"J. Chromatogr. B"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"103120","DOI":"10.1016\/j.eti.2023.103120","article-title":"Rapid Elimination of Dicarboximide Fungicides and Their Metabolite 3,5-Dichloroaniline from Soils by Immobilized Bacterial Consortia","volume":"30","author":"Dong","year":"2023","journal-title":"Environ. Technol. Innov."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"300","DOI":"10.1016\/j.jhazmat.2017.02.047","article-title":"Sorption Potential of Different Biomass Fly Ashes for the Removal of Diuron and 3,4-Dichloroaniline from Water","volume":"331","author":"Quirantes","year":"2017","journal-title":"J. Hazard. Mater."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"1253","DOI":"10.1080\/19440049.2019.1615642","article-title":"Determination of Selected Dichloroanilines and Phthalates in Lyophilised Mussels Samples with Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry after QuEChERS Clean-Up","volume":"36","author":"Tsochatzis","year":"2019","journal-title":"Food Addit. Contam. Part A"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"108558","DOI":"10.1016\/j.foodhyd.2023.108558","article-title":"Structure Identification of the Oligosaccharides by UPLC-MS\/MS","volume":"139","author":"Yang","year":"2023","journal-title":"Food Hydrocoll."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"500","DOI":"10.1016\/j.microc.2018.07.023","article-title":"Impact of Humic Acids, Temperature and Stirring on Passive Extraction of Pharmaceuticals from Water by Trihexyl (Tetradecyl) Phosphonium Dicyanamide","volume":"144","author":"Stepnowski","year":"2019","journal-title":"Microchem. J."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"411","DOI":"10.1016\/j.foodchem.2017.02.014","article-title":"Determination of Hymexazol in 26 Foods of Plant Origin by Modified QuEChERS Method and Liquid Chromatography Tandem-Mass Spectrometry","volume":"228","author":"Jiang","year":"2017","journal-title":"Food Chem."},{"key":"ref_32","first-page":"178","article-title":"The Fate of Spirotetramat and Dissipation Metabolites in Apiaceae and Brassicaceae Leaf-Root and Soil System under Greenhouse Conditions Estimated by Modified QuEChERS\/LC\u2013MS\/MS","volume":"603\u2013604","author":"Mojsak","year":"2017","journal-title":"Sci. Total Environ."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"380","DOI":"10.1016\/j.foodchem.2015.12.007","article-title":"Matrix Effect in Guava Multiresidue Analysis by QuEChERS Method and Gas Chromatography Coupled to Quadrupole Mass Spectrometry","volume":"199","author":"Guedes","year":"2016","journal-title":"Food Chem."},{"key":"ref_34","unstructured":"(2020). SANTE Guidance Document on Analytical Quality Control and Method Validation Procedures for Pesticide Residues Analysis in Food and Feed, European Commission Directorate General for Health and Food Safety Brussels. SANTE\/12682\/2019, Implemented by 01.01.2020."},{"key":"ref_35","unstructured":"(2023, March 24). Guidelines on Performance Criteria for Methods of Analysis for the Determination of Pesticide Residues in Food and Feed. Available online: http:\/\/www.fao.org\/fao-who-codexalimentarius\/thematic-areas\/pesticides\/en\/."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"6091","DOI":"10.1021\/acs.jafc.5b05981","article-title":"Multiresidue Analysis of Pesticides in Straw Roughage by Liquid Chromatography\u2013Tandem Mass Spectrometry","volume":"64","author":"Zhang","year":"2016","journal-title":"J. Agric. Food Chem."}],"container-title":["Foods"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2304-8158\/12\/15\/2875\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T20:21:49Z","timestamp":1760127709000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2304-8158\/12\/15\/2875"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,7,28]]},"references-count":36,"journal-issue":{"issue":"15","published-online":{"date-parts":[[2023,8]]}},"alternative-id":["foods12152875"],"URL":"https:\/\/doi.org\/10.3390\/foods12152875","relation":{},"ISSN":["2304-8158"],"issn-type":[{"value":"2304-8158","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,7,28]]}}}