{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,17]],"date-time":"2026-04-17T04:52:50Z","timestamp":1776401570234,"version":"3.51.2"},"reference-count":44,"publisher":"MDPI AG","issue":"7","license":[{"start":{"date-parts":[[2023,4,4]],"date-time":"2023-04-04T00:00:00Z","timestamp":1680566400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Special Project on Basic Work of Science and Technology","award":["2013FY110100-2"],"award-info":[{"award-number":["2013FY110100-2"]}]},{"name":"Special Project on Basic Work of Science and Technology","award":["2022YFD1600803"],"award-info":[{"award-number":["2022YFD1600803"]}]},{"name":"National Key Research and Development Programme of China","award":["2013FY110100-2"],"award-info":[{"award-number":["2013FY110100-2"]}]},{"name":"National Key Research and Development Programme of China","award":["2022YFD1600803"],"award-info":[{"award-number":["2022YFD1600803"]}]}],"content-domain":{"domain":["www.mdpi.com"],"crossmark-restriction":true},"short-container-title":["Molecules"],"abstract":"<jats:p>Alkylphenol ethoxylates (APEOs) represent a non-ionic surfactant widely used as adjuvants in pesticide formulation, which is considered to cause an endocrine-disrupting effect. In the current study, we established a detection method for the APEOs residue in tea based on solid-phase extraction (SPE) for the simultaneous analysis of nonylphenol ethoxylates (NPEOs) and octylphenol ethoxylates (OPEOs) by UPLC\u2013MS\/MS. In the spiked concentrations from 0.024 to 125.38 \u03bcg\/kg for 36 monomers of APEOs (nEO = 3\u201320), the recoveries of APEOs range from 70.3\u2013110.7% with RSD \u2264 16.9%, except for OPEO20 (61.8%) and NPEO20 (62.9%). The LOQs of OPEOs and NPEOs are 0.024\u20136.27 and 0.16\u20135.01 \u03bcg\/kg, respectively. OPEOs and NPEOs are detected in 50 marketed tea samples with a total concentration of 0.057\u201312.94 and 0.30\u2013215.89 \u00b5g\/kg, respectively. The detection rate and the range of the monomers of NPEOs are generally higher than those of OPEOs. The current study provides a theoretical basis for the rational use of APEOs as adjuvants in commercial pesticide production.<\/jats:p>","DOI":"10.3390\/molecules28073216","type":"journal-article","created":{"date-parts":[[2023,4,5]],"date-time":"2023-04-05T01:39:26Z","timestamp":1680658766000},"page":"3216","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["SPE\u2013UPLC\u2013MS\/MS for Determination of 36 Monomers of Alkylphenol Ethoxylates in Tea"],"prefix":"10.3390","volume":"28","author":[{"given":"Qin","family":"Lin","sequence":"first","affiliation":[{"name":"Tea Research Institute, Chinese Academy of Agricultural Sciences, Hangzhou 310008, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yujie","family":"Qin","sequence":"additional","affiliation":[{"name":"Tea Research Institute, Chinese Academy of Agricultural Sciences, Hangzhou 310008, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Hezhi","family":"Sun","sequence":"additional","affiliation":[{"name":"Tea Research Institute, Chinese Academy of Agricultural Sciences, Hangzhou 310008, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Xinru","family":"Wang","sequence":"additional","affiliation":[{"name":"Tea Research Institute, Chinese Academy of Agricultural Sciences, Hangzhou 310008, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Mei","family":"Yang","sequence":"additional","affiliation":[{"name":"Tea Research Institute, Chinese Academy of Agricultural Sciences, Hangzhou 310008, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7369-5761","authenticated-orcid":false,"given":"Xinzhong","family":"Zhang","sequence":"additional","affiliation":[{"name":"Tea Research Institute, Chinese Academy of Agricultural Sciences, Hangzhou 310008, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Li","family":"Zhou","sequence":"additional","affiliation":[{"name":"Tea Research Institute, Chinese Academy of Agricultural Sciences, Hangzhou 310008, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Fengjian","family":"Luo","sequence":"additional","affiliation":[{"name":"Tea Research Institute, Chinese Academy of Agricultural Sciences, Hangzhou 310008, China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2023,4,4]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"131819","DOI":"10.1016\/j.foodchem.2021.131819","article-title":"Multi-residue analytical method development and risk assessment of 56 pesticides and their metabolites in tea by chromatography tandem mass spectroscopy","volume":"375","author":"Wu","year":"2021","journal-title":"Food Chem."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"1122","DOI":"10.1016\/j.clnu.2022.03.020","article-title":"Tea consumption and risk of bladder cancer in the Bladder Cancer Epidemiology and Nutritional Determinants (BLEND) Study: Pooled analysis of 12 international cohort studies","volume":"41","author":"Wesselius","year":"2022","journal-title":"Clin. Nutr."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"128984","DOI":"10.1016\/j.foodchem.2020.128984","article-title":"Occurrences of eight common-used pesticide adjuvants in ten vegetable species and implications for dietary intake in North China","volume":"347","author":"Jiang","year":"2021","journal-title":"Food Chem."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"763","DOI":"10.2478\/pjvs-2013-0111","article-title":"Alkylphenol ethoxylates and alkylphenols--update information on occurrence, fate and toxicity in aquatic environment","volume":"16","author":"Kovarova","year":"2013","journal-title":"Pol. J. Vet. Sci."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"9","DOI":"10.1016\/j.chemosphere.2019.02.136","article-title":"Alkylphenol ethoxylate metabolites in coastal sediments off southwestern Taiwan: Spatiotemporal variations, possible sources, and ecological risk","volume":"225","author":"Shiu","year":"2019","journal-title":"Chemosphere"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"171","DOI":"10.1016\/j.talanta.2013.02.027","article-title":"Analysis of alcohol polyethoxylates and polyethylene glycols in marine sediments","volume":"110","year":"2013","journal-title":"Talanta"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"113655","DOI":"10.1016\/j.marpolbul.2022.113655","article-title":"Occurrence of alkylphenols and alkylphenol ethoxylates in North Sea sediment samples collected across oil and gas fields","volume":"178","author":"McLaren","year":"2022","journal-title":"Mar. Pollut. Bull."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"189","DOI":"10.1016\/j.envpol.2012.11.012","article-title":"National inventory of alkylphenol ethoxylate compounds in U.S. Sewage sludges and chemical fate in outdoor soil mesocosms","volume":"174","author":"Venkatesan","year":"2013","journal-title":"Environ. Pollut."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"221","DOI":"10.1111\/wej.12090","article-title":"Distribution and geochemical behaviour of anionic surfactants determined as ethyl violet active substances in Lake Biwa, Japan","volume":"29","author":"Hiroo","year":"2015","journal-title":"Water Environ. J."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"361","DOI":"10.1007\/s00244-014-9998-5","article-title":"Occurrence of endocrine-disrupting phenols and estrogens in water and sediment of the Songhua River, northeastern China","volume":"66","author":"Zhang","year":"2014","journal-title":"Arch. Environ. Contam. Toxicol."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"11922","DOI":"10.1007\/s11356-015-4430-x","article-title":"Alkylphenol ethoxylates and brominated flame retardants in water, fish (carp) and sediment samples from the Vaal river, South Africa","volume":"22","author":"Chokwe","year":"2015","journal-title":"Environ. Sci. Pollut. Res."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"384","DOI":"10.1016\/j.envpol.2007.08.026","article-title":"Occurrence and fate of alkylphenols and alkylphenol ethoxylates in sewage treatment plants and impact on receiving waters along the Ter River (Catalonia, NE Spain)","volume":"153","author":"Lacorte","year":"2008","journal-title":"Environ. Pollut."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"101","DOI":"10.1007\/s10661-016-5114-9","article-title":"Pollution by endocrine disruptors in a southwest European temperate coastal lagoon (Ria de Aveiro, Portugal)","volume":"188","author":"Rocha","year":"2016","journal-title":"Environ. Monit. Assess."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"114010","DOI":"10.1016\/j.ijheh.2022.114010","article-title":"Nonylphenol (np) exposure in germany between 1991 and 2021: Urinary biomarker analyses in the German environmental specimen bank (esb)","volume":"245","author":"Ringbeck","year":"2022","journal-title":"Int. J. Hyg. Environ. Health"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"1792","DOI":"10.1271\/bbb.66.1792","article-title":"Isolation of bacterial strains that produce the endocrine disruptor, octylphenol diethoxylates, in paddy fields","volume":"66","author":"Nishio","year":"2002","journal-title":"Biosc. Biotech. Bioch."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"37","DOI":"10.1016\/j.procbio.2020.06.015","article-title":"Analysis of alkylphenol ethoxylates (APEOs) from tannery sediments using LC-MS and their environmental risks","volume":"97","author":"Mahalakshmi","year":"2020","journal-title":"Process Biochem."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"971","DOI":"10.1292\/jvms.14-0070","article-title":"Alkylphenol polyethoxylate derivatives in groundwater and blood samples collected from pig herds in Taiwan","volume":"76","author":"Chiu","year":"2014","journal-title":"J. Vet. Med. Sci."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"161","DOI":"10.1016\/j.chroma.2017.10.035","article-title":"Fast determination of alkylphenol ethoxylates in leafy vegetables using a modified quick, easy, cheap, effective, rugged, and safe method and ultra-high performance supercritical fluid chromatography-tandem mass spectrometry","volume":"1525","author":"Jiang","year":"2017","journal-title":"J. Chromatogr. A"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"473","DOI":"10.1016\/j.foodchem.2014.03.004","article-title":"Determination of nonylphenol ethoxylate and octylphenol ethoxylate surfactants in beehive samples by high performance liquid chromatography coupled to mass spectrometry","volume":"158","author":"Chen","year":"2014","journal-title":"Food Chem."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"1279","DOI":"10.1016\/j.chemosphere.2008.04.060","article-title":"Alkylphenols and their ethoxylates in seafood from the Tyrrhenian Sea","volume":"72","author":"Ferrara","year":"2008","journal-title":"Chemosphere"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"217","DOI":"10.1016\/j.talanta.2016.01.039","article-title":"Use of oleic-acid functionalized nanoparticles for the magnetic solid-phase microextraction of alkylphenols in fruit juices using liquid chromatography-tandem mass spectrometry","volume":"151","author":"Torres","year":"2016","journal-title":"Talanta"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"105000","DOI":"10.1016\/j.jece.2020.105000","article-title":"Laccase immobilization on core-shell magnetic metal-organic framework microspheres for alkylphenol ethoxylate compound removal","volume":"9","author":"Wang","year":"2021","journal-title":"J. Environ. Chem. Eng."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"143","DOI":"10.1016\/S0960-0760(98)00027-2","article-title":"An updated review of environmental estrogen and androgen mimics and antagonists","volume":"65","author":"Sonnenschein","year":"1998","journal-title":"J. Steroid Biochem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"151361","DOI":"10.1016\/j.scitotenv.2021.151361","article-title":"Synthetic surfactants in Swiss sewage sludges: Analytical challenges, concentrations and per capita loads","volume":"808","author":"Schinkel","year":"2022","journal-title":"Sci. Total Environ."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"1530","DOI":"10.1016\/j.scitotenv.2018.04.079","article-title":"Endocrine-disrupting metabolites of alkylphenol ethoxylates\u2014a critical review of analytical methods, environmental occurrences, toxicity, and regulation","volume":"635","author":"Acir","year":"2018","journal-title":"Sci. Total Environ."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"1452","DOI":"10.1016\/j.scitotenv.2018.07.012","article-title":"Alcohol ethoxylates significantly synergize pesticides than alkylphenol ethoxylates considering bioactivity against three pests and joint toxicity to Daphnia magna","volume":"644","author":"Li","year":"2018","journal-title":"Sci. Total Environ."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"21","DOI":"10.1007\/BF02986370","article-title":"Toxicity, uptake and metabolism of 4-n-nonylphenol in root cultures and intact plants under septic and aseptic conditions","volume":"5","author":"Bokern","year":"1998","journal-title":"Environ. Sci. Pollut. Res."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"1044","DOI":"10.1016\/j.chemosphere.2010.10.064","article-title":"Alkylphenols in adipose tissues of Italian population","volume":"82","author":"Ferrara","year":"2011","journal-title":"Chemosphere"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"984","DOI":"10.1016\/j.envint.2008.03.001","article-title":"Nonylphenol and octylphenol in human breast milk","volume":"34","author":"Ademollo","year":"2008","journal-title":"Environ. Int."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"608","DOI":"10.1093\/jat\/bks072","article-title":"Determination of nine environmental phenols in urine by ultra-high-performance liquid chromatography-tandem mass spectrometry","volume":"36","author":"Chen","year":"2012","journal-title":"J. Anal. Toxicol."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"463624","DOI":"10.1016\/j.chroma.2022.463624","article-title":"Fast removal of phenolic compounds from water using hierarchical porous carbon nanofibers membrane","volume":"1685","author":"Zhou","year":"2022","journal-title":"J. Chromatogr. A"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"2118","DOI":"10.1016\/j.chemosphere.2007.02.002","article-title":"Octyl and nonylphenol ethoxylates and carboxylates in wastewater and sediments by liquid chromatography\/tandem mass spectrometry","volume":"68","author":"Rice","year":"2007","journal-title":"Chemosphere"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"51","DOI":"10.1016\/j.chroma.2005.04.010","article-title":"Evaluation of a new hypercrosslinked polymer as a sorbent for solid-phase extraction of polar compounds","volume":"1075","author":"Fontanals","year":"2005","journal-title":"J. Chromatogr. A"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"154","DOI":"10.1016\/j.chroma.2013.07.017","article-title":"Rapid liquid chromatography-tandem mass spectrometry-based method for the analysis of alcohol ethoxylates and alkylphenol ethoxylates in environmental samples","volume":"1305","author":"DeArmond","year":"2013","journal-title":"J. Chromatogr. A"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"580","DOI":"10.1016\/j.foodchem.2017.02.081","article-title":"Multiresidue method for the determination of pesticides in oolong tea using QuEChERS by gas chromatography-triple quadrupole tandem mass spectrometry","volume":"229","author":"Wu","year":"2017","journal-title":"Food Chem."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"122441","DOI":"10.1016\/j.talanta.2021.122441","article-title":"A multi-family offline SPE LC-MS\/MS analytical method for anionic, cationic and non-ionic surfactants quantification in surface water","volume":"232","author":"Wiest","year":"2021","journal-title":"Talanta"},{"key":"ref_37","first-page":"197","article-title":"A review on the environmental behavior of the polyoxyethylene type nonionic surfactants adjuvants in pesticides","volume":"34","author":"Kong","year":"2017","journal-title":"J. Agric. Resour. Environ."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"1007","DOI":"10.1080\/10807030802387705","article-title":"C8- and C9-alkylphenols and ethoxylates: I. Identity, physical characterization, and biodegradation pathways analysis","volume":"14","author":"Staples","year":"2008","journal-title":"Hum. Ecol. Risk Assess."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"701","DOI":"10.1016\/j.jhazmat.2010.07.083","article-title":"Determination of alkylphenol polyethoxylates, bisphenol-a, 17\u03b1-ethynylestradiol and 17\u03b2-estradiol and its metabolites in sewage samples by SPE and LC\/MS\/MS","volume":"183","year":"2010","journal-title":"J. Hazard. Mater."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"124","DOI":"10.1016\/j.scitotenv.2007.01.024","article-title":"Quantitative determination of octylphenol, nonylphenol, alkylphenol ethoxylates and alcohol ethoxylates by pressurized liquid extraction and liquid chromatography-mass spectrometry in soils treated with sewage sludges","volume":"378","author":"Andreu","year":"2007","journal-title":"Sci. Total Environ."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"66","DOI":"10.1016\/j.chroma.2012.01.077","article-title":"Development and optimisation of an on-line solid phase extraction coupled to ultra-high-performance liquid chromatography-tandem mass spectrometry methodology for the simultaneous determination of endocrine disrupting compounds in wastewater samples","volume":"1230","year":"2012","journal-title":"J. Chromatogr. A"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"3331","DOI":"10.1007\/s00216-016-9403-5","article-title":"Fully automated on-line solid phase extraction coupled to liquid chromatography-tandem mass spectrometry for the simultaneous analysis of alkylphenol polyethoxylates and their carboxylic and phenolic metabolites in wastewater samples","volume":"408","author":"Ciofi","year":"2016","journal-title":"Anal. Bioanal. Chem."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"113279","DOI":"10.1016\/j.ecoenv.2022.113279","article-title":"Concentrations, leachability, and health risks of mercury in green tea from major production areas in China","volume":"232","author":"Wang","year":"2022","journal-title":"Ecotoxicol. Environ. Saf."},{"key":"ref_44","unstructured":"State Administration for Market Regulation and Standardization Administration (China) (2023, February 25). Textiles\u2013Determination of surfactant\u2013Alkyphenols and Alkylphenol Ethoxylates, Available online: https:\/\/openstd.samr.gov.cn\/bzgk\/gb\/newGbInfo?hcno=22CC306762497933A6EC5EEF88B511F0."}],"updated-by":[{"DOI":"10.3390\/molecules30071547","type":"correction","label":"Correction","source":"publisher","updated":{"date-parts":[[2023,4,4]],"date-time":"2023-04-04T00:00:00Z","timestamp":1680566400000}}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/28\/7\/3216\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,8,3]],"date-time":"2025-08-03T13:47:52Z","timestamp":1754228872000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/28\/7\/3216"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,4,4]]},"references-count":44,"journal-issue":{"issue":"7","published-online":{"date-parts":[[2023,4]]}},"alternative-id":["molecules28073216"],"URL":"https:\/\/doi.org\/10.3390\/molecules28073216","relation":{"correction":[{"id-type":"doi","id":"10.3390\/molecules30071547","asserted-by":"object"}]},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,4,4]]}}}