{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,24]],"date-time":"2026-10-24T00:35:38Z","timestamp":1792802138178,"version":"4.5.0"},"reference-count":47,"publisher":"MDPI AG","issue":"7","license":[{"start":{"date-parts":[[2026,4,3]],"date-time":"2026-04-03T00:00:00Z","timestamp":1775174400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100005047","name":"Natural Science Foundation of Liaoning Province","doi-asserted-by":"crossref","award":["2025-MSLH-035"],"award-info":[{"award-number":["2025-MSLH-035"]}],"id":[{"id":"10.13039\/501100005047","id-type":"DOI","asserted-by":"crossref"}]},{"name":"National Key Research and Development Program of China","award":["2025YFD2400200"],"award-info":[{"award-number":["2025YFD2400200"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Foods"],"abstract":"<jats:p>Sulfur fumigation, as a highly effective method for preservation and appearance enhancement, has been widely applied in fruits, vegetables, and food products. However, excessive sulfur fumigation can pose safety risks. Currently, there is limited research on the bound sulfites produced by sulfur fumigation, and no consensus has been reached regarding their structure and toxicity. Using ultra-performance liquid chromatography\u2013quadrupole time-of-flight tandem mass spectrometry (UPLC-Q-TOF-MS\/MS), a total of 34 compounds were identified in 12 lily bulb samples subjected to different sulfur fumigation durations. These derivatives were all hypothesized to form via nucleophilic addition to carbon\u2013carbon double bonds. Based on multivariate statistical analysis, 9 characteristic markers were established to rapidly differentiate between non-fumigated (NF) and sulfur-fumigated (SF) samples. The practicality of this strategy was validated using 18 commercial batches. Molecular docking simulations predicted that the modifications might enhance toxicity toward liver injury-related targets, both by altering the spatial conformation of the compounds and because the sulfonic acid group itself serves as an ideal hydrogen-bond acceptor. Overall, mild fumigation led to a gradual accumulation of free sulfur dioxide in lily bulbs, increased the total content of phenolic components and antioxidant capacity, and did not generate excessive bound sulfur dioxide. However, with further extension of fumigation time, the content of sulfur-containing derivatives rose rapidly, accompanied by a noticeable decline in antioxidant activity. This study elucidates the sulfur-driven chemical transformation mechanisms in lily bulbs and establishes a targeted methodology for the quality control and safety assessment of processed herbal products.<\/jats:p>","DOI":"10.3390\/foods15071228","type":"journal-article","created":{"date-parts":[[2026,4,6]],"date-time":"2026-04-06T00:19:32Z","timestamp":1775434772000},"page":"1228","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Sulfur Fumigation-Induced Chemical Transformations in Lily Bulbs (Lilium brownii var. viridulum): Structural Characterization, Marker Identification, and Toxicity Implications"],"prefix":"10.3390","volume":"15","author":[{"given":"Ruiqi","family":"Xu","sequence":"first","affiliation":[{"name":"SKL of Marine Food Processing & Safety Control, National Engineering Research Center of Seafood, School of Food Science and Technology, Dalian Polytechnic University, Dalian 116034, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dingjiang","family":"Xuan","sequence":"additional","affiliation":[{"name":"SKL of Marine Food Processing & Safety Control, National Engineering Research Center of Seafood, School of Food Science and Technology, Dalian Polytechnic University, Dalian 116034, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ping","family":"Li","sequence":"additional","affiliation":[{"name":"SKL of Marine Food Processing & Safety Control, National Engineering Research Center of Seafood, School of Food Science and Technology, Dalian Polytechnic University, Dalian 116034, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zheng","family":"Zhou","sequence":"additional","affiliation":[{"name":"SKL of Marine Food Processing & Safety Control, National Engineering Research Center of Seafood, School of Food Science and Technology, Dalian Polytechnic University, Dalian 116034, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tingyu","family":"Zhu","sequence":"additional","affiliation":[{"name":"SKL of Marine Food Processing & Safety Control, National Engineering Research Center of Seafood, School of Food Science and Technology, Dalian Polytechnic University, Dalian 116034, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qi","family":"Wu","sequence":"additional","affiliation":[{"name":"Sub-Institute of Agriculture and Food Standardization, China National Institute of Standardization, Beijing 100088, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lin","family":"Zhu","sequence":"additional","affiliation":[{"name":"SKL of Marine Food Processing & Safety Control, National Engineering Research Center of Seafood, School of Food Science and Technology, Dalian Polytechnic University, Dalian 116034, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shuhong","family":"Ye","sequence":"additional","affiliation":[{"name":"SKL of Marine Food Processing & Safety Control, National Engineering Research Center of Seafood, School of Food Science and Technology, Dalian Polytechnic University, Dalian 116034, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8431-7694","authenticated-orcid":false,"given":"Yan","family":"Ding","sequence":"additional","affiliation":[{"name":"SKL of Marine Food Processing & Safety Control, National Engineering Research Center of Seafood, School of Food Science and Technology, Dalian Polytechnic University, Dalian 116034, China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2026,4,3]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"330","DOI":"10.1016\/j.fshw.2019.09.001","article-title":"A critical review on chemical constituents and pharmacological effects of Lilium","volume":"8","author":"Wang","year":"2019","journal-title":"Food Sci. Hum. Wellness"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"113852","DOI":"10.1016\/j.jep.2021.113852","article-title":"Genus Lilium: A review on traditional uses, phytochemistry and pharmacology","volume":"270","author":"Zhou","year":"2021","journal-title":"J. Ethnopharmacol."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"107445","DOI":"10.1016\/j.intimp.2021.107445","article-title":"Immunoregulatory activities of the selenylated polysaccharides of Lilium davidii var. unicolor Salisb in vitro and in vivo","volume":"94","author":"Li","year":"2021","journal-title":"Int. Immunopharmacol."},{"key":"ref_4","doi-asserted-by":"crossref","unstructured":"Tang, Y.C., Liu, Y.J., He, G.R., Cao, Y.W., Bi, M.M., Song, M., Yang, P.-P., Xu, L.-F., and Ming, J. (2021). Comprehensive analysis of secondary metabolites in the extracts from different lily bulbs and their antioxidant ability. Antioxidants, 10.","DOI":"10.3390\/antiox10101634"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"12577","DOI":"10.1021\/acs.jafc.2c05710","article-title":"Impact of sulfur fumigation on ginger: Chemical and biological evidence","volume":"70","author":"Zhang","year":"2022","journal-title":"J. Agric. Food Chem."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"110854","DOI":"10.1016\/j.foodres.2021.110854","article-title":"Analysis of edible characteristics, antioxidant capacities, and phenolic pigment monomers in Lilium bulbs native to China","volume":"151","author":"Liang","year":"2022","journal-title":"Food Res. Int."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"112168","DOI":"10.1016\/j.radphyschem.2024.112168","article-title":"X-ray irradiation delayed the browning development of fresh-cut bulbs of Lanzhou Lily (Lilium davidii) during room temperature storage","volume":"226","author":"Ji","year":"2025","journal-title":"Radiat. Phys. Chem."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"7984106","DOI":"10.1155\/2024\/7984106","article-title":"Postharvest Light Irradiation Induces Anthocyanin Accumulation in Fresh-Cut Lily Bulb (Lilium davidii var. unicolor) Scales","volume":"2024","author":"Fan","year":"2024","journal-title":"J. Food Process. Preserv."},{"key":"ref_9","first-page":"45","article-title":"Study on the change rules of lily storage quality at different temperatures","volume":"25","author":"Gao","year":"2025","journal-title":"Storage Process"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"1034","DOI":"10.1039\/C5AY01404B","article-title":"UPLC-QTOF-MS based metabolomics coupled with the diagnostic ion exploration strategy for rapidly evaluating sulfur-fumigation caused holistic quality variation in medicinal herbs, Moutan Cortex as an example","volume":"8","author":"Li","year":"2016","journal-title":"Anal. Methods"},{"key":"ref_11","doi-asserted-by":"crossref","unstructured":"Deng, A.P., Kang, C.Z., Kang, L.P., Lyu, C.G., Zhang, W.J., Wang, S., Wang, H.-Y., Nan, T.-G., Zhou, L., and Huang, L.-Q. (2022). Practical protocol for comprehensively evaluating sulfur-fumigation of Baizhi based on metabolomics, pharmacology, and cytotoxicity. Front. Pharmacol., 12.","DOI":"10.3389\/fphar.2021.799504"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"107767","DOI":"10.1016\/j.microc.2022.107767","article-title":"Discrimination of raw and sulfur-fumigated ginseng based on Fourier transform infrared spectroscopy coupled with chemometrics","volume":"181","author":"Li","year":"2022","journal-title":"Microchem. J."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"16640","DOI":"10.3390\/molecules191016640","article-title":"Influence of sulfur fumigation on the chemical constituents and antioxidant activity of buds of Lonicera japonica","volume":"19","author":"Guo","year":"2014","journal-title":"Molecules"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"4598","DOI":"10.1002\/jsfa.14277","article-title":"Influence of sulfur fumigation on the volatile composition of lily bulbs evaluated by HS-SPME\/GC\u2013MS and multivariate statistical analysis","volume":"105","author":"Li","year":"2025","journal-title":"J. Sci. Food Agric."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"221","DOI":"10.1016\/j.jhazmat.2017.07.003","article-title":"A practical protocol for comprehensive evaluation of sulfur-fumigation of Gastrodia Rhizoma using metabolome and health risk assessment analysis","volume":"340","author":"Kang","year":"2017","journal-title":"J. Hazard. Mater."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"119","DOI":"10.1016\/j.foodchem.2015.07.003","article-title":"Sulfur dioxide residue in sulfur-fumigated edible herbs: The fewer, the safer?","volume":"192","author":"Duan","year":"2016","journal-title":"Food Chem."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"137360","DOI":"10.1016\/j.foodchem.2023.137360","article-title":"Tryptophan sulfonate: A new chemical marker for accurate and efficient inspection of sulfur-treated food products","volume":"434","author":"Chan","year":"2024","journal-title":"Food Chem."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"97","DOI":"10.1016\/j.phymed.2012.09.030","article-title":"Sulfur fumigation, a better or worse choice in preservation of Traditional Chinese Medicine?","volume":"20","author":"Jiang","year":"2013","journal-title":"Phytomedicine"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"111293","DOI":"10.1016\/j.lwt.2021.111293","article-title":"A comprehensive evaluation protocol for sulfur fumigation of ginseng using UPLC-Q-TOF-MS\/MS and multivariate statistical analysis","volume":"145","author":"Zhang","year":"2021","journal-title":"LWT"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"115773","DOI":"10.1016\/j.jep.2022.115773","article-title":"Exploring the nephrotoxicity of sulfur-containing derivatives in sulfur-fumigated Panacis Quinquefolii Radix based on chemical profiling and untargeted metabolomics","volume":"301","author":"He","year":"2023","journal-title":"J. Ethnopharmacol."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"132685","DOI":"10.1016\/j.foodchem.2022.132685","article-title":"Effects of sulfite treatment on the quality of black fungus","volume":"385","author":"Ren","year":"2022","journal-title":"Food Chem."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"4839","DOI":"10.1111\/1750-3841.17147","article-title":"Untargeted metabolomics combined with vitro antioxidant to comprehensively evaluate the effect of sodium sulfite immersion on the holistic quality of mung bean sprouts","volume":"89","author":"Li","year":"2024","journal-title":"J. Food Sci."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"141927","DOI":"10.1016\/j.foodchem.2024.141927","article-title":"Untargeted metabolomics reveals the formation pathways of bound sulfite in sodium metabisulfite-soaked Hemerocallis citrina Baroni","volume":"465","author":"Li","year":"2025","journal-title":"Food Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"115250","DOI":"10.1016\/j.jep.2022.115250","article-title":"Effects and contributory factors of sulfur-fumigation on the efficacy and safety of medicinal herbs evaluated by meta-analysis","volume":"293","author":"Liu","year":"2022","journal-title":"J. Ethnopharmacol."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"19","DOI":"10.1016\/j.jpba.2017.03.003","article-title":"Influence of sulfur fumigation on the chemical profiles of Atractylodes macrocephala Koidz. evaluated by UFLC\u2013QTOF\u2013MS combined with multivariate statistical analysis","volume":"141","author":"Sun","year":"2017","journal-title":"J. Pharm. Biomed. Anal."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"8741","DOI":"10.1080\/10408398.2023.2203737","article-title":"Novel insight into the role of sulfur dioxide in fruits and vegetables: Chemical interactions, biological activity, metabolism, applications, and safety","volume":"64","author":"Li","year":"2024","journal-title":"Crit. Rev. Food Sci. Nutr."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"114574","DOI":"10.1016\/j.jpba.2021.114574","article-title":"Holistic quality evaluation of commercial Agastache rugosa by multiple chromatographic and chemometric analysis","volume":"210","author":"Hou","year":"2022","journal-title":"J. Pharm. Biomed. Anal."},{"key":"ref_28","unstructured":"(2022). National Food Safety Standard - Determination of Sulfur Dioxide in Foods (Standard No. Standard\u2019s GB 5009.34-2022)."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"76","DOI":"10.1016\/j.jep.2019.01.026","article-title":"Chemical profiles, antioxidant activity and acute toxicity of raw and sulfur-fumigated Smilacis Glabrae Rhizoma","volume":"234","author":"Yuan","year":"2019","journal-title":"J. Ethnopharmacol."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"130","DOI":"10.1016\/j.algal.2017.11.027","article-title":"A comparative assessment of the activity and structure of phlorotannins from the brown seaweed Carpophyllum flexuosum","volume":"29","author":"Zhang","year":"2018","journal-title":"Algal Res."},{"key":"ref_31","doi-asserted-by":"crossref","unstructured":"Eastman, P., Swails, J., Chodera, J.D., McGibbon, R.T., Zhao, Y., Beauchamp, K.A., Wang, L.-P., Simmonett, A.C., Harrigan, M.P., and Stern, C.D. (2017). OpenMM 7: Rapid development of high performance algorithms for molecular dynamics. PLoS Comput. Biol., 13.","DOI":"10.1371\/journal.pcbi.1005659"},{"key":"ref_32","first-page":"64","article-title":"Effect of sulfur fumigation on effective components of lily","volume":"20","author":"Li","year":"2006","journal-title":"J. Shanghai Univ. Tradit. Chin. Med."},{"key":"ref_33","first-page":"660","article-title":"Effect of sulfur fumigation on quality and safety of lily medicinal materials","volume":"48","author":"Zhang","year":"2023","journal-title":"China J. Chin. Mater. Medica"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"126708","DOI":"10.1016\/j.saa.2025.126708","article-title":"Rapid discrimination of sulfur-fumigated lily by mid-infrared, near-infrared and synchronous fluorescence spectroscopy and chemometrics: A comparative study","volume":"344","author":"Tan","year":"2025","journal-title":"Spectrochim. Acta Part A Mol. Biomol. Spectrosc."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"462980","DOI":"10.1016\/j.chroma.2022.462980","article-title":"In-depth exploration and comparison of chemical constituents from two Lilium species through offline two-dimensional liquid chromatography combined with multimode acquisition of high-resolution mass spectrometry","volume":"1670","author":"Wu","year":"2022","journal-title":"J. Chromatogr. A"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"112137","DOI":"10.1016\/j.foodres.2022.112137","article-title":"Effect of boiling and roasting on phenolic components and their bioaccessibilities of highland barley","volume":"162","author":"Wang","year":"2022","journal-title":"Food Res. Int."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"131499","DOI":"10.1016\/j.ijbiomac.2024.131499","article-title":"Extraction, purification, structural characteristics, biological activities, and applications of polysaccharides from the genus Lilium: A review","volume":"267","author":"Wang","year":"2024","journal-title":"Int. J. Biol. Macromol."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"9361","DOI":"10.3390\/molecules17089361","article-title":"Phenolic compounds and antioxidant activity of bulb extracts of six Lilium species native to China","volume":"17","author":"Jin","year":"2012","journal-title":"Molecules"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"2427","DOI":"10.1080\/00032719.2016.1151438","article-title":"Characterization of the processing of dry lily (Lilium davidii Duch.) bulbs by mid-infrared spectroscopy","volume":"49","author":"Guo","year":"2016","journal-title":"Anal. Lett."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"807","DOI":"10.1111\/j.1365-2621.1966.tb03253.x","article-title":"Effect of sulfite and ascorbic acid on mushroom phenol oxidase","volume":"31","author":"Markakis","year":"1966","journal-title":"J. Food Sci."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"138816","DOI":"10.1016\/j.molstruc.2024.138816","article-title":"Near-infrared colorimetric fluorescent probe for detecting HSO3\u2212 and its practical application","volume":"1314","author":"Zhang","year":"2024","journal-title":"J. Mol. Struct."},{"key":"ref_42","doi-asserted-by":"crossref","unstructured":"Kang, C., Lv, C., Yang, J., Kang, L., Ma, W., Zhang, W., Wang, S., Wang, T., Sun, J., and Ge, Y. (2020). A practical protocol for a comprehensive evaluation of sulfur fumigation of trichosanthis radix based on both non-targeted and widely targeted metabolomics. Front. Plant Sci., 11.","DOI":"10.3389\/fpls.2020.578086"},{"key":"ref_43","doi-asserted-by":"crossref","unstructured":"Xu, W., Jin, H., Wang, Y., Wei, F., and Liu, J. (2025). Sulfur fumigation of botanical drugs: Impact on chemical composition and pharmacological properties, and advances in detection technologies. Front. Pharmacol., 16.","DOI":"10.3389\/fphar.2025.1635850"},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"21293","DOI":"10.1021\/acsomega.3c02729","article-title":"Impact of sulfur fumigation on the chemistry of dioscoreae rhizoma (Chinese yam)","volume":"8","author":"Chan","year":"2023","journal-title":"ACS Omega"},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"4584","DOI":"10.1021\/acs.jafc.6b01005","article-title":"Stability of hydroxycinnamic acid derivatives, flavonol glycosides, and anthocyanins in black currant juice","volume":"64","author":"Makila","year":"2016","journal-title":"J. Agric. Food Chem."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"84","DOI":"10.3389\/fphar.2011.00084","article-title":"Sulfur fumigation processing of traditional Chinese medicinal herbs: Beneficial or detrimental?","volume":"2","author":"Kan","year":"2011","journal-title":"Front. Pharmacol."},{"key":"ref_47","doi-asserted-by":"crossref","unstructured":"Chen, C.J., Cheng, M.C., Hsu, C.N., and Tain, Y.L. (2023). Sulfur-containing amino acids, hydrogen sulfide, and sulfur compounds on kidney health and disease. Metabolites, 13.","DOI":"10.3390\/metabo13060688"}],"container-title":["Foods"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2304-8158\/15\/7\/1228\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,4,8]],"date-time":"2026-04-08T04:14:49Z","timestamp":1775621689000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2304-8158\/15\/7\/1228"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,4,3]]},"references-count":47,"journal-issue":{"issue":"7","published-online":{"date-parts":[[2026,4]]}},"alternative-id":["foods15071228"],"URL":"https:\/\/doi.org\/10.3390\/foods15071228","relation":{},"ISSN":["2304-8158"],"issn-type":[{"value":"2304-8158","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,4,3]]}}}