马 倩，杨春梅*，李兴玉，冯一杰，周晓群

（成都产品质量检验研究院有限责任公司，成都610100）

摘要：真菌毒素具有强致癌性、致畸性和免疫抑制性，对人体健康构成严重威胁。柑橘类水果及其制品在储藏和生产过程中易受真菌毒素污染。该研究采用超高效液相色谱-四极杆/静电场轨道阱高分辨质谱仪（UHPLC-Orbitrap Exploris HRMS），建立并优化了55种真菌毒素的检测方法。样品经前处理后，采用0.1%甲酸水（含2.5mmol/L乙酸铵）和乙腈作为流动相进行洗脱。使用Waters ACQUITY UPLC HSS T3色谱柱分离待测物，并采用Full MS/dd-MS2进行定性分析。优化了NCE等质谱参数，建立了55种真菌毒素的本地质谱库。同时对链格孢酚、链格孢酚甲醚、伏马毒素B2、T-2三醇、麦角考宁和疣孢菌醇6种真菌毒素进行方法学考察，检出限为0.0002～0.02 μg/g，定量限为0.000 6～0.06 μg/g，低、中、高3 个梯度加标回收率范围在81.1%～94.6%，相对标准偏差（RSD）均小于5%，对16组霉变柑橘及其制品的筛查和定量结果显示，链格孢酚、链格孢酚甲醚、T-2三醇和疣孢菌醇4种真菌毒素有检出。该研究方法可用于真菌毒素的快速筛查，为保障居民膳食安全和加强食品安全监管提供技术支持。

关键词：高分辨质谱；柑橘；真菌毒素；毒素筛查

中图分类号：TS207.5 文献标识码：A 文章编号：1674-506X（2025）03-0119-0009

Screening Mycotoxins in Citrus and Its Processed Products Based on UHPLC-Orbitrap Exploris-HRMS

MA Qian，YANG Chunmei*，LI Xingyu，FENG Yijie，ZHOU Xiaoqun

(Chengdu Institute of Product Quality Inspection and Research Co.，Ltd.，Chengdu 610100，China)

Abstract: Mycotoxins are highly carcinogenic， teratogenic and immunosuppressive， posing a serious threat to human health. Citrus fruits and their processed products are prone to mycotoxin contamination during storage and production processes. In this study，using ultra high performance liquid chromatography coupled with quadrupole/electrostatic field orbitrap high resolution mass spectrometry （UHPLC- Orbitrap Exploris HRMS）， a detection method for 55 mycotoxins was developed and optimized. After sample pretreatment， the analytes were eluted using a mobile phase consisting of 0.1% formic acid water solution （containing 2.5 mmol/L ammonium acetate） and acetonitrile. Separation of the analytes was achieved using a Waters ACQUITY UPLC HSS T3 chromatographic column， and qualitative analysis was performed using Full MS/dd- MS2 mode. Mass spectrometry parameters， such as normalized collision energy （NCE）， were optimized and a local mass spectrometry library for 55 mycotoxins was established. Methodology validation was conducted for alternariol， alternariol monomethyl ether，fumonisin B2，T-2 triol，ergocornine，and verrucarol with detection limits ranging from 0.000 2～0.02 μg/g and quantification limits ranging from 0.000 6～0.06 μg/g. The spiked recovery rates of low，medium，and high gradient ranged from 81.1% ～94.6% ， with relative standard deviation （RSD） all below 5% . Screening and quantitative results for 16 groups of moldy citrus fruits and their processed products showed the detection of 4 mycotoxins： alternariol， alternariol monomethyl ether， T-2 triol， and verrucarol. The research method can be applied to rapid screening of mycotoxins， providing technical support for ensuring citizen’s dietary safety and strengthening food safety supervision.

Keywords: high resolution mass spectrometry; citrus; mycotoxins; mycotoxins screening

doi: 10.3969/j.issn.1674-506X.2025.03-018