Article(id=1320881183332872951, tenantId=1146029695717560320, journalId=1260987677001138203, issueId=1320881182762447607, articleNumber=null, orderNo=null, doi=10.13386/j.issn1002-0306.2025070246, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1753027200000, receivedDateStr=2025-07-21, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1792852214891, onlineDateStr=2026-10-24, pubDate=1786723200000, pubDateStr=2026-08-15, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792852214891, onlineIssueDateStr=2026-10-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792852214891, creator=13701087609, updateTime=1792852214891, updator=13701087609, issue=Issue{id=1320881182762447607, tenantId=1146029695717560320, journalId=1260987677001138203, year='2026', volume='47', issue='16', pageStart='1', pageEnd='537', issueExtLink='null', onlineDate='null', pubDate='1786723200000', pubDateStr='2026-08-15', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792852214756, creator='13701087609', updateTime=1792852214756, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext=null, issueFiles=null, downloadFileDto=null}, startPage=525, endPage=537, ext={EN=ArticleExt(id=1320881183542588152, articleId=1320881183332872951, tenantId=1146029695717560320, journalId=1260987677001138203, language=EN, title=Research Progress on the Generation, Metabolism and Control Methods of Semicarbazide in Aquatic Products, columnId=1261343851327906245, journalTitle=Science and Technology of Food Industry, columnName=Reviews, runingTitle=null, highlight=null, articleAbstract=

Semicarbazide (SEM) is widely monitored as a metabolite of the nitrofuran antibiotic nitrofurazone (NFZ). In recent years, frequent occurrences of excessive SEM residues in aquatic products have seriously hindered the export trade and sustainable development of the Chinese aquaculture industry. Studies have shown that SEM derives from both exogenous and endogenous sources. Exogenous sources include illegal drug use, contamination from water, feed, and algae, and chemical reactions during processing. Endogenous formation, conversely, occurs through pathways such as amino acid metabolism, the urea cycle, and chitin metabolism. This review systematically examines the sources, formation mechanisms, and metabolic behavior of SEM in aquatic products with a focus on advanced detection methods, including metabolomics, transcriptomics, and high performance liquid chromatography. Furthermore, targeted control strategies are proposed, encompassing aquaculture environmental management, optimization of processing procedures, and regulation of key metabolites. This review aims to provide a scientific foundation for the effective prevention and control of SEM contamination in aquatic products in China.

, authors=Honglin ZHANG1, Wanting CHEN1, Xiaoyan WANG1, Yongchang SU2, *, Xiaoting CHEN2, Yihui CHEN1, Zhiyu LIU2, 3, *, Yuejian HE4, authorsList=Honglin ZHANG, Wanting CHEN, Xiaoyan WANG, Yongchang SU, Xiaoting CHEN, Yihui CHEN, Zhiyu LIU, Yuejian HE, authorCompany=null, correspAuthors=Yongchang SU, Zhiyu LIU, authorNote=null, correspAuthorsNote=null, copyrightStatement=Copyright © 2026 Science and Technology of Food Industry. All rights reserved., copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1320881186134668033, articleId=1320881183332872951, tenantId=1146029695717560320, journalId=1260987677001138203, language=CN, title=水产品中氨基脲的产生、代谢及控制方法研究进展, columnId=1261343852603031688, journalTitle=食品工业科技, columnName=专题综述, runingTitle=null, highlight=null, articleAbstract=

氨基脲(Semicarbazide,SEM)常作为硝基呋喃类药物呋喃西林(Nitrofurazone,NFZ)的代谢产物被检测。近年来,水产品中SEM残留超标现象频发,严重影响我国水产品的出口贸易和水产养殖业的可持续发展。研究表明,SEM不仅来源于外源性因素(如非法用药、水体、饲料及藻类污染、加工过程中的化学反应等),还可能通过内源性代谢途径(如氨基酸代谢、尿素循环、甲壳素代谢等)产生。本文综述了水产品中氨基脲的来源、产生机理及代谢规律,探讨了基于代谢组学、转录组学和高效液相色谱等技术的研究方法,并从养殖环境控制、加工过程优化、关键代谢物质调控等方面提出了针对性的控制措施,旨在为我国水产品中SEM污染的有效防控提供理论依据。

, authors=张泓麟1, 陈婉婷1, 王晓燕1, 苏永昌2, *, 陈晓婷2, 陈艺晖1, 刘智禹2, 3, *, 何跃建4, authorsList=张泓麟, 陈婉婷, 王晓燕, 苏永昌, 陈晓婷, 陈艺晖, 刘智禹, 何跃建, authorCompany=null, correspAuthors=苏永昌, 刘智禹, authorNote=

张泓麟(2000−),女,硕士研究生,研究方向:水产品加工与贮藏,E-mail:

, correspAuthorsNote=
苏永昌(1982−),男,博士,副研究员,研究方向:水产品加工与综合利用研究,E-mail:。
刘智禹(1972−),男,博士,教授级高级工程师,研究方向:水产品加工与综合利用研究,E-mail:。
, copyrightStatement=版权所有 © 2026《食品工业科技》编辑部, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=tL+7/ZSD/LJPVVawQKOtrg==, magXml=+LwNUs8buFEuAc+OCP4J5Q==, pdfUrl=null, pdf=50PKPKaMvagH8wPg3z8xew==, pdfFileSize=1878955, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=IRZzSR/em9pD4V9geQ35Eg==, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=uKk3+Y5XRj/Uu2SBSZunzA==, mapNumber=null, fund=null)}, authors=[Author(id=1320881652990062765, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881183332872951, orderNo=0, firstName=null, middleName=null, lastName=null, nameCn=null, orcid=null, stid=null, country=null, authorPic=null, dead=0, email=13850415648@163.com, emailSecond=null, emailThird=null, correspondingAuthor=0, authorType=1, ext={EN=AuthorExt(id=1320881653069754543, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881183332872951, authorId=1320881652990062765, language=EN, stringName=Honglin ZHANG, firstName=Honglin, middleName=null, lastName=ZHANG, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=1, address=1College of Food Science, Fujian Agriculture and Forestry University, Fuzhou 350002, China, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null), CN=AuthorExt(id=1320881653141057712, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881183332872951, authorId=1320881652990062765, language=CN, stringName=张泓麟, firstName=null, middleName=null, lastName=null, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=1, address=1福建农林大学食品科学学院,福建福州 350002, bio={"content":"

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label=Table 1, caption=

Comparison of advantages, disadvantages, and application scope of SEM detection methods in aquatic products

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检测方法优缺点应用范围
HPLC检测灵敏度高,标准性、可靠性好;但衍生化反应时间长,检测效率低适用于NFZ代谢物及其他水产养殖常用药物代谢物的检测分析
HPLC-MS高灵敏度、选择性,具备良好分离能力和分析性能;但仪器昂贵,维护成本高,实验操作复杂适用于水产品中SEM的严格定性、定量及微量分析
ELISA反应灵敏、特异性高、检测时间短;但制备困难,易产生假阳性或假阴性结果适用于大批量水产品快速分析及样本初筛
电化学检测准确性、灵敏度和重现性高;但抗干扰能力较差,方法多处于实验室阶段适用于水产品快速分析和检测,开发便携式检测设备
), ArticleFig(id=1320881660464312552, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881183332872951, language=CN, label=表1, caption=

水产品SEM检测方法优缺点及应用范围比较

, figureFileSmall=null, figureFileBig=null, tableContent=
检测方法优缺点应用范围
HPLC检测灵敏度高,标准性、可靠性好;但衍生化反应时间长,检测效率低适用于NFZ代谢物及其他水产养殖常用药物代谢物的检测分析
HPLC-MS高灵敏度、选择性,具备良好分离能力和分析性能;但仪器昂贵,维护成本高,实验操作复杂适用于水产品中SEM的严格定性、定量及微量分析
ELISA反应灵敏、特异性高、检测时间短;但制备困难,易产生假阳性或假阴性结果适用于大批量水产品快速分析及样本初筛
电化学检测准确性、灵敏度和重现性高;但抗干扰能力较差,方法多处于实验室阶段适用于水产品快速分析和检测,开发便携式检测设备
), ArticleFig(id=1320881660539810025, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881183332872951, language=EN, label=Table 2, caption=

SEM detection technology in aquatic products

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方法检测样品检出限回收率(%)参考文献
HPLC-FLD面包0.20~0.30 μg/kg93.6~94.0[80]
虾94.5~98.0
对虾92.5~97.5
HPLC-FLD虾0.20~0.26 μg/kg84.7~94.7[81]
HPLC-MS/MS日本沼虾0.25~0.5 μg/kg83.4~112.5[82]
LC-MS/MS虾0.043 ng/g96.1~100.0[83]
鲇鱼0.013 ng/g96.6~104.0
酶联免疫吸附测定法鱼肉0.236 μg/kg75~120[85]
虾0.229 μg/kg
背景荧光猝灭免疫层析测定法鱼肉0.12 μg/kg73.5~109.2[76]
虾肉0.15 μg/kg
电化学检测虾肉0.025 μg/kg83.16~93.4[87]
GC-C-IRMS虾0.21 μg/kg74~95
毛蟹0.54 μg/kg71~92
), ArticleFig(id=1320881660598530282, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881183332872951, language=CN, label=表2, caption=

水产品SEM检测技术

, figureFileSmall=null, figureFileBig=null, tableContent=
方法检测样品检出限回收率(%)参考文献
HPLC-FLD面包0.20~0.30 μg/kg93.6~94.0[80]
虾94.5~98.0
对虾92.5~97.5
HPLC-FLD虾0.20~0.26 μg/kg84.7~94.7[81]
HPLC-MS/MS日本沼虾0.25~0.5 μg/kg83.4~112.5[82]
LC-MS/MS虾0.043 ng/g96.1~100.0[83]
鲇鱼0.013 ng/g96.6~104.0
酶联免疫吸附测定法鱼肉0.236 μg/kg75~120[85]
虾0.229 μg/kg
背景荧光猝灭免疫层析测定法鱼肉0.12 μg/kg73.5~109.2[76]
虾肉0.15 μg/kg
电化学检测虾肉0.025 μg/kg83.16~93.4[87]
GC-C-IRMS虾0.21 μg/kg74~95
毛蟹0.54 μg/kg71~92
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水产品中氨基脲的产生、代谢及控制方法研究进展
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张泓麟 1 , 陈婉婷 1 , 王晓燕 1 , 苏永昌 2, * , 陈晓婷 2 , 陈艺晖 1 , 刘智禹 2, 3, * , 何跃建 4
食品工业科技 | 专题综述 2026,47(16): 525-537
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食品工业科技 |专题综述 2026 , 47 (16) : 525 -537
水产品中氨基脲的产生、代谢及控制方法研究进展
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张泓麟1 , 陈婉婷1, 王晓燕1, 苏永昌2, * , 陈晓婷2, 陈艺晖1, 刘智禹2, 3, * , 何跃建4
作者信息
  • 1福建农林大学食品科学学院,福建福州 350002
  • 2福建省水产研究所,福建省海洋生物增养殖与高值化利用重点实验室,福建厦门 361013
  • 3泉州师范学院海洋与食品学院,福建泉州 362000
  • 4葛兰瑞克(厦门)食品科技有限公司,福建厦门 361013
通讯作者:
苏永昌(1982−),男,博士,副研究员,研究方向:水产品加工与综合利用研究,E-mail:。
刘智禹(1972−),男,博士,教授级高级工程师,研究方向:水产品加工与综合利用研究,E-mail:。
作者简介:

张泓麟(2000−),女,硕士研究生,研究方向:水产品加工与贮藏,E-mail:

Research Progress on the Generation, Metabolism and Control Methods of Semicarbazide in Aquatic Products
Honglin ZHANG1 , Wanting CHEN1, Xiaoyan WANG1, Yongchang SU2, * , Xiaoting CHEN2, Yihui CHEN1, Zhiyu LIU2, 3, * , Yuejian HE4
Affiliations
  • 1College of Food Science, Fujian Agriculture and Forestry University, Fuzhou 350002, China
  • 2Fujian Key Laboratory of Marine Biological Aquaculture and High-value Utilization, Fujian Fisheries Research Institute, Xiamen 361013, China
  • 3College of Oceanology and Food Science, Quanzhou Normal University, Quanzhou 362000, China
  • 4Gelan Ruike (Xiamen) Food Technology Co., Ltd., Xiamen 361013, China
出版时间: 2026-08-15 doi: 10.13386/j.issn1002-0306.2025070246
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氨基脲(Semicarbazide,SEM)常作为硝基呋喃类药物呋喃西林(Nitrofurazone,NFZ)的代谢产物被检测。近年来,水产品中SEM残留超标现象频发,严重影响我国水产品的出口贸易和水产养殖业的可持续发展。研究表明,SEM不仅来源于外源性因素(如非法用药、水体、饲料及藻类污染、加工过程中的化学反应等),还可能通过内源性代谢途径(如氨基酸代谢、尿素循环、甲壳素代谢等)产生。本文综述了水产品中氨基脲的来源、产生机理及代谢规律,探讨了基于代谢组学、转录组学和高效液相色谱等技术的研究方法,并从养殖环境控制、加工过程优化、关键代谢物质调控等方面提出了针对性的控制措施,旨在为我国水产品中SEM污染的有效防控提供理论依据。

水产品  /  呋喃西林  /  氨基脲  /  产生机理  /  检测方法

Semicarbazide (SEM) is widely monitored as a metabolite of the nitrofuran antibiotic nitrofurazone (NFZ). In recent years, frequent occurrences of excessive SEM residues in aquatic products have seriously hindered the export trade and sustainable development of the Chinese aquaculture industry. Studies have shown that SEM derives from both exogenous and endogenous sources. Exogenous sources include illegal drug use, contamination from water, feed, and algae, and chemical reactions during processing. Endogenous formation, conversely, occurs through pathways such as amino acid metabolism, the urea cycle, and chitin metabolism. This review systematically examines the sources, formation mechanisms, and metabolic behavior of SEM in aquatic products with a focus on advanced detection methods, including metabolomics, transcriptomics, and high performance liquid chromatography. Furthermore, targeted control strategies are proposed, encompassing aquaculture environmental management, optimization of processing procedures, and regulation of key metabolites. This review aims to provide a scientific foundation for the effective prevention and control of SEM contamination in aquatic products in China.

aquatic products  /  nitrofurazone  /  semicarbazide  /  generation mechanism  /  detection technology
张泓麟, 陈婉婷, 王晓燕, 苏永昌, 陈晓婷, 陈艺晖, 刘智禹, 何跃建. 水产品中氨基脲的产生、代谢及控制方法研究进展. 食品工业科技, 2026 , 47 (16) : 525 -537 . DOI: 10.13386/j.issn1002-0306.2025070246
Honglin ZHANG, Wanting CHEN, Xiaoyan WANG, Yongchang SU, Xiaoting CHEN, Yihui CHEN, Zhiyu LIU, Yuejian HE. Research Progress on the Generation, Metabolism and Control Methods of Semicarbazide in Aquatic Products[J]. Science and Technology of Food Industry, 2026 , 47 (16) : 525 -537 . DOI: 10.13386/j.issn1002-0306.2025070246
氨基脲(Semicarbazide,SEM),又名氨基甲酰肼,分子式为CH5N3O,分子量为75.1,极易溶于水,水中溶解度为100.0 g/L(20 ℃),不溶于乙醚及乙醇[1−2]。呋喃西林(Nitrofurazone,NFZ)是硝基呋喃类(Nitrofurans,NFs)药物的一类,在水产养殖中常用于预防和治疗水产细菌性疾病,一直以来,SEM被认为是NFZ的代谢产物[3],常作为监测水产品中非法使用NFZ的标志物。NFZ在动物体内代谢迅速,半衰期仅为2~5 h[4],而SEM在动物体内可与蛋白质结合并可在动物体内长期稳定存在[5−6],且具有一定的蓄积性。研究显示,动物源性食品中残留的SEM可通过食物链传递给人类,长期摄入会对人体有致癌、致畸等不良影响[7]。在《关于开展2016年国家产地水产品质量安全监督抽查工作的通知》中,将SEM的残留限量值定为1.0 µg/kg。2002年,我国农业部发布《食品动物禁用兽药及其他化合物清单》,明确禁止在所有食品动物中使用NFZ[8],但我国出口的水产品中却时常检测出SEM,这表明水产品中的SEM残留不仅仅是由于NFZ的代谢产生。因此,明确水产品中SEM的来源并采取有效的控制措施既能促进我国水产品养殖和进出口贸易的发展又能保障水产品的食用安全性。
目前关于水产品中SEM的超标问题备受关注,近年来我国甲壳类水产品药物残留中SEM的检出超标率高达50%[9];泰国、文莱、巴西等国家报道了多起虾中SEM残留超标事件[10]。研究表明水产品中SEM的残留除了具有致癌、致畸性外,还可能导致神经毒效应,并对内分泌系统的功能产生影响[11]。Lu等[12]利用蛋白质组学和代谢组学技术探究海参在SEM胁迫下的生长特性,结果表明SEM抑制了海参的生长并伴有严重的氧化应激和炎症反应。根据水产品中SEM的来源途径可分为内源性SEM和外源性SEM,由于其来源途径多样[3],如:水产品中的氨基酸和甲壳素代谢产生、热加工过程产生、水产品所处水体环境及藻类的污染导致的SEM积累以及消毒处理及非法用药等的影响,使得SEM的检测和控制具有一定的难度。本文主要从水产品中SEM的来源途径、产生机理与代谢规律、检测方法与控制措施等方面进行综述,以期为有效控制水产品中的SEM提供理论依据。
水产品中的SEM既可通过氨基酸代谢和尿素循环过程产生,也可由外界环境污染以及加工过程中的添加剂分解迁移产生,其来源多样,使得水产品中SEM的检测和控制具有一定难度,严重影响了我国水产品养殖、加工与进出口贸易的发展。图1展示了水产品中SEM的主要来源,按来源途径可分为内源性SEM和外源性SEM。
尽管目前NFZ在水产品养殖过程中已经被禁止使用,但仍有检测出水产品中SEM含量超标[13],特别是甲壳类水产品。舒秀君等[14]探究了养殖日本沼虾体内SEM变化规律及存在特征,尽管养殖过程中无人为使用NFZ,池塘水体和所用饲料经检测均不含SEM成分,但在养殖的不同时期均有检出SEM,且含量均超过我国限量要求(<1.0 μg/kg)。朱盼盼[11]分别对养殖和野生日本沼虾中SEM含量进行检测以及统计分析,发现尽管日本沼虾在养殖过程中没有使用NFZ等药物,但其不同组织中的SEM含量均高于野生日本沼虾。杨慧荣等[15]对牛蛙中4种NFs药物的代谢物含量进行测定,在不使用任何药物养殖的前提下,从封闭养殖的牛蛙中检出SEM,检出值为0.58 μg/kg,并指出牛蛙中SEM的生成和代谢可能与肝脏有关。这也进一步证实了水产品除了受到外源药物的影响产生SEM,也可能通过一系列代谢过程产生内源性SEM(图2)。
研究表明NFZ的代谢降解并不是水产品中SEM残留的唯一来源[16]。2004年Saari等[17]首次提出内源性SEM的存在,Hoenicke等[18]推测SEM是由具有酰胺基或脲基残基的含氮物质降解形成的。近年来的研究认为SEM前体包括尿素、肼、精氨酸、组氨酸、瓜氨酸、赖氨酸和谷氨酰胺等[19−20],结构分析表明,SEM和氨基酸都是高含氮物质,因此猜测SEM可能是通过降解氨基酸或其他含氮化合物形成的[21]。Zhang等[20]使用21种不同的氨基酸,通过模拟氨基酸代谢途径探讨了虾体内源性SEM的转化机制,结果发现具有酰胺结构的氨基酸以及在代谢过程中能够转化为酰胺结构的氨基酸可能是形成SEM的关键中间体。
Abernethy等[1]研究表明,肼是尿素循环中的关键中间产物,能够与酸根离子发生反应生成SEM,因此在酸性条件下,一些高氨氮含量的食品中可能会产生SEM。由于尿素和SEM在结构上有一定的相似性,因此推测尿素循环的过程与SEM的产生有潜在关系。精氨酸是甲壳类水产品中含量最高的氨基酸,可被精氨酸酶水解为鸟氨酸和尿素进入尿素循环[21],Zhang等[20]在精氨酸、瓜氨酸、赖氨酸和谷氨酰胺中加入尿素,发现这些氨基酸代谢产生SEM的含量有所增加,因此证明了内源性SEM产生的途径可能与氨基酸和尿素有关。有研究发现水环境中盐度和氨氮含量的增加促使虾体内尿素循环加快,尿素循环相关物质飙升。Yu等[22]对南美白对虾各组织的SEM含量进行了检测,发现鳃中的SEM含量高于其他组织,而虾鳃中的精氨酸酶活性最高,这也间接证实了SEM与精氨酸的分解有一定的关系,结合尿素循环中主要物质的变化分析,鉴于精氨酸酶是参与尿素循环的重要物质,因此推测SEM的产生可能与尿素循环有关。
甲壳类水产品的壳质由30%~40%的蛋白质、30%~50%的碳酸钙、磷酸盐以及20%~30%的甲壳素组成[23]。由于SEM主要集中在甲壳类水产品中,对比罗氏沼虾虾壳和虾肉中的SEM含量,发现虾壳中的SEM含量(>25 μg/kg)远高于虾肉(<0.5 μg/kg),由于甲壳素是虾壳的主要结构成分之一,因此推测SEM可能是甲壳素等天然组分代谢生成[10]。研究发现甲壳素和氨基酸在前处理过程中能产生SEM,这一途径可能是导致中华绒螯蟹中内源性SEM残留的原因[24],将甲壳素与17种氨基酸混合物经前处理后,SEM检出值为10.28 μg/kg,与蟹壳中SEM检出浓度较为接近,由此推断蟹壳中SEM检出可能是甲壳素和氨基酸在SEM测定前处理过程中发生化学反应,从而导致中华绒螯蟹中存在内源性SEM。彭婕等[25]分析发现在中华绒螯蟹的肌肉、性腺和鳃中几乎没有检出SEM,而蟹壳中检出率为100%,但其认为壳中的SEM并非源自甲壳素,可能与甲壳中结合蛋白水解氨基酸变化有关。关于甲壳类水产品的内源性SEM是否由甲壳素代谢生成仍需进一步的研究验证。
水产品食用前通常经过一系列高温烹调处理,在此过程中发生美拉德反应以及脂质氧化等一系列反应,赋予其特殊的风味。以江浙地区最具代表的虾干为例,经过热风干燥处理后的虾干,不仅保留了虾的营养成分,还使虾肉中游离氨基酸和呈味核苷酸含量相对增加,赋予其鲜美的滋味和富有嚼劲的口感[26]。但与此同时,水产品中的水分流失,蛋白质发生高温变性,氨基酸代谢加速,可能在一定程度上导致水产品中的SEM含量上升。
Zhang等[27]调查了浙江代表性对虾、蟹等各种水生甲壳类水产品的SEM来源,测试了热处理对SEM含量的影响,结果表明对虾和螃蟹中的SEM在热处理后均大幅增加,并且首次指出SEM含量与热处理温度的关系是呈高斯分布,而非线性关系。Yu等[16]运用了油炸、清蒸、烘焙等方式对虾进行加工后发现虾中的SEM含量均显著升高,且温度、水分等因素都会影响SEM的形成,这很可能是由于氨基酸等成分在高温下代谢分解产生。曹爱玲等[28]将南美白对虾和中华鳖分别在70、100和130 ℃条件下烘干48 h,随着温度梯度升高,壳中的蛋白含量在逐渐减少,SEM检出量明显增加,说明蛋白质受热而逐渐分解产生SEM,并且在烘干过程中水分逐渐减少,样品逐渐浓缩,也会在一定程度上导致SEM浓度增加。
除了内源性SEM外,水产品所处水体环境的污染,以及养殖过程中的非法用药,饲料、藻类中的SEM残留及消毒处理等均可能导致水产品中外源性SEM残留(图3)。
水生环境中的SEM主要来自农田废水、日常用水和工业废水,且SEM具有高亲水性,难以通过沉降作用与颗粒结合,容易被雨水冲刷到海中。由于所处环境受到污染,SEM逐渐在体内积蓄,导致了水产品中的SEM含量超标。2010年首次报告了在水生环境中检测到SEM,我国某些沿海SEM的平均浓度为14.4 μg/L,水生生物(贝类和鱼类)中的SEM水平介于0.82 ng/g和6.46 ng/g之间[29],这不仅影响了水产品的质量和安全,对人类健康也造成了威胁。
Zhang等[27]采集了水样进行检测,结果表明淡水样品中SEM含量高达0.162±0.044 ng/mL,远高于海水样品0.0086±0.0015 ng/mL,且淡水甲壳类水产品中的SEM也远高于海水甲壳类水产品。Tian等[30]监测了山东莱州湾西部海水、沉积物和生物中SEM的分布和含量,他们发现SEM在甲壳类水产品中的残留量在0.32~0.46 μg/kg,且随海水中SEM浓度的增加而增加。徐英江等[29]对山东潮河河口区水体、沉积物和贝类中的SEM状况进行了研究,发现调查区域贝类中SEM的含量在0.82~6.46 µg/kg,而水体中SEM含量为0.18~70.6 µg/L、沉积物中SEM含量为0.26~18.9 µg/kg,两种介质中SEM的浓度都呈辐射形向外逐渐降低,这说明潮河污水排放是污染的重要来源。Xing等[31]将扇贝暴露在含有浓度分别为10、100和1000 μg/L SEM的海水中(10 ℃,30 d),探究扇贝组织中SEM的积累、分布,发现扇贝中的SEM残留与海水中SEM浓度呈正相关(P<0.01)。Mccracken等[32]测定了不同水域中罗氏沼虾体内SEM含量,发现不同生长环境下的罗氏沼虾体内所含SEM含量具有一定的差异,肌肉和壳中检测到的SEM浓度分别为0.10~0.12 ng/g和3.91~8.88 ng/g。由此可见SEM的来源多种多样,当其排放到环境中时会造成水体污染,并在水生生物中积累,造成水产品中SEM的污染和残留。
NFZ是一种人工化学合成的广谱抗生素,对大多数真菌和病毒具有较好的杀灭作用,具有广谱抗菌、不易产生抗药性且低成本的特点而被广泛用于水产养殖中[33]。由于NFZ的“三致”风险,在美国、欧盟、日本及中国先后规定禁止在畜禽和水产养殖中使用NFZ,但是由于其价格低廉,仍有发现在养殖过程中非法使用NFZ的情况。
赵飞越[34]通过NFZ暴露模拟药物滥用过程,结果表明NFZ会造成克氏原鳌虾SEM含量的显著超标(16.20~73.34 µg/kg),且产生的SEM主要富集在克氏原鳌虾肌肉中。Van等[10]用含有一定浓度NFZ(50 mg/L)的海水浸泡虾,检测发现虾壳中的结合态SEM浓度达到50 ng/g,显著高于对照组虾壳中的SEM浓度(27.2 ng/g),这表明滥用NFZ会导致虾体内SEM超标,但Phansawat等[35]用添加了NFZ的饲料喂养虾却未发现虾壳中的SEM超标,这些两种实验结果相互矛盾的原因可能与不同的实验条件及不同给药途径有关。例如,虾养殖期间口服NFZ药物后,代谢物SEM可能从血淋巴液分布到肌肉,而很难到达外壳;而在虾的养殖水体中使用NFZ后,NFZ可直接与虾壳接触,并且代谢产物SEM积聚在虾壳中,从而出现了不同的实验结果,但导致这种差异存在的原因仍需要进一步的实验加以证实。截至目前已有诸多研究结果表明滥用NFZ会造成水产品中SEM含量超标,且SEM会与蛋白质结合从而在水产品机体中稳定存在,并且会通过食物链被人体摄入,造成食用风险,因此有关部门应进一步完善监督管理措施,严厉打击水产养殖过程中NFZ等药物的违法使用。
尽管养殖日本沼虾中SEM含量普遍高于野生日本沼虾,证明水产品中内源性SEM的存在,但由于饲养条件复杂,无法完全排除养殖环境以及饲料、底泥等外在条件的影响。氮源是影响藻类生长和蛋白质含量的关键因素之一,有研究表明,氮水平对类藻生长及其代谢产物有重要影响[36],渔民在水产品的养殖过程中也会在养殖池塘里面泼洒尿素以促进池塘底部的水草等植物的生长。田秀惠[37]对山东省金城湾、四十里湾和莱州湾西部进行调查发现SEM在藻类中有很强的富集能力,富集系数在145.3~200.0之间。由于对虾的养殖过程中会在饲料里添加微藻以促进幼虾的生长[38],因此可能通过转化和富集藻类或其他生物体中的氨基酸来积累SEM[32]。丁军伟等[39]发现水生动物摄入含有NFZ的饲料后,无法实现完全代谢,且代谢物SEM会长期残留,最终对人体产生毒副作用。更有调查表明在许多养虾场的沉积物和水样中发现了高水平的SEM残留物,这可能是由于养殖使用的饲料沉积以及养殖场周围污染水体的引入造成[40]。因此在水产品的养殖过程中应杜绝使用含有NFZ的饲料,防止SEM在水体中残留而被藻类富集,并注意合理添加氮肥,避免水体中的尿素含量过高导致水产品在养殖过程中产生SEM。
由于水产品在贮藏、运输过程中易受外源微生物和空气氧化等因素影响而发生腐败变质,不仅造成产品货架期缩短与经济损失,还可能对消费者身体健康产生威胁,因此许多商家会对水产品进行消毒杀菌或保鲜处理,以保持水产品的品质,延长货架期[41]。研究表明SEM可以在加工后的不同食品中形成[42−43],且一些食品添加剂在加工过程中代谢分解或迁移也可能导致水产品中SEM含量升高[44]。
次氯酸钠主要通过其极强的氧化性使细菌蛋白质变性,从而达到杀菌的目的[45],因而在水产品加工过程中得到广泛的应用,但次氯酸钠处理过后的样品在高pH条件下可以通过霍夫曼反应产生SEM[46]。次氯酸钠溶液中的氨基甲酸根离子可能与水产品中的氨或酸性酰胺反应生成肼,肼再与尿素和其他化合物通过尿素循环反应形成SEM[1]。此外,次氯酸钠消毒剂的使用和残留与克氏原螯虾中的含氮物质反应也会造成克氏原鳌虾组织中SEM的产生,且容易在肝胰腺中形成富集[34],因此在实际养殖和消毒中要严格按照配比配置消毒液,并做好养殖用具的清洗工作,防止残留的次氯酸钠导致的SEM的残留。
除了水产品外,冰鲜鸡肉在加工、运输及贮藏过程中也容易被微生物污染致使其货架期缩短,因此目前肉鸡行业主要通过向预冷池中连续添加次氯酸钠对宰后鸡胴体进行消毒,以减少表面初始微生物数量[47]。早前美国发现鸡肉在冷冻过程中SEM含量不断增加[48],原因是使用了氧化性的抗菌剂[49]。Xing等[50]在使用了次氯酸钠加工后的即食燕窝样品中检测到了SEM。还有研究指出在角叉菜聚糖中也检测到了SEM,这是因为其生产过程中通常需要加入含有0.050%~0.10%活性氯的次氯酸盐溶液对海藻进行漂白处理[51]。沈金灿等[52]探究了不同条件对次氯酸钠消毒剂处理后的鸡爪中SEM产生量的影响,结果显示浸泡温度和有效氯质量浓度、浸泡液pH越高,鸡爪中产生SEM的量也显著升高,且随处理时间的延长而逐渐增大,在8 h后趋于稳定。次氯酸钠作为食品消毒剂具有“双刃剑”效应,在有效杀菌的同时,其本身的残留以及引发的一系列化学反应也是导致水产品中SEM产生的原因之一,因此在水产品加工中应注意合理使用次氯酸钠,严格控制其使用条件,避免SEM的产生。
酸性电解水的制备过程会产生大量的有效氯和活性氧,具有良好的杀菌能力,因此常用于水产品的保鲜中[53],由于具有与次氯酸钠相似的有效氯成分(次氯酸根、次氯酸等)[54],因此用酸性电解水处理水产品的过程中也可能会产生SEM,但其中的有效氯具有时效性且极不稳定,导致SEM的生成量没有明显的规律性。Yu等[55]采用不同浓度的酸性电解水处理氨基酸和尿素等含氮物质,结果显示,经浓度为110 mg/L的酸性电解水处理的精氨酸中产生少量的SEM,当有效氯浓度≥100 mg/L时,尿素基团会被氧化形成SEM。马姗[56]探究了酸性电解水对凡纳对虾SEM生成量的影响,结果发现使用有效率浓度分别为35和110 mg/L的酸性电解水处理后,虾壳SEM含量分别在36和12 h达到最大值2.72和2.54 μg/kg,但由于酸性电解水中的有效氯具有时效性,随着浸泡时间的延长其中的有效氯浓度呈下降趋势,虾中SEM的产生量降低。未来应深入研究酸性电解水与水产品中SEM产生量的关系,采取合适的处理条件对水产品进行杀菌和保鲜。
除了次氯酸钠和酸性电解水外,其他具有氧化性的化学消毒剂,如:双氧水、臭氧等,也可能对水产品中的SEM含量产生影响。有研究指出SEM可通过吖嗪中间体从天然食品化合物中生成,与食品中的过氧化氢、次氯酸盐或氧气发生反应生成肼,在含有尿素类化合物的情况下生成SEM[1]。魏云计等[57]在宠物食品生产过程中对每道工序产生的半成品进行了检测分析,在添加双氧水工序中的半成品中检测到了SEM,其原因可能是因为双氧水会使原料中的动物组织释放出游离氨基酸,其分解可能会产生SEM,且氨基酸代谢过程中会产生尿素和氨,与双氧水在特定条件下可以发生反应,进而生成SEM。马姗[56]用3 mg/L和5 mg/L的臭氧水对凡纳对虾进行处理,两种不同浓度的臭氧水处理均有SEM生成,处理10 min后SEM的生成量分别为4.30 μg/kg和0.80 μg/kg,之所以出现浓度越高的臭氧水处理后SEM的产生量更少的现象,可能是因为高浓度臭氧水的强氧化性使虾体内发生了其他化学反应所导致。由此可见,具有氧化性的化学消毒剂是导致水产品在加工过程中产生SEM的主要原因,这些消毒剂的氧化作用引起水产品中的氨基酸、吖嗪中间体等反应,与尿素结合生成SEM,未来在水产品的生产过程中应严格控制氧化性消毒剂的使用。
偶氮二甲酰胺(Azodicarbonamide,ADC)在食品加工中作为食品添加剂添加入面粉中,以改善面粉的强度和柔韧性[58],市面上常见的面包虾等经过加工出售的水产品中使用了含有ADC的面粉也是导致SEM超标的原因之一。ADC可以在潮湿和酸性条件下转化为联二脲(Biurea,BIU),BIU通过热分解生成SEM[59]。郭思言等[60]将BIU作为判别SEM是否由ADC降解产生的标志性物质,结果表明用含有ADC的面粉处理后的炸虾肉中的SEM一部分来源于NFZ代谢,另一部分来源于面粉中ADC的降解产生。近年来,在虾加工过程中常出现原料虾中未检出药物残留,但加工后的产品却发现SEM含量超标,尤其在面包虾产品中常有出现,且ADC添加量、加水量、加热温度和加热时间等条件对产生的SEM含量也有影响[58]。黄晓姗[61]探究了温度对ADC转化为SEM的影响,结果表明随着烘烤温度的增加,SEM的生成量明显上升,当烘烤温度达到200 ℃时,SEM的生成率最高(0.094%),但当温度继续升高后,可能由于过高的温度会使得生成的SEM进一步分解,从而导致SEM的生成率急剧下降。由此可见,使用含有ADC的面粉制作面包虾等,会导致加工后的产品中产生SEM。
代谢组学是近年来发展起来的新兴技术,通过全谱代谢轮廓差异分析,研究组间样品小分子代谢产物(分子量<1500 Da)的差异[12]。代谢组学技术以内源性的所有小分子代谢物为分析对象,采集经由不同药物干扰或不同暴露程度的生物样本(组织、内脏、血液、尿液等),与阴性样本比较代谢指纹图谱差异[62],更为全面系统追踪整体代谢变化,最大限度地挖掘样品信息,结合化学计量学,发现新的代谢标志物,建立新的残留表征技术和分析方法[63]。由于水产品中的SEM有多种来源途径,其产生机理也复杂多样,研究起来具有一定难度,随着代谢组学技术的进一步发展,目前已有诸多研究人员运用代谢组学对水产品中SEM的产生机理进行研究,为今后水产品中SEM的控制和消除奠定了基础,在一定程度上促进我国水产品养殖业和进出口贸易的健康发展。
高芳芳[64]通过对罗氏沼虾进行不同浓度的精氨酸饲喂实验和尿素胁迫实验证明精氨酸和尿素能够显著增加罗氏沼虾中SEM的检出含量,通过非靶向代谢组学研究表明,精氨酸和尿素是罗氏沼虾SEM产生的关键前体物质,通路归属分析表明尿素胁迫显著改变了罗氏沼虾中氨基酸和核苷酸的代谢和合成,进而影响了罗氏沼虾中鸟氨酸循环的关键物质,从而产生SEM。Li等[65]采用代谢组学和转录组学相结合的方法,系统研究了尿素胁迫下罗氏沼虾SEM的内源产生机制,揭示了尿素胁迫显著破坏了罗氏沼虾体内甘氨酸、丝氨酸和苏氨酸代谢和α-酮戊二酸代谢关键途径,从而突出了氨基酸代谢在SEM形成中的作用。陈霞霞等[66]采用超高效液相色谱-四极杆/静电场轨道阱高分辨质谱代谢组学技术分析SEM的代谢组学特征,并通过体外模拟验证实验检验相关通路物质产生SEM的可能情况,研究结果发现NFZ胁迫影响克氏原螯虾体内牛磺酸及次牛磺酸代谢、精氨酸生物合成、丙氨酸、天冬氨酸和谷氨酸代谢及D-谷氨酰胺和D-谷氨酸代谢相关的通路,并通过体外模拟氨基酸代谢途径验证了精氨酸、丙氨酸、牛磺酸、次牛磺酸、天冬氨酸及D-谷氨酰胺在尿素结合下氧化后能够产生SEM。综上所述,水产品中SEM的产生机理主要是由尿素、NFZ以及其他外界条件的胁迫影响氨基酸代谢和尿素循环的关键物质及相关代谢通路,进而产生SEM(图4)。
研究表明,NFZ在肌肉中的消除半衰期较短[66-67],而SEM在肌肉中的消除半衰期比NFZ长得多,约为7~15 d [68]。除了不同物种之间代谢速率不同的影响外,温度对于代谢时间也有一定的影响[69],机体的温度越高,代谢速率越快,药物消除的速度也就越快[70],虾和鱼等水生动物是变温动物,体温与周围的水相似,因此体内的SEM的代谢速度较慢[71]。汤水粉等[33]在菊黄东方鲀养殖过程中以剂量为0.05 g/m3的NFZ对养殖池进行全池泼洒,定期随机采集菊黄东方鲀肌肉样品测定肌肉中的SEM质量浓度,结果发现菊黄东方鲀体内SEM消除速率呈现先上升后下降的趋势,并在较长时间内维持一定的浓度范围,直至实验结束(77 d)时仍检出约2.50 µg/kg的SEM残留量。Xing等[31]研究发现当扇贝体内SEM积累到平衡点时,生物富集因子(BCF)与所处环境中SEM浓度存在显著的负相关(P<0.01),扇贝的BCF随着所处环境SEM浓度的增加而降低,这很可能与代谢功能有关,由于水生动物可以显著提高其抗氧化酶活性,以减少污染物及其代谢物造成的损害[72],暴露于高浓度SEM环境中会导致排泄时间延长,因此扇贝通过自我调节做出反应以减少机体的损伤。李东利等[73]以30 mg/kg体重剂量投喂对虾NFZ药饵(5 d)后,检测对虾各组织中SEM浓度和肝胰腺中的药物代谢酶活性,结果表明,SEM在对虾体内消除半衰期较长,并对乙氧基香豆素-O-脱乙基酶(ECOD)、氨基比林-N-脱甲基酶(APND)酶活性可能有“抑制后效应”,高浓度SEM抑制ECOD和APND的活性,当SEM降低到一定浓度时ECOD和APND酶活性又开始升高,因此推测ECOD、APND可能参与NFZ在对虾体内的代谢消除。
大多数SEM以蛋白质结合的形式存在于生物组织中,在酸性条件下水解以从样品中释放,然后经衍生化反应后提取、纯化和测定。目前常用的SEM检测方法包括高效液相色谱法(HPLC)[74]、高效液相色谱-串联质谱法(HPLC-MS)[75]、免疫测定法(ELISA)[76]和电化学检测法[77](表1~表2)。
高效液相色谱-串联质谱(HPLC-MS/MS)分析方法具有良好的分离能力和优越的定性定量分析性能,广泛应用于NFZ代谢物及其他水产养殖常用药物代谢物的检测分析[78]。Leitner等[79]首先通过优化前处理、色谱条件和质谱建立了HPLC-MS/MS检测SEM的方法。Yu等[80]建立了一种简单灵敏的高效液相色谱-荧光检测法(HPLC-FLD),用于检测虾样品中的代谢物,检测限在0.20~0.30 μg/kg之间。Du等[81]采用HPLC-FLD同时检测到虾体内的4种NFZ代谢物,检测限为0.20~0.26 μg/kg。由于甲壳类水产品中的SEM具有游离态和结合态两种存在形态,一般检测方法难以区分,徐磊等[82]用66.7%甲醇水溶液对游离态SEM进行洗脱,再运用HPLC-MS/MS检测出了日本沼虾不同组织中总SEM和结合态SEM含量,为后续进一步研究日本沼虾中SEM本底特征、存在形态及分布特征奠定了一定的科学基础。
由于SEM分子结构小,缺乏可检测的UV和荧光发色团,且其高水溶性和在反相色谱中较差的保留性能,使其在质谱仪上直接检测时易受共存小分子的干扰,检测时灵敏度较低。在新发布的标准(GB 31656.13-2021)中,使用2-硝基苯甲醛作为衍生剂,需要在37 ℃摇床上振摇16 h。尽管衍生化反应增加了衍生化SEM的疏水性,使它在有机溶剂中比在水基溶液中更可溶,可用于从水性杂质中提取和分离水溶性目标分子,提高色谱保留性能和检测灵敏度,但在实际工作中,水解衍生反应时间的延长严重影响了检测效率。为了解决这一问题,许多研究报道了辅助水解和衍生化技术来缩短反应时间。例如:采用微波衍生、自动固相萃取和LC-MS/MS技术相结合的方法,可在6 h内测定水产品中的NFZ代谢物[83],该方法的准确度高,相对标准偏差≤8.3%。
免疫分析方法具有反应灵敏、特异性高、技术要求相对较低、时间短等优点,广泛用于食品安全、环境和临床检测,但由于可能会产生假阳性或假阴性的错误结果[84],通常需要HPLC-MS/MS进行验证,因此制备稳定的信号标记对于提高免疫测定的准确性和灵敏度是十分必要的。徐冬梅等[85]建立动物源性食品中NFZ代谢物酶联免疫吸附测定方法,检测灵敏度为0.03 mg/kg,在0.03~2.43 mg/L范围内呈线性,鱼肉组织样本、虾肉组织样本的检测限分别为0.236 µg/kg和0.229 µg/kg,回收率均在75%~120%之间。Wu等[76]构建了一种背景荧光猝灭免疫层析测定法(bFQICA),运用金纳米粒子(AuNPs)猝灭背景荧光基板的荧光,使用便携式荧光免疫定量分析仪和内置标准曲线的二维码可以直接显示SEM的定量结果,使得检测过程更加高效便捷,该技术对鱼肉和虾肉中SEM的检测限分别为0.12和0.15 µg/kg,线性范围为0.08~0.41 µg/L,回收率在73.5%至109.2%之间,变异系数小于15%,整个检测过程仅需13 min。为了满足更高的检测要求,未来还需要不断开发超灵敏、高准确性、具有多种检测能力的免疫分析技术,利用高质量的抗体和新的特异性识别元件提升检测性能[86]。此外,制备稳定的信号标记、提高免疫测定的准确性和灵敏度、发展多重检测技术也是今后免疫分析发展的必然趋势。
电化学检测技术是一种快速而直接的方法,依赖于界面反应和信号识别传感,具有高准确度、灵敏度和重现性,目前已广泛用于食品安全快速分析和检测。Yu等[87]使用由分子印迹聚合物、羧基化单壁碳纳米管和壳聚糖组成的复合材料作为电化学传感界面来检测SEM,检测限为0.025 µg/kg。He等[88]通过用纳米金/石墨烯复合材料修饰薄膜金电极开发了一种用于检测NFZ和SEM的电化学传感器,NFZ的检出限为0.13 μmol/L,SEM的检出限为0.0047 μmol/L。
除了电化学检测技术之外,还有许多快速、便携的SEM检测技术。Wang等[89]基于吡咯并吡咯花菁荧光探针(PPCy-1)固定化试纸构建了一个智能手机辅助便携式测试平台并带有彩色扫描APP,用于实时和现场检测SEM,10 min即可完成检测,检出限为0.18 μmol/L,为可视化SEM检测提供了低成本、方便、快速的分析方法,在食品安全监测中具有潜在的应用价值。Yin等[90]使用优异的光热TA/MoS2制造了一种具有双读数(光热/比色)的新型比色免疫层析分析技术,用于蜂蜜样品中的SEM检测,这种双信号读出模式可以显著提高免疫测定的准确性和多功能性,显著降低了检测成本和周期时间。Cheng等[91]制备出一种新的多模态信号示踪剂,成功应用于开发检测NFZ代谢物的多模态测流免疫层析测定(LFIA)平台。Wu等[13]开发了化合物特异性气相色谱-燃烧-同位素比质谱(GC-C-IRMS)分析结合两步柱前衍生化法测定虾蟹中SEM的氮稳定比,通过氮稳定同位素比值分析(NSIRA)追踪水产品中的内源性SEM和外源性SEM。SEM分子(CH5N3O)含有三个氮原子,氮的质量百分比高达56%,作为NFZ的降解产物,外源性SEM分子中的三个氮原子完全来自其前体,与之相比的内源性SEM由生物含氮氨基酸或组织蛋白代谢的氮稳定同位素比值显著升高,这两种SEM分子之间氮稳定同位素比值的变化可能是体内SEM来源判定的特定指标,这为克服内源性SEM对于相关食品安全法律判决的干扰提供新思路和新方法。
鉴于我国水产品中SEM残留超标现象时有发生,已严重影响我国水产品的出口贸易,并对我国水产养殖业造成了较大冲击。以下针对水产品中SEM的几种典型来源途径,提出相应的控制措施,旨在从源头有效控制SEM污染,为我国水产养殖业及进出口贸易的可持续发展提供参考建议。
ADC是塑料虾筐、泡沫、橡胶制品等中常用的发泡剂,在食品行业中还可作为面粉改良剂添加到面粉等小麦制品中[92],因此,为了防止ADC污染导致的SEM超标,应尽可能选用未添加ADC的运输容器,加工过程中应避免使用添加了ADC的面粉,有关部门应修改完善ADC的限量标准或研究开发其他更安全可靠的食品添加剂。
此外,由于食品加工行业中动物制品、豆制品以及水产品加工过程中所形成的废水;制药生产过程中使用的原料、溶剂、催化剂;以及化工行业合成氨、尿素等所产生的废水等都具有较高的氨氮含量,这些高氨氮废水的排放对水生环境具有较大的危害,因此有关企业及单位应将加强对高氨氮废水的整治工作,如:添加硝化促进剂,遵循共代谢原理及污水处理原理,结合微生物、营养学、生理学等多个不同学科配制硝化促进剂[93]。合理有效地控制废水的排放,对养殖水体中尿素含量、亚硝酸盐和 pH等进行严格控制,防止水产品受所处水生环境中SEM的污染。
由于甲壳类水产品中会产生内源性SEM,且热处理过程导致甲壳类水产品中的SEM含量显著增加,无法准确判断其中的SEM是否是由于滥用药物导致,根据《农业农村部关于印发〈2022年国家产地水产品兽药残留监控计划〉〈2022年国家水生动物疫病监测计划〉的通知》(农渔发〔2022〕7号),对虾、蟹中NFZ代谢物SEM残留不作判定[94],许多养殖者趁此钻了空子,仍然在养殖过程中非法使用NFZ。近年来,研究人员提出了其他潜在的NFZ代谢物作为检测非法使用NFZ的标志物[46,95],这些代谢物包括5-硝基-2-糠醛(5-NF)、5-硝基-2-糠醛-2,4-二硝基苯肼以及谷胱甘肽和NFZ代谢物形成的复合物。其中,5-NF是最常提及的潜在代谢物,但由于其光敏性和空气敏感性,检测该物质具有一定的难度。Wang等[67]在用NFZ饲喂鲶鱼后观察到氰化物代谢物在肌肉中的半衰期为81 h,残留期超过14 d,证明其作为确定水产品中非法使用NFZ的新标志物的可行性。Zhang等[96]提出采用5-NF作为标记代谢物,用2,4-二硝基苯肼(DNPH)进行柱前衍生以区分内源性SEM和NFZ衍生的SEM。未来相关单位应加强SEM风险监测与监督抽查的数据积累,严格执法,加大违法处理力度,对养殖场所实施注册登记或备案管理,保证监管的有效性。此外还应强化对NFZ药物的管理,同时开发替代NFZ的新型抗菌药物。
根据目前研究表明,水产品中的内源性SEM可能由氨基酸代谢与尿素循环过程产生,尿素、肼、精氨酸、组氨酸、瓜氨酸、赖氨酸和谷氨酰胺等可能是SEM产生的主要前体物质[20],内源性SEM的形成与精氨酸的酰胺基及瓜氨酸和尿素的酰胺结构密切相关[22]。但目前关于从水产品代谢过程中采取方法控制SEM的研究鲜有报道,未来可进一步深入研究代谢过程中相关物质的变化,通过减少或去除某些关键前体物质,从而达到控制或减少SEM产生的目的。
水产品中SEM的来源复杂多样,非法使用NFZ药物、所处环境污染、加工过程中的化学反应以及自身的氨基酸代谢、尿素循环过程中均可能导致水产品中SEM产生和积累。近年来,代谢组学、转录组学和高效液相色谱等技术的发展为研究SEM的产生机理以及水产品中SEM的检测技术提供了有力支持,但在实际应用中仍面临检测效率低、内源性与外源性SEM难以区分等问题,且由于各种快速检测技术尚未普及,加之成本和技术方面的限制,在实际运用方面仍存在一定局限性。此外,关于SEM的产生机理的研究相对较少,SEM的控制措施也仅限于从外源性SEM来源途径进行干预,目前未见有研究报道从水产品自身代谢过程对SEM进行控制。深入分析研究水产品中SEM的产生机理及消除方法对于保障我国水产养殖业健康发展具有重大意义,未来应进一步明确内源性SEM的产生途径和关键前体物质,优化检测技术,开发高灵敏度、高特异性的快速检测方法,尤其是能够区分内源性和外源性SEM的检测手段,以满足实际监管需求,完善相关法律法规,加大对非法使用NFZ药物的打击力度,保障水产品的质量安全和国际贸易的健康发展。

参考文献 引证文献
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2026年第47卷第16期
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doi: 10.13386/j.issn1002-0306.2025070246
  • 接收时间:2025-07-21
  • 首发时间:2026-10-24
  • 出版时间:2026-08-15
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  • 收稿日期:2025-07-21
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    1福建农林大学食品科学学院,福建福州 350002
    2福建省水产研究所,福建省海洋生物增养殖与高值化利用重点实验室,福建厦门 361013
    3泉州师范学院海洋与食品学院,福建泉州 362000
    4葛兰瑞克(厦门)食品科技有限公司,福建厦门 361013

通讯作者:

苏永昌(1982−),男,博士,副研究员,研究方向:水产品加工与综合利用研究,E-mail:。
刘智禹(1972−),男,博士,教授级高级工程师,研究方向:水产品加工与综合利用研究,E-mail:。
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2种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)
属
Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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