Article(id=1217529312698355805, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1217529305693864468, articleNumber=null, orderNo=null, doi=10.19812/j.cnki.jfsq11-5956/ts.20250314003, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1741881600000, receivedDateStr=2025-03-14, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1768211208747, onlineDateStr=2026-01-12, pubDate=1752508800000, pubDateStr=2025-07-15, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1768211208747, onlineIssueDateStr=2026-01-12, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1768211208747, creator=13701087609, updateTime=1768211208747, updator=13701087609, issue=Issue{id=1217529305693864468, tenantId=1146029695717560320, journalId=1149652044408987649, year='2025', volume='16', issue='13', pageStart='1', pageEnd='320', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1768211207077, creator=13701087609, updateTime=1768212057891, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1217532874337730593, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1217529305693864468, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1217532874337730594, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1217529305693864468, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=1, endPage=7, ext={EN=ArticleExt(id=1217529314589987004, articleId=1217529312698355805, tenantId=1146029695717560320, journalId=1149652044408987649, language=EN, title=Research progress on detection and control of N-nitrosamines in aquatic products, columnId=1217529307430306336, journalTitle=Journal of Food Safety & Quality, columnName=Highlight: Processing and Quality Safety of Aquatic Products, runingTitle=null, highlight=null, articleAbstract=

N-nitrosamines (NAs) are a class of strongly carcinogenic compounds with high contamination levels in aquatic products, posing significant risks to human health. Recent random inspections in China have revealed that excessive N-nitrosodimethylamine (NDMA) content has become a major factor disqualifying processed aquatic products, seriously hindering the healthy development of the aquatic product processing industry. Therefore, elucidating the formation mechanisms and influencing factors of NAs in aquatic products, along with controlling their levels through processing technologies and multidisciplinary approaches, has become a key research focus. This review systematically examined various formation pathways of NAs in aquatic products, pretreatment methods, and analytical techniques compliant with national food safety standards. It further summarized comprehensive strategies for NAs control, including reduction of NAs precursor intake, blocking of NAs formation pathways, and decomposition of existing NAs. The paper aimed to address the excessive NAs levels in aquatic products, thereby ensuring the quality and safety of aquatic products and promoting sustainable development of the industry.

, correspAuthors=Feng-Yan ZHANG, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, 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, authorCompany=null, fund=null, authors=null, authorsList=Ya-Hui LI, Jian-Bing LI, Jian-Min HAN, Ying-Ying SANG, Hui-Min MENG, Lei ZHANG, Feng-Yan ZHANG), CN=ArticleExt(id=1217529315168801035, articleId=1217529312698355805, tenantId=1146029695717560320, journalId=1149652044408987649, language=CN, title=水产制品中N-亚硝胺类物质的检测与控制研究进展, columnId=1217529307631632938, journalTitle=食品安全质量检测学报, columnName=本期重点:水产品加工与质量安全, runingTitle=null, highlight=null, articleAbstract=

N-亚硝胺类化合物(N-nitrosamines, NAs)是一类强致癌性污染物, 广泛存在于水产制品中并对人体健康构成严重威胁。近年我国市场监管抽检显示, 水产加工品中N-二甲基亚硝胺(N-nitrosodimethylamine, NDMA)超标问题突出, 已成为产品不合格的主要因素之一, 严重影响了水产品加工行业的健康发展。因此, 明确水产制品中NAs的形成机制和受影响因素, 通过加工工艺和多种技术控制其含量是目前大家关注的重点。本文综述了水产制品中NAs的多种形成因素, 及满足食品安全国家标准限量要求的多种前处理方法和测定方法。并从减少NAs前体物质摄入、阻断NAs的生成、分解已生成的NAs等方面总结各种控制方式, 以期解决水产制品中NAs超标问题, 保障水产制品质量安全和行业良好发展。

, correspAuthors=张凤艳, authorNote=null, correspAuthorsNote=
*张凤艳(1979—), 女, 硕士, 高级工程师, 主要研究方向为食品污染物检测技术。E-mail:
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李亚慧(1990—), 女, 硕士, 工程师, 主要研究方向为食品污染物检测技术。E-mail:

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李亚慧(1990—), 女, 硕士, 工程师, 主要研究方向为食品污染物检测技术。E-mail:

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The 9 kinds of most common volatile NAs

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编号 缩写 英文名 中文名 CAS号
1 NDMA N-nitrosodimethylamine N-二甲基亚硝胺 62-75-9
2 NDEA N-nitrosodiethylamine N-二乙基亚硝胺 55-18-5
3 NDPA N-nitrosodipropylamine N-二丙基亚硝胺 621-64-7
4 NPYR N-nitrosopyrrolidine N-亚硝基吡咯 930-55-2
5 NPIP N-nitrosopiperidine N-亚硝基哌啶 100-75-4
6 NEMA N-nitrososomethylethylamine N-甲基乙基亚硝胺 10595-95-6
7 NDBA N-nitrosodibutylamin N-二丁基亚硝胺 924-16-3
8 NMOR N-nitrosomorpholine N-亚硝基吗啉 59-89-2
9 NDphA N-nitrosodiphenylamine N-亚硝基二苯 86-30-6
), ArticleFig(id=1217901255951827422, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529312698355805, language=CN, label=表1, caption=

9种常见挥发性NAs

, figureFileSmall=null, figureFileBig=null, tableContent=
编号 缩写 英文名 中文名 CAS号
1 NDMA N-nitrosodimethylamine N-二甲基亚硝胺 62-75-9
2 NDEA N-nitrosodiethylamine N-二乙基亚硝胺 55-18-5
3 NDPA N-nitrosodipropylamine N-二丙基亚硝胺 621-64-7
4 NPYR N-nitrosopyrrolidine N-亚硝基吡咯 930-55-2
5 NPIP N-nitrosopiperidine N-亚硝基哌啶 100-75-4
6 NEMA N-nitrososomethylethylamine N-甲基乙基亚硝胺 10595-95-6
7 NDBA N-nitrosodibutylamin N-二丁基亚硝胺 924-16-3
8 NMOR N-nitrosomorpholine N-亚硝基吗啉 59-89-2
9 NDphA N-nitrosodiphenylamine N-亚硝基二苯 86-30-6
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水产制品中N-亚硝胺类物质的检测与控制研究进展
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李亚慧 1 , 李建兵 2 , 韩建敏 2 , 桑迎迎 2 , 孟慧敏 1 , 张磊 1 , 张凤艳 2, *
食品安全质量检测学报 | 本期重点:水产品加工与质量安全 2025,16(13): 1-7
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食品安全质量检测学报 | 本期重点:水产品加工与质量安全 2025, 16(13): 1-7
水产制品中N-亚硝胺类物质的检测与控制研究进展
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李亚慧1 , 李建兵2, 韩建敏2, 桑迎迎2, 孟慧敏1, 张磊1, 张凤艳2, *
作者信息
  • 1 青岛市食品药品检验研究院, 青岛 266071
  • 2 青岛市产品质量检验研究院, 青岛 266100
  • 李亚慧(1990—), 女, 硕士, 工程师, 主要研究方向为食品污染物检测技术。E-mail:

通讯作者:

*张凤艳(1979—), 女, 硕士, 高级工程师, 主要研究方向为食品污染物检测技术。E-mail:
Research progress on detection and control of N-nitrosamines in aquatic products
Ya-Hui LI1 , Jian-Bing LI2, Jian-Min HAN2, Ying-Ying SANG2, Hui-Min MENG1, Lei ZHANG1, Feng-Yan ZHANG2, *
Affiliations
  • 1 Qingdao Institute for Food and Drug Control, Qingdao 266071, China
  • 2 Qingdao Product Quality Testing Research Institute, Qingdao 266100, China
出版时间: 2025-07-15 doi: 10.19812/j.cnki.jfsq11-5956/ts.20250314003
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N-亚硝胺类化合物(N-nitrosamines, NAs)是一类强致癌性污染物, 广泛存在于水产制品中并对人体健康构成严重威胁。近年我国市场监管抽检显示, 水产加工品中N-二甲基亚硝胺(N-nitrosodimethylamine, NDMA)超标问题突出, 已成为产品不合格的主要因素之一, 严重影响了水产品加工行业的健康发展。因此, 明确水产制品中NAs的形成机制和受影响因素, 通过加工工艺和多种技术控制其含量是目前大家关注的重点。本文综述了水产制品中NAs的多种形成因素, 及满足食品安全国家标准限量要求的多种前处理方法和测定方法。并从减少NAs前体物质摄入、阻断NAs的生成、分解已生成的NAs等方面总结各种控制方式, 以期解决水产制品中NAs超标问题, 保障水产制品质量安全和行业良好发展。

水产制品  /  N-亚硝胺类化合物  /  影响因素  /  控制措施

N-nitrosamines (NAs) are a class of strongly carcinogenic compounds with high contamination levels in aquatic products, posing significant risks to human health. Recent random inspections in China have revealed that excessive N-nitrosodimethylamine (NDMA) content has become a major factor disqualifying processed aquatic products, seriously hindering the healthy development of the aquatic product processing industry. Therefore, elucidating the formation mechanisms and influencing factors of NAs in aquatic products, along with controlling their levels through processing technologies and multidisciplinary approaches, has become a key research focus. This review systematically examined various formation pathways of NAs in aquatic products, pretreatment methods, and analytical techniques compliant with national food safety standards. It further summarized comprehensive strategies for NAs control, including reduction of NAs precursor intake, blocking of NAs formation pathways, and decomposition of existing NAs. The paper aimed to address the excessive NAs levels in aquatic products, thereby ensuring the quality and safety of aquatic products and promoting sustainable development of the industry.

aquatic products  /  N-nitrosamines  /  influencing factors  /  control measures
李亚慧, 李建兵, 韩建敏, 桑迎迎, 孟慧敏, 张磊, 张凤艳. 水产制品中N-亚硝胺类物质的检测与控制研究进展. 食品安全质量检测学报, 2025 , 16 (13) : 1 -7 . DOI: 10.19812/j.cnki.jfsq11-5956/ts.20250314003
Ya-Hui LI, Jian-Bing LI, Jian-Min HAN, Ying-Ying SANG, Hui-Min MENG, Lei ZHANG, Feng-Yan ZHANG. Research progress on detection and control of N-nitrosamines in aquatic products[J]. Journal of Food Safety & Quality, 2025 , 16 (13) : 1 -7 . DOI: 10.19812/j.cnki.jfsq11-5956/ts.20250314003
N-亚硝胺类化合物(N-nitrosamines, NAs)主要是由亚硝酸盐和胺类物质在酸性条件下反应生成的, 其中N-二甲基亚硝胺(N-nitrosodimethylamine, NDMA)是毒性最强的[1-2], 严重危害人体健康。目前, 不同国家均规定了水产制品中NAs的限量标准, 其中俄罗斯、乌克兰对水产制品中的总亚硝胺(NDMA和N-二乙基亚硝胺)的限定值为3.0 μg/kg[3], 冰岛对水产制品的总亚硝胺限定值为10.0 μg/kg[4], GB 2762—2022《食品安全国家标准 食品中污染物限量》中对水产制品(水产品罐头除外)中NDMA的限定值为4.0 μg/kg。近几年频繁出现水产制品中NDMA检测不合格的情况, 引起国内外的普遍关注。2019年、2021年国家市场监管总局两次通告鳕鱼片和香辣小黄鱼NDMA检测不合格[5-6]。HUANG等[7]2020—2022年度在国内网络、超市、农产品市场采购198批次样品, 包括干制水产品、熟制水产品、咸鱼、鱼糜制品, 其中NDMA检出率77.8%, 不合格率28.8%。WANG等[8]2023年报道青岛干制水产品NDMA的不合格率35%, NAs超标已经成为水产制品不合格的主要因素之一。本文概述影响水产制品中NAs形成的多种因素(如理化、生产工艺、添加剂等), 共同作用影响其最终含量。对于有法规限量要求的NDMA的前处理方法和测定方法进行分析比较, 可根据不同基质和方法特点进行选择。最后通过减少NAs生成、降解已生成的NAs等控制手段, 确保水产制品中NAs超标问题得到解决, 降低NAs对人体健康造成的危害。
NAs是一类含有R1R2-N-N=O结构的强致癌性化合物, 毒性随着取代基碳链的延长而逐渐降低[9]。NAs种类繁多, 分为挥发性和非挥发性两大类。诸多研究认为非挥发性亚硝胺为弱致癌物, 所以目前大多研究集中于毒性较大的挥发性亚硝胺。食品中9种常见的挥发性亚硝胺见表1, 其中NDMA是毒性最强的[10]。NDMA不仅通过长期低剂量接触引发肝癌、胃癌等, 单次高剂量暴露也可能导致急性中毒, 表现为肝损伤、血小板破坏等症状[11-13]。国际癌症研究机构(International Agency for Research on Cancer, IARC)将NDMA、NDEA归为A类强致癌性物质[12]
研究发现NAs主要由二级胺在酸性条件下与亚硝酸经亚硝基化生成, 亚硝化机制见图1。水产制品中的NAs主要来源于两个方面, 一方面来自外源性摄入, 在水产品腌制等过程中使用的粗盐可能引入硝酸盐, 硝酸盐氧化成为亚硝酸盐[14], 水产品中富含的氧化三甲胺(trimethylamine oxide, TMAO)可分解成二甲胺[15], 在腌制、熏制、油炸、烘干等加工过程中生成NAs; 另一方面来自内源性合成, 人体摄入含有硝酸盐的水产制品后, 与内源蛋白酶和微生物酶分解产生的胺类物质在胃酸环境中反应形成NAs。
影响水产制品中NAs的因素很多, 包括加工工艺、pH、微生物、NAs前体浓度、添加剂及脂肪等。
加工参数对NAs生成具有显著调控作用。不同加工方式通过改变前体物浓度和反应条件影响NAs生成路径: (1)腌渍加工中盐分渗透促进蛋白质降解[16]; (2)干制过程水分活度下降导致前体物浓缩[17]; (3)熏制过程烟气携带NOx加速亚硝化反应[18-19]。值得注意的是, 复合加工方式(如先盐渍后熏制)会产生协同效应, 使NDMA生成量较单一工艺增加。
亚硝酸盐不能直接与胺类物质发生反应。在H+存在条件下, 亚硝酸盐与H+反应生产亚硝酸, 进而分解生成亚硝酐(N2O3)后, 才能与胺类物质反应生成NAs。pH通过调控亚硝化反应动力学影响NAs生成[20]。研究表明, NDMA生成存在显著pH阈值效应[21]: 当pH<3.0时, H+浓度过高导致胺类质子化, 抑制反应进行; pH为3.0~4.0时亚硝酸盐转化效率最高, NDMA生成量达峰值52.2 μg/mL; 而当pH>5.0时反应速率急剧下降96.4%, 这与N2O3的稳定性变化直接相关。
肠杆菌属(Enterobacter)和厌氧芽孢杆菌属(Clostridium)细菌具有合成NAs的能力, 还有一些细菌能够促进NAs的形成。青霉素及根霉素属在NAs的合成反应中具有生物催化作用, 硝酸盐还原菌能使体内摄入的硝酸盐转化为亚硝酸盐从而促进NAs的合成。某些特定细菌还能产生一种蛋白质降解酶来促进亚硝化反应, 也能通过形成稳定的酸性反应条件催化NAS的生成[22]。孙瑛等[23]研究了海水鱼腌制过程细菌群落多样性和NAs变化的关系, 认为海水鱼腌制过程中的嗜冷杆菌属(Psychrobacter)与NAs变化有关。YURCHENKO等[4]认为爱沙尼亚市场上几种腌渍鱼类中不同含量的NDMA一定程度上与一种耐盐并具有硝酸盐还原能力的金黄色葡萄球菌(Staphylococcus aureus)污染有关联。
虽然水产制品中NAs反应机制尚不明确, 一般认为氧化三甲胺分解产物二甲胺和三甲胺, 是生成NAs的重要前体物质, 可与亚硝酐(N2O3)生成NAs。不同水产品含有的氧化三甲胺含量不同, 与种类、生存环境等密切相关[24]。另外不新鲜的水产品蛋白质分解也较多, 存在更多的生物胺(如尸胺、腐胺、组胺等), 能在微生物和酶的作用下亚硝化反应生成NAs[25-26]
GB 2760—2024《食品安全国家标准 食品添加剂使用标准》不允许水产制品直接添加硝酸盐和亚硝酸盐。天然或合成的抗氧化剂能抑制NAs的形成[27-30], 包括抗坏血酸、维生素E、香辛料类、酚类、巯基化合物等。
脂肪能促进NAs的生成。研究发现, 脂肪氧化产生的丙二醛以及游离脂肪酸释放的自由基能促进NAs的形成。MOTTRAM等[31]将腊肉分离成瘦肉和脂肪两部分, 经油煎后, 瘦肉中NDMA含量为2.6 μg/kg, 脂肪中NDMA为14.9 μg/kg, 完整腊肉中NDMA为6.7 μg/kg。熊凤娇等[32]发现过氧化值较高的花生油比过氧化值低的葵花籽油促进NAs生成的作用更明显。
目前, 对水产品中挥发性亚硝胺的检测方法研究较多, 特别是NDMA, 受法规和标准限量要求, 方法开发也集中于这类化合物, 非挥发性NAs的研究相对较少。
水产品基质复杂, NDMA限定值4.0 μg/kg, 需要方法选择性强, 灵敏度高, 检出限低, 还需要简洁有效的前处理技术, 前处理技术是关键和难点。前处理方法包括水蒸气蒸馏法、固相萃取法、QuEChERS法、固相微萃取法、化学衍生法等。测定方法主要包括: 气相色谱-串联质谱法(gas chromatography-tandem mass spectrometry, GC-MS/MS)、液相色谱-串联质谱法(liquid chromatography-tandem mass spectrometry, LC-MS/MS)、气相-色谱热能分析法(gas chromatography-thermal energy analysis, GC-TEA)等。
水蒸气蒸馏法是水产制品中挥发性亚硝胺检测的传统方法。该方法通过样品和水混合, 同时加入NaCl, 通过水蒸气蒸馏并冷却后用二氯甲烷收集, 能去除大部分非挥发性杂质, 还可实现样品高倍数浓缩, 但该法样品前处理复杂、样品用量大、耗时长, 使用大量二氯甲烷, 不适用于高通量分析, 也不适用于检测非挥发性亚硝胺类化合物。马兴等[33]自主研发快速水蒸气蒸馏仪, 结合GC-TEA技术快速测定肉制品和水产制品中的13种NAs, 平均蒸馏时间15 min, 大大提高效率, 同时采用N-亚硝二异丙胺为内标有效提高方法稳定性和回收率, 是对国家标准方法的有效改进。
固相萃取法是一种替代液液萃取法的集样品分离、富集、净化、溶剂转化于一体的技术。固相萃取技术具有富集效果好、回收率高, 操作简单等优点, 广泛应用于食品中污染物的分离和富集, 是目前干鱼、香肠、烤羊肉等各类食品中NAs污染物测定的主要前处理方法之一。SANNINO等[34]测定肉制品中9种挥发性NAs含量选用ChemElut和Florisil商品化固相萃取柱, 所得方法精密度高、重复性好、回收率好。使用固相萃取法可以减少取样量, 减少前处理时间, 实现高通量处理。但固相萃取法在净化过程中容易出现堵塞管柱, 解析时间长的问题, 提取净化难度大。研究发现使用氢氧化钡碱性溶液处理样品, 能有效解决上述问题, 还能促进蛋白沉淀, 使黏度变小, 有利于后续固相萃取柱净化富集[35-36]
QuEChERS法前处理步骤简单、成本低、选择性好, 能有效提高检测速度和准确度。近年来国内外食品中NAs的前处理方法也以QuECHERS法为主, GB 5009.26—2023《食品安全国家标准 食品中N-亚硝胺类化合物的测定》也将QuEChERS法作为NDMA检测的一种前处理方法。该法是将固相分散剂直接加入到提取液里面, 且固相分散剂不是吸附被测物, 而是吸附提取液中的杂质干扰物, 达到净化效果。国内外学者都建立了用QuEChERS法分析不同样品中挥发性NAs的含量, 方法准确定好, 回收率高[35,37]
固相微萃取法可用于肉制品[38-39]、药品[40]、生活饮用水和啤酒[41]中NAs的测定, 缺点是萃取头价格昂贵、使用次数有限。
化学衍生法原理是NAs在含有氢溴酸的乙酸溶液中反硝化反应产生胺类物质, 然后与丹磺酰氯等类衍生试剂反应生成可用荧光检测器检测的物质[42-43], 该前处理方法专一性好, 灵敏度高, 检出限低, 但需要衍生过程比较复杂, 反应时间长, 反应不完全等缺点。
NAs的前处理方法很多, 各有优缺点, 水产品本身会有高蛋白、高脂肪、高色素、高糖、高盐、在加工过程中还会添加各种添加剂, 都给前处理带来困难, 此外后续不同的检测仪器, 由于原理不同, 对前处理的要求也有差异, 因此需要分类系统选择水产制品中NAs检测的前处理方法, 确保后续各类基质中NAs检测结果的准确性。
GC-TEA是NAs检测国标方法之一, 其工作原理是自GC分离后的NDMA在热解室中经特异性催化裂解产生一氧化氮基团, 后与臭氧反应生成激发态, 返回基态时发出近红外光, 并被检测。热能分析仪只能检测NO-基团, 成为NAs的专用检测器。这种方法针对性强, 灵敏度高, 可以实现较低的检出限, 但该方法样品前处理复杂、耗时长、有机溶剂用量大, 实验室配备率低。
GC-MS/MS具有高抗干扰能力和高选择性, 已逐步成为水产制品中NAS检测的常用方法。GB 5009.26—2023中新增的前两种方法均采用GC-MS/MS。王艳丽等[44]利用通过式固相萃取技术, 结合GC-MS/MS测定了动物源性食品中11种NAs, 实现了动物源性食品中NAs的快速测定。陈丽香等[45]建立了一种同时检测干制水产品中9种NAs的GC-MS/MS方法, 采用外标法定量, 9种NAs在0.3~0.5 μg/L范围内线性关系良好, 相关系数r2>0.999, 检出限为0.3 μg/kg, 定量限为1.0 μg/kg, 样品回收率在80.41%~113.73%。目前针对GC-MS/MS法测定食品中挥发性NAs的研究较多, 能满足线性标准下的限量要求, 但该法对于沸点高、热稳定性差的NAs不适用。
LC-MS/MS不仅可以检测挥发性NAs, 对非挥发性、热不稳定性或分子量较大的NAs也有良好的分析能力, 同时结合大气压化学电离源(atmospheric pressure chemical ionization, APCI)可以检测挥发性NAs, 用途广泛且分析速度远快于GC-MS/MS法。HERRMANN等[46]采用液相色谱-(大气压化学电离/电喷雾电离)串联质谱法[liquid chromatography-(atmospheric pressure chemical ionization/ electrospray ionization) tandem mass spectrometry, LC- (APCI/ESI)MS/MS]同时测定肉制品中挥发性和非挥发性NAs含量, 检出限分别是0.2 μg/kg和1.0 μg/kg。AMELIN等[47]采用超高效液相色谱-高分辨飞行时间质谱法检测食品中7种NAs, 对液态食品(水、啤酒)中的线性范围为2~100 ng/mL, 对固态食品(肉、鱼、贻贝、麦芽、谷物、香肠和腊肠)中检测范围为4~100 ng/g, 对液态和固态的检出限分别是0.0005~2 ng/mL和2~5 ng/g, 回收率分别为62%~105%, 相对标准偏差小于等于17%。LC-MS/MS检测食品中NAs具有前处理过程简单、基质干扰小, 检出限低等优点, 具有巨大的发展前景。
控制措施方面主要从减少NAs前体物质摄入、阻断NAs的生成、分解已生成的NAs方面进行总结。
粗盐中可能含有亚硝酸盐, 粗盐腌制咸鱼的NAs含量高于精盐[48], 要控制粗盐的使用。另外水产品原料的腐败会增加生物胺的浓度, 腐胺、尸胺在酶的作用下亚硝化反应生成NAs[27]。采购新鲜原料并控制贮存温度, 规范解冻操作规程, 控制加工车间温度和时间, 避免加工过程导致产品腐败, 是减少NAs前体物质的有效措施。
腌制、干制、熏制、蒸煮及加工贮存过程中温度、pH、微生物的变化均影响NAs的生成。比如腌制过程中腌制温度、盐鱼比例、腌制时间均影响NAs的生成[49]。干制过程的温度、时间也影响前体物的浓度, 进而影响亚硝化反应速率。如HWANG等[50]研究发现温度较低的冷风干燥能明显降低生物胺的含量, 进而减少NAs的生成。因而冷风干燥替代热风、实时监测确定合适的比例和时间都是有效的方法。
应用阻断剂阻断NAs形成是控制水产制品中NAs含量的重要措施, 目前已经发现的阻断剂有抗坏血酸、维生素E、果蔬类、香辛料类、酚类、酮类、巯基化合物等。周火兰[51]发现大蒜的乙醇浸提液对鱼露中组胺、总生物胺都有很强的抑制作用。VIVAR-VERA等[52]在猪肉、火鸡肉的混合物中添加了杨桃膳食纤维浓缩物, 使维也纳香肠的抗氧化能力上升, 亚硝酸盐含量大幅度降低。张建斌等[53]选择了部分抗氧化活性较高的香辛料, 研究了这些香辛料对NDMA形成的阻断效果, 结果表明八角和丁香的抑制效果随着添加量的增加而增强, 抑制率最高90%以上。唐远谋等[54]研究表明在模拟胃液条件下苦荞叶提取物对NAs的合成具有阻断作用, 其作用强于甘草提取物。
有些微生物能有效降解亚硝酸盐和生物胺等NAs前体物质[55], 如研究发现弯曲乳杆菌能有效降低NDEA、NDPA、NPIP的含量[56], 好氧假单胞菌菌株Y-11对硝酸盐和亚硝酸盐表现出较高的去除能力[57], 这些微生物发挥作用也需要合适的温度、时间和pH, 有望在发酵和腌制鱼产品中应用, 有待进一步研究。辐照对NAs也具有一定的降解作用[58]。目前辐照技术较多运用于食品的冷杀菌, 较少运用于NAs的降解, 也有待进一步研究。
水产制品口味丰富, 深受消费者的喜爱, 具有广阔的发展前景。未来通过深入研究水产加工制品中NAs的产生机制和影响因素, 改进工艺和创新控制技术来解决NAs超标问题, 对水产制品行业的发展尤为重要。未来研究趋势有: (1)检测技术向高灵敏(检出限小于0.1 μg/kg)、多靶标(同时检测15种以上NAs)发展; (2)控制策略从单一阻断转向全程防控, 如“原料-加工-储运”全链条监控系统; (3)新型阻断剂和生物降解技术的应用。多种措施提高我国水产加工品的安全性。另外, 可通过建立体外胃肠模拟实验, 研究NAs内源性形成和外源性来源的人体暴露情况, 结合NAs污染水平, 进行风险评估。
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2025年第16卷第13期
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doi: 10.19812/j.cnki.jfsq11-5956/ts.20250314003
  • 接收时间:2025-03-14
  • 首发时间:2026-01-12
  • 出版时间:2025-07-15
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  • 收稿日期:2025-03-14
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    1 青岛市食品药品检验研究院, 青岛 266071
    2 青岛市产品质量检验研究院, 青岛 266100

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*张凤艳(1979—), 女, 硕士, 高级工程师, 主要研究方向为食品污染物检测技术。E-mail:
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

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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