广东省市售鳜和鲩体内孔雀石绿与硝基呋喃类及其代谢物残留现状研究

目的研究广东省市售鳜和鲩体内孔雀石绿(malachite green,MG)与硝基呋喃类(nitrofurans,NFs)及其代谢物残留现状。方法 111份鳜和鲩样品分别购自广州、深圳、佛山、中山、汕头和茂名等地,采用高效液相色谱-串联质谱法检测孔雀石绿与硝基呋喃类及其代谢物。结果孔雀石绿及其代谢物检出率和硝基呋喃类代谢物检出率分别为33%和14%;孔雀石绿残留主要是隐色孔雀石绿,硝基呋喃类残留主要为氨基脲和3-氨基-2-恶唑烷酮;中山鳜鱼中孔雀石绿和氨基脲检出率最高,分别为83%和50%,佛山鲩体内隐色孔雀石绿检出率为20%;批发市场鳜中孔雀石绿检出率为38%,零售市场高达71%。结论 孔雀石绿及其代谢物检出率高于硝基呋喃类代谢物检出率。孔雀石绿残留主要以其代谢物隐色孔雀石绿形式存在,4种硝基呋喃药物中呋喃唑酮和呋喃西林使用更为普遍。中山和佛山是传统的水产养殖发达地区,孔雀石绿和硝基呋喃类代谢物残留水平相对其他采样点更加严重。与批发市场相比,零售市场鳜鱼孔雀石绿残留检出率更高,应当重点关注。     

广东省鳜鱼和杂交鳢中孔雀石绿和硝基呋喃残留调查及暴露评估

目的了解广东省主要养殖地的鳜鱼和杂交鳢中孔雀石绿及其代谢物和硝基呋喃类代谢物的残留情况。方法利用高效液相色谱-串联质谱法对鱼肉中的孔雀石绿及其代谢物和硝基呋喃类代谢物残留量进行测定。结果2013年孔雀石绿的总检出率为11.7%,硝基呋喃类代谢物的总检出率为20%。2014年孔雀石绿的总检出率为25%,硝基呋喃类代谢物的总检出率为12.5%。近两年总孔雀石绿残留量在0.58~19.1μg/kg之间,总硝基呋喃类代谢物残留量在0.66~36.6μg/kg之间。暴露评估显示:人体每天可能的孔雀石绿的平均暴露量0.24μg,即每人每日膳食暴露量为0.004μg/kg BW,最高暴露量1.10μg,即每人每日膳食暴露量为0.02μg/kg BW;人体可能的每天呋喃西林代谢物的平均暴露量为0.34μg,即每人每日膳食暴露量为0.005μg/kg BW,最高暴露量为0.87μg,即每人每日膳食暴露量为0.01μg/kg BW;人体可能的每天呋喃唑酮代谢物的平均暴露量0.56μg,即每人每日膳食暴露量为0.009μg/kg BW,最高暴露量2.10μg,即每人每日膳食暴露量为0.03μg/kg BW。结论近两年鳜鱼和杂交鳢中孔雀石绿和硝基呋喃类检出率相对较低,膳食暴露评估显示孔雀石绿在此范围内对人体健康损害危险性极小。     

市售鲜活鱼虾中兽药残留检测与分析

建立水产品中4种兽药残留检测方法,并对市售水产品进行检测,为食品安全监管提供参考依据。随机采集市售鲜活鱼虾121份,检测氯霉素、硝基呋喃类及其代谢物、孔雀石绿和恩诺沙星。121份鲜活鱼虾合格率89.26%。禁用药物中氯霉素没有检出,孔雀石绿(含隐性孔雀石绿)和硝基呋喃类及其代谢物有不同程度的检出,其中孔雀石绿的检出率较高,达到7.44%(9/121),最高检出值为621.6μg/kg;限量使用药物恩诺沙星检出率高达87.5%(49/56),但超标率仅为3.57%(2/56)。经过多年管控治理,氯霉素和硝基呋喃类药物已基本检测不到,限用药物恩诺沙星超标率也较低,但是廉价高效的孔雀石绿仍有检出,有必要加强监测和监管。     

2017~2019年昆明市市售食用鱼中几种违禁药物分析

目的 了解2017~2019年昆明市市售食用鱼中违禁药物残留状况。方法 2017~2019年随机采集市售食用鱼142份, 按照《国家食品污染和有害因素风险监测工作手册》检测违禁药物残留, 几种违禁药物都不得检出。结果 142件样品中违禁药物添加检出62件, 检出率39.4%(56件)。孔雀石绿和隐形孔雀石绿, 硝基呋喃代谢物, 喹乙醇及其代谢物检出率分别为2.8%(4件), 28.2%(40件), 8.4%(12件), 检出率最高的是硝基呋喃代谢物。违禁药物检出率最高的是鳝鱼, 其次是泥鳅。结论 昆明市市售食用鱼存在不同程度的违禁药物使用情况, 建议相关部门加大监管力度。     

2020年西安市淡水鱼中兽药残留质量分析

目的 分析2020年西安市淡水鱼中的兽药残留情况。方法 在西安市不同区域随机抽取淡水鱼242批次，采用液相色谱-串联质谱法检测淡水鱼中孔雀石绿、隐色孔雀石绿、氯霉素、硝基呋喃类、地西泮及喹诺酮类等10种兽药残留，并对实验数据进行分析。结果 242批次淡水鱼中共有24批次不合格，不合格率为9.9%，不合格项目涵盖恩诺沙星(以恩诺沙星与环丙沙星之和计)、氧氟沙星、地西泮、呋喃唑酮代谢物等，不合格淡水鱼品种涉及泥鳅、鲫鱼、鲤鱼、黑鱼、鲈鱼、草鱼。结论 西安市淡水鱼存在部分兽药残留，需要加强对喹诺酮类和硝基呋喃类药物，尤其是地西泮等禁用药物在生产、销售和使用过程的管理。     

烟台市动物源性食品中硝基呋喃的污染状况调查

目的对烟台市动物源性食品中硝基呋喃的污染状况进行调查,了解烟台市动物源性食品中硝基呋喃的污染情况。方法采用随机采样的方法,于2012~2017年于烟台辖区内养殖环节、运输环节、流通环节和餐饮环节,共采集动物源性食品样本250份,采用液相色谱-串联质谱法定量检测硝基呋喃类药物残留。结果烟台市售动物源性食品中硝基呋喃类药物总检出率为1.6%(4/250)。双壳类和鱼类水产品中有硝基呋喃代谢物检出,检出率分别为5%(2/40)和2.47%(2/81),甲壳类水产品、畜肉类、禽肉类和蛋类中硝基呋喃代谢物均未检出。4种硝基呋喃代谢物中3-氨基-2-恶唑烷基酮(3-amino-2-oxazole alkone,AOZ)的检出率最高(1.2%,3/250)。结论烟台市动物源性食品中硝基呋喃污染总体较轻,但在一定程度上存在硝基呋喃的残留,应加强监督管理,保障食品安全。     

江西省水产动物源食品中鳜鱼的兽药残留分析

近年来,随着人们物质生活水平的提高,动物源性食品的安全亦成为社会关注的食品安全焦点之一,兽药残留是动物性食品最主要的污染源之一。随着消费市场对鳜鱼需求量日益增长,人工繁育苗种和商品鳜鱼养殖日益趋向规模化的发展。由于抗生素、激素等兽药在降低发病率和死亡率、促进生长和改善水产品品质等方面发挥着重要作用,已成为现代渔业不可或缺的物质基础。然而兽药的滥用甚至违禁使用,不仅会直接对人体产生急慢性毒性作用,引起细菌耐药性的增加,还可以通过环境和食物链的作用间接对人体健康造成潜在危害,并且涉及到生产经营企业的经济利益和国家经济的发展。要保证水产食品的安全,保障人民身体健康,兽药残留监控是关键。本文通过利用高效液相色谱-串联质谱法(LC-MS/MS)对鳜鱼肉中的四类兽药残留进行测定,以了解江西省水产市场鳜鱼中9种磺胺类、7种喹诺酮类、3种氯霉素类和4种硝基呋喃类兽药残留情况。实验结果显示:检测的150份鳜鱼产品中孔雀石绿的检出率为:5%-10%,喹诺酮类的检出率为:5%-12.5%,磺胺类、氯霉素类和硝基呋喃类均未检出,从而得出如下结论:江西省部分地区市售水产品中鳜鱼存在兽药残留,具有一定的食品安全隐患,应该引起重视。     

深圳市淡水鱼类中孔雀石绿及结晶紫残留状况的调查分析

目的调查分析深圳市市售水产品鱼类中孔雀石绿及其代谢物、结晶紫及其代谢物的残留情况。方法样品依据GB/T 19857-2005经超高效液相色谱-串联三重四极杆质谱法(ultra performance liquid chromatography-triple quadrupole mass spectrometry,UPLC-MS/MS)测定样品中的孔雀石绿、隐性孔雀石绿、结晶紫、隐性结晶紫。结果 300份鱼类样品孔雀石绿及其代谢物的检出率为1.67%(5/300)、结晶紫及其代谢物的检出率为23.67%(71/300);500份鱼养殖水样品中结晶紫及其代谢物的检出率为0.6%(3/500),孔雀石绿及其代谢物无检出。不同种类养殖鱼间比较,鲈鱼、生鱼、黄骨鱼的检出率均在36%以上。结论深圳市在售鱼类中存在孔雀石绿/结晶紫及其代谢物检出率高而暂养水检出率低的情况,因此鱼类运输、批发零售环节添加孔雀石绿/结晶紫的可能性较小,养殖环节的滥用值得关注。     

2013~2015年湖北地区虾中硝基呋喃代谢物残留的监测分析

目的 分析湖北省2013年～2015年347份虾产品中硝基呋喃类药物的残留情况,以期为硝基呋喃代谢物的来源和危害分析提供科学依据。方法 采用超高效液相色谱串联质谱法（UPLC-MS/MS）检测湖北9个地区多种虾产品中四种硝基呋喃类代谢物残留量,并用Excel 和SPSS16.0对实验数据进行统计学分析。结果 硝基呋喃类药物的代谢产物的总体检出率为27.09%,检出的代谢物均为氨基脲（SEM）,河虾的检出率最高,为61.54%,其次是基围虾为6.78%;最低是小龙虾为1.38%;对于整体匀浆的带壳河虾样品,检出率高达91.67%,而去壳的河虾虾肉样品没有检出SEM。结论 湖北地区的虾产品中存在不同程度的硝基呋喃污染情况,同时,发现河虾中有内源性的SEM的存在。结合湖北地区居民的膳食消费结果,进行虾中SEM的风险评估,发现虾中SEM暴露对人类健康危害较小。     

广州市食用农产品监督抽检不合格情况分析

正本文主要分析2017年下半年广州市食用农产品监督抽检不合格样品的情况,以利于以后对食用农产品更有针对性地监管。分析结果:2017年下半年食用农产品的不合格率为1.98%,不合格的样品主要是水产品,不合格项目主要为硝基呋喃类、氯霉素、孔雀石绿及其代谢物隐色孔雀石绿。结论:政府监管部门需要通过提高监管水平,对广大养殖户进行宣传教育,严惩违规使用禁用兽药的生产经营者,提高监督抽检的频次,请专业部门研究开发针对水产     

Validation of an LC-MS/MS method for malachite green (MG), leucomalachite green (LMG), crystal violet (CV) and leucocrystal violet (LCV) residues in fish and shrimp

A quantitative liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the simultaneous analyses of malachite green (MG), crystal violet (CV) and its major metabolites, leucomalachite green (LMG) and leucocrystal violet (LCV) residues in fish and shrimp samples has been validated. Fish and shrimp samples were extracted with citrate buffer/acetonitrile, and the extracts were purified on strong cation-exchange (SCX) solid-phase extraction (SPE) cartridge. After conversion of LMG into MG using a post column oxidation reactor containing lead (IV) oxide (PbO(2)), the effluents were analysed. Residues were analysed using positive-ion electrospray ionisation (ESI). Identification and quantification of analytes were based on the ion transitions monitored by multiple reaction monitoring (MRM). Validation of the method was carried out in accordance with the Decision 2002/657/EC, which establishes criteria and procedures for the validation of methods. The following parameters were determined: decision limit (CCα), detection capability (CCβ), linearity, accuracy, precision, selectivity, specificity and matrix effect. The decision limits (CCα) for MG, LMG, CV and LCV were 0.164, 0.161, 0.248 and 0.860 μg kg(-1). The respective detection capabilities (CCβ) were 0.222, 0.218, 0.355 and 1.162 μg kg(-1). Typical recoveries (intermediate precision) in shrimp, for MG, CV, LMG and LCV for 2.0 μg kg(-1) level fortified samples using the optimised procedure were in the range 69%, 97%, 80.3% and 71.8%, respectively. The findings demonstrate the suitability of the method to detect simultaneously MG, CV and its metabolite (LMG and LCV) in fish and shrimp.     

水产品中孔雀石绿检测方法的研究进展

孔雀石绿(malachite green, MG)由于其对水产品疾病防治的高效性和低廉的成本而被广泛用作水产养殖业的杀菌剂和杀寄生虫剂, 因此常见于水产品和环境用水中。但是, MG及其主要代谢产物隐性孔雀石绿(leuco-malachite green, LMG)也是有毒的有机污染物, 对人体和其他生物的健康有害。近年来, 已经提出了用于检测MG和LMG的多种方法。用于测定各种基质中MG和LMG的分析方法包括高效液相色谱法(与紫外-可见、荧光、质谱等检测器联用)、光谱法(紫外-可见分光光度法、荧光法、表面增强拉曼光谱法等)、电化学方法、免疫学测定法(酶联免疫法、化学发光免疫法、免疫层析法等)。本文对近10年来孔雀石绿和隐性孔雀石绿的检测方法进行综述, 并讨论了孔雀石绿和隐性孔雀石绿的未来检测发展趋势和所面临的挑战, 为水产中孔雀石绿的检测方法提供一定参考。     

Development of an accelerated solvent extraction, ultrasonic derivatisation LC-MS/MS method for the determination of the marker residues of nitrofurans in freshwater fish

A rapid method using accelerated solvent extraction (ASE) and ultrasound enhanced derivatisation has been developed for the quantitative determination of metabolites of nitrofurans, namely 3-amino-2-oxalidinone (AOZ), 5-morpholinomethyl-3-amino-2-oxalidinone (AMOZ), 1-amino-hydantoin (AHD) and semicarbazide (SEM), in muscle and skin of carp and finless eel. The target analytes were extracted using ASE, ultrasonic derivatisation for 1?h and then purified by solid phase extraction. Averaged decision limits (CCα) and detection capability (CCβ) of the method were in the range of 0.07-0.13 and 0.31-0.49?μg?kg?1 in carp and finless eel, respectively. The accuracy in terms of recovery was in the range 77.2-97.4%. The simplified and traditional methods were compared with incurred residue samples. The simplified method reduced the derivatisation time and has been applied to the determination of nitrofurans residues in fish.     

Fluorescence Quenching Immunoaffinity Test Column with Quantum Dots as Fluorescence Donors for the Quick Detection of Malachite Green and Crystal Violet in Aquatic Products

A visual fluorescence quenching immunoaffinity test column (FQ-ITC) assay was developed for the simultaneous detection of malachite green (MG) and crystal violet (CV) residues in aquatic products. The proposed FQ-ITC assay was based on fluorescence resonance energy transfer from the fluorescence donor (quantum dot) to the fluorescence acceptor (MG or CV) and the specific identification between the analytes and their polyclonal antibodies. The process can be completed within 10 min, and the results can be observed by the naked eye. After the evaluation of the specificity and sample matrix effect, the established FQ-ITC was found to be successfully applied in the detection of MG or CV in grass carp, striped bass, carp, and shrimp, with a visual limit of detection of 2 μg/kg. The accuracy of the FQ-ITC assay was verified by comparison with liquid chromatography-tandem mass spectrometry. The simple, time-saving, sensitive, and visual observation characteristics make the established FQ-ITC assay an effective analytical tool for the simultaneous detection of MG and CV in aquatic products.     

分子印迹固相萃取—高效液相色谱法检测鱼肉中的孔雀石绿和结晶紫

将分子印迹固相萃取和高效液相色谱法联用,建立一种检测鱼肉中孔雀石绿和结晶紫及其代谢产物残留的新方法。以孔雀石绿为模板分子,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,本体聚合法合成分子印迹聚合物。并制成分子印迹固相萃取柱,优化分子印迹固相萃取的实验条件。鱼肉样品经过超声提取后,采用分子印迹固相萃取富集净化,用高...     

Development of an accelerated solvent extraction,ultrasonic derivatisation LC‐MS/MS method for the determination of the marker residues of nitrofurans in freshwater fish

A rapid method using accelerated solvent extraction (ASE) and ultrasound enhanced derivatisation has been developed for the quantitative determination of metabolites of nitrofurans, namely 3‐amino‐2‐oxalidinone (AOZ), 5‐morpholinomethyl‐3‐amino‐2‐oxalidinone (AMOZ), 1‐amino‐hydantoin (AHD) and semicarbazide (SEM), in muscle and skin of carp and finless eel. The target analytes were extracted using ASE, ultrasonic derivatisation for 1?h and then purified by solid phase extraction. Averaged decision limits (CCα) and detection capability (CCβ) of the method were in the range of 0.07–0.13 and 0.31–0.49?µg?kg^?1 in carp and finless eel, respectively. The accuracy in terms of recovery was in the range 77.2–97.4%. The simplified and traditional methods were compared with incurred residue samples. The simplified method reduced the derivatisation time and has been applied to the determination of nitrofurans residues in fish.     

市售淡水鱼中孔雀石绿及其代谢物残留量的调查研究

目的 了解福建省餐饮环节淡水鱼孔雀石绿(MG)及其代谢物无色孔雀石绿(LMG)的残留情况.方法207份样品来自福建省6个市有关餐饮场所,共28个品种,制作为鱼肉浆,经前处理后,采用高效液相色谱/荧光法对鱼内浆中孔雀石绿及其代谢物的残留总量进行检测,阳性样品再用高效液相色谱/质谱法确证.结果 15个品种的48份样品检出孔雀石绿及其代谢物,检出率为23.2％,总MG含量在0.54～8 099μg/kg之间.桂花鱼检出率最高,达到92.9％ (26/28),草鱼检出率较低,为2.38％ (2/84).结论 餐饮环节销售的淡水鱼孔雀石绿及其代谢物的检出率相对较高,在某些品种淡水鱼供应链中滥用MG的现象较为突出,需要有关监管部门加大打击滥用MG的力度,确保淡水鱼的消费安全.     

基于空间夹角判据测定水产品中孔雀石绿残留量

通过高效液相色谱-光谱联用采集数据,应用向量-子空间夹角计算判据,建立水产品中孔雀石绿的快速分析方法。先采用全波长紫外-可见光纤光谱仪建立孔雀石绿的标准光谱数据库,以及市售水产品样品的紫外-可见光谱数据,再通过高效液相色谱-光谱联用方法,建立扣除水产品中待测组分孔雀石绿的本底光谱数据库;运用向量-子空间夹角判据计算草鱼、罗非鱼、黄蜂鱼、海蟹、海虾、玉米螺样品中孔雀石绿的含量。结果表明,在0.2～4.0 μg/mL的线性范围内,孔雀石绿标准工作曲线的线性相关系数r=0.999 7（λ=618 nm）,加标回收率为99.24%～109.38%,相对标准偏差小于5.0%。此方法可用于水产品中孔雀石绿残留量的快速检测。