元素分析-稳定同位素质谱法结合化学计量学鉴别橄榄油掺假

为建立快速鉴别橄榄油掺假的检测方法,以特级初榨橄榄油、玉米油、猪油、牛油和鸭油为实验材料,通过元素分析-稳定同位素质谱仪测定油脂的δ¹³C、δ¹⁸O和δ²H,并结合化学计量学鉴定橄榄油掺假。采用主成分分析(PCA)和正交偏最小二乘法判别分析(OPLS-DA)两种统计分析方法建立不同油脂的鉴别模型和橄榄油掺假鉴别模型。结果表明：橄榄油的δ¹³C、δ¹⁸O和δ²H范围分别在-30.411×10^-3～-28.996×10^-3、23.583×10^-3～25.581×10^-3、-163.611×10^-3～-132.251×10^-3之间;橄榄油与玉米油、猪油、牛油和鸭油的OPLS-DA鉴别模型准确性稍好,3个变量δ¹³C、δ²H和δ¹⁸O对不同油脂区分的贡献度VIP值分别为...     

Study on distribution pattern of stable carbon isotope ratio of Chinese honeys by isotope ratio mass spectrometry

The δ ¹³C values of 26 varieties of Chinese pure single‐flower honeys, 323 census samples of six varieties of single‐flower honeys and one multi‐flower honey as well as 20 888 commercial honey samples from 135 honey‐related enterprises in 25 provinces of China were analysed by stable carbon isotope ratio mass spectrometry between 1998 and 2004. It was found that the δ ¹³C values of different Chinese honeys fell within the ranges of values proposed by JW White. This shows that White's theory of the stable carbon isotope ratio of honeys is applicable to Chinese honeys and further demonstrates that the theory is universal to honeys from all over the world. The study also confirmed that the δ ¹³C values of honeys do not bear much relation to the environment in which the honey plants are grown, e.g. geographical area, water and soil, climate, etc., but do vary slightly with the honey plant species. Copyright © 2005 Society of Chemical Industry     

液相色谱/元素分析仪-同位素质谱法鉴定蜂蜜 掺假的方法改进

目的改进液相色谱/元素分析仪-同位素质谱法鉴别蜂蜜掺假的方法。方法对现有欧盟标准方法优化液相色谱条件,结合元素分析仪-同位素质谱法,将二糖分离为麦芽糖、蔗糖,提出一个新的参数—麦芽糖、蔗糖δ~(13)C值之差δ~(13)C_(M-S)。结果根据本研究检测113个国内外不同来源纯正蜂蜜样本的数据,提出纯正蜂蜜δ~(13)C值新要求:蜂蜜蛋白质与蜂蜜同位素差值δ~(13)C_(P-H)大于-0.97‰;果糖、葡萄糖δ~(13)C值之差δ~(13)C_(F-G)在-0.60‰至0.56‰范围内;麦芽糖、蔗糖δ~(13)C值之差δ~(13)C_(M-S)在-0.73‰至0.98‰范围内;各个组分δ~(13)C最大差值δ~(13)C_(max)小于2.05‰;根据上述4个参数来确认蜂蜜是否掺假。在日常检测和市场销售的160个样品中,原方法阳性检出率为16.2%,而新方法阳性检出率达21.9%。结论本研究提升了蜂蜜掺假检测能力,此方法的建立更好、更精确打击掺假的同时,也维护消费者权益。     

基于超高效液相色谱-四极杆-静电场轨道阱高分辨质谱法结合化学计量学鉴别新鲜和反复冻融牛肉

目的 建立利用超高效液相色谱-静电场轨道离子阱质谱(UHPLC/Q-Orbitrap-MS)结合化学计量学鉴别新鲜和反复冻融牛肉的方法。方法 样品经过前处理后,采用UHPLC/Q-Orbitrap-MS获得新鲜和反复冻融牛肉指纹图谱信息。运用SIMCA软件结合模式识别方法对数据进行分析,建立新鲜和反复冻融牛肉的主成分分析模型（PCA）和正交偏最小二乘-判别分析模型（OPLS-DA）。结果 PCA模型选择了前10个主要成分,解释了总方差（R2）的70.9%,其预测能力（Q2）为52.1%,结果表明可以对新鲜和反复冻融牛肉进行有效区分。OPLS-DA模型中的R2、Q2均接近于1,说明模型的预测能力以及准确性较好。采用变量重要性因子（VIP）筛选出冻融过程中11种可能的差异代谢物,进一步进行结构确证,确定了乳酸、烟酸和酪胺为生物标志物。 结论 UHPLC/Q-Orbitrap-MS结合化学计量学的方法可以用于新鲜和反复冻融牛肉有效鉴别。     

元素分析-同位素质谱法鉴定麦卢卡蜂蜜中碳-4植物糖掺假

目的建立元素分析-同位素质谱法(elementanalyzerstableisotopeproportionalmassspectrometry,EA-IRMS)鉴定麦卢卡蜂蜜中碳-4植物糖掺假的新方法。方法样品经前处理后,利用元素分析-同位素质谱仪测定蜂蜜的碳同位素比值δ~(13)C_H、蜂蜜中总蛋白质的碳同位素比值δ~(13)C_P、蜂蜜中花粉的碳同位素比值δ~(13)C_F。用麦卢卡蜂蜜中δ~(13)C值更为稳定的δ~(13)C_F值为标准,δ~(13)C_H值与其进行比较,参照GB/T 18932.1-2002《蜂蜜中碳-4植物糖含量测定方法稳定碳同位素比率法》计算方式,来建立新的计算麦卢卡蜂蜜中碳-4植物糖含量X(%)的计算方式。结果对纯正麦卢卡蜂蜜提出:0X(%)7,δ~(13)C_Fδ~(13)C_Pδ~(13)C_H。新方法利用测定麦卢卡蜂蜜中δ~(13)C值更为稳定的δ~(13)C_F值,代替了原有的比较不稳定的δ~(13)C_P为标准,解决了原方法对于麦卢卡蜂蜜中碳-4植物糖检测的假阳性问题。结论本方法显示出较好的准确度,大大提高了掺假检测的能力。     

稳定同位素比质谱法鉴别焦亚硫酸钠处理大蒜

目的 基于硫稳定同位素比质谱法鉴别焦亚硫酸钠处理的大蒜。方法 通过收集全国主要食品级商家的焦亚硫酸钠与山东、黑龙江和辽宁三省大蒜,比较δ³⁴S值的分布差异,进而开展焦亚硫酸钠模拟浸泡实验以获得大蒜硫同位素的比值变化(Δδ³⁴S)。结果 焦亚硫酸钠的δ³⁴S值分布在-2.0‰～2.0‰和4.0‰～12.0‰两个区间。山东、黑龙江、辽宁三省大蒜δ³⁴S范围分别为1.0‰～8.2‰、1.3‰～6.5‰和1.7‰～6.3‰,东北两省大蒜硫同位素值均小于8.0‰。采用δ³⁴S值为10.6‰的焦亚硫酸钠浸泡东北大蒜,浸泡前后?δ³⁴S发生显著变化。未剥皮组大蒜在质量浓度为5～100 g/L时,?δ³⁴S基本不变,约为1.0‰;剥皮组大蒜在质量浓度为0～20 g/L范围内,?δ³⁴S逐渐升高,在质量浓度为20～100 g/L时,?δ³⁴S基本不变,其值约为1.8‰。结论 硫稳定同位素比质谱法可鉴别焦亚硫酸...     

Correlation between multielement stable isotope ratio and geographical origin in Peretta cows' milk cheese

The aim of this study was to characterize the isotopic composition and protect “Peretta” cows’ milk cheese, a typical product of Sardinia, against other cheeses of the same appearance sold under the same name, but made of raw materials from northern Europe. The study was concerned with 3 types of cheese: those produced in local dairies from milk from free-grazing or pasture-grazing cows in Sardinia (local dairy product), cheeses made on an industrial scale from milk produced by intensive farming in Sardinia (factory cheese), and cheeses made with raw materials imported from other countries (imported product). To distinguish the Sardinian cheeses from the imported product, the stable isotope ratios ¹³C/¹²C, ¹⁵N/¹⁴N, D/H, ³⁴S/³²S, and ¹⁸O/¹⁶O were used. Determination of the isotopic data δ¹³C, δ¹⁵N, δ²H, and δ³⁴S was performed in the casein fraction, whereas δ¹⁸O and δ¹³C were determined in the glycerol fraction. Measurements were performed by isotope ratio mass spectrometry. A comparison between mean values of the isotope ratios by statistical analysis (ANOVA and Tukey's test) showed that the greatest difference between the 3 types of cheese (local dairy, factory, and imported products) was in the ¹³C/¹²C, ³⁴S/³²S, and ¹⁸O/¹⁶O isotope ratios. In the other parameters, either no differences (δ¹⁵N) or minimal differences (δ²H) were found. Evaluation of the data by multivariate statistical analysis (principal component analysis and hierarchical cluster analysis) revealed that the isotope characteristics of the factory products were similar to those of the cheeses produced from imported raw materials, whereas a difference was found between the local dairy-produced cheeses and the products in the other 2 categories.     

国外果汁产地溯源技术的研究进展

随着人们生活水平的提高和食品安全问题的频频发生,消费者更加关注食品的来源。果汁产品的产地溯源也面临着巨大的挑战。本文综述了近年来几种常用于果汁产品产地溯源技术的应用研究进展,主要包括质谱技术、色谱技术、光谱技术和其他技术,并展望了今后果汁产品产地溯源技术研究的发展趋势。     

稳定同位素质谱法鉴别芝麻油中掺杂大豆油、玉米油的研究

利用稳定同位素质谱法进行芝麻油掺杂鉴别的研究。选定C3植物油大豆油、C4植物油玉米油作为掺杂油,测定了芝麻油掺入质量分数分别为5%、10%、15%、20%、30%、50%、80%掺杂油的δ¹³C、δ²H、δ¹⁸O值。结果表明:用δ¹³C、δ²H二维稳定同位素比值对大豆油掺杂油样品进行判别,比仅依靠单一δ¹³C值或δ²H值进行判别的灵敏度有所提升,同时发现δ¹⁸O值与掺杂油的比例没有明显的线性关系。二元回归模型可以对芝麻油中掺杂10%大豆油或5%玉米油定量判别。     

Stable C and N isotope ratio analysis for regional geographical traceability of cattle in China

The aim of this study was to examine the variation in carbon and nitrogen stable isotope ratios in cattle tissues from different provinces in China, and to investigate the correlations of δ¹³C and δ¹⁵N values between different cattle tissues. Furthermore, the success rate of classification using δ¹³C and δ¹⁵N values to distinguish the geographical origin of cattle was analyzed. Fifty nine cattle samples were collected from Jilin, Ningxia, Guizhou and Hebei provinces in China, and the δ¹³C and δ¹⁵N values of de-fatted beef, crude fat and tail hair were measured using isotope ratio mass spectrometry (IRMS). There were highly significant regional differences in the mean values of δ¹³C and δ¹⁵N values in the cattle tissues. A significant correlation was found in δ¹³C and δ¹⁵N between de-fatted beef, crude fat and tail hair, which indicated that all of these matrices could be used to trace cattle to their geographical origin. The results of discriminant analysis showed that δ¹³C was the better indicator for cattle origin traceability than δ¹⁵N. The classification success rate could be improved greatly by combining the two indicators. It was concluded that stable isotope analysis of C and N in cattle tissue can be used to trace cattle diet and origin in China.     

电感耦合等离子体质谱法（ICP-MS）测定葡萄中微量硼

微波消解样品,用电感耦合等离子体质谱法（ICP-MS）,采用在线加入内标,可直接测定葡萄中的微量硼,方法简单、快速,加标回收率在98.65%～101.62%之间,测定结果较为满意。     

Determination of pesticide residues in olive oils with protected geographical indication or designation of origin

Seventy olive oil samples with protected geographical indication (PGI) or designation of origin (PDO) were analysed for fifty‐one target pesticides by means of gas chromatography coupled to mass spectrometry. The highest detection rates were observed for penconazole (n = 20), α‐endosulfan (n = 18), β‐endosulfan (n = 16) and flufenoxuron (n = 12). Four of the seventy investigated samples contained pesticide residues in levels exceeding MRLs. However, the investigated samples showed decreased occurrence and levels of pesticides residues in comparison with previous studies concerning samples from Greek conventional and organic cultivations. According to Spearman matrix, powerful correlations were obtained between α‐endosulfan and β‐endosulfan, detected as pair in thirteen samples and between flufenoxuron and penconazole detected as pair in eleven samples. Among Greek olive oil samples, the Cretan ones showed the lower detection rates and the lowest average number of detected pesticides per sample (1.75) in the case of pesticides positive samples.     

Contributions of mass spectrometry in the Australian Wine Research Institute to advances in knowledge of grape and wine constituents

Since 1971 mass spectrometry (MS) has made a significant contribution to wine research at the Australian Wine Research Institute (AWRI). In the past decade (1995–2004), MS has been involved in an expanded range of studies and now accounts for approximately 40% of AWRI publications appearing in peer‐reviewed scientific journals. Studies involving MS include the analysis of grape‐derived and fermentation‐derived volatiles, oak volatiles, taint compounds, proteins, pigments and tannins. We discuss the contribution MS has made to wine research at the AWRI and the significant advances made by key scientists in this area. In particular, this review focuses on three main areas of analysis of compounds important to wine quality – volatile aroma and off‐flavour compounds, involatile larger molecules such as proteins and tannins, and investigations into taint problems.     

稳定同位素质谱在酿造调味品真伪鉴别中的应用进展

稳定同位素质谱技术（IRMS）作为一种新的检测手段,近年来已经较多地应用于食品质量、真实性鉴定和掺假等研究中。该文简述了稳定同位素质谱技术的发展及检测原理,重点论述近年来该技术在食醋和酱油酿造调味品的掺假及真实性鉴定等方面的研究和应用进展,并对其在食品质量与安全方面的应用研究进行了展望。     

Determination of multi-class pesticide residue in dietary supplements from grape seed extracts by ultra-high-performance liquid chromatography coupled to triple quadrupole mass spectrometry

A new method was developed and validated for the determination of multi-class pesticide residues in nutraceutical products obtained from grape seed extracts. The extraction procedure was based on QuEChERS methodology using ethyl acetate as solvent and a dispersive solid-phase extraction (dSPE) clean-up stage with C₁₈ was included to minimise matrix effects. Pesticides determination was achieved using ultra-high-performance liquid chromatography coupled to triple quadrupole mass spectrometry (UHPLC-QqQ-MS/MS); total running time was 11 min. Pesticides were quantified using matrix-matched calibration. The developed method was validated in terms of matrix effect, linearity, selectivity, limits of detection and quantification, trueness, repeatability and inter-day precision at three concentration levels (10, 50, 100 µg kg^?1). Suitable recovery values were obtained for 76% of analysed pesticides at the lowest concentration (10 µg kg^?1). For most of the compounds, relative standard deviation values were lower than 20% and 25% for intra- and inter-day precision, respectively. Finally, 106 pesticides were determined, and the method was applied to seven dietary supplements from grape seed extract, obtaining various positive results for piperonyl butoxide, cyromazine and diniconazole at concentrations ranging from 2.0 to 13.4 µg kg^?1.     

高效液相色谱-四极杆轨道阱高分辨质谱对动物 源食品中抗生素类成分的快速筛查

目的 建立动物源食品中抗生素快速筛查的Q-Exactive方法。方法 采用酸性乙腈提取动物源食品中的抗生素类化合物, QuEChERS净化, 乙腈水定容, ACQUITY BEH C18色谱柱分离, 以0.1%甲酸-乙腈为流动相, 梯度洗脱分离。Q-Exactive一级全扫描得到的准分子离子的精确质量数用于快速筛选分析, 保留时间和离子阱的二级质谱数据用于进一步定性确证。结果 31 种抗生素的精确质量相对偏差小于5×10?6,线性相关系数均大于0.99, 最低检出限(limit of detection, LOD)均≤10 μg/kg。结论 应用该方法对鱼、牛奶、蜂蜜等实际样品筛查的分析结果良好, 说明该方法是动物源食品中抗生素类成分快速筛选和确证的有效方法。     

元素分析/液相色谱-碳同位素比值质谱法在纯正 苹果汁掺假鉴别中的应用

目的建立一种鉴别检测苹果汁掺假情况的元素分析/液相色谱-同位素比值质谱法(elemental analysis/liquid chromatography-isotope ratio mass spectrometry,EA/LC-IRMS)。方法通过对不同产区不同种类118个纯正苹果汁的糖、有机酸、果糖、葡萄糖、二糖、寡糖碳同位素比值(δ~(13)C值)的测定,建立纯正苹果汁同位素数据库进而提出纯正苹果汁应满足的δ~(13)C值要求。结果有机酸和糖差值Δδ~(13)CO-S在-1.38‰至1.09‰范围内,果糖和葡萄糖差值Δδ~(13)CF-G在-0.70‰至0.57‰范围内,而各组分最大差值Δδ~(13)Cmax4.36‰。对市售105个苹果汁进行检测,采用本方法检出32个阳性样品,而采用本实验室的糖浆标志物法仅检出12个阳性样品。结论本方法大大提高了苹果汁的掺假鉴别,有很大的实际应用潜力。     

超高效液相色谱-串联质谱法测定动物源食品中克霉唑的残留量

目的建立QuEChERS提取和净化、超高效液相色谱-串联质谱(ultraperformanceliquid chromatography-tandem mass spectrometry, UPLC-MS/MS)测定猪肉、牛肉、羊肉、鸡肉等畜禽肉和猪肝、猪肾、羊肝、鸡心等畜禽内脏中克霉唑残留的分析方法。方法样品经正己烷饱和的乙腈提取,提取液经乙腈饱和的正己烷液液分配除脂,并经含PSA和C18粉末的净化管进一步净化。采用0.1%甲酸和乙腈作为流动相进行梯度洗脱,多反应监测模式(multiplereactionmonitoring,MRM)测定,同位素内标法定量。结果本方法在7 min内完成分离分析,方法在0.2～20.0μg/L范围内线性关系良好,相关系数r为0.9999。在0.2、2.0和20μg/kg添加水平下的回收率为78.5%～111.9%,相对标准偏差小于11.1%,方法定量限为0.2μg/kg。结论该方法快速、准确、灵敏,适合动物源食品中克霉唑残留量的测定。