我国市售酱油氯丙醇污染研究:地区间污染水平的比较

采用稳定性同位素稀释气相质谱法定量测定多组分氯丙醇,调查了我国市售酱油氯丙醇的污染水平。调查分3次进行,所抽查的629份市售酱油产于2003~2004年间,来自我国11个省、市。各地区样品3-氯-1,2-丙二醇(3-MCPD)的检出率均较高,在90%~100%之间,3-MCPD水平在0.003~189 mg/kg之间,几何均数为21.1μg/kg;2-氯-1,3-丙二醇(2-MCPD)的检出率在14.3%~83.8%之间;1,3-二氯-2-丙醇(1,3-DCP)、2,3-二氯-1-丙醇(2,3-DCP)的检出率分别在0%~24%、0~18.9%之间,全部样品的几何均数低于定量限。总体上,我国市售酱油氯丙醇污染水平有明显下降,但以各地有限的抽查样品评价,污染的地区差异明显,来自河南、广西、浙江样品污染水平以及检出率相对较高,而福建、江苏、北京以及上海样品污染水平较低。     

Determination of 1,3-dichloropropanol in soy sauces by automated headspace gas chromatography-mass spectrometry.

There has been recent concern about the levels of carcinogenic chloropropanols in some soy sauces. We have devised and tested a new automated headspace GC-MS technique for the analysis of 1,3-dichloropropan-2-ol (1,3-DCP) in soy sauce and similar products. The method incorporates the use of cryogenic trapping and a deuterium-labelled internal standard. The limit of detection was 0.003 mg kg(-1). After in-house validation testing, the method was applied to soy sauce samples that had previously been analysed for the related contaminant 3-monochloropropanediol (3-MCPD). 1,3-DCP was detected in 10 of 40 sauces, all of which also contained 3-MCPD. The highest level was just >1 mg kg(-1). There was no correlation between the levels of 1,3-DCP and 3-MCPD.     

气相色谱-质谱联用法测定液体调味料中4种氯丙醇的含量

选取酱油、鱼露与水解植物蛋白液为试验样品,建立了液体调味料中3-氯-1,2-丙二醇（3-MCPD）、2-氯-1,3-丙二醇（2-MCPD）、1,3-二氯-2-丙醇（1,3-DCP）和2,3-二氯-1-丙醇（2,3-DCP）的气相色谱-质谱联用（GC-MS）检测方法。以样品加入稳定同位素内标后进行固相支持液液萃取,以10 m L正己烷淋洗,15 m L乙酸乙酯洗脱,氮吹近干后,七氟丁酰基咪唑衍生,产物经DB-5MS柱分离,质谱采用选择离子监测模式检测。结果表明,四种氯丙醇在0.005～1.6μg/m L质量浓度范围内呈良好线性关系,3-MCPD、2-MCPD、1,3-DCP和2,3-DCP的检出限分别为2.0μg/kg、2.0μg/kg、5.0μg/kg、5.0μg/kg,定量限分别为5.0μg/kg、5.0μg/kg、10μg/kg、10μg/kg,加标回收率在82.4%～107.0%范围内,精密度实验结果的相对标准偏差（RSD）在0.85%～8.58%范围内。该方法前处理简便,定量准确可靠,可用于液体调味料中四种氯丙醇含量的检测。     

固相萃取-气相色谱质谱联用法测定酱油中3种氯丙醇类污染物

目的 建立一种固相萃取-气相色谱质谱联用测定酱油中多组分氯丙醇类污染物的检测方法.方法 酱油样品上样于硅藻土萃取柱,用乙酸乙酯洗脱目标物,再经七氛丁酰基咪唑衍生化,色谱柱为HP-5MS毛细管柱(30 m ×0.25 mm ×0.25μm),采用气相色谱-质谱法测定,内标法定量.结果 本法中的1,3-二氯-2-丙醇(1,3-DCP)、2,3-二氯-1-丙醇(2,3-DCP)及3-氯-1,2-丙二醇(3-MCPD)的检出限分别为0.4,0.6和0.9μg/kg,线性范围5～100μg/kg(r2 ＞0.999);加标回收实验在5、20及50μg/kg浓度下进行,重复测定5次,3种添加浓度下1,3-DCP、2,3-DCP及3-MCPD的平均回收率分别为92.3％ ～ 99.2％、99.3％ ～ 103.4％、74.5％ ～ 93.5％,精密度分别为0.5％～5.5％、1.4％～4.6％、3.2％～14.3％.结论本法安全、高效、简单、灵敏,适用于大批量酱油样品中氯丙醇类污染物的检测.     

Survey of chloropropanols in soy sauces and related products

A survey of soy sauces and related products available in the USA was conducted to determine the levels of 3-monochloropropane-1,2-diol (3-MCPD) and 1,3-dichloro-2-propanol (1,3-DCP) in these products. Fifty-five retail samples were purchased and analysed for 3-MCPD. 3-MCPD determinations were made according to a gas chromatography/mass spectrometry method validated by a collaborative trial. Eighty-five per cent of the samples analysed contained greater than the detection limit of 0.005 ppm (μg g^-1) for 3-MCPD. Thirty-three per cent contained greater than 1 ppm; the highest level was 876 ppm 3-MCPD. Thirty-nine of the samples analysed for 3-MCPD also were analysed for 1,3-DCP by using a modified method developed and validated in-house. Fifty-six per cent of the samples analysed for 1,3-DCP contained greater than the detection limit of 0.055 ppb (ng g^-1) for 1,3-DCP; the highest level was 9.8 ppm 1,3-DCP. Products manufactured in Asia contained the highest chloropropanol levels.     

Study of chloropropanols in soy sauce by gas chromatography-triple quadrupole mass spectrometry with coupled column separation without derivatisation

A qualitative and quantitative determination method for chloropropanols in soy sauce was developed by GC-MS/MS with coupled column separation without derivatisation. The target compounds were 1,3-dichloropropan-2-ol (1,3-DCP), 2,3-dichloropropan-1-ol (2,3-DCP), 3-monochloropropane-1,2-diol (3-MCPD) and 2-monochloropropane-1,3-diol (2-MCPD). 3-MCPD-d₅ was used as an isotope internal standard for MCPDs and 1,3-DCP-d₅ for DCPs. After spiking with internal standards and mixed with 1?g of Extrelut? NT, about 1?g of the sample was washed by 4?ml of hexane and the analytes were eluted with 15?ml of 95% (v/v) ethyl ether/hexane mixture. The concentrated extract was directly injected without derivatisation, separated by a coupled column – a 3?m Innowax (polyethylene glycol) combined with a 30?m DB-5?ms ((5%-phenyl)-methylpolysiloxane) by a quartz capillary column connector – and detected by GC-MS/MS. The limits of detection (LODs) in the sample matrix were 1.0, 2.5, 5.0 and 5.0?µg?kg^?1 for the above chloropropanols, respectively. The relative proportions of 2-MCPD/3-MCPD ranged from 0.19 to 3.74 in soy sauce samples. 2,3-DCP and 2-MCPD were more stable than 1,3-DCP and 3-MCPD under alkaline condition. The levels of chloropropanols can be decreased by an alkaline treatment process.     

Survey of chloropropanols in soy sauces and related products purchased in the UK in 2000 and 2002.

The results of surveys to investigate the levels of 3-monochloropropane-1,2-diol (3-MCPD) and 1,3-dichloropropanol (1,3-DCP) in UK retail samples of soy sauces and similar products are reported. The products, sampled in 2000 and 2002, were analysed for 3-MCPD using an established solvent extraction technique with a reporting limit of 0.01 mg kg(-1), which also detected 2-monochloropropane-1,2-diol (2-MCPD), and for 1,3-DCP by an automated headspace method with a reporting limit of 0.005 mg kg(-1), which also detected 2,3-dichloropropanol (2,3-DCP). In the 2000 survey, 3-MCPD was quantified in 32 of 100 samples. After normalization to 40% dry matter, it was quantified at or above 0.02 mg kg(-1) in 25 of the samples and in excess of 1 mg kg(-1) in 16 samples, the highest containing 82.8 mg kg(-1). 2-MCPD was found in 26 samples, at up to 17.6 mg kg(-1) after normalization to 40% dry matter. The presence of 1,3-DCP was detected in 17 of the samples, at levels between 0.006 and 0.345 mg kg(-1). 1,3-DCP was only detected where 3-MCPD was present, but the levels of 1,3-DCP and 3-MCPD were not correlated. 2,3-DCP was detected in 11 samples at levels ranging from 0.006 to 0.043 mg kg(-1). In the 2002 survey, 3-MCPD was quantified (> 0.01 mg kg(-1)) in only eight of 99 samples and 2-MCPD in three samples. After normalization to 40% dry matter, 3-MCPD was present at or above 0.02 mg kg(-1) in seven of these, the maximum level being 35.9 mg kg(-1). 1,3-DCP was detected in this sample alone, at 0.017 mg kg(-1).     

The simultaneous separation and determination of chloropropanols in soy sauce and other flavoring with gas chromatography-mass spectrometry in negative chemical and electron impact ionization modes

Both gas chromatography-mass spectrometry in electron ionization (GC-MS-EI) and negative chemical ionization (GC-MS-NCI) modes are reported in this paper for the simultaneous determination of 1,3-dichloropropan-2-ol (1,3-DCP), 2,3-dichloropropan-1-ol (2,3-DCP), 3-chloropropane-1,2-diol (3-MCPD) and 2-chloropropane-1,3-diol (2-MCPD) in soy sauce and other flavoring. D₅-3-MCPD (for 3-MCPD and 2-MCPD) and d₅-1,3-DCP (for 1,3-DCP and 2,3-DCP) were used as the deuterium isotopic labelled internal standards. The feasibility of using heptafluorobutyric anhydride modified with triethylamine (HFBA-Et₃N) as a new derivatization reagent to replace heptafluorobutyrylimidazole (HFBI) is proposed. Liquid/liquid extraction with hexane was introduced for high lipid content samples. A small survey was carried out of soy sauces (103 samples) and instant noodles (45 samples) and the applicability of GC-MS-NCI and GC-MS-EI was assessed in these different matrices.     

我国市售水解蛋白氯丙醇污染状况研究

采用基质固相分散萃取法(MSPD)进行样品的净化,以稳定性同位素稀释技术结合气相-质谱法(GC-MS)的内标法定量测定氯丙醇,初步调查了我国市售水解蛋白(HVP)氯丙醇的污染水平。发现酸水解HVP产品氯丙醇污染严重,氯丙醇的典型代表3-氯-1,2-丙二醇(3-MCPD)的几何均数达到6.04mg/kg(以液体计),70%的样品3-MCPD含量超过10mg/kg。     

气相色谱-质谱法测定食用植物油中氯丙醇酯的含量方法验证研究

目的建立一种同时测定食用植物油中3-氯-1,2-丙二醇脂肪酸酯(3-MCPD酯)、2-氯-1,3-丙二醇脂肪酸酯(2-MCPD酯)、1,3-二氯-2-丙醇脂肪酸酯(1,3-DCP酯)和2,3-二氯-1-丙醇脂肪酸酯(2,3-DCP酯)含量的气相色谱-质谱(GC-MS)方法。方法植物油样品经叔丁基甲基醚-乙酸乙酯溶液(8∶2,V/V)溶解,在甲醇钠-甲醇溶液中发生酯键断裂反应,用冰乙酸中和正己烷去脂,经硅藻土小柱净化,七氟丁酰基咪唑(HFBI)衍生,以GC-MS法测定,采用同位素内标进行定量。结果经5家检验机构验证,4种氯丙醇酯(以对应的氯丙醇计)在0.02~0.4 mg/L范围内线性良好,相关系数r~2均大于0.999,在0.2~2.0 mg/kg水平的加标回收率在78.5%~109.8%之间,RSD为2.2%~18.8%,检出限均为0.1 mg/kg。结论 2014年英国FAPAS分析实验室能力验证和5家机构协同验证的结果证实,该方法线性良好,准确度、精密度高,检测成本较低,适用于食用植物油中氯丙醇酯的检测。     

Dietary exposure to chloropropanols of secondary school students in Hong Kong

This paper reports levels of 3-monochloropropan-1,2-diol (3-MCPD) and 1,3-dichloro-2-propanol (1,3-DCP) in a wide range of food items and estimates their dietary exposure for secondary school students in Hong Kong. Dietary exposure to chloropropanols was estimated using local food consumption data obtained from secondary school students in 2000 and the concentrations of 3-MCPD and 1,3-DCP in food samples taken from the local market. The dietary exposure to 3-MCPD for an average secondary school student consumer was estimated to be 0.063–0.150 µg kg^?1 body weight (bw) day^?1, whilst that for the high consumer was 0.152–0.300 µg kg^?1 bw day^?1. Both estimates fell below the provisional maximum tolerable daily intake of 2 µg kg^?1 bw established by the Joint Expert Committee on Food Additives (JECFA) and amounted to less than 20% of this safety reference value. The dietary exposure to 1,3-DCP for an average secondary school student consumer was estimated to be 0.003–0.019 µg kg^?1 bw day^?1, whilst that for the high consumer was 0.009–0.040 µg kg^?1 bw day^?1. The resulting margins of exposures were of low concern for human health. It could be concluded that both the average and high secondary school student consumers were unlikely to experience major toxicological effects of 3-MCPD and 1,3-DCP.     

3-Monochloropropane-1,2-diol (3-MCPD) in soy sauces and similar products available from retail outlets in the UK

A survey of the level of 3-monochloropropane-1,2-diol (3-MCPD) in soy sauces and similar products available in the UK is reported. The survey was carried out by the Joint Ministry of Agriculture, Fisheries and Food/Department of Health Food Safety and Standards Group (JFSSG) to check for compliance with the Food Advisory Committee's (FAC) recommended limit for 3-MCPD of 0.01mg/kg following reports that soy sauces in several European countries had been found to contain high levels (up to 124mg/kg) of 3-MCPD. Forty samples of soy sauce and similar products purchased from retail outlets were analysed using a GC-MS procedure which had been formally validated by an earlier collaborative trial. 3-MCPD was undetectable in 21 (52%) of samples analysed in the survey, with a further five samples containing very low levels of between 0.01 and 0.02mg/kg. Five samples (13%) contained 3-MCPD at levels in the range 0.020-1mg/kg while nine samples (23%) were found to contain 3-MCPD at levels greater than 1mg/kg, with the highest level being 30.5mg/kg.     

食用植物油中4种氯丙醇脂肪酸酯的GC-MS测定方法研究

采用气相色谱-质谱(GC-MS)联用技术,建立了同时测定食用植物油中3-氯-1,2-丙二醇脂肪酸酯(3-MCPD酯)、2-氯-1,3-丙二醇脂肪酸酯(2-MCPD酯)、1,3-二氯-2-丙二醇脂肪酸酯(1,3-DCP酯)和2,3-二氯-1-丙二醇脂肪酸酯(2,3-DCP酯)含量的分析方法。该方法在0.005~0.5 mg/L范围内线性关系良好,检出限0.1 mg/kg,定量限0.2 mg/kg,加标回收率在97.2%~106.0%之间,相对标准偏差在3.4%~7.1%之间。该方法操作简便,灵敏度高,重复性好,定性定量准确,对仪器污染小,能满足食用植物油中氯丙醇酯的检测需求。     

氨基酸源对热反应牛肉香精中氯丙醇形成的影响

采用气相色谱-质谱联用(gas chromatography-mass spectrometry,GC-MS)仪对热反应牛肉香精及其原料中的氯丙醇进行了分析,并通过单因素试验考察了水解植物蛋白(hydrolyzed vegetable protein,HVP)液、酵母浸膏、VB1、牛肉酶解物、半胱氨酸、谷氨酸、牛骨素、甘氨酸和丙氨酸等原料对热反应牛肉香精中3-氯-1,2-丙二醇(3-chloro-1,2-propanediol,3-MCPD)生成的影响。结果发现,4种氯丙醇中3-MCPD是牛肉香精的主要污染物,且牛肉香精原料中都含有一定量的3-MCPD;牛肉香精原料中所检测的各种氨基酸源对3-MCPD的含量均有显著影响。     

Determination of 1,3-dichloropropanol in soy and related sauces by using gas chromatography/mass spectrometry

A gas chromatography/mass spectrometry method for 3-MCPD in foods and food ingredients was modified for the determination of 1,3-DCP in soy and related sauces. The method was validated by using a blank soy sauce. The detection limit, quantitation limit and recoveries were determined, and identities were confirmed by mass spectrometry on the basis of analyses of test portions spiked with 1,3-DCP at 10, 25, 50 and 100 ng g^-1. The spiked test portions were quantitated by using an internal standard calibration curve. For the spiked test portions, the mean internal standard-corrected recovery for 1,3-DCP was 100% with a relative standard deviation of 1.32%. The limits of detection and quantitation were determined as 0.055 and 0.185 ng g^-1, respectively. The method also was compared with a headspace GC/MS method recently developed by the UK's Central Science Laboratory. Results from the method comparison showed that the recoveries for the spiked test portions, as well as the amounts of 1,3-DCP found in the retail products, were comparable.     

Migration studies of 3-chloro-1,2-propanediol (3-MCPD) in polyethylene extrusion-coated paperboard food packaging

The manufacturing process of paperboard food packaging can produce small quantities of 3-chloro-1,2-propanediol (3-MCPD or 3-monochloropropane-1,2-diol) when wet-strength resins containing epichlorohydrin are used. 3-MCPD is from the same family as 1,3-dichloro-2-propanol (1,3-DCP), which is known to cause cancer in animals. 3-MCPD has been found in acid hydrolyzed vegetable protein, Asian sauces and paperboard for food contact. In this investigation, we conducted extraction studies to measure 3-MCPD migration into food simulant solvents from the food contact side of polyethylene extrusion-coated paperboard beverage cartons and aqueous extractions of cut pieces from the entire paperboard. We demonstrate that 3-MCPD confirmed present at concentrations up to 9.9 mg kg^?1 within the paperboard matrix does not migrate through the polyethylene-coated food contact surface. The aqueous extraction of the entire paperboard and food contact side extractions with aqueous/acidic food simulants were performed using US Food and Drug Administration (FDA) and European Commission (EU) migration testing protocols. We also show that no significant amount of 3-MCPD migrates through the unskived edges on the inside seam of the paperboard structure. The methodology for the aqueous and migration cell extractions using GC–MS analyses was validated with a limit of quantification (LOQ) of 0.009 mg kg^?1 and a limit of detection (LOD) of 0.005 mg kg^?1.     

哈尔滨市某社区居民对酱油中3一氯一1，2一丙二醇的暴露状况调查

目的了解某品牌酱油对于其消费人群3-氯-1,2-丙二醇(3-MCPD)暴露水平的影响。方法采用国际上通用的检测方法 AOAC 2001.01测定哈尔滨市该品牌6种酱油的3-MCPD含量;2010—2011年以问卷调查的方式在哈尔滨市郊区某农合社区调查18～60岁社区居民1 352人,了解居民关于3-MCPD相关食品的膳食习惯以及该品牌酱油摄入的一般状况,筛选出经常食用该品牌酱油的居民,以酱油中3-MCPD的检测结果为依据计算居民食用酱油的3-MCPD暴露量。结果该社区存在经常食用该品牌酱油人群,被调查的1 352人,其中497人经常食用该品牌1种酱油,食用年限均在4年以上,居民对于酱油的3-MCPD摄入量范围为0.648～34.361μg/(kg bw.d)。结论该社区某品牌酱油的消费人群可能存在3-MCPD的高暴露风险。     

3-Monochloropropane-1,2-diol (3-MCPD) in food ingredients from UK food producers and ingredient suppliers.

A survey of 3-monochloropropane-1,2-diol (3-MCPD) in a range of food ingredients available in the UK is reported. The survey was conducted for the Food Standards Agency to assess the progress made by manufacturers in reducing levels of 3-MCPD in food ingredients in line with the UK Food Advisory Committee's recommendation, i.e. that 3-MCPD is undetectable (i.e. < 0.010 mg kg(-1) in foods and where technologically feasible, in food ingredients as well. Sixty-three samples of food ingredients available in the UK were analysed using a validated method of analysis with a limit of quantification of 0.010 mg kg(-1). Samples included breadcrumbs, caramels, enzyme-hydrolysed vegetable proteins, gelatines, malt products (malt extracts, malt flours and other malt-based in gredients), meat extracts, modified starches, and yeast extracts. 3-MCPD was not quantified in 49 (78%) of the samples analysed. The remaining 14 samples (22%) contained levels of 3-MCPD between 0.014 and 0.488 mg kg(-1), the highest level being in a maize yellow dextrin. Malt-based ingredients accounted for the majority of samples containing 3-MCPD > 0.010 mg kg(-1), with nine of these 24 samples (38%) having quantifiable levels of 3-MCPD.     

Survey of 3-monochloropropane-1,2-diol (3-MCPD) in selected food groups, 1999-2000.

A survey of the levels of 3-monochloropropane-1,2-diol (3-MCPD) in a range of selected food products available in the UK is reported. The survey was carried out on behalf of the Food Standards Agency (FSA) to identify the food groups that might provide a significant contribution to 3-MCPD exposure from the diet. Three hundred samples comprising meat, dairy, cereal, soup and miscellaneous products were purchased from retail outlets and analysed using a GC-MS procedure, which had been formally validated by an earlier collaborative trial. 3-MCPD was detected in 89 (30%) of the samples. Three samples, all crackers, contained levels of 3-MCPD > 0.1 mg kg(-1), the highest level being 0.134 mg kg(-1). Levels of 3-MCPD were generally slightly higher in foods after cooking. In all cases where 3-MCPD was detected in cooked foods, it was also present in the uncooked sample.     

3‐Chloropropane‐1,2‐diol (3‐MCPD) in Soy Sauce: A Review on the Formation,Reduction, and Detection of This Potential Carcinogen

Soy sauce, a dark‐colored seasoning, is added to enhance the sensory properties of foods. Soy sauce can be consumed as a condiment or added during the preparation of food. There are 3 types of soy sauce: fermented, acid‐hydrolyzed vegetable protein (acid‐ HVP), and mixtures of these. 3‐Chloropropane‐1,2‐diol (3‐MCPD) is a heat‐produced contaminants formed during the preparation of soy sauce and was found to be a by‐product of acid‐HVP‐produced soy sauce in 1978. 3‐MCPD has been reported to be carcinogenic, nephrotoxic, and reproductively toxic in laboratory animal testing and has been registered as a chemosterilant for rodent control. 3‐MCPD is classified as a possible carcinogenic compound, and the maximum tolerated limit in food has been established at both national and international levels. The purpose of this review is to provide an overview on the detection of 3‐MCPD in soy sauce, its toxic effects, and the potential methods to reduce its concentration, especially during the production of acid‐HVP soy sauce. The methods of quantification are also critically reviewed with a focus on efficiency, suitability, and challenges encountered in analysis.