南昌市罐装食品中双酚类化合物污染调查与分析

目的了解南昌市市售罐装食品中双酚类化合物污染状况,进一步完善了江西省食品安全风险监测体系。方法在南昌市范围内采集5类共65份样品,采用液相色谱-串联质谱法(liquid chromatography tandem mass spectrometry,LC-MS/MS)进行分析。结果 65份样品总检出率为69.2%,蔬菜类罐头和肉类罐头尤为突出,检出率高达100%,在所有样品均未发现双酚F及其衍生物。但BADGE·2H2O、BADGE·H2O·HCl检出率较高,最大检出值高达761、110μg/kg。结论南昌市罐装食品中双酚类化合物存在一定程度污染。     

杭州市场罐头类食品的双酚A污染调查及其膳食风险评估

目的:调查检测市场上罐头类食品的双酚A含量,明确其膳食暴露风险。方法:在杭州超市采集各类罐头食品样品93个,采用高效液相色谱法测定双酚A含量,采用点评估方法评估其膳食暴露风险。结果:罐头样品双酚A的检出率为29%,平均值为121.7μg/kg,最大值为2 840μg/kg,其中油性的鱼、肉和蔬菜类罐头双酚A含量较高;一般人群来源于罐头食品的双酚A膳食暴露量为0.04—0.20μg/(kg·bw)/d,占TDI的0.4%—2.0%。结论:油性的鱼、肉和蔬菜类罐头食品双酚A含量显著高于饮料和粥类罐头食品;在没有其他重大的暴露来源时,各类人群以罐头类食品为主的双酚A膳食暴露均在可接受的范围内。     

高效液相色谱法检测运动饮料中双酚A的残留

建立一种快速、有效的高效液相色谱法测定运动饮料中双酚A残留的方法。样品经乙醇提取后,采用C18固相萃取小柱进行净化和富集。采用苯基色谱柱(4.6 mm×250 mm,5μm)分离,以乙腈∶水=40∶60(体积比)作为流动相,用PDA检测器检测,外标法峰面积定量。结果表明,双酚A标液在0.10μg/m L~1.00μg/m L浓度范围内线性良好,相关系数r~2为0.999,检出限为5.0μg/kg,定量限为15.0μg/kg,加标回收率达到92.1%~93.8%。该方法具有前处理简单、富集效果好和检测速度快的优点,适用于运动饮料中双酚A残留的定量检测。     

双酚A环氧衍生物在罐头食品中的迁移规律与污染情况研究

罐头内壁涂层双酚A环氧衍生物在食品中的迁移存在安全隐患。本文模拟食品的贮存条件,研究了双酚A环氧衍生物在罐头食品中的迁移规律。实验结果表明,双酚A环氧衍生物在食品中的迁移主要受pH、温度、贮存时间的影响。在酸性条件下双酚A环氧衍生物的迁移量随浸泡时间的增长而增加,在高温下(40℃)迁移总量迅速增加。对34个罐头食品内容物进行检测,共8个样品检出双酚A环氧衍生物,检出率为23.5%。其中饮料罐头的检出率达85.7%,在酸性的饮料罐头中双酚A环氧衍生物的含量随贮存时间的增长而增加。     

食品中双酚A等3种酚类物质含量测定

采用GPC凝胶净化结合快速液相串联质谱法,建立肉、乳、水产品、蔬菜中壬基酚、辛基酚及双酚A的含量检测方法。3种目标化合物线性范围为0.2ng/mL~10.0ng/mL(r=0.998),检出限为0.3μg/kg,定量限为0.8μg/kg,3种化合物在1.0、5.0、10.0μg/kg3个浓度水平不同产品的添加回收率为85.9%~117.0%,RSD%10%。运用建立的方法对市场上销售的各类产品进行检测,结果所有产品均检出不同浓度水平的残留。     

超高效液相色谱串联质谱法测定全蛋粉中的双酚A和双酚S

建立超高效液相色谱-串联质谱测定全蛋粉中双酚A和双酚S的检测方法。全蛋粉经水复溶后经乙腈提取,提取液使用分散系固相萃取-基质增强脂质去除产品进行除脂,使用Oasis PRiME HLB小柱进一步净化,使用超高效液相串联质谱测定,负离子多反应监测(MRM)模式测定,内标法定量。结果显示:双酚A在1~50 μg/kg范围内呈线性,相关系数为0.9991,加标回收率为98.8%~105.0%,日内和日间相对标准偏差分别为3.84%~8.58%和5.65%~8.74%,检出限为0.3 μg/kg,定量限为1.0 μg/kg;双酚S在0.4~20 μg/kg范围内呈线性,相关系数为0.9995,加标回收率为98.5%~102.5%,日内和日间相对标准偏差分别为3.01%~7.86%和3.18%~7.03%,检出限为0.1 μg/kg,定量限为0.3 μg/kg。实际样品测定结果分别为:双酚A 2.4~3.8 μg/kg;双酚S 0.48~0.82 μg/kg。本方法前处理简单、高灵敏度适用于全蛋粉中双酚A和双酚S的日常测定。     

液相色谱-串联质谱法测定食品接触材料中双酚F和双酚S的迁移量

目的 建立液相色谱-串联质谱外标法测定食品接触材料中双酚F和双酚S迁移量的分析方法。方法 样品经水、4%乙酸、10%乙醇、20%乙醇、50%乙醇、95%乙醇和橄榄油等7种食品模拟液浸泡试验后,浸泡液经过滤后进样,以甲醇-水为流动相,经过T₃色谱柱分离,用外标法在负离子模式下以电喷雾电离多反应监测模式进行定量分析。 结果 6种食品模拟物(除橄榄油外)中双酚F和双酚S分别在10.0~200 μg/L和0.500~10.0 μg/L浓度范围内有好的线性,相关系数r均大于0.9995,方法检出限分别为0.002 mg/kg和0.0001mg/kg,定量限分别为0.01mg/kg和0.0005mg/kg,在食品模拟物橄榄油中双酚F和双酚S分别50.0~750 μg/kg和2.50~37.5 μg/kg浓度范围内线性很好,相关系数r均为0.9999,检出限分别为0.01mg/kg和0.0005mg/kg,定量限分别为0.05mg/kg和0.0025mg/kg。在三个浓度水平双酚F加标回收率为90.4%~108%,相对标准偏差(n=6)在0~5.27%之间,双酚S加标回收率为84.4%~107%,相对标准偏差(n=6)在0~4.60%之间。结论 该方法操作简便、灵敏度高、准确性好,能满足食品接触材料中双酚F和双酚S的迁移量的检测。     

高效液相色谱法测定皮革中的双酚A、双酚F和双酚S

建立了一种测定皮革中双酚A、双酚F和双酚S含量的分析方法。皮革样品经甲醇超声提取、旋转蒸发仪浓缩后,在277 nm波长条件下,使用高效液相色谱仪进行分析,经二极管阵列器检测,甲醇-水溶液洗脱后,外标法进行定量。结果显示,双酚A、双酚F和双酚S在1 mg·L^-1～30 mg·L^-1的范围内线性相关系数均大于0.9995,检出限均小于0.64 mg·kg^-1,高、中、低三个水平加标回收率范围为85.8%～97.1%,相对标准偏差为0.11%～2.22%,满足检测要求。     

液相色谱-串联质谱法检测塑料瓶装乳酸饮料中的双酚A含量

目的探讨用液相色谱-串联质谱法检测瓶装乳酸饮料中双酚A的样品前处理及测定方法。方法样品在碱性条件下沉淀蛋白质后,用固相萃取小柱提取,甲醇洗脱。样品经色谱柱(2.1 mm×50 mm,5μm)分离,以纯水-甲醇(40∶60,V/V)为流动相分离。采用电喷雾电离负离子模式(ESI-),多反应监测(MRM),外标法定量分析。结果该方法在2.0~100.0μg/L范围内呈良好线性;仪器检出限0.01 ng;当取样量为10 g,方法检出限为0.001μg/kg;双酚A高、中、低加标浓度(80、50、10μg/L)的平均回收率为100.9%~107.5%,变异系数为6.2%~7.6%。结论该方法适用于塑料瓶装乳酸饮料中双酚A含量的测定,具有灵敏度高、前处理方法简单、可批量检测、检测速度快的特点,可推广检测食品样品中痕量双酚A含量。     

QuEChERS-SPE快速样品制备-超高效液相色谱-串联质谱联用法测定婴幼儿配方奶中双酚类化合物

建立QuEChERS-固相萃取（quick, easy, cheap, effective, rugged, safe-solid phase extraction,QuEChERS-SPE）样品净化,超高效液相色谱-串联质谱测定婴幼儿配方奶中8 种双酚类化合物残留的方法。样品中的双酚类化合物残留经乙腈提取,QuEChERS-SPE净化样品,基质匹配标准校正外标法定量。结果表明,样品经净化和校正后8 种双酚类化合物的基质因子为0.80～1.20;在线性范围内,8 种双酚类化合物线性相关系数（R2）均大于0.999。方法回收率为50.2%～116%（n=6）,相对标准偏差为0.5%～14%（n=6）,方法的检出限和定量限：固体奶粉为0.017～0.78μg/kg及0.055～2.6μg/kg,液体奶为0.0011～0.055μg/L及0.0035～0.18μg/L。采用本方法对中国和加拿大市场购买的婴幼儿配方奶进行检测,根据测定的含量和婴幼儿每天摄入奶量,可分别计算出婴幼儿可能最多摄入双酚A、双酚S、双酚F的量分别为0.065、0.050、0.0059μg/（kg·d）,但均未超过欧洲食品安全协会对双酚类化合物从食品包装材料迁移到食品中限量的规定（4μg/（kg·d））。     

LC-MS/MS analysis of bisphenol S and five other bisphenols in total diet food samples

ABSTRACT

It is already known that bisphenol S (BPS) has been used as a substitute for BPA in thermal papers in recent years. It is not clear, however, if BPS has also been used to replace BPA in can coatings as currently being speculated due to a lack of credible studies on migration of BPS from can coatings and occurrence data of BPS in foods. In this study, an LC-MS/MS method was developed for the analysis of BPS, along with several other bisphenols, and method detection limits for BPS varied from 0.0017 to 3.1 ng/g depending on the type of sample matrix and the amount of sample analysed. This method was used to analyse 159 different food composite samples from a recent Canadian total diet study. Bisphenol E (BPE), bisphenol B (BPB), and bisphenol AF (BPAF) were not detected in any of the 159 food composite samples, bisphenol F (BPF) was detected in only three samples (25–2360 ng/g), and bisphenol A (BPA) was detected in 10 samples (5.3–41 ng/g) which were all prepared from canned foods. BPS was not detected in any of the canned food composite samples but was detected in nine food composite samples prepared from meat and meat products (1.2–35 ng/g), indicating sources for BPS other than can coatings may be possible, which will be investigated in future studies.     

Survey of bisphenol A and bisphenol F in canned foods.

Bisphenol A (BPA) and bisphenol F (BPF) have been determined in a range of canned foods. Sixty-two different canned foods were purchased from retail outlets in the UK from January to November 2000 and the contents extracted and analysed by GC-MS for BPA and BPF isomers. The following canned products were analysed: fish in aqueous media, 10 samples; vegetables, 10; beverages, 11; soup, 10; desserts, five; fruit, two; infant formula, four; pasta, five; and meat products, five. BPF isomers were not detected in any of the canned foods with detection limits of 0.005 mg kg(-1) for the 2,2' and 2,4' isomers and 0.01 mg kg(-1) for the 4,4' isomer. BPA was detected in 38 samples with a detection limit of 0.002 mg kg(-1). Of these, BPA was quantified in 37 canned foods at levels from 0.007 mg kg(-1), with one sample of meat containing a mean level of 0.38 mg kg(-1). All other samples contained <0.07 mg kg(-1) BPA.     

Simultaneous determination of bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether and their hydrolysis and chlorohydroxy derivatives in canned foods

A new method for the simultaneous determination of bisphenol A-diglycidyl ether (BADGE), bisphenol F-diglycidyl ether (BFDGE) and their hydrolysis and chlorohydroxy derivatives in canned foods is presented. Oily and aqueous food samples were extracted with tert-butyl methyl ether and acetonitrile, respectively. The compounds in both extracts were determined by using reverse-phase gradient high-performance liquid chromatography with fluorescence detection. Optimization of extraction and chromatographic determination is outlined in detail. After validation the method was used to analyze various canned food samples, such as tuna and sardine in oil, vegetables, fruit cocktails, etc. In none of the samples were significant amounts ( >100 μg/kg) of BADGE or BFDGE found, whereas in most samples BADGE/BFDGE chlorohydroxy compounds were detected. These originate most probably from the use of organosol varnishes instead of epoxy resins. Risk assessment and regulations of these compounds by the European Union are urgently needed. Additionally, the syntheses and characterization of the not available standard compounds bisphenol A-p-glycidyl-p′-(3-chloro-2-hydroxypropyl) ether (BADGE.HCl) and bisphenol A-p-(2,3-dihydroxypropyl)-p′-(3-chloro-2-hydroxypropyl) ether (BADGE.HCl.H₂O) are presented. Received: 28 July 1999 / Revised version: 29 October 1999     

Determination of bisphenol A in foods using GC/MS

An analytical method using GC/MS was developed for bisphenol A (BPA) in foods and BPA was determined in canned foods and fresh foods such as vegetables, fruit and meat. BPA was extracted with acetone from the samples and the extract was concentrated at under 40 degrees C in vacuo to afford an aqueous solution, which was washed with hexane after alkalization and extracted with 50% diethyl ether-hexane after acidification. Extracts were cleaned up on a PSA and/or a C18 cartridge column, and BPA was derivatized with heptafluorobutyric anhydride and determined by GC/MS (SIM). This method was applicable to the detection and determination of BPA residues in food samples at the level of 1 ng/g. Among canned foods, BPA was found in 6 corned beef, 1 chicken, 9 sweet corn and 3 bean samples at the levels of 17-602 ng/g, 212 ng/g, 2.3-75 ng/g and 3.5-26 ng/g, respectively. BPA was also detected in 1 retort soup and 1 retort pack product at the levels of 11 ng/g and 86 ng/g, respectively. As for dairy products, BPA was not detected in butter and milk. Among fresh foods, BPA was detected in 2 fish and 3 liver samples at the levels of trace (tr)-6.2 ng/g and tr-2.2 ng/g, respectively. In vegetables, fruits and chocolates, a trace level of BPA was detected in only 1 chocolate. Traces of BPA were also detected in 3 samples of 6 boxed lunches.     

Determination of bisphenol A in canned fish by sol–gel immunoaffinity chromatography,HPLC and fluorescence detection

The paper presents a highly selective analysis method for the determination of bisphenol A (BPA) in canned fish. The procedure consists of sample clean-up by sol–gel immunoaffinity chromatography followed by high performance liquid chromatography and fluorescence detection. BPA concentrations were determined in nineteen tuna, sardine and mackerel cans by analysing the solid and the liquid parts of the contents separately. In different tested matrices limits of detection (S/N=3) ranged from 0.2 ng/g (sardines) to 1.8 ng/ml (oil) and limits of quantification (S/N=6) from 0.4 ng/g to 3.8 ng/ml, respectively. In the solid part (fish) very low BPA levels (2–4 ng/g) were found in mackerels, the highest level (59 ng/g) in tuna. In oil significantly higher BPA concentrations were found than in brine. In all samples BPA concentrations were significantly lower than the Specific Migration Level of 0.6 mg/kg for BPA migration into food established by the EU Commission in 2004.     

Determination of bisphenol A in canned fatty foods by coacervative microextraction,liquid chromatography and fluorimetry

Decanoic acid reverse micelle-based coacervates were used to provide simple, rapid and almost solventless extraction of bisphenol A (BPA) from canned fatty foods. The procedure involved the extraction of 200–400 mg of homogenised food sample with an aqueous solution containing 20% THF and 200 mg of decanoic acid, conditions under which the coacervate (around 550 µl) formed in situ and instantaneously. The overall sample treatment took about 30 min and several samples could be simultaneously treated using conventional laboratory equipment. No clean-up or solvent evaporation were required before determination of BPA by liquid chromatography and fluorescence detection. Recoveries in samples were between 90 and 99%, with relative standard deviations in the range 2–7%. The limit of quantification ranged 29–15 ng g^?1 for 200–400 mg of sample, being far below the current specific migration limit (SML) set by the European Commission (600 ng g^?1). The method was successfully applied to the determination of BPA in the solid content of canned fish (from 20 to 129 ng g^?1) and meat (from undetected to 37 ng g^?1).     

Survey of bisphenol a diglycidyl ether (BADGE) in canned foods.

2,2-Bis(4-hydroxyphenyl)propane bis(2,3-epoxypropyl) ether (BADGE) is used in the manufacture of lacquers for coating the inside of food and beverage cans. In June 1996 the EC Scientific Committee for Food temporarily increased the specific migration limit applying to BADGE to 1 mg/kg pending consideration of additional toxicological data. In order to find out if there is migration of BADGE from can coatings into foods, a 'worst case' sampling exercise has been conducted to survey those canned foods where the propensity for migration of BADGE was judged to be highest. The foods surveyed include canned fish in oil, meat and milk and, altogether, BADGE was determined in 181 retail samples. Analysis for BADGE was conducted, in duplicate, by HPLC with fluorescence detection with confirmation of BADGE identity by GC/MS analysis using selected ion monitoring. BADGE was found at levels exceeding 1 mg/kg in seven of the 15 canned anchovy samples and five of the 22 sardine samples purchased during the period September 1995-July 1996. Infrared analysis of the can coatings provided strong evidence that the higher BADGE levels found were associated with use of PVC organosol lacquers, although in some cases cans coated with organosols gave low BADGE results. For canned sardine samples found to contain greater than 0.5 mg/kg BADGE in the total contents, a replicate can was opened and separate analyses performed on the drained fish and the oil. The results clearly showed that BADGE concentrations in the oil were about 20 times higher than in the drained fish. Further samples of canned sardines and anchovies were purchased in June/July 1997 and, in all cases, BADGE levels were found to be below 1 mg/kg. In the other retail canned foods, BADGE was not detectable (DL = 0.02 mg/kg) or detected at concentrations well below the temporary SML of 1 mg/kg.     

Concentrations of bisphenol A in the composite food samples from the 2008 Canadian total diet study in Quebec City and dietary intake estimates

A total of 154 food composite samples from the 2008 total diet study in Quebec City were analysed for bisphenol A (BPA), and BPA was detected in less than half (36%, or 55 samples) of the samples tested. High concentrations of BPA were found mostly in the composite samples containing canned foods, with the highest BPA level being observed in canned fish (106 ng g(-1)), followed by canned corn (83.7 ng g(-1)), canned soups (22.2-44.4 ng g(-1)), canned baked beans (23.5 ng g(-1)), canned peas (16.8 ng g(-1)), canned evaporated milk (15.3 ng g(-1)), and canned luncheon meats (10.5 ng g(-1)). BPA levels in baby food composite samples were low, with 2.75 ng g(-1) in canned liquid infant formula, and 0.84-2.46 ng g(-1) in jarred baby foods. BPA was also detected in some foods that are not canned or in jars, such as yeast (8.52 ng g(-1)), baking powder (0.64 ng g(-1)), some cheeses (0.68-2.24 ng g(-1)), breads and some cereals (0.40-1.73 ng g(-1)), and fast foods (1.1-10.9 ng g(-1)). Dietary intakes of BPA were low for all age-sex groups, with 0.17-0.33 μg kg(-1) body weight day(-1) for infants, 0.082-0.23 μg kg(-1) body weight day(-1) for children aged from 1 to 19 years, and 0.052-0.081 μg kg(-1) body weight day(-1) for adults, well below the established regulatory limits. BPA intakes from 19 of the 55 samples account for more than 95% of the total dietary intakes, and most of the 19 samples were either canned or in jars. Intakes of BPA from non-canned foods are low.     

Sensitive determination of bisphenol A and bisphenol F in canned food using a solid-phase microextraction fibre coated with single-walled carbon nanotubes before GC/MS

A reliable and sensitive method for simultaneous determination of bisphenol A (BPA) and bisphenol F (BPF) in canned food by gas chromatography-mass spectrometry (GC/MS) is described after extraction and pre-concentration by a new solid-phase microextraction (SPME) adsorbent. The potential of single-walled carbon nanotubes (SWCNTs) as SPME adsorbent for the pre-concentration of environmental contaminants has been investigated in recent years. This work was carried out to investigate the feasibility of SWCNTs as a headspace SPME adsorbent for the determination of bisphenol derivatives in canned food. Potential factors affecting the extraction efficiency, including extraction time, extraction temperature, desorption time, desorption temperature, and salinity were optimized. Calibration curves were linear (r ²≥ 0.994) over the concentration range from 0.30 to 60 µg kg^?1. For both target analytes, the limit of detection (LOD) at signal-to-noise (S/N) ratio of 3 was 0.10 µg kg^?1. In addition, a comparative study between the SWCNT and a commercial polydimethylsiloxane (PDMS) SPME fibre for the determination of bisphenol derivatives in canned food was conducted. SWCNT fibre showed higher extraction capacity, better thermal stability (over 350°C) and longer life span (over 150 times) than the commercial PDMS fibre. The method was successfully applied to determine BPA in canned food samples which were purchased from local markets. BPA was found in some of the samples within the concentration range from 0.5 to 5.2 µg kg^?1.