Occurrence of polybrominated diphenyl ethers and polychlorinated biphenyls in shark liver oil supplements

Results are reported of a pilot survey of concentrations of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in shark liver oil supplements. Eleven brands of dietary supplements were analysed using an isotope dilution GC/MS method. Total concentrations of 10 PBDE congeners (BDE-28, -47, -49, -66, -99, -100, -153, -154, -155 and -183) ranged from 0.1 to 53 ng g^-1 oil weight and total concentrations of six PCB congeners (CB-28/31, -52, -118, -153 and -180) in the samples ranged from 16 to 340 ng g^-1 oil weight (undetected values are not included). Two brands of Japanese deep-sea shark liver oil contained the highest levels of PBDEs (49-53 ng g^-1 oil weight) and PCBs (290-340 ng g^-1 oil weight). These results indicate that PBDEs may have entered Japanese deep-sea waters.     

Development and application of a simplified clean-up procedure for the determination of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in horse fat by gas chromatography-tandem mass spectrometry (GC-MS/MS)

A simplified clean-up procedure was developed in combination with gas chromatography-tandem mass spectrometry (GC-MS/MS) for the determination of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in adipose tissue. Clean-up was performed by the successive application of a Mega Bond Elut® silica column and a Bond Elut® PCB column. Validation of the method was conducted according to European Union Commission Decision 2002/657/EC. In order to evaluate the applicability of the method, 44 horse fat samples were analysed. The total PCB concentration (sum of PCBs 28, 52, 101, 118, 138, 153 and 180) ranged from 5.35 to 140 ng g^-1 lipid weight. The total PBDE concentration (sum of BDEs 28, 47, 99, 100, 153, 154 and 183) ranged from below the decision limit to 6.34 ng g^-1 lipid weight.     

Children's daily exposure to polychlorinated biphenyls from dietary supplements containing fish oils

In children, omega-3 polyunsaturated fatty acids (PUFAs) may elicit a suite of health benefits including enhancement of cognitive development. Subsequently, dietary supplements containing omega-3 PUFAs have become increasingly popular. Often, the largest source of beneficial PUFAs in these supplements is fish oil, which may contain significant levels of contaminants such as polychlorinated biphenyls (PCBs). The objectives of this study were to evaluate congener-specific PCB concentrations in 13 over-the-counter children's dietary supplements containing fish oils/powders and assess potential PCB exposures through ingestion of these products on a daily basis. Every supplement analysed contained PCBs, with a mean concentration of 9?±?8?ng PCBs/g supplement. When following serving size suggestions, mean daily exposure values ranged from 2.5 to 50.3?ng PCBs/day. Daily exposures for children's supplements were significantly lower than those previously reported for adult supplements and may be explained, in part, by the variability in the amount of fish oil (and PUFA content) in a serving size. Based on this study, factors such as fish oil purification methods (e.g., molecular distillation) and the trophic level of the fish species used to make the fish oil cannot be used as indicators of PCB levels within children's supplements. Fish supplements may decrease or increase daily PCB exposure compared with ingestion of fresh fish. However, eating fish high in omega-3 PUFAs and low in PCBs may reduce PCB exposure compared with daily supplementation with fish oils for some products studied.     

Intakes of omega-3 polyunsaturated fatty acids, polybrominated diphenyl ethers and polychlorinated biphenyls via consumption of fish from Taihu Lake, China: A risk-benefit assessment

Exposure risks of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) via consumption of nine fish species from Taihu Lake in China and associated benefits, through ingestion of ω-3 polyunsaturated fatty acids (ω-3 PUFAs) in fish, were evaluated. The concentrations of PBDEs, PCBs and ω-3 PUFAs in fish from Taihu Lake ranged from 98.2 to 269 pg/g, from 279 to 1071 pg/g and from 0.9 to 2.0 mg/g, respectively. Omega-3 PUFAs accounted for 11.2-20.9% of the total fatty acid amounts. The PBDE/PCB contamination levels were moderate. To achieve the recommended intake of 250 mg/d of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), the associated PUFA and PBDE/PCB intakes from the species were estimated. Consumption of the species, to achieve the recommended EPA + DHA intake, did not exceed the allowable daily consumption of contaminated fish. Even though, consumers should make a sensible choice for fish species to maximise benefits and minimise risks.     

Dietary exposure of the Hong Kong adult population to polybrominated diphenyl ethers (PBDEs): results of the first Hong Kong Total Diet Study

Polybrominated diphenyl ethers (PBDEs) are a group of industrial chemicals that are persistent and can bioaccumulate. In the first Hong Kong Total Diet Study, the dietary exposure of Hong Kong adults to PBDEs was estimated to assess the associated health risks. Food samples, which represented the Hong Kong people’s diet, were collected and prepared in table-ready form for analysis. Concentrations of PBDEs were determined in 142 composite samples. The dietary exposures were estimated by combining the analytical results with the local food consumption data of the adults. The mean and 95th percentile of dietary PBDEs exposures of the Hong Kong people were 1.34 and 2.90 ng kg^?1 body weight day^?1, respectively. The main dietary source of PBDEs was “fish and seafood and their products”, which contributed 27.3% of the total exposure, followed by “meat, poultry and game and their products” (20.7%), “cereals and their products” (15.9%), and “fats and oils” (15.9%). The large margins of exposure (MOE) (>2.5) calculated following the European Food Safety Authority (EFSA) approach for four important congeners, BDE-47, BDE-99, BDE-153 and BDE-209, indicate that the estimated dietary exposures are unlikely to be a significant health concern.     

上海市淡水水产品中多溴联苯醚和多氯联苯的监测研究

目的了解上海淡水水产品中多氯联苯(polychlorinated biphenyls,PCBs)和多溴联苯醚(poly brominated diphenyl ethers,PBDEs)的污染状况,并进行相关的人体健康风险评估。方法水产品经冷冻干燥后,经加速溶剂萃取(accelerated solvent extraction,ASE)提取、分散固相萃取(dispersive solid phase extraction,D-SPE)除脂、串联固相萃取(solid phase extraction,SPE)深度净化后,用气相色谱-串联质谱(gas chromatography-tandem mass spectrometry,GC-MS/MS)检测。结果 14类97件样品中,PCBs的平均检出率为97%,PBDEs的平均检出率为61%~71%。∑_(51)(PCBs)的平均浓度值为2588 pg/g ww,范围为328~12724 pg/g ww,中位值为2135 pg/g ww,∑_(39)(PBDEs)的平均值浓度为454 pg/g ww,范围为56~2210 pg/g ww,中位值为294 pg/g ww。结论目前上海居民食用淡水水产品不会因PBDEs和PCBs残留而对人体健康构成危险,但对于大量食用鱼和虾的婴幼儿(一般指2~3岁)应适当减少食用量。     

Dioxins and polychlorinated biphenyls (PCBs) in fish oil dietary supplements: Occurrence and human exposure in the UK

Commercially available fish oil supplements sourced from retail outlets in the UK, as well as by mail order, were surveyed in 2000-02 for dioxin (PCDD/Fs) and polychlorinated biphenyl (PCB) content. Sampled products were representative of market share. The WHO-TEQ values for these products ranged from 0.18 to 8.4 ng kg^-1 for ΣPCDD/F and from 1.1 to 41 ng kg^-1 for Σ dioxin-like PCBs. The results suggest a downward trend in the levels of dioxins in fish oil supplements over the last decade, since levels for similar products ranged from 0.3 to 10 ng kg^-1 for ΣPCDD/F WHO-TEQ in 1996. Levels of ICES (International Council for the Exploration of the Seas) 7 PCBs in the current study ranged from 8.3 to 267 µg kg^-1. Subsequent to this survey, European Union legislation has been introduced that includes a maximum limit of 2 ng kg^-1 WHO-TEQ for dioxins in fish oil products for human consumption. Twelve of the 33 products reported here would have exceeded this limit. Negotiations are in progress to incorporate dioxin-like PCBs into the European Union regulations. When manufacturer-recommended doses were applied to the observed levels, the estimated upper bound human exposure to dioxins and dioxin-like PCBs from dietary intake of these products ranged from 0.02 to 7.1 pg WHO-TEQ kg^-1 body weight day^-1 for adults and from 0.02 to 10 pg WHO-TEQ kg^-1 body weight day^-1 for schoolchildren. This level rises to 1.8-8.9 pg WHO-TEQ kg^-1 body weight day^-1 for adults and 1.4-14 pg WHO-TEQ kg^-1 body weight day^-1 for schoolchildren when combined with the average exposure from the whole diet in 1997. Again, subsequent to this survey, the Committee on Toxicity of Chemicals in Food, Consumer Products and the Environment (COT) revised the UK tolerable daily intake (TDI) for mixtures of dioxins and dioxin-like PCBs from 10 to 2 pg WHO-TEQ kg^-1 body weight day^-1. This is in line with the tolerable weekly intake (TWI) of 14 pg WHO-TEQ kg^-1 body weight set by the Scientific Committee on Food (SCF).     

河北省沿海地区鱼肉中多溴联苯醚的测定

目的建立气相色谱-负化学离子源-质谱法检测海产品中8种代表性多溴联苯醚(polybrominated diphenyl ether, PBDEs)的分析方法。方法冻干后的样品经加速溶剂提取,硅胶氧化铝复合层析柱净化后,采用气相色谱-负化学离子源-质谱(GC-NCI-MS)联用仪分析,内标法定量。结果不同地区海鱼中PBDEs的污染水平无显著差异,Σ_(3-7)BrPBDEs的平均值为24.0ng/g湿重,BDE209的平均值为20.7ng/g湿重。海鱼中BDE209的含量最高(占样品总量的46.2%),其次是BDE47(14.9%), BDE28(1.2%)的贡献率最低。结论 PBDEs污染水平虽然不高,但与沿海居民健康密切相关,应持续关注海域环境中生物体内PBDEs的污染状况。     

食品中多溴二苯醚类化合物检测技术研究进展

多溴二苯醚是一类持久性有机污染物,普遍应用在日常产品的防火;因其性质具有潜在致癌性且有高疏水性和抗降解性,已成为人类健康和环境的一大问题。在生物体内积累的多溴二苯醚会通过食物富集于人体,从而对健康饮食和人体寿命构成一定威胁。本文综述了近年来常见多溴二苯醚的种类、提取方法、净化方法、检测技术以及多溴二苯醚的生物危害性;探讨了各项分析检测技术的现存劣势。目前国内有多溴二苯醚消费品检测标准,但无相关食品基质检测标准,因其物质种类繁多和迥异的性质导致检测技术存在巨大挑战;文中也对后续的检测技术发展提出展望,以此为食品中多溴二苯醚检测技术发展和研究提供一定的支持。     

Dioxin-like polychlorinated biphenyls in marine fish from Shandong,China, and human dietary exposure

The occurrence and human dietary exposure of 12 dioxin-like polychlorinated biphenyls (DL-PCBs) in 41 marine fish samples from Shandong Province of China were investigated. The DL-PCB congeners were extracted using automated Soxhlet extraction, purified via a composite column clean-up procedure and analysed by gas chromatography-triple quadrupole mass spectrometry. DL-PCB congeners were found in all analysed samples, with a mean concentration of 0.887 ng/g ww (wet weight). The TEQ concentrations of DL-PCBs in individual fish samples ranged from 0.011 to 9.214 pg WHO TEQ/g ww. The mean dietary intake for all fish species was 36.5 pg TEQ/kg bw/month, which was lower than the provisional tolerable monthly intake of 70 pg TEQ/kg bw/month set by the Joint FAO/WHO Expert Committee on Food Additives. To monitor the trend of DL-PCBs in fish for food safety control, it is necessary to maintain a surveillance programme.     

鱼油中多氯联苯检测方法的研究

目的建立毛细管气相色谱法测定鱼油中多氯联苯的方法。方法用氢氟酸和浓硫酸的混合溶液消解样品,以正己烷提取、浓硫酸净化后,用毛细管气相色谱法测定。结果方法的回收率为92.6%~105.2%,相对标准偏差(RSD)为2.98%~4.71%,最低检出限为0.25~0.48μg/kg。结论该方法简便、快捷,其灵敏度、准确度和精密度均能满足鱼油中多氯联苯分析的要求。     

GCMS/MS 同时测定鱼样中39 种多溴联苯醚

目的 采用快速溶剂萃取(ASE)、系列固相萃取(SPE, 包括分散性固相萃取(DSPE)和串联SPE柱)和GCMS/MS, 建立一个便捷、高效测定鱼样中39种多溴联苯醚(PBDEs)的检测方法。方法 代表性鲈鱼样品(脂肪含量11%)经冷冻干燥后ASE提取, 然后采用DSPE去除脂肪和串联SPE柱净化, 最后采用GCMS/MS检测, 同位素内标法定量。结果 本方法的检测限(MDLs)为0.16~3.29 pg/g; 具有良好的线性范围(R2>0.998)、准确度(除BDE30为53%以外, 其他组分回收率为62%~1139%)和精密度(RSD<20%); 测定参考物质的结果均在标准值范围内, 与气相色谱磁场电场双聚焦高分辨质谱(GC/HRMS)测定结果一致。结论 本方法为鱼样中PBDEs检测提供了一个快速、简便和可靠的方法, 适用于对痕量PBDEs残留水平的食用鱼进行人体健康风险评价研究。     

Rapid determination of polybrominated diphenyl ethers (PBDEs) in fish using selective pressurized liquid extraction (SPLE) combined with automated online gel permeation chromatography-gas chromatography mass spectrometry (GPC-GC/MS)

A rapid method for the determination of seven predominant polybrominated diphenyl ethers (PBDEs) in fish was developed. The analysis could be completed in 1 h. The PBDEs in the sample were extracted with fat by selective pressurized liquid extraction (SPLE) using acid alumina as a fat retainer. After concentration, the extract was directly injected into online gel permeation chromatography with gas chromatography-mass spectrometry (GPC-GC/MS) in negative chemical ionization (NCI) mode. Method detection limits of seven PBDEs were between 0.002 and 0.005 ng g^?1 fat. Quantitative recoveries ranging from 81.9% to 110.3% were obtained by analysis of spiked fish. The relative standard deviations were less than 15% (n = 6). The method was applied to a certified reference material of fish; all results were in the reference ranges. It was shown to be a rapid and reliable alternative in the routine analysis for PBDEs.     

稻米中多氯联苯及多溴联苯醚残留及风险评估

通过分析稻米样品中指示型多氯联苯(PCBs)和12种代表性多溴联苯醚(PBDEs)的存留状况及含量水平,通过膳食风险评估,阐明PCBs和PBDEs在稻米中的安全风险。稻米样品粉碎后,采用直接提取法–酸性硅胶净化法对样品进行前处理,通过气相色谱–串联质谱法对其中7种指示型PCBs和12种代表性PBDEs进行同时检测。45个稻米样品中,PCBs的检出率为42%,合计含量水平在0～78pg/g干重之间,稻米中PCBs主要检出单体为PCB-28和PCB-52,特征符合我国多氯联苯的生产历史情况;仅在一个样品中检出PBDEs,合计含量为41 pg/g干重。稻米中的PCBs和PBDEs污染水平低,经过风险评估,其未造成稻米的食品安全风险。     

气相色谱-串联质谱法测定蔬菜中8种多溴联苯醚

目的 建立气相色谱-串联质谱法测定蔬菜中8种多溴联苯醚方法。方法 样品采用正己烷：丙酮（V:V,1:1）提取,用25 mg N-丙基乙二胺(primary secondary amine, PSA)、150 mg MgSO4净化,利用气相色谱-串联质谱在多反应离子监测模式下进行检测,外标法定量。结果8种溴代阻燃剂的相关系数（r）均大于0.99,方法检出限范围为0.0001-0.0009 mg/kg。在3 种不同蔬菜基质中3 个添加水平（0.005、0.02、0.2 mg/kg）的平均回收率为91.1～114%,相对标准偏差为1.7%～8.7%。结论 该方法前处理简单快速、灵敏度高,具有良好的回收率和稳定性,适用于不同种蔬菜中8种多溴联苯醚的测定。     

固相萃取-气相色谱法测定螺旋藻中指示性 多氯联苯

目的建立气相色谱法测定螺旋藻中痕量多氯联苯的分析方法,以考查螺旋藻中7种指示性多氯联苯(polychlorinated biphenyls,PCBs)的残留情况。方法乙腈提取样品后,选用弗罗里矽柱对螺旋藻中指示性多氯联苯净化。色谱条件为:DB-17(30 m×0.25 mm,0.25μm)石英毛细管柱,采用程序升温分离,流速为1.0m L/min,进样量为1.00μL,电子捕获检测器检测。结果在优化的条件下,7种指示性多氯联苯在10~50μg/L范围内线性良好,相关系数(r)大于0.999,在螺旋藻空白样品中添加25、35、45μg/kg 3个水平的7种指示性多氯联苯,其加标回收率范围为90.8%~112%,相对标准偏差(RSD)范围为0.526%~3.89%。结论该方法具有操作简便、快速、准确的特点,适用于螺旋藻试样中指示性多氯联苯痕量残留的分析。     

Dietary intake estimations of polybrominated diphenyl ethers (PBDEs) based on a total diet study in Osaka,Japan

This study presents the results of a total diet study performed for estimating the dietary intake of polybrominated diphenyl ethers (PBDEs) in Osaka, Japan. The concentrations of 36 PBDEs were measured in samples from 14 food groups (Groups I–XIV). PBDEs were detected only in Groups IV (oils and fats), V (legumes and their products), X (fish, shellfish, and their products), and XI (meat and eggs) at concentrations of 1.8, 0.03, 0.48, and 0.01 ng g^?1, respectively. For an average person, the lower bound dietary intakes of penta- and deca-formulations were estimated to be 46 and 21 ng day^?1, respectively. A high proportion of the decabrominated congener (DeBDE-209) was observed in Group IV. To confirm the presence of DeBDE-209 in vegetable oils, an additional analysis was performed using 18 vegetable oil samples. Of these, seven contained ng g^?1 levels of DeBDE-209.     

加速溶剂萃取-高效液相色谱法检测瓦楞纸箱(板)中的多溴二苯醚

目的建立一种加速溶剂萃取提取多溴二苯醚的高效液相色谱检测方法。方法将多层瓦楞纸箱(板)剪至1 cm×1 cm大小,取适量样品,以乙醇-丙酮(1:1,V:V)为萃取溶剂,加速溶剂萃取温度为150℃,萃取压力为1500 psi,静态萃取10 min,重复萃取3次后,用甲醇-水为流动相,进行梯度洗脱,226 nm波长进行检测。结果对8种PBDEs的回收率在95%~105%之间,精密度试验(n=6)的RSD3%,检测限为0.1~0.2μg/m L,线性回归系数0.999。结论建立的方法与标准方法 GB/Z 21276-2007检测结果无明显差异,可以用于瓦楞纸箱(板)中的PBDEs检测。     

Persistent Organic Pollutants in Fish Oil Supplements on the Canadian Market: Polychlorinated Dibenzo-p-Dioxins, Dibenzofurans, and Polybrominated Diphenyl Ethers

ABSTRACT:  Canadians are interested in improving their diet through the consumption of fish oil food supplements, which are marketed to be rich in omega-3 fatty acids. Convenience samples of omega-3 enriched dietary supplements ( n  = 30) were collected in Vancouver, Canada, between 2005 and 2007. All of the omega-3 supplements were analyzed for polychlorinated dibenzo- p -dioxins/furans (PCDD/Fs) and polybrominated diphenyl ethers (PBDEs) and, although every sample was found to contain detectable residues of PBDEs, only 24 samples were found to have PCDD/F concentrations above the level of detection. PCDD/F concentrations ranged from 0.05 pg TEQ/g lipid to 45.7 pg TEQ/g lipid in salmon and shark oils, respectively. Maximum PBDE concentrations similarly were observed in shark oil (113 μg/kg lipid), however, most supplements had concentrations below 5 μg/kg lipid. Average PCDD/F and PBDE intake estimates, based on consumption of maximum supplement dose following product label recommendations, were 4.32 pg TEQ/d and 25.1 ng/d lipid, respectively.     

Balancing the risk of dioxins and polychlorinated biphenyls (PCBs) and the benefit of long-chain polyunsaturated fatty acids of the n-3 variety for French fish consumers in western coastal areas

A study of 401 fish-eating adults living in a coastal region of France was undertaken to establish exposure to dioxins/polychlorinated biphenyls and the intake of long-chain polyunsaturated fatty acids of the n-3 variety. Fish consumption was estimated using food frequency diaries and the dioxin/polychlorinated biphenyl data collected by the French control authorities was used to calculate dietary exposure. The results showed that for a group of adult subjects selected because of their consumption of fish, 60% achieved the nutritional recommendation for long-chain n-3 polyunsaturated fatty acids and 79% were exposed to total dioxins below the toxicological threshold of 14 pg kg^?1 body weight week^?1. Nevertheless, only 41% of these subjects had an optimal balance between the risk and benefit of eating fish, because 19% were meeting the nutritional recommendation but exceeding the toxicological threshold, whereas 38% were exposed below the toxicological threshold but failed to reach the recommended intake of long-chain n-3 polyunsaturated fatty acids. Similar results were found regarding the balance between long-chain n-3 polyunsaturated fatty acids and polychlorinated biphenyls even if a toxicological threshold was not established for these compounds. The results show that meeting the nutritional requirements of 0.5 mg day^?1 of long-chain n-3 polyunsaturated fatty acids is compatible with respect to toxicological thresholds, while an intake higher than 1.5 g day^?1 is likely to lead to a dietary exposure above the provisional tolerable weekly intake for dioxins.