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。     

高效液相色谱-串联质谱法测定多种食品和饲料中的胶霉毒素

建立了加压溶剂萃取结合全自动固相萃取技术-高效液相色谱-串联质谱法(high performance liquid chromatography-mass spectrometry,HPLC-MS/MS)测定玉米和小麦等禾谷食品、猪的肌肉和肝脏等动物源食品及猪和鸡的饲料中胶霉毒素的液相色谱串联质谱法。前处理时依次采用加压溶剂萃取(pressurized liquid extraction,PLE)和全自动固相萃取(automated solid phase extraction,ASPE)技术,乙腈/水(50/50,V/V)为玉米、小麦及饲料样品的加压溶剂萃取液,乙腈/正己烷(60/40,V/V)为猪的肌肉和肝脏样品的加压溶剂萃取液,甲醇/水(85/15,V/V)为所有样品的全自动固相萃取洗脱液。HPLC-MS/MS检测,基质匹配工作曲线外标法定量。结果表明,不同样品中胶霉毒素在0.2~100μg/L范围内具有良好的线性关系,相关系数R2≥0.995 8;不同样品中的胶霉毒素最低检出限在0.09~0.15μg/kg,最低定量限在0.23~0.31μg/kg;添加不同浓度水平的胶霉毒素,平均回收率为81.8%~95.4%,变异系数≤13.2%。     

同位素稀释法-超高效液相色谱-串联质谱法测定豆芽中6种喹诺酮类药物残留

目的建立通过式固相萃取(solid phase extraction,SPE)柱净化、氘代同位素内标、超高效液相色谱-串联质谱法同时测定豆芽中6种喹诺酮类药物残留的方法。方法用0.1%甲酸-乙腈作为提取溶剂,经通过式固相萃取柱净化提取液,超高效液相色谱-串联质谱测定豆芽中6种喹诺酮药物残留。结果 6种喹诺酮在5.0～200μg/L范围内线性关系良好,r~2≥0.999;方法检出限(S/N=3)为0.7μg/kg,定量限(S/N=10)为2.0μg/kg;加标水平为2.0～80μg/kg时,平均回收率在85.5%～119.4%,相对标准偏差(relative standard deviation,RSD)(n=6)为0.13%～9 93%。结论本方法前处理简单,定量结果准确,回收率高,可以应用于大批次豆芽中喹诺酮药物残留的监测。     

SPE净化-UPLC-MS/MS法测定食品中二氢槲皮素

试验旨在建立食品中二氢槲皮素的超高效液相色谱-串联质谱定性定量检测方法.试样经甲醇-2％乙酸(1∶1,V/V)超声提取后,采用亲水-疏水平衡固相萃取柱(hydrophile-lipophile balance,HLB)固相萃取(solid phase extraction,SPE)净化,HSS T3色谱柱分离,以乙腈-...     

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。     

食用植物油中农药残留检测技术的研究进展

我国农产品中农药残留的中毒事件和进出口贸易中农药残留超标事件时有发生,已成为影响农业可持续发展的重要问题,因此农药残留检测技术也在迅速发展。文章综述了现阶段对植物油中农药残留检测技术的研究进展。主要从前处理和检测方法 2方面进行分析,根据前处理方法和检测方法的不同,分别介绍了各类前处理方法如液液萃取法(liquid-liquid extraction,LLE)、固相萃取法(solid phase extraction,SPE)、基质固相分散萃取法(matrix solid phase dispersion,MSPD)、分散固相萃取(disperse solid phase extraction,d SPE)法、凝胶渗透色谱法(gel permeation chromatography,GPC)等方法的原理和过程,以及各类检测方法如气相色谱法、气相色谱-质谱联用法(gas chromatography-mass spectrometry,GC-MS)、液相色谱法和液相色谱-串联质谱联用法(liquid chromatography-tandem mass spectrometry,LC-MS/MS)等的特点和应用范围。文章总结各类方法的优缺点,并提出了食用植物油中农药残留分析方法的发展趋势。     

基于固相微萃取(SPME)和同时蒸馏萃取(SDE)分析大麦苗粉对白鲢鱼糜制品的去腥作用

该研究采用感官评价、电子鼻及顶空固相微萃取(headspace solid phase microextraction,HS-SPME)和同时蒸馏萃取(simultaneous distillation extraction,SDE)结合气质联用(gas chromatography-mass spectrometry...     

GC-MS/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(D-SPE)和串联SPE柱]和GC-MS/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D-SPE去除脂肪和串联SPE柱净化,最后采用GC-MS/MS检测,同位素内标法定量。结果本方法的检测限(MDLs)为0.16～3.29pg/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%～139%)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,以便于日常监测和评估鱼中残留PBDEs对人体健康风险的研究。     

固相萃取与气相色谱-质谱联用分析调味料中3-氯-1,2-丙二醇

建立固相萃取与气相色谱-质谱联用(solid phase extraction with gas chromatography-mass spectrometry,SPE-GC-MS)测定调味料中3-氯-1,2-丙二醇的新方法。对影响分析物SPE萃取效率的诸因素如洗脱溶剂、洗脱溶剂的体积和上样体积等进行详细考察和优化。最佳萃取条件为5.0g样品与5mol/L氯化钠溶液混匀,经SPE萃取净化、衍生后,以GC-MS进行测定,该方法对3-氯-1,2-丙二醇的检出限为0.15μg/kg,线性范围为0.51～6144μg/kg,相关系数和相对标准偏差(relative standard deviation,RSD)(n=5)分别为0.9998和8.8%。该方法成功应用于调味料3-氯-1,2-丙二醇的分析,加标回收的回收率为87.2%～109.4%。     

分散固相萃取-液相色谱串联质谱法快速测定牛奶中利福昔明残留量

目的建立分散固相萃取-液相色谱串联质谱法快速测定牛奶中利福昔明残留的分析方法。方法牛奶样品用乙腈提取,提取液采用分散固相萃取(dispersive solid phase extraction,DSPE)净化,采用超高效液相色谱-串联质谱法(ultra performance liquid chromatography-tandem mass spectrometry, UPLC-MS/MS)在多反应正离子监测模式下进行监测。以离子对m/z 786.3/151.0进行定性分析、m/z 786.3/754.4进行基质校准外标法定量分析。结果方法的检出限(limit of detection, LOD)和定量限(limit of quantitation, LOQ)分别为0.2μg/kg和0.6μg/kg。方法基质标准曲线线性方程为Y=159.27X+8.25, r~2=0.9998, 4个浓度水平加标回收率在77.1%～102%之间,批内相对标准偏差为2.4%～7.1%,批间相对标准偏差为3.9%～6.2%。结论方法简便、快速、准确,可用于牛奶样品中利福昔明的药物残留快速确证检测分析。     

Use of volatile compound metabolic signatures in poultry liver to back-trace dietary exposure to rapidly metabolized xenobiotics

The study investigated the feasibility of using volatile compound signatures of liver tissues in poultry to detect previous dietary exposure to different types of xenobiotic. Six groups of broiler chickens were fed a similar diet either noncontaminated or contaminated with polychlorinated dibenzo-p-dioxins/-furans (PCDD/Fs; 3.14 pg WHO-TEQ/g feed, 12% moisture), polychlorinated biphenyls (PCBs; 0.08 pg WHO-TEQ/g feed, 12% moisture), polybrominated diphenyl ethers (PBDEs; 1.63 ng/g feed, 12% moisture), polycyclic aromatic hydrocarbons (PAHs; 0.72 μg/g fresh matter), or coccidiostats (0.5 mg/g feed, fresh matter). Each chicken liver was analyzed by solid-phase microextraction - mass spectrometry (SPME-MS) for volatile compound metabolic signature and by gas chromatography - high resolution mass spectrometry (GC-HRMS), gas chromatography - tandem mass spectrometry (GC-MS/MS), and liquid chromatography - tandem mass spectrometry (LC-MS/MS) to quantify xenobiotic residues. Volatile compound signature evidenced a liver metabolic response to PAH although these rapidly metabolized xenobiotics are undetectable in this organ by the reference methods. Similarly, the volatile compound metabolic signature enabled to differentiate the noncontaminated chickens from those contaminated with PBDEs or coccidiostats. In contrast, no clear signature was pointed out for slowly metabolized compounds such as PCDD/Fs and PCBs although their residues were found in liver at 50.93 (±6.71) and 0.67 (±0.1) pg WHO-TEQ/g fat, respectively.     

Assessment of human exposure to polybrominated diphenyl ethers in China via fish consumption and inhalation

This study examined human exposure to polybrominated diphenyl ethers (PBDEs) associated with fish consumption and inhalation in China. The median intake of sigma7 PBDEs via human milk was 48.2 ng/day for nursing infants (0-1 years old) (a range of 23.4-99.1 ng/day). For all other age groups, the median intake of sigma11 PBDEs via fish consumption was 1.7-12.9 ng/day with a range of 0.59-56.3 ng/g. Additionally, human exposure to PBDEs via inhalation was 2.7-9.2 ng/day (a range of 0.72-108 ng/day). The median total sigma11 PBDEs intakes for nursing infants (6874 and 7372 pg/ kg b.w./day for males and females, respectively) were much higher than other age groups (215-608 pg/kg b.w./ day). No significant difference in the total PBDEs intakes was found between males and females. Of the 11 PBDEs congeners, BDE-47 was predominant in the total intake for nursing infants with a mean contribution of 38%, whereas BDE-209 was the dominant congener of total intake for other age groups, varying from 44 to 61%. Currently, the PBDEs levels in Chinese consumer fish and the total intakes of PBDEs via fish consumption were at the lower end of the global range. Compared with similar studies in other countries, however, human exposure to PBDEs via inhalation in China was relatively high. Overall, estimated daily intake of total PBDEs in the Chinese population was far below the LOAEL. However, studies are needed to further understand the fate and impact of PBDEs as PBDE-containing products are still used widely in large quantities in China.     

Brominated flame retardants in US food

We and others recently began studying brominated flame retardant levels in various matrices in the US including human milk and other food. This paper reviews the food studies. In our studies, ten to thirteen polybrominated diphenyl ether (PBDE) congeners were measured, usually including BDE 209. All US women's milk samples were contaminated with PBDEs from 6 to 419 ng/g, lipid, orders of magnitude higher than levels reported in European studies, and are the highest reported worldwide. We compared our market basket studies of meat, fish and dairy products with other US food studies of meat and fish. US studies showed somewhat higher levels of PBDEs than reported elsewhere. Fish were most highly contaminated (median 616 pg/g), then meat (median190 pg/g) and dairy products (median 32.2 pg/g). However, unlike some European countries where fish predominates, dietary intake of PBDEs in the US is mostly from meat, then fish and then dairy products. Broiling can decrease the amount of PBDEs per serving. We also measured levels of hexabromocyclododecane (HBCD), another brominated flame retardant, in human milk. The levels are lower than PBDEs, 0.16-1.2 ng/g, similar to European levels, unlike PBDEs where US levels are much higher than European levels.     

Persistent halogenated hydrocarbons in consumer fish of China: regional and global implications for human exposure

Concentrations of persistent halogenated hydrocarbons (PHHs) were determined in 13 consumer fish species (a total of 390 individuals) collected from a major fish-farming region of China. The potential health risks of PHHs associated with consumption of fish from China was also systematically assessed regionally and globally. In all fish samples, DDTs, HCHs, PCBs, and PBDEs were the predominant PHH residues, with the median levels (ranges) being 6.0 (0.14-698.9), 0.50 (0.13-24.06), 0.10 (< 0.02-7.65), and 0.15 (< 0.0012-3.85) ng/g wet weight, respectively. The upper-bound (90th percentile) values of estimated daily intakes of DDT, HCHs, PCBs, and PBDEs via fish consumption were 45.5, 1.35, 0.46, and 0.30 ng/kg bw/d (urban), and 15.9, 0.47, 0.16, and 0.10 ng/kg bw/d (rural). Globally, the upper-bound outflows via fishery exportation of DDT, HCHs, PCBs, and PBDEs were 185, 5.51, 1.86, and 1.22 kg, respectively, in 2005. Japan was the largest recipient of PHHs, followed by Korea and the United States. Fish consumption assessments indicated that consumption of freshwater farmed and wild marine fish generally does not subject consumers to significant health risk as far as PHHs are concerned, while limited consumption of seawater farmed fish is advised.     

湖北省部分地区牛奶中多氯联苯的污染水平和暴露分析

目的调查湖北省部分地区牛奶样品中6种指示性多氯联苯(polychlorinated biphenyls,PCBs)的含量水平。方法 2014年在湖北省部分地区共采集了30份本地产牛奶样品,利用同位素稀释-高分辨气相-高分辨磁质谱(HRGC-HRMS)法测定牛奶样品中6种指示性PCBs浓度水平和指纹特征。同时计算湖北省居民单位体重通过牛奶的指示性PCBs的日摄入量,并与国内外研究比较,评估其暴露风险。结果牛奶样品中指示性PCBs总含量为107.2~4 311.2 pg/g fat,平均值为699.9 pg/g fat,中位数为433.9 pg/g fat。牛奶样品中贡献率最高的化合物为PCB-28,其次是PCB-153和PCB-138。湖北省居民单位体重通过牛奶的指示性PCBs的日摄入量的平均值和高端暴露值(以P95计)分别为0.001 47和0.005 25 ng/kg BW。结论湖北省牛奶中指示性PCBs含量处于较低水平,居民通过牛奶摄入指示性PCBs的健康风险较低。     

Body burdens of persistent halogenated compounds during different development stages of anadromous brown trout (Salmo trutta)

Polychlorinated biphenyls (PCBs), DDTs, and polybrominated diphenyl ethers (PBDEs) were followed through the five life stages of a wild population of anadromous brown trout and related to variations in lipid content and exposure situations. Anadromous brown trout exhibits great variations in lipid content during its life cycle in the freshwater and marine environments. The results indicated substantial differences in PBDE and organochlorine exposure, with apparently more recent sources of PBDEs in the freshwater environment relative to the marine environment. Lipid and contaminant transfer were not always identical: The concentrations of PCBs, DDTs, and PBDEs (ng/g lipid weight) were about 15 times lower in the eggs compared to the muscle of their mother (e.g., 823 ng PCB/g Iw vs. 12,565 ng PCB/g lw, respectively). During the starving period from maiden to spawning trout the contaminant load increased by a higher factor than the lipid use. The data suggest a decoupling between lipid content and organohalogen concentrations for anadromous brown trout, which may contribute positively to reduce any potential negative effects of the transferred contaminants on eggs and fry.     

Elevated levels of urinary 8-hydroxy-2'-deoxyguanosine in male electrical and electronic equipment dismantling workers exposed to high concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans, polybrominated diphenyl ethers, and polychlorinated biphenyls

To investigate the occupational exposure levels to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), and polychlorinated biphenyls (PCBs), indoor dust (n = 3) in workshops and hair samples from male workers (n = 64) were collected at two electrical and electronic equipmentwaste (E-waste) dismantling factories located in the LQ area in east China in July 11--13, 2006. Pre- and postworkshift urines (64 of each) were also collected from the workers to study oxidative damage to DNA using 8-hydroxy-2'-deoxyguanosine (8-OHdG) as a biomarker. The concentrations of PCDD/Fs, PCDD/F-WHO-TEQs, PBDEs, PCBs and PCB-WHO-TEQs were (50.0 +/- 8.1) x 10(3), 724.1 +/- 249.6, (27.5 +/- 5.8) x 10(6), (1.6 +/- 0.4) x 10(9), (26.2 +/- 3.0) x 10(3) pg/g dry weight (dw) in dust, and (2.6 +/- 0.6) x 10(3),42.4 +/- 9.3, (870.8 +/- 205.4) x 10(3), (1.6 +/- 0.2) x 10(6), 41.5 +/- 5.5 pg/g dw in hair, respectively. The homologue and congener profiles in the samples demonstrated that high concentrations of PCDD/Fs, PBDEs, and PCBs were originated from open burning of E-waste. The 8-OHdG levels were detected at 6.40 +/- 1.64 micromol/mol creatinine in preworkshift urines. However, the levels significantly increased to 24.55 +/- 5.96 micromol/mol creatinine in postworkshift urines (p < 0.05). Then, it is concluded that there is a high cancer risk originated from oxidative stress indicated by the elevated 8-OHdG levels in the E-waste dismantling workers exposed to high concentrations of PCDD/Fs, PBDEs, and PCBs.     

Polychlorinated dioxins, furans, and biphenyls, and polybrominated diphenyl ethers in a U.S. meat market basket and estimates of dietary intake

Persistent environmental contaminants including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), non-ortho-polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) were analyzed in 65 meat samples collected from supermarkets across the U.S. in 2001. The samples included hamburger, sirloin steaks, pork chops, bacon, and whole chickens from nine different cities. The average PCDD/F/non-ortho-PCB toxic equivalency (TEQ) for all the samples was 0.55 pg/g of lipid (nd (nondetect) = DL (detection limit)/2) with a range from nondetectable to 3.21 pg/g of lipid. For PBDEs, eight congeners were routinely found in the meat samples with an average sum of 1.71 ng/g of lipid (nd = DL/2) and a range from nondetectable to 16.6 ng/g of lipid. While average TEQs were similar to recent values reported in Europe and Asia, the sums of PBDEs in chicken and pork were 3-20 times higher than levels reported in Spain and Japan for these foods. The presence of a few outliers raised the average PBDE sums and indicated that isolated sources of contamination may exist that, if identified, could be removed from the U.S. animal production chain. Using these TEQ and PBDE values and USDA food consumption data, the estimated dietary intake ranges from meat products were 5.3-16.0 pg TEQ and 14.9-44.7 ng of PBDEs/d or 0.1-0.3 pg TEQ and 0.3-0.5 (ng of PBDEs/kg of body mass)/d for an average individual, similar to intakes in other countries.