程序升温大体积进样在HRGC-HRMS法测定食品中PCDD/F的应用

目的通过优化程序升温蒸发进样口的相关参数,建立测定食品中多氯代二苯并二噁英和多氯代二苯并呋喃(PCDD/Fs)的程序升温大体积进样高分辨气相色谱-高分辨质谱(HRGC-HRMS)方法。方法食品样品提取、净化分离和浓缩按《GB/T 5009.205-2007食品中二噁英及其类似物毒性当量的测定》规定进行,待测试样进样15μL,应用HRGC-HRMS结合同位素稀释技术测定其中PCDD/Fs。结果最佳条件为进样口初始温度115℃,蒸发相温度140℃,蒸发相吹扫流速为5 mL。大体积进样所获得的待测物峰面积及S/N存在显著增加(P0.05)。结论程序升温大体积进样方式能显著提高食品基质中PCDD/Fs的检测能力,有助于保证食品安全风险评估结果的准确可靠。     

婴儿配方乳粉中二噁英及其类似物污染分析

目的 了解婴儿配方乳粉中二噁英及其类似物污染水平,为相关研究提供基础数据.方法 采集601份市售婴儿配方乳粉,按照GB 5009.205-2013《食品安全国家标准食品中二噁英及其类似物毒性当量的测定》对17种多氯代苯并二噁英和多氯代苯并呋喃(PCDD/Fs)和12种二噁英样多氯联苯(dl-PCBs)进行测定.结果 P...     

深圳市部分市售禽类制品二噁英污染水平研究

目的了解深圳市部分市售禽类制品(鸡肉、鸭肉、鸡蛋、鸭蛋)中17种二噁英污染情况。方法于2004年12月至2008年10月期间,随机采集深圳市市售的26份禽类样品,参照美国国家环保局EPA1613方法,采用索式抽提装置和FMS自动纯化系统分别对样品进行提取和净化,采用同位素稀释技术,用高分辨气相色谱/高分辨双聚焦磁式质谱联用(HRGC/HRMS)的超痕量有机分析技术平台,对样品中的二噁英进行定量分析检测。结果禽肉中PCDD/Fs含量(pgWHO-TEQ/g脂肪)范围是0.03～1.61,平均含量为0.50;禽蛋中PCDD/Fs含量范围是0.22～5.66,平均含量为1.43。其中有1份鸡肉和1份鸡蛋中二噁英含量超过欧盟执行标准,含量分别为1.61和5.66。结论本次调查的禽类制品中二噁英平均含量低于欧洲标准,但个别样品存在二噁英污染现象。     

自动样品净化系统分析鱼样中二(口恶)英和共平面多氯联苯

为评价自动样品净化系统在分析食品样品中17种二(口恶)英(PCDD/Fs)与12种共平面多氯联苯(PCBs)上的应用,以鱼样有证标准参考物对系统进行验证.鱼肉标准参考物质经索式抽提、FMSPower Prep系统净化后浓缩,使用高分辨气相色谱-高分辨质谱联用仪以多离子检测方式和同位素稀释技术对样品中的目标化合物进行定性和定量.样品中PCDDs/Fs同位素内标的平均回收率为62.4%～84.3%,共平面PCBs同位素内标的平均回收率为53.1%～89.2%.3个不同浓度水平的有证标准参考物的TEQ测定值均与参考值符合.FMS Power Prep样品净化系统可以满足食品样品中PCDD/Fs和共平面PCBs的分析要求.     

甘肃省市售食品中二噁英类化合物污染现状研究

摘 要：目的 了解甘肃省居民市售食品中二噁英类化合物污染现状。方法 按总膳食研究方法,对我省8类市售食品样品（水产及其制品、肉类及其制品、蛋及其制品、乳及乳制品、谷类及其制品、薯类及其制品、豆类及其制品、蔬菜类及其制品）中17种多氯代苯并二噁英和多氯代苯并呋喃（polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, PCDD/Fs）同系物和12种二噁英样多氯联苯（dioxin like polychlorinated biphenyls, dl-PCBs） 同系物进行含量测定和毒性当量浓度汇总分析和评价。结果 甘肃省送检的食物样品中水产、肉类均检出二噁英类化合物,其余6类食品样品个别同系物未检出。按TEQ 计时,肉类食品样品中PCDD/Fs和dl-PCBs毒性当量浓度最高,均为0.08pgTEQ/g。结论 甘肃省8类市售食品样品中动物性食品二噁英类化合物检出率高于植物性食品,肉类食品样品中PCDD/Fs和dl-PCBs毒性当量浓度均高于全国平均水平。建议对我省二噁英类化合物暴露水平高的食品进行长期监测,提出相应的风险管理措施。     

甘肃省3个非暴露地区居民母乳中二噁英负荷水平与影响因素分析

摘要：目的 调查甘肃省非暴露地区母乳中二噁英类化合物污染水平，分析影响当地人群二噁英类化合物污染的相关因素。方法 在甘肃省城区、近郊区和远郊区3个采样点各采集50份顺产初产妇产后第3-8周的母乳样品，以高分辨气相色谱-高分辨质谱分析仪分析样品中多氯代苯并二噁英和多氯代苯并呋喃(PCDD/Fs)和多氯联苯(PCBs)含量，计算总毒性当量浓度（TEQ）。结果 （1）PCDD/Fs和 dl-PCBs在甘肃省母乳样品中普遍存在，dl-PCBs含量远高于PCDD/Fs，但按TEQ计时，PCDD/Fs贡献高于dl-PCBs；（2）甘肃省PCDD/Fs组分含量最高的OCDD，含量在102.08~195.18?pg/g脂肪之间，来源可能与垃圾焚烧导致污染有关；母乳中PCBs污染分布呈现出城市点（2436.88 pg/g）>近郊区（1118.16?pg/g）>远郊区（989.87?pg/g）的特征，可能与居民肉蛋奶等动物性食品摄入频次较高有关。结论 甘肃省非暴露区母乳中二噁英类化合物含量均低于全国水平，总体上城市高于农村，但个别同系物数值农村点与城市点接近甚至高于城市点，这提示甘肃省不同地区人体暴露情况有其独特性和复杂性。     

气相色谱-串联质谱法(GC-MS/MS)测定大米中25种农药及其代谢物残留

建立气相色谱-串联质谱法同时测定大米中25种农药及其代谢物残留的方法.样品经粉碎后,用乙腈-水-乙酸溶液(70∶29∶1)提取,提取液经无水硫酸镁和氯化钠盐析,再采用无水硫酸镁、PSA和C18净化后,直接进行气相色谱-串联质谱(GC-MS/MS)分析,采用保护剂基质内标法进行定量.结果表明,待测物质在2.5～100 μ...     

高分辨气相色谱-高分辨质谱法同时测定生活用纸制品中的二噁英及其类似物的含量

建立了生活用纸制品中17种二噁英(PCDD/Fs)及12种二噁英类似物多氯联苯(DL-PCBs)的高分辨气相色谱-高分辨质谱法(HRGC-HRMS)的检测方法。样品剪碎后匀浆,采用水浴振荡提取,提取液浓缩后依次经硫酸、多段硅胶柱、氧化铝柱净化和分离后浓缩,保留时间及高分辨质谱定性,稳定性同位素稀释法定量。本方法 PCDD/Fs和DL-PCBs检测限在0. 01～0. 10ng/kg之间,样品加标平行6次的检测结果 PCDD/Fs平均回收率在70. 3%～92. 1%,RSD为2. 34%～7. 48%,DL-PCBs平均回收率在72. 4%～88. 3%,RSD为2. 19%～6. 95%,具有检测限低,回收率良好和精密度高,满足日常检测要求。在实际样品检测中PCCD/Fs~(13)C_(12)标记同位素定量内标回收率为70. 7%～92. 9%,DL-PCBs~(13)C_(12)标记同位素定量内标回收率为70. 1%～88. 6%。该方法准确、快速、可靠,可应用于生活用纸制品中17种二噁英(PCDD/Fs)及12种二噁英类似物多氯联苯(DL-PCBs)的含量分析。     

同位素稀释高分辨气相色谱-高分辨磁质谱法测定大闸蟹中二噁英及其类似物

建立了同位素稀释高分辨气相色谱-高分辨磁质谱法测定大闸蟹中二噁英类化合物及二噁英类多氯联苯。对大闸蟹的白肉及棕肉分别进行测定,样品经加速溶剂萃取(丙酮-正己烷-二氯甲烷：20:40:40,体积比)、酸化硅胶初步净化、全自动二噁英净化系统净化后,分别收集PCDD/ Fs、DL-PCBs的净化液,浓缩后上机分析。采用选择离子监测模式进行测定,白肉PCDD/ Fs的检出限在0.016ng/kg~0.106 ng/kg范围内,DL-PCBs的检出限在0.105 ng/kg~0.252 ng/kg范围内;棕肉PCDD/ Fs的检出限在0.053 ng/kg ~0.353 ng/kg范围内,DL-PCBs的检出限在0.120 ng/kg~0.840 ng/kg范围内。大闸蟹白肉PCDD/ Fs、DL-PCBs的同位素定量内标溶液的平均回收率分别为73.4%~103.5%、74.8%~93.0%;RSD分别为6.4%~21.5%、10.5%~24.7%;大闸蟹棕肉PCDD/ Fs、DL-PCBs的同位素定量内标溶液的平均回收率分别为59.8%~90.1%、65.7%~92.1%;RSD分别为7.5%~23.5%、7.5%~24.8%。本文建立的方法灵敏度高,干扰小,能完全满足国内外的检测需要。     

基于GC-MS/MS法测定鱼肉中二噁英和二噁英类多氯联苯

建立基于GC-MS/MS方法,采用稳定性同位素稀释法测定鱼肉中二噁英及二噁英类多氯联苯。样品经快速溶剂萃取仪提取3次,以酸化硅胶除脂,经多层硅胶柱、碱性氧化铝柱和活性炭柱净化,分别收集含PCDD/Fs和DL-PCBs组分,经浓缩复溶后供GC-MS/MS测定。结果表明:在净化步骤中,PCDD/Fs和DL-PCBs受洗脱液的体积以及收集步骤的影响较大,分开收集PCDD/Fs和DL-PCBs,先对PCDD/Fs的收集液进行测定,然后将其和DL-PCBs的收集液合并完成DL-PCBs的测定,从而对DL-PCBs进行准确定量。采用鱼肉为样品基质时,该方法PCDD/Fs和DL-PCBs的内标回收率为63.3%～106.8%,RSD为0.4%～9.6%;目标物的回收率为93.6%～114.5%,RSD为0.9%～9.2%,方法线性和检出限达到国家标准GB 5009.205的要求,适用于鱼肉样品中PCDD/Fs和DL-PCBs的测定。     

牛乳中二噁英类化合物标准物质的研制

研制乳粉中非添加二噁英类化合物的标准物质,加强我国二噁英类化合物实验室检测质控能力建设。方法 选择满足侯选物筛选原则和要求的牛乳样品作为候选物,经混匀、分装、冻干后,以高分辨气相色谱-高分辨质谱法同位素稀释技术测定多氯代苯并二噁英、多氯代苯并呋喃(PCDD/Fs)和二噁英样多氯联苯(dl-PCBs),经均匀性和稳定性试验后,采用多家实验室联合定值方法对样品中二噁英类化合物含量进行定值及不确定度分析。结果 经单因素方差分析和F检验,瓶间均匀性试验的检验值F均小于临界值F0.01(9,40)。室温下1年的稳定性试验结果显示,定值化合物一元线性拟合方程中斜率|b₁|均小于t(0.95,3)×s(b₁),表明特征值变化趋势无统计学意义。结论 本研究提出了二噁英类化合物定值结果,为二噁英检测提供质控参考和能力评价。     

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.     

Congener-specific distribution of polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls in animal feed.

Polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) were extracted by accelerated solvent extraction from animal feed samples and analysed by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). In all of the feed samples analysed, the concentrations of PCDD/Fs and PCBs were below the existing tolerance limit of 5 pg I-TEQ g(-1) and 200 ng g(-1) fat, respectively. The mean concentrations of the total PCDDs, total PCDFs and total PCBs were 1.73-11.50 pg g(-1), 0.23-11.91 pg g(-1) and 60.00-234.40 pg g(-1) feed, respectively. Investigation of the correlations among the concentrations of PCDDs, PCDFs and PCBs showed that samples containing increased amounts of PCDFs also contained higher concentrations of PCDDs, with an average ratio of PCDF:PCDD of about 1.23:1 (r(2)=0.72, p<0.05). The correlation between the concentrations of PCDD/Fs and PCBs was positive but not significant.     

QuEChERS结合质谱法测定食用菌中13种农药残留

本文目的在于建立QuEChERS前处理方法测定食用菌中13种农药残留量同时供气相色谱—串联质谱仪和液相色谱—串联质谱仪测定的分析方法。本实验采用冬菇、草菇和金针菇三种食用菌,分别以乙腈提取,改良的QuEChERS(Quick、Easy、Cheap、Effective、Rugged、Safe) 方法净化,气相色谱-串联质谱法采用Agilent HP-5MS ultralnert 柱 (30.0 m×250μm×0.25μm) 柱上分离,液相色谱-串联质谱法采用农残色谱柱ACQUITY UPLC? BEHC181.7um 2.1x50mm Column分离。结果表明,在添加水平< 0.1mg/kg 时,13种农药的回收率在 60% ～ 120% 之间,添加水平在 0.1～1mg/kg 时,13种农药的回收率在80% ～ 110% 之间。相关系数>0.99,符合农药残留国家标准要求。此方法适用但不限用于食用菌中13种农药残留测定。     

二噁英、多氯联苯和氯丙醇的痕量与超痕量检测技术研究

为建立食品中二噁英、多氯联苯和氯丙醇的检测技术并达到国际水平，将稳定性同位素稀释质谱技术应用到中国食品安全和环境分析领域，针对不同目标化合物分别建立了高分辩磁质谱、四极杆低分辩质谱和离子阱串联质谱的标准化检测技术，特别是采用双同位素稀释同时测定4种氯丙醇的技术。通过对EPA1613A／1668A、FDA4084和EPSI／RM／31、AOAC2000．01等国际先进方法用食品（鱼、鱼油、鹿肉、奶粉和猪油）和环境样品（飞灰、土壤和底泥）开展对比筛选和一系列实验室闻协同性验证，确立了二噁英和多氯联苯的稳定性同位素稀释质谱检测方法，建立了用双稳定性同位素进行酱油中单氯取代和双氯取代氯丙醇同时测定的方法，提出了符合国际规范的技术方案，作为国家标准方法待颁布。利用该检测技术在中国首次开展鱼贝类和土壤中污染的二噁英和多氯联苯同系物类型特征指纹库研究和酱油中氯丙醇的大规模调查，获得了中国人群膳食二噁英毒性当量和氯丙醇摄入状况的暴露数据，不仅证明所建立的方法实用、可行，也为我国履行承诺摸清了家底，提供了依据。     

PBDDs/Fs and PCDDs/Fs in the raw and clean flue gas during steady state and transient operation of a municipal waste combustor

Concentrations of polybrominated dibenzo-p-dioxins, and -dibenzofurans (PBDDs/Fs) and polychlorinated dibenzo-p-dioxins, and -dibenzofurans (PCDDs/Fs), were determined in the pre- and post-air pollution control system (APCS) flue gas of a municipal waste combustor (MWC). Operational transients of the combustor were found to considerably increase levels of PBDDs/Fs and PCDDs/Fs compared to steady state operation, both for the raw and clean flue gas; ΣPBDDs/Fs increased from 72.7 to 700 pg dscm(-1) in the raw, pre-APCS gas and from 1.45 to 9.53 pg dscm(-1) in the post-APCS flue gas; ΣPCDDs/Fs increased from 240 to 960 ng dscm(-1) in the pre-APCS flue gas, and from 1.52 to 16.0 ng dscm(-1) in the post-APCS flue gas. The homologue profile of PBDDs/Fs and PCDDs/Fs in the raw flue gas (steady state and transients) was dominated by hexa- and octa-isomers, while the clean flue gas homologue profile was enriched with tetra- and penta-isomers. The efficiency of the APCS for PBDD/F and PCDD/F removal was estimated as 98.5% and 98.7%, respectively. The cumulative TEQ(PCDD/F+PBDD/F) from the stack was dominated by PCDD/F: the TEQ of PBDD/F contributed less than 0.1% to total cumulative toxic equivalency of MWC stack emissions.     

Characteristics of PCDD/F distributions in vapor and solid phases and emissions from the Waelz process

The Waelz process is a classic method used for recovering zinc from electric arc furnace (EAF) dusts containing relatively high concentrations of PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans) as well as volatile metals, such as Zn, Pb, and Cu, and chlorine. As a result of the operating temperature in the cooling process and high carbon and chlorine contents, significant PCDD/Fs are formed in the typical Waelz process, causing public concerns regarding PCDD/F emissions. In this study, flue gas and ash samplings are simultaneously conducted at different sampling points to evaluate the removal efficiency and the partitioning of PCDD/Fs between the vapor and solid phases in the Waelz plant investigated. With the environment (temperature window, sufficient retention time, chlorine, and catalysts available) conducive to PCDD/F formation in the dust settling chamber (DSC), a significantly high PCDD/F concentration (1223 ng TEQ/Nm3) is measured in flue gas downstream from the DSC of the Waelz plant investigated. In addition, the cyclone and bag filter adopted in this facility can only remove 51.3% and 69.4%, respectively, of the PCDD/Fs in the flue gas, resulting in a high PCDD/F concentration (145 ng TEQ/Nm3) measured in the stack gas of the Waelz plant investigated. On the basis of treating 1 ton of EAF dust, the total PCDD/F discharge (stack gas emission + ash discharge) is 840 ng TEQ/kg EAF dust of the Waelz plant investigated. Because of the lack of effective air pollutant control devices for PCDD/Fs, about 560 ng TEQ/kg EAF dust are discharged via stack gas in this facility.     

Application of electron beam for the reduction of PCDD/F emission from municipal solid waste incinerators

The electron-beam technology was applied to reduce the emission of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in a flue gas of 1000 m(3)N/h from the municipal solid waste incinerator (MSWI) at a temperature of 200 degrees C. More than 90% decomposition of PCDD/Fs was obtained using an electron accelerator at a dose of 14 kGy. The decomposition was initiated through reactions with OH radicals produced by the irradiation of flue gases, followed by oxidation such as the ring cleavage of the aromatic ring, the dissociation of ether bond, and dechlorination. The cost analysis estimated that the electron-beam system can cut the annualized cost by approximately 50% for the treatment of PCDD/Fs in a pre-dusted MSWI flue gas as compared with a bag-filter system when operating on electricity generated from an incineration. Electron-beam technology is an economically and technologically useful method for reducing PCDD/Fs in an incineration flue gas.     

Levels and trends of PCDD/Fs and DL-PCBs in Polish animal feeds, 2004–2017

Feed control is essential for the safety of animal-origin food. It is estimated that more than 80% of human exposure to dioxins and related compounds comes from the consumption of animal-origin food, and farm animals are exposed to dioxins mainly through the feed. A monitoring programme for dioxins (polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs)) and dioxin-like polychlorinated biphenyls (DL-PCBs) was conducted in the Polish feed market between 2004 and 2017. Using two complementary ISO 17025-accredited analytical methods (bioassay and high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS)), 2919 samples of plant, animal and minerals origin were analysed. The total number of samples exceeding the maximum limit (ML) was 52, which is 1.8% of all tested samples. They all contained PCDD/Fs in concentrations over the ML, and in 16 samples the limit for the sum of PCDD/F/DL-PCBs was also exceeded. The highest dioxins level was found in feedstuffs derived from Baltic fish; the fish oil was followed by fish meal. Low-chlorinated furans (2.3,7,8 TCDF, 2,3,4,7,8-PCDF and 1,2,3,7,8-PeCDF) were dominant and these congeners accounted for the toxicity expressed in WHO toxic equivalents (WHO-TEQ). In this category, 155 out of the 498 samples (32%) exceeded the action threshold (AT) for PCDD/Fs and in 10 samples (2.0%) for DL-PCBs. Non-compliant fish meals were found in 34 (5.6%) of the tested samples, in 0.7% of compound feeds, and in 1.5% of plant-origin materials. Seven dried plant-derived materials contained PCDD/F level above ML, including alfalfa, maize, apple, basil and beet pulp pellets containing molasses. The dry vegetable materials were mostly contaminated by the 2,3,7,8-furans, the congeners arising from a faulty drying process. No significant time trend can be seen. From the obtained results, it can be concluded that concentrations of PCDD/Fs and DL-PCBs in Polish feed materials were sufficiently low to ensure low concentrations in animal-derived products.     

PCDD/F contamination over time in Japanese paddy soils

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs)were analyzed in preserved paddy soils periodically collected from 7 sites around Japan since 1960 to trace the changes in concentrations, to elucidate their sources, and to estimate their mass balance in Japanese paddy fields. Concentrations of sigma PCDD/Fs in paddy soils from all sites increased during the 1960s and the 1970s, then decreased. The results of principal component analysis and chemical mass balance based on functional relationship analysis indicate that the increase in sigma PCDD/F concentrations in paddy soils was due to the increased use of pentachlorophenol (PCP) and chlornitrofen (CNP); more than 95% of PCDD/Fs in all paddy soils were derived from impurities in these herbicides. The half-lives of PCDD/F for disappearance from the paddy soils were estimated to be 10 to 20 years (mean: 17.3 years). The estimated PCDD/F mass balance using the above half-life during the past 40 years in paddy fields indicates that about 80% of PCDD/Fs have disappeared. The soil puddling (mechanically mixing of paddy soil with pooled irrigation water) is implied as one reason for the PCDD/F disappearance from paddy fields. However, as the amounts of PCDD/Fs added through the use of PCP and CNP were extremely large, PCDD/F concentrations in Japanese paddy soils will decrease gradually, and PCDD/F runoff from paddy fields to surrounding catchments will continue.