大流量采样-GC-NCI-MS测定环境空气中的多溴联苯醚

建立了大流量采样-气相色谱负化学电离质谱法测定环境空气中痕量多溴联苯醚的方法.用PS-1型大流量空气采样器采集环境空气样品,样品经提取、纯化后采用气相色谱负化学电离质谱法测定环境空气中多溴联苯醚.方法的线性范围在5～10000 pg/m3之间,检出限1～50 pg/m3.用于检测2006年5月在广州市采集的环境空气样品,多溴联苯醚组分含量在5.4～4989 pg/m3范围.该方法适合用于监测环境空气中的痕量PBDEs.     

气相色谱柱对多溴联苯醚分析的影响

基于气相色谱-电子捕获检测器法对11种代表性多溴联苯醚进行分析,考察不同类型气相色谱柱对多溴联苯醚分离分析的影响. 结果表明:色谱柱极性是影响分离和响应的主要因素,极性较大的固定相上多溴联苯醚各单体的保留时间变长,响应降低,尤其是高取代多溴联苯醚的响应受到的影响最大. 柱长较短、液膜较薄的色谱柱有助于高取代多溴联苯醚的分析. 不同品牌的色谱柱受生产工艺的影响,对多溴联苯醚的响应产生较大影响.     

高效液相色谱法测定电子电气产品中多溴联苯和多溴联苯醚

提出了高效液相色谱法测定电子电气产品中多溴联苯和多溴联苯醚含量的方法。普通塑料样品采用正己烷-丙酮(1+1)混合溶液作为提取溶剂进行微波萃取,含金属的塑料样品采用乙酸乙酯作为提取溶剂进行超声波萃取,提取液采用NUCLEODUR Sphinx RP C18色谱柱为分离柱分离,以不同体积比混合的水和乙腈为流动相进行梯度洗脱,检测波长为226nm。多溴联苯和多溴联苯醚的质量浓度在0.2～50mg.L-1范围内与峰面积呈线性关系,测定下限(10S/N)在2.3～5.0mg.kg-1之间。     

大流量采样高分辨气相色谱/高分辨质谱法测定大气中的多氯联苯和多溴联苯醚

建立了大流量空气采样高分辨气相色谱/高分辨质谱(HRGC/HRMS)同时分析测定大气样品中多氯联苯(PCBs)和多溴联苯醚(PBDEs)的分析方法。结果表明在采样过程中污染物没有发生穿透。通过添加 13C同位素标准物质进行评价,PCBs和PBDEs的加标回收率分别为60.7%～121.4%和69.9%～140.4%,均符合美国环保署相关方法的要求。PCBs和PBDEs的方法检出限分别低于0.019 pg/m3和0.189 pg/m3;色谱分离效果良好,可以满足大气样品中PCBs和PBDEs的监测需要。     

全二维气相色谱/飞行时间质谱法定性筛查鱼肉组织中含卤有机污染物

采用全二维气相色谱/飞行时间质谱(GC×GC-TOFMS),建立了鱼肉样品中含卤有机污染物的定性和定量分析方法.鱼肉样品用正己烷丙酮(1∶1,V/V)提取,凝胶色谱和复合硅胶柱净化,浓缩富集,全二维气相色谱联用飞行时间质谱(DB-5MS毛细管色谱柱联HT-8色谱柱)检测.软件自动识别后,经三步筛查,共鉴定出含氯或溴化合物72种,其中包括33种多氯联苯,9种有机氯农药,4种多溴联苯醚,4种DDT代谢产物,2种氯代茴香醚,2种氯苯乙烯,1种氯代茴香硫醚及1种甲基三氯生.另外,从质谱信息上看,有16种化合物明显含氯或含溴,但是因为缺少必要的谱库信息不能准确识别.采用外标定量法,对鱼肉样品中检出的主要的10种多氯联苯和1种多溴联苯醚进行了准确定量分析.     

斑马鱼卵中多溴联苯醚及其衍生物的同步分析

建立了液液萃取耦合气相色谱/质谱联用(GC/MS/MS)分析斑马鱼卵中10种多溴联苯醚(PBDEs),12种甲氧基化多溴联苯醚(MeO-PBDEs)和9种羟基化多溴联苯醚(HO-PBDEs)不同极性组分的同步分析方法。优化了前处理步骤和色谱质谱条件,采用液液萃取法提取目标化合物,不必分离即可实现目标化合物的衍生化,使样品前处理时间大大缩短,实现了不同极性组分化合物的同步分析。采用干法制备酸性硅胶柱纯化,用15 mL正己烷和15 mL二氯甲烷正己烷(1:1,V/V)混合溶剂洗脱效果良好。31种化合物在4.0～500μg/L浓度范周内线性良好,相关系数均大于0.99,回收率在71.6%～133.0%之间;相对标准偏差低于21.5%;检出限在0.09～17.0 ng/g之间。本方法应用到斑马鱼亲子代间转移研究中,对实际样品的检测良好,并发现BDE-47,6-HO-BDE-47,6-MeO-BDE-47,2’-HO BDE-28和2’-MeC-BDE 28可通过母代斑马鱼暴露后,不同程度地转移到子代中。     

气相色谱-离子阱质谱法测定海洋贝类中多残留有机氯农药、多氯联苯和多环芳烃

本研究建立了凝胶渗透色谱和铝硅胶柱前处理,气相色谱-离子阱质谱法测定海洋贝类体内20种有机氯农药、28种多氯联苯和16种多环芳烃的多残留分析方法。通过对凝胶渗透色谱的组分收集时间和铝硅胶柱的正戊烷淋洗体积的实验条件优化,实现了样品索氏提取液的凝胶渗透色谱初步净化、铝硅胶柱色谱的组分分离和进一步去除干扰物质。结果表明,多氯联苯、有机氯农药和多环芳烃各化合物的方法检出限分别为0.01~0.14,0.02~0.17和0.52~0.81ng/g(湿重),样品的加标回收率和相对标准偏差分别为:多氯联苯84.1%~120.2%、5.6%~15.9%;多环芳烃62.3%~123.1%、8.7%~20.5%;有机氯农药77.3%~127.5%、3.1%~18.7%。本方法降低了样品的前处理成本,缩短了样品处理时间,可应用于海洋贝类体内持久性有机污染物的实际监测。     

气相色谱-质谱法检测沉积物中自由态与束缚态多溴联苯醚和四溴双酚-A

建立了一种同时测定沉积物中不同赋存形态的多溴联苯醚(PBDEs)和四溴双酚A(TBBPA)的分析方法.样品由等体积的丙酮和正己烷混合溶剂抽提得到自由态目标物,再通过碱性水解反应释放束缚态目标化合物.通过调节酸度(pH值)实现PBDEs和TBBPA的分离和提取.PBDEs由复合硅胶柱净化,运用气相色谱-质谱(负离子化学源)-分时段选择离子监测技术测定;TBBPA经重氮甲烷衍生化反应后由酸性硅胶柱预纯化,运用气相色谱-质谱(电子轰击源)-分时段选择离子监测技术测定.8种低溴联苯醚(BDE28,-47,-66,-100,-99,-154,-153,-183),十溴联苯醚(BDE209)和TBBPA的检出限分别为0.6～12.5 pg/g,172 pg/g,4 2 pg/g.方法具有良好的准确度和精确度,回收率均在74%～106%之间,RSD≤10%.对东江沉积物样品的分析表明,本方法能够实现不同形态的PBDEs 和TBBPA的有效检测.     

气相色谱-负化学源质谱法测定海洋生物中的多溴联苯醚

建立了气相色谱-负化学源质谱(GC-NCI-MS) 法分析海洋贝类样品中多溴联苯醚(PBDEs) 的方法. 样品采用索氏提取、多层硅胶柱分离纯化及外标法定量, 7种BDE单体的基质加标回收率平均值为67.4%～101%, 相对标准偏差为4.0%～18%. 对采自大连的白蛤、菲蛤、牡蛎等样品进行分析, 结果表明负化学源分析方法适用于海洋贝类中PBDEs的检测.     

固定源废气中二噁英及多氯联苯、溴代阻燃剂和溴代二噁英的分析

建立了同时分离分析固定源废气中二噁英(PCDD/Fs)、二噁英类多氯联苯(dl-PCBs)、溴代阻燃剂(BFRs)和溴代二噁英(PBDD/Fs)的方法。废气样品经甲苯索氏提取,硫酸处理和多层硅胶柱净化后,应用活性炭分散硅胶翻转淋洗技术分离4类目标物。气相色谱使用耐高温薄膜短色谱柱配合高压进样,高分辨质谱使用低能量电离,一次性测定高/低溴代化合物。方法检出限分别为:PCDD/Fs 0.081~1.2 pg、dl-PCBs0.10~0.32 pg、多溴联苯醚(PBDEs)0.14~12 pg、新型BFRs 0.26~16 pg、四~七溴代PBDD/Fs 0.44~3.6 pg、八溴代PBDD/Fs(OBDD/F)8.2~12 pg。废气空白基质加标回收率(RSD)分别为:PCDD/Fs 88%~115%(2.9%~6.1%)、dl-PCBs 84%~118%(3.2%~10%)、PBDEs 71%~135%(2.1%~18%)、新型BFRs 71%~114%(2.9%~7.4%)、四~七溴代PBDD/Fs 83%~127%(5.2%~10%)、OBDD/F 52%~149%(23%~24%)。将本方法用于废气样品分析,所有质量控制指标均符合相关标准规定。     

Method development for the analysis of polybrominated diphenyl ethers, polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins and dibenzo-furans in single extract of sediment samples

A comprehensive method was developed for quantitative analysis of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzo-furans (PCDD/Fs) in one single extract of environmental samples. The sample preparation procedure included two fractionation steps using silver nitrate silica chromatography to separate PBDEs from PCBs and PCDD/Fs and florisil column to separate PCBs from PCDD/Fs. Acidic silica, acidic alumina and gel permeation chromatography (GPC, for PCBs) or activated carbon column (for PCDD/Fs) were used for further clean-up. The sample extracts were analyzed by using high-resolution gas chromatography/high-resolution mass spectrometry. The entire method was validated from the analysis of mixed standards of PBDEs, PCBs and PCDD/Fs (n = 3); the analysis of certified reference biota (WMF-01). The method was applied for the analysis of 10 sediment samples collected from Haihe River and Dagu Drainage River in Tianjin City. No significant PBDEs pollution was found in the areas.     

自动样品前处理在乳品中二恶英和共平面多氯联苯同时测定中的应用

采用索氏提取及自动净化处理系统对乳品进行提取和净化,在高分辨气相色谱-高分辨双聚焦质谱仪(HRGC/HRMS)上进行定性和定量检测。在3种不同残留水平的奶粉样品中,17种多氯代二苯并-对二恶英和多氯代二苯并呋喃（PCDD/Fs）的测定结果与给定值具有很好的一致性,且所有具有保证值的二恶英同系物测定结果的相对标准偏差（RSD）均小于20%;12种共平面多氯联苯（PCBs）测定结果的RSD均在15%以内,内标物的回收率为44%～133%,完全符合国际标准方法的要求。母乳样品的国际考核结果表明本方法在不同实验室间具有良好的准确度和精密度。本方法定量准确可靠,适用于乳品中二恶英及共平面PCBs的同时检测。     

Separation of polychlorinated dibenzo-p-dioxins/furans,non-ortho/mono/di/tri/tetra-ortho-polychlorinated biphenyls,and polybrominated diphenyl ethers groups of compounds prior to their determination with large volume injection gas chromatography—Quadrupole ion storage tandem mass spectrometry

Polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) are important environmental contaminants. Their maximum legally allowable levels in food and environment are in the low pg g⁻¹ range. Therefore some highly selective and sensitive analytical methods must be used to determine them. Prior to final determination by GC/MS the cleaned-up samples have to be split into some fractions in view of large differences in concentrations of various analytes and existence of numerous chromatographic co-elutions (which in any case cannot be fully avoided). The aim of this study was to: (i) develop a robust, time-saving analytical method to isolate, clean-up and fractionate PCBs, PBDEs and PCDD/Fs prior to their determination with gas chromatography/ion trap mass spectrometry; (ii) assess method performance using laboratory validation data and some certified reference materials; (iii) use the developed method to assess PCB/PBDE/PCDD/F levels in samples of commercially available food. A combination of alumina, florisil, modified silica gel and two carbon columns were used for sample cleanup and fractionation. Separate fractions containing dioxins/furans, PBDE, non-ortho, mono-ortho and di-/tri-/tetra-ortho PCBs were obtained. The method statistical parameters were compatible with 1883/2006 EC Regulation (80–120%, RSD below 15%). The method performance was successfully used to evaluation of some real life food samples.     

气相色谱/高分辨质谱联用测定环境样品中的二噁英和类二噁英多氯联苯

样品采用索氏抽提,抽提液依次经酸性硅胶床、多段混合硅胶柱和凝胶渗透色谱柱(GPC)净化后,用Florisil硅藻土柱分离出样品中的二噁英(PCDD/Fs)和类二噁英多氯联苯(dioxin-like PCBs),采用同位素稀释法和气相色谱/高分辨质谱联用仪(GC/HRMS)测定了其中的17个2,3,7,8-氯取代二噁英类化合物和12个类二噁英多氯联苯。结果表明,用该法分析二噁英和多氯联苯标准溶液,平行4次的分析结果为:RSD(PCDD/Fs)<8.9%,RSD(PCBs)<11.4%;回收率可达60%-105%。PCDD/Fs和PCBs的检出限分别为0.1-0.8 pg/g和0.05-0.6 pg/g。应用本方法成功测定了沉积物、淤泥、土壤和飞灰中的二噁英和类二噁英多氯联苯,并计算出它们的毒性当量。     

同位素稀释的气相色谱/高分辨质谱联用测定食品中二噁英和共平面多氯联苯

采用HRGC/HRMS和同位素稀释定量技术对样品中17种4~8个氯原子取代的二噁英和呋喃(PCDDs/Fs)与12种共平面多氯联苯(PCBs)定量分析。样品经索式抽提、FMSPowerPrep系统净化、浓缩,利用高分辨气相色谱/高分辨质谱联用仪的多离子检测方式,同位素稀释技术对样品中的目标化合物进行定性和定量。该方法的检出限为pg/g水平。13C同位素内标回收率范围为47%~100%。对3个CRM鱼样中17个PCDDs/Fs和4个PCBs的检测值均在标准定值允许误差范围内。对5个不同的实际样品鱼进行测定表明,样品的回收率在48%~100%之间,回收率的相对标准偏差小于20%;对同一样品进行定量检测的精密度测试结果表明,17种PCDDs/Fs浓度的RSD低于16%,12种PCBs浓度的RSD低于11%。本方法定量分析重现性良好。     

Comprehensive two-dimensional gas chromatography in the screening of persistent organohalogenated pollutants in environmental samples

Separations of eight persistent organohalogenated classes of pollutants, organochlorinated pesticides (OCPs), polychlorinated biphenyls (PCBs), polychlorinated diphenyl ethers (PBDEs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated naphthalenes (PCNs), polychlorinated terphenyls (PCTs) and toxaphene (CTT) by comprehensive two-dimensional gas chromatography (GC x GC) were evaluated. Columns with different polarity and selectivity, including ZB-5, HT-8, DB-17 and BP-10, were selected as first dimension and combined with columns of increasing polarity in the second dimension, i.e. HT-8, BPX-50 and Carbowax (or Supelcowax-10). In total nine column combinations were tested. Because the main interest of the study was fast screening of the test xenobiotic families in complex matrices, in all cases, attention was primarily focussed on group-type separation. Nevertheless, within-group separation was also considered, especially for those classes containing particularly toxic congeners, such as PCBs and PCDD/Fs. Although none of the assayed column sets allowed the simultaneous and complete separation of all pollutants classes, some column combinations provided satisfactory separations among selected families and the rest of pollutants investigated. That was, for instance, the case of HT-8 x BPX-50 for PBDEs and PCDD/Fs, DB-17 x HT-8 for PCNs and OCPs and BP-10 x BPX-50 for CTT, PCDD/Fs and PBDEs. The feasibility of the proposed approach for the fast screening of the target classes of pollutants in complex samples was illustrated by the analysis of food and marine fat samples prepared using simplified miniaturised sample treatment methods.     

加速溶剂萃取-硅胶柱净化-碱性氧化铝柱分离-气相色谱三重四极杆质谱法测定土壤中的二噁英类化合物

建立了加速溶剂萃取(ASE),酸性硅胶柱、复合硅胶柱及碱性氧化铝柱纯化分离,气相色谱-三重四极杆质谱测定土壤中二噁英/呋喃(PCDD/Fs)、多氯联苯(PCBs)、多氯萘(PCNs)的分析方法.选用正己烷-二氯甲烷(50∶50, V/V)作为ASE的提取溶剂,设定提取温度为120℃,加标回收实验表明本方法可行.用100 mL正己烷-二氯甲烷(95∶5, V/V)及50 mL正己烷-二氯甲烷(50∶50, V/V)依次淋洗碱性氧化铝柱,得到组分A(PCBs及PCNs)与组分B(PCDD/Fs),实现了PCDD/Fs与另外两种化合物的分离,排除了同系物间及其它杂质的干扰.使用同位素稀释-气相色谱三重四极杆质谱法(GC-MS/MS), 在选择反应监测(Selected reaction monitoring, SRM)模式下测定PCDD/Fs、PCBs和PCNs,3种化合物的仪器检出限(LOD)范围分别为0.04~0.25 μg/L, 0.10~0.20 μg/L和0.01~0.05 μg/L,目标物平均相对响应因子(RRF)的相对标准偏差(RSD)均小于13%.基质土加标实验中,3种化合物13C标记的同位素内标回收率的范围分别为50%~95%,51%~103%, 49%~74%.实际样品的分析结果表明,PCDD/Fs、PCBs及PCNs在土壤样品中的总含量范围分别为16.1~1148 pg/g、6.6~152.6 pg/g及10.9~99.5 pg/g,且样品测定结果与高分辨质谱测定结果相吻合.     

杭州市冬季大气气溶胶PM2.5中二恶英和多氯联苯的污染特征

2014年1月在杭州市选择5个点位采集大气颗粒物PM_2.5样品,采用同位素稀释高分辨气相色谱/高分辨质谱测定PM_2.5中的二恶英（PCDD/Fs）和多氯联苯（PCBs）,对PM_2.5的污染状况以及PM_2.5中PCDD/Fs和PCBs的污染水平及分布特征进行了研究。PM_2.5的质量浓度范围为85~168 μg/m³,PM_2.5污染较重,但与2004年同期相比明显降低。PM_2.5中PCDD/Fs的毒性当量（TEQ）为0.277~0.488 pg I-TEQ/m³,明显高于2004年同期采集样品。颗粒物中PCDD/Fs以八氯代二苯并-对-二恶英（OCDD）为主,毒性当量主要贡献者为2,3,4,7,8-五氯代二苯并呋喃（2,3,4,7,8-PeCDF）。PM_2.5中PCBs的质量浓度范围为2.9~8.1 pg/m³,二恶英类多氯联苯（DL-PCBs）的毒性当量范围为2.6~6.1 fg WHO-TEQ/m³,污染较低。PCBs在颗粒物中分布以PCB-28为主,但对毒性当量贡献最大的为PCB-126。PCDD/Fs和PCBs的气-固分配特征表现为PCDD/Fs主要分布于颗粒物中,而PCBs主要分布于气相中。     

Quantification of PCDD/Fs and dioxin-like PCBs in small amounts of human serum using the sensitive H1L7.5c1 mouse hepatoma cell line: optimization and analysis of human serum samples from adolescents of the Flemish human biomonitoring program FLEHS II

Since the CALUX (Chemically Activated LUciferase gene eXpression) bioassay is a fast and inexpensive tool for the throughput analysis of dioxin-like compounds in a large number of samples and requires only small sample volumes, the use of this technique in human biomonitoring programs provides a good alternative to GC-HRMS. In this study, a method for the separate analysis of PCDD/Fs and dioxin-like PCBs (dl-PCBs) in human serum with the new sensitive H1L7.5c1 mouse hepatoma cell line was optimized.Sample dilution factors of 5 and 2.4 were selected for routine analysis of respectively the PCDD/Fs and dl-PCBs. The validation studies showed that repeatability and within-lab reproducibility for the quality control (QC) standard were within the in-house criteria. A long-term within-lab reproducibility of 25% for the PCDD/F fraction and 41% for the dl-PCB fraction for the analysis of pooled serum samples, expressed as pg BEQ/g fat, was determined. CALUX recoveries of the spiked procedural blanks were within the acceptable in-house limits of 80-120% for both fractions and the LOQ was 30.3 pg BEQ/g fat for the PCDD/Fs and 14.5 pg BEQ/g fat for the dl-PCBs. The GC-HRMS recovery of a C13-spiked pooled serum sample was between 60 and 90% for all PCDD/F congeners and between 67 and 82% for the non-ortho PCBs. An adequate separation between both fractions was found. The CALUX/GC-HRMS ratio for a pooled serum sample was respectively 2.0 and 1.4 for the PCDD/Fs and the dl-PCBs, indicating the presence of additional AhR active compounds. As expected, a correlation was found between human serum samples analyzed with both the new H1L7.5c1 cell line and the more established H1L6.1c3 cell line. The geometric mean CALUX-BEQ values, reported for the adolescents of the second Flemish Environment and Health Study (FLEHS II) recruited in 2009-2010, were 108 (95% CI: 101-114) pg CALUX-BEQ/g fat for the PCDD/Fs and 32.1 (30.1-34.2) pg CALUX-BEQ/g fat for the dioxin-like PCBs.