环境介质与生物样品中三氯生残留检测方法研究进展

综述了环境介质与生物样品中三氯生残留的检测方法研究进展。检测方法有气相色谱-质谱法、液相色谱法、液相色谱-质谱联用以及分光光度法、酶联免疫分析方法和电化学法等。气相色谱-质谱法检测三氯生线性关系良好，检出限、定量限低，精密度、准确度较高，但样品需要衍生化前处理，操作较为复杂。液相色谱法操作相对于气相色谱-质谱法更为简便，且具有选择性强、线性范围宽、定量准确和精密度高等优点，目前高效液相色谱法是大多数实验室的首选。液相色谱-质谱法是在液相色谱的基础上，采用质谱法对样品中的三氯生残留进行定性定量，定量准确，检出限低。其他方法的使用率较低，但也可满足环境介质与生物样品中三氯生残留的检测。目前乃至未来的一段时间内，环境介质及生物样品中三氯生残留的检测方法将以色谱-质谱法为主。目前仪器检测技术条件已经相对成熟，因此应积极寻找适合不同样品的前处理方法，使检测结果更加准确和精确，实验过程更加快捷方便。     

环氧树脂相对分子质量测试方法研究进展

综述了环氧树脂相对分子质量测试方法研究进展。环氧树脂相对分子质量测试方法现有凝胶色谱法、质谱法、核磁共振波谱法、蒸汽压渗透法等,不同的方法获得不同类型的相对分子质量。凝胶色谱法适用于大部分环氧树脂样品测试,可同时获得样品的数均相对分子质量、重均相对分子质量及相对分子质量分布等多种信息;质谱法对样品要求较高,且要选择合适的基质和离子化试剂;蒸汽压渗透法可测定样品的数均相对分子质量,但影响因素较多,需根据样品及溶剂特征考察仪器参数的影响;核磁共振波谱法不需要标准样品校准,测得样品的绝对相对分子质量,但对样品纯度、结构有一定要求。在实际应用过程中,需根据样品特点及测试需求选择适用于被测样品的测定方法。随着仪器灵敏度和精密度不断提高,对环氧树脂相对分子质量测定范围将更广,精确度将更高,为环氧树脂的研制与生产提供更丰富的信息。     

国外饲料中有害物质检测的研究进展

综述了国外饲料中有害物质检测的研究进展,包括样品前处理方法、检测方法(高效液相色谱法、高效液相色谱-质谱法、紫外吸收光谱法和快速检测)、协同研究、转基因检测和二噁英分析(引用文献41篇)。     

气相色谱-离子阱二级质谱对照高分辨质谱对食品中二噁英类多氯联苯的测定

确定了气相色谱-离子阱二级质谱在分析食品中12种二噁英类多氯联苯残留的定性参数;优化了分析过程的质谱条件;研究了实际样品(河豚、鳗鱼、甜虾、鸡脂肪、奶粉、猪肠衣)离子阱串联质谱测定值与高分辨质谱值的准确度差异.样品采用加速溶剂萃取方法提取、流体控制系统净化及离子阱二级质谱和高分辨质谱测定.两种方法测定值之间的回归方程和相关系数分别为:4种非邻位取代二噁英类多氯联苯,y=0.781 5x,r=0.933 1;8种邻位取代二噁英类多氯联苯,y=0.807 3x,r=0.996;样品中12种多氯联苯总毒性当量(Total TEQ):y=0.518 1x 0.125 5,r=0.992.离子阱二级质谱和高分辨质谱的检出限分别为0.5ng/kg和0.1ng/kg,样品中同位素内标的回收率为41%～102%.     

高效液相色谱（HPLC）测定芦丁纯度和含量

研究了一种用于芦丁含量测定与纯度检验的高效液相色谱法（ＨＰＬＣ），该法具有较高精度和良好专属性，适于例行分析，分离在Ｃ８柱上进行，流动相为ＴＨＦ（四氢呋喃）－磷酸缓冲液，检测波长为２８０ｎｍ，检测限为０．５μｇ／ｍＬ，可检出０．０５％的杂质用于某些实际样品分析，结果良好。     

烟碱样品前处理及分析方法研究进展

烟碱是评价烟草及其制品的感官品质及内在质量的重要指标,同时也是监测食品、环境及人体中尼古丁暴露程度的关键因素。烟碱所在基质复杂,样品多样,针对不同检测环境及要求选择合适高效的分析方法对成功测定烟碱含量至关重要。该文介绍了测定烟草及生物样品中烟碱含量的样品前处理技术（固相/液相微萃取技术和分子印迹法）和常用的检测方法（分光光度法、液相色谱法、气相色谱法、毛细管电泳法、电化学法）,评述了每种方法的适用范围、应用实例和研究进展,并讨论了各种检测方法的灵敏度、准确性和检测效率等。     

生物样品中镇静类药物检测的研究进展

综述了近10年来生物样品中镇静类药物的检测方法(包括高效液相色谱法、气相色谱-质谱法、液相色谱-串联质谱法和液相色谱-高分辨质谱法等)和样品预处理方法(包括液液萃取法、固相萃取法、分散固相萃取法和柱切换法等)的研究进展,并对其前景作了简要展望(引用文献45篇)。     

加速溶剂萃取-流体控制系统净化-高分辨气相色谱/高分辨质谱定量测定底泥中的二噁英

采用高分辨气相色谱/高分辨质谱(HRGC/HRMS)定量测定了底泥中的17种2,3,7,8位多氯代二噁英和呋喃(PCDD/Fs) ,并测定了四至八氯取代的二噁英和呋喃总量。样品经加速溶剂萃取,然后通过流体控制系统（FMS）自动过硅胶柱、氧化 铝柱和碳柱净化,最后浓缩。以HRGC/HRMS电压选择离子检测模式对样品中的PCDD/Fs进行了定性分析,采用同位素稀释 技术定量,该方法可精确定量到pg/g水平。结果表明该方法分析的17种二噁英和呋喃异构体的检出限可达0.1 pg/g。同 位素标准的回收率为49.8%～85.3%,样品中各异构体的回收率为93.2%～115.6%。该方法不但满足国际标准的要求,还大 大提高了分析速度,使分析周期从原来的2周缩短到2 d以内。     

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。     

国内外常用降凝剂成分分析及性能表征

采用红外光谱法、凝胶色谱法、超导核磁共振波谱法、皂化滴定法以及气相色谱-质谱法等对国内外10种常用柴油降凝剂进行了成分分析,以寻找其成分对降凝剂性能的影响。结果表明:10种柴油降凝剂均属乙烯-乙酸乙烯酯聚合型降凝剂,样品聚合物部分相对分子质量较低,乙酸乙烯酯聚合物的质量分数一般在27%～37%之间,样品溶剂为重芳烃、以C₁₀为主的烷烃或者它们的混合物。其中,国外产品的相对分子质量较高（M_r>3 700）,乙酸乙烯酯聚合物质量分数大于30%,且溶剂添加了少量含氮类分散剂。     

Energy recovery

Incinerators in use, power-generating incinerators and pollution-prevention methods in energy recovery from waste incineration are briefly reviewed. Results of a recent energy recovery experiment under real operating conditions are described: The addition of waste plastic to municipal solid waste brought about more stable combustion and no increase in the concentrations of dioxins. It is remarked that energy recovery through incineration is probably the best currently available means of disposal for plastics which are too difficult to recycle.     

Mechanism of formation of polychlorinated dibenzo-p-dioxins produced on municipal incinerator flyash from reactions of chlorinated phenols

All incinerators burning municipal waste produce chlorinated dioxins. The mechanism by which these compounds are formed is unknown. Experiments were performed that show these compounds can be produced from known precursors by surface catalysed reactions on the flyash particulates present in the incineration process. A full range of the tetra- through octachlorinated dibenzo-p-dioxins were produced from 13C-labelled pentachlorophenol and two trichlorophenols on the surface of flyash from an Ontario municipal incinerator that had been previously freed from organic material. A simple flow-tube apparatus at 300 degrees C under a 10-ml/min nitrogen flow was used for the experiments. The use of 13C-labelled pentachlorophenol gave a direct measure of the extent of the catalytic reactivity of the flyash surface. Much lower amounts of chlorinated dioxins were produced in similar experiments with flyash from a modern Japanese incinerator whose effluents are normally extremely low in these compounds. Only small amounts of octachlorodioxin, the thermal condensation product expected, were formed using ground firebrick or an empty flow-tube for the reactive surface. These results indicate that the flyash surface has constituents and properties that promote the production of chlorinated dioxins from chlorinated phenols and support the catalyzed surface reaction mechanism previously proposed.     

Analysis of polychlorodibenzo‐p‐dioxins and polychlorodibenzofurans in stationary source emissions in GC–MS/MS using hydrogen as the carrier gas

The European and American methods for the determination of polychlorodibenzo‐p‐dioxins and polychlorodibenzofurans in stationary source emissions require a high‐resolution mass spectrometer detector. At the same time, all of the 17 toxic 2,3,7,8‐chlorine‐substituted isomers have to be separated by an appropriate chromatographic method. The resulting analysis has long runtimes and sometimes a double‐column run is needed, which results in a huge waste of time, money and manual labor. To obtain a fast and cost‐effective but still reliable analytical system, a single‐column gas chromatography with hydrogen as carrier gas and tandem mass spectrometry detection is proposed. The use of hydrogen as the carrier gas is a good choice to shorten runtimes and improve the chromatographic resolution, while tandem mass spectrometry is a well‐known alternative for this analysis. All the chromatographic and mass spectrometric parameters fill the requirements of the reference methods with a 35% reduction of runtimes. The accuracy is tested with three fly ash samples of a proficiency interlaboratory test. A good correlation between the results is obtained (R ² = 0.992, slope = 0.9675), and no coelutions are noted. The system robustness is tested during 5 years of constant use and the maximal relative standard deviation of the relative response factor is 18.8%.     

Dioxin analysis in feed: cell-based assay versus mass spectrometry method

In the determination of contaminants (dioxins, polychlorinated biphenyls, polyaromatic hydrocarbons), cell-based assays are useful methods for screening purposes: they are mainly characterized by high sample throughput and lower costs than the Mass Spectrometry (MS)-based methods. Although cell-based assays can be sensitive enough for the determination of dioxins and related substances in agreement with the presently tolerable limits in food and feed (Regulation No. 2375/2001/EC and Directive 2003/57/EC respectively), their lack of specificity make their use rather questionable in control laboratories. In this paper, we present and compare results obtained from the analysis of a limited number of feed samples by both gas chromatography-high resolution mass spectrometry (GC-HRMS) and cell-based assay (DR-CALUX: dioxin responsive-chemically activated luciferase gene expression) methods. The DR-CALUX screening led to less than 10% false non-compliant and no false compliant results. In addition, there is a good correlation between GC-HRMS and DR-CALUX data. However, these preliminary results have to be confirmed on a larger number of samples to demonstrate that total toxic equivalent (TEQ), including dioxins, furans and dioxin-like polychlorobiphenyls (PCBs) can be monitored in feed and food with a cell-based assay. Presented at AOAC Europe/Eurachem Symposium March 2005, Brussels, Belgium     

Partitionings and kinetic behaviors of major-to-ultratrace elements between industrial waste incineration fly and bottom ashes as studied by ICP-AES and ICP-MS.

The partitionings of major-to-ultratrace elements between industrial waste incineration fly ash (IWIFA) and industrial waste incineration bottom ash (IWIBA) in industrial waste incinerators were investigated by measuring their concentration distributions, where the incineration ash samples were collected from three different types of industrial waste incinerators. The concentrations of the elements in the incineration ash samples were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). As a result, ca. 40 elements in the concentration range from mg g(-1) to sub-microg g(-1) could be determined in both IWIFA and IWIBA samples. The concentration ratios of CF/CB (CF, concentration in fly ash; CB, concentration in bottom ash) for analyte elements were used to evaluate the partitionings of the elements between fly and bottom ashes. Then, the correlations between the CF/CB values of the elements and the dissociation energies of their monoxides were examined to evaluate the kinetic behaviors of the elements during the incineration processes. It was found that lithophile and siderophile elements, which have a large affinity with oxygen, were almost equally distributed between fly and bottom ashes, regardless of the dissociation energies of their monoxides. On the other hand, chalcophile elements with rather large volatility provided different behaviors; the elements with the smaller dissociation energies of monoxides were more partitioned in fly ashes than those with the larger ones.     

Use of Carbon-13 Labelled Dioxins Mixture for Analysis of Polychlorinated Dibenzo-p-Dioxins in Environmental Samples by GC-MS

Abstract

Positive identification and quantitation of polychlorinated dibenzo-p-dioxins (PCDD) in complicated environmental samples is described using a C-13 labelled dioxin mixture as an internal reference standard. Environmental samples are spiked with the C-13 labelled dioxin mixture and monitored for labelled and unlabelled dioxins using GC-MS in the electron impact selected ion monitoring (EISIM) mode. The C-13 labelled dioxin mixture and a municipal solid waste (MSW) incinerator fly ash extract show the same number of isomers in each tetra to octa-chlorodioxin congener groups. Quantitation of the C-13 labelled dioxin mixture was carried out using a reference standard mixture of unlabelled dioxins consisting of at least one isomer for each congener group. The C-13 labelled dioxin standard is highly useful for the determination of retention windows for tetra- to octa-chlorodioxins, identification of dioxins in each congener group, and calculation of the recovery of dioxins in samples that require extensive sample clean-up prior to GC-MS analysis. Its application for retention time window determination and as an internal reference standard for quantitation of dioxins in MSW incinerator fly ash extract and identification of dioxins in a complex sample from a PCB fire is demonstrated.     

Approaches to dioxin analysis by HRGC-HRMS and hybrid HRGC-MS-MS

A hybrid mass spectrometer with an EBQQ configuration was used to investigate two approaches to trace dioxin analysis: high resolution gas chromatography – high resolution mass spectrometry (HRGC-HRMS) and high resolution gas chromatography – mass spectrometry – mass spectrometry (HRGC-MS-MS). It is shown that selected ion monitoring (SIM) HRGC-HRMS exhibits better selectivity for dioxins separated on a cyanopropyl column than is otherwise obtained under medium resolution mass spectrometry (3,000 resolution), while optimization of conditions for HRGC-MS-MS allowed the observation of 350 femtograms of the highly toxic 2,3,7,8-TCDF at a S/N ratio of 5:1. Both methods were applied to environmental samples with good results.     

HRGC-LRMS测定垃圾焚烧炉布袋飞灰中的二噁英类物质

利用高分辨气相色谱-低分辨质谱(HRGC-LRMS)测定了某垃圾焚烧厂布袋飞灰中的二(口恶)英类物质,结果表明对于测定二(口恶)英类浓度相对较高的垃圾飞灰而言,采用HRGC-LRMS是一种可行的方法,回收率在74％～114％之间。该飞灰样品中以二(口恶)英为主,呋喃的含量相对较低,二(口恶)英／呋喃值为4.6,二(口恶)英类物质总量为211.7ng／g,折算到毒性当量为0.69ngI-TEQ／g。     

Analytical pyrolysis of re-circulated leachates: Towards an improved municipal waste treatment

The harmless removal of municipal solid waste (MSW) requires the biodegradation of organic matter to decrease the risk of gaseous emissions and leaching of contaminants. We studied the re-circulation of leachates from an aerobic treated MSW in a lysimeter and compared these results with a similar laboratory study using small-scale reactors. The reduction of total organic C and biological and chemical oxygen demands provided clear evidence for the biodegradation of organic matter in MSW after 12 months of leachate re-circulation. Curie-point pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and pyrolysis-field ionization mass spectrometry (Py-FIMS) revealed that the biodegradation was more efficient in the large-scale lysimeter than in the laboratory reactors. Different from the laboratory experiments, carbohydrates and N-containing compounds were decomposed almost completely after 2 months. Furthermore, temperature-resolved Py-FIMS showed that leachate re-circulation led to a higher thermal stability of the residual, non-decomposed organic matter. In summary, the two analytical pyrolysis methods proved that the re-circulation of leachates through MSW promoted organic matter biodegradation and offers an improved aerobic waste treatment technology.     

城市生活垃圾焚烧体系化学热力学平衡分析

采用化学热力学平衡分析方法，分析城市生活垃圾焚烧体系污染物的排放特性。主要计算了聚氯乙烯（PVC）及典型城市垃圾焚烧过程氯元素的化学平衡组成及其浓度，同时研究了脱氯剂对PVC及垃圾中氯转化的影响。计算结果表明，PVC热态反应的主要产物是HCl气体，在加入脱氯剂后温度低于600℃时，脱氯剂对HCl的脱除作用很明显；城市生活垃圾热解和燃烧过程中在温度超过600 ℃，垃圾中的有机氯和无机氯都将转化为HCl气体，而此时脱氯剂失去效果。由计算结果得到控制HCl生成，消除二口恶英污染物的生成反应工艺条件。