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1.
Analyses of dioxins in food have become increasingly important since the European Commission has enforced maximal toxic equivalent concentration (TEQ) levels in various food and feed products. Screening methodologies are usually used to exempt those samples that are below the maximum permitted limit and that can, therefore, be released to the market. In addition, one needs to select those samples that require confirmation of their dioxin TEQ level. When bioassays are used as screening tools, the interpretation of the obtained results should consider the higher variability and uncertainty associated with them. This paper explores the use of CALUX data as quantitative screening results. The validation of the method for the polychlorinated dibenzo-p-dioxins (PCDD)/F TEQ determination in milk samples is described with emphasis on the decision limit (CC) and the precision of the method. The decision limit amounts to 4.53 pg TEQ/g fat. Repeatability and within-lab reproducibility coefficients of variation are below 30%. The newly introduced parameter CC* of 1.47 pg TEQ/g fat delimits with CC a range of suspicious results. These data are not significantly different from the maximum limit of 3 pg TEQ/g fat and should be confirmed by a confirmatory analytical method such as HRGC–HRMS.  相似文献   

2.
Maternal body burden of organochlorine pesticides and dioxins.   总被引:1,自引:0,他引:1  
To investigate the body burden of organochlorine pesticides and dioxins in Japanese women, 125 milk samples were collected from 41 mothers in 1994, 42 in 1995, and 42 in 1996. Of the 125 samples, 82 were from primipara mothers (first delivery) and 43 were from multipara mothers (second or later delivery). By using capillary gas chromatography with electron capture detection, beta-HCH and p,p'-DDE were detected as the major chlorine pesticides in human milk. Average levels of beta-HCH and p,p'-DDE were 475 and 368 ng/g lipid, respectively, in primipara breast milk, 314 and 259 ng/g lipid in multipara breast milk, and 420 and 330 ng/g lipid in total breast milk. Dieldrin, heptachor epoxide, oxychlordane, trans-chlordane, and cis-chlordane were detected at lower average levels of 3, 4, 34, 41, and 5 ng/g lipid, respectively. By using high-resolution gas chromatography with mass spectrometric detection, dioxins were detected in all samples. Average levels of total polychlorinated dibenzo-p-dioxin (PCDD), total polychlorinated dibenzofuran (PCDF), total PCDD + PCDF, total coplanar polychlorinatedbiphenyl (CoPCB), and total dioxin were 10.0, 7.8, 17.7, 9.9, and 27.5 TEQ (toxic equivalent) pg/g lipid, respectively, in primipara breast milk; 7.0, 5.8, 12.8, 7.3, and 20.1 TEQ pg/g lipid in multipara breast milk; and 8.9, 7.1, 16.1, 8.9, and 25.0 TEQ pg/g lipid in total breast milk. In primipara breast milk, significant correlations were found among levels of beta-HCH, p,p'-DDE, total PCDD-TEQ, total PCDF-TEQ, total CoPCB-TEQ, and total TEQ except for less correlation between p,p'-DDE and total PCDF-TEQ. Levels of these analytes also significantly increased depending on mother's age, except for total Co-PCB-TEQ. For the correlation with food habit, the only positive correlation was between total PCDF-TEQs and fish intake.  相似文献   

3.
A method to analyze polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/DFs, dioxins) and coplanar polychlorinated biphenyls in environmental samples is developed and used to determine the levels of PCDD/DFs in 13 soil and 4 fish samples collected around a waste pentachlorophenol manufacturing plant. The 2,3,7,8-tetrachlorodioxin toxic equivalents (TEQ) values range from 0.239 ng-TEQ/g to 1357 ng-TEQ/g in soil samples and 0.041 ng-TEQ/g to 0.247 ng-TEQ/g in fish samples. A broader survey of PCDD/DF contamination in the vicinity around the manufacturing plant is strongly recommended.  相似文献   

4.
McAlister DR  Fern MJ  Allen RL 《Talanta》2008,74(4):992-997
A method for the estimation of polychlorinated dibenzo-p-dioxin and furan (PCCD/F) toxicity equivalent quotient (TEQ) of soil and sediment matrices is described. The method includes extraction, isolation of the PCDD/Fs from interfering compounds, such as polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs), and measurement of PCDD/F using the PROCEPT aryl hydrocarbon (AhR) receptor based polymerase chain reaction (PCR) assay. The values obtained using the PROCEPT assay correlate well with reference TEQ values generated from gas chromatography-high resolution mass spectrometry (GC-HRMS), with a linearity coefficient (R(2)) of 0.94. Applied in a screening mode at 50pg/g PCDD/F TEQ, the PROCEPT assay yielded five false positive results (2.6%) and no false negative results for 196 analyses of spiked soils and environmental samples obtained from US EPA Superfund sites.  相似文献   

5.
2,3,7,8-Substituted polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/Fs) and non-ortho-substituted polychlorinated biphenyls (PCBs) account for almost all of the total toxic equivalents (TEQ) in environmental samples. Activated carbon columns are used to fractionate the samples for GC-MS analysis or bioassay. Micropore-free surface-activated carbon is highly selective for PCDD/Fs and non-ortho-PCBs and can improve the conventional activated carbon column clean-up. Along with sulfuric acid-coated diatomaceous earth columns, micropore-free surface-activated carbon provides a rapid, robust, and high-throughput sample preparation method for PCDD/Fs and non-ortho-PCBs analysis.  相似文献   

6.
Summary Six laboratories in four European countries (GER, GB, S, NL) have conducted an interlaboratory comparison study on the analysis of dioxins in cow's milk. The study comprised a cross comparison of standards and the analysis of the 2,3,7,8-substituted congeners of PCDD/Fs in three different milk pools (no spiking). Participants used their own procedures and methods for the determination of the fat content and PCDD/F levels in biological samples, all using non-polar gas chromatography and medium to high resolution mass spectrometry (RP=3.000–10.000). Quantification was performed by the use of a common quantification standard mixture of the native PCDD/Fs (4 labs) or the own quantification standards (2 labs). Within-laboratory reproducibilities for the determination of the major toxic congeners and the total TCDD toxicity equivalence (TE) level were between 2 and 16% (RSD) with a mean variation of 6% on TE basis. The interlaboratory comparison for TE values agreed within 10–17% (RSD) for TE values between 10.4 and 2.8 pg TE/g milk fat. Reliabilities of both participants and the common standards were difficult to assess and probably less good than expected. Differences in these standards were typically within 25% of expected concentrations up to 50% for some congeners by some laboratories.  相似文献   

7.
European legislation laid down maximum tolerable levels of dioxin in feed and food as well as analytical method requirements. In order to face with large monitoring programs, it was foreseen in the EU strategy to integrate screening methods, using either a qualitative (screening) approach, or a quantitative approach. In this study, dioxin results obtained using the Dioxin Responsive Chemical-Activated LUciferase gene eXpression (DR-CALUX®) cell-based assay (quantitative approach), were compared with gas chromatography–high resolution mass spectrometry (GC–HRMS) analyses data. Instead of using World Health Organization–toxic equivalent factor (WHO–TEF), the comparison was based on the assessment of relative effective potencies (REPs) for each congener of the 17 toxic 2,3,7,8-polychlorodibenzo-p-dioxins/furans (PCDD/Fs) and 12 dioxin-like polychlorobiphenyls (DL-PCBs). According to published data, DR-CALUX®-REP evaluated here appear similar to WHO–TEF for PCDD/Fs while lower values were observed for DL-PCBs.

We analyzed two “home made” contaminated fat samples, displaying both the same WHO–toxic equivalent quantities (WHO–TEQ) concentration (12 pg WHO–TEQ g−1). They were spiked with either a low or a high amount of DL-PCBs. In both cases, the DR-CALUX® measured concentration (picogram 2,3,7,8 tetrachlorodibenzo-p-dioxin (TCDD) eq. g−1) corresponded to the PCDD/Fs WHO–TEQ concentration only. A good agreement was nevertheless found between the DR-CALUX® measurements and the recalculated DR-CALUX®-TEQ contents (using DR-CALUX®-REP instead of WHO–TEF), demonstrating that the observed response was due, in both cases, to the addition of the responses of the standards added to the fat. By contrast, in real contaminated samples (feed or cod liver samples), DR-CALUX® measured concentrations were similar to WHO–TEQ GC–HRMS measured concentrations. But, depending on the PCDD/Fs and DL-PCBs congener content, the DR-CALUX® measured concentrations were either lower or higher than calculated DR-CALUX®-TEQ contents, demonstrating that possible co-extracted contaminants contributed to the CALUX response.

Owing to these divergences, the quantitative determination of dioxin-like content in food and feed using CALUX as screening method is questionable, except for samples displaying constant congener patterns, in which cases, correction factors could be applied.  相似文献   


8.
2014年1月在杭州市选择5个点位采集大气颗粒物PM2.5样品,采用同位素稀释高分辨气相色谱/高分辨质谱测定PM2.5中的二恶英(PCDD/Fs)和多氯联苯(PCBs),对PM2.5的污染状况以及PM2.5中PCDD/Fs和PCBs的污染水平及分布特征进行了研究。PM2.5的质量浓度范围为85~168 μg/m3,PM2.5污染较重,但与2004年同期相比明显降低。PM2.5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)。PM2.5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。  相似文献   

9.
Summary The results obtained by applying a modular stopped-flow system for the determination of creatinine by the alkaline picrate method are reported. The stopped-flow technique allows the simple and rapid determination of creatinine in human serum and food samples. The calibration graph is linear in the range 1–100 g ml–1 of creatinine and the precision is close to 3%. The method features acceptable selectivity. The initial rate is measured in only 5 s, which allows the easy application of the method to routine analyses. No pretreatment of the serum samples is required. For food samples, total creatine and creatinine have been determined in dehydrated soup and meat extract samples.
Stopped-flow-Bestimmung von Creatinin in Humanserum und Nahrungsmitteln
  相似文献   

10.
A sensitive procedure was developed for determination of bismuth (Bi) in milk samples by hydride generation atomic fluorescence spectrometry (HG-AFS) after microwave-assisted sample digestion with HNO3 and H2O2. The method provides a sensitivity of 1832 fluorescence units (ng/mL) with a detection limit of 0.01 ng/mL, which corresponds to 20 pg absolute limit of detection, equivalent to 0.50 ng/g in the original sample. Application of the methodology to cow milk samples from the Spanish market showed the presence of Bi at a concentration of 11.8-28.8 ng/g, which compared well with data obtained after dry ashing of samples and with data obtained by inductively coupled plasma-mass spectrometry after microwave-assisted digestion.  相似文献   

11.
An investigation is conducted on the status of trace and minor elements in some foodstuffs (cereals, vegetables, milk, egg and fish), commonly consumed in Bangladesh, using proton induced X-ray emission (PIXE) and radioisotope-induced X-ray fluorescence (XRF) techniques. In PIXE measurements, the samples were irradiated in air with 2.0 MeV (energy on the target) protons having the beam intensity of 30 nA for characteristic X-ray excitation, while in XRF analysis, the samples were excited for 5000 seconds with a 10 mCi Cd-109 annular X-ray source. The elemental concentration of K, Ca, Mn, Fe, Ni, Cu, Zn, Se, As, Br, Rb, Sr, Mo, and Pb were determined in the samples by comparison with X-ray yield curves constructed from IAEA and NBS standard reference materials. The validity of the analytical procedures (PIXE and XRF) followed in this study has been confirmed by comparative measurements of Cu, Zn and Mn in some varieties of rice with atomic absorption spectrophotometry. The results indicate that none of the food regimes investigated here is burdened with heavy metals beyond permissible limits except five species of vegetables with chromium having the range of 0.99–3.59 mg/kg compared to the literature value of 0.0–0.36 mg/kg (dry weight basis). An average value of 0.2 mg/kg of arsenic was observed both in IRRI (n=16) and local Aman (n=12) varieties of rice and only one hen egg contained 1.7 mg/kg of lead in yolk. The zinc content in some marine fish from Bay of Bengal was reported to be 5.4–19.5 mg/kg, whereas in the present study of sweet-water fish, the level is found to be 15.2–62.1 mg/kg (fresh weight basis) for five species. In human milk, both Cu (0.12–0.25 mg/l, n=8) and Zn (0.28–1.80 mg/l, n=8) levels appear to be almost half the literature values (n=25). On the other hand formula milk has higher values of Cu (0.32–1.63 mg/kg, n=16) and Zn (5.16–19.8 mg/kg, n=16).  相似文献   

12.
Gas chromatography coupled to ion trap tandem mass spectrometry (CG-MS-MS) has been evaluated for the analysis of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in vegetable oil samples containing different concentration levels (0.2-6 pg WHO-TEQ g(-1) for both PCDD/Fs and dl-PCBs) of the 29 toxic congeners of PCDD/F and dioxin-like PCBs. The effect of potential interfering compounds such as polychlorinated naphthalenes (PCNs), polychlorinated biphenyls (PCBs) and polychlorinated diphenylethers (PCDEs) on the quantification of mono-ortho PCBs has been investigated. In addition, the influence of the clean-up procedure on the final determination by CG-MS-MS was studied, showing that the quality of the results depends to a great extent on this analytical step. Quality parameters have been established and good precisions (CV: 3-19%) and low limits of detection for PCDD/Fs (0.04-0.20 pg g(-1) oil) and dl-PCBs (0.08-0.64 pg g(-1) oil) were obtained. The method was validated by a comparison of the CG-MS-MS results with those obtained by GC-HRMS.  相似文献   

13.
张庆华  吴文忠  占伟  徐盈 《色谱》2000,18(1):21-24
 采用浓硫酸对5种不同来源的四氯苯醌和“永固紫”染料样品进行溶解分散,用甲苯提取和 多层色谱柱纯化,利用同位素稀释法及高分辨气相色谱/质谱 (HRGC/HRMS)联用技术,测定 了其中的多氯代二苯并二/呋喃(PCDD/F)的质量比。结果表明“永固紫”染料及其原料中P CDD/F的质量比异常高,八氯代二苯并二/呋喃(OCDD/F)已达到μg/g级甚至100 μg/g级,七氯代二苯并二/呋喃(HpCDD/F)和六氯代二苯并二/呋喃(HxCDD/F)质量比也达到 ng/g级。所有样 品的毒性当量浓度(TEQ)均已超过10 pg/g的危险水平,是纺织品中PCDD/F的一类重要污染源 。并进一步探讨了PCDD/F的来源。  相似文献   

14.
Analytical procedures for the determination of polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF) and non-ortho polychlorinated biphenyls (PCB) require a fractionation step to separate PCDD/F from planar PCB and the bulk of PCB. An HPLC method which achieves the separation of the bulk of PCB (0–6 mL of hexane), mono-ortho PCB (6–8 mL of hexane), non-ortho PCB (8–15 mL of hexane) and PCDD/F (15–50 mL of toluene) on a PYE column (2-(1-pyrenyl) ethyldimethylsilylated silica gel) in a single step without the use of backflush as other authors proposed was developed. The method shows a good accuracy and precision and it is linear in the range studied, e.g from 5.8 to 2420 pg injected in HPLC for TCDD/F, from 28.8 to 12100 pg for PeCDD/F, HxCDD/F, HpCDD/F and from 57.6 to 24200 pg for OCDD/F. It has been successfully applied to the analysis of technical mixtures of PCB (Aroclors), a pine wood sample and several water samples of different origins. Received: 29 November 1998 / Revised: 25 February 1999 / Accepted: 3 March 1999  相似文献   

15.
Analytical procedures for the determination of polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF) and non-ortho polychlorinated biphenyls (PCB) require a fractionation step to separate PCDD/F from planar PCB and the bulk of PCB. An HPLC method which achieves the separation of the bulk of PCB (0–6 mL of hexane), mono-ortho PCB (6–8 mL of hexane), non-ortho PCB (8–15 mL of hexane) and PCDD/F (15–50 mL of toluene) on a PYE column (2-(1-pyrenyl) ethyldimethylsilylated silica gel) in a single step without the use of backflush as other authors proposed was developed. The method shows a good accuracy and precision and it is linear in the range studied, e.g from 5.8 to 2420 pg injected in HPLC for TCDD/F, from 28.8 to 12100 pg for PeCDD/F, HxCDD/F, HpCDD/F and from 57.6 to 24200 pg for OCDD/F. It has been successfully applied to the analysis of technical mixtures of PCB (Aroclors), a pine wood sample and several water samples of different origins. Received: 29 November 1998 / Revised: 25 February 1999 / Accepted: 3 March 1999  相似文献   

16.
The chemical-activated luciferase expression (CALUX) assay is a reporter gene assay that detects dioxin-like compounds based on their ability to activate the aryl hydrocarbon receptor (AhR) and thus expression of the reporter gene. In this paper, the CALUX assay was examined for its application in the screening of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) in retail fish. The sample extracts were cleaned up on a sulfuric acid-silica gel column followed by an activated carbon column, and the AhR activity of the separated PCDD/F and dioxin-like PCB fractions was determined using the assay. The quantitative limit for 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) was 0.98 pg ml(-1) (0.19 pg assay(-1) in the standard curve, corresponding to 0.16 pg g(-1) of CALUX-based toxic equivalency (2,3,7,8-TCDD equivalents) in the tested sample. Recovery tests in which dioxins were added to fish samples resulted in acceptable recoveries (77-117%). The CALUX assay performed well in the analysis of dioxins in fish samples and a comparative study revealed a strong correlation between the CALUX assay and high-resolution gas chromatography-high-resolution mass spectrometry analysis for the determination of PCDD/Fs (r = 0.89) and dioxin-like PCBs (r = 0.91) in retail fish (n = 22). These data revealed that the CALUX assay would be a useful screening method for PCDD/Fs and dioxin-like PCBs in retail fish.  相似文献   

17.
Summary Differential pulse anodic stripping voltammetry (DPASV) and isotope dilution mass spectrometry (IDMS) were used to analyse heavy metals in Antarctic snow samples. It was possible to determine Pb and Cd with DPASV at the German Antarctic station Georg-von-Neumayer whereas the analyses of Pb, Cd, Tl, Cr, Ni, Cu, Zn, and Fe with IDMS were carried out at the University of Regensburg. 80% of the elemental concentrations in surface snow samples analysed with IDMS lay in the following ranges: Pb=3–40 pg/g, Cd<0.2–3 pg/g, Tl<0.2 pg/g, Cr<0.8–15 pg/g, Ni<4.8–40 pg/g, Cu<11–30 pg/g, Zn=30–500 pg/g, and Fe=(0.5–1.5)×103 pg/g. In most cases an acceptable agreement between the DPASV and IDMS results was obtained for Pb and Cd. More than 50% of all Pb analyses agreed within a deviation of 0–10 pg/g. The Cd results between both methods usually deviated by less than 1 pg/g. Slightly higher Pb concentrations were analysed in the average with IDMS compared with DPASV. This effect was not observed for the Cd data. A possible explanation for this fact are non-ionic Pb species in the melted snow samples, which cannot be analysed by DPASV. One particular investigation of Pb concentrations showed that the analysed data with DPASV decreased with the increasing length of sun-shine after a snowfall when samples of the same origin were determined. Blank control is the major requirement for accurate analysis results of heavy metals in this low concentration range. On the other hand, accuracy must always be tested by independent analytical methods. In this work it is shown that Pb and Cd can be analysed directly in the Antarctica with DPASV and that the result of this method is in acceptable agreement with the definitive method IDMS.
Bestimmung von Schwermetallen im pg/g Bereich in antarktischen Schneeproben durch differentielle Pulsinversvoltammetrie und massenspektrometrische Isotopenverdünnungsanalyse
  相似文献   

18.
We report on the content of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in 15 breast milk samples of nursing women living in the city of Taranto (Southern, Italy) or nearby. Breast milk samples were collected over the 2008–2009 period and analyzed by gas chromatography coupled with high-resolution mass spectrometry (GC-HRMS) upon accelerated solvent extraction (ASE) using acetone/n-hexane mixture 1:1 (v/v). The method was validated demonstrating good performing features. Profiles of PCDD/PCDF congeners in breast milk samples exhibited a prevalence of PCDFs compared to PCDDs. Toxic equivalents (TEQs in picogram per gram fat) of four breast milk were far above the legal limit for human consumption of 3.0 pg/g; their estimated daily and weekly dietary intake were almost 5–20 and 10–40 times higher, respectively, than the tolerable intake values established by the World Health Organization.
Figure
Occurrence of the toxic micropollutants in breast milk samples of mothers living in or nearby Taranto  相似文献   

19.
A novel method for the determination of trace elements in microliter samples using the tantalum filament electrothermal vaporization/low-pressure inductively coupled plasma (ETV/LP-ICP) atomic emission spectrometry has been developed. An improved tantalum filament ETV was directly coupled with LP-ICP system for efficient vaporization of microliter samples and further quantitative analysis. The experimental parameters including ETV current, rf power and mass flow rate of argon carrier gas were optimized using the copper emission signal produced by 5 μl of standard solution (5 μg/ml). Under the optimized condition, the analytical performances including linearity, precision and detection limit for the developed system were investigated. Absolute detection limits in the range of 22–391 pg for selected eight elements (Fe, Cu, Cr, Mn, Pb, K, Zn and Mg) were obtained with satisfactory precision (<8.9% RSD). The feasibility of the developed system has been demonstrated by analyzing wheat gluten NIST standard sample.  相似文献   

20.
随机选择空白的和经过印刷的新闻纸和复印纸,粉碎后用溶剂提取并经多步色谱柱纯化,采用同位素稀释、高分辨气相色谱/高分辨质谱(HRGC/HRMS)联用技术分析了其中的二含量。结果表明:新闻纸中二的总量高于复印纸,但是毒性当量却低于复印纸;经过印刷的新闻纸和复印纸中二的含量均高于空白的新闻纸和复印纸;新闻纸和复印纸中相同二异构体的含量 是不同的。空白的和经过印刷的新闻纸中二毒性当量分别为0.48 ng/kg和0.61 ng/kg,而空白的和经过印刷的复印纸中二恶英毒性当量分别为0.74 ng/kg和0.79  相似文献   

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