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1.
Chlorobiphenyl congeners (CBs) are used as indicator compounds in analysis performed to determine whether or not PCB concentrations in food products, waste mineral oil, and environmental samples comply with the maximum levels permitted by legislation. Seven of these compounds have been checked for coelution with other CB congeners by means of a multidimensional gas chromatographic method utilizing a combination of two narrow bore columns, one coated with a conventional non-polar stationary phase and the other with a liquid crystalline (smectic) stationary phase. Peaks of the relevant CBs have been transferred, by heart cutting, from the non-polar column to the liquid crystal column, on which unambiguous separation from possible coeluting CB congeners was obtained. It has been shown that if the seven congeners are analyzed solely on a single, non-polar capillary column the results obtained for two of them may be affected by coelution of other compounds.  相似文献   

2.
A total of 196 out of 209 polychlorobiphenyl (PCB) congeners were resolved using GC×GC-TOFMS with a non-polar/ionic liquid column series consisting of poly(50%-n-octyl-50%-methyl)siloxane and (1,12-di(tripropylphosphonium)dodecane bis(trifluoromethansulfonyl)amide) in the first and second dimension, respectively. It has been found that 13 PCB congeners overlap in five doublets (CB12+CB13, CB62+CB75, CB70+CB76, CB97+CB125 and CB153+CB168) and one triplet (CB90+CB101+CB113). All toxic, "dioxin like" congeners were separated with no interferences from any PCB congener. The 109 PCBs present in Aroclor 1242 and the 82 PCBs present in Aroclor 1260 were resolved GC×GC-TOFMS analysis on this column set.  相似文献   

3.
PCB patterns in a new pigment brand are characterized using GC-MS in the single ion monitoring (SIM) mode. Specific PCBs are then used as external standards for GC-ECD quantification. The following PCB isomers or groups of isomers have to be determined (CB = chlorobiphenyl): total diCBs, 3,3′ diCB, 2,4,5-triCB, 2,2′,4,4′-tetraCB, 2,2′,5,5′-tetraCB, total pentaCB, total hexaCB. Capillary gas chromatography is performed on preseparated solutions (LC) of pigment. An electron caputure detector (ECD) is used for PCB detection and quantification. Calibration is based on the peak areas of external standards and the PCB isomers in the samples, all normalized for internal standard peak areas. Total concentrations of diCB, hexaCB, or pentaCB in a sample are calculated by summing the individual PCB isomer concentrations within the correcsponding elution ranges. Determination limits lie in the range of 1 mg/PCB-isomer/kg pigment.  相似文献   

4.
13C-labeled compounds are often employed as surrogate or internal standards to monitor the performance of extraction and instrumental analysis procedures for their unlabeled counterparts. However, labeled and unlabeled counterparts most often coelute chromatographically with overlapping mass ion fragments, posing a challenge to the accurate quantification of these compounds. In the present study, an analytical scheme, using coeluting unlabeled and 13C-labeled polychlorinated biphenyl (PCB) congeners as the model compounds, was developed with a low-resolution tandem mass spectrometer (MS/MS) to determine the appropriate ranges of PCB congener concentrations that satisfy the no-interference condition. Interferences from unlabeled PCBs to quantitation of labeled counterparts could be minimized when 13C-labeled PCB congeners were quantified in the MS/MS mode within a certain concentration range. In addition, good agreements between the measured and theoretically predicted quantitation errors were observed for all labeled PCB congeners except PCB 180. The exception with labeled PCB 180 was mainly attributed to the occurrence of instrumental analytical uncertainty, as analytical error was also observed with absence of unlabeled PCB 180. These results indicate that MS/MS techniques can serve as a useful tool to minimize interferences with quantitation of isotopically labeled compounds from their unlabeled counterparts, which possess partially overlapping ion fragment profiles.  相似文献   

5.
Polychlorinated naphthalenes (PCNs) are candidates for inclusion in the Stockholm Convention on persistent organic pollutants. PCNs are structurally and toxicologically similar to 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) and its analogues. Intake in food is considered to be an important human exposure pathway for PCNs. In this preliminary study, cheese and butter samples were analysed for PCNs, polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) using an isotope dilution gas chromatography high-resolution mass spectrometry method. The aim of this study was to evaluate the PCN concentrations in the cheese and butter samples and to compare them with the PCDD, PCDF and PCB concentrations. The PCN concentrations were 5.6–103 pg g?1 of wet weight in the seven cheese samples tested and 5.0–199 pg g?1 of wet weight in the seven butter samples tested. The mass concentrations of lower chlorinated congeners were greater than those of the higher chlorinated congeners. Congeners of CN45/36, CN27/30 and CN33/34/37 were much more abundant than other congeners found in tetrachlorinated PCNs. Congeners of CN51, CN66/67 and CN73 were determined to be the predominant congeners in penta-, hexa- and heptachlorinated homologs, respectively. The PCNs contributed around 5% of the total PCN, PCDD, PCDF and PCB toxic equivalence (TEQ) values. CN73 was found to be the dominant PCN congener and contributed more than 40% to the PCN TEQ value. Congeners CN66/67, CN69 and CN63 were also found at relatively high levels. The PCB congener CB118 was the predominant congener (by mass-based concentration) of the 12 dioxin-like PCBs (dl-PCBs). The PCBs contributed 53.8% of the total TEQ, and congener CB126 contributed more than any other compound that was analysed to the total TEQ. The PCDDs and PCDFs contributed 11.6% and 29.7% of the total TEQ values, respectively.  相似文献   

6.
Multidimensional chromatography was used to resolve the specific chlorobiphenyl (CB) congeners 28, 52, 101, 118, 138, 153, and 180 in technical aroclor standards. Single column analysis of polychlorinated biphenyls (PCBs) results in co-elution of key congeners with other components in the mixture; therefore using two columns of different selectivity was necessary to enhance the resolution achievable on just one column. The HT8 column (8% phenylpolycarborane-siloxane phase) has been reported to have specific selectivity characteristics for improved PCB separation. When coupled with a BPX5 column (5% phenylpolysiloxane-silphenylene phase), it has been shown here to provide unambiguous identification of 7 marker compounds which are used to monitor PCB occurrence and distribution. All seven marker CBs are present in aroclor 1254, and by adjusting the size of the heartcut window, it was possible to obtain resolution of the marker congeners from other congeners. Single column analysis is unable to achieve this result. This offers an alternative to GC-MS analysis.  相似文献   

7.
The concentrations of a wide range of polychlorinated biphenyl congeners (PCBs) and chlorinated pesticides in a fish tissue Standard Reference Material (SRM) have been determined using multiple methods of analysis. This material, SRM 1946, Lake Superior Fish Tissue, was recently issued by the National Institute of Standards and Technology (NIST) and complements a suite of marine environmental natural-matrix SRMs that are currently available from NIST for the determination of organic contaminants such as aliphatic hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), PCBs, and chlorinated pesticides. SRM 1946 is a fresh tissue homogenate (frozen) prepared from filleted adult lake trout (Salvelinus namaycush namaycush) collected from the Apostle Islands region of Lake Superior. SRM 1946 has certified and reference concentrations for PCB congeners, including the three non- ortho PCB congeners, and chlorinated pesticides. Certified concentrations are available for 30 PCB congeners and 15 chlorinated pesticides. Reference concentrations are available for 12 PCB congeners and 2 chlorinated pesticides. In addition, SRM 1946 is characterized for additional chemical constituents and properties: fatty acids, extractable fat, methylmercury, total mercury, selected trace elements, proximates, and caloric content. The characterization of chlorinated compounds is described in this paper with an emphasis on the approach used for the certification of the concentrations of PCB congeners and chlorinated pesticides. The PCB congener and chlorinated pesticide data are also compared to concentrations in other marine natural-matrix reference materials available from NIST (fish oil, mussel tissue, whale blubber, and a second fresh frozen fish tissue homogenate prepared from filleted adult lake trout collected from Lake Michigan) and from other organizations such as the National Research Council Canada (ground whole carp), the International Atomic Energy Agency (fish homogenate), and the European Commission Joint Research Centre [fish oils (cod and mackerel) and mussel tissue].  相似文献   

8.
Quantitative measurement of polychlorinated biphenyl (PCB) isomers by response factor calibration (RFC) is evaluated with gas chromatography and the Hall electrolytic conductivity detector. The procedure requires neither isomer identification nor reference compounds identical to each measured PCB isomer. Weight percent chlorine is determined for five Aroclor mixtures by RFC and compared within a few percent of expected values. Individual PCB isomers are measured and quantitatively compared for Aroclor mixtures. Also, RFC determinations for ten PCB isomers contained in a test material reference solution are compared to the supplier's stated concentrations. These RFC measurements provide quantitative analyses in the absence of a standard for each measured component.  相似文献   

9.
Abstract

In Intern. J. Enuiron. Anal. Chem. 66 (1989), 155-161, Roos et al.1 reported on problems encountered in the determination of 2,3,4-2′,4′,5′-hexachlorobiphenyl (CB 138) in environmental samples. These authors indicated that an interference was present for the capillary column gas chromatographic (HRGC) determination of CB 138. This interference was tentatively identified (without standard) as 2,3,5,6-3′,4′-hexachlorobiphenyl (CB 163). We have synthesized CB 163 and can confirm that it co-elutes with CB-138 on the widely used HRGC phase for polychlorinated biphenyl (PCB) analysis, 5%, phenyl, 95% methylpolysiloxane (CP-SIL8-CB) even on a 50m column. However, we managed to separate CB 163 from CB 138 on the very polar phase, bis-cyanopropylphenyl polysiloxane (SP-2330), using a 30 m column. We have quantified CB 163 and CB 138 in various environmental and technical samples and have found CB 163 to CB 138 ratios from I: 10 up to 3: 10.  相似文献   

10.
Abstract

Retrospective analysis of archived soil samples collected and stored from long-term agricultural experiments in the UK has shown how soil organic chemical composition has changed over time. High molecular weight polycyclic aromatic hydrocarbons (e.g. benzo[a]pyrene) and polychlorinated dibenzo-p-dioxins and -furans have increased in concentration through this century as a result of cumulative atmospheric depositional inputs. Concentrations of polychlorinated biphenyls and low molecular weight hydrocarbons (e.g. phenanthrene) peaked in the late 1960s/early 1970s, but have declined subsequently. This reflects declining atmospheric inputs of these compounds and losses from surface soils by volatilisation back to the atmosphere and biodegradation. PCBs and low molecular weight PAHs exist predominantly in the vapour phase in air, whilst heavy PAHs and PCDD/Fs are predominantly particulate-bound. Outgassing from soils is probably the most important contemporary source of PCBs to the atmosphere in the UK. Future UK PCB air concentrations will presumably therefore be influenced (controlled) by the rate of desorption and outgassing, as soil and air concentrations move towards a condition of equilibrium partitioning. Archived soils collected and stored before the commercial manufacture of PCBs contain no PCBs indicating that there is no ‘natural production’ of these compounds. However, within a few hours of exposure to contemporary air these samples contain detectable quantities of PCBs. Short-term air-soil exchange, such as during soil drying in the laboratory, can lead to contamination of samples which contain low concentrations of PCBs and loss from samples which contain high concentrations.  相似文献   

11.
As cannabinoid CB2 receptors (CB2R) possess various pharmacological effects—including anti-epilepsy, analgesia, anti-inflammation, anti-fibrosis, and regulation of bone metabolism—without the psychoactive side effects induced by cannabinoid CB1R activation, they have become the focus of research and development of new target drugs in recent years. The present study was intended to (1) establish a double luciferase screening system for a CB2R modulator; (2) validate the agonistic activities of the screened compounds on CB2R by determining cAMP accumulation using HEK293 cells that are stably expressing CB2R; (3) predict the binding affinity between ligands and CB2 receptors and characterize the binding modes using molecular docking; (4) analyze the CB2 receptors–ligand complex stability, conformational behavior, and interaction using molecular dynamics; and (5) evaluate the regulatory effects of the screened compounds on bone metabolism in osteoblasts and osteoclasts. The results demonstrated that the screening system had good stability and was able to screen cannabinoid CB2R modulators from botanical compounds. Altogether, nine CB2R agonists were identified by screening from 69 botanical compounds, and these CB2R agonists exhibited remarkable inhibitory effects on cAMP accumulation and good affinity to CB2R, as evidenced by the molecular docking and molecular dynamics. Five of the nine CB2R agonists could stimulate osteoblastic bone formation and inhibit osteoclastic bone resorption. All these findings may provide useful clues for the development of novel anti-osteoporotic drugs and help elucidate the mechanism underlying the biological activities of CB2R agonists identified from the botanical materials.  相似文献   

12.
This paper investigates the use of NiO particles to enhance the vapour sensing properties of polyethylene adipate (PEA)\carbon black (CB) composite materials. Four PEA\CB suspensions were prepared with 0, 10, 20 and 30 w/w% NiO, respectively. Hypermer PS3 surfactant was shear mixed into each of the suspensions for 300 s to achieve a homogenous dispersion and to prevent reagglommeration of both the CB and NiO particles. A 0.1 μl drop of each composite was deposited between Cu electrodes on a printed circuit board (PCB) substrate using a microlitre syringe. The samples were allowed to dry for 24 h in an oven at 333 K to remove any remaining solvent. After preparation, the sensors were exposed to propanol and butanol at concentrations ranging from 0 to 25 000 ppm in steps of 5000 ppm. The response of the PEA\CB sensors improved significantly as the concentration of NiO particles in the material increased and maximum relative differential responses as high as 37% and 92.8% were recorded after exposure to 25 000 ppm propanol and butanol, respectively. This high response can be explained using the Flory–Huggins interaction parameter along with structural changes in the polymer composite caused by the addition of NiO. This paper concludes that NiO particles can be used as a method to increase the sensitivity of existing conducting polymer composite gas sensing materials.  相似文献   

13.
Four mineral oil certified reference materials (CRMs), NMIJ CRM 7902-a, CRM 7903-a, CRM 7904-a, and CRM 7905-a, have been issued by the National Metrology Institute of Japan, which is part of the National Institute of Advanced Industrial Science and Technology (NMIJ/AIST), for the determination of polychlorinated biphenyls (PCBs). The raw materials for the CRMs were an insulation oil (CRM 7902-a and CRM 7903-a) and a fuel oil (CRM7904-a and CRM 7905-a). A solution of PCB3, PCB8, and technical PCB products, comprising four types of Kaneclor, was added to the oil matrices. The total PCB concentrations in the PCB-fortified oils (CRM 7902-a and CRM 7904-a) are approximately 6 mg kg−1. In addition, the mineral oils which were not fortified with PCBs were also distributed as CRMs (CRM 7903-a and CRM 7905-a). Characterization of these CRMs was conducted by the NMIJ/AIST, where the mineral oils and the PCB solution were analyzed using multiple analytical methods such as dimethylsulfoxide extraction, normal-phase liquid chromatography, gel permeation chromatography, reversed-phase liquid chromatography, and chromatography using sulfoxide-bonded silica; and/or various capillary columns for gas chromatography, and two ionization modes for mass spectrometry. The target compounds in the mineral oils and those in the PCB solution were determined by one of the primary methods of measurement, isotope dilution–mass spectrometry (ID-MS). Certified values have been provided for 11 PCB congeners (PCB3, 8, 28, 52, 101, 118, 138, 153, 180, 194, and 206) in the CRMs. These CRMs have information values for PCB homologue concentrations determined by using a Japanese official method for determination of PCBs in wastes and densities determined with an oscillational density meter. Because oil samples having arbitrary PCB concentrations between respective property values of the PCB-fortified and nonfortified CRMs can be prepared by gravimetric mixing of the CRM pairs, these CRMs can be used for validation of PCB analyses using various instruments which have different sensitivities. Figure Preparation and certification processes of the mineral oil CRMs (example shown is polychlorinated biphenyls in insulation oil, high/low concentrations) Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

14.
Modulation of the endocannabinoid system (ECS) is of great interest for its therapeutic relevance in several pathophysiological processes. The CB2 subtype is largely localized to immune effectors, including microglia within the central nervous system, where it promotes anti-inflammation. Recently, a rational drug design toward precise modulation of the CB2 active site revealed the novelty of Pyrrolo[2,1-c][1,4]benzodiazepines tricyclic chemotype with a high conformational similarity in comparison to the existing leads. These compounds are structurally unique, confirming their chemotype novelty. In our continuing search for new chemotypes as selective CB2 regulatory molecules, following SAR approaches, a total of 17 selected (S,E)-11-[2-(arylmethylene)hydrazono]-PBD analogs were synthesized and tested for their ability to bind to the CB1 and CB2 receptor orthosteric sites. A competitive [3H]CP-55,940 binding screen revealed five compounds that exhibited >60% displacement at 10 μM concentration. Further concentration-response analysis revealed two compounds, 4k and 4q, as potent and selective CB2 ligands with sub-micromolar activities (Ki = 146 nM and 137 nM, respectively). In order to support the potential efficacy and safety of the analogs, the oral and intravenous pharmacokinetic properties of compound 4k were sought. Compound 4k was orally bioavailable, reaching maximum brain concentrations of 602 ± 162 ng/g (p.o.) with an elimination half-life of 22.9 ± 3.73 h. Whether administered via the oral or intravenous route, the elimination half-lives ranged between 9.3 and 16.7 h in the liver and kidneys. These compounds represent novel chemotypes, which can be further optimized for improved affinity and selectivity toward the CB2 receptor.  相似文献   

15.
Blood serum concentrations of polychlorinated biphenyls (PCB) and organochlorine pesticides (OCP) such as dichlorodiphenytrichloroethane and its metabolites (DDTs), hexachlorobenzene (HCB) and hexachlorocyclohexane isomers (HCHs) were measured in maternal serum (n = 82) from mothers living in different regions in Tunisia. Gas chromatography with electron capture detection was used to quantify residue levels on a volume basis of the organochlorine compounds (OCs). The pattern of OCP in human serum showed that DDTs was consistently the prevalent OC in blood. p,p′-DDE, the major metabolite of p,p′DDT, and HCB were found in all serum samples with mean concentrations of 1.69 and 0.42 ng mL?1, respectively. PCB congeners 138, 153 and 180 were the predominant congeners measured in all serum samples with a detection frequency of 80%, 72% and 83%, respectively. In general, results found in the investigated group are lower than the concentrations measured in serum blood in other countries.  相似文献   

16.
A study was undertaken to determine the extent of organochlorine pesticide (OP) and polychlorinated biphenyl (PCB) contamination in infant formula milk and in the human milk, fat and serum of women from an agricultural area in Southern Spain. A procedure is proposed that simultaneously detects trace levels of lindane, endosulfan-ether, vinclozolin, aldrin, endosulfan-lactone, endosulfan-alpha, 4,4'DDE, 2,4'DDT, endosulfan-beta, 4,4'DDT, kepone, endosulfate-sulfate, methoxychlor, mirex, 2,3,4 PCB, 2,2',4,5 PCB, 2,3,4,5 PCB and 2,2',3,3',6,6'PCB. After liquid-liquid or solid-liquid extraction, the extract of the sample was cleaned by high performance liquid chromatography (HPLC) and the fi rst eluted fraction was analysed by gas chromatography (GC) with mass spectrometry (MS) detector in tandem mode. To evaluate the validity of the method the following parameters were studied: linearity, detection limits, quantification limits, specificity, percentage recovery and precision. A study of the uncertainty associated with the analytical method was also carried out.  相似文献   

17.
张一清  郭珊珊  孙倩 《色谱》2021,39(8):827-834
有机新污染物是一类在先进分析技术帮助下新鉴定的、现有法规未管制的、人为源的有机污染物.有机新污染物主要包括药品与个人护理、农药、全氟化合物、内分泌干扰物等,其会产生内分泌干扰效应、诱发抗性基因传播,还对人类和野生生物的生存与发展构成潜在威胁,因此检测环境样品中的有机新污染物浓度对生态环境和人体健康具有重大意义.由于环境...  相似文献   

18.
An automated clean-up system was evaluated for the simultaneous analysis of polychiorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF), and biphenyls (PCB) in different foods. In addition to the seventeen 2,3,7,8-substituted PCDDIPCDF and four non-ortho PCB, by use of the clean-up system studied, it was possible to collect the eight mono-ortho and two di-ortho PCB and the seven indicator PCB in two separate fractions during the same clean-up run. The study was first performed using standard mixtures containing PCDD, PCDF and PCB, and a certified reference material. The recoveries of the 13C-labeled compounds ranged from 51 to 90%, indicating that the PCDD, PCDF, and PCB clean-up worked satisfactorily. Next, the automated system for PCDD, PCDF, and PCB analysis was evaluated for foods such as milk, egg, meat (beef, chicken, and pork), mussel, and olive oil. The recoveries of the 13C-labeled compounds ranged from 40 to 120% for PCB and from 57 to 113% for PCDD/ PCDF, meeting the requirements of well accepted methods. Thus, the automated clean-up system studied is a suitable alternative to conventional clean-up methods.  相似文献   

19.
Samples of 3 matrices (air, superficial dust and subsurface soil) from an aged PCB-containing landfill were extracted and the extracts refined for bioassay. Acetone: hexane extraction was modestly selected for non-planar compounds. Coplanar PCBs and PCDFs were enriched about 2-fold in the subsequent benzene:methylene chloride extracts of the soil. Extract refinement with Florisil slurry and alumina column chromatography did not appreciably change the composition of the extracts. CB 28 (2,4,4′-triCB) dominated in all extracts. The congener composition of soil and air were surprisingly similar, being enriched in tri- and tetraCBs while dust retained higher proportions of congeners with 4 and 5 chlorines. It is postulated that anaerobic dechlorination in the moist subsurface soil depleted the higher chlorinated congeners; more volatile congeners escaped into the atmosphere while moderately chlorinated congeners were trapped in the superficial dust and debris. The refined extracts represent distinct compositions of environmental PCB mixtures suitable for bioassay.  相似文献   

20.
A method for the determination of non-, mono- and di-ortho substituted polychlorinated biphenyls in human blood plasma is presented. The non-ortho CBs are isolated from the bulk of PCBs by HPLC on a dinitroanilino-propyl silica column and collected as a heart-cut fraction that is transferred on-line to GC-MS utilizing concurrent solvent evaporation technique. The on-line coupling serves to lower the limit of determination and to partly automate the sample clean-up. The di- and mono-ortho CBs are analyzed by off-line GC-ECD using two different columns. Sample pre-treatment is performed by extraction with organic solvents and fractionation on silica gel. A high reproducibility and an absolute over-all recovery of approximately 70 % is demonstrated. The method is applied to samples of blood from 5 individuals. All the samples demonstrated a similar relative concentration profile. It was also shown that three CB congeners (CB 126, CB 156 and CB 170) contributed to the major part of the toxic equivalent quantity of the PCB content in the blood.  相似文献   

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