摘要:

of the Analytical Division ofThe Chemical SocietyCONTENTS231232 Summaries of Papers232 'Air and Water Pollution'237 'Drug Metabolism and Analysis'240 Equipment News244 Chemical and Isotopic Reference1977 CS Award for ChemicalAnalysis and I nst ru men t at ionMaterials in the Nuclear FuelCycleUniversities, Polytechnics andCollegesService Award248 Analytical Chemistry in UK250 Analytical Division Distinguished250 Conferences and Meetings251 Courses252 Analytical Division DiaryVolume 15 No 8 Pages 231 -252 August 197PADSDZ 15(8)231-252(1978)ISSN 0306-1 396August 1978PROCEEDINGSOF THEANALYTICAL DIVISION OF THE CHEMICAL SOCIETYOfficers of the Analytical Divisionof The Chemical SocietyPresidentR. BelcherHon. SecretaryP. G.W. CobbHon. Treasurer Hon. Assistant SecretariesJ. K. Foreman D. I. Coomber, O.B.E.; D. C. M. Squirrel1Secretary Editor, ProceedingsMiss P. E. Hutchinson P. C. WestonProceedings is published by The Chemical Society.Editorial: The Director of Publications, The Chemical Society, Burlington House, London, W1 V OBN.Telephone 01 -734 9864. Telex 268001.Subscriptions (non-members): The Chemical Society, Distribution Centre, Blackhorse Road,Letchworth, Herts., SG6 1 HN.Non-members can only be supplied with Proceedings as part of a combined subscription with The Analystand Analytical Abstracts,@ The Chemical Society 1978VERLAG CHEMIEOrders to: THE CHEMICAL SOCIETY,Distribution Centre, Blackhorse Road,Letchworth, Herts SG6 IHN.Methods ofSeawater Analysisby Klaus GrasshoffThe intention of this book is not only to give aprecise recipe for analytical procedures but also togive a general account of the occurrence of thecompound or the element in marine environmentand all concentration ranges which may be en-countered under natural conditions.Brief contentsSampling and sampling techniques; Filtration andstorage; Determination of the salinity; Determinationof oxygen; Determination of hydrogen sulphide;Determination of thiosulphate; Determination of thepH; Determination of alkalinity and total carbonate;Determination of nutrients; Determination of tracemetals; Determination of the major constituents;Determination of organic constituents; Automatedchemical analysis; Appendix; Index.Cloth bound 336pp 99” x 7” 3 52725631 8 f 29.0

ISSN:0306-1396    

DOI:10.1039/AD97815FX030

出版商:RSC    

年代:1978

数据来源: RSC

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Analytical Division DiarySEPTEMBERThursday, 14th, 2 p.m.: LondonMicrochemical Methods G Y O U ~ : DiscussionMeeting on “Determination of Halogens,Sulphur and Other Elements in OrganicCompounds.” Introduction : “The Deter-mination of Halogens, Phosphorus andSulphur,” by I. G. Blackwell, J. H.Thompson and B. T. Saunderson.Room G3, City of London Polytechnic,School of Navigation, 100 Minories, TowerHill, London, E.C.3.Thursday, 14th, 4 p.m. : GlasgowScottish Region, jointly with the ChemistryDepartment of Strathclyde University.“Plasma Sources for Atomic Emission Spec-trometry, MIP and ICP,” by ProfessorL. de Galan.University of Strathclyde, Glasgow.Tuesday to Thursday, 19th to 21st:CoventryCS Autumn Meeting : Analytical DivisionSymposium on “Lasers and their AnalyticalApplications.’’Wednesday, 20th-Introductory Lecture by Professor C.GreyMorgan.“Uses of Narrow-band Tunable Dye Laserst o Excite Molecular Fluorescence,” byM. A. A. Clyne.“Laser Spectroscopy of Molecular Systems,”by P. B. Davies.“The Use of a Laser for Cutting BoneSamples Prior to Chemical Analysis,” byJ. S. Hislop.“Laser Remote Sensing of AtmosphericPollutants,” by B. L. Sharp.“Automated Aerosol Sizing by Holography,”by R. Bexon.“Particle Characterisation by Intensity Fluc-tuation Spectroscopy,” by P. N. Pusey.“The Applications of Laser Raman Spec-“Particle Characterisation with Crossed LaserThuvsday, 2M-troscopy,” by P. J. Hendra.Beams,” by A. K. Jones.“Measurement of Particle/Droplet Size Dis-tribution by Laser Diffraction,” by P.G.Felton.“Development of a Laser-based InstrumentSystem for Monitoring Concentration andCharacteristics of Solids in Suspension,”by N. Stanley-Wood and A. Taylor.“Laser Doppler Technology,” by A. J . Yule.University of Warwick, Coventry.Thursday and Friday, 21st and 22nd : BristolWestevn Region and Micvochemical MethodsGroup: Meeting on “The Use of Micro-chemistry in the Bristol Area.”Thursday, Zlst-“Microchemistry, Yesterday and Today,”by Professor L. S. Bark.“ Environmental Analysis and Carbon Skele-ton Gas Chromatography,” by G. Nickless.“The Determination of Uranium in SeaWater,” by W. J. Williams.“The Spectroscopic Examination of NuclearMaterials. Part I : ESCA, Auger and XRFAnalysis of Unirradiated Fuel Materials,”by G. C. Allen.“Part I1 : Characterisation of Irradiated FuelElements by Micro-y-scanning and XRF,”by D. A. Hilton.Fviday, 22~ad-“Microchemistry and Meat,” by R. L. S.Patterson.“GC -MS Studies of Trace Quantities ofVolatile Compounds in Fruit Juices andCiders,” by 0. G. Tucknott.“The Determination of Residual Solvents inFlexible Packaging Materials,” by W. J.Carpenter.“Microchemistry at Imperial Tobacco Ltd.,”by D. Spincer.“Microchemistry and the Local Authority,”by A. J. Harrison.“Microchemical Methods in a Home OfficeForensic Science Laboratory,” by M. W.Duckworth.“Trace Organics in Water-Present Practiceand Future Aspirations,” by J. G. Jones.School of Chemistry, The University, Bristol .Printed by Heffers Printers Ltd Cambridge Englan

ISSN:0306-1396    

DOI:10.1039/AD97815BX032

出版商:RSC    

年代:1978

数据来源: RSC

摘要:

Vol. 15 No. 8 August 1978 of the Analytical Division of the Chemical Society 1977 CS Award for Chemical Analysis and Instrumentation The fourth CS Award for Chemical Analysis and Instrumentation, sponsorcd by Perkin-Elmer Ltd., has been made to Professor John H. Knox, Director of the Wolfson Liquid Chro- matography Unit in the Chemistry Department of the University of Edinburgh, for his work on high-performance liquid chromatography (HPLC).Professor Knox first became intcrested in chromatography in 1953 as a graduate student at Cambridge where, with J. H. Purnell, hc built his first gas chromatograph. This early work led him to exploit gas chromatography as the major analytical tool in his research work on gas reaction kinetics, which was his main interest over the next 10 to 15 years.His interest in gas kinetics led to an interest in the kinetic aspects of chromatography and in 1961 he published what turned out to be a key paper on the role of pressure as a limiting factor in the speed at which substances can be resolved in chromatography. In 1964 he spent a fruitful &month period with Professor J. C. Giddings a t the university Professor Knox ( R ) receiving his awuvd from DY.T. M . Sugden, President of the CS. of Utah as an XSF Senior Fellow. There he worked on band dispersion in packed beds and substantiatcd ideas that had been formulated by Giddings. These experiments were carried out with liquids because of the high reduced velocities that could easily be achieved. His interest in high-performance liquid chromato- graphy dates from this time.In particular, he was able to predict theore- tically t h a t microparticles used in wide columns would give the optimum performance in HPLC. These predictions have of course, been fully confirmed by the technology in current use. Knox and his co-workers were among the first to make accurate rncasurements of peak dis- persion in liquid chromatography and to show, for example, that the performance of a bonded phase with unimolecular surface treatment was at least as good as t h a t of the material from which i t was originally made.In 1972 Profcssor Knox and Dr. R. A. Wall were awarded a grant of i 9 2 500 by the Wolfson Foundation to set up a unit to exploit their work on liquid chromatography by collaboration with UK instrument firms.After one false start an agreement was signed with Shandon Southcrn Products Ltd. in July, 1975, which initiated collaboration on the commercial development of HPLC instrumcntation and packing materials backed up by high quality work on applications. This collaboration has proved most success- ful. Several new packing materials were introduced in 1976 a t thc International Sym- posium on Chromatography held in Birmingham.Thesc materials were based upon a spherical silica gel developed in thc Wolfson Unit. Later this year a high-performance liquid chromatograph will be introduced. I t has been the philosophy of the Unit that HPLC instrumentation, to be successful, must be backed by the availability of high grade packing materials and by the efforts of a research team working at the frontier of the 231232 AIR AND WATER POLLUTION Proc.AnaZyt. Div. Chern. SOC. technique. A substantial part of the effort of the Wolfson Unit has therefore been devoted to research into applications of HPLC in pharmaceutical and ’ clinical chemistry with some ten publications resulting in the last few years. Clearly HPLC is still a rapidly developing subject and in Professor Knox’s research group work is being carried out on a variety of topics in HPLC, such as novel detectors and high-performance, gel-permeation chromato- graphy. Much of this work has been, and continues to be, generously supported by the Science Research Council. A final aspect of the work of the Wolfson Unit and Professor Knox’s research group has been the mounting of two highly successful “Intensive Courses on HPLC.” These were held under the auspices of the Scottish Region of the Analytical Division of the Chemical Society.

ISSN:0306-1396    

DOI:10.1039/AD9781500231

出版商:RSC    

年代:1978

数据来源: RSC

摘要:

232 AIR AND WATER POLLUTION Proc. AnaZyt. Div. Chern. SOC. Air and Water Pollution The following is a summary of one of the papers presented at a meeting of the East Anglia Region and the Microchemical Methods Group held on February 8th, 1978, at The Polytechnic, Hat field. Analytical Methods for Organic Micropollutants in Water A. Waggott Water Research Centre, Elder Way, Stevenage, Hertfordshire, SG1 1 T H Although, correctly employed, biological sewage-treatment processes are efficient at removing polluting organic substances in crude sewage, there is a hard core of organic material that is resistant to the processes and which is inevitably discharged to surface waters in sewage effluents. Re-use of water within a catchment in which effluents are discharged to rivers can, in some instances, lead to increasing concentrations of such refractory organic substances.It is therefore important to determine the nature and concentration of the residual organic com- pounds in surface waters used for potable water supply, placing special emphasis on substances known, or thought, to be toxic, so that the degree of hazard to human health can be assessed.In this connection it is long-term toxicity, i.e., chronic toxicity, which is of importance. The incidence of short-term, acute toxicity as a result of accidental contamination of drinking- water supplies is fortunately extremely rare. Methods of Approach The composition and physical properties of the organic matter in effluents and surface waters vary so widely that a variety of methods is required for extraction and concentration of trace pollutants before comprehensive analysis can be attempted.1 Many of the methods in common use have certain limitations, which often result in the loss of (or constitutional changes in) a fraction of the organic material extracted, or the introduction of artefacts. There is no ideal technique and in practice the flexible application of many techniques is required.There are three main approaches which are generally adopted in the course of analysis of waters for trace organic contaminants. These are non-specific general group analysis, anzlysis of specifically known pollutants and broad screening analysis for unknown pollutants. The three major concentration and extraction techniques that have been employed a t the Water Research Centre are a form of headspace analysis,2 which has proved suitable for the more volatile and odorous compounds, a sequential liquid - liquid extraction technique for volatile and semi-volatile compounds3 and freeze-drying followed by liquid - solid extraction for a fraction of the non-volatile compounds.3 These techniques generally allow recovery of approximately 70% of the total organic carbon content from most of the water samples examined.Other back-up techniques frequently employed at the Water Research Centre are vacuum evaporation,3 steam di~tillation,~ foam concentration4 and adsorption on to synthetic resins5 Very little of the organic matter in effluent discharges and surface waters (sometimes less than loyo, even after the formation of derivatives) is amenable to gas - liquid chromatographicA ugust, 19 78 AIR AND WATER POLLUTION 233 separation and therefore to analysis by combined gas chromatographic - mass spectrometric techniques.The Centre has therefore put considerable effort into the development of high- performance liquid chromatography (HPLC) techniques for the separation of non-volatile fractions6 However, until fairly recently, the main approach when attempting more detailed analyses of water samples was to aim at a broad characterisation of the organic matter present in terms of groups of substances or classes of compounds.Table I shows a typical result of analysis of a sample of domestic sewage effluent obtained by adopting this approach.' The broad characterisation has in this instance accounted for approximately 95% of the total organic carbon present and serves as a useful starting point for a more detailed analysis.The application of more advanced analytical instrumental techniques makes possible a more detailed analysis of individual compounds. Table I1 shows a representative selection of results obtained by applying various approaches to the analysis of domestic sewage effluent.s The examples indicate that it is necessary to apply a wide variety of techniques in order to determine a wide range of compound types over a large concentration range.TABLE I RESULTS OF ANALYSIS OF A SAMPLE OF DOMESTIC SEWAGE EFFLUENT THAT HAD BEEN FILTERED TO REMOVE PARTICLES OF SIZE GREATER THAN 0.3 pm (REFERENCE 7) Some results were based on analysis of freeze-dried solids derived from the original sample.Total Concentration/ organic Analysis mg 1-1 carbon, yo Dialysable matevial- Carbohydrates (as glucose) 0.1 0.2 Amino acids (as leucine) 1.44 4.6 Volatile acids (as C) 0.92 5.4 Non-volatile acids (as C) 1.89 11.8 Steroids (as cholesterol) 0.165 0.8 Non-ionic surfactant (as Lissapol NX) 0.53 1.6 Organochlorine compounds 0.000 35 _- Optical whitener (as Blankophor MBBH) 0.14 0.5 EDTA 0.15 0 .3 Unaccounted for 1.25 4.7 Non-dialysable matevial- Pol ysaccharides (as glucose) 1.7 4.0 Protein (as leucine) 0.49 1.7 Humic substances 17.2 53.0 Total - 100.0 Neutral volatiles (as C) 0.52 3.1 Tannins (as tannic acid) 1.6 5.1 Anionic surfactant (as Manoxol OT) 1.0 3.2 TABLE I1 SOME RESULTS OF ANALYSIS OF A DOMESTIC SEWAGE EFFLUENT (PARTICLES GREATER THAN 0.3 pm REMOVED) BY VARIOUS ADVANCED INSTRUMENTAL TECHNIQUES~ Substance Alanine Aniinostilbene optical whiteners n-Butyric acid Cholesterol Dibutyl phthalate Dieldrin Fluoranthene Glucose Stearic acid Urea Concentration / pg 1-1 5 0.12 5 20 200 0.04 0.01 34 50 20 Analytical technique* HPLC - reagent colorimetric detection system TLC - fluorescence detection GLC - aqueous injection - FID HPLC - differential refractometer detection system GLC - MS - computer library search GLC - electron capture detection HPLC - fluorescence detection Silyl derivative formation - GLC - FID GLC - MS - computer library search HPLC - reagent colorimetric detection system *TLC, thin-layer chromatography; GLC, gas - liquid chromatography; FID, flame ionisation detection : MS, mass spectrometry.234 AIR AND WATER POLLUTION Proc.Analyt. Dia. Chem. SOC. Techniques For the screening analysis of water samples, an ideal analysis scheme should be simple to apply, produce clean extracts that will not irreversibly contaminate chromatographic columns (especially glass capillary columns), allow good recovery of as wide a polarity and volatility range of organic compounds as possible, maintain the integrity of the extracted organic com- pounds, provide a large concentration factor so that trace substances can be determined and, finally, allow a t least semi-quantitiative analysis to be carried out.20 Headspace Analysis A technique which is being applied routinely to a wide range of sample types, and which fulfils many of the ideal requirements listed above, is a form of headspace analysis which is widely known as the Grob strip technique.2 It was developed by Grob for the, analysis of relatively pure water samples, e.g., tap waters and underground waters, but it has been applied successfully at the Water Research Centre for the analysis of a wider range of more polluted water samples.Briefly, the technique involves a closed-loop stripping of the water sample and adsorption of the stripped organic vapours on to a small activated-carbon filter. Air within the system is circulated by means of a small, inert metal bellows pump. Adsorbed organic substances are recovered by elution from the carbon filter with a very small volume of organic solvent, carbon disulphide or dichloromethane.A factor of major concern in adapting the technique to more polluted water samples is the capacity of the carbon filter, which usually contains only 2 mg of carbon. The results shown in Fig. 1 indicate that the absolute capacity of a 1.5-mg filter for a homologous series of 1- chloro-n-alkanes was 6 pg for complete recovery.The effect was investigated in greater detail across a range of volatilities. Maximum recovery was obtained between C, and C,, in the 1-chloro-n-alkane series. Because of the increased compe- tition for active sites, recovery from spiked effluents was invariably lower. The results are shown in Fig. 2. - High-performance Liquid Chromatography Because the greater proportion of the organic material in water samples is non-volatile, and therefore not amenable to gas - liquid chromatographic analysis, the Water Research Centre has an interest in developing a routine HPLC system that is capable of separating unknown and complex extracts with the best possible resolution of individual non-volatile components.During the past few years a system based upon that of Scott and Kucerag has been developed,A ugust, 19 78 AIR AND WATER POLLUTION 235 0' I I I I # I -X- c6 c8 c10 c12 c14 c16 c18 CaO c6 c8 ClO c12 c14 c16 c18 c20 Carbon number Carbon number Fig. 2.C,-C,, 1-chloro-n-alkanes (10 p g 1-1 concentration of each) : (a), average of 3 results for 2-h strip (-), distilled water [(- - -), 6-h strip]; ( b ) , average of 6 results for 2-h strip, spiked sewage effluent (-) and spiked settled sewage (- - -).employing liquid - solid adsorption chromatography with gradient elution by the application of a series of solvents of rising polarity. A schematic diagram of the system is shown in Fig. 4. A series of solvent reservoirs is connected via a programmable multiple-port rotary valve to a solvent mixing chamber containing primary solvent.A high-pressure reciprocating pump draws solvent from this system at the same time, causing a solvent gradient to be generated by J 1 + a, .- I Fig. 3. Gas - liquid chromatographic capillary column profile of a head-space analysis extract obtained from an industrial effluent. Sample size, 2.5 p1; solvent, dichloromethane : column, 50-m glass capillary containing OV-1; detector, flame ionisa- tion; conditions, 30-200 "C a t 4 "C min-1.236 AIR AND WATER POLLUTION Proc.AnaZyt. Div. Chem. SOC. pulling a secondary solvent from one of the reservoirs into the mixing chamber. Solvent combinations are changed a t appropriate intervals by switching the rotary valve position. Sample introduction is effected by loop or septum injection. The column is a high efficiency 250 x 4.2 mm prepacked column containing microparticulate silica.The detectors incorpor- ated into the system are a combined, variable wavelength ultraviolet and fluorescence photo- meter and a transport ionisation detector. Pressure gauge Fig. 4. Schematic diagram of a system for multiple-solvent gradient elution HPLC.There remains some doubt concerning the optimum number of solvents to be employed in the multiple-solvent, gradient-elution programme. Scott and Kuceras recommend a twelve- solvent series, while SnyderlO proposed a six-solvent series to cover the entire polarity range adequately. Fig. 5 compares the effect of a twelve- and a six-solvent series on the separation of a butanol extract of settled sewage.It is apparent that the reduced series results in de- creased band widths at the expense of some resolution and there is a suspicion of the introduc- tion of displacement effects at the start of some solvent combinations. i , I I I 8 7 6 5 4 TIME ( h 1 Fig. 5. Extract in butanol of settled sewage: (a) Scott and Kucera (reference 9) ; (b) Snyder (reference 10).August, 1978 DRUG METABOLISM AND ANALYSIS 237 Mainly because of sample complexity and the relatively complicated concentration and extraction procedures generally required to obtain workable extracts, the analysis of organic micropollutants in water is one of the more difficult fields of analytical chemistry in which to work.In this field, the development and application of advanced instrumental techniques are still in a relatively early phase and most of them are generally stretched to the limits of their capabilities in terms of, for example, resolution and sensitivity. The work has been carried out under contract from the Department of the Environment and is published with their permission.References 1 . 2. 3. 4. 5. 6. 7 . 8. 9. 10. Rndelman, J.B., and Caruso, S . C., i n Ciaccio, L. L., Editor, “Water and Water Pollution Handbook,” Grob, K., and Zurcher, F., J . Chromat., 1976, 117, 285. Waggott, A., and Saunders, C. L., “Analysis of the Organic Carbon Content of Sewage Effluent: Methods of Concentration and Extraction,” Technical Report TR 30, Water Research Centre, Stevenage, Herts, 1976. Wickbold, R., Tenside Detevgents, 1971, 2, 61. Gardiner, J., “Analysis of the Organic Carbon Content of Sewage Effluent : Concentration and Extrac- tion of Relatively Non-polar Compounds using Amberlite XAD-2,” Technical Report, Water Research Centre, Stevenage, Herts, in the press. Waggott, A., and Reid, W. J., “Separation of Non-volatile Organic Carbon in Sewage Effluent Using High-Performance Liquid Chromatography (Part I) ,” Technical Report TR 52, Water Research Centre, Stevenage, Herts, 1977. Waggott, A., and Britcher, H. V., “Analysis of the Organic Carbon Content of Sewage Effluent: General and Specific Group Analysis,” Technical Report TR 29, Water Research Centre, Stevenage, Herts, 1976. Volume 2, Marcel Dekker, New York, 1971. Water Research Centre, unpublished work. Scott, R. P. W., and Kucera, P., Analyt. Chem., 1973, 45, 749. Snyder, L. R., Analyt. Chem., 1974, 46, 1384.

ISSN:0306-1396    

DOI:10.1039/AD9781500232

出版商:RSC    

年代:1978

数据来源: RSC

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August, 1978 DRUG METABOLISM AND ANALYSIS 237 Drug Metabolism and Analysis The following is a summary of the paper presented at a meeting of the Midlands Region and the Loughborough University Student Chemical Society held on February 21st, 1978, at Loughborough University of Technology. Analytical Chemistry and Drug Metabolism A. C. Moffat Home O-fJice Central Research Establishmertt, Aldermaston, Reading, Berkshire, RG7 4PN A knowledge of the metabolic routes and pharmacokinetics of a drug may be of considerable use in forensic toxicology. The identity of a drug in a biological fluid can be confirmed by the presence of its metabolites and the relative proportions of these compounds in blood and urine can give an indication of how much drug was taken and when.This paper des- cribes some of our studies on the assay of lysergide (LSD), Ag-tetrahydrocannabinol (THC) and their metabolites in biological fluids.Drug metabolites are normally more polar than the parent compound and can be con- jugated to form glucuronides, sulphates, etc. In many instances the first step of an analysis is to hydrolyse the biological sample by enzymes, acid or alkali to obtain unconjugated238 DRUG METABOLISM AND ANALYSIS PYOC.Analyt. Div. Chem. SOC. CH3 I CH3 LS D THC metabolites. These metabolites can then be extracted into organic solvents at various pH values to give extracts containing the acidic, neutral and basic metabolite fractions. The individual metabolites can then be identified and quantified by chromatographic and spectro- scopic procedures. Radioactively labelled drugs are very useful in the early stages of drug metabolism studies because direct counting of the biological materials gives quantitative data for the metabolites without the need for extraction procedures. The use of tritium-labelled drugs with liquid scintillation counting gives very high sensitivities of detection.Unfortunately, the position of labelling may also be a position for metabolic attack or the tritium label may be labile. In these instances the use of 14C-labelled materials may be preferred.Although sensitivity is lost in this way, the use of the radioactively labelled drug still means that metabolic and kinetic data can be obtained easily without the need to develop specific methods involving other techniques.Thin-layer chromatography is often used for separating drugs and metabolites, but gas - liquid chromatography (GLC) may be preferred because it has the advantages of greater resolution and sensitivity. By using a mass spectrometer in the multiple-ion detection mode as the GLC detector, only a few picograms of material may be needed for an assay. This type of approach has been used for the determination of THC in plasma1 and it can also be used for the assay of its metabolites. Because LSD is thermolabile, high-performance liquid chromatography (HPLC) has been found to be superior to GLC for the separation of this drug and its metabolites. Reversed- phase HPLC columns are particularly useful as substances elute according to their polarity ( i e ., the order of elution is conjugates first, then non-conjugated metabolites and finally the parent drug). A fluorimeter can be used as the HPLC detector when determining LSD because of its excellent fluorescence characteristics. If a valve is incorporated between the column and the detector a chromatographic peak may be trapped in the fluorimeter flow cell and the excitation and emission spectra can then be obtained.2 Hence the information gained from HPLC - fluorimetry is not only the elution volume of the compound, but also its spectral characteristics.Another property of LSD that can be used for characterisation is its conversion into the non-fluorescent lumi-LSD with ultraviolet (UV) irradiation. The identity of the compound can thus be confirmed by constantly irradiating the trapped eluate in the flow cell with UV light so that the fluorescence decreases as the LSD is decomposed. In contrast to the situation with LSD, cannabinoids are not naturally fluorescent but some, e.g., cannabinol (CBN), can be converted into highly fluorescent compounds when irradiated with UV light.This phenomenon has been used in an on-line photochemical derivatisation method for the detection of CBN in biological fluid^.^ When a sample is chromatographed the HPLC eluate passes into a photochemical reactor, where it is subjected to a high flux of UV light for a few seconds, which converts CBN into a fluorescent derivative.The eluate then passes to a fluorimeter, which detects the fluorescent photoproduct with a sensitivity of less than 1 ng.If the biological sample is re-chromatographed with the lamp in the photo- chemical reactor turned off, only the naturally fluorescent compounds are seen. The com- parison of the two chromatograms gives a very high specificity to the method. Radioimmunoassays (RIAs) have been reported for both THC4 and LSD.5 This tech- nique has the advantages that it can be used directly on both plasma or urine without ex- traction, it has a high sensitivity down to the 1 ng ml-l level, it requires only small sample volumes (10-100 pl) and both drug and metabolites are normally assayed together.The RIA for THC, for example, cross-reacts with a number of its metabolites, which is an essen-August, 1978 DRUG METABOLISM AND ANALYSIS 239 tial characteristic when assaying urine because THC itself is not present in this body fluid (only the metabolites are present).Several millilitres of urine or plasma can be injected on to a reversed-phase column provided that, with plasma, the protein has been removed by centrifugation after the addition of a few volumes of methanol. The HPLC eluate is collected in a fraction collector after the column has separated the parent drug and metabolites from each other.The RIA is then used as the HPLC detector. This approach has been developed successfully for the identification and assay of LSD2 and cannabinoid9 in biological fluids and is routinely in use for forensic samples. Fig. 1 shows a typical separation of THC and its metabolites in a plasma sample from a subject who had smoked THC.The large first peak has the retention volume corres- ponding to THC-1 l-oic acid and metabolite conjugates. The other areas of cross-reaction observed in the chromatogram have retention volumes corresponding to THC, CBN and monohydroxylated and dihydroxylated metabolites. The combination of HPLC with RIA gives the advantages of both techniques. Fig.1. An HPLC - RIA chromatogram of a plasma sample from a subject who had smoked THC. There is probably no best single technique for studying the metabolism of a drug-the best combination of techniques should be chosen from a knowledge of the known or expected physicochemical properties of the drug and its metabolites. References 1. 2. 3. 4. Agurell, S., Gustafsson, B., Holmstedt, B., Leander, K., Lindgren, J. E., NilsTon, I., Sandberg, F., and Twitchett, P. J., Fletcher, S. M., Sullivan, A. T., and Moffat, A. C., J . Chromat., 1978, 150, 73. Twitchett, P. J., Williams, P. L., and Moffat, A. C., J. Chromat., 1978, 149, 683. Teale, J. D., Forman, E. J., King, L. J., Piall, E. M., and Marks, V., J . Pharm. Phavmac., 1975, 27, Ratcliffe, W. A., Fletcher, S. M., Moffat, A. C., Ratcliffe, J . G., Harland, W. A,, and Levitt, T. W., Williams, P. L., Moffat, A. C., and King, L. J., J . Chromat., in the press. Asberg, M., J . Pharm. Pharmac., 1973, 25, 554. 465. Clin. Chem., 1977, 23, 169. 5. 6.

ISSN:0306-1396    

DOI:10.1039/AD9781500237

出版商:RSC    

年代:1978

数据来源: RSC

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240 EQUIPMENT NEWS Proc. Analyt. Div. Chem. Soc. Equipment News Low-energy Ions A low-energy, saddle-field, ion source, Model B13, which produces ions with energies from less than 100 eV up to 3 650 eV, has now been introduced. The B13 is supplied as a nude source for installation within an existing vacuum system and is also available as an ultra-high vacuum compatible version, Model B15, which is mounted on a standard bakable stainless-steel flange.Operating characteristics are typically a 100 ,LA ion current produced from a 2-mm cathode aperture with a beam spread of 9" total angle. The B13 and B15 will produce ions of argon and lighter or heavier gases including many reactive gases. Ion Tech Limited, 2 Park Street, Teddington, Middlesex, TW 11 OLT. 14C Monitoring Now available is a sensitive monitor of 14C designed to detect the minimum permissible level, pCicm-2.The 271C monitor in- corporates a large area detector, using a Geiger-Muller tube with a thin window, and will detect 14C over 6 counts s-1 above the very low background. The 271 instrument is a battery operated portable using the inter- national R20 (U2) batteries, giving a working life of approximately 300 h a t 4 h d-l.A large meter with a 600 counts s-l semi- logarithmic full scale deflection is used to give good accuracy and avoid reading errors. ESI Nuclear, Klempfern House, Holmesdale Road, Reigate, Surrey, RH2 OBQ. Parabolic and Elliptical Metal Mirrors A complete line of parabolic and elliptical metal mirrors for a variety of high efficiency light collection and light concentration systems is available, with light collecting powers much greater than with conventional glass mirrors.Produced by an electrolytic process, these mirrors are made of nickel and are coated with a very hard and durable rhodium coating. They can withstand high temperatures, adverse climatic conditions, are practically unbreakable and much lower in weight than glass mirrors of comparable size.Melles Griot B.V., Nieuwe Kade 10, Postbus 567, Arnhem, The Netherlands. Ultraviolet Monitors An ultraviolet-monitoring system for column chromatography in aqueous or organic solvents is announced. The UV-2 Monitor is a dual- beam, dual-pathlength unit, which operates with two independent monitoring systems simultaneously. This enables the detection of very minor impurities or components while still obtaining correctly-shaped peaks for the major substances.Perfect peaks are obtained up to 20 times the absorbance with 0.005 full-scale sensitivity at the same time. Each path length can be monitored at 254 or 280 nni and results can be expressed in absorbance or transmission, yo. Excellent linearity enables easy and accurate quantification and setting up is extremely simple.The temperature range is 0-40 "C and the fused quartz cell is temperature compensated. Noise levels and temperature drift are small, thus enabling the optimum detection a t high sensitivity. The UV-1 is a dual-beam, single-pathlength model with a choice of 3- or 10-mm path lengths. Full-scale ranges are from 0.01 to 2 absorbance units and the unit is very compact (4.72 litres, Pharmacia (Great Britain) Ltd., Paramount 3.5 kg).House, 75 Uxbridge Road, London, W5 5%. Optical Multi-channel Vidicon Analyser System A recently developed optical multi-channel vidicon-based spectral analysing system, the OSA 500, which couples the image detecting ability of a vidicon with a microprocessor based control console is announced.The system consists of a detector head or camera, which can be remote (up to 10 m) from the control console, and an analog to digital converting circuit, so that it can be used as a digital camera for real-time readouts without the console. A range of cameras is available. The standard vidicon, the ST 500, covers the spectral range from 320 to 1100nm, has a sensitivity of about 2 500 photons count-l and can be used, with the addition of a scintillator, down to 100nm.The Silicon Intensified Target vidicon, the SIT 500, covers the spectral range 320-850nm but has a sensitivity of 15 photons count-l. Other vidicons are available which cover the spectral range up to 20 pm. The OSA 500 is an optical multi-channel analyser with almost infinitely expandable capability.The detector head is constructed around a Thompson 1st Quality vidicon and is available in standard, intensified or double- intensified form. It is a true 500-channel, simultaneous, parallel detector for light signalsAugGst, 1978 EQUIPMENT NEWS 24 1 in the wavelength range 150-1 100 nm with vidicons or 1-20 pm with pyricons. The controlling console has two 500-channel memories but more can be added a t will.The digitised, stored spectrum can be output to a computer, punched tape, a recorder or a printer as required. In addition, complete spectra are available in real time a t 30 ms intervals. For very low light signals, or to improve the signal to noise ratio, signal averaging over the whole spectrum can be performed. Cooled detector heads, extended delay units and two- dimensional scanning options are available.EDT Research, 65 Ivy Crescent, London, W4 5NG. Image Analyser The Quantimet 360 Mark 2 is a high-speed image analyser for measuring non-metallic inclusions in steel. In less than 1 min it makes an analysis based on more than 30 separate measurements on 500 image fields. The Quantimet 360 Mark 2 produces a complete statistical description of the inclusion popula- tion in terms of average values, standard deviation, most frequently occurring fields, worst fields, etc.A complete distribution of all field values is generated, together with the length distributions in 32 size classes for the oxide and sulphide inclusions. The instrument can store all selected data for retrieval a t will, in order to generate general statistical sum- maries or trends for large numbers of samples evaluated over long periods of time.Cambridge Scientific Instruments Ltd., Mel- bourn, Royston, Hertfordshire, SG8 6E J . Mercury Vapour Monitor The Racharach (J-W) MV2 Mercury Vapour Sniffer is a portable, lightweight (2.7 kg) instrument, with carrying handle, two simple controls and an indicating meter mounted on the top cover of the 289 x 120 x 11 1 mm case. A detachable 300-mm probe facilitates checking in inaccessible places.A bullt-in suction fan draws samples through the probe into an absorption chamber, where an ultraviolet photometer detects the presence of mercury vapour. A rotary switch selects either the low range (0-0.2 mg m--3 for toxicity and contamina- tion investigations) or the high range (0-1.0 mg m-3 for pinpointing mercury vapour sources).Sensitivity is better than 0.01 mg m-3; response speed is 5 s to 90%) The MV2 is powered by a rechargeable battery, giving up to 4 h continuous operation between charges, and incorporates a built-in filter, which permits accurate zero adjustments even in contaminated atmospheres.Shawcity Ltd., 5 Church Street, Wantage, Oxfordshire, OX12 8BL. Organic Vapour Analyser Lightweight flame-ionisation detectors, BASEEFA approved, can be supplied with or without chromatographic capability with the choice of logarithmic or linear scales. The response time of the detector is less than 2 s. All organic vapours can be detected and an electronic gas selection device gives the possi- bility of an accurate interpretation of the readings.The sensitivity is 0.2 p.p.m. on the linear scale models and 1 p.p.m. on the logarithmic scale models. The range limit on both models is 10 000 p.p.m. Quick-exchange chromatographic columns permit individual qualitative identification of a large variety of components. After the detection of potentially toxic vapours, a sample can be injected into the gas-chromatographic system by pressing the sampling valve.Component vapours will elute separately from the column into the flame- ionisation detector for subsequent display on the meter and the strip-chart recorder. D. A. Pitman Ltd., Mill Cooks, Jessamy Road, Weybridge, Surrey, KT 13 8LE. Liquid Chromatograph Microprocessor An improved version of the Hewlett-Packard 1 084 microprocessor-based, high-performance liquid chromatograph enables the user to pro- gramme changes of separation parameters, calibration factors and calculation procedures and to implement them between analytical runs.With an automatic sampling system that holds up to 60 samples, the instrument now can perform unattended long series of varied analyses and produce complete, detailed reports. Wavelength combinations of the new ultraviolet - visible detector can be programmed to change automatically during an analysis or between one analysis and the next so that individual sample components can be detected a t their optimum wavelength.At the press of a button, solvent flow is stopped and the detector automatically sweeps through its wavelength range to examine any selected component.The microprocessor of the HP 1084B controls solvent flow-rate, gradient elution, sample in- jection and solvent temperatures, and the de- tector wavelength settings. Hewlett Packard Ltd., King Street Lane, Winnersh, Wokingham, Berkshire, IiGl 1 5AR.242 EQUIPMENT NEWS Proc. Analyt. Div. Chem. SOC.Automatic Sampler for Liquid Chromato- A new automatic sampler, the Model 420, for automatic injection of liquid samples into high performance liquid chromatographs is now available; it is readily usable with almost any modern liquid chromatograph and integrator. The sampler operates in either the isocratic or gradient modes, and can perform automatic analyses of up to 42 consecutive samples.Multiple input - output connections allow the autosampler to be operated by either the liquid chromatographic system or the timed event output of integrator - computer systems, and it can also be used to control the liquid chromatographic and integrating systems. Sample carry-over is less than 0.01%. Perkin-Elmer Ltd., Post Office Lane, Beaconsfield, Buckinghamshire, HP9 10A. graphy Programmed Thermal Desorber A new thermal desorber for air sample collector tubes provides high desorption efficiency, reduces sample degradation and provides means for multiple sample injection into a gas chromotograph.The sorbent material in the collector tube is heated convectively with purge gas (air or other), which is drawn through the tube with a mechanism similar to a large 300-cm3 stainless-steel syringe.The syringe purges the contaminant from the tube, starting immediately after the tube is inserted in an oven. After the desorption cycle, the syringe retains the contaminant, re-concentrated in a fixed volume of purge gas. Analytical-size samples of this gas can then be manually or automatically injected into a gas chromatograph for analysis.Replicate samples can be with- drawn from the syringe without sample dilution as the syringe piston self-adjusts. Calibration and calculation of time weighted average (TWA) are readily accomplished by factoring the p.p.m. level measured on the gas chromato- graph by ratio of the volume of air sampled to the fixed volume (300cm3) of the syringe mechanism. D. A.Pitman Ltd., Mill Works, Jessamy Road, Weybridge, Surrey, KT13 8LE. Portable Air Sampling Pump The CAP 130 electronically timed, positive- displacement, portable air sampling pump can be used with a variety of air sample collecting devices for indoor or outdoor environmental monitoring. It operates on the principle of timed strokes from positive displacement bellows and will run for long periods on two “C” cells.The pre-set flow-rate is maintained over a wide range of collector tube restrictions and an audible flow-rate failure alarm is in- corporated. A mechanical stroke counter is included to measure “on” time of the pump as well as to verify the total volume of air pumped. D. A. Pitman Ltd., Mill Works, Jessamy Road, Weybridge, Surrey, KT13 8LE. Trace Moisture Analysis in Solvents The Carle Basic gas chromatograph, Model 8717, for trace moisture analysis, typically 200 p.p.m., in solvents, offers advantages over the traditional technique of titration by the Karl Fischer method.By back-flushing the major constituent to vent, the technique produces a single water peak in just over 1 min. The Carle Basic 8717 is supplied complete with heated valve and column; nothing more is required other than injection of the sample and the turning of the back-flush valve after the water has eluted.Techmation Ltd., 58 Edgware Way, Edgware, Middlesex, HA8 8JP. Portable Gas Monitor A portable gas monitor - analyser, Model 6509, which will measure a wide range of gases is announced. The Model 6509 analyser is housed in a plastic attachk/brief case.It is self-contained, with batteries, electric sampling pump, dis- posable filters, a katharoineter and the direct reading indicator, all fitted within the case. It weighs only 5.9 kg (13 lb), and accuracy, discrimination and repeatability are all typi- cally 1 2 % . It is calibrated directly in terms of one gas in a combination of gases, including hydrogen, oxygen, nitrogen, air, carbon dioxide, argon, methane, helium, nitrous oxide, carbon monoxide and respired air.George Kent Electronic Products Ltd., 4 Rosemary Lane, Coldhams Lane, Cambridge, CB1 3LQ. Low Temperature Cabinets Low temperature cabinets are available in two models with ’ temperature ranges down to -70 and -85 “C. The cabinets use semi- hermetic compressors with a slow running speed.The chamber has five stainless-steel shelves, repositionable a t 4’’ intervals and insulated by individual inner doors with mag- netic latches. The cabinets will maintain their performanceAugust, 1978 EQUIPMENT NEWS 243 regardless of repeated door opening. Facilities for auxiliary water cooling are available in order to allow the units to be used a t ambient temperatures above 30 "C.Optional extras include an audible/visual alarm, 7-d recorder and back-up liquid carbon dioxide system. Boro Labs Ltd., Paice's Hill, Aldermaston, Berkshire, RG7 4QU. Dewar Flasks -4 new range of Dilvac SS series Dewar flasks with outer containers manufactured in stainless steel is announced. The SS series is available in 1-, 2- and 4.5-1 capacities; they have easy to replace top- loading refills of borosilicate glass, which are interchangeable with the other Dilvac de- signs.These Dewar flasks include a chromed carrying handle and a double skin, stainless, vented, insulated lid, which can be secured to the body by toggle clamps, thus allowing secure transportation of a wide range of materials. A. Gallenkamp & Co. Ltd., P.O.Box 290, Christopher Street, London, EC2P 2Eli. Metering Valves Nupro fine metering valves with vernier or micrometer handles for rapid, accurate, re- peatable flow settings are now available. The lightweight plastic micrometer and vernier handles are moulded in black nylon with a matt finish, with white, hot-stamped numerals. A dead stop is built in to avoid overtightening.The new line includes three sizes: S (0.031 in orifice), M (0.055 in orifice), and L (0.125 in orifice). They are available in brass, 316 stainless steel or Monel, with end connections ranging from 1/16 in to 3/8 in Swagelok, 1/8 in female NPT and 1/8 in and 1/4 in male NPT. Patterns include straight, anglc, cross and double. Pressure ratings are 1000 p.s.i.g. (M and L series) or 2 000 p.s.i.g.(S series). Temperature ratings on all models are 200 O F with the plastic micrometer or vernier handles or 400 O F with a metal handle. Eight to twelve turns of actu- ation assure a rapid, repeatable set point within each range. Techmation Ltd., 58 Edgware Way, Edg- ware, Middlesex, HA8 8 JP. Gel-filled pH Electrode A permanently gel-filled, combination pH electrode with an unbreakable epoxy outer body that also protects the bulb from severe shocks is announced.MSE Scientific Instruments, Manor Royal, Crawley, Sussex, RHlO 2QQ. Portable Digital pH Meter The Model 202 combines solid-state circuitry, high stability, low drift and fast response with an easy to read LED display. It operates on either batteries or a 220-V mains adapter. The Model 202 is supplied as a complete pack- age, including the meter, mains adapter, unbreakable gel-filled combination pH electrode, three plastic containers and a carrying case.MSE Scientific Instruments, Manor Royal, Crawley, Sussex, RHlO 2QQ. Muscle pH Measuring System The system, which permits convenient moni- toring of skeletal muscle pH fluctuations, includes a muscle pH electrode and a precision pH meter. The shape and small size of the electrode allows small incisions and gives good muscle contact. The meter is readable to 0.01 pH over the range of physiological interest. Electrical shock hazards are prevented with the battery powered meter. MSE Scientific Instruments, Manor Royal, Crawley, Sussex, RHlO 2QQ. Electrolyte Measurement The Orion Space-Stat 30 sodium - potassium analyser is completely self-contained, and gives results within 1 min of sampling by simply injecting the whole sample and reading the results at the push of a button. MSE Scientific Instruments, Manor Royal, Crawley, Sussex, RHlO 2QQ. Thyroid Function Testing The Quantimune neonatal T-4 RIA assay is announced. The system utilises a filter-paper spot saturated with neonatal blood incubated a t room temperature with labelled T4 and T4 Immunobeads for the separation of bound and unbound fractions, and is provided with a set of lyophilised serum standards covering the range 0-30 pg dl-I. Bio-Rad Laboratories Ltd., Caxton Way, Holywell Industrial Estate, Watford, Hert- fordshire, WD 1 SRP.

ISSN:0306-1396    

DOI:10.1039/AD9781500240

出版商:RSC    

年代:1978

数据来源: RSC

摘要:

244 CHEMICAL AND ISOTOPIC REFERENCE MATERIALS Proc. AnaZyt. Div. Chew SOC. Chemical and Isotopic Reference Materials in the Nuclear Fuel Cycle An Advisory Group meeting on the topic “Chemical and Isotopic Reference Materials in the Nuclear Fuel Cycle” was held at the International Atomic Energy Agency (IAEA) Headquarters, Vienna, from November 8-10, 1977. Participants from Euratom, France, Germany (Federal Republic), the Netherlands, Poland, the United Kingdom and the United States took part, as well as representatives of the International Union of Pure and Applied Chemistry (IUPAC), the International Organi- zation for Standardization (ISO) and IAEA.This was the second meeting of its kind; the observations and recommendations of an earlier Group (1972) were not widely publicised or circulated.The main topics of discussion at the present meeting were as follows. (i) What is the present status of reference materials for nuclear material analysis and safeguards purposes ? (ii) What new reference materials are re- quired, and can the Agency expedite the pro- vision of such materials? (iii) To what extent should the Agency be involved in the area of reference materials for nuclear materials analysis and safeguards purposes ? (iv) Should a compilation be published listing the available reference materials, their cost and the mechanism for their procurement ? Some General Observations It was emphasised by several participants that production quality control and safe- guarding of nuclear materials implied strict analytical quality assurance programmes and that the calibration and continuous monitoring of analytical procedures, based on certified reference materials, were fundamental elements of such quality assurance programmes.Stress was placed on the fact that primary and secon- dary reference materials were precious, and that their preparation and characterisation required a highly technical effort by experienced scientists. Accordingly, these substances should be used sparingly and, wherever possible, working calibration and test materials charac- terised relative to the primary reference sub- stances should be employed.The measurement of plutonium and uranium and the determination of isotopic content was the main subject matter of this meeting. There was insufficient time to consider other topics, such as cladding, structural materials, modera- tors, etc.The participants had no information on the special requirements of, and availability of reference materials from, countries such as the USSR, Japan, and developing nations; it was felt, however, that their general requirements would be similar to those of the other countries and organisations represented at the meeting.Recommended Additional Reference Mate- rials A list of the reference materials needed to satisfy present and anticipated future needs was compiled (see Table I). Several members of the group offered the services of their insti- tutions to help in the production and analysis of these materials. In this way, substances prepared at one institution could be charac- terised on a cost-free basis at others that have the appropriate expertise.It was emphasised that multiple-laboratory characterisation of reference materials was very desirable, es- pecially when the laboratories were highly qualified for this work. Current and Anticipated Activities of Some Standardisation Organisations Participants from the US National Bureau of Standards (NBS) described some continuing and planned future activities at their Insti- tution.Two isotopic reference materials with higher 240Pu contents than those at present available will be prepared on an absolute basis by blending the chemically characterised en- riched isotopes. The current NBS plutonium standards, which were certified relative to the uranium isotopic reference materials based on the assumption of equal mass discrimination effect, will be re-characterised relative to the new standards.The following standards are also planned for preparation: a solution certi- fied for 233U atoms per mass and/or per am- poule; a solution of 230Th; natural Th metal; a sample from Zaire certified for natural uranium isotope content; three samples of UF, with 235U enrichment to 4.5%, certified for isotopic and uranium content; and natural Nd,O, and Sm20, certified for isotopic content.In addi- tion, the existing series of 19 uranium isotopic standards will be re-certified within narrower precision limits. The New Brunswick Laboratory (NBL) is preparing several secondary reference materials.August, 1978 CHEMICAL AND ISOTOPIC REFERENCE MATERIALS Material 24aPu solution (metal ?) 244Pu solution (metal ?) 233U Pu isotopic reference materials UF, (depleted, natural, or low enriched) 23SU .(enrichment > 99.5%) (enrichment > 99.99 yo) nat*Nd203 238U nat.Sm20, D2O (U, PU)O, pellets U - Pu = 3 : 1 (U, PU)O, PUO, ( 10-1 2 yo 24OPu) pellet Th metal TRISO BISO T h - U 1 0 ~ 1 nat.UC I 93% 235U PUCS (nat.U, Pu) CS uo2 (Gd20,) (1,3,5,7 or 9% Gd20,) (23sU = 1-4y0) UO, UA1 Different alloys made to customers' request (20-25% U, 93% 23sU) *By the end of 1978.Preferably 5 g. Lower priority. TABLE I NEEDED REFERENCE MATERIALS Amount per package Low mg Low mg 1 mg 8-l in -10-g amp o u 1 e s (0.1-10 pg g-1) (0.1-10 .pg g-1) Low mg Low mg 100 mg per ampoule 100 mg per ampoule 10-3 g 10-3 g 5-10 g -1 g -1 g 1-10 g 1-10 g 5t-15 3-5 g These include (235U, Th) carbide fuel beads con- taining highly enriched uranium and a speci- men of 93% 235U.Both samples will be characterised for uranium. Depleted uranium Characterised for- 242Pu atoms per g or per vial 244Pu atoms per g or per vial 233U atoms per g or per vial Isotope ratios Isotopic composition Isotope ratios 230Th atoms per g or per vial Isotopic composition Isotopic composition Isotopic composition Isotopic composition, purity Isotopic composition Isotopic composition U and Pu element content, isotopic composition O/M = 1.98 Pu element content, isotopic composition Th element content U element content, U isotopic composition, Th element content U element content, isotopic composition, C element content O/M ratio, U element content, Gd element content, U isotopic composition U element content U element content, U isotopic composition U or Pu element content, U or Pu isotopic composition 245 Supplier NBS, CBNM NBS ? CBNM CBNM, NBS, CENG Grenoble CBNM, NBL, CEA NBS (on absolute basis), CBNM (on absolute basis) CBNM CBNM, NBS CBN", NBS, BNFL, Capenhurst Cogema, Pierrelatte NBS NB S NBS NBS CBNM CEA, NBL - NBS, CBNM - TU US, UK, FKG collectively BNFL Windscale, CBNM-NBS collectively NBS* NUKEM, KFA-Karlsruhe CBNM, AERE-TU RBU (supplier), USA-KFK (characterisation) BNFL, Springfields CBNM CBNM metals characterised for assay and isotopic composition will also be made available.At CBNM, Gee1 (Euratom), the following reference materials have recentlv been me-246 CHEMICAL AND ISOTOPIC REFERENCE MATERIALS Proc.AnaZyt. Div. Chem. SOC. pared or will shortly be made available: heavy water (99.7% D,O) ; 233U and 242Pu (in ampoules, certified for number of atoms); 244P~ (pending provision of material by the US); UF, (up to an enrichment of 5% 235U); and packaged uranium oxide for calibration of non-destruc- tive analytical procedures (joint project with NBS and NBL). Homogeneous alloys can also be made according to customer specifications by levitation melting.The Commissariat A 1’Energie Atomique (CEA) plans to prepare a 2-3 kg batch of mixed oxide pellets, which will be characterised for Pu assay, U to Pu ratio, U and Pu isotopic contents and ten metallic impurities at a level of about 100 p.p.m.each. The participants from France did not expect any additional new reference materials to be made available in the near future. However, samples listed in the CEA catalogue (Echantillons de Reference, CEA, November 1975), will be replenished as supplies diminish. The representative of the United Kingdom stated that his country had no official pro- gramme for the preparation of reference materials.However, some working materials at present being used in various UK labora- tories could be transferred for certification and distribution to recognised suppliers. These materials include natural uranium metal, sintered UO,, UF, (with 0.3% natural, and 93% 235U enrichment) and high-purity PuO, with O/M = 2.000. General Recommendations to the Agency The participants agreed that the Agency would meet an important responsibility by providing the following services to Member States.(a) Within statutory limitations, to arrange for ready transfer among them of reference materials to be used for chemical and isotopic analyses of nuclear materials, as legal and administrative rules often render such trans- fers complicated and time-consuming. (b) Review on a regular basis their require- ments (kinds and amounts) for reference mate- rials, collect information from them concerning their activities in relation to the production and characterisation of such materials, and convene at suitable intervals an Advisory Group to assess the status of, and priority needs for, reference materials identified in these in- quiries. (c) Encourage them to provide, characterise and distribute reference materials to fulfil the identified requirements.(d) Promote the periodic publication of an updated edition of the existing Euratom compilation (‘‘Catalogue of Reference Materials of Interest to Nuclear Energy,” Report No. EUR 5229e, Central Bureau for Nuclear Measurements, Geel, Belgium, 1974), listing available reference materials, their cost and mechanisms for procurement.This updating procedure should be carried out in collaboration with CBNM personnel, and the information supplied to IS0 for inclusion in its compilation of reference materials. ( e ) Examine the possibility of more efficiently utilising existing inter-laboratory measurement evaluation programmes. Several organisations (NBL, CBNM and NBS) have offered assistance in supplying and/or characterising material for use in these programmes.Specific Recommendations to the Agency The Advisory Group recommended that several actions should be taken by the Agency. Details of those recommendations are as follows. (a) The continuous production and guaran- teed supply of those enriched isotopes which are of fundamental importance to the pre- paration of reference materials should be en- couraged.It was stated that definite and substantial steps would have to be taken by the Agency to help overcome delivery difficulties, for example, export restrictions or trans- portation limitations. (b) A practical solution of the problems associated with the disposal of wastes con- taining fissile materials resulting from veri- fication measurements should be negotiated with Member States.(c) Participants stressed at some length the great importance of accurate measurements of plutonium and uranium in dissolver solutions of spent fuel from reprocessing plants. It was recommended that substantial support be given to the development and application of suitable in situ spiking techniques to be used on, preferably, undiluted dissolver solutions, even if this required a relatively high consumption of separated isotopes.The supply of these isotopes, a serious problem in terms of avail- ability and cost, is a critical consideration in view of the importance of measuring and safe- guarding plutonium to the highest possible reliability at the input of reprocessing plants.It was recommended that the Agency explore the feasibilty of financing a supply of these isotopes. (d) Inter-comparison of existing national reference materials should be encouraged in order to strengthen international nuclearAugust, 1978 CHEMICAL AND ISOTOPIC REFERENCE MATERIALS 247 material measurement knowledge. Thus, for example, the existing UF, isotopic reference materials should be compared.(e) To promote the proper use of reference materials and compliance with internationally recommended norms, the Agency should organise the distribution of appropriate docu- ments related to the preparation, characteri- sation, certification, sampling and analysis of such materials. Thus, contact should be maintained with international standard writing organisations, such as ISO, BSI, ASTM and IUPAC, to ensure that the Agency information is adequately updated and that the require- ments of Member States are taken into con- sideration.It was also suggested that con- sideration be given to the possibility of utili- sing INIS for the systematisation and distri- bution of information on written standards in co-operation with NBS and organisations such as ISO.ASTM and BSI. Specific Recommendations to Member States The Advisory Group directed some specific recommendations to the Member States of the Agency. (a) Acceptance of a reference material and its use should be based exclusively on the demonstrated high quality of its preparation and characterisation, and not on consensus. (b) Certificates of analysis should have some uniformity and should be more detailed than they usually are.The IS0 representative at the meeting provided a list of items that should be included in such certificates and, following discussion, the following desiderata were re- commended for uranium and plutonium con- taining materials : (i) name and address of certifying organis- ation ; (ii) identification of personnel and organi- sations involved in the preparation and characterisation of the reference material, to whom technical inquiries can be addressed ; (iii) name and batch identification code; (iv) date of issue; (v) source of material and a discussion of its preparation, if appropriate : (vi) measurement methods used for charac- terisation ; (vii) values for certified components, addi- tional values for non-certified components, if appropriate, and discussion of factors affecting the accuracy of the measurement methods employed ; (viii) uncertainties associated with the certified values, including details on the statistical treatment used to establish those uncertainties ; (ix) information specifying proper use of the material, limiting conditions beyond which certified values no longer apply and, if appropriate, the minimum amount required to assure homogeneity : (x) information on stability, and an expiration date for the validity of the certi- fied values, if appropriate ; (xi) with plutonium reference materials, the decreasing plutonium assay value, in- creasing uranium content, changing pluton- ium isotopic values, and increasing ameri- cium-241 content should be given as a function of time, as appropriate: ( x i i ) literature references should be cited in which more detailed information about the preparation, characterisation, and statistical data treatment of the material can be found.( c ) Whenever possible, existing reference materials intended for either fissionable isotope or element assay should be certified for both measurements.(d) Half-lives of the plutonium isotopes should be determined as accurately as possible as these data have a crucial bearing on accurate element and isotope assay as well as on plutonium accountancy. ( e ) There is a need for continuous inter- laboratory measurement evaluation program- mes for fissionable element and isotope assay. Such programmes should : ( i ) demonstrate the inter-laboratory spread of measurement results ; (ii) give participating laboratories the opportunity to judge their performances relative to other laboratories ; (iii) use materials that have carefully characterised assay and isotope values so that accuracy can be assessed ; (iv) employ coded participation (code identity should only be disclosed with the consent of the laboratory concerned and on a case-to-case basis) ; Several of the recommendations directed specifically to the Agency Secretariat are being actively implemented. A follow-up Advisory Group meeting will be held in 1980. P. A. G. O’Hare Department of Research and Isotopes, International A tomic Energy Agency, Kavntner Ring 11, A-1011 Vienna, Azsstvia (v) have voluntary participation.

ISSN:0306-1396    

DOI:10.1039/AD9781500244

出版商:RSC    

年代:1978

数据来源: RSC

摘要:

248 ANALYTICAL CHEMISTRY IN UK UNIVERSITIES Proc. AaaZyt. Div. Chenz. SOC. Analytical Chemistry in UK Universities, Polytechnics and Colleges This article is the first in a series that will describe current activities in analytical chem- istry departments and sections in UK Uni- versities, Polytechnics and Colleges. It is hoped that the details that will be given of individual projects being undertaken by the various members of staff in each establishment will be of use to analytical chemists elsewhere and will help to generate contacts between workers in similar areas who may be unaware of research being carried out within their own sphere of interest.As far as possible the names of staff and their current research activities will be detailed in order to facilitate personal contacts.Several articles have been invited so far and will be published at intervals ; however, con- tributions from any departments with an interest in analytical chemistry are welcome and should be sent to the Editor, who will also be pleased to advise on the general content of the articles. Analytical Chemistry in the Queen‘s University of Belfast Queen’s University is unique in the United Kingdom for its current acceptance and regard for analytical chemistry, which is demon- strated by having an established Chair of Analytical Chemistry and an associated sub- department.There is, in addition, a, very diverse base of analytical practice, expertise and collaboration within the University. The history of analytical chemistry at Queen’s goes back to the first Professor of Chemistry, Thomas Andrews, who published several papers on analytical topics, although his major work (continuity of states, thermo- chemistry) was carried out in physical chern- istry.l His successor, Edmund Letts, was primarily interested in analytical chemistry and its applications.He was an internationally recognised authority on the pollution of rivers, estuaries and tidal waters.2 The Chair of Analytical Chemistry was the first UK personal chair of the subject (1958), established as the Inorganic and Analytical Chair (1963) and then split into two established chairs (1968), Inorganic and Analytical Chemistry.The analytical chairs were held by C. L. Wilson until his untimely death (in 1974). The four sub- departments of the Department of Chemistry function collectively in providing degree courses, service teaching and in central services.The activities of the Analytical Chemistry Sub-department (D. Thorburn Burns, Pro- fessor; G. Svehla, Reader; M. A. Leonard, Senior Lecturer; W. J . Swindall, Senior Re- search Officer; I. Jack, Research Officer) comprise undergraduate teaching, an MSc course (recognised by the SRC and the Ministry of Education NI), research and oversight of the analytical services unit.Current post- graduate student numbers are: MSc course, 3 full time, plus 5 part time; and Research, 4 full time, 14 part time research students and 1 post- doctoral fellow. Professor D. Thorburn Burns joined Queen’s in 1975 from Loughborough University. His interest in applied analytical work was started by 7 years vacation work a t BBA Ltd.under Dr. C. C. Addingley. It is encouraged and facilitated by almost daily contact with the Analytical Services Unit. Current research interests include : elemental analysis of organo- metallic compounds (with Professor F. Glock- ling, W. J. Swindall, and H. B. McKnight), HPLC of organotin compounds (with F.Glockling and M. Harriott), precision spectro- photometric assay of chrome ores (with M. E. N. Abdel Aziz), labile amino acid analysis (with E. L. S. Tolland), luminescence studies of alkaloids (with J . N. McNirlan), fluorogenic ion pair extractants (with Miss P. Hanprasop- wattana), fluorimetric determination of cerium and lanthanum in a variety of matrices, includ- ing Mourne Granites (with M.Y. Qureshi, I. Jack and J. P. Magennis), determination of phos- phorus in soils (with J . J . McAllister), atomic- absorption studies of organogermanium and organoaluminium compounds (with D. Dadgar) and separations of zirconium and hafnium (with S. Raghunathan). Interest in the origin and nature of qualitative inorganic reactions and active membership of the Midlands Association for Qualitative Analysis will shortly culminate in what is intended to be a definitive two- volume text based on the Association’s work over 25 years (Editors D.Thorburn Burns, A. Townshend, A. H. Carter and A. G. Catch- pole). Intermittent studies of historical aspects of analytical chemistry are currently centred on the European aspects of Irish Chemists’A ugust, 1978 ANALYTICAL CHEMISTRY IN UK UNIVERSITIES 249 work, typified by R.Boyle and R. Kirwan. It is hoped in the near future to undertake a systematic study of the determination of oxygen in organic and organometallic com- pounds, provided that the apparatus and necessary additional technical assistance is funded. Dr. G. Svehla came to Belfast from Budapest via Aberdeen in 1966 and since then he has been concerned with theoretical and practical aspects of catalytic analysis and electrochemical re- search, particularly in the areas of radio- frequency titration and the applications of cyclic voltammetry. He is also the Editor of the series “Wilson and Wilson’s Comprehensive Analytical Chemistry.” Dr.Svehla’s current research interests include : new catalytic methods based on Landolt reactions (with E.L. Dickson), catalytic methods based on chemiluminescence (with I. Ling), the appli- cation of potentiometric (with R. E. Gardiner and with D. J. Reid), amperometric (with J. J. Marks) and radiofrequency conductimetric (with D. J. Reid) monitoring in catalytic analysis, physico-chemical studies of analy- tically important chemiluminescent reactions (with R.J. Murphy), radiofrequency titrations in non-aqueous media (with J . McCready) and the optimisation and elimination of inter- ferences in the atomic-absorption spectro- metry of tin (with S. J . A. Hawthorne). Dr. M. A. Leonard came to Belfast in 1963 after a brief spell in the Analytical Research Group at Boots, Nottingham, prior to which he completed his PhD at Birmingham Uni- versity with Professor R.Belcher and T. S. West on the now famous reagent, alizarin fluorine blue. He has since developed and investigated in considerable detail the use of sulphonated alizarin fluorine blue. Current interests include the determination of fluoride by photometric titration and by precision colorimetry in diverse materials including aluminosilicates.The industrial influence is apparent in the interest taken in applied problems arising in the Analytical Services Unit. Future research is planned into the investigation of the potential and utilisation of high precision photometric titrations. The Analytical Services Unit (W. J. Swin- dall, Senior Research Officer plus 3 tech- nicians) deals with organic elemental and functional group analysis, thermal analysis (DTA, TG and DSC) and inorganic analysis by atomic-absorption, emission-spectrographic and wet chemical methods.The sample type provided for and the work requested from the unit varies greatly and comes from a variety of sources both within and without the University and Province, including work on EEC standard reference materials.The variety of samples serves a useful role in intitiating the development of special methods €or particular analyses, a recent problem being that of the determination of mercury in sterically hindered organosilylmercury compounds.3 Nuclear magnetic resonance and mass spec- troscopy services are provided centrally, as are a wide range of chromatographic syGtems and spectroscopic instruments for under- graduate and postgraduate student use.A number of departments, including Agri- cultural and Food Science, Biochemistry, Geology, Geography, Pharmacy, various Medical departments and the Palaeoecology Laboratory, provide their own specialised analytical services and, in certain instances, undertake appropriate analytical research. The Agriculture and Food Science Depart- ment (Professor J.R. Todd) has probably the greatest routine analysis throughput of any laboratory in the Province. The department has a dual role in that as well as research it provides analytical services for the advisory and statutory activities of the Department of Agriculture for Northern Ireland. It analyses annually some 12 000-15 000 soil samples, 2 000-3 000 forages and feedingstuffs, 80 000- 90 000 milk samples for advisory purposes and also 3 000-4 000 samples of dairy products on behalf of the EEC Intervention Board for Agricultural Produce.Current analytical re- search (Professor J. R. Todd and G. Benions) is concerned with method development for the application of an argon plasma emission echelle spectrometer to the analysis of inorganic constituents of soil extracts and plant materials.The Department of Geology have recently acquired an energy dispersive analyser for their Geoscan electron probe microanalysis system, which has been found to be 20-30 times faster than the wavelength dispersive system for major elements. The above, plus an XRF PW1410 system and X-ray powder facilities, are used to determine a large range of trace and major elements in rocks and single crystals and for compositional mapping of a variety of single crystals.The Department of Biochemistry uses radio- immunoassays and immunoaffinity chromato- graphy extensively in the study of, for example, glucagon, secretin and their precursors in the gastrointestinal tract and have developed the first satisfactory radioimmunoassay for secretin and for the blood-clotting protein, factor X (Professor D.T. Elmore and R. F.250 AD DISTINGUISHED SERVICE AWARD Proc. Analyt. Din. Cdzem. SOC. Murphy). Enzyme immunoassays are being developed for a variety of biologically active molecules, including proteins, specific anti- bodies, viruses and drugs. The emphasis is on novel labelling and assay techniques and it is hoped to develop systems for animal viruses that can be conducted in the field (G.B. Wisdom). One of the most significant advances in radiocarbon dating as an absolute technique has been the improvements in the liquid scintillation counting of 14C,H, carried out in the Palaeoecology Laboratory (G. W. Pearson) . 4 Over-all experimental precisions are better than f25 years standard deviation.Cali- bration of 1000 years of the radiocarbon time- scale using dendrochronologically dated Irish sub-fossil oaks gave an apparently normal distribution around a linear regression line “reducing” the previous ambiguity of cali- brated radiocarbon dates over the period investigated. Future work will be to extend the 14C calibration graph and compare results with other timescales, such as Palaeomagnetic and the Egyptian historical timescale.Earlier analytical chemistry in these Islands owes much to the contribution of chemists of Ireland,2 such as R. Boyle, R. Kirwan, W. N. Hartley, etc. It is hoped that this brief survey indicates the present breadth and the continually developing tradition in analytical chemistry a t The Queen’s University of Belfast. References 1. Tait, P. G., and Crum Brown, A., “The Scientific Papers of the late Thomas Andrews, MD, FRS, with a Memoir, Macmillan, London, 1889. 2. Thorburn Burns, D., Proc. Analyt. Div. Chem. Soc., 1977, 14, 171. 3. Thorburn Burns, D., Glockling, F., Mahale, V. B., and Swindall, W. J., Analyst, 1978, 103, 985. 4. Pearson, G. W., Pilcher, J. R., Baillie, M. G. L., and Hillam, J., Nature, Lond., 1977, 270, 25. D. Thorburn Burns Department of Analytical Chemistry, Queen’s University of Belfast, Belfast, B T 9 5AG, Northern Ireland

ISSN:0306-1396    

DOI:10.1039/AD9781500248

出版商:RSC    

年代:1978

数据来源: RSC

摘要:

250 AD DISTINGUISHED SERVICE AWARD Proc. Analyt. Din. Cdzem. SOC. Conferences and Meetings Safety Aspects of Instrumentation September 20 and 21, 1978, London A conference with the above title is to be held a t the City University. It is designed to be of interest to commercial producers of instruments, to those responsible for the specification and purchasing of such equipment, and to Safety Officers and Safety Representatives in academic and industrial establishments. The programme will include discussions on the safety aspects of instrument design and servicing (both commercial equipment and that designed and built “in-house”), ergonomics, machine guarding, and hazards of equipment in use. In addition, two important features will be discussions on standardisation and legal implications.A detailed programme will be available soon and should be requested from Beverly Humphrey, Scientific Symposia Ltd., 33/35 Bowling Green Lane, London, EClR ODA.August, 1978 CONFERENCES AND MEETINGS 251 The Use of Microchemistry in the Bristol Area Septevtzbev 21 and 22, 1978, Byistol This meeting, the programme for which is given in the Analytical Division Diary on page 252, will be held in the Chemistry Department, University of Bristol. The meeting will cover a wide range of analytical techniques and is expected to be of interest not only to the general analyst, but also to the student of analytical chemistry, who will be able to see how the various techniques are used in practice.Further details, including a registration form, are in the Groups' Bulletin or can be obtained from the Honorary Secretary of the Micro- chemical Methods Group, Mr.P. R. W. Baker, Chemical Research Laboratory, Wellcome Re- search Laboratories, Langley Court, Beckenham, Kent, BR3 3BS. 1979 Pittsburgh Conference Mavch 5-9, 1979, Cleveland, Ohio, USA The 1979 Conference will be held a t the Cleve- land Convention Center.A number of symposia have already been organised but papers can be submitted on all aspects of analytical chemistry and applied spectroscopy. Authors wishing to submit a paper should send a 300-word abstract, with the name of the author who will present the paper underlined and a signature and date in verification of the fact that the material in the paper has not been published or presented previously, to Mrs.Linda Briggs, 1979 Pitts- burgh Conference, 437 Donald Road, Pittsburgh, Pa. 15235, USA. Colloquium Spectroscopicurn Internationale XXI July 1-6, 1979, Canzbvidge The XXI CSI, which includes the 8th Inter- national Conference on Atomic Spectroscopy, will be organised by the' Association of British Spectroscopists. The scientific programme will encompass all branches of spectroscopy with particular emphasis on the theme of analytical spectroscopy.There will be 1-, 2- and 3-day symposia devoted to particular areas and specific applications of spectroscopy. Each symposium will open with an invited lecture on a topic of special significance by an inter- nationally recognised speaker. Poster sessions will also be featured a t the Conference. Papers describing original work are invited and intending authors should submit the title of their contribution and an abstract of 50 words to the Secretariat by September 4, 1978, in the language of presentation. Authors of accepted papers will receive special typing paper on which to submit a 300-word extended abstract in English, French or German for publication in the Official Conference Book of Abstracts. For further details of the Conference contact the Association of British Spectroscopists, P.O. Box 109, Cambridge, CB1 2HY.

ISSN:0306-1396    

DOI:10.1039/AD978150250b

出版商:RSC    

年代:1978

数据来源: RSC

摘要:

August, 1978 CONFERENCES AND MEETINGS 251 Courses Industrial Water Management September 17-24, 1978, Loughborough This course reviews the spectrum of industrial operations involving water supply, treatment and use, and the disposal of effluent, to examine how effective cost reductions can be made. For further details write to the Centre for Extension Studies, University of Technology, Loughborough, Leicestershire, LE 11 3TU.EDT Optoacoustic Spectroscopy Seminars September 18-22 In response to the demand for information about optoacoustic spectroscopy, following the recent introduction of the Model OAS 400 optoacoustic spectrometer, EDT Research is organising a series of seminars on the subject throughout the UK. These seminars will each be half-day meetings, designed to introduce the technique and describe its applications.The precise venues have still to be decided; they will depend upon where the most interest lies. The Model OAS 400 will be demonstrated at each seminar and those attending will be invited to bring samples to the seminars. Persons interested in attending should con- tact EDT at 14 Trading Estate Road, London, NWlO 7LU, suggesting a suitable date and venue. Disposal of Chemical Wastes September 24-26, 1978, Loughborough This course will look at the problems and the techniques available for disposal of chemical wastes in the light of current UK legislation and EEC regulations. Waste as a source of raw material for recovery and re-use will also be considered. For further details write to the Centre for Extension Studies, University of Technology, Loughborough, Leicestershire, LE11 3TU.

ISSN:0306-1396    

DOI:10.1039/AD9781500251

出版商:RSC    

年代:1978

数据来源: RSC