Encyclopedia of Analytical Science [10 Volumes, analytical chemistry]

5276 Pages·2004·115.64 MB·English

by  Worsfold

Editors
Paul Worsfold, University of Plymouth, Plymouth, UK
Alan Townshend, University of Hull, Hull, UK
Colin Poole, Wayne State University, Detroit, MI, USA
Editorial Advisory Board
Freddy Adams, University of Antwerp, Antwerp, Belgium
Jonathan W Aylott, University of Hull, Hull, UK
Damia Barcelo, Institut d’ Investigacions Qu!ımiques i Ambientals de Barcelona, Consejo Superior de
Investigaciones Cient!ıficas, Barcelona, Spain
Alan M Bond, Monash University, Melbourne, VIC, Australia
Chris Burgess, Burgess Consultancy Co., Durham, UK
Marcela Burguera, Universidad de los Andes, Merida, Venezuela
John Chalmers, VS Consulting, Stokesley, UK
Richard Dams, Instituut voor Nucleaire Wetenschappen (INW), Gent, Belgium
Cees Gooijer, Free University, Amsterdam, The Netherlands
John D Green, Beverley, UK
Elo H Hansen, Technical University of Denmark, Lyngby, Denmark
Steve J Hill, University of Plymouth, Plymouth, UK
Jerry W King, Los Alamos National Laboratory, Los Alamos, NM, USA
Larry J Kricka, Medicine Centre University of Pennsylvania, Philadelphia, PA, USA
Maria D Luque de Castro, Universidad de Co´rdoba, Co´rdoba, Spain
Pierre Margot, Universite´de Lausanne, Lausanne, Switzerland
Philip J Marriott, RMIT University, Melbourne, VIC, Australia
Ian D McKelvie, Monash University, Melbourne, VIC, Australia
Veronika R Meyer, EMPA St Gallen, St Gallen, Switzerland
Heinrich H D Meyer, Institut fur Physiology, Munchen, Germany
Jim N Miller, Loughborough University of Technology, Loughborough, UK
Pavel N Nesterenko, Lomonosov Moscow State University, Moscow, Russia
Reinhard Niessner, Technische Universitat Munchen, Munchen, Germany
Matthias Otto, Institute for Analytical Chemistry, Freiberg, Germany
Pier G Righetti, University of Verona, Verona, Italy
Alfredo Sanz-Medel, University of Oviedo, Oviedo, Spain
Malcolm R Smyth, Dublin City University, Dublin, Republic of Ireland
Robert E Synovec, University of Washington, Seattle, WA, USA
Peter C Uden, University of Massachusetts at Amherst, Amherst, MA, USA
Miguel Valca´rcel, Universidad de Co´rdoba, Co´rdoba, Spain
Wolfhard Wegscheider, University of Leoben, Leoben, Austria
Ian D Wilson, Astra Zeneca Pharmaceuticals, Macclesfield, UK
Otto S Wolfbeis, University of Regensburg, Regensburg, Germany
Elias Zagatto, Universidade de Sa˜o Paulo, Piracicaba, Brazil
Yury Zolotov, USSR Academy of Sciences, Moscow, Russia
PREFACE ix
Preface
Analyticalscienceimpactsonallaspectsoflifeinthetwenty-firstcentury.Reliable,high-qualityanalyticaldata
are essential prerequisites for monitoring health (and disease), for enhancing the efficiency of industrial
processes, improving product quality and reducing emissions, and for studying complex biogeochemical
interactionsintheenvironment.Newanalyticaltechniquesandmethodsarekeydriversforadvancesindrug
discovery, forensic science, and life sciences, for monitoring the quality of foodstuffs, pharmaceuticals, and
other consumer products, for furthering our understanding of environmental processes, and for monitoring
compliancewithlegislation.
Themeansbywhichanalysesareachievedvariesfromsimplecolortestsforthequalitativeidentificationof
anions and cations through to complex and expensive computer-controlled instrumentation for quantitative
determination of trace amountsof a single organic compound or element in a complex matrix. Increasingly,
such instrumentation is a hybrid of techniques for separation and detection that requires extensive data
processing.SowidehasthesubjectofAnalyticalSciencebecomethatcompletecoverage,providinginformation
thatiscomprehensibletoaninterestedscientist,canonlybeachievedinamulti-volumeencyclopediasuchas
this.Eventhen,thelengthofeachoftheapproximately550articlesneedstobelimitedinordertokeepthesizeof
theencyclopediamanageable.
Theencyclopediacoversallfacetsofmodernanalyticalscience,witharticlesfromaninternationalauthorship
of experts in their specialist fields. The articles cover three broad areas: analytical techniques (e.g., mass
spectrometry,liquidchromatography,atomicspectrometry);areasofapplication(e.g.,forensic,environmental,
clinical);andanalytes(e.g.,arsenic,nucleicacids,polycyclicaromatichydrocarbons).TheauthorsandEditorial
AdvisoryBoardmembersaredrawnfromallcontinentsandwearegratefultothegreatmajoritywhomettheir
deadlines.
TheboundariesofAnalyticalSciencesareconstantlypushingintonewareasandwehavetakenabroadview
ofwhatmaterialshouldbeincluded.Comprehensiveindexingandcross-referencingareimportantfeaturesthat
shouldallowrapidaccesstorelevantinformationforusersoftheencyclopedia.
Thefirsteditionofthisencyclopedia,publishedin1995,wastheinspirationofRobertMacrae.Followingthe
successoftheEncyclopediaofFoodScience,FoodTechnologyandNutrition,ofwhichhewasaleadingeditor,
herealizedhowvaluableasimilarEncyclopediaofAnalyticalSciencewouldbe.Dr.Macraeservedasmanaging
editorofthefirsteditionuntilhisunexpecteddeathinNovember1993.Withouthimthisencyclopediawould
neverevenhavebegun.
PaulWorsfold,AlanTownshendandColinPoole
INTRODUCTION xi
Introduction
Itisincreasinglyappreciatedthatknowledgeofthenatureandcompositionofmaterialsgivesagreatercontrol
of their properties. As the range of materials becomes more diverse and valuable, analytical science, which
determinesthisnatureandcomposition,alsoachievesgreaterrecognitionandattention.
Manyattemptshavebeenmadetoprovideasatisfactorydefinitionofanalyticalscience.Themostrecentis
thatproposedbytheWorkingPartyonAnalyticalChemistryoftheFederationofEuropeanChemicalSocieties
(AnalyticalChemistry(1994)66;98A–101A);itreads:
Analyticalchemistryisascientificdisciplinethatdevelopsandappliesmethods,instruments,andstrategiestoobtain
informationonthecompositionandnatureofmatterinspaceandtime.
Thus, analytical science includes within its remit not only a considerable amount of chemistry, but also an
increasing proportion of biochemistry, physics and electronics, computer science, mathematics and chemo-
metrics,andevenmanagementandeconomics.Butthesearecombinedintoadistinctareaofsciencewithitsown
philosophy,procedures,andobjectives.
Theincreasingscopeandtheimpressiverateofchangeofanalyticalscienceoverthe10yearsthathaveelapsed
sincethepublicationofthefirsteditionofthisencyclopediaarereflectedintheextensivechangesthathavebeen
made to the contents in producing this second edition. The majority of the articles are new or have been
extensivelyrewritten,andalltopicshavebeenselectedonthebasisoftheirrelevancetoanalyticalscienceatthe
beginningofthetwenty-firstcentury.NewarticlesincludeDNAsequencing,endocrinedisruptingchemicals,
‘lab-on-a-chip’ technologies, field flow fractionation, nitric oxide, prions, and solid-phase microextraction,
againgivingaflavorofthebreadthandrelevanceofmodernanalyticalscience.Inasimilarvein,subjectsnow
consideredtobelessappropriatehavenotbeenincludedinthissecondedition.
Thelargenumberofarticlesinthisencyclopediaandthewidevarietyofthesubjectmatteremphasizethe
considerablescopeofmodernanalyticalscience.Thearticlesfallmainlyintothreeclasses:
* Analysisforparticularanalytes
* Analysisofparticulartypesofsamples
* Analyticaltechniques
Particularanalytesthatarethesubjectsofarticlesintheencyclopediaincludeawiderangeofclassesoforganic
compounds(e.g.,aminoacids,dioxins,humicandfulviccompounds,lipids,nucleicacids,polycyclicaromatic
hydrocarbons,proteins)aswellasspecificcompounds(e.g.,ethanol,glucose).Thereisalsoanextensiveselection
ofcompoundshavingparticulartypesoffunction(e.g.,antioxidants,neurotoxins,pesticides,vitamins).Inorganic
elementsarenotassignedindividualarticles,exceptforthoseelementswheretheirspeciationprovidessignificant
analytical challenges (e.g., arsenic, carbon, chromium, selenium, sulfur). The concentrations at which such
analytescanbedeterminedrangefrompercentlevels,throughtraceconcentrations(mgml(cid:1)1)toultratracelevels
(ngml(cid:1)1,pgml(cid:1)1,andevenless).Suchisthesensitivityofsomemodernanalyticaltechniquesandproceduresthat
thedetectionofindividualmoleculesisnowpossibleinsomeinstances.
The types of sample that must be analyzed are numerous. They include raw materials, intermediates,
products,andeffluentsofindustrialprocesses.Analysisisessentialforcontrollingthemanufacturingprocess,
the quality of the product, and the hazards of any discharges into the environment. Articles are included,
therefore,onsuchdiverseproductsasadhesives,buildingmaterials,ceramics,glasses,andpaints,aswellason
processanalysisperse.Thereisasectiononfoodanalysisandonpharmaceuticalcompounds.Othergroupsof
materialsthatarethesubjectofmanyarticlesareclinicalsamplesandforensicspecimens.Specificmaterialsthat
meritindividualarticlesincludeblood,coal,fertilizers,andmeat.Particularimportanceisplacedonthemeans
of obtaining representative samples, and the processes to which they may be subjected before the analytical
measurementismade.Equally,thequalityoftheanalyticalprocessisamatterthatisdealtwithinsomedepth,
includingstandards,traceability,accreditation,andinterlaboratorystudies.
A considerable proportion of the encyclopedia is dedicated to descriptions of techniques and to the wide
range of applications for which they are used. These include the instrumentation available for making the
analytical measurement, for example, atomic absorption and emission spectrometry, chromatography and
xii INTRODUCTION
electrophoresis,fluorimetry,massspectrometry,nuclearmagneticresonancespectroscopy,X-rayfluorescence
spectrometry,andthevarioussurfaceanalysistechniques.Othertechniquesofgreatutilityaredescribed,suchas
immunoassays,amplificationreactions(includingthepolymerasechainreaction),andradiochemicalmethods.
Withsuchadiversityoftopics,someoverlapbetweenarticlesisinevitableand,indeed,desirable.Eacharticle
isintendedtobeself-contained,butextensivecross-referencesareincludedtoenablefurtherinformationon
particulartopicstobefoundelsewhereintheencyclopedia.Eveninarticleswheretheremight,atfirstsight,
scopeforduplication,itwillbeseenthateacharticlehasitsowndistinctperspective.Forexample,thereare
articlesonethanol,onforensicsciences,determinationofalcoholinbodyfluids,andonfoodandnutritional
analysis,alcoholicbeverages,butitcanreadilybeseenthattheemphasisineacharticleisverydifferent.
Aglanceatthetableofcontents,involume10,willshowthatsometopicsmeritalargenumberofarticles,a
reflectionoftheirimportanceincurrentanalyticalscience.Severaltechniques,forexample,massspectrometry,
nuclear magnetic resonance spectroscopy, atomic emission spectrometry, microscopy, the various chro-
matographictechniques(e.g.,gas,liquidandthin-layer),andelectrophoresis,meritaseriesofarticles, asdo
areassuchasfoodandnutritionalanalysis,forensicsciences,archaeometry,pharmaceuticalanalysis,sensors,
andsurfaceanalysis.Eachofthesecollectionsofarticles,writtenbyexpertsintheirfields,providesatleastas
muchup-to-dateinformationonthatparticularsubjectasacompletetextbook.
Inconclusion,thisencyclopediaprovidesdetailedinformationbyacknowledgedexpertsonmostaspectsof
modern analytical science. It is designed to be easy to access and, if further information is required,
bibliographies are provided. The grouping of subjects and the cross-referencing should emphasize both the
varietyandtheunityofanalyticalscience;thatthereisathreadthatlinkswhatatfirstsightareverydiverse
topics,butwhichinfactdemandacommonphilosophy.This‘analyticalapproach’iswhattheencyclopedia
isallabout.
PaulWorsfold,AlanTownshendandColinPoole
Dedication
The original idea for the Encyclopedia of Analytical Science came from Dr. Robert Macrae, who played a
large part in its realization of the first edition, and scientific editor, until his sudden, untimely death in
November 1993. This work is dedicated to him; we hope that it will serve as a lasting memorial to his
enthusiasm for publishing, and commitment to scientific endeavor.
Disclaimer
This encyclopedia is a guide providing general information concerning its subject matter; it is not a
procedural manual. The readers should consult current procedural manuals for state-of-the-art instructions
andapplicablegovernmentsafetyregulations.Thepublisherandtheauthorsdonotacceptresponsibilityfor
any misuse of this encyclopedia, including its use as a procedural manual or as a source of specific
instructions.
Permission Acknowledgments
The following material is reproduced with kind permission of the American Association for the
Advancement of Science
Figure 6 of LIQUID CHROMATOGRAPHY | Chiral Analysis of Amino Acids
http://www.sciencemag.org
The following material is reproduced with kind permission of Oxford University Press
Figure 2 of DNA SEQUENCING
Figure 1 of ELECTRON SPIN RESONANCE SPECTROSCOPY | Principles and Instrumentation
Table 1 of ELECTROPHORESIS | Principles
Figures 1, 2, and 5 of MICROSCOPY | Overview
Figure 2 of SPECTROPHOTOMETRY | Biochemical Applications
http://www.oup.com
A
ACCREDITATION
See QUALITY ASSURANCE: Accreditation
ACID–BASE INDICATORS
See INDICATORS: Acid–Base
ACID–BASE TITRATION
See TITRIMETRY: Overview;Potentiometric; Photometric
ACTIVATION ANALYSIS
Contents
Neutron Activation
Charged-Particle Activation
Photon Activation
activity, and there from the concentration of the ele-
Neutron Activation
ment in the sample. Although access to a reactor is
requiredfortheirradiation,thesamplesmaythenbe
SJ Parry,Imperial Collegeof London,Ascot,UK transferred to another laboratory for analysis, in
&2005,ElsevierLtd.AllRightsReserved. contrast to prompt activation where analysis is car-
ried out while the sample is being irradiated. The
Thisarticleisreproducedfromthepreviousedition,pp.8–16,
advantages of the technique over other multielement
&1995,ElsevierLtd.
methodsfortraceelementsarethat:(1)solidscanbe
analyzed without any sample dissolution, and con-
sequently the method is particularly useful for the
Introduction
analysis of insoluble materials like plastics, carbon
Neutron activation analysis is a powerful nonde- fiber, and boron compounds, and in the determina-
structive multielement technique that can be applied tion of volatile elements that may be lost on disso-
to the determination of over 60 elements in a broad lution, such as arsenic, selenium, and mercury; (2)
rangeofmatrices.Themethodinvolvesactivationof extremely low detection limits may be attained,
thesampleinasourceofneutronsfollowedbyg-ray for example, the detection limit for gold in a 10g
spectrometry to identify and quantify the induced sample of silicon is 6pg perg; and (3) the method is