Encyclopedia of Analytical Science.pdf

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 Quımiques i Ambientals de Barcelona, Consejo Superior de

Investigaciones Cientıﬁcas, 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

Analytical science impacts on all aspects of life in the twenty-ﬁrst century. Reliable, high-quality analytical data

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

interactions in the environment. New analytical techniques and methods are key drivers for advances in drug

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

compliance with legislation.

The means by which analyses are achieved varies from simple color tests for the qualitative identiﬁcation of

anions and cations through to complex and expensive computer-controlled instrumentation for quantitative

determination of trace amounts of 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. Sowide has the subject of Analytical Science become that complete coverage, providing information

that is comprehensible to an interested scientist, can only be achieved in a multi-volume encyclopedia such as

this. Even then, the length of each of the approximately 550 articles needs to be limited in order to keep the size of

the encyclopedia manageable.

The encyclopedia covers all facets of modern analytical science, with articles froman international authorship

of experts in their specialist ﬁelds. The articles cover three broad areas: analytical techniques (e.g., mass

spectrometry, liquid chromatography, atomic spectrometry); areas of application (e.g., forensic, environmental,

clinical); and analytes (e.g., arsenic, nucleic acids, polycyclic aromatic hydrocarbons). The authors and Editorial

Advisory Board members are drawn from all continents and we are grateful to the great majority who met their

deadlines.

The boundaries of Analytical Sciences are constantly pushing into new areas and we have taken a broad view

of what material should be included. Comprehensive indexing and cross-referencing are important features that

should allow rapid access to relevant information for users of the encyclopedia.

The ﬁrst edition of this encyclopedia, published in 1995, was the inspiration of Robert Macrae. Following the

success of the Encyclopedia of Food Science, Food Technology and Nutrition, of which he was a leading editor,

he realized how valuable a similar Encyclopedia of Analytical Science would be. Dr. Macrae served as managing

editor of the ﬁrst edition until his unexpected death in November 1993. Without him this encyclopedia would

never even have begun.

Paul Worsfold, Alan Townshend and Colin Poole

INTRODUCTION xi

Introduction

It is increasingly appreciated that knowledge of the nature and composition of materials gives a greater control

of their properties. As the range of materials becomes more diverse and valuable, analytical science, which

determines this nature and composition, also achieves greater recognition and attention.

Many attempts have been made to provide a satisfactory definition of analytical science. The most recent is

that proposed by the Working Party on Analytical Chemistry of the Federation of European Chemical Societies

( Analytical Chemistry (1994) 66; 98A–101A); it reads:

Analytical chemistry is a scientific discipline that develops and applies methods, instruments, and strategies to obtain

information on the composition and nature of matter in space and time.

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, and evenmanagement and economics. But these are combined into a distinct area of sciencewith its own

philosophy, procedures, and objectives.

The increasing scope and the impressive rate of change of analytical science over the 10 years that have elapsed

since the publication of the ﬁrst edition of this encyclopedia are reﬂected in the extensive changes that have been

made to the contents in producing this second edition. The majority of the articles are new or have been

extensively rewritten, and all topics have been selected on the basis of their relevance to analytical science at the

beginning of the twenty-ﬁrst century. New articles include DNA sequencing, endocrine disrupting chemicals,

‘lab-on-a-chip’ technologies, ﬁeld ﬂow fractionation, nitric oxide, prions, and solid-phase microextraction,

again giving a ﬂavor of the breadth and relevance of modern analytical science. In a similar vein, subjects now

considered to be less appropriate have not been included in this second edition.

The large number of articles in this encyclopedia and the wide variety of the subject matter emphasize the

considerable scope of modern analytical science. The articles fall mainly into three classes:

* Analysis for particular analytes

* Analysis of particular types of samples

* Analytical techniques

Particular analytes that are the subjects of articles in the encyclopedia include a wide range of classes of organic

compounds (e.g., amino acids, dioxins, humic and fulvic compounds, lipids, nucleic acids, polycyclic aromatic

hydrocarbons, proteins) as well as specific compounds (e.g., ethanol, glucose). There is also an extensive selection

of compounds having particular types of function (e.g., antioxidants, neurotoxins, pesticides, vitamins). Inorganic

elements are not assigned individual articles, except for those elements where their speciation provides signiﬁcant

analytical challenges (e.g., arsenic, carbon, chromium, selenium, sulfur). The concentrations at which such

analytes can be determined range from per cent levels, through trace concentrations (mgml 1 ) to ultratrace levels

(ngml 1 ,pgml 1 , and even less). Such is the sensitivityof somemodern analytical techniques andprocedures that

the detection of individual molecules is now possible in some instances.

The types of sample that must be analyzed are numerous. They include raw materials, intermediates,

products, and efﬂuents of industrial processes. Analysis is essential for controlling the manufacturing process,

the quality of the product, and the hazards of any discharges into the environment. Articles are included,

therefore, on such diverse products as adhesives, building materials, ceramics, glasses, and paints, as well as on

process analysis per se. There is a section on food analysis and on pharmaceutical compounds. Other groups of

materials that are the subject of many articles are clinical samples and forensic specimens. Specific materials that

merit individual articles include blood, coal, fertilizers, and meat. Particular importance is placed on the means

of obtaining representative samples, and the processes to which they may be subjected before the analytical

measurement is made. Equally, the quality of the analytical process is a matter that is dealt with in some depth,

including standards, traceability, accreditation, and interlaboratory studies.

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

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