8N JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY FEBRUARY 1993 VOL. 8 Book Reviews ~~ Statistics in Spectroscopy Howard Mark and Gerry Workman. Pp. xiii + 3 13. Academic Press. 199 1. Price E54.40. ISBN 0 12 472530 9. This slim volume is really a collection of the short articles that were origi- nally published in ‘Spectroscopy’. Their compilation in one volume has the advantage of convenience for ref- erence but several drawbacks. The 38 chapters in 3 13 pages corresponding to the original articles do not make a logical division of the subject matter. For example the division of Chapter 30 ‘Pitfalls of statistics,’ from Chapter 3 1 ‘Pitfalls of statistics continued’ is unhelpful and generally leads to un- necessary repetition. The writing style is very colloquial which can work well in a single article but does tend to pall when chapters are read consecutively as a book.The description of the statistical methods is generally good assuming little prior knowledge of statistics. In the latter chapters however this does tend to grate when that knowledge has already been covered in a previous chapter. Referencing between chapters is generally poor. For example h e a r regression is described in one chapter but the critically important tests for whether the regression parameters are statistically significant are not dis- cussed in that chapter. The reader is told only that they will be discussed ‘in a later chapter’ unspecified. There is a wide coverage of the traditional statis- tical techniques for univariate and bivariate measurements.Multivariate techniques such as the increasingly popular principal component analysis are not covered; nor are the non- parametric techniques. Overall the book will be useful to suggest as a second alternative to the standard texts such as Miller and Miller (1988 Ellis Horwood). The informal style may help to clarify the techniques to some readers. It is how- ever unlikely to become a classic reference work in the field of statistics for the analytical chemist. Michael H. Ramsey Department of Geology Imperial College London SW7 ZBP UK Handbook of Inductively Coupled Plasma Mass Spectrometry Edited by K. E. Jarvis A. L. Gray and R. S. Houk. Pp. xi + 380. Blackie. 1991. Price €72. ISBN 0 216 92912 1; USA 0 412 02501 9. This book is presented as a handbook of inductively coupled plasma mass spectrometry (ICP-MS) and in all re- spects fulfills that function. The book is divided into 11 chapters each deal- ing with a specific aspect of the instru- mentation or applications.Chapter 1 covers the origin and development of the technique and two of the principal authors (A.L.G. and R.S.H.) were based at the two laboratories where the first experi- mental ICP mass spectrometers were built. Both have therefore been in- volved with ICP-MS since its incep- tion and are the best qualified persons to review the origins and development of ICP-MS. The chapter gives a brief description of the development which will provide the newcomer with an insight into the early period of ICP- MS and because of the comprehensive references provided allow the inter- ested reader to find more detailed descriptions if necessary.Chapter 2 covers the instrumenta- tion available for ICP-MS. Each com- ponent is described in detail providing information about its function and optimization. The variations available from the principal commercial manu- facturers are described and the merits of each evaluated. There is no bias in the description of these options. This chapter is excellent and will help to overcome the ‘black box’ approach toJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY FEBRUARY 1993 VOL. 8 9N such sophisticated analytical instru- mentation. Chapter 3 contributed by J. G. Williams covers the field of instru- ment options. This chapter forms a complement to Chapter 2 and de- scribes the component parts which in solution introduction mode can either be modified or a number of options are available.The components covered are nebulizers; spray chambers; torches and the interface. The descrip- tion of nebulizers deals with concen- tric cross-flow Babington frit and ultrasonic types. In the sub-section on the function of the spray chamber wash-out times and thermal stability are described. Torch types and the interface are explained although the new micro-skimmer system used in VG instruments is not described. Chapter 4 contributed by J. G. Williams covers sample introduction for liquids and gases. This is a long and comprehensive chapter which deals with liquid other than by nebuliza- tion and gaseous sample introduction. The chapter again covers the main options available from instrument manufacturers as well as several ‘home-made’ modifications.In Chap- ter 4 the emphasis changes to illus- tration by reference to analytical applications showing how analytical requirements have driven the develop- ment of these additional sampling techniques. Electrothermal vaporiza- tion (ETV) is explained and illustrated by reference to geological bio-medical and environmental examples. Vapour generation for hydrides together with volatile mercury OsO and reactive gases is presented and illustrated with examples. The section on liquid chro- matography (LC) contains a useful table summarizing the range of appli- cations of LC-ICP-MS. Flow injection is described and its advantages enume- rated followed by a short section on applications.Finally the direct sample insertion method is briefly covered. The references given throughout are comprehensive allowing the reader to find the key works in each of the topics covered. Chapter 5 is concerned with inter- ferences. In any handbook such a section is of vital importance. This chapter covers the subject matter in a systematic and comprehensive fashion. The interferences are divided into two types ‘spectroscopic’ and ‘non-spectroscopic’ and each type is described. The chapter makes exten- sive use of published studies many by the authors themselves to provide the reader with an understanding of the measures that must be taken to mini- mize the problems. This excellent chapter explains the theoretical con- siderations of interferences (such as oxides polyatomic species and refrac- tory formation) and offers some help in minimizing some of the problems.For both the new user and the experi- enced operator reading this chapter could eliminate many costly hours of collecting useless data. Chapter 6 covers calibration and data handling. The chapter begins with a description of the different modes of data acquistion and then describes methods of calibration. The basis of the so-called ‘semi-quantitative Cali- bration’ is explained followed by a section on fully quantitative analysis. Calibration techniques and the func- tion of internal standards are de- scribed. In this section the potential problems posed by the incorrect choice of internal standards are displayed. The chapter ends with a description of the isotope dilution method including its advantages and disadvantages. Chapter 7 contributed by I.Jarvis deals with sample preparation for ICP- MS. This is a long chapter which comprehensively covers a wide range of topics. The reagents commonly used in sample preparation are reviewed and the laboratory apparatus de- scribed. Recommendations are made on the choice of both reagent and apparatus. Sample digestion is sen- sibly divided into open acid diges- tion closed acid digestion (including microwave digestion) and alkali fu- sion. Detailed methods are described for a range of sample types (plant animal geological environmental and metal) which will prove valuable to those faced with new or difficult sample types. The merits of closed digestion procedures are discussed and specific methods described.The chap- ter concludes with a section on separa- tion and preconcentration methods giving details of methods for rare earth elements precious metals and Hf Nb Ta and Zr in geological samples. Chapter 8 is concerned with elemen- tal analysis of solutions and applica- tions. This chapter complements the material presented in Chapter 7. The start of the chapter contains a table of preferred isotopes for elemental analy- sis which also gives information about interferences and sample preparation methods. A suggestion is made for a typical quantitative multi-element procedure. The chapter is sub-divided into sections dealing with different areas of application geological envi- ronmental nuclear industrial and bio- logical. Within these sections groups of elements are considered instrumental parameters listed and results obtained for reference materials given.In this section there is extensive information on potential interference problems which is useful for those planning ICP- MS applications for specific sample types. Chapter 9 contributed by J. W. McLaren deals with the analysis of natural waters by ICP-MS. Following a useful introduction section which covers some of the regulatory con- siderations for detection limits in fresh waters the author describes sampling procedures. The chapter is then divi- ded into sections on the direct an- alysis chemical separation and/or preconcentration for water analysis. Methods for the analysis of sea-water are described as well as the preconcen- tration of fresh water.In the last section calibration strategies are re- viewed. Chapter 10 covers the analysis of solid samples. This chapter deals with a wide range of methods of solid sample introduction but concentrates on two slurry nebulization and laser ablation. A brief discussion of the problems of calibration with such techniques is presented. The section on slurry nebulization deals with the important aspects of grinding tech- niques dispersing agents particle size distribution applications detection limits precision and accuracy. Two specific applications the determina- tion of chlorine and the determination of the rare earth elements are de- scribed. Results for some reference materials are presented. The section on laser ablation briefly explains the construction and operation of a laser and then covers system configuration laser operation sample preparation calibration interferences detection limits practical considerations and applications.In the laser ablation sec- tion many of the possible advantages such as the reduction of polyatomic interferences in a dry plasma and the ability to perform spatial analysis are given. The results from a number of unpublished studies are presented illustrating the potential of the laser for bulk sample analysis. Three short sections conclude the chapter covering direct sample insertion powdered solids and arc nebulization. Chapter 11 considers isotope ratio measurement. The authors review traditional methods for these deter- minations and then deal with the instrument performance of the ICP mass spectrometer.The main part of the chapter is concerned with applica- tions and methods and is divided according to the element concerned. The elements for which applications exist are arranged in ascending mass. The applications described are geo- logical bio-medical and environmen- tal. The elements described are Li B Fe Zn Rh and Os Pb and U. The chapter ends with a short section on other elements.1 ON JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY FEBRUARY 1993 VOL. 8 The handbook has three appendices. The first listing the sources of refer- ence materials cited in the text and the second tabulating the naturally occur- ring isotopes relative abundances atomic mass and first and second ionization energies. The third appen- dix is a useful glossary. The comprehensive reference sec- tion reflects the fact that the book is very well referenced throughout.This book is both comprehensive in its subject matter and logically laid out and illustrated throughout and is hard- bound. No ICP-MS laboratory should be without a copy and anyone consi- dering using an ICP-MS should con- sult this book. The book is expensive at E72.00 and as such I feel that laboratories and libraries will be able to purchase it but the price may be beyond the individual purchaser. Per- haps the publishers can be persuaded to produce a soft cover version that is more reasonably priced. W. Perkins Institute of Earth Sciences University College of Wales Aberystwyth UK Applications of Plasma Source Mass Spectrometry Edited by Grenville Holland and Andrew N.Eaton. Pp viii + 222. Royal Society of Chemistry. 1991. f37.50. ISBN 085186 566 6. This book contains 21 of the papers presented at the 2nd International Conference on Plasma Source Mass Spectrometry held at Durham in Sep- tember 1990. The contributions range widely from fundamental aspects of ion formation and transmission into the mass spectrometer to analyses of a variety of different types of sample. Three chapters deal with applica- tions of new high resolution (HR) double-focusing instruments. Tsumara and Yamaski used ultrasonic nebuliza- tion and measured directly incredibly low levels 0.5-23 pg 1-I of rare earth elements plus U and Th in terrestrial waters. Except for La and Dy they achieved excellent agreement with results obtaining using normal resolu- tion ICP-MS following copre- cipitation on Fe(OH),.Yamasaki et al. used HR-ICP-MS also with ultrasonic nebulization to measure trace ele- ments in plant Standard Reference Materials (SRMs) following mi- crowave-heated acid digestion. The result for eight elements in 10 SRMs was in agreement with the certified values but interference from Arc and from CaO and NaCl caused overesti- mates of Cr and Ni respectively. Walsh et al. used pneumatic nebuliza- tion of semiconductor grade acids and reagents for the direct analysis of trace elements at the pg g-I level. The high resolution overcame many polyatomic ion interferences e.g. from ArNH nominal mass 55 on 55Mn. The effects of plasma gas flow rates and r.f. power on the axial distribu- tions of ions and ion oxides in ICP-MS were studied by Jakubowski et al.who used a computer-controlled stepper motor to vary sampling depth in the plasma. Turner gives an excellent dis- cussion of the causes of mass-bias effects in ICP-MS and describes the use of a three aperture ion extraction system to eliminate them. Glow discharge MS is comprehen- sively reviewed by Stuewer who details ways to overcome interferences and to ensure analytical accuracy. Two papers deal with the use of laser ablation for analysis by ICP-MS. Abell used time resolved analysis to optim- ize laser energy and repetition rate and also investigated pre-ablation times and depth of focus. With optimized laser parameters excellent RSDs (1.0-2.7%) were obtained for the analysis of minor elements in steels.Denoyer found that although loose powders could be analysed directly using laser ablation the results were more accurate and precise when the samples were pelletized using either plaster cellulose or paraffin. Electrothermal vaporization (ETV) and hydride generation (HG) proce- dures for sample introduction into an r.f. plasma were evaluated by Vollkopf et al. Using ETV-ICP-MS the detec- tion limits were excellent with either single ion (1-70 fg) or multi-element (3-40 fg) modes for analysis. The RSDs for multi-element analysis at only 1 pg 1 - I were in the range 10-25%. Using HG-ICP-MS with a flow injection system detection limits of 3-15 ng 1-I were obtained for As Sb Bi Te and Hg; the detection limit for Se was 60 ng I-'. Ek et al. also used a continuous flow HG system for measuring Se in biological samples following HN03-HC104 digestion and HC1 conversion of selenate into selen- ite.A separately nebulized solution of In was used as internal standard. This method gave excellent agreement with certified values for Se in five different biological reference materials i. e. bone liver muscle oyster tissue and wheatflour. Two chapters demonstrateclearly the suitability of ICP-MS for multi-element analysis of waters. Johansson and Lilje- fors report data that is in agreement within +- 1 O% with certified values for 13 elements in a reference water using only a semiquantitative procedure. Veldeman et al. analysed thermal waters for 12 elements by ICP-MS following filtration and acidification and obtained results that agreed well with those from INAA and four spectroscopic methods.Samples requiring more involved pre-treatment are discussed by Kawa- saki et al. and by Ishanullah and East. The former compared seven different methods of preparation of organic fertilizers for multi-element analysis whereas the latter gave extensive de- tails of preparation of several environ- mental samples for measurement of 99Tc. Three chapters are concerned with the analysis of biological samples Lutz et al. critically evaluated the constitu- ents of a diluent which enabled whole blood to be analysed for many trace elements following a simple dilution. The retention and distribution of platinum in animals following the ad- ministration of cisplatin was studied by Tothill et a[.who were able to measure levels below 1 ng g-l in blood and in tissues. Templeton and Vaughan describe the use of principal component analysis (PCA) to correct for isobaric interferences in the mea- surement of Fe and Ni in body fluids. Using the spectra from pure standards of Ca Na plus K and acid digestion blanks they were able to correct inter- ferences and detect 1 pg 1-' of Ni in urine and to measure enriched 57Fe and 58Fe concentrations in whole blood affording the possibility of dual isotope dilution studies. An unusual application of ICP-MS to aid gold prospecting is reported by Perry and van Loon who used the weakly bound gold content of humus samples (ppb levels) as an indication of bedrock gold mineralization. Camp- bell et al. used isotope dilution with ICP-MS to give accurate and precise determination of lead in plant and river sediment reference materials.A good analytical protocol is described by Vanhaecke et al. for measuring B in Ti. The detection limit was lowered by 0.4 pg 1-l by using a PTFE spray chamber. The only criticisms of this book are the variety of type-faces used which presumably relate to the editors policy of minimum intervention and the order of presentation of the chapters. Notwithstanding these the editors have produced a book with a wealth of data on ICP-MS which will be of value to all who use this technique and at a price which is less than that of a litre of vacuum-pump oil. H. T. Delves Trace Element Unit Southampton General Hospital Southampton SO9 4XY UKJOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY FEBRUARY 1993 VOL.8 1 IN XRF Analysis of Ceramics Minerals and Allied Materials Harry Bennett and Graham Oliver. Pp. xv + 298. Wiley. 1992. Price f 45. ISBN 0 471 93457 7. There are several notable and refresh- ing aspects to this book. The first is the outer cover. At first glance what ap- pears to be a spectacular abstract painting in reds and oranges is re- vealed on closer inspection to be a photograph of a molten glass being poured out of a platinum crucible into a casting dish. Second the contents which are drawn directly from the per- sonal experience of the two authors Harry Bennett now retired from the British Ceramic Research Association and Graham Oliver who is employed by its successor Ceram Research Ltd. at Stoke-on-Trent UK.This is a book about the fusion of samples using a suitable flux and casting dish for analy- sis by XRF. As such it is essential reading for anyone employing this form of sample presentation. The book has 19 chapters and 5 appendices. Chapter 1 (1 1 pp.) is an introduction which covers both the impact that the introduction of XRF had on analysis in the ceramics industry and the aims and scope of the present book. Chapter 2 (25 pp.) covers apparatus and equip- ment and gives a valuable over-view of crushing grinding splitting and drying procedures and equipment for fusing samples (and includes details of the author’s prototype platinum crucible for the combined fusion and casting of glass discs). Instrumentation for XRF is summarized briefly. The determina- tion of elements that cannot be deter- mined by XRF are considered in Chapter 3 (8 pp.) in particular borate sulfur carbon lithia halogens sele- nium and volatile or alloying elements.Considerable attention is paid to loss- on-ignition measurements in Chapter 4 (1 9 pp.). Given the current turmoil within the CEC I could not help smiling at the selection of 1025 “C as the commonly accepted temperature for LO1 measurements as a com- promise between 1000 “C (accepted widely in the UK) and 1050 “C (as used on the European continent). Having covered the preliminaries the decomposition of samples by fu- sion is covered comprehensively in Chapter 5 (27 pp.) which includes a wealth of practical experience. Aspects of XRF analysis conditions are con- sidered in Chapters 6 (‘Selection of instrumental parameters’ 10 pp.) and Chapter 7 (‘Element line selection’ 40 pp.).The latter includes sections on individual elements with a commen- tary on the mode of occurrence of the element in ceramic samples selection of spectrometer conditions (with a justification) and an outline of analyti- cal problems which may be encoun- tered. ‘The Standard Procedure’ is described in Chapter 8 (9 pp.) ‘Cali- bration’ in Chapter 9 (2 1 pp.) ‘Presen- tation of the sample bead and comple- tion of the analysis’ in Chapter 10 (8 pp.) and ‘Routine techniques for ma- terial types’ in Chapter l l (7 pp.). The last seven chapters are devoted to procedures for particular categories of samples as follows calcium-rich ma- terials (Chapter 1 3); magnesium-rich materials (Chapter 14); zirconium- bearing materials (Chapter 1 5); vari- ous oxides and titanates (Chapter 16); glasses glazes and frits (Chapter 17); reduced materials (Chapter 18) and samples of unknown composition (Chapter 19). The Appendices sum- marize further practical information covering loss-on-ignition procedures and specific fusion techniques for a wide range of sample types what to do about problem elements or oxides values in relevant certified reference materials and finally details of labora- tory accreditation requirements with particular emphasis on the UK’s NA- MAS scheme. This volume is fairly specific in scope. The general instrumental char- acteristics of XRF specific details of instrumentation and correction proce- dures and alternative forms of sample preparation are not considered in de- tail. However given the wealth of practical expertise within the stated scope this is no disadvantage. For anyone interested in or involved with XRF using samples prepared as glass discs this book is essential reading and should be available for consulta- tion within the laboratory. Phil Potts Department of Earth Sciences Open University Milton Keynes