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LC/MS, Hazardous Metals, and Complexation Chromatography Liquid C h r o m a t o g r a p h y - M a s s Spectrometry. Wilfried Niessen and J a n Van der Greef. 496 pp. Marcel D e k k e r , 270 M a d i s o n A v e . , N e w York, NY 10016. 1992. $165 Reviewed by Richard B. van Breemen, Department of Chemistry, Box 8204, North Carolina State University, Raleigh, NC 27695-8204 Not since Volume 7, Fundamentals of Integrated GC-MS, has the 58-volume Chromatographic Science Series fo­ cused on t h e u s e of MS a s a chro­ matographic detector. Unlike the mature technique GC/MS, LC/MS has undergone rapid development in the past 20 years. Because LC/MS is more routine and more widely avail­ able to researchers, a text devoted to L C / M S s h o u l d be of i n t e r e s t to a large readership, including mass spectrometrists, chromatographers, and o t h e r s c i e n t i s t s i n t e r e s t e d in using LC/MS. Because of the rapid evolution of LC/MS interfaces, capabilities, and applications, a n y textbook on t h i s subject can at best provide a histori­ cal perspective, a n a n a l y s i s of t h e theories a n d principles underlying the various techniques, and an eval­ u a t i o n of t h e i r a p p l i c a t i o n s . This book a c c o m p l i s h e s t h e f i r s t t w o tasks, but applications of LC/MS are only briefly considered. The a u t h o r s have presented a well-written and interesting histori­ cal account of t h e d e v e l o p m e n t of commercially manufactured LC/MS interfaces, including moving-belt, di­ rect liquid introduction, continuousflow fast atom bombardment, parti­ cle beam, thermospray, electrospray, and ion s p r a y i n t e r f a c e s . Also in­ cluded are a thorough discussion of how t h e s e interfaces function a n d d e s c r i p t i o n s of r e l a t e d i o n i z a t i o n techniques and mechanisms, includ­ ing electron impact ionization; chem­ ical ionization; fast atom bombard­ ment; and ion evaporation, which is an ionization mechanism underlying electrospray, ion spray, a n d t h e r ­

mospray. The five-page subject in­ dex is useful. The weakest aspect of this book is the limited attention given to LC/MS applications; only one chapter out of 20 specifically addresses this topic. Each chapter concerning a particular LC/MS interface ends with a table t h a t lists classes of compounds t h a t have been analyzed using that LC/MS technique and includes perti­ nent references. Special chapters on S F C / M S a n d C E / M S also a r e i n ­ cluded. Except for a brief introduc­ tory chapter on LC, however, these are the only chapters t h a t emphasize the chromatographic aspects of LC/ MS. Otherwise, t h e book is written from a MS perspective.

Any text on this subject can at best provide & bitstuticcdJ perspective· The most recent references and ex­ amples are from 1989 with a few ci­ tations from 1990 and 1991. For ex­ ample, the chapters describing electrospray, ion spray, and CE/MS interfaces a r e t h e most u p to d a t e and contain references from 1991. T h e c h a p t e r s on c o n t i n u o u s - f l o w fast atom bombardment and particle b e a m L C / M S i n c l u d e some refer­ ences from 1991, but the discussions a r e l i m i t e d to r e s u l t s p u b l i s h e d through 1989. Despite t h e lack of a t t e n t i o n to

LC/MS applications, the book does provide a thorough discussion of the theoretical a n d operational aspects of LC/MS interfaces as well as the h i s t o r y of t h e i r d e v e l o p m e n t . Al­ though techniques such as electro­ spray and ion spray are widely used, techniques such as the moving-belt interface are being abandoned. This book provides a perspective on early LC/MS interfaces and their impact on the development of newer m e t h ­ ods t h a t eventually replaced them, and on the development of the most p r o m i s i n g c u r r e n t t e c h n i q u e s . By reading this book, chromatographers will learn t h a t a m a s s spectrometer is an unusually challenging and de­ manding HPLC detector, mass spec­ trometrists will learn more about the history of their field, and both will learn about new aspects of LC/MS.

Hazardous Metals in the Environ­ ment. M. Stoeppler, Ed. χ + 542 pp. E l s e v i e r Science P u b l i s h i n g , P.O. Box 882, Madison S q u a r e S t a t i o n , New York, NY 10159. 1992. $226 Reviewed by Eric H. de Carlo, Depart­ ment of Oceanography, University of Ha­ waii, 1000 Pope Road, Honolulu, HI 96822 The title of this book suggests an en­ vironmental geochemistry text. How­ ever, t h e book really describes t h e s t a t e of a n a l y t i c a l methodology in t h e field—this is a review text n e ­ cessitated by the rapid development of a n a l y t i c a l t e c h n i q u e s a n d t h e i r a p p l i c a t i o n to e n v i r o n m e n t a l sci­ ences in t h e p a s t 1 0 - 2 0 y e a r s . As with any other edited volume, it ex­ hibits a range of styles; some chap­ ters are primarily literature reviews, w h e r e a s o t h e r s delve into descrip­ tions of methods and applications. The book is arranged in two sections, w i t h seven g e n e r a l topic c h a p t e r s followed by nine chapters on the de­ t e r m i n a t i o n of i n d i v i d u a l m e t a l s . Two environmentally important met­ alloids, As and Se, are also discussed.

ANALYTICAL CHEMISTRY, VOL. 65, NO. 18, SEPTEMBER 15, 1993 · 795 A

BOOKS The first section discusses challenges i n h e r e n t i n e n v i r o n m e n t a l analyses, including appropriate sampling and sample storage (e.g., Chapter 2) as well as long-term specimen banking (Chapter 3). Chapter 4 describes wine as an example of specimen banking and is mostly of historical interest. Chapter 5 is of major importance because it a l e r t s t h e r e a d e r to t h e common pitfalls of sample treatment. It comprehensively covers identification and avoidance of systematic err rors as well as ways to minimize (or eliminate) sample loss and contamination during sample processing, using detailed examples for a variety of sample types. A rather general but thorough survey of currently available analytical and i n s t r u m e n t a l m e t h o d s is provided in Chapter 6. Chapter 7, which emphasizes the use of wet chemistry to evaluate the environmental mobility of metals, is particularly interesti n g . A l t h o u g h some s e c t i o n s a r e rather elementary, providing only a cursory look at metal speciation and transformations in t h e environment, the chapter is replete with specific

"Metal* of significant

environmental interest art covered

broadly examples a n d should be of use to a great many readers. C h a p t e r s 8 - 1 6 describe specific metals and metalloids individually. I couldn't find any particular logic to t h e s e q u e n c i n g of t h e c h a p t e r s by metal type. Metals of significant env i r o n m e n t a l i n t e r e s t a r e covered

INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH

broadly, although a discussion of tin is noticeably absent. Because of the diverse professional backgrounds of t h e chapter authors, t h e r e a d e r will find t h e t e c h n i c a l content somewhat inconsistent. Some a u t h o r s do a splendid j o b of describing the relevant environmental c h e m i s t r y of each m e t a l in t h e context of its analytical chemistry. A few focus purely on t h e analytical aspects, and others present material in a manner similar to that of the biennial reviews in Analytical Chemistry. The organization of the book leads to a certain amount of repetition in t h e description of a n a l y t i c a l techniques. Certain a u t h o r s discuss t h e specifics of instrumental techniques in too much detail. The editor might have eliminated some of t h e r e d u n dancy by encouraging authors to refe r e n c e o t h e r t e x t s or t o r e f e r to Chapter 6. Chapter 8 (Cd) is a good compilation of methods in a variety of matrices. I t is t h o r o u g h , provides good background information, and includes a helpful section on speciation. However, very little environm e n t a l geochemistry is p r e s e n t e d .

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796 A · ANALYTICAL CHEMISTRY, VOL. 65, NO. 18, SEPTEMBER 15, 1993

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Chapter 9 is truly abbreviated, con­ sidering the ubiquity of lead pollu­ tion. It fails to describe t h e use of stable Pb isotope analysis (e.g., the e l e g a n t w o r k p e r f o r m e d by C l a i r P a t t e r s o n ) , which h a s g r e a t l y e n ­ hanced our understanding of the glo­ bal environmental chemistry of this metal. In contrast, Chapters 10 (Hg) and 11 (As) are exhaustive in their p r e s e n t a t i o n s of cycling a n d i n t e r conversion of metal species; Chapter 11 strongly e m p h a s i z e s speciation analysis and exhibits the most cos­ mopolitan reference list. Chapter 12 (Tl) focuses on modern techniques and references only older methods or those less applicable to analysis a t e n v i r o n m e n t a l concen­ trations. Chapter 13 places the ana­ lytical chemistry of Cr in a broad en­ vironmental context and provides a vast range of references. Some repe­ tition of instrumental techniques ap­ p e a r s in C h a p t e r 14 (Co, Ni) a n d could easily have been omitted, but the section on electrochemical meth­ ods is outstanding. Chapters 14 and 15 (Al) m a k e excellent use of tables to present background information and recommended procedures.

Chapter 16 reads like the Analyti­ cal Chemistry biennial reviews, which may be appropriate considering the broad range of environmental con­ centrations of Se. Much of Chapter 17, which covers quality a s s u r a n c e a n d v a l i d a t i o n of r e s u l t s , reflects common sense, b u t t h e s e practices are essential for performing reliable analyses and for comparing results from different laboratories or tech­ niques. The organization and scope of the metals chapters are good, although a European slant to the book surfaces in t h e r e f e r e n c e s cited. However, given t h e large a m o u n t of environ­ m e n t a l work performed in Europe, this is not surprising. The reference lists for the c h a p t e r s are generally comprehensive through the late 1980s. Overall, many aspects of environ­ mental analytical chemistry are well described, and the reader is provided w i t h a b r o a d r a n g e of r e f e r e n c e s . This book will be a useful addition to t h e reference l i b r a r i e s of e n v i r o n ­ m e n t a l scientists but may not be of widespread use as a graduate text in environmental analytical chemistry.

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Complexation Chromatography. D. Cagniant, Ed. vii + 294 pp. Marcel D e k k e r , 270 M a d i s o n Ave., N e w York, NY 10016. 1992. $100 Reviewed by Jerome W. O'Laughlin, De­ partment of Chemistry, University of Mis­ souri, Columbia, MO 65211 In the preface to this text, the editor introduces three fundamental types of molecular interactions t h a t give rise to charge-transfer absorption or electron donor-acceptor (EDA) chro­ matography, argentation chromatog­ raphy, and ligand-exchange chroma­ t o g r a p h y (LEC). The t e x t r e v i e w s these t h r e e types of interactions in chromatography u n d e r the general heading of complexation chromatog­ raphy. Many of the applications discussed in this volume are taken from the lit­ e r a t u r e of the 1960s and 1970s, be­ fore capillary columns were as widely used as they are today and prior to t h e d e v e l o p m e n t of t h e efficient H P L C c o l u m n s now a v a i l a b l e . It might be questioned w h e t h e r many of the applications presented in the text would even be considered today.

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ANALYTICAL CHEMISTRY, VOL. 65, NO. 18, SEPTEMBER 15, 1993 · 797 A

BOOKS However, some difficult chromatographic separations are greatly facilitated by EDA-type interactions, and the use of such interactions in conjunction with efficient columns may permit the rapid separation of species t h a t cannot readily be separated by any other means. In C h a p t e r 1, " C o m p l e x a t i o n in Chromatography," L. Nondek gives a general overview of the applications of EDA interactions in chromatography. Nondek notes t h a t only weak labile EDA complexes with interaction energies of a few kilocalories per mole are useful in chromatography. EDA interactions are classified with respect to the type of donor and acceptor orbitals involved, u s i n g t h e h a r d - s o f t a c i d - b a s e theory to estim a t e which type of a c i d - b a s e reaction will be facile. General examples of EDA complexes in GC and LC are presented, as are t h e use of linear free energy relationships and simple quantum mechanical models to predict selectivity in EDA interactions. The use of metal complexes in chrom a t o g r a p h y , including m e t a l chel a t e s a n d silver s a l t s , is also d i s cussed briefly.

A concise source for argentation and complexation methods should prove useful to chromatograpners· Chapter 2, with 54 tables, surveys s t a t i o n a r y phases t h a t are used as packings in EDA chromatography. G. Felix discusses the use of silver salts, other metals, other elements such as I 2 , and organic acceptors (e.g., tetrachlorophthalates and 2,4,7-trinitro-

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798 A · ANALYTICAL CHEMISTRY, VOL. 65, NO. 18, SEPTEMBER 15, 1993

fluorenone) as stationary phases for GC. He also reviews the use of similar compounds and chiral ligands as packings for thin-layer chromatography (TLC) and metals coated or chelated onto supports as packings for LEC. Felix discusses organic donoracceptor species a n d describes t h e many chiral stationary phases proposed by Pirkle and co-workers and by M a t l i n a n d c o - w o r k e r s . Refere n c e s for 596 p a p e r s a r e g i v e n through 1987. In Chapter 3 Cagniant covers c h a r g e - t r a n s f e r (CT) a b s o r p t i o n chromatography or EDA with applications for determining polycyclic aromatic compounds, aromatic amines, azaarenes, and biological compounds. He notes t h a t no fundamental new work h a s b e e n p u b l i s h e d on EDA c o m p l e x e s a p p l i e d to TLC p l a t e s since 1974, and he briefly presents older work in this area. His review of CT i n t e r a c t i o n s in LC i n c l u d e s a brief coverage of pre-1982 papers on bonded phases for HPLC separation of polycyclic aromatic hydrocarbons (PAHs) as well as a more compreh e n s i v e look a t l a t e r p a p e r s on bonded nitroderivatives and on other bonded EDA compounds. Applicat i o n s of CT i n t e r a c t i o n s to g a s liquid chromatography (GLC) and to the separation of racemic polycyclic aromatic compounds by LC are also described; a similar discussion of aromatic amines and azaarenes covers TLC, LC, and GLC methods. Separation of biological compounds, probably the most important topic in the chapter, is covered from research by P o r a t h ' s g r o u p in t h e early 1970s through work reported in 1987. In Chapter 4 Cagniant reviews argentation chromatography. He notes t h a t it is difficult to decide whether s e p a r a t i o n s based on complexes of metal ions with organic compounds should be considered as CT complex chromatography or LEC. He then focuses on the separation of olefins by argentation chromatography, including classic examples of steric effects on the stability of olefin-Ag + complexes as well as less familiar cases in which argentation chromatography gives unique separations. Complexation of olefins with other metals is discussed briefly. Covered in considerable detail are the application of argentation chromatography to the separation of lipids, fatty acids, and their methyl esters as well as separ a t i o n s of p r o s t a g l a n d i n s , l e u k o trienes, neutral and polar lipids, steroids, and N- and S - s u b s t i t u t e d heterocyclic compounds. V. A. Davankov describes LEC of

chiral compounds in Chapter 5, which includes a discussion of the re­ q u i r e m e n t s for chiral s e l e c t o r s , stereodependent interactions be­ tween chiral ligands and enantio­ meric analytes in LEC, and the ther­ modynamics of enantioselectivity. He also discusses a number of chiral LEC systems, TLC systems, and LC systems in which the chiral com­ plexes are added to the mobile phase. This chapter contains the most re­ cent references in the book; many of the 243 cited are from the late 1980s. The last chapter is written by Cagniant and covers applications of complexation chromatography to the analysis of coal and petroleum prod­ ucts, including the separation of sul­ fides and sulfur heterocycles, nitro­ gen compounds and azaarenes from petroleum products, and PAHs with nitroaromatic acceptors and other bonded phases. This chapter is more specialized than the others and ap­ pears to overlap s o m e w h a t w i t h Chapter 4. As noted by the editor, there has not been much recent work in sev­ eral of the areas reviewed in the text. Exceptions are the development of chiral phases and some of the newer phases for fractionating PAHs. The development of new HPLC columns and fused-silica capillary columns for GC has probably led to the de­ clining interest in methods such as argentation and complexation chro­ matography. However, these tech­ niques, used in conjunction with effi­ cient modern c o l u m n s , are s t i l l useful for some very difficult separa­ tions, and a concise source for these methods should prove useful to chromatographers. This text should also be of interest to teachers and others interested in the effect of secondary equilibrium processes on chromato­ graphic separations.

Books Received Advances in Chromatography. Vols. 31 and 32. J. Calvin Giddings, Eli Grushka, and Phyllis R. Brown, Eds. xix + 393 pp., xx + 270 pp. Marcel Dekker, 270 Madison Ave., N e w York, NY 10016. 1992. $150, $125 Volume 31, with a primary focus on methods, contains chapters on nonlinear chromatography, SEC, TLC, countercurrent chromatogra­ phy of peptides, boronate affinity chromatography, and chromato­ graphic methods for the determina­ tion of benz[c]acridine. Volume 32 is geared toward applications and in­ cludes such topics as biomedical ap­

plications of porous graphitic carbon, tryptic mapping of p e p t i d e s by RPLC, determination of dissolved gases in water by GC, separation of polar lipids by planar and column chromatography, forensic applica­ tions, and HPLC of explosives. Both volumes contain chapter ref­ erences through the late 1980s.

Newfangled? Old Fashioned?

Preparative and Production Scale Chromatography. G. Ganetsos and P. E. Barker, Eds. xiv + 786 pp. Mar­ cel Dekker, 270 Madison Ave., New York, NY 10016. 1992. $195 This text is grouped into six sec­ tions that cover batchwise opera­ tions and practical considerations for scaleup, cross-current chromatogra­ phy, countercurrent chromatography with moving-column and simulated moving-column systems, combined reaction and separation mechanisms in LC and GC, biotechnology applica­ tions, and mathematical modeling and computer simulation of batch and continuous systems. The chap­ ters contain notation glossaries and references through 1991. A Practical Guide to HPLC Detec­ tion. Donald Parriott, Ed. χ + 293 pp. Academic Press, 1250 Sixth Ave., San Diego, CA 92101. 1993. $60 This book contains contributed chapters on HPLC detection schemes that are based on refractive index, UV—vis absorbance, fluorescence, e l e c t r o c h e m i s t r y , MS, and p o s t column derivatization. Other modes of detection presented include IR, beta and gamma radiation, optical activity, and light-scattering detec­ tion, as well as fraction collection and a n a l y s i s , m u l t i d i m e n s i o n a l chromatography, NMR, and flame methods. Illustrated with numerous s c h e m a t i c d i a g r a m s and s a m p l e chromatograms, the chapters discuss modes of operation, troubleshooting, factors affecting S/N, and the advan­ t a g e s and d i s a d v a n t a g e s of each method. 13

C NMR of Natural Products. Vols. 1 and 2. Atta-ur-Rahman and Viqar Uddin Ahmad, χ + 967 pp. Plenum Press, 233 Spring St., New York, NY 10013. 1992. $135 These books present 1 3 C NMR chemical shift data, structures, sol­ vents, natural sources, and refer­ ences for monoterpenes and sesqui­ terpenes (Vol. 1) and diterpenes (Vol. 2) reported through late 1989. The terpene compounds are grouped by structural types and are indexed by name, source, compound type, molec­ ular formula, and molecular weight.

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ANALYTICAL CHEMISTRY, VOL. 65, NO. 18, SEPTEMBER 15, 1993 · 799 A