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Practical Guide to ICP MS A Tutorial for Beginners 2nd
Edition Robert Thomas Digital Instant Download
Author(s): Robert Thomas
ISBN(s): 9781420067866, 1420067869
Edition: 2
File Details: PDF, 6.51 MB
Year: 2008
Language: english
PRACTICAL GUIDE TO ICP-MS
A Tutorial for Beginners

SECOND EDITION
 PRACTICAL SPECTROSCOPY
A SERIES

1. Infrared and Raman Spectroscopy (in three parts), edited by

Edward G. Brame, Jr., and Jeanette G. Grasselli
2. X-Ray Spectrometry, edited by H. K. Herglotz and L. S. Birks
3. Mass Spectrometry (in two parts), edited by Charles Merritt, Jr.,
and Charles N. McEwen
4. Infrared and Raman Spectroscopy of Polymers, H. W. Siesler
and K. Holland-Moritz
5. NMR Spectroscopy Techniques, edited by Cecil Dybowski
and Robert L. Lichter
6. Infrared Microspectroscopy: Theory and Applications, edited by
Robert G. Messerschmidt and Matthew A. Harthcock
7. Flow Injection Atomic Spectroscopy, edited by Jose Luis Burguera
8. Mass Spectrometry of Biological Materials, edited by Charles N. McEwen
and Barbara S. Larsen
9. Field Desorption Mass Spectrometry, László Prókai
10. Chromatography/Fourier Transform Infrared Spectroscopy and Its
Applications, Robert White
11. Modern NMR Techniques and Their Application in Chemistry,
edited by Alexander I. Popov and Klaas Hallenga
12. Luminescence Techniques in Chemical and Biochemical Analysis,
edited by Willy R. G. Baeyens, Denis De Keukeleire,
and Katherine Korkidis
13. Handbook of Near-Infrared Analysis, edited by Donald A. Burns
and Emil W. Ciurczak
14. Handbook of X-Ray Spectrometry: Methods and Techniques, edited by
René E. Van Grieken and Andrzej A. Markowicz
15. Internal Reflection Spectroscopy: Theory and Applications, edited by
Francis M. Mirabella, Jr.
16. Microscopic and Spectroscopic Imaging of the Chemical State,
edited by Michael D. Morris
17. Mathematical Analysis of Spectral Orthogonality, John H. Kalivas
and Patrick M. Lang
18. Laser Spectroscopy: Techniques and Applications, E. Roland Menzel
19. Practical Guide to Infrared Microspectroscopy, edited by
Howard J. Humecki
20. Quantitative X-ray Spectrometry: Second Edition, Ron Jenkins,
R. W. Gould, and Dale Gedcke
21. NMR Spectroscopy Techniques: Second Edition, Revised and Expanded,
edited by Martha D. Bruch
22. Spectrophotometric Reactions, Irena Nemcova, Ludmila Cermakova,
and Jiri Gasparic
23. Inorganic Mass Spectrometry: Fundamentals and Applications, edited by
Christopher M. Barshick, Douglas C. Duckworth, and David H. Smith
24. Infrared and Raman Spectroscopy of Biological Materials, edited by
Hans-Ulrich Gremlich and Bing Yan
25. Near-Infrared Applications In Biotechnology, edited by
Ramesh Raghavachari
26. Ultrafast Infrared and Raman Spectroscopy, edited by M. D. Fayer
27. Handbook of Near-Infrared Analysis: Second Edition, Revised
and Expanded, edited by Donald A. Burns and Emil W. Ciurczak
28. Handbook of Raman Spectroscopy: From the Research Laboratory
to the Process Line, edited by Ian R. Lewis and Howell G. M. Edwards
29. Handbook of X-Ray Spectrometry: Second Edition, Revised
and Expanded, edited by René E. Van Grieken and Andrzej A. Markowicz
30. Ultraviolet Spectroscopy and UV Lasers, edited by Prabhakar Misra
and Mark A. Dubinskii
31. Pharmaceutical and Medical Applications of Near-Infrared
Spectroscopy, Emil W. Ciurczak and James K. Drennen III
32. Applied Electrospray Mass Spectrometry, edited by
Birendra N. Pramanik, A. K. Ganguly, and Michael L. Gross
33. Practical Guide to ICP-MS, Robert Thomas
34. NMR Spectroscopy of Biological Solids, edited by A. Ramamoorthy
35. Handbook of Near-Infrared Analysis, Third Edition, edited by
Donald A. Burns and Emil W. Ciurczak
36. Coherent Vibrational Dynamics, edited by Sandro De Silvestri,
Giulio Cerullo, and Guglielmo Lanzani
37. Practical Guide to ICP-MS: A Tutorial for Beginners, Second Edition,
Robert Thomas
PRACTICAL SPECTROSCOPY SERIES VOLUME 37

PRACTICAL GUIDE TO ICP-MS

A Tutorial for Beginners

SECOND EDITION

ROBERT THOMAS

Boca Raton London New York

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Library of Congress Cataloging-in-Publication Data

Thomas, Robert.
Practical guide to ICP-MS : a tutorial for beginners / Robert Thomas. -- 2nd ed.
p. cm. -- (Practical spectroscopy)
Includes bibliographical references and index.
ISBN 978-1-4200-6786-6 (alk. paper)
1. Inductively coupled plasma mass spectrometry. I. Title. II. Series.

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Dedication
A great deal has happened to me since I published the first edition of a Practical
Guide to ICP-MS in 2004. I compiled and wrote a cookbook, which has been a
dream of mine for a long time because of my love of cooking. I became a U.S. citi-
zen after living here for almost 20 years, which means I can now finally vote for any
one of the 3 presidential candidates still left in the primary race. Oh, and I forgot
to mention, I also had a heart attack. I must admit, the first two events were excit-
ing and extremely rewarding, but the third just wasn’t as much fun. In fact, there
wouldn’t have been a second edition of the book if I hadn’t made it through sextuple
(yes, that’s six) cardiac bypass surgery in August 2005. The U.S. health care system
has many undesirable characteristics, but there is no doubt in my mind that it is the
best in the world. Having been born and raised in the United Kingdom, I can speak
with some authority that if I had experienced my heart attack there, I might not have
been so fortunate. So I dedicate this book to the medical team from Washington
Adventist Hospital in Tacoma Park, Maryland, including Dr. Gregory Kumkumian,
who carried out the initial catheterization procedure, and Dr. Anjum Qazi, who did
the bypass surgery. There’s no doubt that their skill saved my life and gave me the
opportunity to write the second edition of my book. So, since this is a dedication to
them, please allow me a few minutes of your time to fill you in on the details. If it
encourages just one person to change their lifestyle for the better, it will be worth it.
Monday, August 15, 2005, began like any other summer’s day. It was extremely
hot and humid, which you come to expect for the middle of August in Laytonsville,
Maryland. My wife’s family was in town for our annual reunion. It was something
we did every year … get together for a week of activities, plenty of good food, drink-
ing more than we should, and just having a great time together.
Sporting activities have always been a big part of our family get-togethers. This
year was no exception. We had 10 of her immediate family staying with us, so we
decided to play a game of soccer. It started at a frantic pace. It was clear we couldn’t
keep this going for the entire game. Feet were flying everywhere and bodies were
constantly tumbling to the ground. There was no plan or strategy. It was basically
kick and rush and shoulder-charge whoever got in your way. My team quickly went
into a 3–0 lead, but then after about 20 minutes the game slowed to a crawl.
Everyone was feeling the effects of the heat so a time-out was called. Anyway,
after a few sips of water I started to feel dizzy. This was unusual for me because I was
used to running in the heat. I then began to feel slightly nauseous and experienced
some discomfort in my chest. I thought that maybe it was related to the extreme heat
and that it would just pass. After about 5 minutes, everyone headed back to the field.
At this point, I began to experience severe indigestion. I knew something was wrong,
so I told them I had to go to the bathroom. When I got to the house, I immediately
took an antacid tablet and lay down on the sofa.
I was having difficulty in breathing. The panic was setting in. I knew I had to
go back out and tell someone. I got as far the picnic table when the nausea hit me

vii
viii Dedication

again. I had to sit down. Fortunately, my wife had walked back to the house to see
where I was. I told her I felt really strange. She called to the others for help, as I was
perspiring rather heavily. Their first thought was that it was heat exhaustion, so they
suggested I cool off in the pool. I slowly walked there and sat down on the step with
my body immersed under the water. That had no effect so someone started to hose
me down with extremely cold well water (ouch). It wasn’t helping either as I then
started to shiver violently. When I told them I was getting chest pains, there was a
realization that I could be having a heart attack.
A decision was then made to drive me to the local hospital (Montgomery Gen-
eral in Olney) and not wait for an ambulance. It all became a blur when we got to the
ER. I just remember getting hooked up to an EKG machine and being intravenously
pumped with nitroglycerine, which eventually relieved the chest pain somewhat.
After about an hour I was medevaced to Washington Adventist Hospital … not what
I imagined my first ride in a helicopter would be like! That evening I underwent an
emergency cardiac catheterization procedure, where they inserted a metal stent
through my groin into a blocked artery on the right side of my heart. It was dur-
ing this procedure that they found that arteries on the other side of my heart were
75–90% blocked. The next morning I had open-heart surgery, where they carried out
six bypasses. Unfortunately, there were problems, and I went back into surgery twice
more with bleeding complications (I required 6 units of blood). I eventually came
out of the anesthetic early the next morning, 17 hours after they began the surgery. I
will not go into the fine details, but the next 3 months were extremely traumatic, both
physically and mentally, as I slowly recovered from the ordeal.
Anyway, I recently passed the second-year anniversary of my brush with the
“after-life.” I look back on the experience and realize I was very lucky that my fam-
ily was with me when it happened. If I had been out jogging on my own, who knows
what the outcome would have been? There was no indication beforehand that I had
such serious blockages. I was 56 years old, but had maintained a high fitness level.
Running had been a part of my life for 40 years. (I had run 2 marathons, 5 half-
­marathons, and numerous 5 and 10 Ks.) I had never smoked and always ate a reason-
ably healthy diet. I thought I was doing everything right.
Thankfully, I made a complete recovery. I started an exercise program a few
weeks after I got home from the hospital. The doctors said that my active lifestyle
played a vital role in getting back to health so quickly. I am probably in better shape
now than before the heart attack. I am eating more wisely and exercising (running
or lifting weights) every other day of the week. If there is anything to learn from
this life-changing experience, it is that you never know when something like this is
going to happen. It is absolutely essential to get checked out on a regular basis, make
intelligent dietary choices, don’t ever think about smoking, and probably the most
important decision—make exercise a part of your lifestyle. Trust me, these decisions
could possibly save your life one day … and maybe give you the opportunity to write
a chemistry textbook!

Robert Thomas
November 2007
Contents
Foreword.................................................................................................................xvii
Preface.....................................................................................................................xix
Author.....................................................................................................................xxv

Chapter 1 An Overview of ICP Mass Spectrometry.............................................1

Principles of Operation...............................................................................................1

Chapter 2 Principles of Ion Formation...................................................................7

Ion Formation..............................................................................................................7
Natural Isotopes..........................................................................................................8

Chapter 3 Sample Introduction............................................................................ 13

Aerosol Generation................................................................................................... 13
Droplet Selection....................................................................................................... 15
Nebulizers................................................................................................................. 16
Concentric Design......................................................................................... 16
Cross-Flow Design........................................................................................ 18
Microflow Design.......................................................................................... 18
Spray Chambers........................................................................................................20
Double-Pass Spray Chamber.........................................................................20
Cyclonic Spray Chamber............................................................................... 21
References................................................................................................................. 22

Chapter 4 Plasma Source..................................................................................... 23

The Plasma Torch.....................................................................................................24
Formation of an ICP Discharge................................................................................26
The Function of the RF Generator............................................................................26
Ionization of the Sample...........................................................................................28
References................................................................................................................. 29

Chapter 5 Interface Region.................................................................................. 31

Capacitive Coupling.................................................................................................. 32
Ion Kinetic Energy....................................................................................................34
Benefits of a Well-Designed Interface...................................................................... 36
References................................................................................................................. 37

ix
x Contents

Chapter 6 Ion-Focusing System........................................................................... 39

Role of the Ion Optics............................................................................................... 39
Dynamics of Ion Flow.............................................................................................. 41
Commercial Ion Optic Designs................................................................................ 43
References.................................................................................................................46

Chapter 7 Mass Analyzers: Quadrupole Technology.......................................... 47

Quadrupole Mass Filter Technology........................................................................ 47
Basic Principles of Operation................................................................................... 48
Quadrupole Performance Criteria............................................................................ 49
Resolution...................................................................................................... 50
Abundance Sensitivity................................................................................... 52
Benefit of Good Abundance Sensitivity........................................................ 53
References................................................................................................................. 54

Chapter 8 Mass Analyzers: Double-Focusing Magnetic Sector Technology...... 57

Magnetic Sector Mass Spectroscopy: A Historical Perspective............................... 57
Use of Magnetic Sector Technology for ICP-MS..................................................... 58
Principles of Operation of Magnetic Sector Systems............................................... 59
Resolving Power............................................................................................60
Other Benefits of Magnetic Sector Instruments....................................................... 63
References................................................................................................................. 63

Chapter 9 Mass Analyzers: Time-of-Flight Technology..................................... 65

Basic Principles of TOF Technology........................................................................ 65
Commercial Designs.................................................................................................66
Differences Between Orthogonal and On-Axis TOF............................................... 68
Benefits of TOF Technology for ICP-MS................................................................. 70
Rapid Transient Peak Analysis...................................................................... 70
Improved Precision........................................................................................ 70
Rapid Data Acquisition.................................................................................. 71
References................................................................................................................. 72

Chapter 10 Mass Analyzers: Collision/Reaction Cell and

Interface Technology........................................................................... 73
Basic Principles of Collision/Reaction Cells............................................................ 74
Different Collision/Reaction Cell Approaches......................................................... 75
Collisional Mechanisms Using Nonreactive Gases and Kinetic Energy
Discrimination.................................................................................... 76
Reaction Mechanisms with Highly Reactive Gases and Discrimination
by Selective Bandpass Mass Filtering................................................80
Contents xi

The Collision/Reaction Interface..............................................................................84

Using Reaction Mechanisms in a Collision Cell...................................................... 85
Detection Limit Comparison.................................................................................... 89
Summary................................................................................................................... 89
References................................................................................................................. 91

Chapter 11 Ion Detectors....................................................................................... 93

Channel Electron Multiplier..................................................................................... 93
Faraday Cup..............................................................................................................94
Discrete Dynode Electron Multiplier........................................................................ 95
Extending the Dynamic Range.................................................................................96
Filtering the Ion Beam...................................................................................96
Using Two Detectors......................................................................................96
Using Two Scans with One Detector.............................................................96
Using One Scan with One Detector...............................................................97
Extending the Dynamic Range Using Pulse-Only Mode......................................... 98
References............................................................................................................... 100

Chapter 12 Peak Measurement Protocol.............................................................. 101

Measurement Variables........................................................................................... 101
Measurement Protocol............................................................................................ 102
Optimization of Measurement Protocol................................................................. 106
Multielement Data Quality Objectives................................................................... 107
References............................................................................................................... 113

Chapter 13 Methods of Quantitation................................................................... 115

Quantitative Analysis.............................................................................................. 115
External Standardization............................................................................. 116
Standard Additions...................................................................................... 117
Addition Calibration.................................................................................... 118
Semiquantitative Analysis...................................................................................... 118
Isotope Dilution...................................................................................................... 120
Isotope Ratios......................................................................................................... 123
Internal Standardization......................................................................................... 123
References............................................................................................................... 124

Chapter 14 Review of Interferences..................................................................... 125

Spectral Interferences............................................................................................. 125
Oxides, Hydroxides, Hydrides, and Doubly Charged Species.................... 127
Isobaric Interferences.................................................................................. 128
xii Contents

Ways to Compensate for Spectral Interferences.......................................... 128

Mathematical Correction Equations................................................. 128
Cool/Cold Plasma Technology.......................................................... 130
Collision/Reaction Cells................................................................... 131
High-Resolution Mass Analyzers..................................................... 132
Matrix Interferences............................................................................................... 132
Compensation Using Internal Standardization............................................ 133
Space-Charge-Induced Matrix Interferences.............................................. 134
References............................................................................................................... 135

Chapter 15 Contamination Issues Associated with Sample Preparation............ 137

Collecting the Sample............................................................................................. 137
Preparing the Sample.............................................................................................. 138
Grinding the Sample............................................................................................... 138
Sample Dissolution Methods.................................................................................. 139
Choice of Reagents and Standards......................................................................... 141
Vessels, Containers, and Sample Preparation Equipment...................................... 142
The Environment.................................................................................................... 145
The Analyst............................................................................................................. 146
Instrument and Methodology.................................................................................. 147
References............................................................................................................... 149

Chapter 16 Routine Maintenance........................................................................ 151

Sample Introduction System................................................................................... 152
Peristaltic Pump Tubing............................................................................... 152
Nebulizers.................................................................................................... 152
Spray Chamber............................................................................................ 154
Plasma Torch................................................................................................ 155
Interface Region...................................................................................................... 156
Ion Optics................................................................................................................ 157
Roughing Pumps..................................................................................................... 158
Air Filters................................................................................................................ 159
Other Components to Be Periodically Checked..................................................... 159
The Detector................................................................................................ 159
Turbomolecular Pumps................................................................................ 160
Mass Analyzer............................................................................................. 160

Chapter 17 Alternative Sample Introduction Techniques.................................... 163

Laser Ablation......................................................................................................... 164
Commercial Systems for ICP-MS............................................................... 165
Excimer Lasers............................................................................................ 165
Benefits of Laser Ablation for ICP-MS....................................................... 166
Optimum Laser Design Based on Application Requirements..................... 167
Contents xiii

Flow Injection Analysis.......................................................................................... 171

Electrothermal Vaporization................................................................................... 174
Chilled Spray Chambers and Desolvation Devices................................................ 178
Water-Cooled and Peltier-Cooled Spray Chambers.................................... 178
Ultrasonic Nebulizers.................................................................................. 179
Specialized Microflow Nebulizers with Desolvation Techniques............... 181
Direct Injection Nebulizers..................................................................................... 183
Rapid Sampling Procedures.................................................................................... 184
References............................................................................................................... 185

Chapter 18 Coupling ICP-MS with Chromatographic Techniques for Trace

Element Speciation Studies............................................................... 187
HPLC Coupled with ICP-MS................................................................................. 190
Chromatographic Separation Requirements........................................................... 191
Ion Exchange Chromatography (IEC)......................................................... 191
Reversed-Phase Ion Pair Chromatography (RP-IPC).................................. 192
Column Material.......................................................................................... 193
Isocratic or Gradient Elution....................................................................... 193
Sample Introduction Requirements........................................................................ 195
Optimization of ICP-MS Parameters...................................................................... 196
Compatibility with Organic Solvents.......................................................... 197
Collision/Reaction Cell or Interface Capability.......................................... 197
Optimization of Peak Measurement Protocol............................................. 199
Full Software Control and Integration.........................................................200
Summary................................................................................................................. 201
References...............................................................................................................202

Chapter 19 ICP-MS Applications........................................................................ 203

Environmental.........................................................................................................204
Biomedical..............................................................................................................208
Sample Preparation......................................................................................209
Interference Corrections.............................................................................. 210
Calibration................................................................................................... 210
Stability........................................................................................................ 211
Geochemical........................................................................................................... 211
Determination of Rare Earth Elements....................................................... 212
Analysis of Digested Rock Samples Using Flow Injection......................... 214
Geochemical Prospecting............................................................................ 215
Isotope Ratio Studies................................................................................... 216
Laser Ablation............................................................................................. 218
Semiconductor........................................................................................................ 219
Nuclear....................................................................................................................224
Applications Related to the Production of Nuclear Materials..................... 226
Applications in the Characterization of High-Level Nuclear Waste........... 227
xiv Contents

Applications Involving the Monitoring of the Nuclear Industry’s

Impact on the Environment.............................................................. 227
Applications Involving Human Health Studies........................................... 228
Other Applications.................................................................................................. 229
Metallurgical Applications.......................................................................... 229
Petrochemical and Organic-Based Samples................................................ 231
Food and Agriculture................................................................................... 234
Summary................................................................................................................. 236
References............................................................................................................... 236

Chapter 20 Comparing ICP-MS with Other Atomic Spectroscopic

Techniques......................................................................................... 241
Flame Atomic Absorption...................................................................................... 242
Electrothermal Atomization................................................................................... 243
Radial-View ICP Optical Emission........................................................................ 243
Axial-View ICP Optical Emission.......................................................................... 243
Inductively Coupled Plasma Mass Spectrometry................................................... 243
Define the Objective....................................................................................244
Establish Performance Criteria....................................................................244
Define the Application Task........................................................................244
Application........................................................................................244
Installation........................................................................................ 245
User................................................................................................... 245
Financial........................................................................................... 245
Comparison of Techniques.......................................................................... 245
Detection Limits............................................................................... 245
Analytical Working Range...............................................................246
Sample Throughput........................................................................... 249
Interferences...................................................................................... 251
Usability............................................................................................ 252
Cost of Ownership............................................................................ 252
Cost per Sample................................................................................ 257
Conclusion............................................................................................................... 259
References............................................................................................................... 259

Chapter 21 How to Select an ICP Mass Spectrometer: Some Important

Analytical Considerations................................................................. 261
Evaluation Objectives............................................................................................. 261
Analytical Performance............................................................................... 262
Detection Capability......................................................................... 263
Precision............................................................................................ 267
Isotope Ratio Precision..................................................................... 269
Accuracy........................................................................................... 271
Dynamic Range................................................................................ 272
Contents xv

Interference Reduction...................................................................... 274

Reduction of Matrix-Induced Interferences...................................... 281
Sample Throughput...........................................................................284
Transient Signal Capability............................................................... 285
Usability Aspects......................................................................................... 286
Ease of Use....................................................................................... 286
Routine Maintenance........................................................................ 287
Compatibility with Alternative Sampling Accessories..................... 288
Installation of Instrument................................................................. 288
Technical Support............................................................................. 289
Training............................................................................................. 289
Reliability Issues.......................................................................................... 289
Service Support................................................................................. 290
Financial Considerations......................................................................................... 291
The Evaluation Process: A Summary..................................................................... 292
References............................................................................................................... 293

Chapter 22 Glossary of ICP-MS Terms............................................................... 295

Chapter 23 Useful Contact Information............................................................... 333

Index....................................................................................................................... 341
Foreword
Much has changed in the field of inductively coupled plasma mass spectrometry
(ICP-MS) since the publication of the first edition of this book as illustrated by
the recent program of the 2008 Winter Conference on Plasma Spectrochemistry
(www.icpinformation.org). Basic ICP and MS instrumentation has changed little,
however. The major growth areas of ICP-MS have been its applications. So what’s
new to justify another edition of a “Practical Guide to ICP-MS: A tutorial for begin-
ners”? Rob Thomas has taken his very successful 1st edition and updated the ­majority
of the chapters to reflect the development of the technology over the past four years.
In addition, he has included new material, based on published application work being
carried by the ICP-MS analytical community and written it in a way a novice audi-
ence can understand.
For example, he has added a chapter on elemental speciation, which has probably
been the most rapidly developing application area of ICP-MS during the past four
years, especially for biological and environmental materials. The complementary
nature of elemental (with ICP and glow discharge ion sources) and molecular (e.g.,
electrospray ion sources) mass spectrometry has strengthened the analyst’s capabil-
ity to identify and quantitate many different species of interest. Elemental speciation
of solids lags other applications, and these analyses typically require surface and
other techniques that don’t use ICP-MS. However, spatial distribution studies and
quantitative mapping (imaging) of elemental distributions in hard and soft tissues,
gels, or membranes, for example, has developed rapidly during the past few years
with progress in matrix assisted laser desorption/ionization (MALDI), secondary
ionization MS and laser ablation ICP-MS (LA-ICP-MS). With that in mind, Rob has
put together a very informative chapter on laser ablation systems, together with a very
good overview of all the new sampling devices and desolvation systems currently
available, in the updated chapter on alternative sample introduction approaches.
His expanded chapter on collision/reaction cells and interfaces for resolving mass
spectral interferences shows how the appeal of this technology has grown signifi-
cantly in the past four years. His assessment of the different commercial approaches,
particularly regarding their application strengths and weaknesses is a much needed
addition to the often confusing information about collision/reaction cells in the pub-
lic domain for the novice user. With real-world analyses in mind, Rob’s expanded
chapter on applications gives a very good overview of what is currently being car-
ried out by routine laboratories, as well as giving the reader a glimpse into what
novel applications will emerge in the not-to-distant future. In particular, geochemi-
cal applications of the high-end ICP-MS systems (i.e., high resolution and/or multi­
collector MS) have opened significant new directions in geochronology, for example,
but accurate isotope ratio determinations still require careful chemical pretreatment
and stable ion signals and/or simultaneous detection. Research and development in
microplasma sources and their applications, modern materials analyses, and prove-
nance of everything from food to ancient art objects are stimulating areas of ICP-MS

xvii
xviii Foreword

waiting for new users to explore. Instrumental developments of solid state (focal-
plane array) systems for simultaneous multichannel detection (by Hieftje et al.), and
novel experiments with ICP ion trap MS especially a linear ion trap/orbital trapping
arrangement for very high-resolution measurements (by Koppenaal et al.) potentially
hold the future to significant improvements in commercial ICP-MS systems. How-
ever, these topics are beyond the scope of this introductory text. On the other hand,
a critical need exists for novel academic, commercial, and industrial research to
extend the ICP source, as well as sample introduction and MS systems. We encour-
age readers to assist their spectroscopy societies, universities, and research funding
programs by attending meetings, contributing to funding appeals, and expressing the
need for research support.
Rob has also put together an excellent “Glossary of Terms” for the ICP-MS begin-
ner. His straight forward A-Z descriptions and explanations of terms used in ICP-MS
are quite refreshing amongst the multitude of articles and papers we see published
today. He takes complex topics and attempts to simplify and demystify them for
someone who is new to the technique. Continuing on the theme of educating the user,
numerous educational courses on ICP-MS topics are now offered commercially by
instrument manufacturers and major national and international spectroscopy confer-
ences such as the Pittsburgh Conference on Analytical Chemistry and Applied Spec-
troscopy and the Winter Conference on Plasma Spectrochemistry in Asia, Europe,
and America. For example, more than 30 introductory and advanced courses were
presented in January 2008 at the Winter Conference in Temecula, California. Read-
ers are encouraged to continue their ICP-MS exposure and education after reading
this tutorial by enrolling in one of these training programs.
On a personal note, Rob’s recovery from a heart attack is a blessing to his family
and friends, and we are especially fortunate that he has completed the second edition
of his book. We wish him continued good health, so that future revisions and edi-
tions will appear at regular intervals as ICP-MS continues its progress.

Ramon M. Barnes
Amherst, Massachusetts
January 26, 2008
Preface
I cannot believe that it has been 4 years since I published the first edition of this
textbook. What was originally intended as a series of tutorials on the basic principles
of ICP-MS for Spectroscopy in 2001 quickly grew into a textbook focusing on the
practical side of the technique. With over fifteen hundred copies of the English ver-
sion sold and a Chinese (Mandarin) version now in print, I’m very honored that the
book has gained the reputation as being the reference book of choice for novices and
beginners to the technique. Sales of the book have exceeded my wildest expecta-
tions. Of course, it helps when it is “recommended reading” for a short course I teach
twice a year on “How to Select an ICP-MS.” It also helps when you get the visibility
of your book being displayed at 15 different vendors’ booths at the Pittsburgh Con-
ference every year. But there is no question in my mind that the major reason for its
success is that it presents ICP-MS in a way that is very easy to understand for begin-
ners, and also shows the practical benefits of the technique for carrying out routine
trace element analysis.
However, 4 years is a long time for a book to remain current, even if sales of
the book in its fourth year were almost as high as they were in its first year in 2004.
For that reason, it made sense to not only write an updated version to represent
the current state of the technology, but also to incorporate all the great feedback I
received from users and vendors over the past few years. Still, it should not lose sight
of the fact that its target audience was going to be users who had just started with
ICP-MS or analytical chemists who were in the process of thinking about investing
in the technique. So with that in mind, I present to you the second edition of Practi-
cal Guide to ICP-MS: A Tutorial for Beginners. Below is a summary of the major
changes from the first edition.
I have included two new chapters:

• Coupling ICP-MS with Chromatographic Techniques for Trace Ele-

mental Speciation Studies: The demand for trace element speciation stud-
ies, particularly using liquid chromatography coupled with ICP-MS, has
sky-rocketed in the past few years, especially in the environmental, toxico-
logical, and clinical fields. This new chapter attempts to capture the current
state of this exciting hyphenated technique, with particular emphasis on the
most common applications being carried out and the optimum hardware
and software configurations for both the liquid chromatographic separation
and ICP-MS detection, to ensure the most successful speciation analysis.
• Glossary of ICP-MS Terms: I regret not putting this chapter in the first
edition of my book, based on feedback I received. So I knew when I got
around to writing the next edition, a basic dictionary or glossary of ICP-MS
terms was an absolute necessity. I have therefore put together a list of expla-
nations and definitions of the most common words, expressions, and terms
used in this book. It is aimed specifically at beginners to use as a quick

xix
xx Preface

r­ eference guide, without having to go looking for a more detailed explana-

tion of the subject matter somewhere else in the book.

There are also major rewrites and significant additions to the following chapters:

• Collision/Reaction Cell and Interface Technology: Collision and reac-

tion cells and interfaces have revolutionized ICP-MS analysis since their
commercialization in 1999. They are allowing determinations that were
previously difficult if not impossible to carry out using quadrupole-based
instrumentation. However, as more and more applications are getting devel-
oped, it is clear that all the different commercial designs on the market
approach the analytical determinations differently. This extended chapter
on collision/reaction cells will attempt to clarify the strengths and weak-
nesses of each design and how they impact the strategy for developing a
method and the analysis of unknown samples.
• Alternative Sample Introduction Techniques: Nonstandard sampling
accessories like laser ablation systems, flow injection analyzers, electro-
thermal vaporizers, cooled spray chambers, desolvation equipment, direct
injection nebulizers, and automated sample delivery systems and dilu-
tors are considered critical to enhancing the practical capabilities of the
technique. Their use has increased significantly over the past few years as
ICP-MS is being asked to solve more and more diverse application prob-
lems. This chapter reflects the increased interest in sampling accessories,
especially in the area of specialized sample introduction and desolvation
devices to reduce the impact of common interferences.
• ICP-MS Applications: As ICP-MS is getting less expensive, it is being
installed in more and more routine labs and, as a result, is being asked to
solve more diverse application problems every year. In addition, the power
of ­collision/reaction cell/interface technology is taking the technique into
application areas that previously required high-resolution instrumentation
to carry out the analysis. This chapter, while still emphasizing the most
common routine-type applications, also gives insight into the emerging new
application areas being addressed.
• Comparison of ICP-MS with Other Atomic Spectroscopy Techniques:
This chapter has been updated to compare the performance capabilities of
modern ICP-MS (with collision/reaction cell/interface capabilities) with the
latest ICP-OES, GFAA, and FAA instrumentation. In addition, the section
on “cost of analysis” has been updated to reflect the price of gases, electric-
ity, and instrument consumables in 2007–2008, compared to 4 years ago.
• How to Select an ICP-MS System: The Most Important Analytical Con­
siderations: My experience of teaching two short courses a year on this
subject has given me a unique insight into the kinds of questions that most
novices have when evaluating commercial instrumentation. This chap-
ter focuses on the most important analytical considerations when going
through the evaluation process, with particular emphasis on what I have
learned from teaching my course over the past four years.
Preface xxi

In addition, I have made minor modifications to many of the other chapters in the
book to reflect the advancement of the technology over the past 4 years.

ICP-MS Marketplace
Before I go on to talk about the technique in greater detail, it is definitely worth
reiterating what I said in the preface of my first book and give you an update on the
current size of the ICP-MS marketplace. In 2007, 24 years after ICP-MS was first
commercialized, there are approximately 8000 systems installed worldwide. If this
is compared with ICP-OES, first commercialized in 1974, the difference is quite
significant. In 1998, 24 years after ICP-OES was introduced, about 20,000 units
had been sold, and if this is compared with the same time period that ICP-MS has
been available, the difference is even more staggering. From 1983 to the present
day, approximately 40,000 ICP-OES systems have been installed—about five times
more than the number of ICP-MS systems. If the comparison is made with all atomic
spectroscopy (AS) instrumentation (ICP-MS, ICP-OES, electrothermal atomization
[ETA], and FAA), the annual sales for ICP-MS is less than 7.5% of the total AS mar-
ket—900 units compared to approximately 12,000 AS systems. It is worth empha-
sizing that the global ICP-MS market is growing at about 7% annually, compared to
approximately 3% for ICP-OES and a virtually flat growth for AA instrumentation
(1). This makes the comparison a little more positive for ICP-MS as compared to the
numbers I presented in my first book, but it is still unclear to me as to why ICP-MS
is not growing at a faster rate. It is even more surprising when one considers that the
technique offers so much more than the other AS techniques, including superb detec-
tion limits, rapid multielement analysis, and isotopic measurement capabilities.

ICP-MS: Research or Routine?

Clearly, one of the many reasons that ICP-MS has not become more popular is its rel-
atively high price-tag—an ICP mass spectrometer still costs 2x more than ICP-OES
and 3x more than ETA. But in a competitive world, the “street price” of an ICP-MS
system is much closer to a top-of-the-line ICP-OES with sampling accessories or an
ETA system that has all the “bells and whistles” on it. So if ICP-MS is not signifi-
cantly more expensive than ICP-OES and ETA, why has it not been more widely
accepted by the analytical community? It is still my firm opinion that the major rea-
son ICP-MS has not gained the popularity of the other trace element techniques lies
in the fact that it is still considered a complicated research-type technique, requiring
a very skilled person to operate it. Manufacturers of ICP-MS equipment are con-
stantly striving to make the systems easier to operate, the software easier to use, and
the hardware easier to maintain, but even after 25 years, it is still not perceived as
a mature, routine technique like FAA or ICP-OES. The picture is even fuzzier now
that most instruments are sold with collision/reaction cells/interfaces. This means
that even though this exciting new technology is making ICP-MS more powerful and
flexible, the method development process for unknown samples is generally still a
little more complex. In addition, vendors of this type of equipment are very skilled
at inflating the capabilities of their technology while at the same time pointing out
xxii Preface

the limitations of other approaches, making it even more confusing for the inexpe-
rienced user.
The bottom line is that ICP-MS has still not gained the reputation as a technique
that you can allow a complete novice to use with no supervision, for the fear of gener-
ating erroneous data. This makes for all the more reason why there is still a need for
a good textbook explaining the basic principles and application benefits of ICP-MS
in a way that is interesting, unbiased, and easy to understand for a novice who has
limited knowledge of the technique. There is no question that there are some excel-
lent books out there (2,3,4,5,6,7), but they are mainly written or edited by scientists
who are not approaching the subject from a beginner’s perspective. So they tend to
be technically “heavy” and more biased towards fundamental principles and less on
how ICP-MS is being applied to solve real-world application problems.

ICP-MS for Dummies?

I would hesitate to call my book ICP-MS for Dummies, but it is definitely intended
for analytical chemists who might be termed “ionically-challenged” (if you do fall
into this category, the glossary of ICP-MS terms was written especially for you). So
for those of you who think an ion is used to put a crease in your pants, this book is
yours. Inside you will find chapters not only on the fundamentals and basics of the
technique, but also on practical issues like contamination control, routine mainte-
nance, and when best to use the many kinds of sampling accessories. I also felt it was
important to compare ICP-MS with other trace element techniques, like FAA, ETA,
and ICP-OES, focusing on criteria like elemental range, detection capability, sam-
ple throughput, analytical working range, interferences, sample preparation, main-
tenance issues, operator skill level, and running costs. This kind of head-to-head
comparison will enable the reader to relate both the advantages and dis­advantages of
ICP-MS to other atomic spectroscopy instrumentation they are more familiar with. I
included this because there is still a role for the other techniques, and some vendors
who do not offer the full range of AS instrumentation might embellish the benefits
of ICP-MS over other techniques. In addition, in order to fully understand its practi-
cal capabilities, it is important to give an overview of the most common applications
currently being carried out by ICP-MS and its sampling accessories. This will give
you a flavor of the different industries and markets that are benefiting from the tech-
nique’s enormous potential, especially the newer application segments, such as trace
element speciation analysis using HPLC coupled with ICP-MS. And for those of
you who might be interested in purchasing the technique, I have included a chapter
on the most important selection criteria. This is a critical ingredient in presenting
ICP-MS to a novice, because there is very little information in the public domain to
help someone carry out an evaluation of commercial instrumentation. Very often,
people go into this evaluation process completely unprepared and as a result may
end up with an instrument that is not ideally suited for their needs…something I am
very well aware of, based on teaching my Short Course at the Pittsburgh Conference
for the past 5 years.
Hopefully, after having completed the book, there is still a serious interest in
investing in ICP-MS instrumentation—unless, of course, you have purchased one
Preface xxiii

before reading the final chapter! Even though this might sound a little ambitious,
the main objective is to make ICP-MS a little more compelling to purchase and
ultimately open up its potential to the vast majority of the trace element community
who have not yet realized the full benefits of its capabilities. So with this in mind,
please feel free to come in and share my thoughts on a Practical Guide to ICP-MS:
A Tutorial for Beginners…edition number two.

Acknowledgment
Having worked in the field of ICP-MS for over 20 years, my incentive for writing
this book was based on a realization that there were no textbooks being written
specifically for beginners with a very limited knowledge of the technique. I quickly
came to the conclusion that the only way this was going to happen was to write it
myself. So in 2002, I set myself the objective of putting together a reference book
that could be used by both analytical chemists and senior management who were
experienced in the field of trace metal analysis, but only had a limited knowledge of
ICP-MS. The first edition of the book, published in 2004, represented the fruits of
my effort. As I mentioned earlier, it has definitely reached its target audience, having
sold over fifteen hundred copies worldwide.
About 12 months ago, we got a request from a Chinese publisher to get it trans-
lated into Mandarin. Knowing China’s record on copyright infringement, this was
a major achievement. As a result, the book became “legitimately” available to the
Chinese marketplace in the summer of 2007 and has sold over three hundred copies
already. I want to personally thank my U.S. publisher, CRC Press/Taylor and Fran-
cis, and the Chinese publisher, Atomic Industry Press of Beijing, for making this
happen.
So now in 2008, as the second edition hits the “book stands,” I would like to take
this opportunity once again to thank some of the people and organizations that have
helped me put the book together. First, I would like to thank the editorial staff of
Spectroscopy magazine, who gave me the opportunity to write a monthly tutorial on
ICP-MS back in the spring of 2001…this was most definitely the spark I needed to
start the original project. They also allowed me to use many of the figures from the
series, together with material from other ICP-MS articles I wrote for the magazine.
Second, I would like to thank all the manufacturers of ICP-MS instrumenta-
tion, ancillary equipment, sampling accessories, consumables, calibration standards,
chemical reagents, and high-purity gases, who supplied me with the information,
data, drawings, figures and schematics, etc., and particularly their willingness over
the past 4 years to display the book at their Pittsburgh Conference exhibition booths.
In fact, at last year’s show in Chicago, we had 15 vendors showing the book. This
alone has made a huge difference to the visibility of the book, and its success would
not have been possible without their help.
Third, I would like to thank Dr. Ramon Barnes, Director of the Research Insti-
tute for Analytical Chemistry in Amherst, MA and the driving force behind the
Winter Conference on Plasma Spectrochemistry, for the kind and complimentary
words he wrote in the Foreword of both the first and second editions of my book.
xxiv Preface

Finally, I would like to thank my wife, Donna Marie, and two daughters, Glenna
and Deryn for their encouragement and enthusiasm as I agonized over the decision
to do a second edition, knowing the time, effort, and commitment needed to write
the first edition. Anyone who lives in a house full of females knows how persuasive
a wife and two teenage daughters can be!

References
1. Analytical Instruments Global Assessment Report, Ninth Edition, Strategic Directions
International, Inc., Los Angeles, July 2006.
2. Inorganic Mass Spectrometry: F. Adams, R. Gijbels, R. Van Grieken, Eds., Wiley and
Sons, New York, 1988.
3. K. E. Jarvis, A. L. Gray, R. S. Houk, Handbook of Inductively Coupled Plasma Mass
Spectrometry, Blackie, Glasgow, 1992.
4. A. Montasser, Inductively Coupled Plasma Mass Spectrometry, Wiley-VCH, New
York, 1998.
5. H. E. Taylor, Inductively Coupled Plasma Mass Spectrometry: Practices and Tech-
niques, Elsevier Science, Amsterdam, 2001.
6. Inductively Coupled Plasma Mass Spectrometry Handbook: S. Nelmes, Ed., CRC
Press, Boca Raton, 2005.
7. Inorganic Mass Spectrometry: Principles and Applications: Sabine Becker J., John
Wiley and Sons, UK, 2008.
Author
Robert J. Thomas is principal of Scientific Solutions, a consulting company based
in Gaithersburg, Maryland, that serves the application, training, and technical writ-
ing needs of the trace element analysis user community. He has worked in the field of
atomic spectroscopy (AS) for more than 30 years, with almost 20 years’ experience
in ICP-MS applications, product development, and marketing support at Perkin­
Elmer Life and Analytical Sciences. He has written over 60 technical publications
covering a wide variety of AS subjects, including the fundamental principles of solv-
ing real-world application problems with analytical instrumentation. He received his
advanced degree in analytical chemistry from The University of Wales, Newport,
Ghent in the United Kingdom, and is also a graduate member of the Royal Society
of Chemistry and a Fellow of the Chemical Society of the United Kingdom.

xxv
 1 An Overview of ICP
Mass Spectrometry
ICP-MS not only offers extremely low detection limits in the sub parts per
trillion (ppt) range, but also enables quantitation at the high parts per mil-
lion (ppm) level. This unique capability makes the technique very attractive
compared to other trace metal techniques such as ETA, which is limited to
determinations at the trace level, or FAA and ICP-OES, which are traditionally
used for the detection of higher concentrations. In Chapter 1 we will present an
overview of ICP-MS and explain how its characteristic low detection capabil-
ity is achieved.
Inductively coupled plasma mass spectrometry (ICP-MS) is undoubtedly the fast-
est growing trace element technique available today. Since its commercialization in
1983, approximately 8000 systems have been installed worldwide for many varied
and diverse applications. The most common ones, which represent approximately
80% of the ICP-MS analysis being carried out today, include environmental, geo-
logical, semiconductor, biomedical, and nuclear application fields. There is no ques-
tion that the major reason for its unparalleled growth is its ability to carry out rapid
multielement determinations at the ultratrace level. Even though it can broadly deter-
mine the same suite of elements as other atomic spectroscopic techniques, such as
flame atomic absorption (FAA), electrothermal atomization (ETA), and inductively
coupled plasma optical emission (ICP-OES), ICP-MS has clear advantages in its
multielement characteristics, speed of analysis, detection limits, and isotopic capa-
bility. Figure 1.1 shows approximate detection limits of all the elements that can be
detected by ICP-MS, together with their isotopic abundance. For actual elemental
detection limits and isotopic abundances, please refer to Table 20.1 and Figure 2.5
respectively.

Principles of Operation
There are a number of different ICP-MS designs available today that share many
similar components, such as nebulizer, spray chamber, plasma torch, and detector,
but can differ quite significantly in the design of the interface, ion-focusing system,
mass separation device, and vacuum chamber. Instrument hardware is described in
greater detail in the subsequent chapters, but let us begin here by giving an overview
of the principles of operation of ICP-MS. Figure 1.2 shows the basic components that
make up an ICP-MS system. The sample, which usually must be in a liquid form,
is pumped at 1 mL/min, usually with a peristaltic pump into a nebulizer, where it is
converted into a fine aerosol with argon gas at about 1 L/min. The fine droplets of the
aerosol, which represent only 1–2% of the sample, are separated from larger droplets

1
 1 30 2
2
H Zn Atomic Number, Symbol He
Isotopic Abundance
64 Most Abundant Isotope
1 4
3 Li 4 Be Detection Limit Ranges 5 B 6 C 7 N 8 O 9 F 10 Ne
< 0.1–1 ppt
1–10 ppt
7 9 11 12 14 16 19 20
10–100 ppt
11 Na 12 Mg 13 Al 14 Si 15 P 16 S 17 Cl 18 Ar
0.1–1 ppb
1–10 ppb
23 24 27 28 31 32 35 40
19 K 20 Ca 21 Sc 22 Ti 23 V 24 Cr 25 Mn 26 Fe 27 Co 28 Ni 29 Cu 30 Zn 31 Ga 32 Ge 33 As 34 Se 35 Br 36 Kr

39 40 45 48 51 52 55 56 59 58 63 64 69 74 75 80 79 84
37 Rb 38 Sr 39 Y 40 Zr 41 Nb 42 Mo 43 Tc 44 Ru 45 Rh 46 Pd 47 Ag 48 Cd 49 In 50 Sn 51 Sb 52 Te 53 I 54 Xe

85 88 89 90 93 98 99 102 103 106 107 114 115 120 121 130 127 132
55 Cs 56 Ba 57 La 72 Hf 73 Ta 74 W 75 Re 76 Os 77 Ir 78 Pt 79 Au 80 Hg 81 Tl 82 Pb 83 Bi 84 Po 85 At 86 Rn

133 138 139 180 181 184 187 192 193 195 197 202 205 208 209
87 Fr 88 Ra 89 Ac

58 Ce 59 Pr 60 Nd 61 Pm 62 Sm 63 Eu 64 Gd 65 Tb 66 Dy 67 Ho 68 Er 69 Tm 70 Yb 71 Lu

140 141 142 152 153 158 159 164 165 166 169 174 175
90 Th 91 Pa 92 U 93 Np 94 Pu 95 Am 96 Cm 97 Bk 98 Cf 99 Es 100 Fm 101 Md 102 No 103 Lr

232 231 238

Figure 1.1 Approximate detection capability of ICP-MS, together with elemental isotropic abundance (copyright © 2003–2007, all
Practical Guide to ICP-MS: A Tutorial for Beginners, Second Edition

rights reserved, Perkin­Elmer Inc.).

An Overview of ICP Mass Spectrometry 3

MS
interface
Ion detector

ICP Torch
Ion optics
Mass separation Spray
device chamber

Nebulizer

Turbo Turbo
RF power
molecular molecular
supply
pump pump Mechanical
pump

Figure 1.2 Basic instrumental components of an ICP mass spectrometer.

by means of a spray chamber. The fine aerosol then emerges from the exit tube of the
spray chamber and is transported into the plasma torch via a sample injector.
It is important to differentiate between the roles of the plasma torch in ICP-MS
compared to ICP-OES. The plasma is formed in exactly the same way, by the inter-
action of an intense magnetic field (produced by radio frequency (RF) passing
through a copper coil) on a tangential flow of gas (normally argon), at about 15 L/
min flowing through a concentric quartz tube (torch). This has the effect of ionizing
the gas, which when seeded with a source of electrons from a high-voltage spark,
forms a very-high-temperature plasma discharge (~10,000 K) at the open end of the
tube. However, this is where the similarity ends. In ICP-OES, the plasma, which is
normally vertical, is used to generate photons of light by the excitation of electrons
of a ground-state atom to a higher energy level. When the electrons “fall” back to
ground state, wavelength-specific photons are emitted that are characteristic of the
element of interest. In ICP-MS the plasma torch, which is positioned horizontally,
is used to generate positively charged ions and not photons. In fact, every attempt is
made to stop the photons from reaching the detector because they have the potential
to increase signal noise. It is the production and detection of large quantities of these
ions that gives ICP-MS its characteristic low-ppt detection capability—about three
to four orders of magnitude better than ICP-OES.
Once the ions are produced in the plasma, they are directed into the mass spec-
trometer via the interface region, which is maintained at a vacuum of 1–2 torr with
a mechanical roughing pump. This interface region consists of two metallic cones
(usually nickel), called the sampler and a skimmer cone, each with a small orifice
(0.6–1.2 mm) to allow the ions to pass through to the ion optics, where they are
guided into the mass separation device.
The interface region is one of the most critical areas of an ICP mass spectrometer,
because the ions must be transported efficiently and with electrical integrity from the
plasma, which is at atmospheric pressure (760 torr), to the mass spectrometer ana-
lyzer region, which is at approximately 10 −6 torr. Unfortunately, there is capacitive
coupling between the RF coil and the plasma, producing a potential difference of a
4 Practical Guide to ICP-MS: A Tutorial for Beginners, Second Edition

few hundred volts. If this is not eliminated, an electrical discharge (called a second-
ary discharge or pinch effect) between the plasma and the sampler cone would occur.
This discharge would increase the formation of interfering species and also dramati-
cally affect the kinetic energy of the ions entering the mass spectrometer, making
optimization of the ion optics very erratic and unpredictable. For this reason, it is
absolutely critical that the secondary charge be eliminated by grounding the RF coil.
There have been a number of different approaches used over the years to achieve
this, including a grounding strap between the coil and the interface, balancing the
oscillator inside the RF generator circuitry, a grounded shield or plate between the
coil and the plasma torch, or the use of a double interlaced coil where RF fields go in
opposing directions. They all work differently but basically achieve a similar result,
which is to reduce or eliminate the secondary discharge.
Once the ions have been successfully extracted from the interface region, they
are directed into the main vacuum chamber by a series of electrostatic lens, called
ion optics. The operating vacuum in this region is maintained at about 10 −3 torr with
a turbomolecular pump. There are many different designs of the ion optic region, but
they serve the same function, which is to electrostatically focus the ion beam toward
the mass separation device, while stopping photons, particulates, and neutral species
from reaching the detector.
The ion beam containing all the analyte and matrix ions exits the ion optics and
now passes into the heart of the mass spectrometer—the mass separation device,
which is kept at an operating vacuum of approximately 10 –6 torr with a second tur-
bomolecular pump. There are many different mass separation devices, all with their
strengths and weaknesses. Three of the most common types are discussed in this
book—quadrupole, magnetic sector, and time-of-flight technology—but they basi-
cally serve the same purpose, which is to allow analyte ions of a particular mass-to-
charge ratio through to the detector and to filter out all the nonanalyte, interfering,
and matrix ions. Depending on the design of the mass spectrometer, this is either
a scanning process where the ions arrive at the detector in a sequential manner, or a
simultaneous process where the ions are either sampled or detected at the same time.
Most quadrupole instruments nowadays are also sold with collision/reaction cells or
interfaces. This technology offers a novel way of minimizing polyatomic spectral
interferences by bleeding a gas into the cell or interface and using ion–molecule col-
lision and reaction mechanisms to reduce the impact of the ionic interference.
The final process is to convert the ions into an electrical signal with an ion detec-
tor. The most common design used today is called a discrete dynode detector, which
contains a series of metal dynodes along the length of the detector. In this design,
when the ions emerge from the mass filter, they impinge on the first dynode and are
converted into electrons. As the electrons are attracted to the next dynode, electron
multiplication takes place, which results in a very high stream of electrons emerg-
ing from the final dynode. This electronic signal is then processed by the data-han-
dling system in the conventional way and converted into analyte concentration using
ICP-MS calibration standards. Most detection systems can handle up to eight orders
of dynamic range, which means they can be used to analyze samples from ppt levels
up to a few hundred ppm.
An Overview of ICP Mass Spectrometry 5

It is important to emphasize that because of the enormous interest in the tech-

nique, most ICP-MS instrument companies have very active R&D programs in
place, in order to get an edge in a very competitive marketplace. This is obviously
very good for the consumer, because not only does it drive down instrument prices,
but the performance, applicability, usability, and flexibility of the technique is being
improved at a dramatic rate. Although this is extremely beneficial for the ICP-MS
user community, it can pose a problem for a textbook writer who is attempting to
present a snapshot of instrument hardware and software components at a particular
moment in time. Hopefully, I have struck the right balance in not only presenting
the fundamental principles of ICP-MS to a beginner, but also making them aware of
what the technique is capable of achieving and where new developments might be
taking it.
 2 Principles
Formation
of Ion

Chapter 2 gives a brief overview of the fundamental principles used in

ICP-MS—the use of a high-temperature argon plasma to generate positive
ions. The highly energized argon ions that make up the plasma discharge are
used to first produce analyte ground-state atoms from the dried sample aero-
sol, and then to interact with the atoms to remove an electron and generate
positively charged ions, which are then steered into the mass spectrometer for
detection and measurement.
In ICP-MS, the sample, which is usually in liquid form, is delivered into the sample
introduction system, comprising a spray chamber and nebulizer. It emerges as an
aerosol, where it eventually finds its way, via a sample injector, into the base of the
plasma. As it travels through the different heating zones of the plasma torch, it is
dried, vaporized, atomized, and ionized. During this time, the sample is transformed
from a liquid aerosol to solid particles, and then into a gas. When it finally arrives
at the analytical zone of the plasma, at approximately 6000–7000 K, it exists as
ground-state atoms and ions, representing the elemental composition of the sample.
The excitation of the outer electron of a ground-state atom to produce wavelength-
specific photons of light is the fundamental basis of atomic emission. However, there
is also enough energy in the plasma to remove an electron from its orbital to generate
a free ion. The energy available in an argon plasma is ~15.8 eV, which is high enough
to ionize most of the elements in the periodic table (the majority have first ionization
potentials on the order of 4–12 eV). It is the generation, transportation, and detection
of significant numbers of positively charged ions that gives ICP-MS its character-
istic ultratrace detection capabilities. It is also important to mention that although
ICP-MS is predominantly used for the detection of positive ions, negative ions are
also produced in the plasma. However, because the extraction and transportation of
negative ions is different from that of positive ions, most commercial instruments are
not designed to measure them. The process of the generation of positively charged
ions in the plasma is conceptually shown in greater detail in Figure 2.1.

Ion Formation
The actual process of conversion of a neutral ground-state atom to a positively
charged ion is shown in Figures 2.2 and 2.3. Figure 2.2 shows a very simplistic view
of the chromium atom Cr0, consisting of a nucleus with 24 protons (p+) and 28 neu-
trons (n), surrounded by 24 orbiting electrons (e−). (It must be emphasized that this is
not meant to be an accurate representation of the electron’s shells and subshells, but
just a conceptual explanation for the purpose of clarity.) From this we can conclude

7
8 Practical Guide to ICP-MS: A Tutorial for Beginners, Second Edition

Ions Atoms Gas Solid Liquid

++++
++++
++++ ++++
++++
++++

Ionization Atomization Vaporization Drying

Figure 2.1 Generation of positively charged ions in the plasma.

e-
e- e- e- e-
e-
e- e- e-
e-
24p e- e-
e- e- 28n e-
e- e-
e- e- e-
e- e-
e-
e-
24 e

Figure 2.2 Simplified schematic of a chromium ground-state atom (Cr0).

that the atomic number of chromium is 24 (number of protons) and its atomic mass
is 52 (number of protons + neutrons).
If energy is then applied to the chromium ground-state atom in the form of heat
from a plasma discharge, one of the orbiting electrons will be stripped off the outer
shell. This will result in only 23 electrons left orbiting the nucleus. Because the atom
has lost a negative charge (e−) but still has 24 protons (p+) in the nucleus, it is con-
verted into an ion with a net positive charge. It still has an atomic mass of 52 and an
atomic number of 24, but is now a positively charged ion and not a neutral ground-
state atom. This process is shown in Figure 2.3.

Natural Isotopes
This is a very basic look at the process, because most elements occur in more than
one form (isotope). In fact, chromium has four naturally occurring isotopes, which
means that the chromium atom exists in four different forms, all with the same
Principles of Ion Formation 9

e- e-
e- e- e-
e- e-
e- e- e-
24p
e-
e- e
-
e- 28n e- e-
e- e-
e- e- e- e-
e-
e-
23 e

Figure 2.3 Conversion of a chromium ground-state atom (Cr 0) to an ion (Cr+).

atomic number of 24 (number of protons), but with different atomic masses (num-
bers of neutrons).
To make this a little easier to understand, let us take a closer look at an ele-
ment such as copper, which only has two different isotopes—one with an atomic
mass of 63 (63Cu) and another with an atomic mass of 65 (65Cu). They both have the
same number of protons and electrons, but differ in the number of neutrons in the
nucleus. The natural abundances of 63Cu and 65Cu are 69.1% and 30.9%, respectively,
which gives copper a nominal atomic mass of 63.55—the value you see for copper
in atomic weight reference tables. Details of the atomic structure of the two copper
isotopes are shown in Table 2.1.

Table 2.1
Breakdown of the Atomic Structure
of Copper Isotopes
63 Cu Cu
65

Number of protons (p+) 29 29

Number electrons (e–) 29 29
Number of neutrons (n) 34 36
Atomic mass (p+ + n) 63 65
Atomic number (p+) 29 29
Natural abundance 69.17% 30.83%
Nominal atomic weight 63.55a

a The nominal atomic weight of copper is calcu-

lated using the formula 0.6917n (63Cu) +
0.3083n (65Cu) + p+ and referenced to the
atomic weight of carbon.
10 Practical Guide to ICP-MS: A Tutorial for Beginners, Second Edition

6.0

63Cu+
5.0
69% Abundant

Counts (3×1025) 4.0

3.0
65
Cu+
2.0 31% Abundant

1.0

0.0
61 62 63 64 65 66 67
Mass (u)

Figure 2.4 Mass spectra of the two copper isotopes— 63Cu+ and 65Cu+.

When a sample containing naturally occurring copper is introduced into the

plasma, two different ions of copper, 63Cu+, and 65Cu+ are produced that generate two
different mass spectra—one at mass 63 and another at mass 65. This can be seen in
Figure 2.4, which is an actual ICP-MS spectral scan of a sample containing copper,
showing a peak for the 63Cu+ ion on the left, which is 69.17% abundant, and a peak
for 65Cu+ at 30.83% abundance on the right. You can also see small peaks for two
Zn isotopes at mass 64 (64Zn+) and mass 66 (66Zn+). (Zn has a total of five isotopes
at masses 64, 66, 67, 68, and 70.) In fact, most elements have at least two or three
isotopes, and many elements including zinc and lead, have four or more isotopes.
Figure 2.5 is a chart showing the relative abundance of the naturally occurring iso-
topes of all the elements.
 Relative Abundance of the Natural Isotopes
Isotope % % % Isotope % % % Isotope % % % Isotope % % %
1 H 99.985 61 Ni 1.140 121 Sb 57.36 181 Ta 99.988
2 H 0.015 62 Ni 3.634 122 Sn 4.63 Te 2.603 182 W 26.3
3 He 0.000137 63 Cu 69.17 123 Te 0.908 Sb 42.64 183 W 14.3
4 He 99.999863 64 Zn 48.6 Ni 0.926 124 Sn 5.79 Te 4.816 Xe 0.10 184 Os 0.02 W 30.67
5 65 Cu 30.83 125 Te 7.139 185 Re 37.40
6 Li 7.5 66 Zn 27.9 126 Te 18.95 Xe 0.09 186 Os 1.58 W 28.6
7 Li 92.5 67 Zn 4.1 127 I 100 187 Os 1.6 Re 62.60
8 68 Zn 18.8 128 Te 31.69 Xe 1.91 188 Os 13.3
9 Be 100 69 Ga 60.108 129 Xe 26.4 189 Os 16.1
10 B 19.9 70 Ge 21.23 Zn 0.6 130 Ba 0.106 Te 33.80 Xe 4.1 190 Os 26.4 Pt 0.01
11 B 80.1 71 Ga 39.892 131 Xe 21.2 191 Ir 37.3
12 C 98.90 72 Ge 27.66 132 Ba 0.101 Xe 26.9 192 Os 41.0 Pt 0.79
13 C 1.10 73 Ge 7.73 133 Cs 100 193 Ir 62.7
14 N 99.643 74 Ge 35.94 Se 0.89 134 Ba 2.417 Xe 10.4 194 Pt 32.9
15 N 0.366 75 As 100 135 Ba 6.592 195 Pt 33.8
16 O 99.762 76 Ge 7.44 Se 9.36 136 Ba 7.854 Ce 0.19 Xe 8.9 196 Hg 0.15 Pt 25.3
17 O 0.038 77 Se 7.63 137 Ba 11.23 197 Au 100
18 O 0.200 78 Kr 0.35 Se 23.78 138 Ba 71.70 Ce 0.25 La 0.0902 198 Hg 9.97 Pt 7.2
19 F 100 79 Br 50.69 139 La 99.9098 199 Hg 16.87
Principles of Ion Formation

20 Ne 90.48 80 Kr 2.25 Se 49.61 140 Ce 88.48 200 Hg 23.10

21 Ne 0.27 81 Br 49.31 141 Pr 100 201 Hg 13.18
22 Ne 9.25 82 Kr 11.6 Se 8.73 142 Nd 27.13 Ce 11.08 202 Hg 29.86
23 Na 100 83 Kr 11.5 143 Nd 12.18 203 Tl 29.524
24 Mg 78.99 84 Kr 57.0 Sr 0.56 144 Nd 23.80 Sm 3.1 204 Hg 6.87 Pb 1.4
25 Mg 10.00 85 Rb 72.165 145 Nd 8.30 205 Tl 70.476
26 Mg 11.01 86 Kr 17.3 Sr 9.86 146 Nd 17.19 206 Pb 24.1
27 Al 100 87 Sr 7.00 Rb 27.835 147 Sm 15.0 207 Pb 22.1
28 Si 92.23 88 Sr 82.58 148 Nd 5.76 Sm 11.3 208 Pb 52.4
29 Si 4.67 89 Y 100 149 Sm 13.8 209 Bi 100
30 Si 3.10 90 Zr 51.45 150 Nd 5.64 Sm 7.4 210
31 P 100 91 Zr 11.22 151 Eu 47.8 211
32 S 95.02 92 Zr 17.15 Mo 14.84 152 Gd 0.20 Sm 26.7 212
33 S 0.75 93 Nb 100 153 Eu 52.2 213
34 S 4.21 94 Zr 17.38 Mo 9.25 154 Gd 2.18 Sm 22.7 214
35 Cl 75.77 95 Mo 15.92 155 Gd 14.80 215
36 S 0.02 Ar 0.337 96 Zr 2.80 Mo 16.68 Ru 5.52 156 Gd 20.47 Dy 0.06 216
37 Cl 24.23 97 Mo 9.55 157 Gd 15.65 217
38 Ar 0.063 98 Mo 24.13 Ru 1.88 158 Gd 24.84 Dy 0.10 218
39 K 93.2581 99 Ru 12.7 159 Tb 100 219
40 K 0.0117 Ca 96.941 Ar 99.600 100 Mo 9.63 Ru 12.6 160 Gd 21.86 Dy 2.34 220
41 K 6.7302 101 Ru 17.0 161 Dy 18.9 221
42 Ca 0.647 102 Pd 1.02 Ru 31.6 162 Er 0.14 Dy 25.5 222
43 Ca 0.135 103 Rh 100 163 Dy 24.9 223
44 Ca 2.086 104 Pd 11.14 Ru 18.7 164 Er 1.61 Dy 28.2 224
45 Sc 100 105 Pd 22.33 165 Ho 100 225
46 Ti 8.0 Ca 0.004 106 Pd 27.33 Cd 1.25 166 Er 33.6 226
47 Ti 7.3 107 Ag 51.839 167 Er 22.95 227
48 Ti 73.8 Ca 0.187 108 Pd 26.46 Cd 0.89 168 Er 26.8 Yb 0.13 228
49 Ti 5.5 109 Ag 48.161 169 Tm 100 229
50 Ti 5.4 V 0.250 Cr 4.345 110 Pd 11.72 Cd 12.49 170 Er 14.9 Yb 3.05 230
51 V 99.750 111 Cd 12.80 171 Yb 14.3 231 Pa 100
52 Cr 83.789 112 Sn 0.97 Cd 24.13 172 Yb 21.9 232 Th 100
53 Cr 9.501 113 Cd 12.22 In 4.3 173 Yb 16.12 233
54 Fe 5.8 Cr 2.365 114 Sn 0.65 Cd 28.73 174 Yb 31.8 Hf 0.162 234 U 0.0055
55 Mn 100 115 Sn 0.34 In 95.7 175 Lu 97.41 235 U 0.7200
56 Fe 91.72 116 Sn 14.53 Cd 7.49 176 Lu 2.59 Yb 12.7 Hf 5.206 236
57 Fe 2.2 117 Sn 7.68 177 Hf 18.606 237
58 Fe 0.28 Ni 68.077 118 Sn 24.23 178 Hf 27.297 238 U 99.2745
59 Co 100 119 Sn 8.59 179 Hf 13.629
60 Ni 26.223 120 Sn 32.59 Te 0.096 180 Ta 0.012 W 0.13 Hf 35.100

“Isotopic Compositions of the Elements 1989” Pure Appl. Chem., Vol. 63, No. 7, pp. 991-1002, 1991. © 1991 IUPAC

Figure 2.5 Relative abundance of the naturally occurring isotopes of the elements. (From UIPAC Isotopic
11

Composition of the Elements, Pure and Applied Chemistry 75[6], 683–799, 2003.)
 3 Sample Introduction
Chapter 3 examines one of the most critical areas of the instrument—the sam-
ple introduction system. It discusses the fundamental principles of converting
a liquid into a fine-droplet aerosol suitable for ionization in the plasma, and
presents an overview of the different types of commercially available nebu-
lizers and spray chambers. Although this chapter briefly touches upon some
of the newer sampling components introduced in the past few years, the new
breed of desolvating nebulizers and chilled spray chambers are specifically
addressed in Chapter 17.
The majority of current ICP-MS applications involve the analysis of liquid samples.
Even though the technique has been adapted over the years to handle solids and slur-
ries, it was developed in the early 1980s primarily to analyze solutions. There are
many different ways of introducing a liquid into an ICP mass spectrometer, but they
all basically achieve the same result, which is to generate a fine aerosol of the sample
so that it can be efficiently ionized in the plasma discharge. The sample introduction
area has been called the Achilles’ heel of ICP-MS, because it is considered the weak-
est component of the instrument. Only 2–5% of the sample finds its way into the
plasma, depending on the matrix and method of introducing the sample.1 Although
there has recently been significant innovation in this area, particularly in instrument-
specific components custom built by third-party vendors, the fundamental design of
a traditional ICP-MS sample introduction system has not dramatically changed since
the technique was first introduced in 1983.
Before I discuss the mechanics of aerosol generation in greater detail, let us look at
the basic components of a sample introduction system. Figure 3.1 shows the location of
the sample introduction area relative to the rest of the ICP mass spectrometer, whereas
Figure 3.2 represents a more detailed view showing the individual components.
The traditional way of introducing a liquid sample into an analytical plasma can
be considered as two separate events: aerosol generation using a nebulizer and drop-
let selection using a spray chamber.2

Aerosol Generation
As mentioned previously, the main function of the sample introduction system is to
generate a fine aerosol of the sample. It achieves this with a nebulizer and a spray
chamber. The sample is normally pumped at about 1 mL/min via a peristaltic pump
into the nebulizer. A peristaltic pump is a small pump with lots of minirollers that all
rotate at the same speed. The constant motion and pressure of the rollers on the pump
tubing feeds the sample through to the nebulizer. The benefit of a peristaltic pump

13
14 Practical Guide to ICP-MS: A Tutorial for Beginners, Second Edition

Sample introduction area

Ion MS
detector interface

ICP torch
Ion optics
Mass separation Spray
device chamber

Nebulizer

Turbomolecular Turbomolecular Radio frequency

pump pump power supply
Mechanical
pump

Figure 3.1 Location of the ICP-MS sample introduction area.

Drain
Plasma
Plasma torch
discharge Sample
aerosol
Spray
chamber

Sample Pump
injector tubing
Nebulizer

Argon gas
Peristaltic pump

Sample

Figure 3.2 More detailed view of the ICP-MS sample introduction area.

is that it ensures a constant flow of liquid, irrespective of differences in viscosity

between samples, standards, and blanks. Once the sample enters the nebulizer, the
liquid is then broken up into a fine aerosol by the pneumatic action of a flow of gas
(~1 L/min) “smashing” the liquid into tiny droplets, very similar to the spray mecha-
nism in a can of deodorant. It should be noted that although pumping the sample
is the most common approach to introducing the sample, some pneumatic designs
such as concentric nebulizers do not require a pump, because they rely on the natu-
ral “venturi effect” of the positive pressure of the nebulizer gas to suck the sample
through the tubing. Solution nebulization is conceptually represented in Figure 3.3,
which shows aerosol generation using a cross-flow-designed nebulizer.
Sample Introduction 15

Aerosol (fine droplets)

Argon
gas flow

Nebulizer tips

Liquid sample
from pump

Figure 3.3 Conceptual representation of aerosol generation using a cross-flow nebulizer.

Droplet Selection
Because the plasma discharge is not very efficient at dissociating large droplets, the
function of the spray chamber is primarily to allow only the small droplets to enter
the plasma. Its secondary purpose is to smooth out pulses that occur during the nebu-
lization process, owing mainly to the peristaltic pump. Spray chambers are discussed
in greater detail later in this chapter, but the most common type is the double-pass
design, where the aerosol from the nebulizer is directed into a central tube running
the entire length of the chamber. The droplets then travel the length of this tube,
where the large droplets (greater than ~10 µm dia.) will fall out by gravity and exit
through the drain tube at the end of the spray chamber. The fine droplets (<10 µm
dia.) then pass between the outer wall and the central tube, where they eventually
emerge from the spray chamber and are transported into the sample injector of the
plasma torch.3 Although there are many different designs available, the spray cham-
ber’s main function is to allow only the smallest droplets into the plasma for disso-
ciation, atomization, and, finally, ionization of the sample’s elemental components.
A simplified schematic of this process using a double-pass designed spray chamber
is shown in Figure 3.4.

Spray
chamber Plasma torch
sample injector
Central
tube
Nebulizer
tips

Drain
tube Sample
aerosol

Figure 3.4 Simplified representation of the separation of large and fine droplets in a
­double-pass spray chamber.
16 Practical Guide to ICP-MS: A Tutorial for Beginners, Second Edition

Let us now look at the most common nebulizers and spray chamber designs
used in ICP-MS. We cannot cover every conceivable design, because over the past
few years there has been a huge demand for application-specific solutions, which
has generated a number of third-party manufacturers that sell sample introduction
components directly to ICP-MS users.

Nebulizers
By far the most common design used for ICP-MS is the pneumatic nebulizer, which
uses mechanical forces of a gas flow (normally argon at a pressure of 20–30 psi) to
generate the sample aerosol. Some of the most popular designs of pneumatic nebu-
lizers include the concentric, microconcentric, microflow, and cross-flow. They are
usually made from glass, but other nebulizer materials, such as various kinds of
polymers, are becoming more popular, particularly for highly corrosive samples
and specialized applications. It should be emphasized at this point that nebulizers
designed for use with ICP-OES are far from ideal for use with ICP-MS. This is the
result of a limitation in the quantity of total dissolved solids (TDS) that can be put
into the ICP-MS interface area. Because the orifice sizes of the sampler and skim-
mer cones used in ICP-MS are so small (~0.6–1.2 mm), the matrix components must
generally be kept below 0.2%, although higher concentrations of some matrices can
be tolerated (refer to Chapter 5).4 This means that general-purpose ICP-OES nebu-
lizers that are designed to aspirate 1–2% dissolved solids, or high-solids nebulizers
such as the Babbington, V-groove, or cone-spray, which are designed to handle up
to 20% dissolved solids, are not ideally suited to analyzing solutions by ICP-MS.
Some researchers have attempted to analyze slurries by ICP-MS using this approach.
This is not recommended for high-throughput, routine work because of the poten-
tial of blocking the interface cones, but as long as the particle size of the slurry is
kept below 10 µm in diameter, some success has been achieved using these types of
nebulizers.5 The most common of the pneumatic nebulizers used in commercial ICP
mass spectrometers are the concentric and cross-flow design types. The concentric
design is the most widely used nebulizer for clean samples, whereas the cross-flow
is generally more tolerant to samples containing higher solids and particulate matter.
However, recent advances in the concentric design have allowed for the aspiration of
these types of samples.

Concentric Design
In traditional concentric nebulization, a solution is introduced through a fine-bore
capillary tube, where it comes into contact with a rapidly moving flow of argon gas
at a pressure of approximately 30–50 psi. The high-speed gas and the lower-pressure
sample combine to create a venturi effect, which results in the sample being sucked
through to the end of the capillary, where it is broken up into a fine-droplet aerosol.
Most concentric nebulizers being used today are manufactured from borosilicate
glass or quartz. However, polymer-based materials are now being used for appli-
cations that require corrosion resistance. Typical sample flow rates for a standard
concentric nebulizer are on the order of 1–3 mL/min, although lower flows can be
Sample Introduction 17

Nozzle 6 mm Shell or barrel Capillary Seal Radius

Shoulder

Annulus Capillary

4 mm Uptake tube
Sample
(liquid input)
passage

Nozzle end
surface
Maria
Sidearm
(gas input)

Figure 3.5 Schematic of a glass concentric nebulizer (courtesy of Meinhard Glass Products).

Figure 3.6 Aerosol generated by a concentric nebulizer (courtesy of Meinhard Glass

Products).

used to accommodate more volatile sample matrices, such as organic solvents. A

schematic of a glass concentric nebulizer with the different parts labeled is shown
in Figure 3.5, and the aerosol generated by the nebulization process is shown in
Figure 3.6.
The standard concentric pneumatic nebulizer will give excellent sensitivity and
stability, particularly with clean solutions. However, the narrow capillary can be
plagued by blockage problems, especially if heavier-matrix samples are being aspi-
rated. For that reason, manufacturers of concentric nebulizers offer modifications to
the basic design utilizing different size capillary tubing and recessed tips to allow
aspiration of samples with higher dissolved solids and particulate matter. There are
even specially designed concentric nebulizers with a smaller-bore input capillary
to significantly reduce the dead volume for better coupling of a high-performance
18 Practical Guide to ICP-MS: A Tutorial for Beginners, Second Edition

liquid chromatography (HPLC) system to the ICP-MS when carrying out trace ele-
ment speciation studies.

Cross-Flow Design
For the routine analysis of samples that contain a heavier matrix, or maybe small
amounts of undissolved matter, the cross-flow design is probably the more rugged
design. With this nebulizer, the argon gas is directed at right angles to the tip of a
capillary tube, in contrast to the concentric design, where the gas flow is parallel to
the capillary. The solution is either drawn up through the capillary tube via the pres-
sure created by the high-speed gas flow, or, as is most common with cross-flow nebu-
lizers, fed through the tube with a peristaltic pump. In either case, contact between
the high-speed gas and the liquid stream causes the liquid to break up into an aero-
sol. Cross-flow nebulizers are generally not as efficient as concentric nebulizers at
creating the very small droplets needed for ionization in the plasma. However, the
larger-diameter liquid capillary and longer distance between liquid and gas injectors
reduces the potential for clogging problems. Many analysts feel that the small penalty
to be paid in analytical sensitivity and precision with cross-flow nebulizers compared
to the concentric design is compensated by the fact that they are better suited for
high-throughput, routine applications. In addition, they are typically manufactured
from plastic materials, which makes them far more rugged than a glass concentric
nebulizer. A cross section of a cross-flow nebulizer is shown in Figure 3.7.

Microflow Design
A new breed of nebulizers has been developed for ICP-MS called microflow or high-
efficiency nebulizers, which are designed to operate at much lower sample flows.
Whereas conventional nebulizers have a sample uptake rate of about 1 mL/min,
microflow and high-efficiency nebulizers typically run at less than 0.1 mL/min.
They are based on the concentric principle, but usually operate at higher gas pressure
to accommodate the lower sample flow rates. The extremely low uptake rate makes
them ideal for applications where sample volume is limited or where the sample or
analyte is prone to sample introduction memory effects. The additional benefit of

Nebulizer
tips

Sample Argon

Figure 3.7 Schematic of a cross-flow nebulizer (copyright © 2003–2007, all rights

reserved, Perkin­Elmer Inc.).
Another Random Scribd Document
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The Project Gutenberg eBook of
Selections from Saint-Simon
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Title: Selections from Saint-Simon

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FROM SAINT-SIMON ***
Transcriber’s Note
Contents
CAMBRIDGE UNIVERSITY PRESS
C. F. CLAY, M a n a g e r
LONDON: FETTER LANE, E.C. 4
NEW YORK: G. P. P U T N A M ’S SONS
BOMBAY MACMILLAN AND CO., L t d .
CALCUTTA
 MADRAS
TORONTO: J. M. DENT AND SONS, L t d .
TOKYO: MARUZEN-KABUSHIKI-KAISHA

ALL RIGHTS RESERVED

SELECTIONS FROM
SAINT-SIMON
EDITED BY
ARTHUR TILLEY, M.A.
FELLOW AND LECTURER OF
KING’S COLLEGE, CAMBRIDGE

CAMBRIDGE
AT THE UNIVERSITY PRESS
1920
 P R E FA C E
I t is not every lover of French literature who has the leisure or the
courage to read the whole of Saint-Simon’s Mémoires, the text of
which fills eighteen and a half volumes of the edition of MM. Chéruel
and Ad. Régnier fils. Nor is it all of equal interest. I thought,
therefore, that a selection might prove acceptable to the busy or
faint-hearted reader, and perhaps even whet his appetite for the
work itself. In making the selection I have practically confined myself
to the first two-thirds of the Mémoires, that is to say, to the reign of
Louis XIV, and I have chosen the passages with a view to illustrating
that reign during the period of its declining splendour. In the first
four chapters we have the Roi-Soleil and Mme de Maintenon
presented to us in their daily life. There follows the account of the
review at Compiègne, which gives us some measure of Louis’s
boundless extravagance, and the greater part of the famous
chapters on the death of Monseigneur, surely one of the greatest
things in literature. Lastly there are thirteen portraits, including such
masterpieces as Conti, Cardinal d’Estrées, Fénelon, the Duke and
Duchess of Burgundy, and the Duke of Orléans. In my notes I have
confined myself to the modest task of illustrating Saint-Simon from
himself, and of supplying such other biographical details as seemed
necessary. No one can annotate Saint-Simon without being indebted
to M. de Boislisle’s masterly edition now in progress, but for my
purpose the full and careful index of MM. Chéruel and Régnier has
been of even greater service. The index to vols. I.-XXVIII. of M. de
Boislisle’s edition appeared after my work was practically finished.
 A. T.
Cambridge,
December, 1919.
 C O N T E N TS

PAGE
INTRODUCTION ix
I. LOUIS XIV 1
II. MME DE MAINTENON 42
III. THE DAILY LIFE OF LOUIS XIV 69
IV. MADAME AND MME DE MAINTENON 90
V. THE REVIEW AT COMPIÈGNE 93
VI. THE DEATH OF MONSEIGNEUR 106
VII. PORTRAITS:
1. Achille de Harlay 140
2. Mme de Castries 142
3. Le Nostre 143
4. Vendôme 144
5. Vauban 146
6. D’Antin 152
7. Le Prince de Conti 157
8. Le Duc et la Duchesse de Bourgogne 160
9. Cardinal d’Estrées 172
10. Beauvillier 177
11. Fénelon 180
12. Villeroy 189
13. Le Duc d’Orléans 191
VIII. THE ABBÉ DUBOIS AND THE SEE OF CAMBRAI 210
APPENDIX A. T h e C o u n c i l s a n d t h e S e c r e ta r i e s o f
S tat e 215
APPENDIX B. E x t r a c t s f r o m V a u b a n , Projet d’une dîme
royale 217
Index of Persons mentioned in the Notes 219
Plan of the Château de Versailles 66
 INTRODUCTION
“P e o p l e who are old enough to write memoirs have usually lost their
memory.” This epigrammatic remark with which a recent writer, not
old enough to have lost his memory, opens his reminiscences, has
considerable truth in it. Historians now recognise that “memoirs do
not supply the certainty of history,” for if the writers have dim
memories, they have also lively imaginations. Saint-Simon, the
prince of memoir-writers, did not, it is true, begin to transcribe his
memoirs till he was well past sixty, but from the age of twenty he
had collected materials and made systematic notes. His memoirs
were not merely the pastime of his old age but the serious business
of his whole life. The result is that he has left us a picture of the
Court of Versailles at the close of the seventeenth century and the
beginning of the eighteenth which is unsurpassed in interest. This
interest is above all things human. The men and women who fill his
canvas are vividly alive. With a few powerful and incisive strokes he
first sketches their lineaments and then with merciless penetration
proceeds to lay bare their souls. But his memoirs are also coloured
by his own alert and energetic personality. They not only portray his
age, but they reveal himself; to judge of the fidelity of the picture,
we must know something of the man.
Saint-Simon came of an ancient stock, being descended in the
direct male line from Matthieu de Rouvroy, surnamed Le Borgne,
who fought at Crécy and Poitiers, and Marguerite de Saint-Simon.
His immediate ancestors, a branch of the family which dropped the
name of Rouvroy for that of Saint-Simon, if not exactly illustrious,
followed their monarchs loyally in war and administered their estates
successfully in peace. His father, Claude de Saint-Simon, who was
born in 1607, chiefly owing to his address in the hunting field rose
into high favour with Louis XIII, who created him a duc et pair in
1636. But he fell into disgrace soon afterwards and was ordered by
Richelieu to retire from the Court to the fortress of Blaye on the
Gironde, of which he was governor. His vacillating attitude on the
outbreak of the Fronde made him acceptable neither to Mazarin nor
to the rebellious princes, and he did not return to Paris till after the
troubles were over. In 1672 he married as his second wife Charlotte
de l’Aubespine, by whom he had an only son, born on January 16,
1675, and christened Louis after his royal godfather. At the age of
seven, the young Vidame de Chartres, according to the custom of
many noble families, was put under the charge of a governor, but his
character and opinions were largely moulded by his father and
mother. The latter, a highly virtuous woman of method and good
sense, applied herself assiduously to the development of his mind
and body. From his father he imbibed a profound antipathy for
Mazarin, the families of Lorraine, Bouillon, and Rohan, and all
Secretaries of State.
In December, 1691, when he was nearly seventeen, he was
formally presented to the King, and enrolled as a cadet in the
regiment of the Grey Musketeers. In this capacity he took part in the
siege of Namur, which is the first event recorded in his memoirs. In
1693, having been given the command of a company of cavalry, he
fought at Neerwinden, and at the end of the campaign bought the
colonelcy of a regiment. Shortly before this he had succeeded his
father as governor of Blaye and Senlis. He was only nineteen, when
he gave a signal proof of his energy and of the importance which he
attached to matters of precedence, by helping to organise a
resistance to the claim of the Maréchal de Luxembourg to take
precedence of all ducs et pairs except the Duc d’Uzès. The Dukes
lost their case, largely, Saint-Simon alleges, owing to the partiality of
the First President of the Parlement, Achille de Harlay.
 In the following year (1695) he married Gabrielle de Durfort, the
eldest daughter of the Maréchal-Duc de Lorges, a nephew of
Turenne. She was a blonde with a fine complexion and figure, and
being a modest and excellent woman made him an admirable wife.
He on his side was a devoted husband, and he always speaks of her
in his Memoirs with the greatest affection and esteem.
After the Peace of Ryswick (1697) his regiment was disbanded,
and, on the outbreak of the War of the Spanish Succession, five
years later, failing to receive a nomination as Brigadier, he retired
from the service on the plea of ill-health. “Voilà encore un homme
qui nous quitte,” said the King, and he looked coldly on Saint-Simon
in consequence. It was characteristic of the little Duke’s overweening
sense of his own importance that before taking this step he held a
solemn consultation with six distinguished friends, the Chancellor
Pontchartrain, and five Dukes, Lorges, Durfort-Duras, Choiseul,
Beauvillier, and La Rochefoucauld, of whom the first three were
Marshals of France.
The loss to the army was not irremediable, and the gain to
literature was immense. Henceforth Saint-Simon could devote
himself with singleness of purpose to the real business of his life. It
was in July, 1694, in the camp of Germersheim on the Old Rhine,
that “he began to write his memoirs,” by which expression we must
understand, not that he began to write a continuous narrative, but
that from this time he systematised his observations and inquiries
and made careful notes of the results. We learn from a letter to his
friend, M. de Rancé, the famous reformer of La Trappe, that his
original intention was to relate in detail all personal matters and
merely to touch superficially on general events. But he soon
abandoned this idea and in his account of the years immediately
succeeding his retirement from the army there is little mention of
himself.
His chief friends and allies at this period were all men
considerably older than himself—the two inseparables, the Duc de
Beauvillier and the Duc de Chevreuse, who had both married
daughters of Colbert, the Maréchal de Boufflers, the Chancellor
Pontchartrain, and Chamillart, the Secretary of State for War. It was
through the good offices of Chamillart and Maréchal, the King’s
surgeon, that “he became reconciled,” as he characteristically
expresses it, with Louis XIV. But he had his enemies as well as his
friends, and chief among them were the members of the coterie
which, as so often happens towards the end of a long reign, the
common hope of favours to come had attracted round the heir to
the throne. An important member of this “Cabale de Meudon,” as
Saint-Simon calls it, was the Duc de Vendôme, and when in 1708
Louis XIV made the mistake of associating his grandson, the Duc de
Bourgogne, with him in the command of the army of Flanders, and
dissensions arose between the two commanders, the Cabal warmly
espoused Vendôme’s cause. Their unscrupulous intrigues against the
Duc de Bourgogne roused the wrath of Saint-Simon, who as the ally
of M. de Beauvillier, the young Prince’s former governor, was well
disposed in his favour. Throughout the years 1708 and 1709 he
threw himself into the contest with his accustomed vigour, and in the
following year he helped to achieve a notable victory over the hated
Cabal in another field, that of the marriage of the Duc de Berry,
Monseigneur’s youngest son. The candidate of Monseigneur’s party
was Mlle de Bourbon, while the Duchesse de Bourgogne, well served
by Saint-Simon and his friends, favoured the daughter of the Duc
d’Orléans. Saint-Simon’s organisation of the “Cabale de
Mademoiselle” was a masterpiece of skilful intrigue, and he
conducted the campaign with a passionate energy which is faithfully
reflected in his narrative. When, however, the coarse and depraved
character of the new Duchess revealed itself he bitterly regretted his
success.
But the marriage had one beneficial, if unlooked for, result. The
Duchesse de Saint-Simon, greatly against her inclination and that of
her husband, was appointed lady-in-waiting to the new Duchess,
and had assigned to her a set of apartments at Versailles, consisting
of an antechamber and five rooms, each with a dark little cabinet
opening out of it. In one of these Saint-Simon established himself
with his books and his bureau de travail. It was an unrivalled post of
observation, which his friends christened appropriately “his
workshop.” Meanwhile his intimacy with Beauvillier and Chevreuse
brought him into relations with the Duc de Bourgogne, and the only
thorn in his felicity was the Cabale de Meudon, which he believed to
be bent on his destruction. But from this he was delivered by the
Dauphin’s death from small-pox in April, 1711. The next ten months
were the happiest of his whole life at Court. His relations with the
new Dauphin became more intimate, and in numerous private
conversations he discussed with him projects of political reform.
Then in 1712 the French Marcellus, the star of noble hopes and
aspirations, followed his father to the grave. The blow hit Saint-
Simon almost as hard as it did Fénelon. “The sense of my personal
loss, the immeasurably greater loss of France, and above all the
vanished figure of that incomparable Dauphin pierced my heart and
paralysed my faculties.”
Two years later he refers in melancholy accents to his changed
position. Chevreuse, Beauvillier, and Boufflers were dead,
Pontchartrain had retired from office, Chamillart was in disgrace. The
one link left to him with the Court was the Duc d’Orléans, who by
the death of the Duc de Berry in May, 1714, was marked out as the
future regent of the kingdom. In spite of his unpopularity Saint-
Simon, who had for some years now been on friendly terms with
him, drew to him more closely. He reprobated his licentious and
scandalous life, but he defended him against the false accusations of
his enemies, and effectively countermined the intrigues of the party
that was plotting against him in favour of the Duc du Maine.
On Louis XIV’s death it was partly owing to Saint-Simon’s
vehement and energetic insistence that Orléans roused himself from
his habitual indolence and persuaded the Parlement to set aside the
testament of the late King, which, while it conferred on him the
Regency, had put the real power in the hands of the Duc du Maine.
Saint-Simon was made a member of the Council of Regency, and the
introduction of departmental Councils, in place of the Secretaries of
State, was more or less in accord with his own proposals.
 The new form of administration, however, was not a success and
after a trial of two years was abandoned. Nor did Saint-Simon
himself shew any political capacity. He was wanting in tact and
adaptability, and worse than this he frittered away on futile
questions of precedence and etiquette the time and energy that
might have been given to really important matters. Such influence as
he had with the Regent came to an end with the rise to power of
Dubois, who gladly furthered his request to be sent on a special
mission to Spain (1721).
On the death of the Regent (1722) he left the Court and lived for
some time with his family in a house which he rented in the Rue
Saint-Dominique. But after the marriage of his two sons he resided
for at least half the year at his château of La Ferté-Vidame, about 30
miles north-west of Chartres. The château itself, which, as we know
from engravings, had the air of a feudal fortress, and in every room
of which hung a portrait of Louis XIII, no longer exists. But the park,
enclosed by a wall of nearly nine miles, and the forest beyond have
preserved their original character.
Here Saint-Simon began and completed the definitive version of
his Memoirs, and here in 1743, to his overwhelming grief, he lost his
wife, his faithful companion of nearly fifty years. Other misfortunes
followed; his two sons preceded him to the grave, and he was driven
by his debts to make over the whole of his property to his creditors.
He died at Paris in 1755 at the age of eighty. The lives of his father
and himself cover between them nearly a century and a half.
Saint-Simon, as we see him in Rigaud’s portrait, was small and
delicate—a typical old man’s child—with an extremely alert and
eager face. It has been observed that he is seldom mentioned in
contemporary memoirs, but these are not numerous for the latter
part of the reign of Louis XIV, while three of the chief memoir-writers
of the Regency, when Saint-Simon was most prominent, Barbier,
Buvat, and Marais, did not belong to Court circles. When he is
mentioned it is in no complimentary terms. D’Argenson attacks him
for advocating severe measures against the Duc du Maine after the
conspiracy of Cellamare. “Mark,” he says, "the odious and
bloodthirsty character (anthropophage) of this little saint without
genius." But then Saint-Simon in his on the whole highly favourable
portrait of D’Argenson’s father, the celebrated head of the Paris
police, had said that his character was supple, and that his terrifying
appearance resembled that of the three judges of Hades.
It was inevitable that Saint-Simon’s irascibility, intractability, and
aristocratic pretensions should arouse considerable enmity, and in
the songs and satires of the day he is attacked under the name of
boudrillon (bout d’homme) and petit furibond. Mme de Maintenon
declared that he was “glorieux, frondeur et plein de vues,” and we
have an interesting commentary on this remark in his report of a
conversation which took place between the Duchesse de Bourgogne
and his wife. The Duchess told her that he had many powerful
enemies and that the King had conceived a strong prejudice against
him. His intelligence, she said, and his knowledge and capacity for
ideas were recognised as far above the ordinary, but everybody was
afraid of him, and they could not endure his arrogance and his
outspoken criticisms on persons and institutions.
These criticisms would have been more valuable if they had been
less concerned with futilities, and less biased by aristocratic
prejudices. But Saint-Simon was at heart a true patriot, and was
keenly alive to the evils which were sapping the forces of his
country. He agreed with reformers like Fénelon and Chevreuse and
the Abbé de Saint-Pierre in regarding the absolutism of the King as
the chief source of danger, and he shared their dislike of the
Controller-General and the four Secretaries of State as the agents of
this absolutism. He strongly reprobated the King’s love of war and
glory, and the boundless extravagance, which he not only practised
himself but encouraged in others. Like La Bruyère and Fénelon,
Saint-Simon saw with a compassionate eye the wide-spread misery
by which all this glory and magnificence was purchased. He has
drawn a moving picture of the terrible winter of 1708-1709, when
famine stalked through the land and crushing taxation on the top of
high prices “completed the devastation of France.”
 Mme de Maintenon further complained that he was “plein de
vues,” by which she doubtless meant much the same thing as
Louis XIV, when he called Fénelon chimerical. For in Saint-Simon’s
schemes for reform, as in Fénelon’s, there was a strong Utopian
element, which did not sufficiently take into account the hard facts
of political life and the shortcomings of human nature. They both
looked back too fondly on the past, they both exaggerated the value
of the nobles and the Estates General—Saint-Simon laying more
stress on the former, Fénelon on the latter—as checks to absolutism.
That there should be a certain similarity between their ideas is only
to be expected, for though they were not personally acquainted,
they had a common link in the Duc de Bourgogne, and it was just at
the time that Saint-Simon was having frequent conferences with the
latter that his two great friends, the Duc de Beauvillier and the Duc
de Chevreuse, held long conversations on affairs of state with
Fénelon at Chaulnes (November, 1711). From the conferences of
Saint-Simon and the Duc de Bourgogne sprang the Projets de
gouvernement, the manuscript of which was found among Saint-
Simon’s papers, and which is undoubtedly from his pen. The
conversations at Chaulnes were summarised in the series of short
maxims, known as the Tables de Chaulnes, which represent
Fénelon’s nearest approach to practical politics.
However deserving of consideration Saint-Simon’s views may
have been, his insistence on them in season and out of season
cannot have helped to commend them or to make him popular at
Court. In his old age he is said to have been a delightful talker, but
at Versailles he must have sometimes proved an intolerable bore. “Il
faut tenir votre langue,” said Louis XIV to him when he accepted the
appointment for his wife. One wonders at the patience with which
the Duke of Orleans endured his moral lectures and political
disquisitions. But the Duke was too indolent to escape them, and
while he must have derived considerable amusement from the
peculiarities of his friend’s character he evidently appreciated his
transparent honesty. For with all his faults and prejudices, his vanity,
his hate, and his vindictiveness, Saint-Simon was essentially honest.
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