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Practical Guide to ICP MS A Tutorial for Beginners
Third Edition Robert Thomas Digital Instant Download
Author(s): Robert Thomas
ISBN(s): 9781466555433, 1466555432
Edition: 3
File Details: PDF, 9.82 MB
Year: 2013
Language: english
 T h i rd E d i t i o n

Practical Guide to
ICP-MS
A TUTORIAL FOR BEGINNERS

R OB E RT TH OMAS
 T h i rd E d i t i o n
Practical Guide to
ICP-MS
A TUTORIAL FOR BEGINNERS
 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 Ramen 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, edited by 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 Guglielmo Lanzani,
Giulio Cerullo, and Sandro De Silvestri
37. Practical Guide to ICP-MS: A Tutorial for Beginners, Second Edition,
Robert Thomas
38. Practical Guide to ICP-MS: A Tutorial for Beginners, Third Edition,
Robert Thomas
 T h i rd E d i t i o n
Practical Guide to
ICP-MS
A TUTORIAL FOR BEGINNERS

R OB E RT TH OMAS

Boca Raton London New York

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Contents
Foreword................................................................................................................... xv
Preface.....................................................................................................................xix
Acknowledgment....................................................................................................xxv
Author...................................................................................................................xxvii

Chapter 1 An Overview of ICP-MS....................................................................... 1

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

Chapter 2 Principles of Ion Formation...................................................................5

Ion Formation........................................................................................ 5
Natural Isotopes....................................................................................7

Chapter 3 Sample Introduction............................................................................ 11

Aerosol Generation.............................................................................. 11
Droplet Selection................................................................................. 13
Nebulizers........................................................................................... 14
Concentric Design.......................................................................... 15
Cross-Flow Design......................................................................... 16
Microflow Design........................................................................... 16
Spray Chambers.................................................................................. 18
Double-Pass Spray Chamber.......................................................... 19
Cyclonic Spray Chamber................................................................ 19
Aerosol Dilution........................................................................20

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

The Plasma Torch................................................................................24
Formation of an ICP Discharge...........................................................26
The Function of the RF Generator...................................................... 27
Ionization of the Sample.....................................................................28

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

Capacitive Coupling............................................................................ 33
Ion Kinetic Energy.............................................................................. 34
Benefits of a Well-Designed Interface................................................. 36

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

Role of the Ion Optics.......................................................................... 39

vii
viii Contents

Dynamics of Ion Flow......................................................................... 41

Commercial Ion Optic Designs........................................................... 43

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

Quadrupole Technology......................................................................48
Basic Principles of Operation.............................................................. 48
Quadrupole Performance Criteria....................................................... 50
Resolution....................................................................................... 51
Abundance Sensitivity.................................................................... 52
Benefit of Good Abundance Sensitivity......................................... 53

Chapter 8 Mass Analyzers: Double-Focusing Magnetic Sector Technology...... 55

Magnetic Sector Mass Spectroscopy: A Historical Perspective......... 55
Use of Magnetic Sector Technology for ICP-MS................................ 56
Principles of Operation of Magnetic Sector Technology.................... 58
Resolving Power............................................................................. 58
Other Benefits of Magnetic Sector Instruments..................................60
Simultaneous Measurement Approach Using One Detector.......... 62
Summing Up.......................................................................................64

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

Basic Principles of Time-of-Flight (TOF) Technology....................... 65
Commercial Designs...........................................................................66
Differences between Orthogonal and On-Axis TOF.......................... 69
Benefits of TOF Technology for ICP-MS............................................ 70
Rapid Transient Peak Analysis....................................................... 70
Improved Precision......................................................................... 71
Rapid Data Acquisition.................................................................. 71

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 KED....... 76
Reaction Mechanisms with Highly Reactive Gases
and Discrimination by Selective Bandpass Mass Filtering............ 80
Dynamic Reaction Cell.................................................................. 80
Low Mass Cut-Off Collision/Reaction Cell...................................84
“Triple Quadrupole” Collision/Reaction Cell................................ 86
MS Mode........................................................................................ 87
MS/MS Mode................................................................................. 87
On-Mass MS/MS Mode................................................................. 87
Contents ix

Mass-Shift MS/MS Mode.............................................................. 89

The Collision/Reaction Interface........................................................90
Using Reaction Mechanisms in a Collision Cell................................. 92
The “Universal” Cell...........................................................................96
Detection Limit Comparison............................................................... 96
Summing Up....................................................................................... 97

Chapter 11 Ion Detectors.......................................................................................99

Channel Electron Multiplier................................................................99
Faraday Cup...................................................................................... 100
Discrete Dynode Electron Multiplier................................................ 101
Extending the Dynamic Range......................................................... 102
Filtering the Ion Beam.................................................................. 102
Using Two Detectors.................................................................... 102
Using Two Scans with One Detector............................................ 103
Using One Scan with One Detector............................................. 103
Extending the Dynamic Range Using Pulse-Only Mode................. 106
Simultaneous Array Detectors..................................................... 106

Chapter 12 Peak Measurement Protocol.............................................................. 109

Measurement Variables..................................................................... 109
Measurement Protocol...................................................................... 110
Optimization of Measurement Protocol............................................ 114
Multielement Data Quality Objectives.............................................. 115
Data Quality Objectives for Single-Particle ICP-MS Studies...... 121

Chapter 13 Methods of Quantitation................................................................... 123

Quantitative Analysis........................................................................ 123
External Standardization.............................................................. 124
Standard Additions....................................................................... 125
Addition Calibration..................................................................... 126
Semiquantitative Analysis................................................................. 126
Isotope Dilution................................................................................. 128
Isotope Ratios.................................................................................... 131
Internal Standardization.................................................................... 131

Chapter 14 Review of Interferences..................................................................... 133

Spectral Interferences........................................................................ 133
Oxides, Hydroxides, Hydrides, and Doubly Charged Species..... 135
Isobaric Interferences................................................................... 136
Ways to Compensate for Spectral Interferences........................... 136
Mathematical Correction Equations........................................ 136
x Contents

Cool/Cold Plasma Technology................................................ 138

Collision/Reaction Cells.......................................................... 139
High-Resolution Mass Analyzers............................................ 140
Matrix Interferences.......................................................................... 140
Compensation Using Internal Standardization............................ 141
Space-Charge-Induced Matrix Interferences............................... 142

Chapter 15 Sample Preparation........................................................................... 145

Collecting the Sample....................................................................... 145
Preparing the Sample........................................................................ 146
Grinding the Sample......................................................................... 146
Sample Dissolution Methods............................................................. 147
Choice of Reagents and Standards.................................................... 149
Vessels, Containers, and Sample Preparation Equipment................. 150
The Environment............................................................................... 153
The Analyst....................................................................................... 154
Instrument and Methodology............................................................ 155

Chapter 16 Routine Maintenance ....................................................................... 159

Sample Introduction System............................................................. 160
Peristaltic Pump Tubing............................................................... 160
Nebulizers..................................................................................... 161
Spray Chamber............................................................................. 163
Plasma Torch................................................................................ 164
Interface Region................................................................................ 165
Ion Optics.......................................................................................... 166
Roughing Pumps............................................................................... 167
Air Filters.......................................................................................... 168
Other Components to Be Periodically Checked............................... 168
The Detector................................................................................. 168
Turbomolecular Pumps................................................................ 169
Mass Analyzer and Collision/Reaction Cell................................ 169
Summing Up..................................................................................... 170

Chapter 17 Alternative Sample Introduction Techniques.................................... 171

Laser Ablation................................................................................... 172
Commercial Systems for ICP-MS................................................ 173
Excimer Lasers............................................................................. 173
Benefits of Laser Ablation for ICP-MS........................................ 174
Optimum Laser Design Based on Application Requirements..... 175
193-nm ArF Laser Technology..................................................... 178
Flow Injection Analysis..................................................................... 179
Electrothermal Vaporization............................................................. 182
Chilled Spray Chambers and Desolvation Devices.......................... 186
Contents xi

Water-Cooled and Peltier-Cooled Spray Chambers..................... 187

Ultrasonic Nebulizers................................................................... 188
Specialized Microflow Nebulizers with Desolvation
Techniques.................................................................................... 190
Direct Injection Nebulizers (DIN).................................................... 192
Enhanced Productivity Sampling Systems....................................... 193
Faster Analysis Times.................................................................. 194
Automated Inline Autodilution and Autocalibration................... 195
Automated Inline Chemistry Methods......................................... 197

Chapter 18 Coupling ICP-MS with Chromatographic Techniques for Trace

Element Speciation............................................................................ 201
HPLC Coupled with ICP-MS............................................................204
Chromatographic Separation Requirements.....................................205
Ion Exchange Chromatography (IEC).......................................... 205
Reversed-Phase Ion Pair Chromatography (RP-IPC)..................206
Column Material..........................................................................207
Isocratic or Gradient Elution........................................................207
Sample Introduction Requirements...................................................208
Optimization of ICP-MS Parameters................................................ 210
Compatibility with Organic Solvents........................................... 211
Collision/Reaction Cell or Interface Capability........................... 211
Optimization of Peak Measurement Protocol.............................. 212
Full Software Control and Integration......................................... 215
Summing Up..................................................................................... 215

Chapter 19 Common ICP-MS Applications........................................................ 217

Environmental................................................................................... 218
Biomedical......................................................................................... 223
Sample Preparation.......................................................................224
Interference Corrections...............................................................224
Calibration.................................................................................... 225
Stability........................................................................................ 226
Geochemical...................................................................................... 227
Determination of Rare Earth Elements........................................ 228
Analysis of Digested Rock Samples Using Flow Injection (FI)... 229
Geochemical Prospecting............................................................. 231
Isotope Ratio Studies.................................................................... 232
Laser Ablation..............................................................................234
Semiconductor................................................................................... 235
Nuclear.............................................................................................. 239
Applications Related to the Production of Nuclear Materials...... 242
Applications in the Characterization of High-Level Nuclear
Waste............................................................................................ 242
xii Contents

Applications Involving the Monitoring of the Nuclear

Industry’s Impact on the Environment......................................... 243
Applications Involving Human Health Studies............................244
Other Applications............................................................................244
Metallurgical Applications........................................................... 245
Petrochemical and Organic-Based Samples................................. 247
Food and Agriculture................................................................... 249
Pharmaceutical............................................................................. 253
Summing Up..................................................................................... 255

Chapter 20 Emerging ICP-MS Application Areas............................................... 257

Analysis of Power Plant Flue Gas Desulfurization
Wastewaters (FGDW)....................................................................... 257
Draft of U.S. EPA ICP-MS Standard Operating Procedure
for FGDW Samples...................................................................... 259
Method of Sample Preparation.....................................................260
Instrument Parameters.................................................................260
Proposed U.S. EPA FGDW Methodology....................................260
Multielement Analysis of Seawater Using Automated Inline
Chemistry Procedures....................................................................... 262
Analytical Methodology...............................................................264
Sample Preparation.......................................................................264
ICP-MS Instrumental Parameters................................................264
seaFAST 3 Modes of Operation...................................................264
Results..........................................................................................266
Characterization of Nanoparticles by ICP-MS.................................268
Engineered Nanomaterials (ENMs).............................................268
Potential for Environmental Impact............................................. 269
Analytical Methodologies............................................................ 270
Single Particle ICP-MS Studies.................................................... 271
Optimized Measurement Protocol............................................... 273
Field Flow Fractionation (FFF) Coupled with ICP-MS.................... 274
FFF Coupled with ICP-MS.......................................................... 276
Particle Size Reference Standards................................................ 276
Calibration Strategies................................................................... 277
Recovery....................................................................................... 278

Chapter 21 Comparing ICP-MS with Other Atomic Spectroscopic

Techniques.......................................................................................281
Flame Atomic Absorption................................................................. 283
Electrothermal Atomization (ETA)................................................... 283
Radial-View ICP Optical Emission................................................... 283
Axial-View ICP Optical Emission.................................................... 283
Inductively Coupled Plasma Mass Spectrometry..............................284
Contents xiii

Define the Objective.....................................................................284

Establish Performance Criteria....................................................284
Define the Application Task.........................................................284
Application.............................................................................. 285
Installation............................................................................... 285
User.......................................................................................... 285
Financial.................................................................................. 285
Comparison of Techniques........................................................... 285
Detection Limits......................................................................286
Analytical Working Range...................................................... 288
Sample Throughput................................................................. 288
Interferences............................................................................290
Usability................................................................................... 290
Cost of Ownership................................................................... 291
Summing Up..................................................................................... 298

Chapter 22 How to Select an ICP Mass Spectrometer: Some Important

Analytical Considerations................................................................. 301
Evaluation Objectives........................................................................ 301
Analytical Performance................................................................ 302
Detection Capability................................................................ 303
Precision..................................................................................307
Isotope Ratio Precision............................................................309
Accuracy.................................................................................. 311
Dynamic Range....................................................................... 312
Interference Reduction............................................................ 314
Reduction of Matrix-Induced Interferences............................ 322
Sample Throughput................................................................. 324
Transient Signal Capability..................................................... 326
Single-Particle ICP-MS Transient Signals................................... 327
Usability Aspects.......................................................................... 329
Ease of Use.............................................................................. 329
Routine Maintenance............................................................... 330
Compatibility with Alternative Sampling Accessories........... 332
Installation of Instrument........................................................ 332
Technical Support.................................................................... 332
Training................................................................................... 333
Reliability Issues.......................................................................... 333
Service Support....................................................................... 334
Financial Considerations................................................................... 335
Evaluation Process: A Summary....................................................... 336

Chapter 23 Final Thoughts.................................................................................. 337

xiv Contents

Appendix: Useful Contact Information.............................................................. 341

Glossary of ICP-MS Terms.................................................................................. 351
References.............................................................................................................. 393
Foreword
One might think that by 2013 inductively coupled plasma (ICP), atomic/optical emis-
sion (AES), and mass spectrometry (MS) would have outlived their usefulness. After
four decades (for ICP-AES) and three decades (for ICP-MS) of development and
applications, these techniques should have joined classical wet chemical and instru-
mental techniques in the mature stage of their lifetimes. As this third edition of Rob
Thomas’s very popular textbook demonstrates, this prognosis is far from actual-
ity, because ICP remains a vital research and development focus in many academic
laboratories and commercial manufacturers’ development facilities. Something new
seems to be happening at every major spectroscopy conference. Moreover, ICP tech-
nologies have become key in numerous “application” areas such as clinical, forensic,
and medical meetings; geochemical and earth sciences conferences; as well advanced
materials gatherings. For example, during the past decade engineered nanomaterials
(ENM) have become the major focus of materials sciences and engineering, and ICP
measurements have become a mainstay in both these fields and the biology and eco-
toxicology aftermaths once these materials have escaped into the environment (as
exemplified in Chapter 20). Consequently, ICP-MS has been used recently in “single
particle” mode to capture analyte signal pulses originating from individual nanopar-
ticles in the ICP and relate the recorded data to information such as particle count,
size distribution, and analyte mass (Chapter 12). Provenance of environmental pol-
lution, foods, and archeological materials now relies on elemental, isotopic, and spe-
ciation determinations with ICP techniques. For example, transgenerational isotopic
marking with laser ablation ICP-MS (LA-ICP-MS) measurements of fish otoliths has
recently been recognized as an effective tool for mass marking and tracking of indi-
vidual fish to their original source. LA-ICP techniques and multicollector MS instru-
ments (MC-ICP-MS) have impacted geosciences as well. New high precision and
accurate isotopic measurements with ICP approaches have practically opened the
universe. According to Alex N. Halliday, University of Oxford, at the 2013 European
Winter Conference on Plasma Spectrochemistry, “Multiple collector ICP-MS has
provided new opportunities to explore at high precision and in small samples the
innate isotopic diversity of the periodic table, in a fashion that was only being imag-
ined two decades ago. Isotopic systems that offered great potential for understanding
the natural world, but were extremely hard to develop and exploit, became tractable.”
He continued, “Measuring the decay products of short-lived nuclides such as 182Hf
in the early Solar System has yielded the age of Mars and confirmation of the Giant
Impact theory for the origin of the Moon. Mass dependent fractionation has allowed
identification of Si as one of the hotly debated light elements in Earth’s metallic core.
Small mass dependent isotopic fractionations in elements as different as Li, Mg,
Si, V, Fe, Ni, Ge, Mo, and U are being used to explore the [Earth’s] history and nature
of weathering, sedimentary processes, biological productivity, and ocean chemistry
and how these are affected by climatic change.”

xv
xvi Foreword

Classical and novel laser ablation arrangements with ICP-MS detection have
made mapping biological (and botanical) tissues a revolutionary and high-resolution
tool in medical research. Laser ablation’s older cousin, laser-induced breakdown
spectroscopy (LIBS), has reached the ultimate remote measurement on Mars and is
expected to visit Venus in the next decade.
Just as early ICP research spurred advances in flame and furnace atomic absorp-
tion spectrophotometry and vice versa, plasma-based ambient MS sources, glow dis-
charge, and microwave plasma devices have benefited from ICP advances.
One might also assume that ICP instrument development should be mature by
now, and designers may be complacent, but advanced solid state ion detectors, as
pioneered by the cooperation among Bonner Denton, Dave Koppenaal, and Gary
Hieftje and their coworkers, have emerged with the potential to impact ICP-MS
measurement much as solid state photon detectors did for ICP-AES systems a few
decades ago (Chapter 11). Typical users of ICP-AES and ICP-MS always seem to
want more and faster instrument development than currently available, but instru-
ment manufacturers are making instruments easier to operate and service with
improved performance and smaller footprints. Studies of spectral and nonspectral
matrix effects present in ICP-MS have resulted in improved interface designs and
novel spectrometer configurations (Chapter 14). The ICP-MS interface region has
been computationally and experimentally investigated, leading to a variety of cone
designs and improved characterization of the ion sampling processes (Chapter 5).
The collision/reaction cell or interface technology is available in one form or another
with essentially all quadrupole instruments and in effect absent in sector field sys-
tems (Chapter 10). Will this be changing soon? A commercial multiple (“triple”)
quadrupole system was recently introduced as an alternative pathway. Ultrahigh res-
olution (i.e., >10,000) is not yet commercially available, although impressive results
have been reported for laboratory experiments to avoid some of the most difficult
spectral (e.g., isobaric) interferences. Is the ultimate instrument an ultrahigh resolu-
tion, simultaneous detection, and matrix and mass–bias free ICP-MS system?
As research into absolute isotope ratio measurements by MC-ICP-MS contin-
ues, some new limitations have been identified recently. Although in MC-ICP-MS,
mass bias is generally considered to be mass-dependent fractionation (MDF) and
is corrected by various mass-dependent correction models, mass-independent frac-
tionation (MIF) in MC-ICP-MS was described by Lu Yang et al., of the National
Research Council Canada, at the 2013 European Winter Conference on Plasma
Spectrochemistry. Their study looked at numerous elements and concluded that this
appears to be a common phenomenon, and consequently has serious implications on
the absolute isotope amount ratio measurements.
Isotopic tagging with LA-ICP-MS detection has become an important tool
in environmental and biomedical research. For example, stable Hg isotope ratio
analysis is widely used in environmental sciences, essentially for discriminating
Hg sources. Also, manufactured products and living organisms can be isotopically
traced practically by tagging them with enriched isotopes of the same element at a
given molar ratio to produce a unique fingerprint. Applications include the study of
fish population and their migratory routes, the distribution of plant seeds to evaluate
their accommodation to changing climates, and the tagging of inks/paper/paints for
Foreword xvii

forensic purposes. Using elemental labeled antibodies combined with ICP-MS–based

detection in biomedical diagnostics offers the possibility for elegant, straightfor-
ward quantification of the labeled antibodies binding to various targets (e.g., cancer
markers or cellular metabolites). Applications include imaging by LA-ICP-MS or
ICP-MS–based absolute quantification of targets in cellular samples by immunoas-
says. The quantification of biomarkers by immunohistochemical probes was pre-
viously not possible and most often only one marker at a time could be analyzed
by immune-assay. Now ICP-MS can be used to detect many biomarkers simulta-
neously (multiplexing) with high sensitivity and accuracy, and the first examples
were described in which hetero elements (phosphorus, sulfur) or metals were used
as natural tags for specific protein detection. Recently, indirect protein detection via
tagged antibodies has used multielement (particularly lanthanide) tagging strategies
for simultaneous detection of many different proteins in one single immunoassay by
LA-ICP-MS. This has been applied for immunoimaging purposes, using a multiplex
immunohistochemical approach for cancer tissue sections. Furthermore, the use of
metal-containing stains in combination with LA-ICP-MS provides a way to detect
and analyze phosphorylated proteins, and metal-tagged antiphosphoprotein antibod-
ies can be applied for the determination of specific phosporylated proteins.
New configurations, such as distance-of-flight mass spectrometry (DOF-MS), an
offshoot of time-of-flight mass spectrometry (TOF-MS), are being built and evaluated
to extend the possibilities of elemental ionization sources and “universal calibration”
approaches that enable all species in the sample to be determined (Chapter 9).
Chapters on sample introduction and hyphenated sample treatment and ICP
systems have also been further updated since the last edition. No doubt that chro-
matographic, electrophoresis, flow injection and field flow fraction separations have
extended ICP-MS (and AES) measurements as the mainstay of elemental specia-
tion measurements in biological and environmental fields. Without the combination
of these separation techniques and ICP measurements, elemental speciation appli-
cations would be severely hampered… if not impossible (Chapter 18). The abil-
ity to measure P and S with high sensitivity has opened up new opportunities in
proteomics, for example. Species-specific and unspecific isotopic dilution (ID-MS)
has been critical in quantifying speciation analysis and revealing recovery errors
(Chapter 13). Species-specific techniques have been applied to identify species
transformations, resulting in the development of multi-species methods; whereas,
hyphenated species-unspecific ICP-ID-MS determinations of heteroatoms such as
sulfur have become a common quantification technique in proteomics.
New nebulizers and sample introduction systems have benefited from computer
simulation and design. For this reason, it is surprising that the majority of commercial
systems are still sold with “classical” sample introduction systems. As fundamen-
tal studies reveal the dynamics of aerosol production and interaction with the ICP,
refined nebulizers with a high tolerance for total dissolved solids and/or producing
fine aerosols and novel spray chambers optimized for maximum sensitivity or mini-
mum dead volume and wash-out times have been developed (Chapter 3). In another
recent development, which takes advantage of thermal-inkjet technology, individual
ultralow-volume droplets and monodisperse aerosols have been generated by apply-
ing a “drop-on-demand” droplet and aerosol device. From the practical viewpoint,
xviii Foreword

commercial, smart (automated) autosamplers (known as “laboratory workstations”)

have also made ICP analysis easier and more routine for all users (Chapter 17).
Rob’s very comprehensive new edition offers not only a training manual for nov-
ice users, but is also a current benchmark on the progress of ICP technology for the
experienced analyst. Although new ICP-MS users have more choices than in the
past, these choices reflect years of experience and technology resulting in greater
reliability, improved functionality, and improved analytical performance than earlier
designs. The range of commercial ICP-MS systems now available is very impressive.
The penultimate accuracy and reliability of isotopic measurements for geosciences
of the universe or the ultimate sensitivity for semiconductor production require the
finest laboratory facilities and operator experience on one hand, while many ICP-MS
procedures have been codified, such as in the new guidelines of the United States
Pharmacopeia (USP), regulating elemental impurity limits in pharmaceuticals.
Specifically, USP Chapter <232> specifies daily doses and concentration limits of
metallic impurities in pharmaceutical final products, active ingredients, and excipi-
ents, while Chapter <233> discusses the instrumental procedures and methodology
(Chapter 19). There is no question that in the hands of the experienced spectro-
chemist, ICP-MS remains a premium analytical tool and has impacted essentially all
aspects of human achievement. It’s a very exciting time to be a part of this endeavor!

Ramon M. Barnes
Professor Emeritus of Chemistry
University of Massachusetts
Amherst, Massachusetts
Preface
I cannot believe that it has been 9 years since I published the first edition of this text-
book and 4 years since the second edition was launched at the Pittsburgh Conference
in 2008. What was originally intended as a series of tutorials on the basic principles
of ICP-MS for Spectroscopy Magazine in 20011 quickly grew into a textbook focus-
ing on the practical side of the technique. With over three thousand copies of the
English version sold, a Chinese (Mandarin) book in print, and negotiations under-
way with a South American publisher for Portuguese and Spanish versions, I am
very honored that the book has gained the reputation of being the reference book
of choice for novices and beginners to the technique all over the world. Sales of the
book have exceeded my wildest expectations. Of course, it helps when it is “recom-
mended reading” for a Pittsburgh Conference ICP-MS Short Course I teach every
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 PittCon 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 for beginners to understand, 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 have not really declined over the past 2 years. For that reason, it made sense
to not only write an updated version to represent the current state of the technology
and applications being carried out, but also to incorporate all the great feedback I
received from users and vendors over the past few years. I also did not want to lose
sight of the fact that its target audience was always going to be users who had just
started with ICP-MS or analytical chemists who were thinking about investing in the
technique. So with that in mind, I present to you the third edition of Practical Guide
to ICP-MS: A Tutorial for Beginners. Below is a summary of the major changes from
the second edition.
I have included one brand new chapter:

• Emerging ICP-MS Application Areas, including the analysis of flue gas

desulfurization wastewaters, fully automated analysis of seawater samples
using online chemistry procedures, and characterization of engineered
nanoparticles (ENPs). These are three of the most rapidly growing appli-
cation areas for ICP-MS, particularly the explosion in interest in the use
of engineered nanomaterials (ENMs) such as carbon nanotubes, spherical
buckyballs, or ones containing metal such as silver or gold. For example,
detergents containing silver nanoparticles are manufactured in order to kill
bacteria. Unfortunately, these bactericides release silver at varying rates
during the washing cycle, depending on the type of fabric and the washing
conditions. As a result of the increased use of these products, nanoparticles
are more likely to enter the environment. So in order to ensure the continued
development of nanotechnology products, there is clearly a need to evaluate

xix
xx Preface

the risks posed by these engineered nanoparticles, which will require proper
tools to carry out exposure assessment studies to better understand how
they interact with soil, sediment, and water systems. Chapter 20 focuses
on the use of ICP-MS to characterize not only the chemical composition of
these nanoparticles, but also their size and distribution.

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

• Commercial ICP-MS Instrumentation: There has been a great deal of

activity in the number of new instruments introduced in the past 4 years.
For that reason, I discuss the new ICP-MS technology commercialized since
my last edition in 2008, including new offerings from Agilent Technologies,
Bruker Daltonics, PerkinElmer Instruments, Spectro Analytical Instruments,
and Thermo Scientific. This is not covered in one particular chapter, but
addressed in the relevant sections throughout the book.
• Glossary of ICP-MS Terms: This is an updated list of explanations and
definitions of the most common words, expressions, and terms used in
this book. It includes the addition of over 100 new entries. Once again, a
reminder that it is aimed specifically at beginners to use as a quick ­reference
guide, without having to go looking for a more detailed explanation of the
subject matter somewhere else in the book.
• Alternative Sample Introduction Techniques: Nonstandard sampling
accessories such as laser ablation systems, flow injection analyzers, cooled
spray chambers, desolvation equipment, direct injection nebulizers, aero-
sol dilution techniques, 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 has been asked to solve more and more diverse application
problems. Chapter 17 reflects the increased interest in sampling accesso-
ries, especially in the area of specialized sample introduction and desolva-
tion devices to reduce the impact of common interferences with complex
sample matrices.
• Common 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 tech-
nique into application areas that previously required high-resolution instru-
mentation to carry out the analysis. Chapter 19, while still emphasizing
the most common routine-type analyses, also gives insight into additional
applications being carried out in the environmental, clinical/biomedical,
and food chemistry fields, as well as new directives from the United States
Pharmacopeia (USP) on the determination of elemental impurities in phar-
maceutical products and dietary supplements.
• How to Select an ICP-MS System: Some Important Analytical Con­
siderations: My experience of teaching a short course on this subject every
year for the past 10 years has given me a unique insight into the kinds of
Preface xxi

questions that most novices have when evaluating commercial instrumenta-

tion. Chapter 22 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 4 years, espe-
cially as the application demands on the technique are continually evolving.

In addition, I have made minor modifications and additions to just about all the other
chapters in the book to keep up with advancements in the technique and also to
update “Useful Contact Information” to reflect mergers, acquisitions, and changes in
vendor expertise and contact information.

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 to the first and second editions of my book
and give you an update on the current unit size of the ICP-MS marketplace. As of
2012, 29 years after ICP-MS was first commercialized, there are almost 11,000 sys-
tems installed worldwide. If this is compared with ICP-OES, first commercialized
in 1974, the difference is quite significant. In 2002, 29 years after ICP-OES was
introduced, almost 24,000 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 time of writing, approximately 48,000 ICP-OES systems have
been installed—about 4–5 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 flame atomic absorption [FAA]),
the annual unit sales for ICP-MS is approximately 9% of the total AS market—about
1200 units compared to just over 13,000 AS systems (this number was approxi-
mately 7.5% back in 2004 when the first edition of my book was published). It is
worth emphasizing that the global ICP-MS market is growing at about 6.5% annu-
ally, compared to approximately 3.7% for ICP-OES and just over 1.8% for AA instru-
mentation.2 The sales in dollars are a little more encouraging, because of the price
tag of an ICP-MS instrument (quadrupole: $140,000–$200,000; magnetic sector/
triple quads: $250,000–$300,000) compared to ICP-OES ($50,000–$125,000) and
AA (FAA: $10,000–$40,000; ETA: $30,000–$70,000). This translated into annual
dollar sales for ICP-MS, ICP-OES, and AA of approximately $370M, $410M, and
$420M, respectively, in 2012. 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 unit sales of ICP-MS instrumentation 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 detection 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
relatively high price-tag—an ICP mass spectrometer still costs 2 times more than
xxii Preface

ICP-OES and 3 times 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 significantly 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 reason ICP-MS has not gained the popularity of the other trace element
techniques lies in the fact that 30 years after its commercialization, it is still con-
sidered a complicated research-type technique, requiring a very skilled person to
operate it. Manufacturers of ICP-MS equipment are constantly striving to make
the systems easier to operate, the software easier to use, and the hardware easier to
maintain, but 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, and more recently, a triple quadrupole ICP-MS instrument
was introduced into the marketplace to “muddy the waters.” 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 the limita-
tions of other approaches, making it even more confusing for the inexperienced 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 fear of generat-
ing 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,3–8 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 toward fundamental principles and less on how ICP-MS is
being applied to solve real-world application problems.

WHAT’S INSIDE?
The book’s first few chapters present the fundamental principles of the technique…
principles that basically have not changed since the technique was first developed
in the early 1980s. If you manage to get through this section, the book goes on
to discuss practical issues such as contamination control, routine maintenance, 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, such as FAA, ETA, and
ICP-OES, focusing on criteria such as elemental range, detection capability, sample
throughput, analytical working range, interferences, sample preparation, mainte-
nance issues, operator skill level, and running costs. This kind of head-to-head com-
parison will enable the reader to relate both the advantages and dis­advantages of
ICP-MS to other AS instrumentation with which they are more familiar. 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 practical
Preface xxiii

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, characterization of engineered nanomaterials (ENMs), analysis
of flue gas desulfurization waters (FGDW), and the automated determination of trace
elements in seawaters. And for those of you who might be interested in purchasing
an instrument, I have included a chapter on the most important selection criteria. In
my opinion, 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 10 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
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 three.
Acknowledgment
Having worked in the field of ICP-MS for almost 30 years, my incentive for writ-
ing 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 2003, 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 had only a limited knowledge of
ICP-MS. The fruit of this endeavor was the publication of the first edition of the book
in 2004. Then in 2007, my publisher convinced me it was time to update the book,
which eventually resulted in the second edition coming out in 2008. Both editions
have resulted in over 3000 copies being sold worldwide.
In the middle of this, 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 and has sold over a thousand copies already. And as I write the
preface to this edition, we are very hopeful that the book will also be translated into
Portuguese and Spanish next year sometime.
So now in 2013, as the third 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 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 origi-
nal 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 thank all the manufacturers of ICP-MS instrumentation, ancillary equip-
ment, sampling accessories, consumables, calibration standards, chemical reagents, and
high-purity gases who supplied me with the information, data, drawings, figures and
schematics, and so forth, and particularly their willingness over the past 4 years to dis-
play the book at their Pittsburgh Conference exhibition booths. There are way too many
people to name, but at last year’s show in Orlando, 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. In fact, one vendor purchased 100 copies of the
book with their own name and logo on it, which they were planning to give away with the
sale of every instrument, as well as use for training their new sales and marketing person-
nel. We are hoping more vendors will follow suit with the third edition.
And the updated application information, including the new chapter on emerg-
ing ICP-MS application areas, would not have been possible without the expertise,
know-how, and support from a number of real-world laboratories I have worked
with over the past 4 years, including Brooks Rand Labs in Seattle, Washington;
Colorado School of Mines (CSM) in Boulder, Colorado; University of Texas in El
Paso (UTEP); United States Pharmacopeia (USP) in Rockville, Maryland; and the

xxv
xxvi Acknowledgment

National Public Health Institute of Quebec (INSPQ) in Canada. There are many,
many more I have received advice from, consulted with, and written about and I
thank them all for increasing my knowledge base of how ICP-MS is being applied to
solve real-world analytical problems.
I also thank Dr. Ramon Barnes, Director of the Research Institute for Analytical
Chemistry in Amherst, Massachusetts, and the driving force behind the Winter
Conference on Plasma Spectrochemistry, for the kind and complimentary words he
wrote in the Foreword of all three editions of my book. His endorsement is invalu-
able and means the world to me and of course, the credibility of my book.
Finally, I would like to thank again (… and again and again!!!) the medical team
from Washington Adventist Hospital in Tacoma Park, Maryland, who saved my life
after a heart attack in 2005. These include Dr. Gregory Kumkumian, who carried
out the initial catheterization procedure, and Dr. Anjum Qazi, who did the sextuple
(six) bypass surgery. There is no doubt that their skill saved my life and gave me
the opportunity to write the second and third editions of my book. The U.S. health
care system has many undesirable characteristics, but there is no doubt in my mind
that it is the most advanced 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.
Author
Robert J. Thomas, GRIC, FRSC is principal of Scientific Solutions, a consult-
ing company based in Gaithersburg, Maryland, that serves the application, train-
ing, and technical writing needs of the trace element analysis user community. He
has worked in the field of atomic spectroscopy (AS) for almost 40 years, with over
20 years’ experience in ICP-MS applications, product development, sales, and mar-
keting support at PerkinElmer Instruments, Inc. He has written more than 80 tech-
nical publications covering a wide variety of atomic spectroscopic subject matter,
from the fundamental principles of the technique, to articles solving real-world
application problems with AA, ICP-OES, and ICP-MS analytical instrumentation.
He received his advanced degree in analytical chemistry from The University of
Wales, Newport, Gwent in the United Kingdom, and is also a Graduate and a Fellow
of the Royal Society of Chemistry. In addition to his scientific consulting and writ-
ing assignments, he has also been a volunteer in the American Association for the
Advancement of Science Senior Scientists and Engineers (AAAS/SSE) Science,
Technology, Engineering, and Math (STEM) volunteer program, which places senior
and retired scientists and engineers into elementary, middle, and high schools in the
Washington, DC, area with the aim of using their experience and expertise to help
teachers put a spark back into the science classroom. This program, which has more
than 70 active volunteers in the area, asks for a commitment of a few hours to a full
day every week for the entire school year.
For the past three years, he has been volunteering at Sherwood High School in
Sandy Spring, Maryland, where he supports three chemistry teachers one day a week
by talking about the real-world applications of the subject, related to the chemistry
curriculum. Such is the enthusiasm for the program that they are hoping to get an
analytical chemistry elective into the curriculum next year. More recently he has
become a coach to the Science Olympiad team at North Bethesda Middle School
in Bethesda, Maryland, which represented the State of Maryland at the National
Science Olympiad Championships last year.

xxvii
 1 An Overview of ICP-MS
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 million (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 capability is achieved.

Inductively coupled plasma mass spectrometry (ICP-MS) is undoubtedly the fast-

est growing trace element technique available today. Since its commercializa-
tion in 1983, approximately 11,000 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 envi-
ronmental, geological, semiconductor, biomedical, and nuclear application fields.
There is no question that the major reason for ICP-MS’s unparalleled growth is
its ability to carry out rapid multielement determinations at the ultratrace level.
Even though it can broadly determine 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 spectrom-
etry (ICP-OES), ICP-MS has clear advantages in its multielement characteris-
tics, speed of analysis, detection limits, and isotopic capability. 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 21.1 in Chapter 21 and Figure 2.5 in
Chapter 2, 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, interface cones,
vacuum chamber, ion optics, mass analyzer, and detector. However, the engineering
design and implementation of these components can vary significantly from one
instrument to another. Instrument-specific hardware is described in greater detail
in the subsequent Chapters 3–11 on the basic principles of the technique. So 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 by means of a spray chamber. The fine

1
2 Practical Guide to ICP-MS

1 H Atomic number, symbol

30 Zn 2 He
Isotopic abundance
Most abundant lsotope
64
1 4
3 Li 4 Be Detection limit ranges 6 B 6 C 7 N 8 O 9 F 10 Ne
<0.1–1ppt
1–10 ppt
7 9 10–100 ppt 11 12 14 16 19 20
11 Na 12 Mg 13 AI 14 Si 15 P 16 S 17 CI 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 T 38 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 85 86

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

58 Ce 59 Fr 60 Nd 61Pm 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 93Np 94 Pu 95Am 96 Cm 97 Bk 98 Cf 99 Es 100Fm101Md102 No 103 Lr

232 231 238

FIGURE 1.1 Approximate detection capability of ICP-MS, together with elemental iso­tropic
abundance. (Courtesy of PerkinElmer, Inc., © 2003–2012. All rights reserved. With permission.)

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 interac-
tion of an intense magnetic field (produced by radiofrequency [RF] passing through
a copper coil) on a tangential flow of gas (normally argon) at about 15 L/min flow-
ing 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

MS
interface
Ion detector

ICP torch
Ion optics
Mass separation Spray
device chamber

Nebulizer

Turbo- Turbo-
molecular molecular RF power
pump pump Mechanical supply
pump

FIGURE 1.2 Basic instrumental components of an ICP mass spectrometer.

An Overview of ICP-MS 3

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 nor-
mally 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 or three metallic
cones (depending on the design), called the sampler and 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
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 lenses 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 turbo­
molecular pump. There are many different mass separation devices, all with their
strengths and weaknesses. Three of the most common types are discussed in this
4 Practical Guide to ICP-MS

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, elec-
tron multiplication takes place, which results in a very high stream of electrons
emerging from the final dynode. This electronic signal is then processed by the data-­
handling 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.
It is important to emphasize that because of the enormous interest in the tech-
nique, most ICP-MS instrument companies have very active research and develop-
ment 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 him
or her aware of what the technique is capable of achieving and where new develop-
ments might be taking it.
 2 Principles of Ion
Formation
Chapter 2 gives a brief overview of the fundamental principles of ion formation in
ICP-MS—the use of a high-temperature argon plasma to generate positively charged
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 aerosol, 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 one or more electrons 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, transporta-
tion, and detection of significant numbers of positively charged ions that gives ICP-
MS its characteristic ultratrace detection capabilities. It is 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 transpor-
tation of negative ions is different from that of positive ions, most commercial instru-
ments 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

5
6 Practical Guide to ICP-MS

Ions Atoms Gas Solid Liquid

Sample
aerosol

Ionization Atomization Vaporization Drying

FIGURE 2.1 Generation of positively charged ions in the plasma.

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, an orbiting electron 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 converted
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.

e-
e- e- e- e-
e-
e- e- e-

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

e-

24 e-

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

Principles of Ion Formation 7

e-
e-
e- e- e-
e-
e- e- e-

24 p+ e- e-
e- e- e-
e-
28 n
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+).

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
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%, respec-
tively, 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.
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 the 65Cu+ ion on the right, which is 30.83% abundant. You can also see small
peaks for two zinc isotopes at mass 64 (64Zn+) and mass 66 (66Zn+). (Zinc 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 occur-
ring isotopes of all the elements.
8 Practical Guide to ICP-MS

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

Number of protons (p+) 29 29

Number of 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 calculated using the formula

0.6917n (63Cu) + 0.3083n (65Cu) + p+ and referenced to the atomic weight
of carbon.

6.0

Cu+
63
5.0
69% abundant

4.0
Counts (×10–5)

3.0
Cu+
65

31% abundant
2.0

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+.
 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
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 201 Hg 13.18
Principles of Ion Formation

100
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 99.660 100 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 13.629
60 Ni 26.223 120 Sn 32.59 Te 0.096 180 Ta 0.012 W 0.13 Hf 35.100

FIGURE 2.5 Relative abundance of the naturally occurring isotopes of the elements. (From UIPAC Isotopic Composition of the Elements, Pure and
9

Applied Chemistry 75[6], 683–799, 2003.)

Exploring the Variety of Random
Documents with Different Content
could have been dead even before he was missed by Trafford; you
recall the tutor coming here to ask for him that day whilst we were
talking to you? The coal men had been after getting in your supply
—?”
“Yes, yes!” Orbit nodded quickly, impatience at McCarty’s garrulity
evident in his voice now. “Most inconvenient time, too, just before
the arrival of my guests! I had ordered it days before.—But these
idle speculations about Horace won’t help any, I suppose; the
Goddards themselves can scarcely be more anxious than I am for
some real results from this investigation!”
“Well, the inspector’ll be around in a little while, if you’re home.”
McCarty signaled to Dennis with a jerk of his head. “There’s
something in his mind he wants to talk to you about, and maybe you
can help him. We’ve not made much headway, and that’s a fact, but
’tis the worst case ever the department handled.”
There was an injured note in his voice and Orbit responded with
sympathetic tact:
“I’m sure you’re doing all you can and I shall be glad to see the
inspector or either of you at any time.” He pressed the bell and as
Ching Lee threw open the door he added: “The medical examiner
has come to no definite conclusion about the girl’s death? If it was
really gas of some sort it seems odd its nature can’t be determined.
But I speak ignorantly, of course; I know little or nothing of
chemistry in any form.... I shall wait to hear from the inspector.”
“I don’t get you this morning at all!” Dennis remarked plaintively
when the door of Orbit’s house had closed behind them. “While I
waited I saw you kidding the little heathen out in the side court and
then you went to the back, and Orbit came in and I had to string
him. For what did we go there in the first place? You’d little to ask
him and you got less for it, when you did finally come in! Is it
stalling around for time, you are?”
“There’ll be no more stalling, Denny!” There was a new note in
McCarty’s voice. “’Twas little I got from Orbit himself, but we’ll go to
Goddard now. I want to use his telephone.”
“Why didn’t you use Orbit’s?” Dennis demanded. Then a light
broke over his face. “’Tis the inspector you’ll be calling up and
there’s them in that house back there—! Mac, for the love of the
saints, have you found out something? Have you struck it at last?”
The dog Max who was lying in the patch of sunlight that filtered
down between the houses, raised his head at the eager expectancy
of Dennis’ tone and McCarty glanced at him thoughtfully.
“’Twas not me that struck anything, Denny, and ’tis only a guess
yet but ’twas it ought to have struck me before this!” he replied.
“We’ll have a little while to wait, and I’ll thank you to keep Goddard
and that Trafford talking and not leave them out of your sight whilst
I’m telephoning; I don’t want either of them listening in!”
“Then ’tis one of them, as well as somebody in Orbit’s house—!”
Dennis gaped in amazement. “Mac, what kind of a devilish plot is it?
You said last night ’twas too sickening to talk about—!”
“’Tis worse!” McCarty interrupted tersely. “Let be till we see what
comes!”
Winch the butler, looking more aged and fragile than ever, ushered
them into the drawing-room where Goddard presently appeared
followed by Trafford. The stout little man had changed markedly in
the past few days; his eyes were dim and the flesh of his face hung
in folds as though deflated, while his voice had the trembling
overtone of that of an old man.
“You—you have news for us, McCarty? Some word has reached
you of—of Horace?”
“I think I know where he will be in a little while, Mr. Goddard,”
McCarty replied quietly. “I’ll have to ask you to wait, though, till the
inspector gets here, and I’ll have to ’phone him. Can I use the one in
your smoking-room? I want to be dead sure it’s private for I’ve got
to talk confidential.—Thanks, Trafford, I know the way.”
 Waiting only for Goddard’s nod he cast a quick admonitory glance
at Dennis and hastened away. The latter cast about wildly in his
mind for a safe topic to pursue, but the burden was lifted from him.
“What is it, Riordan? For God’s sake, what does McCarty mean?”
Goddard turned to him.
“I’ve no notion,” Dennis replied, truthfully enough. “He’s been
working on something for the last day or two while I was on—on
other duty, but I expect things will be moving now. You’ve heard
nothing yourself?”
“Nothing!” Goddard raised a shaking hand to his forehead. “I tell
you, Riordan, we can’t—we can’t endure much more of this! If my
boy were in his grave we would at least know it and learn somehow
to bear it but the uncertainty is driving us mad! Unless we know the
truth soon I shall lose my wife, too!”
“We’ll know.” Dennis spoke with the assurance of utter conviction.
“Mac’s not one to start anything he can’t finish and I’ve worked on
too many cases with him not to know the signs. If he says the lad
will be found in a little while he means it but—but maybe it’ll be sick
or something he’ll be. Worrying, you see, and being away from
home—!”
Words failed him, for he had read in that ominous quietude of
McCarty’s voice a hint of trouble yet to come. He floundered
desperately in a tender-hearted attempt to pave the way. The
situation was saved for him by the sudden reappearance of McCarty
himself in the doorway.
“Denny, go out and call Yost in; the inspector has instructions for
him.” The latent excitement had intensified in his tone. “Don’t tell
the whole block what you’re doing, either!”
“I don’t know, myself!” Dennis retorted, preparing nevertheless to
obey. “Shall I take his place?”
“Now you’re talking!” McCarty nodded approval. “He’ll have a
message for you when he comes out and ’twill be all right to do
what he says. The other night in my rooms when we were starting
out to pay a couple of calls I gave you something to carry; did you
think to bring it with you now?”
The revolver! Dennis started violently and one hand sought his hip
pocket involuntarily as he nodded.
“All right. You’ll know what to do with it after you’ve talked to
Yost. Send him in.”
Dennis departed, found the headquarters’ man patrolling listlessly
on the sidewalk and delivered the message. Then he paced from
gate to gate in a daze of bewildered thought. Things were indeed
moving. He could not fathom what was in McCarty’s mind, but he
felt a grim portent in the very air of the sunlit, semi-deserted block,
like the shuddering silence before a blast.
The elder Sloane returned; the housemaid from Mrs. Bellamy’s
who had taken charge of little Maude immediately after Wednesday’s
tragedy went out upon an errand and came back before Yost left the
Goddard house. When he reached Dennis’ side his former
listlessness had vanished.
“Who’s gone out of the Mall?” he demanded.
“Only a hired girl from Mrs. Bellamy’s, and she came in again.”
Dennis replied. “What is it? Mac said you’d tell me what to do, and
he asked had I a gun with me. I have.”
“Then go take the east gate.” Yost pointed. “Open it if any one
wants to come in but let no one out if you have to drill them full of
holes! Get me?”
“’Tis the clearest thing I’ve heard this day!” Dennis averred. “I’ll
do no drilling but there’ll no one pass me! What in hell is doing, do
you know?”
“Only that the inspector’s coming as fast as the chief’s own car
can get here and he’s bringing a young army with him! It looks like
the end of it, Riordan!—Hey, there goes the Bellamy butler! I’ll have
to head him off, for I’m taking the west gate myself. There’s
somebody wanting to get in yours.”
Dennis hurried to the gate opening on the Avenue and with much
ceremony admitted an open touring car in which sat a young lady so
bewilderingly beautiful that he gaped after her in respectful
admiration until she disappeared in the Parsons house. Was that the
old gentleman’s niece? He was recalled to his present duties only
when the chauffeur turned and drove straight toward him once
more, halting only a bare few feet away.
“Hi, there! Open the gate!”
“Nothing doing,” Dennis retorted firmly. “Orders from police
headquarters. Them that gets in, stays in.”
“Yah! You green rookie! I’m Mr. Parsons’ chauffeur, if that means
anything to you, and I’m in a hurry!”
“Then you’re going to be disappointed.” With a gingerly reluctance
which would have meant sudden death had he been faced by an
earnest antagonist, Dennis produced his revolver. “’Twould mean
nothing if you drove the chariot of the Angel Gabriel, you’d not get
through that gate!”
A wordy combat ensued interrupted only by the appearance on
the Avenue side of the barrier of young Mr. Brinsley Sloane. He
hesitated, turning slightly pale at sight of Dennis’ formidable
weapon. The latter called out peremptorily:
“’Round to the other gate if you want to get in! This guy’ll get out
if you open this one! Police orders!”
“Really!” Brinsley Sloane stared through his huge-rimmed glasses.
“This is extraordinary! What has the fellow done, officer?”
Dennis swelled visibly at the appellation.
“Nothing yet,” he admitted. “He won’t, either, unless he’s wishful
to croak!”
 “Is the fellow mad?” Young Sloane addressed the chauffeur who,
scenting an ally, broke into injured explanations. The argument
became a triangular affair although the scion of the Sloanes
remained discreetly on the neutral ground beyond the gate. It was
ended at last by a subdued hubbub at the farther one. Dennis
turned to behold the inspector drive slowly in with several familiar
officials of the department; his car was followed by a larger one
packed with husky men and bristling with long-handled shovels.
Dennis uttered a startled exclamation and Brinsley Sloane let
himself hurriedly in with his key while the Parsons’ chauffeur no
longer exhibited any desire to depart. Martin appeared suddenly
from nowhere and addressed the astounded deputy.
“Beat it, Riordan; Mac wants you! I’ll take over your job.”
Dennis needed no second bidding. He set off at a shambling run,
unconsciously brandishing his revolver as he went and Goddard,
Trafford and McCarty emerged from the house to meet him. He
noticed as in a daze that the tutor braced his employer with an
almost filial manner and the older man leaned heavily upon him,
pallid but composed.
The men with the shovels were piling out of the second car and
he saw that they carried in addition enormous sooty baskets. His
eyes turned wonderingly to McCarty as the inspector hurried up.
“All set, Mac! The boys are posted all around the walls. What do
you want done?”
“Open that coal chute first!” McCarty pointed to the square iron
plate like a trap-door in the center of the side court, over which Max
was still hovering. “Then send your men down in Orbit’s cellar to dig
like hell! There’s thirty tons to be moved by the ten of them in an
hour and a thousand dollars from Mr. Goddard to the guy that takes
out the last shovelful. Go to it!”
Ching Lee had appeared in the front door of the Orbit house and
Jean at the side one, while André peered from the kitchen window.
All at once the houseman was brushed aside and Orbit strode out.
 “What’s the meaning of this?” he demanded.
“We’re going to move your coal, Mr. Orbit,—the coal that was put
in so quick the very hour that Horace Goddard disappeared!”
McCarty replied. He turned abruptly to the group who were lifting
the cover of the chute. As it rose and then fell back ringing on the
pavement, a long-drawn howl broke upon the air; Max, tense and
quivering, was gazing down into the aperture and McCarty motioned
toward him.
“’Twas him and not me got the hunch first, inspector. ’Twas the
lad’s pal, here—Max!”
 CHAPTER XXI
THE BLACK PYRE

“G OOD GOD!” Orbit exclaimed in horrified accents. “You don’t

mean that the little fellow tumbled down the chute! That he
was buried beneath the coal!—Goddard, my old friend, what can I
say to you! Surely this is only a vague supposition, a last resort! It
would be too dreadful, too pitiful!”
Goddard’s face worked but he was unable to reply and Orbit
turned to the men who, with baskets and shovels, were filing around
the rear of the house.
“I’ll add a thousand to Mr. Goddard’s! Work as you never did
before!—Inspector, can such a fearful thing have occurred? It is
incredible! How could the little chap have fallen down to the cellar
without being seen? I suppose any outcry he might have made
would have been drowned by the noise of the coal itself but—oh, it
is too utterly horrible!”
His shocked, broken tones trailed away into silence and then from
below there ascended through the open chute the ring of shovels
and the clatter of coal falling rhythmically into the baskets. A
tortured groan was forced from Goddard’s lips. Max crouched with
his forepaws hanging over the edge of the aperture and his nose low
between them, the hair rising in a ridge along his back and a soft,
anxious whine pulsing from his throat.
Dennis turned away with a shiver, and saw that Gardner Sloane
had joined his son on the fringe of the group. Snape and the maids
of Mrs. Bellamy’s staff were gathered in a little knot just behind, with
the Parsons’ chauffeur, Danny Sayre the page boy, and the aged
butler of the Sloanes, while Benjamin Parsons himself had emerged
upon the steps of his home and the lower windows of the Goddard
house were thronged with the servants. From a window just above
Orbit’s conservatory the staring face of little Fu Moy looked down in
shrinking wonder.
The rhythmic, dreadful scrape and rumble from beneath their feet
went on as though it would never end. Goddard swayed weakly but
Trafford flung an arm about his shoulders. The inspector had replied
to Orbit with noncommittal gravity and now they conversed together
in an aside, while Dennis edged over to McCarty.
“Why ever didn’t you tell me?” he whispered. “No wonder you said
’twas fair sickening to think of, Mac! If the poor boy’s found down
there ’twill be one crime that’s no crime at all! How did you know?”
“I don’t know!” McCarty responded candidly. “’Tis the only guess,
though, that will cover the facts as they come to me, but Max
needed none; I’m banking on the dog’s instinct, Denny.”
“Look at the back of him! It makes my own hair lift the hat from
my head to see it!” Dennis shivered again. “Will they never have
done with the shoveling? I could scream like a woman!”
Some of the Bellamy servants had indeed begun to sob
hysterically but they quieted at a look from McCarty. Parsons was
slowly crossing the street and his chauffeur stepped aside for him.
Dennis saw that several older men from the detective bureau were
circulating unobtrusively among the different groups and two of the
officials who had come in the car with the inspector approached him
now. He presented them to Orbit and the interrupted consultation
was resumed now between the four.
Dennis surreptitiously took out his watch, an ancient affair of the
turnip variety. The men had been at work for nearly forty minutes;
he recalled the blowing of the one o’clock whistles when Martin
came to relieve him at the east gate. In a little while, now, they
would know the worst! If only the dog would stop whining!
He looked at Trafford and the young man met his glance with a
stare of agonized inquiry but the man he was supporting reeled and
he braced himself for a firmer hold. Then Benjamin Parsons stepped
quietly to Goddard’s other side.
“Lean on me, my friend.” He spoke in the gentlest of accents. “I
am old but strong, an elder brother here to lend a hand. We will
wait, and pray.”
Goddard’s dull eyes filmed and he rested his hand in the arm
offered, saying no word. A lump rose in Dennis’ throat.
“Mac, for the love of God, will they finish this? ’Tis more than
mortal can bear! I’ve dug at a fallen wall with the bare hands of me
and the best lads of my company buried under it, but ’twas not as
bad as this! Orbit’s all in, and no wonder!”
Henry Orbit had turned and was gazing at the coal chute in
horrified fascination, his highly-bred face quivering and eyes glowing
with an awful intensity. As though drawn toward it against his will he
advanced a step or two and the officials also moved forward. Then
he seemed for the first time to behold McCarty.
“Had you the least suspicion of this when you came to me an hour
or so ago?” he asked, his voice a mere toneless breath. “Why did
you not tell me? I have three strong men in my house and I myself
would have led them! Is this your doing?”
“The inspector brought them, Mr. Orbit.” McCarty replied. “I told
you he was coming in a little while but he don’t always tell me what
he’s got planned.”
“He should at least have notified me!” Orbit ran his hand through
his dark, graying hair. “I could have started the work.—But this is
sheer madness! The child cannot have met such a horrible death!”
“We’ll know soon enough.” McCarty’s tone held a note of
sternness. “In a minute or two more—!”
As though his words were a signal, the clank and rattling patter
from below ceased abruptly and a moment of electrified stillness
ensued. Then it was broken by a rising murmur of hoarse voices
which were in turn drowned by the sustained hail of coal being flung
in every direction.
Orbit uttered a stifled exclamation and then stood immovable as a
second groan forced its way from Goddard. One of the Bellamy
maids shrieked aloud. Then the noise from the cellar ceased once
more and the dog rose slowly lifting his nose into the air. A low,
wailing cry broke from him. At that moment a grimy head and
shoulders rose in the opening of the coal chute and a hoarse,
shuddering voice addressed McCarty.
“We’ve—found it, sir!”
The various groups merged and swept toward the aperture then
shrank back again in horror. A hubbub of subdued cries came from
among them but Eustace Goddard did not hear. His head had fallen
forward, his knees sagged and doubled and he slumped, insensible,
between the two who supported him. Instantly two plainclothes men
were beside them and the unconscious man was carried into his
house.
It was significant that neither McCarty, the inspector, nor the two
officials had moved to assist him. Now as Orbit, after his first
horrified recoil from the brusque announcement, turned and hurried
into the house they followed, with Dennis bringing up the rear.
Aware of his doubtful status in the eyes of the strange officials he
remained discreetly in the background and when he caught up to
the little group they were standing in the rear hall before the open
door leading to the cellar steps, with Orbit at their head and Ching
Lee, André and Jean by the pantry.
Orbit was staring down into the brazen, orange glow of the
electric lights in the cellar, listening to the shuffle of feet and the
murmur of rough voices lowered in pity. Then there came a slow
tread and two of the shovelers appeared bearing between them
something slender and pathetically small wrapped in a heavy dark
cloth.
 As they ascended the stairs the servants and even the officials
drew back but Orbit stood his ground with no sound or movement.
Only his eyes followed the men with their burden as they mounted,
passing him so closely that he could have reached out and touched
them. Then he turned and passed upstairs to his sitting-room,
followed by his uninvited guests.
The murmur outside rose to a swelling chorus of cries and then
was abruptly shut out by the closing of the door. Orbit turned with
both hands raised to his head and a shuddering groan came from his
shaking lips.
“This is horrible!” he gasped. “Gentlemen, I shall ask you for an
explanation, but not at this moment—I am too inexpressibly shocked
—”
“The explaining will have to be done now, Orbit!” McCarty, after a
glance at his superior, stepped forward. “’Twill not come from us,
either!”
“What do you mean?” Orbit demanded. “Surely you are not mad
enough to insinuate that I knew that the child was lying there? It is
monstrous! Do you think I would not have let you know?”
He turned to the inspector.
“Inspector, when did you learn what had become of the poor little
fellow?”
“I didn’t; it was McCarty,” the inspector admitted frankly. “He told
me this morning that he might have news for me by noon but until
he telephoned ordering the squad of men with shovels I hadn’t an
inkling.”
“Then you—?” Orbit turned again to McCarty.
“’Twas the dog first put it in my head by hovering all the time
about that coal chute,” the latter responded. There was a new note
in his voice as he went on. “It struck me too, as kind of funny you’d
be having that coal put in an hour before your party, dirtying the
place all up; even if it had been ordered you could have sent it away
again for you’d not be lighting up your furnace for weeks yet. I
found then that you never ordered it till half an hour before it got
here and you’d ’phoned three times, at that, to hurry it up, yet you
told me this morning that it had been arranged four days ago. About
twenty minutes before you sent for it first you went down to the
kitchen and got a glass of milk from André. Did you drink it yourself,
Henry Orbit?”
“I did not!” Orbit’s eyes seemed burning into his face. “It was for
Vite, the monkey!”
“But Vite was locked up at the top of the house to be out of the
way of the party and Ching Lee had the only key; Fu Moy told me
so.”
“Fu Moy is only a child and does not understand English well; Vite
was not locked up until just before my guests arrived. What are you
trying to insinuate?”
“Nothing. I’m telling you what I know. Fu Moy understands a lot
more than you think, Orbit! What time did Horace Goddard come
over to see you Tuesday afternoon? If that glass of milk was for the
monkey, why didn’t you ring for it instead of going yourself to the
kitchen; was it because you wanted nobody to know the lad was
here? What did you put in that milk, Orbit, to make Horace
unconscious or kill him, the way you poisoned Hughes? I know from
André how you got all the servants out of the kitchen and pantries
after, so you could get the lad’s body down to the cellar without
being seen but why did you do it? What reason had you for bringing
such a horrible death on the child who’d done you no harm? What
reason did you have for murdering the valet who’d looked out for
your comfort for more than twenty years? Why did you put poison
gas made from the formula you bought from Hinton Sherard into the
Bellamy baby’s toy balloon to kill both her and her nurse? How did
you fix it to burst when it did and what chance had you to pump the
gas into it? You’re far from crazy, Orbit! Why did you take the lives of
these people you had no grudge against, no reason for wanting out
of the way? Was it because of the blood that’s in you from
generations back urging you on? Answer me that, Henry Orbit!”
“I shall answer nothing—to you.” Orbit’s dark eyes blazed but his
voice was dangerously calm. “You admit that I am not insane; I
cannot say as much for you in the face of these monstrous
accusations!—Inspector, if you are in authority at this highly irregular
proceeding, am I to understand that I am formally charged with this
atrocious series of crimes? Am I to consider myself under arrest?”
Inspector Druet glanced uncertainly at McCarty and the latter
nodded, a world of mingled demand and entreaty in the slight
gesture. The inspector hesitated for a moment and then drew a
deep breath.
“You are!” he replied. “I arrest you, Henry Orbit, for the murders
of Alfred Hughes, Horace Goddard and Lucette Guerin!”
The two other officials after a startled glance between them
advanced one on each side of Orbit, but he shrugged and took a
step forward.
“That being the case, I shall not say another word. Now you may
play on this ridiculous farce for the moment. In the meantime, may I
ask your indulgence for a few minutes? I desire merely to seat
myself at that desk over there and write a short note to the one
person in the world most interested, besides myself, in this
extraordinary situation. I shall seal and address the envelope and
leave it upon the desk, for you to deliver at your discretion. Lock the
drawers of the desk if you will; I can assure you, however, that I
have no intention of taking any weapon from them to defend myself
or attempt assault upon you!”
The contempt in his tone was galling and even the inspector
winced beneath it, so compelling and dominant was the personality
of the man before him. He nodded.
“Write your note, Mr. Orbit, only make it short. If the news of this
gets out before we can take you downtown all the reserves in the
city couldn’t protect you!”
 Dennis turned in stupefied amazement to McCarty, but the latter
was watching Orbit who had seated himself at the desk. He wrote,
not hurriedly but without hesitation; a faintly amused smile curved
his mobile lips, and when he had finished he sealed the envelope
with a steady hand, wrote a name and a single line beneath it,
propped it against the inkwell and rose.
“Now, gentlemen, I am at your disposal,” he said. “I am ready to
accompany you—if you can find me!”
The last words were uttered in a tone of ringing challenge and his
hand slipped beneath the edge of the desk. On the instant, before
the five men grouped before him could move or draw a breath the
room was filled with rolling billows of black, foul smoke which
belched forth in clouds from around the wainscoting of the wall as
from the mouth of a volcano, obliterating everything about them.
Startled, warning exclamations came from the two officials and a
cry from the inspector:
“To the windows! Look out for poison gas!”
McCarty had groped grimly forward but Dennis was more
thoroughly at home in the crisis than he had been at any time since
the inception of the affair. He shouted directions and
encouragement, darting about as unconcernedly and with as much
certitude as though his eyes could penetrate the murky, opaque
gloom which enveloped him.
The sound of their own rushing footsteps and the successive crash
of furniture as the officials lunged against it drowned out all others
until close at hand a door slammed and a mocking chuckle of
laughter seemed to drift back to them.
“He’s gone!” One of the officials gasped, as he found a window at
last and flung it open.
“He won’t go far!” the inspector retorted grimly. “Find all the
windows and doors and let’s get a draught through! I want that
letter he wrote!”
 In the rush of fresh air which came swirling in, the room rapidly
cleared and they saw that it was indeed empty of any presence save
their own but the white square of the envelope tilted against the
inkwell was plainly discernible and the inspector seized upon it.
Choking, strangling, with smarting, streaming eyes, he peered
closely at the inscription and then threw up his head.
“Great guns! It’s addressed to McCarty!”
 CHAPTER XXII
ANNIHILATION

M CCARTY stumbled forward and took the envelope held out to

him, turning to the window where he bent forward for the rush
of cool air to play over his face. It was addressed simply to: “Ex-
Roundsman McCarty” and the second line read: “Delivered by hand.”
Slitting it open he glanced quickly down the few lines it contained
and then at his companions.
“’Tis for all of us, I’m thinking,” he said. “Listen!
“‘My dear McCarty. It has been a pleasure to meet such a man as
you and we part with regret, at least on my side. You are quite correct
in your deductions as far as you have expounded them and I regret
that I cannot wait to hear you reconstruct your complete case but
time presses. The last drawer of this desk at which I write has a false
bottom; remove it and you will find a portion of my diary for the past
fortnight, placed there in readiness for this eventuality. I bequeath it
to you for your further information and in most sincere admiration, for
where I go I may take nothing material with me, although I shall not
leave my body behind. I am not going to death but to annihilation.
Checkmate!
“‘Henry Orbit.’”
“What does he mean?” the inspector demanded. “What kind of an
escape has he planned? Not take his body with him and yet not
leave it behind? What’s that about ‘annihilation’?”
“We may know for ourselves if we stand here guessing about it
instead of stopping him!” McCarty thrust the letter into his pocket
and made for the door beyond which the two French servants and
the Chinese one had halted. “He’s planned to destroy himself
entirely, body and all, and if it’s by blowing the whole house up I’d
not be surprised! Come on!”
 The others hurried after him but in the hall he paused to confront
Ching Lee.
“’Twas the man you worked for, Orbit, who was the murderer!” he
announced. “You knew that, though; you suspected it from the first,
after the queer way Hughes took sick from drinking the medicine
Orbit mixed for him before dinner! That’s why you went next
morning dressed like a Chinese laborer down to the quarter where
Hughes died, to get what dope you could about it! If you don’t want
to get pinched for being accessory, you come clean! Which way did
he go just now?”
“I did not see.” Ching Lee’s face had betrayed no slightest flicker
of emotion and his tone was perfectly composed. “I came upstairs
only when the shouts and the odor of smoke led me to think that
the house was on fire. I saw no one, nothing.”
“Where is his laboratory? Where is it that he locks himself away
sometimes, a place that none of the rest of you enters?” McCarty
rapped out the questions like shots from an automatic. “There’s not
a minute to spare! Is it upstairs or down?”
Ching Lee was silent, but Jean with chattering teeth spoke up
suddenly:
“It is upstairs! I see him when I reach the head of the staircase.
He rush’ from that room through all the smoke and he is laughing!
Then he mount to the next floor and on above, and in the attic there
is a room which none but he may enter, which he guards with a
heavy steel door—!”
“Show us where it is!” McCarty ordered. “That’s where I fell down.
I might have figured that a guy with his brains would have looked
out for everything, even failure, and planned a way out for himself!”
He started on a shambling trot for the back stairs, with the others
crowding after, but Jean slipped past him and leaped up three steps
at a time. Past the guest rooms and servants’ quarters to the
storerooms and the attic above the searchers hurried, pausing only
before a small wooden door.
 “I thought you said ’twas made of steel!” McCarty turned the
handle and then put his shoulder to a panel. “We’ll have to break
through.”
“It is but the false one, the cover,” explained Jean. “Just beyond is
the real door of steel.”
“You’re sure he came this way? There’s nowhere else he could be
hiding?” McCarty glanced at the Frenchman and then turned to his
companions. “Stand back! We’ll have this down!”
But the small door was stouter than it looked and it required the
combined efforts of Dennis and one of the officials as well before it
yielded and crashed inward, only to lean, as Jean had said, against a
second door a foot or two beyond, which presented to their
impatient gaze a solid sheet of tempered steel.
“We’d never get through that except with soup and God knows
what’s beyond it that would blow us all into the next world!” McCarty
exclaimed. “Inspector, will you ’phone for an expert from
headquarters? There’s nothing to do but wait. We know where he is,
though; that’s some comfort!”
The inspector hurried downstairs and the others grouped
themselves before the wall of steel separating them from that which
lay on the other side, after clearing away the débris of the wrecked
door.
“There’s not a sound from in there!” Dennis moved over to
McCarty. “What’s he doing, do you suppose? Fixing a train of
powder, belike?”
“He is not!” McCarty responded. “If he’d meant to blow us up he’d
have done it down in his sitting-room instead of turning that infernal
smoke on us. He must have had that all fixed and ready to blind us,
so that he could make whatever kind of a getaway he’d arranged.
You couldn’t hear a cannon go off behind that solid steel, but
whatever he’s doing, ’tis only to himself; you’ll mind the letter he
wrote me? He wouldn’t have spoke of his diary unless he intended
us to read it and it’s all part and parcel of his character, Denny. He
couldn’t bear to go without the world knowing how clever he was!”
“‘Clever!’” Dennis shuddered. “But what did he do it all for, Mac?
You asked him that when you accused him and he didn’t answer.
He’d no reason and yet he wasn’t crazy! He’d such a grand manner
and a way of making you feel like the scum of the earth in his
presence without even trying to, that I would never have suspected
him in the world! How you came to guess it is beyond me!”
“I’d the key to it all right from the start, only I didn’t know it!”
McCarty responded as the inspector bounded up the stairs. “I’m only
disgusted that the truth didn’t come to me sooner, and maybe the
little lad and the nurse Lucette would have been spared.”
“Two of the best men in the department are on their way!” the
inspector announced. “I had to stop to send in a second call for
reserves to hold back the crowd that’s trying to storm the gates, for
the news has got out somehow! Martin and Yost sent in the first call
but the boys who responded can do no more with that mob than a
one-armed sheriff in a riot!—Any sign from in there?”
The officials shook their heads and Jean remarked:
“I have seen once, when he goes in and does not know that I am
near to him. Before he close the door I think that I see others still
beyond this, but they are open and at the end is a room with shelves
covered with bottles and glass tubes of a strange shape. On the floor
is a great round tank of some metal higher than one’s head! I think
then that he is perhaps a scientist, a great man! It is only after
Hughes die and then the little Horace disappear that I begin to think
he is a demon!—Here is André.”
The stout chef had labored up the stairs and behind him the
flowing robes of Ching Lee moved like a shadow.
“You shall get him?” the former demanded. “You shall put him in
that chair of electricity? Parbleu! When I think of the little Lucette so
pretty and good, and the little Horace, I could run my knives through
his heart! It is I who give him with these hands the glass of milk
with which he drugs the little Horace and then I watch while that
mountain of coal descend into the chute and I suspect nothing! It is
only when my countrywoman die there before him and they say it is
the poison gas that I think of this room and the so horrible odors
which come from it when he open the door!”
“When did you see him come here last?” McCarty asked.
“On the afternoon of Wednesday, but a half hour before he cry out
for help from the conservatory where Lucette dies!” He spread out
his small fat hands in an expressive gesture. “I think it is to this
room that he comes for I am in mine with the door a little open and
he pass quickly and without sound; going up the stairs. He carries
something round and blue on the end of a stick and I think that I
must be mistake’ for it appears like the toy balloon of a child!
Nevertheless I watch and in a so short time, a few minutes, he
comes down again, still carrying the balloon. I tell of it to Ching Lee
later but he has not seen it in the conservatory and he does not
believe.”
“Look here, Ching Lee, why didn’t you tell somebody what you
knew?” McCarty addressed the Chinaman who stood aside, silent
and seemingly impassive. “Why did you let Orbit go on with his
crimes when a word to us would have put him where he could do no
more harm?”
“Mr. Orbit is rich, of a great family and power in high places, and—
he is a white man.” Ching Lee responded in his unemotional
singsong tones. “I too am of high degree and not without honor in
my own land but I was forced to leave it and here I am a poor man,
a servant without friends or influence—and I am yellow. Who would
believe my word against his when I had no proof? I would have
been cast into your prison but even there Mr. Orbit would have
reached me and silenced my tongue. There was the little Fu Moy to
consider, my nephew who is to be educated and go back with much
to teach my people; I could not leave him without protection. I could
only wait for you, who are white men, too, to see what lay before
your eyes.”
 “There’s something in that!” McCarty conceded. “Isn’t that the
bell? If it’s the men we’ve sent for bring them right up.”
“It is possible that he have shoot himself before we arrive here,”
remarked Jean. “There is a pistol which he keeps always in a drawer
of the little table beside his bed and to-day when he thrust me aside
at the door of the card-room to rush out and learn why all those
men with shovels have come I feel it in his hip pocket as he pushes
his way past. It is loaded always; that I know, for more than once I
have looked at it.”
Dennis glanced questioningly at McCarty who shook his head.
“He’s taking his body with him where he’s gone,” he reminded the
other in an undertone. “He’ll not do that with the shot of a gun!”
Ching Lee reappeared with the two experts armed with tools and
bags. After a cursory examination of the steel door one of the latter
turned to the inspector.
“Can’t be done in less than an hour unless we take a chance and
blow it off, and you said there might be explosives behind it that
would wreck the block,” he announced. “I don’t promise to do it in
that time but we’ll work as fast as we can.”
“Let’s go and have a look at that diary in the meantime,”
suggested McCarty. “Jean thinks there are more doors beyond like
this one and it may be night before they’re open! The boys can let
us know when they’ve got through.”
“All right.” The inspector turned, addressing the two officials.
“Want to come along? If it really is his diary, it ought to be about the
strangest document that ever fell into the hands of the department.”
With a few minor directions to the rest he led the way back to the
sitting-room and closed the door. The air was now quite clear of
smoke and only a faint, noisome odor lingered behind.
McCarty seated himself in the chair lately occupied by Orbit
himself and drew out the last drawer of the desk. It was filled with
open envelopes bearing cancelled stamps and he scattered them on
the floor in his haste to empty it.
“He told the truth about the false bottom,” he announced. “I can
feel it give but I wonder how does it open?”
One of the officials stepped forward.
“Shall I try, Mac?” he asked. “I was a custom house inspector
years ago and there isn’t a smuggler’s dodge I’m not on to; that
either lifts or slides and there may be a spring.”
“Go to it,” McCarty acquiesced briefly, and the other complied.
“Look here, Mac!” The inspector looked up suddenly. “Who
chloroformed Orbit the other night?”
McCarty chuckled.
“He did, himself! I got that the minute I saw the bottle, for there
wasn’t enough gone from it to put a kitten out! The towel was
soaked, but with water, and he’d just sprinkled enough chloroform
on it to smell. He didn’t want to lose his wits, you see, only to make
us think he was unconscious so he could get a line on what we were
after and hear our talk. He must have heard us coming up the stairs
and looked out or else doped out that it would be us, for it was
Denny and me that broke in that night. He paid me a return call the
next and rigged up a gun to shoot me in the dark, but I found it first
and fired it through the roof!”
“’Twas that I heard!” Dennis exclaimed. “Glory be! Well I knew
you were too old a hand to let it go off accidental, like you told me,
but little I thought you’d been near murdered, or I’d not have left
you, duty or no duty—!”
“There you are!” The detective lieutenant rose from his knees with
the false bottom of the drawer in his hand. “It was a new one on me
after all, but I managed to work it. There’s a lot of papers
underneath that look as though they’d been torn from a blankbook
and they’re covered with writing.”
 “It’s Orbit’s!” McCarty gathered the loose sheets up and spread
them on the desk before him. “Do you mind when he wrote that list
for me here in this very room, of the guests he’d had during the last
few months? The writing is the same, and ’tis dated; it looks like the
diary, all right! Do you want to read it, inspector? I’m not much good
at it, and if he uses as big words as he talks with—!”
Inspector Druet took the pages from him and seated himself near
the window. For a long moment he sat silent glancing over the
papers and as he read his face darkened and then paled. Then with
a sudden start he looked over to McCarty.
“My God, this is frightful! The man was the greatest wretch that
ever lived! He must have been mad, of course, but listen! This is
dated the thirteenth; that would be a week ago last Monday.—‘I
succeeded in making it to-day from the formula and tried it on the
white kitten from next door. The result was amazing! If it had been
known a few years ago the history of the war would have been
changed! If I could only experiment with it on a human, what a
magnificent way it would be for me to learn the thrill of that last
experience that awaits me! To take the place of providence, to play
at fate, to make destiny! The longing haunts me, I cannot rest, I
must know that ultimate sensation of power! I can’t use the gas,
though; I don’t need to see the death I bring about and it must
come far from the house. It will have to be the Calabar bean after
all, but whom shall I choose? Not André, his soufflées are admirable,
and Jean is the only servant who ever dusted my room and left
things where I could find them; not Fu Moy or Ching Lee, for one
never knows with these silent, yellow people when revenge will
come. Hughes’ services are invaluable to me but he is a dead loss to
society, it might even be benefited by his removal. I must decide!’”
“That was it!” McCarty nodded. “The longing for power, to feel
that he was the biggest man in the world; ambition with a warped
turn to it! ’Twas nothing but the lust of killing born in him that he
wouldn’t admit even to himself!—But go on, sir. What’s the next?”
 “Two days later, the fifteenth; that was Wednesday. He says: ‘It
must be Hughes. The neighbors are still amusing after their fashion
and I could not be sure they would go outside of the Mall
immediately. Physostigmine is soluble in alcohol; I could put a grain
or two in wine and leave it about but that will not do. I must give it
to Hughes with my own hand. I shall have to await my opportunity,
then give him a drink and send him on an errand to a strange part of
town. I cannot wait!’—That’s all of that entry and the next one is
midnight after the murder.—‘It is done! Hughes is dead and I have
killed him! I could shout, sing, dance as wildly as a savage about a
pyre and yet I am strangely calm, like a god! I am a god, for I hold
the power of life and death, I know what it is at last! The only
drawback was that it was too easy; Hughes has been dissipating
lately and it gave me an idea to-night. I mixed some bitters together
with a dash of absinthe—just enough for one dose—added two
grains of the powdered bean and put it in an old tonic bottle. When
Hughes came to lay out my things for dinner I told him he looked
badly, needed more air and exercise and persuaded him to go out
and take a long walk, breathing deeply. Then I gave him the drink I
had prepared,—poured it out for him myself and watched it pass
with a gurgle down his gross, fat neck! I looked at him when he put
down the glass and could not realize that it was actually
accomplished! The man standing there before me was a dead man
even though he still moved and talked and probably thought of his
dinner, and it was I who had done this! It had rested in my hands
whether he should live or die and I had condemned and executed
him! I shall never forget that moment of exquisite exhilaration, the
ecstasy of omnipotence! But I was discreet, I controlled myself. I
warned Hughes that the medicine might make him feel a trifle ill,
might even restrict his breathing but he must walk it off and he
would be greatly benefited. He actually thanked me—thanked me for
bringing death upon him! All the evening while Goddard and the
Sloanes were here, I kept my triumph to myself but nothing could
withstand my sense of power. My bridge was unsurpassed—I knew
that—and I played the organ as I never have played before!—And
then it came, that for which I had been waiting. Three blockheads
from the police arrived to tell me of Hughes’ death!’”
McCarty chuckled grimly.
“Fu Moy overheard that conversation and told me about it only to-
day—between Orbit and Hughes, I mean, about the medicine. He
don’t say anything about the fire after, does he?”
Dennis looked up quickly as the inspector glanced ahead and
nodded:
“Here it is.—‘There was only one flaw in this magic evening. I used
the powdered bean from the smaller box and it was just enough. I
did not open the other, forgetting how long it had been since its
contents had been exposed to the air, but thrust it down in a seam
of the cushioned chair and almost immediately after I had gone
downstairs spontaneous combustion occurred.’”
“What-t!” Dennis sat forward tensely, and McCarty chuckled again.
“I tried to read you that about Calabar bean in that article we had
at the fire house yesterday afternoon but you wouldn’t listen!” he
said. “I didn’t know what was this spontaneous combustion at all, till
you happened to explain this morning, little thinking what was on
my mind!... But what else does Orbit say about it?”
“He goes on: ‘Fu Moy discovered it and Ching Lee put it out.
Fortunately they did not find the box of Calabar bean.’—He raves on
again about his feeling of power, glorying in it, but that is all.” The
inspector slipped the page aside and glanced at the next. “This is
dated Sunday, the nineteenth. ‘The police were active yesterday but
they are quite at sea. I have no fear that they will discover anything,
although the one called McCarty seems to be possessed of a certain
amount of native shrewdness and logic. No uproarious comedy has
ever been so excruciatingly amusing as this investigation but I am
maintaining my pose of regretful employer of a worthy servant. I
only wish that I could have used the gas; I made a fresh supply to-
day only to be compelled to dissipate it unused. It is maddening!
The death of Hughes has not satisfied this craving but intensified it.
Death by violence, death that I may experience the sensation of
having caused it, while it is taking place—I hunger for it!’”
The shadows were lengthening in the room and the cries of the
mob outside the gates had subsided to a sullen murmur. In the
moment of silence that followed the inspector’s reading of the
paragraph, soft, slippered feet padded along the hall and Ching Lee
stood before them.
“The door has been opened,” he announced. “There is a second
steel one behind it, even stronger than the first, but the men are
trying a different acid and drill.”
“Very well, Ching Lee. Turn on the lights, will you?” The inspector
motioned toward the switch and in an instant the room was flooded
with a brilliant glow from the low lamps scattered all about. “Tell the
men to be as quick as they can, and let me know when they have
finished; no one is to enter that room until we come.”
The butler bowed and turning went up the stairs again. McCarty
eyed the papers still remaining in the inspector’s hands.
“Is there any entry in the diary for Monday?”
“Only this, but it means a lot, considering what came later: ‘Ching
Lee reminded me that the coal has not been ordered this season.
The dust from it is horrible, defiling my flowers and soiling
everything. I shall not arrange for it until frost has come. Yet there is
something fascinating, relentless, about the way it rushes down the
chute like a miniature, sable avalanche. If we were pigmies, what
death it could deal!’—Oh, there’s no doubt about it, Mac; the man is
unquestionably mad!”
“His ancestors weren’t; not all of them, at any rate!” McCarty
responded grimly. “If the next that he’s written is on Tuesday night,
it’ll be after Horace was killed.”
“It is!” Inspector Druet’s voice shook with loathing. “This is the
most damnable thing, Mac! He must have sat in that very chair
where you are now, gloating over it as he wrote!—‘Once more I
have usurped the prerogative of providence! I have taken a useless,
sickly life, foredoomed to failure because it lacked the stamina to
combat difficulties. Weakness! the only sin in the world! Had Horace
Goddard lived he would have profaned art with mediocrity and as I
look at the masterpieces about me I rejoice that his poor efforts are
destined never to see the light,—destined because I so willed it, I
am destiny! It was the luminal that put the thought into my mind,
although I had no idea then whom I should remove. I forgot I
possessed any till I looked over the store in my laboratory this
morning. Two grains of that innocent looking coal tar product would
bring oblivion in twenty minutes and the coma would last for two or
three hours, during which time death might be brought about in a
dozen different ways! I played with the thought, it fascinated me,
and I could fix my mind on nothing else, although Giambattista was
coming to play this afternoon. If I could only know once more those
intoxicating moments of last Friday night!
“‘It was, then, just after lunch, that Horace slipped over to ask if
he might study my Fragonard for a little while. He came by way of
the side door and none of the servants had seen him. I realized this
and as I looked at him it came to me what a really unnecessary life
his was, except in the fatuous eyes of his parents! What a subject
for that coal tar product—and then I thought of the coal itself, that
Ching Lee had spoken about yesterday. How easy it would be to
render Horace insensible and bury him under an avalanche of coal!
“‘I could not resist the idea, it took possession of me! I coaxed the
boy up to my sitting-room, induced him to drink a glass of milk in
which I dropped two miraculous grains of luminal, and then I went
and telephoned the coal-dealer. If he could not deliver, the boy
would wake none the worse and my plan would only be deferred,
but the order went through and when I rejoined him Horace was
already drowsy. I shall never forget the exquisite agony of suspense
during that half-hour. Horace slept at last and although I had to call
the coal-dealer twice more my plan succeeded! I carried Horace to
the cellar unseen and just in time, for the coal arrived and the crash
of it tumbling down the chute was like the roll of maddening drums!
To hear it was enough, I did not want to see, and I was again in my
sitting-room spraying the black dust from my flowers when the man
McCarty and his associate were ushered in. I am not quite sure
about McCarty; I have not underrated him, he is the type of the one-
time policeman, elemental, phlegmatic, devoted to routine and
without initiative, and yet he seemed to-day to be studying me!’”
“He had me right!” McCarty grinned. “’Twas what I went there
for!”
“And me thinking you were stalling, and not getting it at all!”
Dennis shook his head. “He’d a grand opinion of himself, all right,
but a poorly-read one of you, Mac!”
“Orbit goes on to mention Trafford’s call to inquire for Horace
while you were here.” The inspector had been reading ahead. “Then
he starts on to rave about the musicale and how he felt with the
lad’s body under his very feet; he says that at the organ he
surpassed Giambattista on the violin and he was drunk with what he
had pulled off all the evening.”
“He played all by himself later,” McCarty observed. “A funny,
childish little tune and yet with something threatening and malicious
about it, and whilst Denny was getting shaved this morning I found
out what it was—a witch’s song from an opera called ‘Hansel and
Gretel,’ after the crone has lured children to her house and made
away with them! That ought to have told me something if I’d known
what it was!”
“He says nothing of planning another murder, does he?” Dennis
asked. “He must have run wild when he committed one the very
next day—!”
“The laboratory is open now, sir.” Ching Lee had reappeared so
noiselessly that he seemed to have sprung into being on the
threshold. “No one is there.”
“No one!” The inspector started up with a cry, cramming the
papers into his pocket. “My God, he has escaped, after all!”
 “I don’t think so, sir,” McCarty demurred gravely. “Perhaps the men
didn’t see him, but—we’d better lose no time!”
They sprang up the stairs and passed the two great steel doors
swinging idly on twisted hinges, into a long, low room, looking very
much as Jean had described it. The closed cupboards below the
shelving were too small to have held a human body and there was
no other hiding place nor any way of egress save the door by which
they had entered.
“We’ve been done, Mac!” the inspector exclaimed again, ruefully.
“Unless the boys outside caught him, we’ll have a long chase on our
hands!”
“No.” McCarty stood looking up meditatively at the huge circular
vat which occupied the center of the floor and rose for six or seven
feet like a miniature gas tank. “Give me that step-ladder, will you,
Denny? I want to see is this empty.”
“By the smell of it, it’s not!” Dennis commented. “’Tis worse than
asafœtida!”
He brought the ladder and McCarty ascended cautiously and
peered over the top. The vat appeared to be almost filled with some
thick, murky liquid with an oily film floating on the surface. When he
had stared down into it for some minutes he descended, his ruddy
face pale and tinged with greenish shadows.
“Mac!” Dennis caught him solicitously as he reeled. “It’s sick you
are! Come away out of this! Orbit’s not here!”
“If I’m sick it’s from my own thoughts, Denny!” McCarty replied
shakily. “Where does that pipe lead to from the bottom of the vat?”
“To that huge receptacle over there.” It was the detective
lieutenant who answered, pointing. “It’s to draw off whatever might
be in there, I guess.”
“Turn the cock, then, will you?” McCarty sat down suddenly and
held his head in his hands. “I want to see the bottom of that vat!”
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