CHAPTER 1.

INTRODUCTION TO MASS SPECTROMETRY

Henry P. Longerich and Wilfredo Diegor

Department of Earth Sciences and Centre for Earth Resources Research
Memorial University of Newfoundland
St. John’s, NF A1B 3X5, Canada

INTRODUCTION
This is a general introduction to mass
spectrometry, with special reference to mass
spectrometers (MS) used with an Inductively
Coupled Plasma (ICP) ion source, with further
emphasis on the requirements for sample
introduction to the ICP using Laser Ablation (LA).
Thus the topic is LA-ICP-MS, with all the hyphens
optional depending upon editorial preference. It is
however worth while to start in the beginning as all
stories should. We will look first at the last part and
that is the MS part. Mass spectrometers come in
various kinds and sizes, but have also a lot of
similarities among them. It is worth while to
appreciate not only what makes instruments
different but those aspects which are the same. As
the field is changing with new instruments being
introduced, it is important to understand the
fundamentals of the instrument.
Most mass spectrometers can be easily
divided into four separate parts, discussed in order
below. In some situations these parts become harder
to separate, but the four divisions are still useful.
The four parts are the vacuum system, the ion
source, the analyser, and the detector (Fig. 1.1). The
vacuum system will be discussed first since in many
ways it is the most important and fundamental part,
which will be the cause of most of the “head aches”
of the operator. Secondly is the source from which
ions are created from the sample, focussed, and
accelerated; which for our instrument importantly
contains the ICP where the ions are created. Thirdly
is the analyser which is where ions are separated not
by “mass” but by their mass to charge (m/e) ratio,
using quadrupoles, magnetic fields, time, etc.
Fourthly, and of great importance is the detector

Figure 1.1. Schematic diagram of an inductively coupled plasma mass spectrometer showing the 4 main parts, as
discussed in this chapter: the vacuum system; the ion source or ICP; the analyser; and the detector.

1
along with associated electronics, which converts
the ion beam to a number which can be used by the
computer system.
VACUUM SYSTEM
A vacuum is needed for the simple reason that ions
will not get very far in the presence of one
atmosphere pressure of air. Without a mean path
length of more than one metre, it is simply
impossible to have much of a mass spectrometer. It
is not a trivial matter to obtain and maintain a
suitable low pressure and to monitor this pressure.
Experienced users will confirm that the vacuum
system is the cause of the majority of the problems
with instrument maintenance. This section will
discuss the instrumentation used to obtain the
vacuum, and the equally important devices used to
monitor the system pressure.
Mean Free Path
The fundamental parameter of importance
in vacuum systems is the mean free path which is
the mean or average distance which an ion (or
neutral) can move before it hits another particle.
While clearly longer is better, very low pressures
are not cheaply obtained. In ICP systems it is
especially difficult to obtain very low pressures as
the “hole” in the instrument is in the order of 1mm
in diameter, through which a large volume of gas
flows. Table 1.1 gives mean free path distances in
metres as a function of the system pressure
expressed in units of torr. These values are suitable
for N2 or O2, which together compose 99% of air.
The calculation is based on an ambient temperature
Table 1.1 Mean free path distances as a function of the system pressure
Pressure (torr)
760 (1 atm)
1 0.00005 m (0.05 mm)
0.05
10-5
10-6
10-7
10-8
2
of 25ºC and a molecular diameter of 370 pm.
At atmospheric pressure an ion does not go
very far (0.1 µm) before a collision occurs, clearly
not a satisfactory condition. At a pressure of 10-5
torr, a minimum operational pressure of a quadru-
pole ICP-MS instruments, the mean free path is a
reasonable 5 m in length. This is adequate for many
studies since there is a low probability of an ion
colliding with another ion, molecule, or atom on its
path through the instument. On the other hand there
are high precision applications where even lower
pressures and their accompanying longer mean free
path are needed because even a small amount of
scattering can result in an ion being diverted. With
relative errors of a few ppm, especially when
measuring large isotope ratios, lower pressures are
needed. Typical quadrupole and TOF instruments
are operated at a slightly lower pressure, closer to
10-6 torr. Pressures in “high precision” MS are often
10-8 torr and even lower.
Pressure Units of Measure
Clearly in the “modern” system of SI units
the measurement of pressure should be simple, but
that is not true. As the life of instruments is
approximately 10 years, it takes several decades for
any change to start to take place and even longer
before we can hope for a more limited list of units
of pressure measurement. In the previous table one
of the older units of pressure, the torr, was used
without it having been rigorously defined. This was
done to convince the reader, that a vacuum is
necessary, and now we will further define units of
pressure measurements. Several units are in
Mean Free Path
0.0000001 m (0.1 µm)
0.001 m (1 mm)
5m
50 m
500 m
5,000 m
 Table 1.2. Units of pressure measurement.
Bar
1Bar 1 14.5
1 psi 0.068 9
1 Torr 0.001 33
1 Pascal 0.000 01 0.000 145
from CRC, 2000.
popular and accepted use regardless if we like it or
not (Table 1.2).
Torr or mm of Hg is one of the oldest
units of pressure (vacuum) measure and just will not
go away. It was originally defined as the height of a
column of Hg in a barometer which exerts the same
pressure as does the gas in the vacuum system.
Noting that using units of distance for pressure did
not make sense it was renamed torr after a famous
scientist. As MS system pressures are well less than
one torr, the unit of milli-torr is often encountered.
Torr still remains, if not the proper SI unit, as a
common and well recognised unit.
The unit of atmosphere (atm), while
commonly used in other geological and chemical
calculations, is not usually used in vacuum
system measurements. An atmosphere is equal to
760 torr.
The unit of a bar is of similar vintage as
the atmosphere. High pressures in geological
systems are commonly given in bars or more
practically in kilobars. Recent geochemistry text
books use the bar as a pressure unit in preference to
the atmosphere. The bar is slightly less than one
atmosphere, the bar being equal to 750.062 torr. A
milli-bar is thus not very different from a torr (1
mbar = 0.75 torr), and as a first approximation can
be treated as being equivalent. The use of the bar as
a pressure measurement in vacuum measurement
has returned, after an absence.
The proper SI unit of pressure measure is
the Pascal, which is slowly coming into use in
vacuum pressure measurement alongside the torr
and bar. There are exactly 100 kilopascals in one
bar, explaining the return of the bar as a pressure
unit of measure.
The old English unit of Pounds per
Square Inch (psi), while not used for “high”
psi Torr Pascal
750 100 000
1 51.7 6 895
0.019 3 1 133
0.007 5 1
vacuum system measurement, is used for other
pressure and vacuum measurements and simply will
not go away in North America. There are 14.6959
pounds/in2 (psi) in one atmosphere. This pressure
unit is still commonly used in the gas supplies in the
laboratory, and requires mention for that reason
alone. Vacuum pressure (for very unsophisticated
systems like aspirators and diaphragm pumps) can
be expressed relative to ambient pressure rather
than to a zero of no pressure, adding to the con-
fusion. Note also that in high pressure gas systems
(like your automobile tires) pressure is usually
given in units of Pounds per Square Inch Gauge
(psig) which is the pressure relative to ambient
pressure and not relative to zero. The “gauge”
meaning the pressure difference across the gauge.
Pressure measurement
The measurement of the system pressure is
a non-trivial part of mass spectrometer operation
and requires some note. Pressure measurement is
made difficult for several reasons, one being that the
devices used in the laboratory to measure pressure
typically produce a signal which is not only a
function of the system pressure, but also of the
composition of “residual” gas causing the pressure.
A second major difficulty is the limited dynamic
range of the available pressure measuring devices.
To complicate this discussion some pressure
measurement devices can also affect the pressure in
the system, both in good ways in that the device acts
as a vacuum pump but also in a degrading way in
that gas may be released by the measurement
device. The latter is often caused when part of the
measurement device is heated.
Pirani. This gauge is one of the oldest
gauges, one which can be easily made from a pair of
incandescent light bulbs. It often forms the
3
backbone of the monitoring system, being cheap
and very robust. With the exception of calibration
drift, these units typically last a very long time. The
device is based upon the same principle as that of
your vacuum “Dewar” coffee carafe. As the
pressure in a system is lowered the thermal
conductivity (the rate of transfer of thermal energy
through the media) of the gas is reduced. Thus your
vacuum coffee carafe keeps your coffee warm
because of the low thermal conductivity of the
vacuum. In the Pirani gauge a heated filament (not
too hot, just warm) is placed in the vacuum system
(Fig. 1.2). Heat is transported from the heated
filament through the residual gas in the system to
the walls of the system. The robustness of the
device is related to the fact that the filament is not
operated at incandescence, but at a much lower
temperature, so that convection but not radiation is
the primary means of heat transfer. The lower the
pressure the lower the heat transport and thus the
higher the temperature of the filament. For metallic
filaments the resistance of the wire changes with
temperature and it is thus the resistance which is
measured and calibrated to system pressure.
Unfortunately this gauge is really only useful over a
limited dynamic range from approximately 10-1 torr
to 10-3 torr, the range in which the thermal
conductivity of the system changes. The calibration
Figure 1.2. Schematic diagram of a Pirani gauge.
4
is not linear. The unit is calibrated at one
atmosphere pressure and at a “low” pressure.
Resistance is measured in a Wheatstone bridge
arrangement in which another “identical” filament
contained in a sealed container is used for reference,
resulting in a measurement system of lower drift.
Thermocouple. This gauge has been
around for some time and operates on the same
fundamental principle as does the Pirani, that being
the change in thermal conductivity of a system as a
function of pressure. Having a wider dynamic range
than does the Pirani, it is being used more often in
systems, although sometimes it is not obvious which
kind of gauge head is actually present. The
thermocouple gauge uses a heated filament similar
to that of the Pirani, but instead of monitoring the
temperature of the heated filament, a thermocouple
is positioned near the heated filament. The
temperature of the thermocouple is used to monitor
temperature which is a function of pressure. The
lower the pressure in the system, the lower the
thermal conductivity of the residual gas, and thus
the lower the temperature of the thermocouple. This
gauge is also very robust and tolerant of system
pressures reaching atmosphere. As mentioned, with
only slightly more complexity than the Pirani, this
gauge has a wider (lower pressures) measurement
capability than does the Pirani and is thus often
replacing the Pirani in instruments.
Hot Cathode Ion Gauge. Due to the
inability of the above mentioned gauges, which
operate on the principle of changing thermal
conductivity with pressure, to monitor the pressures
typical of MS operation, systems require a gauge
which is useful at the ultimate system operational
pressure. This often means some kind of hot
cathode gauge. A heated filament is used to create
electrons, which are accelerated through a hundred
volts or so. The electron “beam” creates positive
ions from the residual gas molecules in the system.
The positive ions are then in turn collected on a
wire held at a negative potential. The ion current,
which is measured, is proportional to the pressure.
The “burn out” of the filament is the most common
mode of failure of this detector. However the life
time has been increased by the use of treated
filaments which produce high electron currents
while operating at lower temperatures. They are
thus less prone to “instant” failure if the system is
quickly (accidentally) brought to atmospheric
pressure. During initial turn on, additional pressure
can be created and reported as the gauge outgases
from the filament heat. These gauges are useful to
monitor pressures from 10-3 torr to the lowest
pressures obtained in MS. As the gauge should not
be used at high pressures, it is typically protectively
interlocked to a Pirani.
Cold Cathode Ion Pump This device is
mentioned here, even though as the name implies it
is firstly a pump; however the device also operates
as a gauge. Instead of having a hot cathode, this
device simply has two electrodes, both at ambient
temperature. A “high” voltage of typically from one
to three kilo volts is applied. When a residual gas
molecule gets close to the positive electrode an
electron is removed to the electrode (field
ionisation) and a positive gas phase ion results. This
positive ion is accelerated to the negative electrode,
where it is “buried”. The opposite can occur in
which negative ions form, but positive ion
formation is more probable. Magnetic fields are
used to increase the path length so that
multiplicative effects take place. These devices are
very clean and are found in the lowest pressure
portion of MS systems. As a pressure measuring
device, an error can be exhibited due the significant
ion currents which they create, however this current
is a good indicator of system pressure. They are
extremely reliable, as they use only a moderate
current, and a moderate high voltage supply.
Vacuum Pumps
The “pumps” remove the air from systems
creating the vacuum. Before listing different pumps
and their operation it is important to note that
vacuum systems operate in equilibrium. The
ultimate pressure is an equilibrium between the
pumps removing gas from the system and gas
coming into the system from “leaks” and from “out
gassing” from system walls (especially water from
metallic surfaces). All systems leak and if the pump
is closed off from the system pressure will rise. If
the leak gets too high, then unsatisfactory operation
of the instrument can result, even though the
pressure gauges may be indicating a satisfactory
pressure. If the pressure rises linearly with time
when the pump is isolated from the system, this is
an indication of a leak; otherwise out gassing is
suggested. The pressure is only an indication that
the system leaks are “small enough” to allow good
operation. Thus the concept of the “speed” of a
pump is important, being not the lowest ultimate
5
pressure which the pump can obtain, but the speed
of removal of gas from the system. The pump speed
is often related to pump size, with larger pumps
having a higher speed. In modern MS, the user will
usually find only “rotary mechanical oil pump(s)”
used in conjunction with “turbo molecular pumps”.
Other pumps will be briefly mentioned.
Rotary Mechanical Oil Pumps are the
first line pumps, which are used to drop the pressure
from atmospheric to less than one torr. They are
ultimately capable of, or specified to have, ultimate
pressures of 10-4 torr, a pressure which can
realistically only be reached with a system of almost
zero volume, as the pump speed of these pumps is
not high. They are based upon a simple mechanical
system in which an eccentric rotor isolates a volume
of the system gas, and using oil to make gas tight
seals pushes this volume of gas out of the system to
the ambient atmosphere. They are mechanical and
noisy; the oil becomes contaminated and for long
pump life should be changed frequently (monthly).
Older pumps had belt drives, with frequently belt
failure, but modern units are direct drive. Care is
needed so that in the case of a system failure that oil
does not get “sucked” into the vacuum system,
although modern pumps contain much more robust
protective devices than were available in older
pumps. Systems often include automatic or manual
“Down To Air” valves which open to allow
atmosphere to enter the pump during power
outages. Rotary pumps are fundamental to system
operation as “high vacuum” pumps are invariably
not capable of operating between low pressures and
atmospheric, but do operate between low pressures
and that easily obtained using the rotary pump and
hence the common term “backing” pump in which
the rotary “backs” the low pressure pump. In all
ICP-MS units the rotary pump directly pumps the
expansion region, in which a pressure of between
0.5 and 2 torr is usual. This same rotary pump or an
separate rotary pump maybe used to back the
several turbo (v. i.) pumps.
Turbo Molecular pumps, usually simply
called turbo pumps, are almost universal in modern
instrumentation. The technology has been around
for some time, but the widespread acceptance of the
pump has awaited the “trivial” engineering problem
of creating bearings which will run 24 hours a day
at speeds of up to 100,000 RPM, which is really
“screaming”. The mode of failure is still the
“simple” failure of the bearings resulting in the need
for a replacement or rebuild unit. The pump is very
clean as it consists of 10 to 20 “fan” blades similar
to design of jet engine turbine blades. As residual
gas molecules get close to a blade they are “hit” by
the blade and forced towards the next blade, etc. As
mentioned the pump is “backed” by a mechanical
pump, although in very simple situations the pump
is capable of operating without backing, but with
higher ultimate pressures obtained. Progress has
been made in the development of bearings, with
modern units often being magnetically suspended,
and used without lubrication. The bearings are
sometimes cooled by the instrument water system.
Other pumps Other pumps are not
commonly encountered in new instruments, but will
be briefly mentioned for completeness and because
they may be found on older facilities. Ion pumps
have been mentioned and will still be found in very
low pressure systems; they are simple and reliable.
Diffusion pumps were for decades the pump of
choice. They are cheap to make and can be “home
made” either in metal or glass. The operation
principle is that oil or Hg is heated and the vapour
passed though “jets” at super sonic speeds, after
which some kinetic energy is transferred from the
pumping fluid to the residual gas and forced to the
other end of the pump to which is connected a
rotary pump. The use of oil required periodic
change, however the most serious disadvantage of
“diff” pumps was in the case of system failure when
hot oil vapour was “sucked” into the MS, which in
some organic instruments made the system
unusable. First generation VG ICP-MS, of which a
few are still in use, were supplied with “diff”
pumps. Cryo pumps which can be as simple as a
cooled trap are not commonly used in ICPMS, but
still have a place in the specialised tool box of
vacuum systems. The first generation ICPMS units
from Sciex used a cryo pump which is simply a
refrigeration system which used He as a carrier gas
and operated at 15 K, making a simple fast pump,
however one which took hours to reach operational
pressures and required a weekly “defrosting” of the
system. Various cooled absorbers can be
significantly enhanced by the use of molecular
sieves, charcoal, etc. to enhance removal of gas
phase molecules from the system.
ION SOURCES
At a pressure of less than 10-5 torr it is
possible to have an ion path, which will be
6
discussed in three parts; the ion source, the analyser,
and the detector. The ion source is the place and
means in which ions are created, accelerated in the
desired direction, and focussed to increase the ion
beam current. For the purpose of this essay, of
course the Inductively Coupled Plasma (ICP) is the
ion source of interest. Other ion sources will be
discussed briefly so that the user can appreciate the
differences, advantages, and disadvantages of
various MS systems. In the present time when
finances are limited, it is important that efficient use
of facilities be made. It is important that an
optimum choice of instrumentation and method be
used for each application.
The ICP has long been recognised as a
good source of ions, with some of the choice optical
emission wavelengths being from the photon
emission from ions. The problem which awaited the
mid 80’s was how to get ions from an atmospheric
pressure plasma into a suitable low pressure vacuum
system containing a mass spectrometer. The ICP is
a good source of ions because it has a temperature
which is in the vicinity of 8000 K, or close to the
apparent temperature of the surface of the sun, the
plasma of most familiarity. Most of the elements in
the periodic table which are classified by
geochemists as being in the lithophile or siderophile
geochemical groups exist in the ICP at close to
100% ionised. On the other hand the chalcophile
elements, those being in the upper right hand
portion of the periodic table, can also be found as
ions, but with lower degrees of ionisation. All the
elements with the exception of He, Ne, and F can
clearly be seen in sample spectra; which is not to
say that all elements can be determined with
satisfactory detection limits for the applications
which the user may wish to explore. The capability
and limitations of the detectability of all the
elements in the periodic table will be explored later.
The interface between the atmospheric
pressure ICP and the 10-5 torr vacuum is solved by
not trying to make the lowering of pressure of 8
orders of magnitude in one step. The first step is to
allow or rather “suck” the plasma though a hole
(orifice) of approximately 1 mm in diameter, in a
metal disc (Fig. 1.3). This is called the sampler and
is usually fabricated from Ni, although Al, Cu, and
Pt are also sometimes used. The requirement is that
the metal has good thermal conductivity, so heat
from the plasma can be dissipated to a water cooled
plate. Stainless steel, for example, is not suitable

Figure 1.3. Schematic cross-section of the interface
region of the ICP-MS, with the plasma being
“sampled” by the sampler cone, then “skimmed”
further by the next cone, before being directed
toward the analyser to the left.
due to its poor thermal conductivity. The pressure
drop across the sampler is from atmospheric to
between 0.5 and 2 torr (a lowering of pressure by
three orders of magnitude), the vacuum being
maintained by a rotary pump. The pressure is
affected by the size (speed) of the pump and the
diameter of the orifice. Thus large volumes of gas
are carried to the pump, which has both good and
bad effects on the oil contained in the pump. The
high volume of gases tends to “clean” out the oil,
thus the time needed between oil changes might be
longer than expected, however in our experience a
monthly change contributes to the long life of the
pump. The pressure in the region following the
sampler (expansion region) can affect the
instrumental sensitivity. Gas flow through the
sampler has been estimated at from 1 to 2 litres per
minute (approximately 100% of the sample carrier
gas passes this orifice), and shortly after the sampler
orifice, the gas reaches supersonic velocities, giving
the ions a forward velocity towards the analyser
portion of the instrument.
Following the sampler orifice, by
approximately one centimetre is a second cone with
7
a similar sized orifice. This cone is called the
skimmer, which “skims” the plasma, allowing
through approximately 1% of the sample. The
plasma at this point has expanded significantly, and
while the true temperature has dropped (due to the
expansion) tremendously, the ions in the plasma
seem to have been “frozen” in the more rarified
atmosphere. The pressure behind the skimmer is
typically around 10-4 torr. As for the sampler, this
cone is usually Ni, but Al, Cu, and Pt can be used.
The pressure in this region is, in all modern
instruments, maintained by a turbo pump backed by
a rotary oil pump. Usually, but not always, a
separate rotary oil pump is used to back the turbos
and one is used to pump the expansion region.
Some distance beyond the skimmer
another opening is placed. This opening can be
much larger than the sampler and skimmer orifices,
as it separates the region operating at 10-4 torr from
an slightly lower pressure region operating at 10-6
torr or lower pressure. This is the analyser and
detector region and is usually pumped by a second
turbo pump. An additional vacuum region is
possible in larger sector instruments, especially
important where very high precision isotope ratios
are to be determined.
Various lenses to focus the ion beam into a
smaller solid angle can be found following the
sampler. Various configurations are used in
different instruments, but they are most commonly
cylinders, “donut”-like plates with holes through
which the ions flow, and “discs” or stops around
which the ions must flow. As well as focussing the
ion beam, these “lenses” also serve the function of
removing some of the high energy photons which
can also be detected by some detection systems.
This is accomplished by forcing the ions to go
through various bending and contortions through
which photons, which only go in straight lines, are
absorbed. Different systems are possible, but a
detailed understanding of their operation is not
required for the operator. With experience on a
particular instrument the operator will soon
understand the ranges over which each lens
normally operates, and which lens is most
important. To complicate operation, invariably there
is an interrelationship between the various lenses,
which has seldom if ever well documented.
Especially on quadrupole instruments, there is
usually a “trade off” of sensitivity with various lens
setting; that is, low mass or high mass sensitivity
can be “traded off” one with the other depending on
the application. For quadrupole instruments the
natural circular ion beam is optimal, however for
sector instruments a beam shape with a rectangular
shape is needed requiring other focussing lenses.
Collision/reaction cells v. i. act as ion lenses as well
as forming a place in which gas phase reactions take
place.
Dynamic Reaction Cells or Collision
cells are an recent addition to ICP instruments,
although their potential was suggested many years
ago. Similar reaction cells have been in use in
organic MS for many years, often in the “triple
quad” configuration in which ion-molecule
reactions took place in the centre quad. Reactions
have been shown to reduce the intensity of several
poly-atomic ions, including the famous ArO+ which
interferes with the major isotope of Fe. It has also
been suggested that a “thermalisation” of the ion
beam in reaction cells produces improved isotope
ratio measurements. These cells are currently placed
after the ion lenses and before the analyser.
Quadrupoles, hexapoles, and octapoles are used by
manufacturers to contain the reactants, and when the
cell is placed off axis, improved backgrounds can
result.
Other ion sources are found in a wide
variety of commercial MS instruments and will be
mentioned here, so the reader will have a better
appreciation of the differences between various
instruments. All of these have the function of
converting a gas, liquid, or solid sample into ions.
Important differences in the hardware depend on the
phase (gas, liquid, solid, or plasma) of the sample
which the user wishes to analyse. The process of
volatilization, breaking the sample into molecules,
and atoms, and finally into ions is the function of all
sources. A wide variety of sources are commercially
available both in the area of organic MS and in
inorganic MS. Some instruments support several
sources. While organic MS would seem to be
outside the interest of this essay, we have
participated in work in which Zn isotope ratios were
determined using FAB (Fast Atom Bombardment)
ion source MS and compared to ICP-MS analyses.
Chemical Ionisation (CI), in which energetic
molecules are used to ionise samples are widely
used in organic MS, but are seldom used in
inorganic MS. All MS instruments are potentially
capable of quantitative elemental determinations
and isotope ratio determinations, however usually
8
each instrument has been designed for a particular
application and for this application will be found to
be better (more accurate, more precise, and
cheaper).
In organic MS instruments Electron
Ionisation (EI) is very commonly used. EI is the
source in the first MS instruments and remains a
simple and useful technique to create ions. In EI, an
electron beam with an energy of a few hundred volts
is used to ionise a vapour phase sample. This is the
technique used in geological “stable isotope” mass
spectrometers in which H, C, N, O, and S isotope
ratios are measured on vapour phase samples (H2,
CO2, N2, SO2, or SF6). ICP-MS, for reasons to do
with high backgrounds and large interferences, is
essentially useless for these kind of applications,
even though ion signals are observed from all of
these elements.
Thermal Ionisation (TI) must be
mentioned here as it is one of the very important ion
sources for the study of inorganic radiogenic
isotope systems in the geological sciences. TI-MS,
which has been used for a very long time for several
isotopic systems (esp. Rb/Sr, Nd/Sm, and Pb/U),
has recently been put in competition with new ICP
instruments. In a TI source the sample is placed on
a flat metallic filament having dimensions of
approximately 1 by 10 mm. The analyte is always
separated and concentrated before it is deposited on
the filament, using various solution digestion and
separation methodologies. The filament is then
simply heated and if the chemical “magic” is done
right, ions will be emitted from the filament into the
vapour phase from which they can be accelerated
into the instrument. We will focus here on the most
important characteristics of this source in order to
better understand the differences between an ICP
and a TI source for geological applications.
Filament temperatures are less than 2000ºC,
compared to ICP sources of 8000ºC, thus TI has a
limited capability of producing ions from elements
with high ionisation potentials. Thus the number of
elements in the periodic table is more limited to TI
sources than is available to ICP sources. For
example the Hf/Lu radiogenic system can be
efficiently measured using ICP sources, but not TI
sources.
Mass Fractionation is a term widely used,
often with different meaning by different writers. In
this essay the definition of mass fractionation will
be limited to the phenomena which is observed in
TI, that is - it is caused by the difference in
volatility of isotopes of different masses, as a TI
filament source is heated. Simply, a lighter isotope
is (usually) more volatile than a heavier isotope. In
a process akin to distillation, initially the vapour
phase is enriched in the light isotope compared to
the solid sample. With time, the solid sample
becomes depleted in the light isotope and at some
time the vapour isotopic composition becomes
equal to that of the original sample. This typically
takes place after 2/3 of the sample has been
volatilised from the filament. If sample introduction
continues, the vapour phase composition becomes
depleted in the light isotope relative to the original
sample composition. From a chemometric point of
view, the important fact is that the measured
isotopic composition changes with time because
lighter isotopes are more volatile, the same
phenomena, which can drive stable isotope systems
and makes them useful for geological applications.
Chemometric corrections must be applied to the
measured data for mass fractionation in order to
obtain the true isotopic composition of the original
sample. Further discussions of the chemometrics
will be made, when various data acquisition and
data reduction paradigms are discussed. The
important point here is to appreciate the
fundamentals of the phenomena of mass
fractionation and that mass fractionation is a time
dependent phenomena. Later we will compare this
time dependent mass fraction phenomena with
instrumental variation of sensitivity with mass
which we will call mass bias. Mass bias or mass
discrimination is subject to change from the slow
“drift” or change of instrumental parameters, but
this “drift” is not regularly and simply related to a
real change in the vapour isotopic composition.
Other plasma sources are possible. Some
of the fundamental studies which led to the ICP-MS
were done using MIP (Microwave Induced
Plasma). No commercial MIP-MS has been
produced, however the MIP source is used in
elemental MIP emission spectrometer detectors for
GC systems, and thus suitable sources are available
for experimental studies. The other commercially
available plasma source is the DCP (Direct
Coupled Plasma). This plasma is very robust and
has a small but important place in elemental
emission spectroscopy. Unfortunately the geometry
of this plasma source is such that ions are not
conveniently extracted from the plasma into a
9
vacuum, a problem which is awaiting an ingenious
researcher. The spark/arc plasma, created using a
direct or alternating current source, was formerly
available with MS detection, however its
applications have been entirely replaced by ICP-MS
and GD-MS (v. i.). The spark/arc is similar to the
DCP. Important fundamental elemental analysis was
carried out in the past using spark source MS
instrumentation with isotope dilution procedures. In
these earlier instruments the spark was used to
create the ions for the MS. There have been reports
in which the spark/arc source is used as a sampling
device from which material is carried to an ICP in a
manner similar to laser-ablation sampling.
Other laser-based ion sources have been
used in the past, but are no longer commercially
available. The interest here is to contrast and
compare them to Laser-Ablation (LA)-ICP
instruments. A laser beam focussed onto a sample
creates a plasma containing ions. LAMMA
instrumentation (Laser-Microprobe MAss spectro-
metry) was commercially produced in the past
which relied on the laser-induced plasma to create
the ions which were extracted into a MS for
analysis. Unfortunately the efficiency of the
ionisation process was very variable with different
sample matrices making quantification very
difficult. In LA sampling by the laser is separated
from the ion source (ICP) making, this a very
powerful combination. The separation is similar to
that discussed using spark/arc sampling in
conjunction with an ICP ion source.
Also deserving of mention is MALDI
(Matrix-Assisted Laser-Desorption Ionisation)
source MS. This has become a very powerful
technique for organic analysis. In this method the
sample is mixed with a substance that absorbs laser
radiation and assists in the ionisation of the sample;
only very low laser energies are used although there
are some obvious similarities with LA-ICP methods.
This method has some similarities to reported laser-
ablation sampling of solutions in which compounds
are added to the solution to enhance the absorbance
of the laser energy by the liquid.
Ion Probes or Secondary Ionisation Mass
Spectrometers (SIMS) must be mentioned as a
powerful and older technique which is in
competition with LA-ICP-MS. One of the more
powerful models has taken the name SHRIMP
(Secondary ionisation High Resolution Ion
MicroProbe). In SIMS an ion beam is created, often
from O, Ar, or Cs and these ions are focussed using
a small MS onto the sample. The impact of the ion
beam on the sample creates secondary ions from the
sample which are analysed with the main mass
spectrometer. Capabilities are comparable to that of
LA-ICP-MS. LA systems are cheaper and much
faster than SIMS techniques, but the older SIMMS
instruments are still producing high quality data for
certain applications, and the comparison of the two
instruments requires an extensive examination.
Glow Discharge (GD) instrumentation has
not had much impact in the geological sciences, but
has been the subject of a lot of interest in the
analytical community, with a large number of
applications in the semiconductor and high purity
metals sciences. GD-MS instruments are similar to
ICP-MS instruments, and some researchers have
modified ICP sources to GD sources. The GD
source can be thought of, in a very crude sense, as a
low pressure Ar ICP, in that instead of operating at
atmospheric pressures the GD operates at a few torr.
Solid samples can be analysed, although not at what
would be considered micro dimensions, and depth
profiling can be done very well. GD-MS has in fact
replaced the spark-MS instrumentation in many
applications.
In conclusion it should be emphasised that
a large part of the power of LA-ICP-MS is due to
the separation of the sampling process (LA) and the
ion source (ICP). This allows the separate
optimisation of the two steps in a manner not
possible when both the sampling and ionisation are
done in the same operation. The significant advance
in the science which created LA-ICP-MS was the
combination of three reasonably well understood
parts into the final instrument.
ANALYSERS
Now for the “guts” of the instrument or the
analyser which forms the fundamental part of the
instrument. This is where the ions are separated
according to their mass to charge ratio (m/e). A
mass spectrometer does not measure mass in the
sense that a balance measures mass. A mass
spectrometer does not work without ions, thus the
discussion of ion sources before that of the analyser.
Due to the fact that m/e is measured and not mass
itself, there is a bit of confusion, but mainly plain
disagreement of what to call the units of
measurement. Dalton is the more formal unit of
m/e, but remains one seldom used, at least in
10
friendly conversation. Atomic Mass Unit (AMU or
amu) is often used, without much formal
recognition. “Mass” is clearly formally incorrect,
and when multiply charged ions are detected the
meaning is especially confusing. However, “mass”
remains the colloquial word of choice, in the
laboratory and will be used here, remembering that
m/e is always meant. Fortunately, in ICP-MS most
ions have a single charge; only a few have doubly
plus charge (alkaline earths and light rare earths),
and higher charged ions are not seen.
Later the concept, measurement, and use of
different “resolutions” will be made. Resolution is
one of the important figures of merit of the various
kinds of analysers. While the qualitative definition
refers to the ability to separate one mass from
another, more quantitative measures are needed.
The parameter of choice depends also on the
characteristics of the analyser, with it being
convenient and conventional to chose a parameter
which has a constant value over the mass range.
More fundamental, is what resolution is needed for
the various applications which are anticipated by the
user, and what consequences result from the use of
different resolutions. This discussion will also
explore the potentials of “high resolution” along
with its limitations. But first we will consider the
various analysers.
Analysers
Magnetic Sector Analyser (MSA) was historically
the first analyser and has now become a very
important player in the ICP-MS area. The
fundamental principle, which comes from electricity
and magnetism, is simply that in the presence of a
magnetic field, a moving charge (ion) will travel in
a curved path (Fig. 1.4). When all ions have the
same kinetic energy, it can be shown that the paths
of heavier ions (larger m/e) will be less deflected
than those of lighter ions. Qualitatively a heavy ion
just carries on, while a light ion is easily pushed
sideways by the magnetic field. In some
configuration (Mattauch-Herzog), ions with a wide
range of masses are focussed on a plane; this
configuration was popularly used in spark source
MS and there are research reports on its use with an
ICP source, but no commercial instruments have
been produced. Even though it has been demon-
strated that the Mattauch-Herzog configuration can
be used, sensitivity was very poor in experimental
instruments. In a MSA the ions are accelerated with
 spectrometers are not constructed using an ESA
alone, although the addition of an ESA to an
instrument can be very useful. The ESA separates
ions based upon their energy, so that the theoretical
MSA equation given above can be utilized. This
equation is based upon the assumption that all ions
have the same energy (equal to the accelerating
voltage). The ESA is simply constructed of two
curved conducting plates between which the ions
pass, and a potential difference is applied to the two
Figure 1.4. Schematic diagram of a Magnetic Sector
opposing curved surfaces (Fig. 1.5). In an operation
Analyser (MSA). Patterned after Turner et al.,
some what similar to the MSA, ions going too fast
Instrumentation for low- and high-resolution
hit the outside wall, while ions going too slow are
ICPMS, In: Montaser, A. (Ed.), Inductively
pulled into the inside wall, while ions with just the
Coupled Plasma Mass Spectrometry. Wiley-VCH,
NewYork, pp. 421-501. By permission of John
Wiley & Sons, Inc.

several kilovolts of energy, with higher energies

potentially yielding better sensitivity and resolution.
This is much higher energies than are used with
quadrupole instruments (v. i.), and slightly
complicates instrument construction as one end
(source) or the other (detector) must be at a high
potential. The mathematics is:
2 2
m H r Figure 1.5. Schematic diagram of an Electrostatic
 = Sector Analyser (ESA). ). Patterned after Turner et
e 2V
al., Instrumentation for low- and high-resolution
where: H is the magnetic field, r is the radius, V is ICPMS, In: Montaser, A. (Ed.), Inductively
the accelerating voltage, and (m/e) is the “mass”. In Coupled Plasma Mass Spectrometry. Wiley-VCH,
single detector instrumentation, as a property of the NewYork, pp. 421-501. By permission of John
hardware, r, is fixed, and the instrument can select Wiley & Sons, Inc.
the desired mass by changing either the field (H), or
the accelerating voltage (V). In multicollector
instrumentation, H and V are selected so that the
various ions impact on different detectors
positioned at various positions (different r). Both H
and V are used to select the detected mass, in some
very elegant programmed combinations in ICP-MS.
Note that for constant magnetic field (H) and
accelerating voltage (V), that mass (m/e) varies not
with r, but with r squared. The consequence of this
is that masses become closer to each other as mass
is increased. A practical definition of resolution will
Figure 1.6. Schematic diagram of a double-
be one which reflects this relationship. The
focussing analyser. ). Patterned after Turner et al.,
magnetic field could be supplied by a permanent
Instrumentation for low- and high-resolution
magnet, but with current instruments an
ICPMS, In: Montaser, A. (Ed.), Inductively
programmable electro magnet is always used.
Coupled Plasma Mass Spectrometry. Wiley-VCH,
Electrostatic Sector Analyser (ESA) now
NewYork, pp. 421-501. By permission of John
demand our attention, though the ESA is not
Wiley & Sons, Inc.
actually a mass analyser, it is an energy filter. Mass

11
“right” energy will exit between the two plates.
While the ICP source does produce ions of similar
energy, there is some variation, which degrades
resolution. Note that TI instruments are invariably
single focussing MSA instruments, whereas ICP
instruments are invariably double focussing
instruments, double meaning that an MSA is used in
tandem with a ESA (Fig. 1.6). If the ESA come first
(after the source) the configuration is known as a
Nier-Johnson. If the two sectors are reversed, with
the MSA first, the configuration is called, as might
be expected, a reverse Nier-Johnson. A double
focussing sector instrument is capable of much high
resolution (v. i.), than is possible with a single
focussing instrument. Since TI instrumentation does
not demand high resolution and the energy spread
of the ions is small, only single focussing
instruments are used with a TI source.
Quadrupole (quad) analysers will now be
considered. Quad analysers have a history of more
than half a century, and were the analysers which
were used in the first ICP-MS instruments
produced, and continue to be the majority of all
ICP-MS instruments used. There are various
reasons for this, but before entering a comparative
discussion of the attributes of the various analysers,
we will first briefly review the operation of this
clever device. A thorough understanding requires an
appreciation of second order differential equations
and an ability to visualise in three dimensions. The
student is referred to other references to this theory.
Quad means four, and in this analyser there are four
rods, originally about the diameter of a broom stick,
but now getting smaller. The four rods, about one
foot long, are arranged in a perfect square
arrangement. The rods are ideally of hyperbolic
shape rather than circular. Pairs of opposing rods
are connected together electrically, with the two
connections brought out of the vacuum system to a
combination RF (Radio Frequency), often of 1MHz
frequency, and DC (Direct Current) electrical
supply. Ions enter the region between the four rods
with a low velocity, so that as the ions pass through
the rods they are effected by the RF oscillations.
The more oscillations to which an ion is subject, the
higher the possible resolution. The quad is a mass
filter, allowing to pass only ions of a selected mass.
Mass is selected by applying a calculated value of
the DC plus RF, with the ratio between DC and RF
usually maintained constant at a fixed RF
frequency. Theoretically it is possible to scan with
12
RF frequency, but this is unstable in operation, so in
practice crystal controlled, fixed frequency, RF
supplies are always used. Ions of the selected mass
are subject to several oscillations, but will exit from
the end of the rods, while ions of either higher or
lower mass, either pass between the rods or hit a
rod. Since the quad passes only one mass for a
given set of applied RF and DC, this analyser
operates only as an sequential analyser, with none
of the simultaneous (multichannel) capability of
sector instruments.
Time Of Flight (TOF) is the new analyser
found in commercially produced ICP-MS
instruments, with two manufacturers now producing
instruments. As the first author is most familiar with
the Leco instruments, the specifications of this
manufacturer will be mentioned as an example of
performance. The operation of a TOF is entirely
different from the sector and quad analysers
previously discussed. The principle of the TOF is
indeed the simplest of all, although the time frame
can be difficult to comprehend by geologists used to
thinking in giga years but not nano seconds. In a
TOF instrument ions from the source are collected
in a contained volume for a period of time (5 µs).
This packet of ions are then, after being given
kinetic energy by being accelerated by several
thousand volts, are “thrown” down a long empty
tube (1 m long). Newtonian physics tells us simply
that:
mv2
KE = = eV
2
That is the Kinetic Energy (KE) is a function of the
mass (m) and the velocity (v). Since all ions have
been given the same kinetic energy from the
accelerating potential (V), all ions have a Kinetic
Energy (KE) equal to the product of the electron
charge (e) and the applied potential (V). The
velocity (v) is the path length (L) divided by time
(t).
L
v=
t
Solving for m/e (“mass”) as a function of time (t):
2
 m  2V 2V t  2V  2
 = 2 = 2 = 2 t
e v L L 
Thus mass is a simple function of time (t) for fixed
accelerating voltage (V) and fixed flight length (L).
Qualitatively, if all the ions have the same energy,
the light ones are moving fast and arrive at the end
of the path in a short time, while the heavy ions
move slowly and get there later. Note the syntax, in
that detection in this analyser is sequential in time,
the sampling is “simultaneous”. With a path length
on the order of one metre, the entire mass spectra is
acquired in 50 µs, with a data value being acquired
every 2 ns. The analyser has the characteristics of a
simultaneous device and is expected to have all the
advantages of sampling each ion at the same time.
We might call the analyser pseudo-simultaneous. As
with the MSA analyser the peaks get closer together
as the mass increased, because mass is proportional
to the square of time (t). A complete spectra
contains 25,000 values. Each second 20,000
complete spectra are acquired, consisting of
500,000,000 values. Clearly some very fast
electronics and data preprocessing is required to
make this instrument a reality, and this is one of the
reasons that TOF have only been recently
introduced to the commercial market, although the
theoretical concepts have been well known and used
for a long time.
Ion Trap (IT) is another analyser, which
has been demonstrated in research instruments, but
has not at the present time been introduced in
commercial ICP instrument. The IT is related to the
quadrupole, but in operation ions are collected and
held in the trap. Later ions are then released as a
function of mass. The IT has found a place in
organic MS, and likely will be used in ICP
instruments in the future, if only as a component of
a much more complicated system.
Ion Cyclotron Resonance (ICR) is a very
sophisticated device in research development. Very
high magnetic fields are used, of such strength that
they are only found in very specialised research
facilities. Ions are trapped and held in a circular
motion in the magnetic field. The motion of the ions
are perturbed by applied electrostatic fields, which
results in the production of a Fourier transform of
the mass spectra. Very high mass resolution is
possible with this analyser and hence the research
interest.
Resolution definition
Before discussing the comparative
differences in capability of the various analysers it
is important to quantitatively define and discuss
various measures of mass resolution. Depending
13
upon the application and analyser, indeed different
definitions may be important and useful.
Peak width is the simplest definition of
resolution. The peak width can be measured at any
relative height, and can, depending upon the desires
of a writer, be used to make the analyser look better.
In quad instruments the peak width at 10% peak
maximum is commonly used for alignment. It is
normal practice to set up the instrument so that
resolution, defined this way, is constant. Typical
values are between 0.7 and 1.0 mass units. As is
characteristic of almost all instrumentation, higher
resolution results in a loss of sensitivity.
Valley definition is useful as it gives a
more qualitative indication of what is normally
thought of as resolution. When a valley of 10% of
peak maximum between two peaks of equal height
occurs, resolution is specified as ∆m, the difference
between the position of the two peaks. Since the
possibilities of finding two peaks of equal height is
low, it is useful to note that if two hypothetical
peaks give a valley of 10%, then the peak width at
5% peak maximum is equal to ∆m.
m/∆m definition is useful for sector and
TOF instruments, where “m over ∆m” is constant.
Implied is the previously mentioned fact that
resolution, defined as peak width, is better at low
mass and worse at high mass. Low resolution is
about 300, being equivalent to a peak width
resolution of one at mass 300. Sector instruments
can be operated at “high” resolution of around
10,000. This resolution is easily calculated by
taking the mass (peak centre) divided by the peak
width at 5% peak maximum, although
manufacturers will be found to prefer 10% peak
width which gives a better appearing value.
Abundance Sensitivity is not usually
thought of as a resolution definition, however this
parameter is of fundamental importance, especially
when isotope ratios are determined which have
values far from unity. Abundance sensitivity is the
ratio of the intensity of a mass peak relative to the
intensity of the “tail” of that peak at mass plus one
and at mass minus one. It is thus a measure of the
“interference” of a mass peak on its two neighbours.
Notably for quad instruments there is a larger tailing
on the low mass side compared to the high mass
side. Similarity TOF analysers exhibit a tailing,
except on the high mass side instead of the low
mass side.
High Resolution
What is the interest in having an instrument
which is capable of operating in a high resolution
mode? That is, with resolutions better than unit
resolution (peak width at 10% peak height) or better
than an equivalent m/∆m of 300. To understand the
capabilities and limitations of high resolution, a
consideration of the “mass” of the proton and
neutron need to be made, and the loss of mass as
these fundamental particles combine to form nuclei
where some of the mass is converted to binding
energy. While the manufacturers of high resolution
instrumentation would like buyers to believe that all
possible mono and poly atomic ions can be
separated, that is simply not true. There are however
some interesting applications of high resolution
instrumentation.
The mass of each neutron and proton
which makes up a nuclei each have a mass of
approximately 1 amu or 1 Dalton each. However,
when neutrons and protons combine to form a
nuclei, there is a loss of mass (mass defect) as some
of the mass is converted to binding energy of the
nuclei. The loss of mass is in accordance with the
Einsteinian law that “E” equals “m c squared”. Thus
the exact mass of an ion is not an integer number
Figure 1.7. Plot of the “exact mass” divided by the integer “mass” vs. the integer “mass”.
14
which is equal to the total count of the number of
neutrons and protons. Further, there is not a
constant binding energy due to each neutron and
proton as shown in Fig. 1.7. The figure is a plot of
the “exact mass” divided by the integer “mass” vs.
the integer “mass”. Clearly seen is the extra stability
at mass 4He. Not as clear in this figure, is the extra
stability at mass 12C, 16O, and 20Ne. Note the
minimum which is found at mass 56Fe, the heaviest
“major” element, which reflects that light elements
“fuse” to form heavier nuclei while heavy elements
undergo “fission” forming lighter nuclei, with Fe the
“goal”.
The “mass defect” varies with mass. In
theory, it is possible, knowing the exact mass of an
ion, to determine the element. For example 14C
(important for archeological dating) has a mass of
13.996 758 Dalton, which is different from 14N (the
major interference in the determination of 14C by
mass spectrometric means) which has a larger mass
of 13.996 926 Dalton. The mass difference is 0.000
168 Dalton, so a resolution of 83,000 would be the
minimum required to separate these two ions.
Noting that standard double focussing sector
instruments have a high resolution of around
10,000, the determination of 14C is not practical on
this kind of mass spectrometer. An important
conclusion is that all interferences cannot be
resolved using standard double focussing sector
instruments, and this includes importantly elemental
ion overlaps. The existence of the minimum at 56Fe
has the unfortunate consequence that two nuclei to
the left of the minimum can have a combined mass
very close to one nucleus to the right. For example
51 40
V Ar has an exact mass of 90.906 345 6 and
could only be separated from 91Zr (90.905 644 2)
with an unobtainable resolution of 130,000. In
conclusion high resolution mass spectrometers have
a powerful ability to resolve some overlaps of two
ions having the same nominal mass, but not all over
laps can be resolved. Note also that the calculation
of the minimum required resolution here assumes
the unlikely occurrence that the overlapping ions are
of the same intensity. In the more likely situation in
which one peak is much larger than the other, even
higher resolution would be required.
DETECTORS
Now for the final and “tail end” of the
instrument, where the ion beam is converted to a
computer-usable number, either in pulse counting
(PC) or digital mode in which ions are counted, or
in an analogue mode in which the ion beam current
(amperage) is converted to a potential (voltage)
which is in turn converted to a number using some
kind of analogue-to-digital conversion hardware.
Ideally the user would like to have a detector which
can operate in either mode because the two different
modes are optimum in different intensity ranges.
For low intensity signals, the digital mode is
optimum, from the point of view of the best relative
standard deviation of the signals and minimum
detection limits. At high ion count rates (greater
than approximately 1,000,000 counts per second or
cps) pulse pile up or dead time corrections degrade
quality. Hardware or software corrections may be
applied, but the correction theory has problems as
intensities get too high, and eventually fails entirely.
As a rule of thumb, below about 100,000 cps dead
time is not significant, and the user should be
careful at higher count rates that a correction has
been applied. In any case at sufficiently high count
rates (several million cps), the sequence of pulses
turn into one giant pulse and the digital mode is no
longer operative.
For most hardware, the analogue mode
starts at a ion beam intensity equivalent to about
15
1,000 cps. However at this signal intensity, the
digital mode is superior, a superiority which the
digital mode maintains until near the upper range of
the digital mode. Cross calibration is required if
both modes are to be used, which converts the
analogue value into an equivalent digital count rate.
This is done by making measurements where both
modes are operational (100,000 to 1,000,000 cps).
There is a mass dependence of the cross calibration,
so the cross calibration is usually done with several
elements across the mass range and a curve fitting
applied to the results. The analogue mode is
operational up to somewhere close to 1,000,000,000
equivalent cps, limited by the largest potential
(voltage) input which the analogue digital converter
can allow.
The most common detector (transducer) in
first generation instruments was the Channel
Electron Multiplier (CEM). This device is a one-
piece-cone-like device manufactured in glass, with a
high resistance coating. A moderately high potential
of a few kilo-volts is applied. When an ion impacts
on the first surface several electrons are released.
The following operation is similar to that of a photo
multiplier, in that each subsequent impact of
electrons increases the net electron current flow,
until at the end of the “cone” a current pulse of
multiple electrons is collected. This current pulse is
then counted in the digital mode or the combined
current is measured in the analogue mode. Often to
increase the lifetime of the detector, the applied
“high voltage” is decreased when in the analogue
mode. These devices are moderate cost ($K), and
moderate lifetime (year), but are subject to
deterioration with each ion impact.
The Micro Channel Plate (MCP) device
is based upon the same principle, but contains a
large number of small tubes. Spatial resolution is
possible, but the more common application has been
large area detectors in TOF instruments. However
the more interesting future application will be as a
potential detector for multiple channel applications.
Currently MCP are plagued by low dynamic range
along with low amplification.
More recently a device based upon the
same principles but with discrete dynodes have
been introduced. A resistor chain is used to apply
separate and different potential to each dynode. The
reputed advantage is the lack of need for the high
resistance coating, making what should be a more
reliable device. With some minor mechanical
changes channel electron multipliers can be
replaced with the new discrete dynode multipliers.
In analogue mode the analogue signal can be taken
off at an intermediate dynode, with no change in
applied potentials or removal of the applied
potential to the later dynodes.
The electron multiplying detectors have
low noise gain and are found in essentially all single
detector instruments. They can be operated in either
digital or analogue mode, but if the applied
potential is not reduced when high ion beams are
encountered (analogue mode) a reduced life time is
expected. TOF instruments due to their very high
rate of data acquisition do not have sufficient time
to switch modes and are operated simultaneously in
both analogue and digital modes. There is
insufficient user information to know how much this
will shorten the life time of the detector, although it
should be noted that the detectors used in TOF
instruments are larger in size, which is expected to
result in comparable lifetime. Note that the
operation of all instruments, including TOF
instruments, can and should be operated to “skip”
over very intense ion signals.
For multiple collector instruments (MC),
the detector of choice is the Faraday detector,
named after the famous scientist. The operation is
very simple in that for each singly charged ion
which hits the “bucket” an electron flows through a
resistor, creating a potential difference across the
resistor. The operation is very linear and very
stable, allowing the use of multiple collectors
simultaneously. The detector is 100% efficient
meaning that all ions, which hit and are retained in
the bucket, are detected. The gain is stable as gain is
dependent only on the value of the resistor,
potentially a very stable quantity. Unfortunately the
resistor has a very high resistance (1011 Ω or 100 G
Ω). Noise (standard deviation or root mean square)
in a 100 G Ω resistor, which is due to random
movements of electrons is given by:
1 scintillator at which even more photons are
Noise = 4kTR = 29 µV
2t
≡ 1.6 x10 −19 amp = 1790 ions / sec
Where k is Plank’s constant, T is the absolute
temperature (298°K), R is the resistance 1011 Ω, and
1/(2t) is the frequency band pass where t is the
integration time (1 second equivalent to 0.5 Hz).
16
For a one second integration this gives a RMS noise
of 29 µV, which, using Ohms law is equivalent to an
ion current of 1790 ions/sec. Notably the noise is
constant with increasing ion currents. Thus there is
a rapid improvement in the relative noise (RSD)
with increasing signal compared to a digital signal,
where the noise is the square root of the total
counts, thus the relative standard deviation (RSD)
improves with the square of the intensity. The
important conclusion of this calculation is that the
base line noise is approximately 1790 cps, or a three
sigma detection limit, expressed as a signal, is 5,400
ions/sec, approximately three orders of magnitude
higher than for pulse counting using a quadrupole
analyser. The upper limit of the Faraday detector is
when the potential across the resistor reaches the
maximum allowed by the following analogue to
digital converter. With an upper limit across the
resistor of 10 volts, which is equivalent to 10-10
amp, then the maximum possible intensity is
620,000,000 ions/sec or a range of more than five
orders of magnitude.
A disadvantage of the Faraday detector is
that along with the resistor comes some capacitance,
which makes switching of signal to the detector very
slow. Why is such a very high resistance used, as
clearly from the equation, lower resistance would
lead to lower noise? Note however that lower
resistance reduces the signal linearly with
decreasing resistance, while the noise would
decrease more slowly with decreasing resistance,
being proportional to the square root of the
resistance. Thus the best RSD results when the
highest value possible of the resistor is used, and for
practical reasons of availability that usually means
100 GΩ.
Daly detector systems have been used on
TI instruments for some time, with a similar system
now available on ICP instruments. The Daly system
is based upon positive ions impacting an aluminium
knob held at a negative potential. The impact
produces electrons, which in turn impact a
produced. The photons are in turn detected by a
traditional sealed photomultiplier. This device can
be used either in digital (fast phosphor) or analogue
(persistent phosphor) and has recently been used
with ICP sources. The system is notable for its long
life with the initial ion impact being on a relative
inert aluminium “knob”.
 Photographic detection is obsolete,
requiring processing to “develop” the image,
followed by subsequent digitisation. Silver based
films for MS require an emulsion made with silver
halide only, without the gelatin used in all other
films, making for a difficult medium. As well, the
dynamic range of halide films are limited, requiring
several exposures with different integration times to
acquire the required dynamic range. Photographic
detection was always used with the Mattuch-Herzog
analyser configuration in which the entire spectrum
was simultaneously obtained. This detector is
mentioned as the future may include a simultaneous
MS instrument using the Mattuch-Herzog
configuration and some kind of array detector,
possibly a scintillator followed by a suitable array
photo-detector. Current problems are effects of the
magnetic field on the electronic photo-detectors and
very low sensitivity of the instrument, both
problems which it is hoped will be solved by
advanced engineering. This could be the “dream”
instrument of the future. Again it is noted that this
the Mattuch-Herzog configuration was used for
years with spark source MS and contributed
significantly to geoanalysis.
INSTRUMENTS
Having defined basic terminology and an
understanding of various kinds of analysers, it is
appropriate to qualitatively discuss similarities,
differences, and figures of merit of various
instruments. All of these instruments have a place in
the analyst’s tool box, and all have demonstrated
some special applications.
Quad instruments, being the oldest and
most common ICP analyser are considered first. A
quad is sequential, but is fast sequential. Settling
time between mass jumps is between 2 and 0.1 ms,
and getting faster and more intelligent. Using “dwell
times” of 8 to 20 ms allows efficient use of the
analyser operating at well above 90%. The settling
time is not a function of the mass change, but jumps
over major intensities (e.g. Ar) can require
additional time. In first generation instruments, we
used an additional mass at the beginning of a sweep,
following the “fly back” to the lowest mass from the
highest mass in the acquisition. Measurement of 100
intensities per second (10 ms per mass total dwell
plus settling) is easily obtained with good
efficiency. The number of complete sweeps per
second, n, obviously depend upon the number of
17
“masses” at which intensity data acquisition is
required, with from 50 sweeps per second (n=2) to
3 sweeps per second (n=33) possible. The analyser
is low cost due its light weight, requiring only
precision machining and precision component
alignment. Resolution is normally unity (peak width
definition), although research is being done to
exploit other operating modes and has been
demonstrated to allow higher resolution. Sensitivity
is high, and until recently the highest. Backgrounds
in the continuum region are typically 10 cps but are
now less than 1 cps with newer instrumentation.
Sector instruments (MSA, ESA), were the
second kind of analysers to be introduced to the
commercial ICP market. If magnetic field changes
are required these instruments are much slower,
although speed is continuing to be improved as
better laminated magnets and magnet power
supplies are being produced. Scanning over limited
mass ranges (20% of starting mass) is possible using
a fixed magnetic field (MSA) and simultaneously
scanning the ESA with the accelerating potential.
The Finnigan instrument allows an elegant
combined ESA/MSA scan in which the MSA is
scanned linearly while a saw tooth wave form is
applied to the ESA. While this mode allows
efficient data acquisition, it forces the operator to
obtain data at masses which are neither wanted or
useful. Settling speed is thus very difficult to
quantitate, as the time is different for every possible
mass jump and depends on the mode used. As many
problems require the signal be acquired for low
mass major elements and high mass trace elements,
the speed of this analyser will often be found to be
inferior to quad instruments. The analyser is of high
cost due, in part to its ton(s) of magnet weight. High
resolution is possible with these instruments.
However a severe loss of sensitivity when changing
from low to high mass, roughly proportional to the
resolution is incurred. Changing from low (300) to
high resolution (10,000) can result in more than a
100 fold loss of sensitivity. As previously discussed,
not all mass overlaps cannot be resolved at the high
mass resolution setting, which makes high
resolution not a panacea. When changing from low
to high resolution, also there is a “sharpening” of
the peak shape, as the peak changes from “flat
topped” to approaching a triangular shape, which
requires a very high “mass calibration” stability
which is not easily obtained. This can force a “scan”
over each peak to ensure that the peak is accurately
located. Note further that a change in resolution is
slow because it requires the mechanical operation of
changing entrance and exit slits, making data
acquisition using different scan modes slow.
Sensitivity is currently the highest of any
instruments, but note that for some time it was
claimed that the sensitivity was high simply because
it was a sector instrument. Recent sensitivity
improvements came with the use of the shield torch
which decreases ion energy variations yielding
better transmission. This improvement is especially
important in sector instruments, but of much less
importance in quadrupole instruments which are
much more tolerant of energy variations in the
incoming ion beam. Backgrounds are very low (0.2
cps) in the continuum region of the spectra in sector
instruments due to the long curved ion path, which
usually is a half circle. Photons are very efficiently
eliminated, along with other ions which may in fact
be important in the formation of the continuum
background. Lower backgrounds lead to lower
detection limits, but note that the improvement is
reduced at low total integration times of one or so
seconds often used in laser-ablation sampling.
Multi-Collector (MC) instruments are
sector instruments, but are discussed separately.
This instrument avoids the need for magnet
changing by incorporating a number of detectors,
which allows simultaneous detection, however only
over a limited mass range. As mentioned, v. s., a
Mattauch-Herzog configuration would not have this
limitation, but this instrument has not been
commercially produced with an ICP source, and the
literature report on research instruments had
extremely low sensitivity. These MC instruments
are uniformly operated in low resolution. MC
instruments are truly simultaneous, giving them all
the advantages thereof. However, for multiple
collection, most instruments use only Faraday
detectors, due to the need to very precisely “match”
the separate detector/amplifiers used. One or more
digital detectors are often available, but the high
precision analysis required for geochronological
and stable isotope applications are almost always
carried out using multiple Faraday detectors. Thus
there is an requirement for high ion currents,
preferably close to 100,000,000 ions per second.
The user must carefully consider the total amount of
sample available in order to obtain such a high
signal for a reasonable period of time (minutes).
18
TOF instruments are sequential in
sampling and extremely fast, with a complete mass
scan acquired in 50 µs equivalent to 20,000
complete scans per second. Due to hardware
limitations, the Leco instrument currently saves
“only” 64 integrated intensities, more than sufficient
for most anticipated applications. The unique
capability of this instrument is currently limited by
low sensitivity, so low that the low sensitivity is not
traded off for by the multiplex advantage of its
simultaneous sampling. Current state-of-the-art TOF
instruments are around 1000 times less sensitive
than state of the art sector instrument, therefore the
multiplex advantage will not improve signal
integration as 1000 “masses” are clearly ridiculous.
Improvement in future instruments is hoped for,
however there may be a limitation to the ability to
hold ions during the ion collection period. If the
collection period could be increased from 5% to
100%, a significant (10 fold) improvement in
sensitivity is possible, but this has not yet been
engineered. Backgrounds are at first view, similar to
quadrupole instruments at 10 cps, however due to
the simultaneous acquisition of the TOF it is
advantageous to integrate over a number of
windows (default of 19 in the Leco instrument) this
gives a background of around 200 cps (10*19).
Resolution is comparable to low resolution modes
of sector instruments and are typically between 300
and 500. Anticipated “killer applications” of the
TOF will be in very fast transient signal acquisition,
but these are yet to be reported due to the very low
sensitivity of the current generation of TOF
instrumentation, which means that although the
scanning hardware is very fast the detector is
essentially blind.
The use of the analogue and digital ranges
in TOF instruments is distinctly different than
described for the other single collector and multiple
collector instruments. In the Leco TOF instrument
the maximum digital count rate is approximately
20,000 cps, much lower than the approximately
3,000,000 cps of other systems. Dead time
considerations are also more complicated as a only
zero or one ion can be collected in each 2 ns
interval, and following the detection of a single ion,
the detector is “dead” for several subsequent bins.
CONCLUSION
Inductively coupled plasma mass
spectrometry, while still undergoing continued
evolutionary development is now a well established
instrument in geoanalytical laboratories. All three
commercial analysers, quad, sector, and time of
flight have been demonstrated to be useful
instruments when used with laser-ablation sample
introduction. As a very small portion of the ions in
the ICP actually reach the detector, there is,
theoretically, the potential for further large increases
in sensitivity. This sensitivity can be used to
measure lower concentrations, or more usefully for
the analysis of smaller volumes of sample. Other
MS configurations which are not currently
commercially available, including notably the
Mattauch Herzog configuration with true
simultaneous detection is an interesting potential
instrument for the future.
Collision/reaction cells will be discussed in
a later chapter in this volume. These cells seem
poised to have a very significant impact on LA
analysis in the future, considering their important
capability of reducing background and background
ions, without an accompanying loss of sensitivity.
The use of these cells will create many new
problems and require many new choices of
operating conditions, which will require some time
for development.
Detector technology is undergoing
continuing development as well. Accompanying the
higher sensitivity of new MS instruments, the need
for increased dynamic range continues in
importance. The speed of switching modes from
analogue to digital is undergoing development, with
a new system being introduced which reduces
sensitivity by changing applied detector potential
instead of switching to an analogue mode. Another
important need is for multicollector ion counting
systems. At present, the drift between separate
detectors is large enough to make their operation
unsatisfactory for high precision isotope ratio
measurements. This results in multicolletor
experiments being carried out with multiple Faraday
detection, with possibly one ion counter detector.
As explained, v. s., while Faraday detection is very
efficient and stable, they have a background noise
level near 1,000 cps, a severe limitation for many
applications.
ACKNOWLEDGEMENTS
This essay is almost entirely based on a
lecture given by HPL as part of an Earth Science
graduate course at Memorial University on
19
analytical methods. This course has developed since
the mid 1980s, and was always deemed to be his
better lectures in the course. The number of mass
spectrometers in the department is and continues to
be large. The department has ICP-MS, gas source
stable isotope MS, TI-MS, and organic MS. At one
time there were nine operating MS instruments in
the department. Other geoscience departments have
or had spark/arc MS, glow discharge MS, rare gas
MS, and secondary ion MS. Thus mass
spectrometry has and continues to have a very
important impact on the geosciences.
Most of the writing in this chapter came
entirely from memory, with only an occasional look
at lecture notes to make sure no important item was
missed in the discussion. It is very difficult to find
references to knowledge, some of which HPL has
been familiar with since graduate student days when
he did his first research using vacuum systems. Text
books from various analytical instrumental
chemistry sources will contain additional reading on
mass spectrometry that will be of use to the reader.
A very useful book on geoanalysis is that by Phil
Potts, which covers mass spectrometry; however the
ICP-MS chapter is seriously outdated and it was
written in the very early development days of ICP-
MS. This book has been reissued in paper back, and
is a highly recommend text covering most of the
important areas of geoanalysis, including other
types of mass spectrometry. In the area of ICP-MS
the volume edited by Akbar Montaser (1998) is a
must desktop reference book. Attendance at the
annual Winter Conference on Plasma
Spectrochemistry held in alternative years in the
southern United States and in Europe is highly
recommended to keep up to date in the field.
REFERENCES
CRC (2000): CRC Handbook of Chemistry and
Physics, 81st edition, Lide, DR, editor-in-
chief, CRC Press, Boca Raton.
MONTASER A. (1998): Inductively Coupled Plasma
Mass Spectrometry, Wiley-VCH.
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