Mass Spectrometry Mass Analyzer Detector

Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt

Technische Universität München
Mass Spectrometry – Mass Analyzer
PD Dr. J. Graßmann; PD Dr. T. Letzel


Parts of a Mass Spectrometer
vacuum
pump
sample
mass
introduction ion source detector computer
analyzer
/inlet
vaccum or atmospheric
pressure vaccum chamber
Double focussing (magnetic & electrostatic) sector mass analyzer

Quadrupole mass analyzer
Time-of-Flight mass analyzer
Ion trap mass analyzer (Quadrupole ion trap, FT-ICR-MS, Orbitrap)


Magnetic sector mass analyzer
- Magnetic sector mass analyzer use a magnetic field to alter the path of ions.
- Within the „magnetic sector“ of the instrument, the magnetic field is applied perpendicular to
the direction of the ions motion.
- The ions trajectories are bend, whereas multiple charged and/or lighter and therefore faster
ions are deflected more pronounced.
- Due to the magnetic-field-induced circular path of the ions, the mass analyzer is designed as an
arc.
- The magnetic field ion separation is often linked to an additional „electric sector“ (electrostatic
analyzer), which focuses ions according to their kinetic energies, to achieve an improved resolution.
 In those so-called double-focusing sector mass analyzers, the ions are focused in direction
as well as velocity.


Magnetic sector mass analyzer Mass filtering
Some ions are lighter or heavier than the
m/z range selected.
+ ++ + + + + + + + +
+
+
+
Ion source
+ +
+
Ion acceleration
+ +
&
focusing +
The ions trajectories are bend, whereas the multiple charged

and lighter and therefore faster ions are deflected more + + +
pronounced.
 The ions radius is distinctive for its m/z ratio.
 Ions, which are too heavy or too light for the selected m/z
range will be dispersed


Electrostatic sector mass analyzer
+ + +
+
+
++ + +
+
+++ +
+ +
++ ++ + +
++ +
Ion source ++ +
Ion acceleration - - +
-
- + +++ + +
-
- +
The ions of the same kinetic energy are focused (i.e. concentrated
into a small area) and ions of different kinetic energies are dispersed.
 Electrostatic sector is not an actual mass analyzer, but sorts ions

according to their kinetic energy. +++ + +
 Isolation of ions with the same kinetic energy.
+++

Double focussing sector mass analyzer
+
+
+
+
+
+
+
+
+
+
+
-
-
+ + +
-
-
- -
+ +
Ion source Detection


Quadrupole analyzer
- Quadrupole analyzers comprises of 4 cylindrical rods, which are set parallel to each other.
- A oscillating electric field is applied to the rods, where opposing rods are connected and the
voltage is applied between one pair of rods. This results in differences in ion trajectory stabilities of
the ions traveling down the quadrupole and thus in the separation of introduced ions.
e.g. a positively charged ion is attracted by the negatively charged rod, which leads to the ion
traveling towards the rod. Before the ion can reach the rod, the potential is changed, so that the ion is
repulsed by the now positively charged rod and changes direction and so on (stable trajectory).
- Ions with a defined m/z ratio will reach the detector, whereas other ions have unstable trajectories,
which results in their collision with the rods and their discharge.
- Quadrupole MS therefore allows either the selection of individual ions of interest or the detection
of a wide range of m/z-values.

Quadrupole analyzer


Quadrupole analyzer
Oscillating electric field applied to the rods (alternating voltage)
+ + +
+ - + - +-
The ions trajectories are affected by the ions mass. The applied alternating voltage results in the
acceleration of the ions, with heavy ions having a low velocity and vice versa.
Depending on their m/z, the ions reach the detector at particular and differing points of time.
Direct current voltage applied to the rods

 Collision of the ions with the rods
 Light ions might pass
+
+ +
+
-

Time-of-flight analyzer
The ions from the ion source are accelerated by an electric field, resulting in all ions with the same
m/z having the same kinetic energy. Their m/z is then determined via the distinct time span the
ions need to pass the distance within the field-free drift tube to the MS detector. In this regard heavier
m/z will have a longer flight time.
Linear ToF MS


Time-of-flight analyzer
Reflecting ToF MS (Reflectron ToF MS)

A reflector within the drift tube is used as an „ion mirror“, which compensates for differences in the
kinetic energy of ions of the same m/z as they enter the drift tube. A reflectron MS therefore
has a higher resolution than a linear ToF MS.


Ion trap
Quadrupole ion trap (QIT)
Ions, which are introduced to the mass analyzer, circulate in a threedimensional path within the
analyzer, due to an alternating voltage applied between the endcap and the ring electrode.
The ions motion is dependent on the voltage applied and their m/z. The ions will be released from
the trap with increasing m/z by changes in potential.
Ion focussing
Endcap Ring electrode Endcap

electrode electrode

Ion trap
FT-ICR-MS (Fourier transform-ion cyclotron resonance-mass spectrometer)
The ions are trapped within a magnetic field with electric trapping plates. An oscillating electric field
(orthogonal to the magnetic field) is applied to excite the ions at their cyclotron frequencies to
determine their m/z. The excitation results in the ions rotation at their specific cyclotron frequencies.
At a pair of electrodes, those circulating ions pass by and induce a charge, which is detected.
The hereby generated signal, free induction decay (FID) is transformed (Fourier transform) into a
mass spectrum.
Detection plate Signal Fourier Mass

(FID) transform spectrum
Excitation plate
Excitation plate
m/z
PD Dr. J. Graßmann; PD Dr. T. Letzel Detection plate


Ion trap
Orbitrap
Ions are trapped within the Orbitrap, due to their electrostatic attraction to the central electrode.
The ions travel around the inner electrode on elliptical trajectories and also move back and forth
along the z-axis of the inner electrode. Ions of a specific m/z spread into rings which oscillate along
the inner electrode. Ion motions are detected by their image current and processed comparable to
FT-ICR-MS, by an outer electrode with two sensors.
Central electrode
Picture source: https://commons.wikimedia.org/wiki/File:Orbitrap.png

Tandem mass spectrometry
Tandem mass spectrometry, MS/MS or MS2 is a multiple-step mass spectrometric selection of ions,
which includes the fragmentation of one or several ions of interest.
Tandem in space (multiple elements/analyzers/filters)

Those multiple elements may be a quadrupole analyzer combined with a time-of-flight analyzer
(QToF = Quadrupole time-of-flight MS) or multiple quadrupoles (QqQ = triple quadrupole MS).
Tandem in time (only one element/analyzer/filter)

This includes techniques like quadrupole ion trap MS or Fourier-transform-ion-cyclotron-resonance.
Ions are trapped in the same place the entire time of multiple analysis steps (MSn, e.g. MS3 involves
three stages of analysis/fragmentation).




Triple quadrupole MS (QqQ)
Single-ion scanning without fragmentation:
Q1 Q2 Q3
Selected m/z Collision cell Selected m/z

Intensity
Intensity
Intensity
m/z m/z m/z

Mass Spectrometry
Single-ion scanning with partial fragmentation:
Q1 Q2 Q3
Precursor ion
Selected m/z Collision cell with Detection of precursor

collision gas, e.g. argon and product ion m/z  scan
or xenon
Intensity
Intensity
Intensity
m/z m/z m/z

Mass Spectrometry
Produt-ion scanning with complete fragmentation:
Q1 Q2 Q3
Precursor ion
Selected m/z Collision cell with Detection of m/z range

collision gas, e.g. argon  scan
or xenon
Intensity
Intensity
Intensity
m/z m/z m/z

Specific MS/MS spectrum of one single
PD Dr. J. Graßmann; PD Dr. T. Letzel precursor ion
Mass Spectrometry
Precursor-ion scanning to determine the precursor ion, which produces a specific
product ion of interest:
Q1 Q2 Q3
Product ion
Precursor ion
Detection of m/z Collision cell with Selected m/z

range  scan collision gas, e.g. argon
or xenon
Intensity
Intensity
Intensity
m/z m/z m/z
Q3 scans the m/z of one particular product m/z

PD Dr. J. Graßmann; PD Dr. T. Letzel only. Q1 scans across a m/z range of interest.
Mass Spectrometry
Neutral loss ion scan is used to detect product ions, which originate from a precursor
ion, which has „lost“ a neutral part, i.e. they differ by a defined molecular weight.
Q1 Q2 Q3
Detection of m/z Collision cell with Detection of m/z

range  scan collision gas, e.g. argon range  scan
or xenon
Intensity
Intensity
Intensity
m/z m/z m/z
Q3 scans a particular mass deviation

PD Dr. J. Graßmann; PD Dr. T. Letzel parallel to m/z detected in Q1
Mass Spectrometry
Neutral Loss Scan
Both, Q1 and Q3 scan over a defined m/z range. Q3 however allows only ions to
pass, which differ by a fixed mass number from ions passed through Q1. This
scanning mode is particularly helpful to detect precursor ions that fragment via a
specific neutral loss (unionized, non-detectable fragment) during fragmentation in
Q2.

Mass Spectrometry
Parts of a mass spectrometer
vacuum
pump
sample
mass
introduction ion source detector computer
analyzer
/inlet
vaccum or atmospheric
pressure vaccum chamber
e.g.
Electron multiplier (discontinuous or continuous)
Faraday cup
Scintillation counter

Mass Spectrometry
MS detectors
Electron multiplier detects the presence of ions from the mass analyzer and multiplies
the charges. The ion strikes a surface, which results in the emission of secondary
electrons.
ion
Discontinuous EM Continuous EM
ion -
- first dynode -
--
-
- --
-
-
etc.
--
--
etc.
Signal Signal
Mass Spectrometry
MS detectors
Within the Faraday cup the ions strike on the collector, which causes electrons to flow.
This results in a drop in potential, which reflects the intensity of the ion beam.
Faraday cup captures

emitted secondary
electrons
- -
Ion beam Induced current

from mass analyzer
- -
to amplifier

Mass Spectrometry
MS detectors
The Scintillator „converts“ a signal caused by an ion, whose impact results in the
emission of electrons towards the scintillator, into the emission of photons. Those are
detected by a photomultplier and furthermore converted into an electric current.
From mass analyzer ions

Emitted
- - - - electrons
Scintillator
Emitted photons
Photomultiplier
Signal

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Lehrstuhl für Siedlungswasserwirtschaft

Ingenieurfakultät Bau Geo Umwelt

Mass Spectrometry – Mass Analyzer

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Mass Analyzer

Double focussing (magnetic & electrostatic) sector mass analyzer

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Mass Analyzer

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Mass Analyzer

The ions trajectories are bend, whereas the multiple charged

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Mass Analyzer

 Electrostatic sector is not an actual mass analyzer, but sorts ions

Mass Spectrometry – Mass Analyzer

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Mass Analyzer

Mass Spectrometry – Mass Analyzer

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Mass Analyzer

Direct current voltage applied to the rods

Mass Spectrometry – Mass Analyzer

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Mass Analyzer

Reflecting ToF MS (Reflectron ToF MS)

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Mass Analyzer

Endcap Ring electrode Endcap

Mass Spectrometry – Mass Analyzer

Detection plate Signal Fourier Mass

PD Dr. J. Graßmann; PD Dr. T. Letzel Detection plate

Mass Spectrometry – Mass Analyzer

Mass Spectrometry – Mass Analyzer

Tandem in space (multiple elements/analyzers/filters)

Tandem in time (only one element/analyzer/filter)

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Mass Analyzer

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Mass Analyzer

Selected m/z Collision cell Selected m/z

m/z m/z m/z

Selected m/z Collision cell with Detection of precursor

m/z m/z m/z

Selected m/z Collision cell with Detection of m/z range

m/z m/z m/z

Detection of m/z Collision cell with Selected m/z

m/z m/z m/z

Q3 scans the m/z of one particular product m/z

Detection of m/z Collision cell with Detection of m/z

m/z m/z m/z

Q3 scans a particular mass deviation

PD Dr. J. Graßmann; PD Dr. T. Letzel

PD Dr. J. Graßmann; PD Dr. T. Letzel

Faraday cup captures

Ion beam Induced current

PD Dr. J. Graßmann; PD Dr. T. Letzel

From mass analyzer ions

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