Session 4

Atomic Mass Spectrometry

Comparison of different
techniques for trace analysis

Crucial steps in atomic

spectroscopies and -metries and
other methods
Laser ablation etc.

Solid/liquid
sample

Nebulisation

Solution

Sample
preparation

M X
+

Desolvation
Vaporisation

M(g) + X(g)
Sputtering, etc.
M+

Atoms in gas
phase

Ionisation

Molecules in
gas phase

MX(g)

Atomisation=
Dissociation
Excitation

Ions

ICP-MS and
other MS methods
(also: ICP-OES)
Adapted from www.spectroscopynow.com (Gary Hieftje)

Excited
Atoms

AAS and AES,

X-ray methods

ICP-MS

Mass spectrometry method: detects ions

distinguished by their mass-to-charge ratio
(m/z value)
Based on ions moving under influence of
electrical or magnetic field
Mass analysers generally require operation
under vacuum, to avoid ions colliding with
other particles
Recommended series of short articles: Robert
Thomas: A beginners guide to ICP-MS

ICP-MS instrumentation and

principle
Plasma generates
positive ions

Under vacuum

Detector
(e.g.
electron
multiplier)

nebuliser
Interface
Spray chamber

Sorted by mass analyser,

e.g. quadrupole,
magnetic sector,
according to m/z ratio

sample

http://www.cee.vt.edu/ewr/environmental/teach/smprimer/icpms/icpms.htm

ICP-MS instrumentation
Sampling cone

Collision cell

ICP Torch

Cones and
Ion Optics

Detector
(discrete
dynode)

Mass Analyser:
Quadrupole

Skimmer
cone

Modern instrument with collision/reaction cell

Recap: Ion formation in an

inductively-coupled plasma

Mostly, singly
charged positive
ions are
generated (>90%
efficiency)

Interface and ion optics

Room temperature,
vacuum

6000 K, ambient pressure

ICP torch

Major challenge in instrumentation: large differences in temperature and pressure. Interface

(consisting of two cones) allows connecting ion source to mass analyser (requires vacuum)
Lens focuses ions. Necessary for getting as many ions as possible into analyser (maximising
signal)

Mass analysers for ICP-MS

Quadrupole: High mass stability, fast

Time-of-Flight (rare)
HR (High-resolution): Uses magnetic sector mass
analyser

Lowest cost option

Highest sensitivity and resolution, but slow and requires stable

working environment
Expensive

Multi-collector (MD): Also with magnetic sector, but with

detector array

Good for accurate and precise isotope ratios

Isotope dilution measurements e.g. for accurate elemental
ratios

Quadrupole mass analyser

Four parallel metal

rods with dc and ac
voltage (alternating
with radiofrequency)
Works as mass filter:
allows passage of
particular m/z ions
only
Can scan over m/z
range spectrum

Atomic mass spectra

Ray and Hieftje, J. Anal. At.
Spectrom., 2001, 16, 12061216

http://www.wcaslab.com/tech/
tbicpms.htm

Typical detection limits of ICP-MS

instrument

http://las.perkinelmer.co.uk/content/TechnicalInfo/TCH_ICPMSThirtyMinuteGuide.pdf

Multi-collector mass analyser

Magnetic sector mass analyser separates ions according to m/z

Simultaneous detection with
array of collectors (Faraday cups)
Best for detn. of isotope ratios
Applications in geochemistry
and biomedical research

Possible factors that can affect

the performance of ICP-MS

Variations in plasma ionization efficiency

Possible clogging or corrosion of cone
apertures
Differing concentrations of other components
in matrix (e.g. acid, bulk elements) in samples
could result in matrix suppression

Ion current influenced by matrix composition

Temperature and humidity fluctuations in the

laboratory environment
Isobaric elemental and polyatomic
interferences: Used to be greatest limitation
for applicability

Polyatomic interferences
in ICP-MS: Origins

Spectral interference:
caused by presence
of species with same
mass as analyte
Often derived from
compounds with Ar

Analyte

Interference

K+

38

Ar1H+

Ca+

40

Ar+

V+

35

Cl16O+

Cr+

40

Ar12C+

Fe+

40

Ar16O+

Cu+

23

Na40Ar+

As+

40

Ar35Cl+

Se+

40

Ar2+

39
40
51
52
56
63
75
80

Overcoming polyatomic
interferences:
Collision/reaction cells (CRC technology)

Various modes of action:

Collision-induced dissociation (less important)

Chemical reaction (major mechanism)
Electron transfer (major mechanism)
KED: kinetic energy discrimination (monoatomic analyte and interfering
Requires reactive
molecules are retarded differently)

Can either affect analyte or interference

Commonly used gases: He, H 2, ammonia

http://breeze.thermo.co
m/collisioncells/
(Webinar)

gas

Polyatomics and high-resolution ICPMS

also no problem with polyatomics, as

there are small, resolvable differences in
mass:
P

31

O16O

16

N16O1H

14

N16O

15

32

30.95

31.00
Mass (u)

31.95

32.00

Stable isotopes and their uses

Most elements have more than one

isotope
E.g. 32S and 34S, or 56Fe and 57Fe
Can use more than one mass for one
element for measurements in ICP-MS
IDSM: Isotope dilution mass
spectrometry: Use particular isotope of
desired analyte as internal standard in
ICP-MS
Can buy enriched compounds, e.g. 67ZnO,
and use as tracers

Example for use of stable

isotopes

Metal-binding protein with 4 Zn(II)

Are all four zinc ions exchangeable ?

Isolated with natural abundance Zn(II

60

50
40

Zn: 4.1%

67

30
20
10
0
64

66

67

68

70

Isotope
Incubated overnight at 37C
with 40 mol equivalents of
67
Zn(II) (93% isotopic purity)
Measured isotopic ratios

Measurement and output

(Thermofinnigan Element2)
Total Zn and total S were determined using standard addition. For Zn quantification, the sum of
the Zn isotopes 64, 66, 67, 68 and 70 was used. S was measured on the 32S isotope. Zn isotopic
distribution (64, 66, 67, 68, 70) was determined. All elements and isotopes were measured in
Medium Resolution (R = 4000). No internal standard has been used. No mass bias correction
(using certified materials) was used for the isotopic distribution measurement.
Sample preparation:
Sample was diluted 1+49 with 18 M water. For blank subtraction, the 10 mM NH 4Acetate buffer
was diluted 1+49 with 18 M water.
Results for sample:

Total S

2.45 mg/L ( 0.2 %)

Total Zn

2.21 mg/L ( 0.6 %)

Ratios:
66

Zn / 64Zn

0.657 0.0028 (n = 7)

67

Zn / 64Zn

4.17 0.025 (n = 7)

68

Zn / 64Zn

0.490 0.0037 (n = 7)

70

Zn / 64Zn

0.01325 0.00007 (n = 7)

S: Zn ratio: 9:4 (as

expected; the protein
contains 9 sulfurs)

Comparison of experimental and

calculated isotopic ratios
Calculated for 4 exchanging Zn(II)

As measured

Calculated for 3
exchanging Zn(II)

66/64

67/64

68/64

70/64

For each isotopic ratio, results agree best with the scenario for 3
exchanging zinc: Clear demonstration that only 3 out of 4 Zn exchange:
The protein has one zinc that is inert towards exchange

ICP-MS and hyphenation

ICP-MS can be coupled with a variety of

separation techniques:
Liquid chromatography HPLC-ICP-MS
Capillary electrophoresis CE-ICP-MS
Advantages of hyphenated techniques:

Laser ablation LA-ICP-MS

better control over matrix

Allows separation of different components: direct
access to speciation
For surface analysis
For materials that are difficult to digest (e.g. alloys)
Is being developed in scanning fashion with m
spatial resolution: Imaging the metal composition of
a material

Caveat: Calibration ?

Laser ablation
Useful for surface analysis of solid samples

monitor camera

Laser

UV light

To ICP

Carrier gas in
sample

The ablation process

Plume of molecules and ions

from a surface hit by a laser
http://kottan-labs.bgsu.edu/pictures/

Comparison: AAS, ICP-OES, and ICPMS

AAS: Single element, ppm/ppb range

ICP-OES: Multi-element, ppb range

Cheap, simple
Small dynamic range
GFAAS about 100 times more sensitive than FAAS,
but also more challenging
Limited spectral interferences, good stability, low
matrix effects

ICP-MS: Multi-element, possible to reach ppt

(or even ppq)

Most complex, most expensive, lowest detection

limits, isotope analysis possible

Comparison: Detection limits

and working ranges

http://pubs.acs.org/hotartcl/tcaw/99/oct/element.html

Synopsis:
Interferences in atomic
spectroscopy
Technique Type of
Method of Compensation
Interference

Flame
AAS

Ionization
Chemical
Physical

Ionization buffers
Releasing agent or nitrous oxide-acetylene
flame
Dilution, matrix matching, or method of
additions

Graphite
Furnace
AAS

Physical and
chemical
Molecular
absorption
Spectral

Spectral Standard Temperature Platform

Furnace (STPF), conditions, standard additions
Zeeman or continuum source background
correction
Zeeman background correction

ICP-OES

Spectral

Background correction or the use of alternate

analytical lines
Internal standardization

Matrix
ICP-MS

Spectral
Matrix

Inter-element correction, use of alternate

masses, higher resolution systems or
reaction/collision cell technology
Internal standardization

http://pubs.acs.org/hotartcl/tcaw/99/oct/table1.html

A technique decision matrix

Exercise: How is this

decision matrix
correlated with
strengths and
limitations of the
various techniques ?
http://las.perkinelme
r.com/content/relate
dmaterials/brochures
/bro_atomicspectrosc
opytechniqueguide.p
df

Other inorganic mass spectrometry

methods

Mainly for surface analysis (depth profiling, imaging) in different

materials (e.g. conducting, semiconducting, and nonconducting
solid samples; technical, environmental, biological, and
geological samples)
Spark source mass spectrometry (SSMS)
Glow discharge mass spectrometry (GDMS)
Laser ionization mass spectrometry (LIMS)
Thermal ionization mass spectrometry (TIMS)
Secondary ion mass spectrometry (SIMS): most sensitive
elemental and isotopic surface analysis technique
Sputtered neutral mass spectrometry (SNMS)
Detection limits for the direct analysis of solid samples by
inorganic solid mass spectrometry: down to ppb levels

SIMS: secondary ion mass

spectrometry
One of the most widespread surface analysis techniques for
advanced material research

Principle: bombard surface with ions,

secondary ions are sputtered from surface
High sensitivity for all elements
Any type of material that can stay
under vacuum (insulators, semiconductors,
metals)
Potential for high-resolution imaging
(down to 40 nm)
Very low background: high dynamic range
(more than 5 decades)
Quantitative work complicated by variations
in secondary ion yields in dependence on
chemical environment and the sputtering
conditions (ion, energy, angle)
Rapid deterioration of bombarded surface
Static SIMS: Molecular and elemental
characterisation of top monolayer

Dynamic SIMS: Bulk composition or depth distribution

of trace