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Instrumentation & Methods:

ICP/MS, Uranium
Jeff Brenner
Minnesota Department of Health
EPA Method 200.8
Overview and Fundamentals of ICP-MS
Determination of Metals Using Inductively
Coupled Plasma Mass Spectrometry
Overview & Fundamentals of ICP-MS
What we will cover
Overview and Fundamentals
ICP-MS Theory
Interferences
Reports
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EPA 200.8
ICP-MS Definition
An analytical technique to
determine Elements using Mass
Spectrometry from Ions generated
by an Inductively Coupled Plasma.
Mass Spectroscopy
Separation and measurement of the
mass of individual atoms making up a
given material
EPA 200.8
Analytical Benefits of ICP-MS
Rapid multi-element quantitative
analysis
Very low detection limits
Rapid semi-quantitative analysis
Wide dynamic range
Isotopic analysis
Spectral simplicity
Speciation (with HPLC)
EPA 200.8
Isotopes and Mass Spectra
Isotopes of an element differ in the
number of neutrons in the nucleus
U Atomic Number 92

234
U has 142 neutrons

235
U has 143 neutrons

238
U has 146 neutrons
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EPA Method 200.8
U Isotope Abundance
Isotope Half Life Natural Specific
Years Abundance Activity (pCi/ug)
234
U 246,000 0.0055 % 6208.2
235
U 700 million 0.72 % 2.17
238
U 4.47 billion 99.27 % 0.336
EPA Method 200.8
Isotopes and Mass Spectra
The Isotopic abundance of most elements
is constant
Pb may differ slightly based on the source
of the Pb
Pb is analyzed as the sum
206
Pb
207
Pb
208
Pb
EPA Method 200.8
Ions and Mass Spectra
Positive ions are produced by the
energy in the plasma
In order to utilize a mass
spectrometer an ion is necessary
ICP-MS analyze isotopic ions
The ions are steered throughout
the ion path of the spectrometer.
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EPA Method 200.8
ICP-MS Spectrum
A series of peaks that correspond to
mass to charge ratio (m/z)
Peaks could be the sum of different
isotopes of different elements
Doubly charged ions will appear
its mass

138
Ba double charges will appear at
138/2 = 69
EPA Method 200.8
Isobaric Spectral Overlaps
Signal at given amu is the
summation of all the isotopes at
that amu
It is best to avoid potential overlaps
by monitoring a clean mass
Overlaps are correctable in software
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EPA Method 200.8
Isobaric Spectral Overlaps
Several factors must be considered
when selection an isotope:
Concentration of analyte
Concentration of interferences
Abundances of isotopes at the given
mass
EPA Method 200.8
Molecular Overlaps
Polyatomic or molecular ions will
occur
Common ones are Ar, O, and H based
Be aware of molecular overlaps that
are formed:
Plasma (Ar)
Solvents (O, H, Cl, N)
Samples (C, Cl, S)
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EPA Method 200.8
Molecular Overlaps
Elements in the ICP do not fully
break apart and recombination of
highly concentrated elements will
occur
Example
56
Fe and
40
Ar+
16
O
Background spectral features have
been well characterized
EPA Method 200.8
Factors Affecting Ion Intensities
Isotopic Abundance Intensity
Intensity of an isotope is proportional to
its natural abundance
The sum of the signals from all isotopes
of an element are compared to the signal
from a mono-isotopic element, the
signals ideally should be equal
Example: Element Percent Relative
Isotope Abundance Intensity
55
Mn 100.0 100.0
234
U 0.0055 0.0055
235
U 0.7200 0.7200
238
U 99.2745 99.7245
EPA Method 200.8
Factors Affecting Ion Intensities
Percent Ionization
Element % Ionized
Na 100
As 50
Se 34
F 0.001
Most elements are ionized greater than
90%.
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EPA Method 200.8
ICP-MS System
Courtesy: Perkin Elmer
EPA Method 200.8
Spray Chamber and Nebulizer
EPA Method 200.8
ICP-MS Ion Source Region
Plasma creates ions from the components in the
sample.
Heat from 6,000K-10,000K dries, aerosol, then
atomize, and ionize components of the sample.
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EPA Method 200.8
ICP-MS Ion Source Region (Plasma)
Plasma is formed by a stream of argon gas flowing
between to quartz tubes.
Radio frequency (RF) power is applied through the
coil, and an oscillating magnetic field is formed.
An electrical discharge creates seed electrons and
ions.
EPA Method 200.8
ICP-MS Ion Source Region (Plasma)
Inside the induced magnetic field,
the charged particles are forced to
flow in a closed annular path.
As they meet resistance, heating
takes place and additional ionization
occurs.
EPA Method 200.8
Reaction Cell
Pressurized with a reactive gas
Convert isobar to a different ion which does
not interfere
Convert analyte to polyatomic ion which is not
interfered
The specific chemistry is dependent on:
Nature and density of the reactive gas
Electrical fields within the cell
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EPA Method 200.8
ICP-MS Ion Source Region (Lens)
Before sampler cone 760 torr
Before skimmer cone 3 torr
After skimmer cone 1e-3 torr
EPA Method 200.8
ICP-MS Ion Source Region (Lens)
Material extracted from the plasma are
composed of a mixture of the following:
Neutral atoms (Ar) Molecules (O
2
)
Positively charged atomic and molecular ions
(Ar+, O
2
+)
Reactive metastable atoms and ions
Negatively charged atomic and molecular ions
Photons
Electrons
EPA Method 200.8
ICP-MS Ion Source Region (Lens)
The lens captures and guides the
positively charged ions to the quadrupole.
By applying a positive potential to the
lens, the ions will be focused to the center
of the lens.
Small ions are optimized at lower
voltages. As the voltage is increased,
higher mass ions are better focused.
If the voltage is to high the ions are
repelled.
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EPA Method 200.8
Reaction Cell or Collision Cell
A reaction gas is introduced into the
cell. The reaction of the gas with
the interfering species is set up to
remove these interferences from
the path.
EPA Method 200.8
Quadrupole
Mass Filtering System
Separates on type of element (ion) from another with
an electromagnetic field.
Only one mass (m/z) will make it through at a time.
Many masses enter, only one makes it out.
Courtesy: Perkin Elmer
EPA Method 200.8
Perkin Elmer Optimization
After initiating the plasma, allow the
instrument to warm up while
aspirating a blank solution for at
least 15 minutes.
Mass Calibration Tune
DRC II Tuning Solution
(1 ppb Mg, In, Ce,Ba,Pb, U) and check
for responses and RSDs. Generate and
evaluate a tune report.
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Perkin Elmer DRC II Optimization
Suggestions
Suggested guidelines for an acceptable tune for method
200.8
Sensitivity:
Mg > 8,000 cts/0.1 sec/10 ppb
In >40,000 cts/0.1 sec/10 ppb
U >30,000 cts/0.1 sec/10 ppb
Precision:
Mg < 5 % RSD (0.1 sec integration time)
In < 5 % RSD ()
U < 5 % RSD ()
Oxides: < 3.0%
Ba++/Ba+ < 3.0%
Background:
Mass 220 < 2 cps
Mass Accuracy: +/- 0.05 AMU
EPA Method 200.8
Daily Performance Check
Sensitivity
Nebulizer
Autolens
x-y adjustment
Detector Optimization
Oxides to High:
Reduce nebulizer flow (plasma temperature increases)
Dirt cones
Reduce peristaltic pump speed
Increase RF power
Double Charged ions too high:
Decreased RF power
Increase nebulizer flow
Check skimmer 0-ring
Poor precision
Check entire sample introduction system
Check the nebulizer
Check that the correct method is used
Perform a visual check of the plasma! Is it stable?
EPA Method 200.8
Isobaric Correction
Counts at mass 114 =
114
Cd +
114
Sn
114
Cd = mass 114 -
114
Sn
We cannot measure the counts of Sn at
mass 114 directly since
114
Cd can also be
present. However, we can measure
another isotope of Sn (118) that is free
from overlap by Cd. Therefore:

114
Cd = mass 114
(a
114
Sn/a
118
Sn)*(
118
Sn)
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EPA Method 200.8
Isobaric Correction
The abundance ratio (a
114
Sn/a
118
Sn) of
these two isotopes is (0.65%/24.23%)
and is reasonably constant. Therefore:

114
Cd = mass 114 (0.65%/24.23%)*(
118
Sn)
Correction = -(0.0268)*(
118
Sn)
EPA Method 200.8
Polyatomic Correction
Interference of Chloride on Arsenic
High concentrations of chloride react with argon
in the plasma to form the following:

40
Ar
35
Cl interfering on
75
As

40
Ar
37
Cl interfering on
77
Se
As has only one isotope at mass 75

40
Ar
35
Cl can cause isobaric overlap &
Erroneously high results
Must measure
40
Ar
35
Cl contribution and subtract
it from the total counts at mass 75
Total counts mass 75 = counts from
75
As
plus counts from
40
Ar
35
Cl
75
As = mass 75-
40
Ar
35
Cl
EPA Method 200.8
Polyatomic Correction
We cannot measure the ArCl contribution at mass
75, however, we can measure the ArCl contribution
from
40
Ar
37
Cl at mass 77
The equation then becomes:

75
As = mass 75- (a
40
Ar
35
Cl/a
40
Ar
37
cl)*(
40
Ar
37
Cl)
The relative intensities of
40
Ar
35
Cl and
40
Ar
37
Cl are
determined by the isotopic ratio of
35
Cl to
37
Cl.
75.77%/24.23%=3.127

75
As = mass 75-3.217*(
40
Ar
37
Cl)
Correction = -3.127*
77
Se
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EPA Method 200.8
Polyatomic Correction
If Se is present in the sample, the
correction becomes more complicated.
77
Se
will contribute intensity counts to mass 77.
Therefore, measure Se at mass 82 and
multiply the result by the ratio of
77
Se to
82
Se.

75
As = mass 75-3.127*(mass77-
77
Se)

75
As = mass 75-3.127*[(mass77-(a
77
Se/a
82
Se)*
82
Se]

75
As = mass 75-3.127*[(mass77-0.874*
82
Se]
Correction -3.127*
77
Se+2.733*
82
Se
EPA Method 200.8
Types of Methods Measuring Uranium
Total concentration method 200.8
Uranium analysis by ICP-MS
Results reported as ug/L
Not very labor intensive
Limitations
Can not detect
234
U and
235
U isotope
Conversion is accurate if isotopes are present
in natural abundance
Bias radioactivity concentration low
EPA Method 200.8
Uranium Calculation
Uranium radioactivity
A
(pCi/L)
= U
(ug/L)
* 0.67
(pCi/ug)
Where: A = activity of uranium
U = uranium concentration
0.67 = conversion factor
40 CFR part 141.25 Analytical methods for radioactivity.
Footnote 12
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EPA Method 200.8
Types of Methods Measuring Uranium
Total activity method 908.0
Uranium chemically separated
Analyzed on alpha-beta proportional counter
Total activity of all three uranium isotopes
Reported as pCi/L
Limitations
Can not distinguish isotope
Conversion is accurate if isotopes are present
in natural abundance
Bias mass concentration high
Labor intensive
EPA Method 200.8
Types of Methods Measuring Uranium
Isotopic activity method
Uranium chemically separated
Similar to total activity
Alpha spectrometer
Able to distinguish uranium isotope
Results can be reported as pCi/L or
ug/L
Limitations
Labor intensive
EPA Method 200.8
U Isotope Abundance
Isotope
234
U
235
U
238
U
Half Life (years) 246,000 700 million 4.47 billion
Natural Abundance 0.0055 % 0.72 % 99.27 %
Specific Activity (pCi/ug) 6,208 2.17 0.336
Relative Intensity 0.0055 0.72 99.27