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Interferences

Section Six1

Interferences
Interferences that are expected:
Physical
Matrix
Spectral
Lead to incorrect results

Physical Interference
Common in ICP emission and ICPMS
Sample matrix effects
Surface tension
Viscosity

Aerosol transport effects


droplet formation by nebulizer
droplet size selection in spray chamber

Physical interferences are compensated for


with the use of Internal Standardization

Matrix Interferences
Affect ion intensity in two different ways
Plasma Loading
Space Charge Effect
Readings are generally suppressed
Routinely compensated for by internal
standardization

Plasma Loading
Energy reduced in plasma
Minimized by:
Keep dissolved solids below 0.5%
Robust plasma conditions
High RF power
Lower Nebulizer flow

Match internal standards by ionization


potentials

Space Charge Effect


High mass matrix elements can suppress low mass analyte
signals
Current instruments much less affected than earlier designs

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Cylinder Lens
(Net + Charge on Lens)

Skimmer

Detection of Matrix Interferences


Spiked samples
Reference materials
Non-linear response after dilution indicates
probable interference
Analyze at different plasma conditions

Internal Standards
Internal Standard Selection
Low concentration or not present in
samples
Not interfered by sample matrix
Do not interfere on analytes
Not common environmental contaminants
Matched to mass(es) of analytes
Reasonable concentrations

Internal Standards
Frequently Employed Internal Standards

Use of Internal Standards


On Line
Tubing wears at different rates
Dilution of sample
Proper mixing important
Off Line
Tedious
Mixing critical
Will correct for more items
Evaporation
Some sample prep errors

On Line Setup
B019-3342

0990-8587
Black/Black

B050-1595
B019-1058

Mixing Block
B050-7962

B019-3873
Pt/Ir Female
Connector

B019-3342
Hose
Adaptor

Tubing Size
Dependant on
Dilution

Internal
Standard
Capillary
0990-8265
To Nebulizer

To Autosampler
Probe

B019-1059

On Line Setup
Internal Standards Kits
Non HF N0774068
HF N0774067
Does not include
Nebulizer
Pump Tubing
Pump

Internal Standards Issues


1. Interference on mass of internal standard
Example: 29Si16O on 45Sc
Use a higher concentration of Sc to minimize error
2. Sample contains internal standard
Example: Li on 6Li
Use a higher standard of 6Li or use another internal
standard
3. Match ionization potentials
Example: Ge for As, Se, Zn
Ge has a higher ionization potential than other typical
internal standards, such a Y or In.

Physical and Matrix Interferences


Class Exercise: Select possible internal standards
for the following analyte/matrix combinations:

Be, Cr, Mn, Fe, Cu in drinking water


Zn, Cd, Pb in river water
Ca, Mg, Na, K in blood serum
Na, Mg, K, Cr, Mn, Cu, Cd, Ba, Hg, Pb, and U in
calcium phosphate rock

Spectral Interference - Isobaric


Isobaric Overlaps
One or more atoms or elements having the same
atomic weights or mass numbers
At some mass numbers, there are naturally
occurring isotopes for more than one element

Spectral Interference - Isobaric


Isobaric Overlaps
Be aware of what is in your samples when
selecting isotopes
Percent Abundance

Element

46

Ca

0.004

Ti

8.0

47

48

49

50

5.5

5.4

0.187
7.3

73.8

Spectral Interference - Isobaric


Isobaric Overlaps
List the elements which have isotopes at the
following masses:

Spectral Interference - Isobaric Correction


Automatically
corrects for
isobaric
overlaps
Similar to IECs
ICP emission
spectroscopy

Isobaric Correction
Counts at mass 114 = Cd 114 + Sn 114
or

Cd 114 = mass 114 - Sn 114


We cannot measure the counts of Sn at mass 114 directly since
Cd can also be present. However, we can measure another
isotope of Sn (118) that is free from overlap by Cd. Therefore:
Cd 114 = mass 114 - (aSn 114/aSn 118)*(Sn 118)
The abundance ratio (aSn 114/aSn 118) of these two isotopes
(0.65%/24.23%) and is reasonably constant. Therefore:

Cd 114 = mass 114 -(0.65%/24.23%)*(Sn 118)


Correction -(0.0268)*(Sn 118)

Isobaric Correction
Write element equations for the following isotopes:

Isotope Element Equation


Fe 54
Zn 64
Ba 138

Spectral Interference - Polyatomic Overlaps


Samples containing particular elements may form
molecular ions. The most common are:

Argon forming or ArX where X=O, Cl, etc


Oxides: MoO, TiO, CaO
Doubly Charged: elements with low second ionization
potentials such as Ba and La
Dimers: Ar2, N2, O2, S2
Hydrides: ArH, BrH
Hydroxides: CaOH, ArOH

Watch for interferences from the matrix at:


H(+1), N(+14), O(+16), Ar(+40) and
doubly charged species at one half of mass

Common Polyatomic Overlaps


Common interferences
High chloride matrices
ClO on 51V
ArCl on 75As

35 + 16 = 51
40 + 35 = 75

High sulfate matrices


SO on 48Ti

32 + 16 = 48

Organic matrices
CO on 28Si
ArC on 52Cr

12 + 16 = 28
12 + 40 = 52

Oxide forming matrices


CaO on 56Fe
MoO on 114Cd

40 + 16 = 56
98 + 16 = 114

Corrections
Isotope Selection
High abundance isotopes for low concentration
elements
Lower abundance isotopes for high concentration
elements
Avoid isotopes with intense background
contributions
Use 54Fe or 57Fe instead of 56Fe to avoid 40Ar16O

Spectral blank subtraction


Matrix match if possible

Plasma and torch conditions


Lowering of oxides

Corrections
Inter-element corrections
Dynamic
Empirical
DRC
Covered later
Minimize water vapor
Different sample introduction
Separation
Hydride

Polyatomic Correction
Dynamic Correction
Determine interfering molecular ion
intensity at an alternative mass.
Example:35Cl16O interference on 51V
V = Intensity51 - a35Cl/a37Cl* Intensity53
Advantages:
Works on wide Cl concentration ranges
Not affected by change in plasma

Dynamic Polyatomic Correction


Interference of Chloride on Arsenic
High concentrations of chloride react with argon in the plasma
to form the following:
40Ar35Cl interfering on 75As
40Ar37Cl interfering on 77Se

As in monoisotopic at 75amu
40Ar35Cl can cause erroneously high results
Measure the 40Ar35Cl contribution and subtract it from the total
counts at mass 75
Counts mass 75 = 75As counts + 40Ar35Cl counts
or
75As = mass 75 - 40Ar35Cl

Dynamic Polyatomic Corrections


Interference of Chloride on Arsenic (cont)
We can determine the ArCl contribution at mass 75, by
referencing the ArCl contribution from 40Ar37Cl at mass
77
The equation then becomes:
75As = mass 75 - (a40Ar35Cl/a40Ar37Cl)*(40Ar37Cl)
The relationship of 40Ar35Cl to 40Ar37Cl are determined
by the isotopic ratio of 35Cl to 37Cl.
75As = mass 75 - (75.77%/24.23%)*(40Ar37Cl)
75As = mass 75 - 3.127 *(40Ar37Cl)
Correction - 3.127 * ArCl 77

Dynamic Polyatomic Corrections


Interference of Chloride on Arsenic (cont)
If Se is present in the sample, the correction is more
complicated. Se 77 will contribute intensity counts
to mass 77.
Therefore, measure Se at mass 82 and multiply the
result by the ratio of Se 77 to Se 82
75As = mass 75 - 3.127*(mass 77 - 77Se)

As = mass 75 - 3.127*[mass 77-(a77Se/a82Se)*82Se]


75As = mass 75 - 3.127*[mass77- 0.874* 82Se]
75

Correction: - 3.127*(ArCl 77 0.874*Se 82)


Or
Correction: - 3.127*ArCl 77 + 2.733*Se 82

Empirical Polyatomic Corrections


Empirical Correction
Empirical approach is second choice to dynamic
correction
Interference ratio determined prior to analysis
0.01 mg/l V

500 mg/l Cl

Sample

i1
i3

35

Cl16O

i4

i2
i51V

35

51

35
i51V = I4 -

51
i2
i1

* i3

35

51

Empirical Polyatomic Corrections


Interference of Calcium Oxide on Iron
High concentrations of Ca (>10 ppm) form oxide and
hydroxide ions at the iron isotopes.

Ca16O+ overlaps 56Fe


40Ca16O1H overlaps 57Fe
Correcting for Interference of Calcium on Iron
Measure intensity of 43Ca and 40Ca16O1H using 50 ppm of high
purity Ca
Correction factor K = 40Ca16O1H /43Ca
Correction Equation:
57Fe
57Fe
43Ca
corr =
meas - K*
40

Interference Summary

Interferences lead to incorrect results


Select the correct technique
Use multiple isotopes
DRC, if available
If possible, verify that corrections work