ICP-MS Application Training

Part 4 – Interferences and

Data handling

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Interference Challenges in ICP-MS

• Generally ICP-MS interferences can be classified into two main

groups:

• Spectral
• isobaric and polyatomic
• often causes incorrectly high results

• Physical
• sample matrix
• often causes incorrectly low results

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Spectral Interferences in ICP-MS

▪ Few chemical interferences in ICP-MS

▪ Two types of spectral interference in nature:

Isobaric Isotope of a different element has same

mass/charge as analyte isotope

Polyatomic A molecule has same mass/charge as

analyte isotope

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Spectral Interferences Examples

• Isobaric Interferences – 114Sn and 114Cd

• fortunately, both elements have other isotopes that are free of
isobaric interference – 118Sn and 111Cd

• Polyatomic Interferences –
In nature, Vanadium has two isotopes:
• 50V (0.25% natural abundance) and 51V (99.75%)
• In chloride matrix, the formation of the 16O35Cl+ polyatomic ion in
the plasma interferes with 51V+
• potentially 50V could be used, it has no polyatomic interference
from chloride matrix
• but 50V has two isobaric interferences from 50Ti (5.4%) and 50Cr
(4.3%)

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Spectral Interferences in ICP-MS

• Polyatomic interferences (oxides, hydroxides and hydrides)

• Produced by elements combining with
• 1H, 16O, 16O1H from either water or air
• form molecular hydride, oxide or hydroxide ions 1, 16 and 17 mass
units higher than element mass
• typically produced in cooler zones of plasma just before interface
• problem when rare earth or refractory type elements are present in
sample, readily form oxides
• 140Ce16O+ ion interferes with 156Gd+
• Doubly Charged Spectral Interferences
• formed when an ion is generated with a double positive charge
• produces a signal at half its mass
• 138Ba++ interferes with 69Ga+

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Common Spectral Interferences

An isotope browser within the software can be used to look at some possible
spectral interferences for selected isotopes

▪Ar40 on Ca40

▪Cr54 on Fe54

▪Ar40O16 on Fe56

▪Ar40Cl35 on As75

▪Xe77 on Se77

▪Ar40Ar38 on Se78

▪Ar280 on Se80

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Spectroscopic Interferences Reductions

• Isobaric elemental
• e.g. 82Kr+ on 82Se+
• choose free mass
• correction equations
• Polyatomic
• e.g. 40Ar35Cl+ on 75As+
• optimize instrument conditions
• correction equations
• iCRC or ‘cool’ plasma technique
• Oxides and doubly charged ions
• optimize instrument conditions

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Interference Correction Equations

Example of mathematical interference corrections*:

• 114Cd has an isobaric interference from 114Sn
• Sn has an interference free isotope, 118Sn
• ratio of 114Sn to 118Sn is known from its natural abundances
• i.e. 114Sn/118Sn = 0.65%/24.23% = 0.0268
• the signal contribution from 114Sn at mass 114 can be determined by
measuring 118Sn signal
• i.e. 114Sn signal = 0.0268 x 118Sn signal
• total signal at mass114 =114Cd signal + 114Sn signal, and therefore:
114Cd signal = mass114 – (0.0268) x 118Sn signal

• Another example - can correct for 16O35Cl on 51V by measuring 16O37Cl

• adjust for natural abundances of 35Cl/37Cl (= 16O35Cl/16O37Cl)
* Correction equation will not work adequately if the signal from interfering element
is many times greater than that from the analyte
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Interferences: Development of correction equations

• Identify the interfering ion(s)

• Identify a free mass of the interfering ion(s)

• By knowing the natural abundances of the interfering ion, derive an equation to

remove the appropriate amount of signal from mass of interest

• As75 = Ar40Cl35 – quadrupole ICPMS cannot distinguish them

• Therefore we also measure Ar40Cl37, since Cl35 is 75.77% and Cl37 24.23% of
total Cl in a fixed ratio.

• Finally, we must also measure Se82 to correct for any Se77 on Ar40Cl37

• The resulting correction equation for ArCl on As is thus :

• As75 = - 3.127 * (?77 - 0.815 * ?82)

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Cool Plasma Technique

• An alternative approach to minimize interferences from severe polyatomic

interferences

• Cool plasma utilizes a low temperature plasma

• minimizes formation of certain Ar-based polyatomic ions
• 38Ar1H+, 40Ar+and 40Ar16O+ interfere on
39K+, 40Ca+ and 56Fe+, respectively

• important trace elemental analysis in semi-conductor industry

• Normal plasma conditions
• RF power = 1.0 ~ 1.5 kW, neb flow = 0.8 ~ 1.0mL/min
• Cool plasma conditions
• RF power = 0.6 ~ 0.8 kW, neb flow = 1.0 ~ 1.2mL/min
• Ionization conditions in plasma are change
• interferences are reduced
• detection limits for these elements are improved
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Limitations of Cool Plasma Technique

Limitations of Cool Plasma technique

• limited to small group of elements prone to Ar-based
interferences
• K, Ca, Fe, Na
• ionization temperature is significantly lower than normal plasma
• can’t be used to overcome 40Ar40Ar+ on 80Se+
• or 40Ar35Cl+ on 75As+
• insufficient ionization of As and Se
• severe signal suppression for analysis of complex samples
• not suitable for using in route environmental analysis

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iCRC Techniques

• Collision/Reaction Cells and iCRC techniques

use ion-molecule collisions and reactions to
remove polyatomic and molecular interferences

• removed before ions entering mass analyzer

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Spectral Interferences Reduction – Summary

Isobaric Isotope correction equations based on isotopic

abundances

Sample pre-treatment prior to analyte detection

Polyatomic Minimize formation – by optimizing plasma conditions

(CeO+/Ce+ ratio a good indicator)
Correction equations
Cool plasma conditions
iCRC with the Analytik Jena PlasmaQuant® MS
Sample pre-treatment

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Physical Interferences

The analyte signal suppressed by the sample matrix. There are two
basic types of matrix-induced interferences

• Sample transport effect

• droplet formation and selection by nebulizer/spraychamber
• differences in sample viscosities and surface tensions
• poor transmission of ions, space-charge effects
• memory effects
• Impact on ionization/plasma temperature
• the ionization conditions in the plasma are fragile
• particularly under cool plasma conditions
• if higher concentrations of solvent are aspirated, it results in severe
suppression of the analyte signal

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Space-Charge Effects

• Suppression of signal due to poorer transmission of ions through ion optics

• result of matrix-induced Space-Charge effects
• Has the effect of defocusing the beam
• lighter elements such as Be and Li are more easily push out
• greater suppression at low mass compared to high mass elements

Ion Beam Cross-Section Expansion of Ion Beam

+ +
+
+ + + + + +
+ + + +
++ + + + + + + + +
+ + + + +
+ + + +
+ + + +
+ +
+ +

Aqueous Standard Sample with Matrix Ions

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Physical Interferences – Memory Effects

• Memory Effects
• Caused by retention of analytes on sample introduction
system, torch, and interface cones
• Elements such as Li, Hg, & B exhibit significant memory
effects
• Monitor with >3 replicates
• Rinse times can be reduced with dilute HNO3 rinse
• Deposition on the Interface Cones
• ICP-MS interfaces exhibit deposition of sample material
under exposure to samples of high TDS (> 0.2%)
• Proper conditioning the cones and optimization of the
interface and vacuum system can improve stability

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Physical Interferences Reductions

• Memory
• Acid rinse, (Au rinse for Hg determination)
• Specialized sampling method

• Interface deposition
• Sample dilution
• Optimize sampling depth

• Matrix effects
• Plasma/Ion Optics optimization
• Matrix matching
• Cone conditioning
• Space-charge effects
• Plasma/Ion Optics optimization
• Sample dilution
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Internal Standard Correction in ICP-MS

• Used to correct for:

• Matrix effects
• Short term signal fluctuations
• Long term signal drift
• Adding internal standard
• to each sample (off-line addition)
• ‘T’ed in to each sample (on-line addition)
• Correction method
• Fixed/Manually
• Automatically
• Interpolated

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Selection of Internal Standard Elements

• Int. Std. elements are not present in samples

• Int. Std. elements should not suffer from or cause isobaric

interferences

• Cover entire mass range of interest

• Closeness in mass to analyte

• Common Int. Std. elements:

• 6Li, 45Sc, 72Ge, 89Y, 103Rh, 115In, 159Tb, 165Ho, 175Lu, 193Ir, 209Bi

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Reduction of Space-Charge Effects

• Internal Standardization can be used to partially correct for space-

charge effects
• doesn’t address fundamental cause of the problem

• Optimization of ion optics is recommended

• steer as many of analyte ions into mass analyzer while rejecting
matrix ions

• Dilution of matrix is the only answer in many cases

• some sensitivity regained due to the reduction of space-charge
effects

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Reduction of Space-Charge Effects, cont

• Optimizing ion lens and optics settings for reducing space-

charge effects

• spike Int. Std. elements into low matrix and high matrix
sample
• blank and real sample
• optimize ion lens and optics settings by alternatively
aspirating the solutions with different matrix until similar
intensities are achieved for spiked IS elements
• or minimum suppression without large decrease in
sensitivity

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Challenges of High Dissolved Solid Samples

Situation Observed Problem in Analysis

Total dissolved solids > 0.3 % Signal drops and/or disappears

blocks cones for all isotopes

High concentration of elements Signal suppression; especially for low

intensifies space-charge effect mass isotopes

Solution properties can vary;

resulting in greater or lesser Unusually high or low results
sample aspirated

These problems generally solved by dilution, disadvantage of dilution is loss of

analyte detection
Internal standards are run with solutions to compensate for signal suppression or
enhancement
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Summary of Interference Reductions

• Matrix removal
• Off-line – precipitating and filtering matrix
• automated/on-line – using LC equivalent techniques
• e.g. trace metal determinations in seawater

• Mathematical Interference Correction Equations

• for isobaric, and less severe polyatomic interferences
• used when no alternative isotope is available

• Internal Standardization
• correction for physical interferences
• correction for long-term drift and short-term fluctuations

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ICP-MS Data Handling

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ICP-MS Data Handling Software

• All ICP-MS instrumentation require PC software to control

• plasma
• mass spectrometer
• perform calculations on collected data

• Software then translates measured ion counts by detector to useful

information

• ICP-MS can provide data in 4 ways

• quantitative
• semi-quantitative
• isotope ratio analysis
• isotope dilution analysis

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ICP-MS Data Acquisition Modes

• Full mass scanning

• Quadrupole is scanned over entire mass range (except
excluded masses)

• Segmented scanning
• Quadrupole scans only mass ranges of interest

• Peak hopping
• Quadrupole acquires only at specific isotopes of interest
• Typically at peak maximum only

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Full Mass Scanning / Segmented Scanning

• Data can be collected in full mass

scanning or segmented scanning mode

• Example of cobalt signal collected in 59Co

segmented scanning mode shown
• Option of point spacing of 0.1 or
0.025amu; 0.1amu spacing normal
• Provides opportunity to view areas
other than what is being quantitated

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Data Acquisition - Peak Hopping

✓ Produces vertical line for each point collected

✓ Best data duty cycle – lowest detection limits
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Semi-Quantitative Analysis by ICP-MS

• Semi-Quantitative Analysis

• Provides fast and semi-accurate analysis for a large number

of elements without calibration

• Only a selected number of elements are determined

quantitatively

• The concentrations of other elements are estimated from

their responses

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Aerosol dilution

▪ Minimizes sample preparation by extending matrix tolerance of ICP-MS

▪ For samples containing 0.2 to 4% Total Dissolved Solids
▪ such as seawater contains ~3.5% TDS

▪ Online dilution via detuning of nebulizer efficiency and sheath gas

dilution effect

▪ Achieve 10-fold dilution without additional sample prep

▪ Suitable for seawater, metals and mining, high TDS effluents

Aerosol Dilution

• NO Hardware Changes Required

Sample Flow

P.G. A.G.

N.G.

S.G.

P.G. – Plasma Gas

A.G. – Auxiliary Gas
N.G. – Nebulizer Gas To Waste

S.G. – Sheath Gas

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Typical Analysis Settings

More efficient
nebulization

0.8-1.1 L/min

0.1-0.3 L/min
Low gas dilution
Aerosol Dilution Settings

Less efficient
nebulization

0.1-0.3 L/min

0.8-1.1 L/min
High gas dilution

▪ Followed by automatic optimization of ion optic settings

Isotope Ratio Measurements

• Few elements have only one isotope

• Being measured in the fields of earth sciences, medical researches,

environmental studies and nuclear industry

• Studies of isotopic variation in ‘natural samples’ are divided into two groups
• stable isotopes
• originate from creation of the galaxy
• isotopic composition has remained constant over time
• radiogenic
• result from radioactive decay of unstable parent isotope

• (Man’s activity may also produce isotopes which fall into above two groups)

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Determination of Isotope Ratios

• Quadrupole ICP-MS has capability of determining isotope ratios of an

element
• precision is in the range of approximately 0.1% RSD on quadrupole
ICP-MS
• therefore, its application is limited with such systems

• Precision on TIMS approximately 10 fold better or more

• slow (1 sample/hr)
• metals with low ionization potentials

• High resolution/Magnetic sector systems are commonly used for high

precision isotope ratio determinations
• precision is in the range of 0.001 - 0.0001% RSD

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Determination of Isotope Ratios, cont.

Important factors in the determination of isotope ratios by ICP-MS

• sensitivity and counting statistics

• scanning dwell time
• dead time
• resolution and abundance sensitivity
• mass bias

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Applications of Isotope Ratio Measurement

• Applications examples on quadrupole ICP-MS

• Geological dating of rocks
• Pb isotopes (isogeneric vs radiogenic)
• 230Th-234U dating in coral to assess El Nini effect on sea temperature
and salinity
• Multi-collector ICP-MS
• Determining source of contaminant
• Pb isotopes to assess impact of leaded fuels
• Nuclear applications
• B and U isotopes
• Biological tracer studies
• Fe isotopes in whole blood
• Medical
• Li isotopes 36
Isotope Dilution Analysis

• Involves addition of a known amount of an enriched isotopic spike

• for a specific element of interest
• The enriched isotope acts as both a calibration standard and internal
standard
• calibration constructed from ratio of selected natural isotope intensity
to spiked isotope intensity vs. concentration of analyte
• same chemical and physical properties as the analyte element
• best possible internal standard
• Hence, isotope dilution is recognized as being the most accurate type of
all analyses
• used to certify SRM

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Isotope Dilution – How?

Spike
Addition

Sample

Abundance of isotope-1 (/spike)

Mixture of Sample & Spike
Abundance of isotope-2 (/reference)
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Isotope Dilution Calculations

Ms K (As – Bs R)
C =
W (B R – A)
Where:
C the analyte concentration in µg/g
Ms mass of the isotope spike in µg
W weight of the sample in g
K ratio of the natural and spike atomic weights of analyte
A abundance of the reference isotope in sample
B abundance of the spike isotope in sample
As abundance of the reference isotope in the spike material
Bs abundance of the spike isotope in the spike material
R measured isotope ratio (reference/spike) in the mixture sample after the
spike addition
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Isotope Dilution Analysis

• Advantages are:
• Ideal internal standard
• immune to physical and chemical interferences
• Some sample loss can be tolerated during sample preparation
• No other calibration techniques matches precision or accuracy

• Disadvantages are:
• Not applicable to mono-isotopic elements
• Limited availability of enriched isotopes
• Expense of enriched isotopes
• Time-consuming sample preparation required to fully equilibrate spike
addition

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Thank you for your attention!