1. Instrumentation & Methods: ICP/MS, Uranium
Jeff Brenner
Minnesota Department of Health

2. EPA Method 200.8 Overview and Fundamentals of ICP-MS
Determination of Metals Using Inductively Coupled Plasma Mass Spectrometry

3. Overview & Fundamentals of ICP-MS What we will cover
Overview and Fundamentals
ICP-MS Theory
Interferences
Reports

4. EPA 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

5. 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)

6. EPA 200.8 Isotopes and Mass Spectra
Isotopes of an element differ in the number of neutrons in the nucleus
U Atomic Number 92
234U has 142 neutrons
235U has 143 neutrons
238U has 146 neutrons

7. EPA Method 200.8 U Isotope Abundance
Isotope Half Life Natural Specific
Years Abundance Activity (pCi/ug)
234U 246, %
235U 700 million %
238U billion %

8. 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

9. 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.

10. 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 ½ its mass
138Ba double charges will appear at 138/2 = 69

11. 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

14. 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

15. 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)

16. EPA Method 200.8 Molecular Overlaps
Elements in the ICP do not fully break apart and recombination of highly concentrated elements will occur
Example
56Fe and 40Ar+16O
Background spectral features have been well characterized

17. 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
55Mn
234U
235U
238U

18. EPA Method 200.8 Factors Affecting Ion Intensities
Percent Ionization
Element % Ionized Na As Se F
Most elements are ionized greater than 90%.

19. EPA Method 200.8 ICP-MS System
Courtesy: Perkin Elmer

20. EPA Method 200.8 Spray Chamber and Nebulizer

21. 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.

22. 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.

23. 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.

24. 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

25. 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

26. 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 (O2)
Positively charged atomic and molecular ions (Ar+, O2+)
Reactive metastable atoms and ions
Negatively charged atomic and molecular ions
Photons
Electrons

27. 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.

28. 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.

29. EPA Method 200.8 Quadrupole Mass Filtering System
Courtesy: Perkin Elmer
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.

30. 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.

31. 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: +/ AMU

32. 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?

33. EPA Method 200.8 Isobaric Correction
Counts at mass 114 = 114Cd + 114Sn
114Cd = mass Sn
We cannot measure the counts of Sn at mass 114 directly since 114Cd can also be present. However, we can measure another isotope of Sn (118) that is free from overlap by Cd. Therefore:
114Cd = mass 114 – (a114Sn/a118Sn)*(118Sn)

34. EPA Method 200.8 Isobaric Correction
The abundance ratio (a114Sn/a118Sn) of these two isotopes is (0.65%/24.23%) and is reasonably constant. Therefore:
114Cd = mass 114 –(0.65%/24.23%)*(118Sn)
Correction = -(0.0268)*(118Sn)
114Cd = mass 114 – (a114Sn/a118Sn)*(118Sn)

35. 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:
40Ar35Cl interfering on 75As
40Ar37Cl interfering on 77Se
As has only one isotope at mass 75
40Ar35Cl can cause isobaric overlap &
Erroneously high results
Must measure 40Ar35Cl contribution and subtract it from the total counts at mass 75
Total counts mass 75 = counts from 75As plus counts from 40Ar35Cl
75As = mass Ar35Cl

36. EPA Method 200.8 Polyatomic Correction
We cannot measure the ArCl contribution at mass 75, however, we can measure the ArCl contribution from 40Ar37Cl at mass 77
The equation then becomes:
75As = mass 75- (a40Ar35Cl/a40Ar37cl)*(40Ar37Cl)
The relative intensities of 40Ar35Cl and 40Ar37Cl are determined by the isotopic ratio of 35Cl to 37Cl.
75.77%/24.23%=3.127
75As = mass *(40Ar37Cl)
Correction = * 77Se

37. EPA Method 200.8 Polyatomic Correction
If Se is present in the sample, the correction becomes more complicated. 77Se will contribute intensity counts to mass 77.
Therefore, measure Se at mass 82 and multiply the result by the ratio of 77Se to 82Se.
75As = mass *(mass77-77Se)
75As = mass *[(mass77-(a77Se/a82Se)*82Se]
75As = mass *[(mass *82Se]
Correction *77Se+2.733* 82Se

38. 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 234U and 235U isotope
Conversion is accurate if isotopes are present in natural abundance
Bias radioactivity concentration low

39. 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 Analytical methods for radioactivity.
Footnote 12

40. 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

41. 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

42. EPA Method 200.8 U Isotope Abundance
Isotope U 235U 238U
Half Life (years) 246, million billion
Natural Abundance % % %
Specific Activity (pCi/ug) 6,
Relative Intensity