1. Advanced Analytical Chemistry – CHM 6157® Y. CAIFlorida International University Updated on 9/14/2006Chapter 3ICPMS-2 2.Interferences in ICPMS 2.1Mass spectral interferences Skoog et al., 1999, Instrumental Analysis

2. Advanced Analytical Chemistry – CHM 6157® Y. CAIFlorida International University Updated on 9/13/2006Chapter 3ICPMS 2.1.1Isobaric overlap Isobaric interferences are due to two elements that have isotopes having substantially the same mass. Quadrupole instruments: differ in mass by less one unit.

3. Advanced Analytical Chemistry – CHM 6157® Y. CAIFlorida International University Updated on 9/13/2006Chapter 3ICPMS Generally  Most elements in the periodic table have one (e.g. 59 Co), two (e.g. Sm, Samarium), or even three (e.g. Sn) isotopes that are free from isobaric overlap.  An isobaric interference occurs with the most abundant (sad!) and thus the most sensitive isotope, e.g. the very large peak for 40 Ar + overlaps the peak for the most abundant calcium isotope 40 Ca + (97%) making it is necessary to use the second most abundant isotope 44 Ca + (2.1%).  Isotopes with odd masses are free from overlap, while with even masses are not.  No isobaric peak interferences below 36 m/z. Isobaric overlaps are exactly predictable!

4. Advanced Analytical Chemistry – CHM 6157® Y. CAIFlorida International University Updated on 9/13/2006Chapter 3ICPMS 2.1.2Polyatomic Polyatomic ion interferences result from interactions between species in the plasma and species in matrix or atmosphere. Argon, hydrogen and oxygen are the dominant species present in the plasma and these may combine with each other or With elements from the analyte matrix or The major elements present in the solvents or acid used during sample preparation (e.g. N, S. and Cl)

5. Advanced Analytical Chemistry – CHM 6157® Y. CAIFlorida International University Updated on 9/13/2006Chapter 3ICPMS Vandercasteele and Block 1997 ?? 3000000

6. Advanced Analytical Chemistry – CHM 6157® Y. CAIFlorida International University Updated on 9/13/2006Chapter 3ICPMS Vandercasteele and Block 1997 This type of interference is found largely at m/z values of below 82.

7. Advanced Analytical Chemistry – CHM 6157® Y. CAIFlorida International University Updated on 9/13/2006Chapter 3ICPMS Jarvis et al., 1997 Polyatomic ion peaks in both H 2 O 2 and HNO 3 are identical to those identified in de-ionized water and these media are therefore considered ideal matrices. However, the spectra in an HCl or H 2 SO 4 matrix are more complex.

8. Advanced Analytical Chemistry – CHM 6157® Y. CAIFlorida International University Updated on 9/13/2006Chapter 3ICPMS Vandercasteele and Block, 1997

9. Advanced Analytical Chemistry – CHM 6157® Y. CAIFlorida International University Updated on 9/13/2006Chapter 3ICPMS Vandercasteele and Block, 1997

10. Advanced Analytical Chemistry – CHM 6157® Y. CAIFlorida International University Updated on 9/13/2006Chapter 3ICPMS Vandercasteele and Block, 1997

11. Advanced Analytical Chemistry – CHM 6157® Y. CAIFlorida International University Updated on 9/13/2006Chapter 3ICPMS  Corrected for using a blanks  Estimate the response of the interference relative to the analyte  Reduce water entering Plasma

12. Advanced Analytical Chemistry – CHM 6157® Y. CAIFlorida International University Updated on 9/13/2006Chapter 3ICPMS 2.1.3Refractory oxide ions Refractory oxide ions occur either as a result of incomplete dissociation of the sample matrix or from recombination in the plasma tail.  16 (MO + ), 32 (MO 2+ ) or 48 (MO 3+ ) mass units above the M + peak  The relative level of oxides can be predicted from the monoxide bond strength of the element concerned. Those elements with the highest oxide bond strength usually give the greatest yield of MO + ions.  Plasma operating conditions can dramatically influence the formation of oxide ions

13. Advanced Analytical Chemistry – CHM 6157® Y. CAIFlorida International University Updated on 9/13/2006Chapter 3ICPMS Jarvis et al., 1997

14. Advanced Analytical Chemistry – CHM 6157® Y. CAIFlorida International University Updated on 9/13/2006Chapter 3ICPMS Jarvis et al., 1997

15. Advanced Analytical Chemistry – CHM 6157® Y. CAIFlorida International University Updated on 9/13/2006Chapter 3ICPMS 2.1.4.Doubly charged ions  The formation of doubly charged ion in the plasma is controlled by the second ionization energy of the element and the condition of plasma equilibrium.  Only those elements with a second ionization energy lower than the first ionization energy of Ar will undergo any significant degree of 2 + formation.  The effect of 2 + ions is two-fold: Sensitivity for the singly charged species Spectrum interferences for others

16. Advanced Analytical Chemistry – CHM 6157® Y. CAIFlorida International University Updated on 9/13/2006Chapter 3ICPMS Jarvis et al., 1997

17. Advanced Analytical Chemistry – CHM 6157® Y. CAIFlorida International University Updated on 9/13/2006Chapter 3ICPMS A note on Interferences: Always consider and compare the relative plasma responses of the analytes of the interest and the interferences. Sometimes, a real experiments may be needed.