UPSC Combined Geo-Scientist, Mains · 2023 · Mains Paper III
Q1(g). Interference of calcium in the ICP–MS determination of iron
Question
How does high concentration of calcium interfere with ICP-MS analysis of iron?
Answer in brief
Calcium forms polyatomic ions in the plasma with the same nominal mass as the iron isotopes: ⁴⁰Ca¹⁶O⁺ falls on ⁵⁶Fe⁺ (m/z 56), so the iron result is too high; the heavy Ca matrix also suppresses the signal and clogs the cones.
Key points
- Spectroscopic (polyatomic) interference: Ca combines with O, H and N; the molecular ions have the same nominal m/z as iron isotopes, unresolved by a quadrupole.
- Overlaps: ⁴⁰Ca¹⁶O⁺ on ⁵⁶Fe⁺, ⁴⁰Ca¹⁶O¹H⁺ on ⁵⁷Fe⁺, ⁴⁰Ca¹⁴N⁺ on ⁵⁴Fe⁺, ⁴²Ca¹⁶O⁺ on ⁵⁸Fe⁺: positive error.
- Matrix effects: signal suppression by space charge and the easily ionised matrix; CaO deposits on the cones cause downward drift.
- Remedies: collision/reaction cell (He with KED; H₂ or NH₃), high-resolution instrument (m/Δm about 2500), dilution, matrix-matched standards, internal standard.
The full model answer
As written for the answer booklet: the diagram carries the working, the lines stay short. Read here only; it is not offered as a download.

CoversICP-MSpolyatomic interferenceCaO+ on Fe-56collision cellmatrix effect
All parts of Question 1
- 1(a) Relative standard deviation of replicate results5 marks
- 1(b) HPLC against GLC; particle size of packed GLC columns5 marks
- 1(c) Sources of radiation for infrared spectrometry5 marks
- 1(d) Graphite-furnace AAS compared with flame AAS5 marks
- 1(e) Calibration of the temperature axis in thermogravimetry5 marks
- 1(f) K and L lines in XRF; wavelength-dispersive spectrum of Zn5 marks
- 1(g) Interference of calcium in the ICP–MS determination of iron5 marks
- 1(h) Type metal: constituents and non-destructive analysis5 marks