AbstractA comparison of slurry sampling (SS)‐ETV‐ICP‐MS and slurry nebulization (SN)‐ICP‐MS for direct determination of trace impurities in titanium dioxide powder is made. The particle size effect, matrix effect and analytical characteristics of SSETV‐ICP‐MS and SN‐ICP‐MS are compared. The results have shown that SSETV‐ICP‐MS has a lower particle size effect and matrix effect compared to SN‐ICP‐MS. The analytical performance of the two methods reveals that SSETV‐ICP‐MS and SN‐ICP‐MS have similar relative detection limits (in the nanogram per liter level); however, the former has a lower absolute detection limit than the latter. Although the precision for SSETV‐ICP‐MS is a little worse than that for SN‐ICP‐MS, it is still acceptable for real sample analysis. The two methods were successfully applied for the determination of trace impurities in titanium dioxide powder samples with particle sizes of less than 50 nm, but only SSETV‐ICP‐MS could be applied for the determination of trace impurities in titanium dioxide powder samples with a particle size of 1 µm. Copyright © 2006 John Wiley & Sons, Ltd.