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A technique for precise boron isotope ratio measurements with a high detection power has been developed by negative thermal ionization mass spectrometry (NTIMS). Relative standard deviations in the range of 0.03–0.3% have been obtained for the determination of the 11B/10B isotope ratio using nanogram amounts of boron. Ba(OH)2 has been applied as ionization promoter for the formation of negative thermal ions. By adding MgCl2 better reproducibilities of the measurement have been achieved. A possible interference of BO- 2 ions at mass number 42 by CNO- could be excluded by the sample preparation technique used.