Interferences affecting the determination of butyltin species by sodium tetraethylborate (STEB) derivatisation followed by purge-trap preconcentration were systematically studied using synthetic solutions, natural water samples and sediment extracts. Substances that did not cause interferences included most common cations (apart from those metal ions listed below), anions, metalloids and polar organic compounds. Natural organic matter (NOM) specifically interfered with tributyltin (TBT) due to a mechanism involving partitioning of the butyltin to the hydrophobic portions of the NOM. The metal ions Ag(I) (greater than or equal to2 muM), Cd(II) (greater than or equal to2 muM), Cu(II) (greater than or equal to0.5 muM) interfered predominantly with the determination of monobutyltin (MBT) due to catalytic degradation of the STEB reagent. Pb(II) (greater than or equal to 14 muM) interfered with butyltin determination by an unknown mechanism. Other interferences to the purge-trap method were shown to occur in the presence of chelating agents (e.g. EDTA) or hydrophobic liquids such as diesel fuel. A mixture comprising methanol (MeOH), EDTA and Mn(II) was used to partially mask the effect of interfering NOM and metals. Spike recoveries (mean +/- S.D. of n = 7 different samples) of MBT, dibutyltin (DBT) and TBT in contaminated natural water samples were improved from 70 +/- 36, 90 +/- 11 and 91 +/- 24 to 102 10, 98 +/- 3 and 98 +/- 4%, respectively. Spike recoveries (mean I S.D. of n = 5 different samples) of MBT, DBT and TBT in aliquots of sediment extracts were improved from 86 +/- 17, 79 +/- 18 and 59 +/- 32 to 97 +/- 6.2, 103 +/- 3.6 and 103 +/- 5.0%, respectively. The ability to analyse larger aliquots of sediment extracts in the presence of the masking mixture improved the detection limit four-fold if MBT and DBT determination was required and 10-fold if only TBT determination was required. (C) 2003 Elsevier B.V. All rights reserved.