Study of matrix effects on the direct trace analysis of acidic pesticides in water using various liquid chromatographic modes coupled to tandem mass spectrometric detection

Abstract

This study investigated the effects of matrix interferences on the analytical performance of a triple quadrupole mass spectrometric (MS–MS) detector coupled to various reversed-phase liquid chromatographic (LC) modes for the on-line determination of various types of acidic herbicides in water using external calibration for quantification of the analytes tested at a level of 0.4 μg/l. The LC modes included (i) a single-column configuration (LC), (ii) precolumn switching (PC-LC) and (iii) coupled-column LC (LC–LC). As regards detection, electrospray (ESI) and atmospheric pressure chemical ionization (APCI) in both positive (PI) and negative (NI) ionization modes were examined. Salinity and dissolved organic carbon (DOC) were selected as interferences to study matrix effects in this type of analysis. Therefore, Milli-Q and tap water samples both fortified with 12 mg/l DOC and spiked with sulfometuron-methyl, bentazone, bromoxynil, 2-methyl-4-chlorophenoxyacetic acid, and 2-methyl-4-chlorophenoxypropionic acid at a level of about 0.4 μg/l were analyzed with the various LC–MS approaches. Direct sample injection was performed with volumes of 0.25 ml or 2.0 ml on a column of 2.1 mm I.D. or 4.6 mm I.D. for the ESI and APCI modes, respectively. The recovery data were used to compare and evaluate the analytical performance of the various LC approaches. As regards matrix effects, the salinity provided a dramatic decrease in response for early eluting analytes ( k value of about 1) when using the LC mode. Both PC-LC and LC–LC efficiently eliminated this problem. The high DOC content hardly effected the responses of analytes in the ESI mode, while in most cases the responses increased when using APCI-MS–MS detection. Of all the tested configurations, LC–LC–ESI-MS–MS with the column combination Discovery C 18/ABZ+ was the most favorable as regards elimination of matrix effects and provided reliable quantification of all compounds using external calibration at the tested low level. The major observed effects were verified with statistical evaluation of the data employing backwards ordinary least-square regression. All tested column-switching modes hyphenated to ESI- or APCI-MS–MS allowed the on-line multi-residue analysis of acidic pesticides in the reference water down to a level of 0.1 μg/l in less than 10 min, emphasizing the feasibility of such an approach in this field of analysis.