The transport and fate of pesticides applied to ornamental plant nursery crops are not well documented. Methodology for analysis of soil and water runoff samples concomitantly containing the herbicides simazine (1-chloro-4,6-bis(ethylamino)-s-triazine) and 2,4-D ((2,4-dichlorophenoxy)acetic acid) was developed in this research to investigate the potential for runoff and leaching from ornamental nursery plots. Solid-phase extraction was used prior to analysis by gas chromatography and liquid chromatography. Chromatographic results were compared with determination by enzyme-linked immunoassay analysis. The significant analytical contributions of this research include (1) the development of a scheme using chromatographic mode sequencing for the fractionation of simazine and 2,4-D, (2) optimization of the homogeneous derivatization of 2,4-D using the methylating agent boron trifluoride in methanol as an alternative to in situ generation of diazomethane, and (3) the practical application of these techniques to field samples.