Solid-phase extraction with styrene–divinylbenzene sorbent for high-performance liquid or gas chromatographic determination of urinary chloro- and methylthiotriazines

Abstract

A solid-phase extraction (SPE) procedure on a styrene–divinylbenzene (SDB-1 cartridge) for extraction and cleaning of the triazine herbicides atrazine, simazine, ametryn, and prometryn and atrazine monodealkylated metabolites from urine samples was developed and optimised for final high-performance liquid chromatographic (HPLC–UV diode array detection) and gas chromatographic (GC–electron-capture detection and GC–thermionic-sensitive detection) analyses. Interfering polar matrices were eliminated by rinsing SDB-1 with 1% acetonitrile in water or with pure water. Extraction recoveries were from 78 to 101% with an RSD of about 10% for all studied compounds. The extraction recovery for the didealkylated atrazine metabolite was significantly lower and this compound cannot be determined with these procedures. Sorbent matrix generated interferences, although not detected by the chromatographic system, lowered the response of nitrogen–phosphorus and electron-capture GC detectors for monodealkylated chlorotriazines when compared to standards prepared in n-hexane. HPLC and GC analysis with SPE (SDB-1) preconcentration showed excellent linearity over the concentration range tested, with detection limits in urine of 10 ng ml −1 for the parent herbicides (HPLC and GC analysis) and 20 ng ml −1 for monodealkylated chlorotriazines (HPLC analysis).