This paper describes the first approach that simultaneously quantifies four polar, water-soluble organophosphorus herbicides, i.e., glyphosate, glufosinate, fosamine and ethephon, at nanogram levels in environmental waters. The target herbicides were separated completely by ion chromatography (IC) on a polymer anion-exchange column, Dionex IonPac AS16 (4.0 mm T 250 mm), with 30 mM citric acid flowing at 0.70 mL min S1 as the eluent. On-line inductively coupled plasma mass spectrometry (ICP-MS) using a quadrupole mass spectrometer was employed as a sensitive and selective detector of the effluents. Various parameters affecting the separation and detection were systematically examined and optimized. Detection limits of the herbicides achieved with the proposed IC/ICP-MS method were 1.1-1.4 mg L S1 (as compound) based on a 500-mL sample injection. Matrix anions, metal ions, phosphate, polyphosphates, non-polar and other polar organophosphorus pesticides showed no interference. The developed method was validated using reservoir water, treated water and NEWater samples spiked at the level of 10-25 mg L S1 with satisfactory recoveries (95-109%). It is applicable to the simultaneous determination of mg L S1 concentrations of the herbicides in polluted water. Copyright # 2007 John Wiley & Sons, Ltd.Toxicological risks from human exposure to pesticides may occur through contaminated drinking water and agricultural products. Glyphosate, glufosinate, fosamine and ethephon are widely used organophosphorus herbicides, and their residues have been found in waters, soils, fruits, crops, vegetables, and even in human sera and urine. Currently, these compounds are regulated worldwide. As summarized in Table 1, all four herbicides have similar chemical properties: strong polarity and in most cases, ionic character, high solubility in water, insolubility in organic solvents (except ethephon which is readily soluble in polar organic solvents and slightly soluble in non-polar solvents), and absence of chromophore or fluorophore in their molecular structures. Therefore, it is challenging to determine such herbicides at mg L À1 or even lower levels. It is also of interest to develop sensitive, rapid and simple methods that are capable of simultaneously quantifying them in water.Of the four herbicides, glyphosate and glufosinate are the more commonly monitored at trace residue levels. The methods primarily include gas chromatography (GC), high-performance liquid chromatography (HPLC), capillary electrophoresis (CE), and enzyme-linked immunosorbent assay (ELISA), as discussed in a review. 1 In GC methods, glyphosate and glufosinate, sometimes together with their metabolites, aminomethylphosphonic acid (AMPA) and 3-methylphosphinicopropionic acid (MPPA), are chromatographed after chemical derivatization and detected by flame photometry, electron capture or mass spectrometry (MS). GC/MS methods with sample preconcentration are sensitive with limits of detections (LODs) of less than 1 mg L À1 . [2][3][4] Liquid chromatography methods for g...