This paper describes the simultaneous quantification of the imidazolinone herbicides (IMIs) imazapyr, m-imazamethabenz, p-imazamethabenz, m,p-imazamethabenz-methyl, imazethapyr, and imazaquin in two types of samples. (a) Groundwater, lake water, and river water samples were enriched by off-line solid-phase extraction with a Carbograph-1 cartridge and analyzed by reversed-phase liquid chromatography using a UV detector (lambda = 240 nm). The overall recoveries of IMIs extracted from 1 L of groundwater (fortified with 500-100 ng/L), 0.5 L of lake water (fortified with 500-100 ng/L), and 0.5 L of river water (fortified with 1000-200 ng/L) samples were not lower than 89%. The mean relative standard deviation (RSD) was 5.1% (ranging from 4.1% to 6.8%) in natural water. The detection limits were 30-39 ng/L in groundwater, 43-51 ng/L in lake water, and 55-67 ng/L in river water. The method involves confirmatory analysis by LC/ES-MS in full-scan mode. The dependence of the ion signal intensities on proton concentration in the mobile phase was investigated with a view to optimizing the sensitivity of the ES-MS detector. When LC/ES-MS was used, the limit of detection, calculated from extracted-ion current profiles (EICPs), was 4-7 ng/L for ground-water and 9-13 ng/L for river water. (b) Soil sample analysis utilized combined soil column extraction (SCE) and off-line solid phase extraction (SPE) for sample preparation, analyzing with LC/ES-MS under selected ion monitoring (SIM). Several different extractants were evaluated for the purpose of SCE optimization. The system that best optimizes the extractability IMIs from the soil was found to be the mixture CH3OH/(NH4)2CO3 (0.1 M, 50:50 v/v). The effect of IMI concentration in the matrix on recovery was evaluated. The total recovery of each IMI from soil at each of the two levels investigated ranged from 87% to 95%. Under three ion SIM conditions, the limit of detection (S/N = 3) was 0.1-0.05 ng/g in soil samples.