Abstract-A new sampling method, termed negligible depletion hollow fiber-protected liquid-phase microextraction, was developed for sensing the freely dissolved concentration (C free ) and evaluating the availability of atrazine (ATR), desethyl atrazine (DEA), and simazine (SIM) in water. The sampling device was prepared by impregnating 1-octanol to both the pores and the lumen of a piece of polypropylene microporous hollow fiber membrane. After equilibrium and negligible depletion extraction, the 1-octanol in the lumen of the hollow fiber (10 l) was collected for determination of triazines. Determination of C free and the distribution coefficient to 1-octanol (D OW ) can be performed with this technique. A wide linear working range (1-200 g/L) and low detection limits (0.1-1 g/L) were obtained for triazines. Measured log D OW values of DEA (1.44 Ϯ 0.04), SIM (2.06 Ϯ 0.06), and ATR (2.33 Ϯ 0.05) agreed well with those reported in the literature. The measured D OW values were independent of the chemical concentration and sample pH (pH 3-10) and negligibly affected by the sample salinity (0-500 mM), suggesting that environmentally relevant pH and salinity have no significant effects on the availability of triazines. Although a slight (Յ31%) increase of C free was observed, one-way analysis of variance indicated the C free of triazines were not significantly affected by the presence of Aldrich humic acid, Acros humic acid, and bovine albumin V (dissolved organic carbon [DOC], 0-100 mg/L). From 3 to 36% of the spiked triazines, however, were found to associate with the dissolved organic matter (DOM) in surface-water samples (DOC, 32.0-61.9 mg/L), suggesting the origin of the DOM is a key parameter in determining its association with and, thus, the availability of triazines.