A hot alkaline extraction method (SW-846 Method 3060A) for total Cr(VI) in soils and sediments has been developed that selectively solubilizes Cr(VI). This paper compares the effectiveness of this extraction method versus four others to solubilize sparingly soluble PbCrO4 spiked into four diverse soil materials. The five extractants were distilled water (pH 5.7); phosphate buffer (5 mM K2HPO4/5 mM KH2PO4; pH 7.0); carbonate/hydroxide solution (0.28 M Na2CO3/0.5 M NaOH; pH 11.8) with and without heating; and hydroxide solution (0.1 M NaOH; pH 13) with sonication. The hot carbonate/hydroxide solution was superior to the other methods in extracting >90% of the spiked PbCrO4 from a redox-inert quartz sand, chromite ore processing residue (COPR)-enriched soil, and a loamy-textured soil (Ultic Hapludalf). Distilled water and phosphate buffer extracted no Cr(VI) spike from these soils, as expected due to the low Ksp of PbCrO4 (1.8 × 10-14). Although it was hypothesized that PbCrO4 would be reduced and not recove...