Heavy metals such as chromium and arsenic are widespread in the environment due to their usage in many industrial processes. These metals may pose significant health risks to humans, especially children, due to their mutagenic and carcinogenic properties. Typically, the health risks associated with the ingestion of soil-bound metals are estimated by assuming that the metals are completely absorbed through the human intestinal tract (100% bioavailable). This assumption potentially overestimates the risk since soils are known to strongly sequester metals thereby potentially lowering their bioavailability. Beginning in 2000, researchers at Oak Ridge National Laboratory, with funding from the Strategic Environmental Research and Development Program (SERDP), studied the effect of soil properties on the bioaccessibility of soil-bound arsenic and chromium. Representative A and upper-B horizons from seven major U.S. soil orders were obtained from the U.S. Department of Agriculture's National Resources Conservation Service and the U.S. Department of Energy's Oak Ridge Reservation. The soils were spiked with known concentrations of arsenic (As(III) and As(V)) and chromium (Cr(III) and Cr(VI)), and the bioaccessibility was measured using a physiologically based extraction test that mimics the gastric activity of children. Linear regression models were then developed to relate the bioaccessibility measurements to the soil properties (Yang et al. 2002; Stewart et al. 2003a). Important results from these publications and other studies include: (1) Cr(VI) and As(III) are more toxic and bioavailable than Cr(III) and As(V) respectively. (2) Several favorable processes can occur in soils that promote the oxidation of As(III) to As(V) and the reduction of Cr(VI) to Cr(III), thereby lowering bioaccessibility. Iron and manganese oxides are capable of oxidizing As(III) to As(V), whereas organic matter and Fe(II)-bearing minerals are capable of reducing Cr(VI) to Cr(III). (3) The ubiquitous metal-sequestering properties of soils significantly lower the bioaccessibility of arsenic and chromium upon ingestion relative to the currently used 100% default values. (4) Key soil physical and chemical properties (particle size, pH, mineral oxide, clay, and organic matter contents) govern the extent of toxic metal bioaccessibility thus providing the necessary conceptual understanding for building accurate predictive models. (5) The As(V) regression model was able to predict the in vivo bioavailability in ten contaminated soils within a root mean square error of <10%. (6) Metal bioaccessibility is controlled by molecular-level speciation, where metal sequestration and solid phase stability are enhanced by increased soil-metal contact time.