A statistical methodology formulated for defining background or baseline levels of constituents of concern in groundwater is presented. The methodology was developed for the case where prior delineation of unimpacted areas is not possible because of site history and a large set of groundwater monitoring measurements exists. Consideration was given to spatial and temporal trends, outliers, and final segregation of wells into impacted or unimpacted categories to develop probability distributions and summary statistics for each constituent evaluated. The formulated approaches were applied to groundwater monitoring data for the U.S. Department of Energy Savannah River Site facility, and results for four representative constituents (aluminum, arsenic, mercury, and tritium) are discussed.