As part of the National Water-Quality Assessment Program, the U.S. Geological Survey collected and analyzed groundwater samples during 1996-2006 from the San Antonio segment of the Edwards aquifer of central Texas, a productive karst aquifer developed in Cretaceous-age carbonate rocks. These National Water-Quality Assessment Program studies provide an extensive dataset of groundwater geochemistry and water quality, consisting of 249 groundwater samples collected from 136 sites (wells and springs), including (1) wells completed in the shallow, unconfined, and urbanized part of the aquifer in the vicinity of San Antonio (shallow/urban unconfined category), (2) wells completed in the unconfined (outcrop area) part of the regional aquifer (unconfined category), and (3) wells completed in and springs discharging from the confined part of the regional aquifer (confined category). This report evaluates these data to assess geochemical evolution processes, including local- and regional-scale processes controlling groundwater geochemistry, and to make water-quality observations pertaining to sources and distribution of natural constituents and anthropogenic contaminants, the relation between geochemistry and hydrologic conditions, and groundwater age tracers and travel time. Implications for monitoring water-quality trends in karst are also discussed. Geochemical and isotopic data are useful tracers of recharge, groundwater flow, fluid mixing, and water-rock interaction processes that affect water quality. Sources of dissolved constituents to Edwards aquifer groundwater include dissolution of and geochemical interaction with overlying soils and calcite and dolomite minerals that compose the aquifer. Geochemical tracers such as magnesium to calcium and strontium to calcium ratios and strontium isotope compositions are used to evaluate and constrain progressive fluid-evolution processes. Molar ratios of magnesium to calcium and strontium to calcium in groundwater typically increase along flow paths; results for samples of Edwards aquifer groundwater show an increase from shallow/urban unconfined, to unconfined, to confined groundwater categories. These differences are consistent with longer residence times and greater extents of water-rock interaction controlling fluid compositions as groundwater evolves from shallow unconfined groundwater to deeper confined groundwater. Results for stable isotopes of hydrogen and oxygen indicate specific geochemical processes affect some groundwater samples, including mixing with downdip saline water, mixing with recent recharge associated with tropical cyclonic storms, or mixing with recharge water than has undergone evaporation. The composition of surface water recharging the aquifer, as well as mixing with downdip water from the Trinity aquifer or the saline zone, also might affect water quality. A time-series record (1938-2006) of discharge at Comal Springs, one of the major aquifer discharge points, indicates an upward trend for nitrate and chloride concentrations, which likely reflects anthropogenic activities. A small number of organic contaminants were routinely or frequently detected in Edwards aquifer groundwater samples. These were the pesticides atrazine, its degradate deethylatrazine, and simazine; the drinking-water disinfection byproduct chloroform; and the solvent tetrachloroethene. Detection of these contaminants was most frequent in samples of the shallow/urban unconfined groundwater category and least frequent in samples of the unconfined groundwater category. Results indicate that the shallow/urban unconfined part of the aquifer is most affected by anthropogenic contaminants and the unconfined part of the aquifer is the least affected. The high frequency of detection for these anthropogenic contaminants aquifer-wide and in samples of deep, confined groundwater indicates that the entire aquifer is susceptible to water-quality changes as a result of anthropogenic activities. L