Chemical hydrogeology, including organic and inorganic aspects, has contributed to an increased understanding of groundwater flow systems, geologic processes, and stressed environments. Most of the basic principles of inorganic-chemical hydrogeology were first established by investigations of organic-free, regional-scale systems for which simplifying assumptions could be made. The problems of groundwater contamination are causing a shift of emphasis to microscale systems that are dominated by organic-chemical reactions and that are providing an impetus for the study of naturally occurring and manmade organic material. Along with the decrease in scale, physical and chemical heterogeneity become major controls. Current investigations and those selected from the literature demonstrate that heterogeneity increases in importance as the study site decreases from regional-scale to macroscale to microscale. Increased understanding of regional-scale flow systems is demonstrated by selection of investigations of carbonate and volcanic aquifers to show how applications of present-day concepts and techniques can identify controlling chemical reactions and determine their rates; identify groundwater flow paths and determine flow velocity; and determine aquifer characteristics. The role of chemical hydrogeology in understanding geologic processes of macroscale systems is exemplified by selection of investigations in coastal aquifers. Phenomena associated with the mixing zone generated by encroaching sea water include an increase in heterogeneity of permeability, diagenesis of minerals, and formation of geomorphic features, such as caves, lagoons, and bays. Ore deposits of manganese and uranium, along with a simulation model of ore-forming fluids, demonstrate the influence of heterogeneity and of organic compounds on geochemical reactions associated with genesis of mineral deposits. In microscale environments, importance of heterogeneity and consequences of organic reactions in determining the distribution and concentrations cf. constituents are provided by several studies, including infiltration of sewage effluent and migration of creosote in coastal plain aquifers. These studies show that heterogeneity and the dominance of organically controlled reactions greatly increase the complexity of investigations.Current investigations and those selected from the literature demonstrate that heterogeneity increases in importance as the study site decreases from regional-scale to macroscale to microscale. Increased understanding of regional-scale flow systems is demonstrated by selection of investigations of carbonate and volcanic aquifers to show how application of present-day concepts and techniques can identify controlling chemical reactions and determine their rates; identify groundwater flow paths and determine flow velocity; and determine aquifer characteristics. The role of chemical hydrogeology in understanding geologic processes of macroscale systems is exemplified by selection of investigations in coastal aquifers. Ore deposits of manganese and uranium, along with a simulation model of ore-forming fluids, demonstrate the influence of heterogeneity and of organic compounds on geochemical reactions associated with genesis of mineral deposits. In microscale environments, importance of heterogeneity is illustrated by studies of infiltration of sewage effluent and migration of creosote in coastal plain aquifers.