Dyes as tracers for vadose zone hydrology

Dyes are important tracers to investigate subsurface water movement. For more than a century, dye tracers have provided clues about the hydrological cycle as well as flow and transport processes in the subsurface. Groundwater contamination often originates in the vadose zone. Agrochemicals applied to the soil surface, toxic compounds accidentally spilled by human activities, and contaminants released from waste repositories leach through the vadose zone and can ultimately pollute groundwater resources. Dyes are an important tool to assess flow pathways of such contaminants. This review compiles information on dyes used as hydrological tracers, with particular emphasis on vadose zone hydrology. We summarize briefly different human‐applied tracers, including nondye tracers. We then provide a historical sketch of the use of dyes as tracers and describe newer developments in visualization and quantification of tracer experiments. Relevant chemical properties of dyes used as tracers are discussed and illustrated with dye intermediates and selected dye tracers. The types of dyes used as tracers in subsurface hydrology are summarized, and recommendations are made regarding the use of dye tracers. The review concludes with a toxicological assessment of dyes used as hydrological tracers. Many different dyes have been proposed as tracers for water movement in the subsurface. All of these compounds, however, are to some degree retarded by the subsurface medium. Nevertheless, dyes are useful tracers to visualize flow pathways.