The dominant use of isotopes in catchment research in the last few decades has been to trace sources of waters and solutes. Generally, such data were evaluated with simple mixing models to determine how much was derived from either of the two (sometimes three) constant-composition sources. This chapter illustrates the environmental isotopes that are natural and anthropogenic isotopes whose wide distribution in the hydrosphere can assist in the solution of hydrogeochemical problems. Water isotopes often provide unambiguous information about residence times and relative contributions from different water sources, and these data can then be used to make hypotheses about water flowpaths. Solute isotopes can provide an alternative, independent isotopic method for determining the relative amounts of water flowing along various subsurface flowpaths. The isotopic and chemical compositions provides very detailed information about sources and reactions in shallow systems This integration of chemical and isotopic data with complex hydrologic models constitutes an important frontier of catchment research.