The efficiency of the study of polycyclic aromatic hydrocarbons (PAHs) as markers of many environmental and hydrological processes is disclosed. On the example of the interaction between sea and river water the flows of substances and problems of their detection in media, as well as the laws of fractionation during phase transitions at geochemical barriers (GCB) are presented. The authors have collected an extensive database for almost all types of natural environments. Own research was conducted at specialized water testing sites (springs, a mud volcano, brine of a lake, the Northern Dvina River, water of Black and White Seas, water bodies of the Moscow Region and Albena region (Bulgaria), etc. This allowed substantiating the optimal markers and creating effective methods for identifying a complex of hydrological processes. © 2020 The Authors, published by EDP Sciences.