The chemistry and stable isotopes ( 18O, D) of highly concentrated chloride brines and minerals from the Asse salt mine in the north of the Federal Republic of Germany were studied. Chemical data indicate the occurrence of three types of brines: (a) Mg-Cl type, of carnallitite origin with Li < 30 mg/kg; (b) Na-Cl type brines, of rock salt origin, with Li > 100 mg/kg; and (c) almost pure MgCl 2-type brines with Li > 100 mg/kg. The first group may be subdivided into brines with Li < 4.0 mg/kg and brines with Li between 18 and 30 mg/kg. Lithium is shown to be an efficient complementary tool in tracing the origin of the brines. The complex evolution of carnallitite-type brines is discussed in detail. Isotopic data of brines that were sampled directly from seepages (presumably unaltered) indicate that these brines are not a mixture with relatively fresh ground water from the overburden sediments. The stable isotope composition ( 18O and D) of hydration water in carnallite, kieserite and polyhalite sampled from the Asse mine were also studied. It is shown that water extracted from the so-called primary carnallite is isotopically different from water extracted from secondary carnallite. The isotopic fractionation factors for 18O and D between carnallite hydration water and mother solution were studied in the laboratory. Assuming that crystallization water of the so-called primary carnallite samples is not altered, the isotopic composition of the mother solution is evaluated.