Recently, flowback chemical analysis has been considered as a complementary approach for evaluating fracturing operations and characterizing reservoir properties. Understanding the source of flowback salts and the mechanisms controlling the water chemistry is essential but also challenging due to the complexity of shale-water interactions. In this study, samples of flowback water and downhole shales are analyzed to investigate the mechanisms controlling the chemistry of flowback water.The water samples at different flowback times and the shale samples are collected from three wells completed in the Muskwa, Otter-Park, and Evie members of the Horn River Basin. The water samples consist of aqueous solution and precipitated salts. The water samples are digested in nitric acid to dissolve the precipitated salts, and are analyzed at both intact and acid-digested conditions using ICP-MS. The flowback salts are weighted and analyzed using XRD and SEM-EDXS. A sequential ion-extraction is performed on the shale samples; and the extracted ions are categorized into three tiers of loosely-, moderately-, and strongly-attached ions.The concentration of monovalent cations in both intact and acid-digested samples is higher than that of divalent cations. Also, the concentration of all cations is higher in the acid-digested samples compared with that in the intact samples. The ratio of divalent cations concentration in the acid-digested samples to that in the intact samples is higher than that for the monovalent cations. This ratio increases for the divalent cations over time, while it remains constant for the monovalent cations. Additionally, for the acid-digested samples the monovalent cations concentration has an initial sharp increase followed by a slower increase at later flowback stages; while the divalent cations concentration increases continuously over time. These results suggest that the majority of the ions in the early flowback water are looselyattached monovalent ions. These ions can be originated from the mixing with in-situ formation brine, dissolution of soluble precipitated salts, or leaching of exchangeable cations from the clay minerals. Similarly, the role of relatively slow water-rock interactions (such as leaching of divalent exchangeable cations, e.g. Ca 2ϩ ,) increases at the later flowback stages. XRD and SEM-EDXS analyzes of the flowback salts indicate that sodium chloride, potassium chloride, and calcium carbonate are the major salts. The sequential ion-extraction reveals that the majority of the monovalent cations are in the loosely-attached tier. However, majority of the divalent cations are moderately-/strongly-attached to the rock. The strongly-attached portion of the ions is determined by acid digestion of the rock sample at the final stage of sequential extraction process. These strongly-attached ions cannot be easily released by hydraulic fracturing and therefore, has small effect on the flowback water chemistry.