The kinetics of the formation of trihalomethanes (THMs) and of chlorine consumption for the chlorination of natural organic matter with an excess of chlorine (50 muM > [Cl-2](o) > 210 muM) was investigated. THM precursors could be divided into a fast and a slowly reacting fraction. Long term chlorine demand and the formation of THM could be described by second order kinetics. Rate constants were between 0.01 and 0.03 M-1 s(-1) in the pH range 7-9 for surface waters and humic materials extracted from surface waters. A groundwater gave a higher rate constant of 0.124 M-1 s(-1). Resorcinol-type structures were tested with respect to kinetics and yield of THM formation. They could possibly be responsible for the fast reacting THM precursors, which represent 15-30% of the THM precursors of natural waters. Additional classes of compounds that might contribute to the initial THM formation include readily enolizable compounds such as beta -diketones and beta -ketoacids. Experiments with phenol showed that slowly reacting THM precursors may consist of phenolic compounds. The influence of pretreatments (UV/visible irradiation, ozone and chlorine dioxide) on chlorine demand and THM formation from NOM was also studied: UV/visible irradiation does not alter THM formation but leads to a higher chlorine demand. Preoxidation with ozone leads to a lower THM formation with an unaltered chlorine demand and preoxidation with chlorine dioxide reduces THM formation and the chlorine demand. (C) 2001 Elsevier Science Ltd. All rights reserved.