An increase in volatile fatty acids (VFA) concentration (or the proportional decrease in carbonate alkalinity concentration) is the first practical measurable indication that an anaerobic treatment system is in a state of stress. If the system is not rectified at this early stage, failure is likely. Current methods for VFA measurement include distillation, colorimetry, gas chromatography and various titration techniques. In terms of simplicity, speed and cost-effectiveness it is generally accepted that titration methods are superior for the purpose of on-site routine monitoring and control, particularly in developing countries. This paper reviews the methods published in the last four decades concerning on-site titration measurement of VFA and carbonate alkalinity concentrations. The review encompasses the following: aquatic chemistry related to the theory on which most of the methods are based, and a detailed description of each of the principal methods published followed by critical and comparative evaluation. (C) 2004 Society of Chemical Industry.