The characteristics of membrane fouling were investigated by examining the behaviors of extracellular polymer substances (EPSs) produced by hydrogen-producing bacteria during hydrogen fermentation from a submerged membrane bioreactor (MBR). The MBR consisted of a 1.4-L submerged membrane filtration tank and 3-L hydrogen fermenter. An intermittent suction operation was selected to maintain stable filtration performance. The operation of the suction pump was alternately shifted to ON for 7 min followed by OFF for 3 min, with bio-gas sparging at a flow rate of 5.0 L/m(2)/h (LMH), and manually regulated. Most of the EPS during the continuous hydrogen fermentation using an MBR had accumulated in the reactor because they were retained by the membrane by adsorption onto the polymeric membrane surface. The amount of proteins in the EPS extracted was increased to 179 mg/Land that of carbohydrates was increased to 58 mg/L Cu2+, Mg2+, Zn2+ in the EPS were increased in the range of 1.6-3.3 mg/L. The high concentration of EPS that is produced has a higher chelation potential in the formation of ligand complexes with metals or cations than that in a conventional continuous stirred tank reactor (CSTR). The EPS directly affected the decrease in the permeate flux, which resulted in the clogging of the membrane. (c) 2008 Elsevier B.V. All rights reserved.