The influence of carbon substrate chemistry on membrane bioreactor (MBR) fouling in anoxic conditions has been evaluated. The use of a weak carboxylic acid (acetic acid) resulted in the production of large open-floc structures (up to 508 mu m) that were susceptible to breakage. Primary particles (d(10) and d(20) particle sizes, 5.5 +/- 1.3 and 15.3 +/- 8.2 mu m, respectively) and macromolecular soluble microbial products (SMPs) were generated, directly impacting on membrane fouling. The use of a primary alcohol (ethanol), on the other hand, encouraged the growth of flocs similar to activated sludge. These flocs produced low concentrations of primary particles (d(10) and d(20) particle sizes, 120.6 +/- 36.1 and 185.2 +/- 62.7 mu m, respectively) and high-molecular-weight SMP, and the particles had sufficient mechanical integrity to withstand shear. Consequently, the use of ethanol resulted in sufficient suppression of fouling to extend the filtration time by a factor of three. An increase in MLSS concentration did not directly impact upon fouling when operating with ethanol, primarily because of the low concentration of particulate matter produced. (c) 2007 Elsevier Ltd. All rights reserved.