High-loading glycerol containing slight amounts of five different monosaccharides was inoculated with seed sludge obtained from a methane fermentation reactor. The use of different monosaccharides as fermentation promoters resulted in changes in fermentation types: in particular, glucose induced the formation of 1,3-propanediol. After 9 days incubation with glucose, glycerol levels had fallen by 81%, while molar yields of organic acids and 1,3-propanediol (per mole of glycerol degraded) were 0.22 and 0.39, respectively. Other monosaccharides enhanced methane production after 14 days of incubation in the following order: galactose, galacturonic acid, mannose and arabinose. Hydrogen was generated (together with a negligible amount of methane) only in the presence of glucose. When glucose was introduced to a methane-producing reactor (promoted by galacturonic acid), hydrogen production began 5 days later and displaced the methane production after 12 days. These results suggest that glucose catalyzes glycerol degradation, resulting in the production of hydrogen. (C) 2012 Elsevier Ltd. All rights reserved.