TECHNOLOGY FOCUS - ORGANIC CHEMISTRY - Preferred Method: The fermenting is conducted without the addition of a significant amount of methane production inhibitors. The time is 1-4 days, preferably 2-3 days. The biomass is not subjected to chemical or enzymatic pretreatment prior to the fermenting which pretreatment would be effective to substantially increase the availability of fermentable substrates in the biomass to the microorganisms. The method further comprises: removing one or more of cells of the microorganisms, lignin-containing residues, or carbonates or other non-carboxylate anions from the medium prior to the electrolysis; concentrating the volatile fatty acids in the medium prior to the electrolysis; extracting or separating the volatile fatty acids from the medium prior to the electrolysis; contacting medium containing the volatile fatty acids with a second inoculum consisting of Clostridium kluyveri, Clostridium butyricum, Clostridium tyrobutyricum, Butyrvibrio fibrisolvens, a mixed culture of microorganisms derived from the rumen, sewage sludge, landfills, soil or aquatic environments and/or a mixed culture of microorganisms derived from the gut of insects, and incubating under anaerobic conditions and for a sufficient time to further increase the production of, or change the molar proportions of, volatile fatty acids in the medium; concentrating the volatile fatty acids in the medium by capacitive deionization prior to the electrolysis; repeating the concentrating and the electrolysis in the electrolysis vessel; adding one or more 8-22C fatty acids or their salts to the medium prior to the electrolysis; and removing the volatile fatty acids from the fermentation medium during the fermenting. The concentrating comprises distillation, filtration, solvent extraction or capacitive deionization. The electrolysis is conducted in an aqueous medium. The electrolysis is conducted in the absence of a significant amount of non-aqueous solvents for the volatile fatty acids. The cells, lignin-containing residues, or carbonates or other non-carboxylate anions are removed by filtration, flocculation, settling, centrifugation and/or precipitation. The volatile fatty acids in the medium are subjected to the electrolysis without extraction. The electrolysis is conducted using carbon or graphite anode electrodes, and cathode electrodes. The conditions of the electrolysis comprise an anode current density above 1 mA/cm2. The conditions of the electrolysis comprise a potential of 2 volts DC or higher. The conditions of electrolysis comprise a potential of 3 volts DC or higher. The anode is separated from the cathode by a semi-permeable membrane effective to substantially prevent the passage of non-carboxylate anions larger than carboxylate anions of the volatile fatty acids. The volatile fatty acids are removed by capacitive deionization or a flow through capacitor. The volatile fatty acids are removed by capacitive deionization comprising positioning an anode and a cathode electrode within the fermentation medium and applying a first voltage which is effective to adsorb and concentrate carboxylate anions of the volatile fatty acids at anode but which first voltage is below the water oxidation voltage. The hydrogen produced by the electrolysis is contacted with the secondary inoculum. Preferred Components: The volatile fatty acids comprise 2-6C straight or their branched chain fatty acids or salts. The volatile fatty acids comprise acetic acid, propionic acid, butyric acid, isobutyric acid, 2-methyl butyric acid, valeric acid, isovaleric acid caproic acid and/or their salts. The hydrocarbons comprise alkanes, alkenes, dienes and/or trienes. The hydrocarbons comprise methane, ethane, propane, butane, pentane, hexane, heptane, octane, ethylene, propylene, butene, pentene, and/or isomers. The fermentation medium further comprises a glycol or alcohol. The fermentation medium further comprises one or more 8-22C fatty acids, and the electrolysis converts the fatty acids or their salts to hydrocarbons and hydrogen. The mixed culture of microorganisms derived from the rumen contents are produced by adaptation to anaerobic growth in a biomass-containing fermentation medium. The inoculum further comprises a supplemental inoculum. The anode comprises a semi-permeable membrane effective to substantially prevent the passage of one or more of non-carboxylate anions larger than carboxylate anions of the volatile fatty acids, lignins, cells, and proteins.