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Efforts to increase H(2) yields from fermentative H(2) production include heat treatment of the inoculum, dissolved gas removal, and varying the organic loading rate. Although heat treatment kills methanogens and selects for spore-forming bacteria, the available evidence indicates H(2) yields are not maximized compared to bromoethanesulfonate, iodopropane, or perchloric acid pre-treatments and spore-forming acetogens are not killed. Operational controls (low pH, short solids retention time) can replace heat treatment. Gas sparging increases H(2) yields compared to un-sparged reactors, but no relationship exists between the sparging rate and H(2) yield. Lower sparging rates may improve the H(2) yield with less energy input and product dilution. The reasons why sparging improves H(2) yields are unknown, but recent measurements of dissolved H(2) concentrations during sparging suggest the assumption of decreased inhibition of the H(2)-producing enzymes is unlikely. Significant disagreement exists over the effect of organic loading rate (OLR); some studies show relatively higher OLRs improve H(2) yield while others show the opposite. Discovering the reasons for higher H(2) yields during dissolved gas removal and changes in OLR will help improve H(2) yields.

Dissolved H(2) and CO(2) were measured by an improved manual headspace-gas chromatographic method during fermentative H(2) production with N(2) sparging. Sparging increased the yield from 1.3 to 1.8 mol H(2)/mol glucose converted, although H(2) and CO(2) were still supersaturated regardless of sparging. The common assumption that sparging increases the H(2) yield because of lower dissolved H(2) concentrations may be incorrect, because H(2) was not lowered into the range necessary to affect the relevant enzymes. More likely, N(2) sparging decreased the rate of H(2) consumption via lower substrate concentrations.

The effects of effluent recycle were examined in a two-phase anaerobic system where the first phase was operated for fermentative hydrogen production and the second for methanogenesis. The hydrogen reactor was operated as a chemostat at 35 degrees C and pH 5.5 with a 10 h hydraulic retention time, and the methane reactor was operated as an up-flow reactor at 28 degrees C and pH between 6.9 and 7.2. Two recycle ratios were examined: 0 and 0.98. Effluent recycle reduced the required alkalinity for pH control by approximately 40%. The H2 productivity metric, with a basis in electrons and incorporating both gaseous and dissolved H2, was developed as a more fundamental reporting method than the molar H2 yield. Without recycle, the H2 productivity was 0.115 g of H2 COD/g of feed COD, but decreased to 0.015 q of H2 COD/g of feed COD with recycle (COD = chemical oxygen demand). Mass balances indicated the lower H2 productivity during recycle was due to electrons being partitioned to methane and less-oxidized soluble constituents such as propionic acid, ethanol, and butanol. The results indicated that achieving high H2 productivity with nonsterile wastewaters will be challenging and membrane filtration of the recycle liquid may be required to exclude the return of hydrogen-consuming organisms.