The wastewater industry is facing a paradigm shift, learning to view domestic wastewater not as a waste stream which needs to be disposed of but as a resource from which to generate energy. The extent of that resource is a strategically important question. The only previous published measurement of the internal chemical energy of wastewater measured 6.3 kJ/L. It has long been assumed that the energy content in wastewater relates directly to chemical oxygen demand (COD). However there is no standard relationship between COD and energy content. In this study a new methodology of preparing samples for measuring the internal chemical energy in wastewater is developed, and an analysis is made between this and the COD measurements taken. The mixed wastewater examined, using freeze-drying of samples to minimize loss of volatiles, had 16.8 kJ/L, while the domestic wastewater tested had 7.6 kJ/L nearly 20% higher than previously estimated. The size of the resource that wastewater presents is clearly both complex and variable but is likely to be significantly greater than previously thought. A systematic evaluation of the energy contained in wastewaters is warranted.

Addressing the need to recover energy from the treatment of domestic wastewater, a 120-L microbial electrolysis cell was operated on site in Northern England, using raw domestic wastewater to produce virtually pure hydrogen gas (100 ± 6.4 %) for a period of over 3 months. The volumetric loading rate was 0.14 kg of chemical oxygen demand (COD) per cubic metre per day, just below the typical loading rates for activated sludge of 0.2-2 kg COD m(-3) day(-1), at an energetic cost of 2.3 kJ/g COD, which is below the values for activated sludge 2.5-7.2 kJ/g COD. The reactor produced an equivalent of 0.015 LH(2)L(-1) day(-1), and recovered around 70 % of the electrical energy input with a coulombic efficiency of 55 %. Although the reactor did not reach the breakeven point of 100 % electrical energy recovery and COD removal was limited, improved hydrogen capture and reactor design could increase the performance levels substantially. Importantly, for the first time, a 'proof of concept' has been made, showing that this technology is capable of energy capture as hydrogen gas from low strength domestic wastewaters at ambient temperatures.

A 100-L microbial electrolysis cell (MEC) was operated for a 12-month period fed on raw domestic wastewater at temperatures ranging from 1°C to 22°C, producing an average of 0.6 L/day of hydrogen. Gas production was continuous though decreased with time. An average 48.7% of the electrical energy input was recovered, with a Coulombic efficiency of 41.2%. COD removal was inconsistent and below the standards required. Limitations to the cell design, in particular the poor pumping system and large overpotential account for many of the problems. However these are surmountable hurdles that can be addressed in future cycles of pilot scale research. This research has established that the biological process of an MEC will to work at low temperatures with real wastewater for prolonged periods. Testing and demonstrating the robustness and durability of bioelectrochemical systems far beyond that in any previous study, the prospects for developing MEC at full scale are enhanced.

The potential benefits of applying microbial electrolysis cell (MEC) technology to wastewater treatment are clear and profound. Previous pilot studies have demonstrated a 'proof of concept' with domestic waste at ambient temperatures, but have not yet treated waste to required discharge standards, and have not reached energy neutrality. In addition, these reactors have been many orders of magnitude smaller than would be needed for full scale wastewater treatment plants. Scale-up affects many of the parameters that underpin performance; understanding its impact will be vital to further progress. Modifying a previously tested cassette-style design, we reduced the internal resistance, and increased the module size by a factor of 16, constructing an MEC with six 1 m 2 anodes. This created an anodic surface area to volume ratio of 34 m 2 m -3 . The system was operated at a hydraulic retention time of 5 hours on settled domestic wastewater for 217 days, producing more current than a scaled-down reactor, which was run in parallel. The large MEC produced 0.8 L of 93% pure H 2 d -1 at ambient winter temperatures (11.4 + 2.5°C). Chemical oxygen demand (COD) removal averaged 63.5% with an average effluent quality of 124.7 mg COD L -1 , achieving the European Urban Wastewater Treatment Directive (1991) consent.

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