Entropy is a concept defined by the second law of thermodynamics. Applying this concept to the world we live in, entropy production must be minimized and negentropy (negative entropy production) should be accelerated, in order to produce a healthy and stable ecological system. The present wastewater treatment, however, contributes to entropy production. This means that conventional wastewater treatment, without recovery of resource and energy, will gradually but inevitably contribute to a deteriorating ecological balance. When the self-cleaning ability of the natural ecological system is limited, the need to develop sustainable wastewater treatment in order to delay entropy production and accelerate negentropy becomes urgent. Resource and energy recovery from wastewater should be the first priority, as they can contribute significantly towards minimizing entropy production and accelerating negentropy. Sustainable wastewater treatment must focus on recovering recyclable high value-added organic chemicals from wastewater and/or excess sludge to minimize entropy production caused by methane (CH₄, once combusted, is converted into CO₂ - an even higher substance in entropy) via anaerobic digestion. Instead of CH₄, thermal energy present in the effluent can be utilized for heating/cooling buildings and also for drying excess sludge towards incineration to recover more energy. Overall, this can lead to a carbon-neutral operation and even creating a “carbon sink” could be possible for wastewater treatment.

Anaerobic digestion (AD) is an effective approach to recovering chemical (organic) energy from excess sludge, but the conversion efficiency for energy is usually not very high. One of the obstacles comes from the severe inhibition of humic acid (HA) on both hydrolytic and methanogenic process on the AD. Therefore, it is necessary to ascertain some effective approaches to relieving the inhibition of HA for obtaining a high methane (CH₄) yield. With the “clean” sludge (cultured by synthetic wastewater) containing almost no HA and metal ions, the inhibition of HA on the AD process was designed by dosing HA at 15% VSS, and relieving the inhibition by metal ions was also designed by dosing the different amounts of Ca²⁺ and Al³⁺. Based on the batch AD experiments, solo Ca²⁺=100 mg /L or Al³⁺=70 mg/L added realized the highest relieved efficiency of 65%, respectively. Interestingly, dual metal ions added at the low concentrations (Ca²⁺=50 mg/L and Al³⁺=10 mg/L) could reach up to 80 % of the relieved efficiency, which was attributed to the synergistic effect of 1+1>2. The mechanisms behind the phenomena could be that metal ions might interact with HA via electrostatic force, cation exchange and sweep flocculation. Thus, some key hydrolytic and methanogenic enzymes could indirectly be reactivated and degradation of organic substances could be enhanced in the AD process. In wastewater treatment plants, metal ions contained in excess sludge would “inherently” relieve the inhibition of HA to an extent, which depends on the effective and/or optimal concentration of metal ions at a free (unabsorbed and/or unwrapped) state.

Conventional wastewater treatment plants (WWTPs) clean wastewater and minimize water pollution; but, while doing so, they also contribute to air pollution and need energy/material input with associated emissions. However, energy recovery (e.g. anaerobic digestion) and resource recovery (e.g. water reuse) allow us to offset the adverse environmental impacts of wastewater treatment. Life cycle assessments (LCA) have been used more and more to evaluate the environmental impacts of WWTPs and to suggest improvement options. There is a need to search for resource recovery applications that genuinely realize a net-zero impact on the total environment of WWTPs. In this work, a scheme with highly efficient energy and resource recovery (especially for thermal energy) is proposed and evaluated. The environmental impact of a conventional WWTP in comparison with the scheme proposed here, with energy/resource recovery included, was calculated, and discussed with reference to LCA methodology. In the process of using LCA, it was necessary to choose a regional situation to focus on. In this case, a Chinese situation was focused as a reference, but the qualitative information gained is of worldwide relevance. The results clearly revealed that conventional WWTP does not benefit the total environment as a whole while the new scheme benefited the total environment via resource/energy recovery-based processes. Among others, thermal energy recovery played a significant role towards a net-zero LCA analysis (contributing around 40%) which suggests that more attention and research should be focused on it.

In dealing with wastewater, chemical energy has traditionally been perceived as the only source of recoverable energy in moving towards the carbon-neutral operation of wastewater treatment plants. Based on an estimation of practically recoverable energy embedded in municipal wastewater, however, the potential for thermal energy (90% recovery from wastewater) is much higher than for chemical energy (COD, 10% recovery). The carrier of chemical energy (COD) has a high exergy value which should, from a sustainability point of view, be utilized to the greatest extent possible. Rather than being converted into methane (and subsequently into carbon dioxide), carbon (COD) contained in wastewater should be converted into highly valuable organic products. Thermal energy could be utilized for district heating/cooling, agricultural greenhouses, and even for drying dewatered sludge. In this way, thermal energy can indirectly offset the energy demand for wastewater treatment. The limitations in utilizing thermal energy are not generally based on technical difficulties; in fact, they can be mainly attributed to supply distances and governmental policies. It would, therefore, be greatly beneficial if municipal authorities would work together to jointly plan utilization of this thermal energy.

Anaerobic digestion (AD) is a technology for recovering chemical energy as methane from excess sludge/waste. Unfortunately, humic acids (HA) contained in excess sludge can have the effects of inhibiting the efficiency of energy conversion. Based on a batch experiment, the impact of HA on a semi-continuous AD process was sequentially investigated, with the impact on the associated enzymes and microorganisms being measured. The results of this semi-continuous experiment indicate that the inhibition of the microbial community increased with an increased HA:VSS ratio. Long-term cultivation did not result in the adaption of methane production to the presence of HA. Moreover, at HA:VSS = 20%, the strongest inhibition (74.3%) on energy conversion efficiency was observed in the semi-continuous experiment, which was two-fold higher than that recorded in the batch experiment. This is attributed to serious and irreversible inhibition of both acidogenic and methanogenic microorganisms, as well as the physical-chemical reactions between HA and the associated enzymes which, it was concluded, were the dominant mechanisms of inhibition in the batch experiment.

Inhibition by humic substances (HSs) on anaerobic digestion of excess activated sludge is one of the limitations for converting more organics into biogas. In order to counteract the inhibition from HSs, the present study was initiated to understand the dynamic changes (content and structure) of HSs during the anaerobic digestion of synthetic and real sludge. For the first time, the present work studied the dynamics of HSs separately in the liquid and solid phases. These observations on HSs conversions by potentiometric titration, UV–Vis, FTIR, and two-dimensional infrared spectra, confirmed that the dynamic changes of HA and FA compositions were caused by losing aliphatic moieties and enriching aromatic moieties in the structural compositions. This changes increased the humification degree, aromaticity, and the amounts of oxygen-containing functional groups. Based on the observations, strategies to alleviate the inhibition effect were discussed.

Methane (CH₄) recovery from excess sludge plays an important role in wastewater treatment aimed at achieving carbon neutrality. Besides pretreatment for excess sludge, exogenous CO₂and even H₂have already been tested in enhancing CH₄production from anaerobic digestion (AD). However, exogenous H₂injected into AD might simultaneously influence both upstream acidogenesis and downstream methanogenesis. In this study, a series of batch tests were conducted to ascertain the influences of hydrogen partial pressure (P_H2) on these two processes. Interestingly, the batch tests demonstrated that injecting exogenous H₂into AD at the beginning of each batch cycle can both stimulate acidogenesis (organic conversion rate) and enhance methanogenesis (both CH₄and biogas productions) at an appropriate P_H2(=0.33 bar) and an optimal revolution (R_s = 200 rpm) of a shaker.