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Anaerobic ponds have the potential to contribute to low carbon wastewater treatment, however are currently restricted by long hydraulic residence time (HRT) which leads to large land requirements. A two-stage anaerobic pond (SAP) design was trialled against a single-stage control (CAP) over four HRTs down to 0.5 days, to determine the lowest HRT at which the ponds could operate effectively. No statistical differences were observed in particulate removal between the ponds over all four HRTs, suggesting solids loading is not a critical factor in AP design. Significantly higher biogas production rates were observed in the SAP than the CAP at 1.5 d and 1.0 d HRT, and microbial community profiling suggests the two-stage design may be facilitating spatial separation of the anaerobic digestion process along reactor length. Hydrogenotrophic methanogensis dominated over aceticlastic, with acetate oxidisation a likely degradation pathway. Experimental tracer studies were compared to CFD simulations, with the SAP showing greater hydraulic efficiency, and differences more pronounced at shorter HRTs. Greater flow recirculation between baffles was observed in CFD velocity profiles, demonstrating baffles can dissipate preferential flow patterns and increase effective pond volume, especially at high flow rates. The study demonstrates the potential of APs to be operated at shorter HRTs in psychrophilic conditions, presenting an opportunity for use as pre-treatments (in place of septic tanks) and primary treatment for full wastewater flows. Two-stage designs should be investigated to separate the stages of the anaerobic digestion process by creating preferential conditions along the pond length.

The non-isothermal drying behavior and kinetics of human feces (HF) were investigated by means of thermogravimetric analysis to provide data for designing a drying unit operation. The effect of heating rate and blending with woody biomass were also evaluated on drying pattern and kinetics. At low heating rate (1 K/min), there is effective transport of moisture, but a higher heating rate would be necessary at low moisture levels to reduce drying time. Blending with wood biomass improves drying characteristics of HF. The results presented in this study are relevant for designing non-sewered sanitary systems with in-situ thermal treatment.

The integration of membrane distillation with reverse electrodialysis has been investigated as a sustainable sanitation solution to provide clean water and electrical power from urine and waste heat. Reverse electrodialysis was integrated to provide the partial remixing of the concentrate (urine) and diluate (permeate) produced from the membrane distillation of urine. Broadly comparable power densities to those of a model salt solution (sodium chloride) were determined during evaluation of the individual and combined contribution of the various monovalent and multivalent inorganic and organic salt constituents in urine. Power densities were improved through raising feed-side temperature and increasing concentration in the concentrate, without observation of limiting behaviour imposed by non-ideal salt and water transport. A further unique contribution of this application is the limited volume of salt concentrate available, which demanded brine recycling to maximise energy recovery analogous to a battery, operating in a ‘state of charge’. During recycle, around 47% of the Gibbs free energy was recoverable with up to 80% of the energy extractable before the concentration difference between the two solutions was halfway towards equilibrium which implies that energy recovery can be optimised with limited effect on permeate quality. This study has provided the first successful demonstration of an integrated MD-RED system for energy recovery from a limited resource, and evidences that the recovered power is sufficient to operate a range of low current fluid pumping technologies that could help deliver off-grid sanitation and clean water recovery at single household scale., Graphical abstract Image 1, Highlights • Membrane distillation with reverse electrodialysis allows off-grid sanitation. • Heat and concentrate development with MD enhance RED power density. • The complex salt matrix within the feed does not limit power density. • Good energy recovery from small salt concentrate volumes with recycle.

Highlights • Membrane distillation configuration studied for water recovery from blackwater. • Selectivity altered by differences in vapour pressure and water flux. • Wetting by organics limited by smaller pore size but decreases mass transfer. • Organics fouling more severe for vacuum configuration. • Air gap provides more robust separation over temperature range studied., Water recovery from concentrated blackwater has been studied using air gap (AGMD), direct contact (DCMD) and vacuum membrane distillation (VMD) to deliver decentralised sanitation. Whilst good water quality was achieved with each configuration, differences in the rejection of volatile compounds was observed. VMD exhibited the highest rejection of volatiles, specifically ammoniacal nitrogen, of all the configurations but fouling inhibited total flux. DCMD exhibited a temperature dependent volatile rejection which resulted in poor rejection at lower feed temperatures (≤40 °C). AGMD was identified as the most promising configuration for application within decentralised sanitation, since the rejection of volatiles was consistent over a range of operating temperatures with ammonia rejection directly related to solution pH. An increase in organic colloids and particles due to faecal contamination reduced COD removal due to the induction of wetting, but was shown to be offset by adoption of a smaller pore size (0.1 μm), and when complemented with upstream solid-liquid separation within a fully integrated system, will provide a robust sanitation solution. Importantly, this work has shown that AGMD can recover water from concentrated blackwater close to international discharge and reuse regulations in a single stage process; this is significant as blackwater consists of only urine and faeces, and is thus 40 times more concentrated than municipal sewage. It is proposed that the water quality produced reflects a step change to delivering safe sanitation, and is complemented by a simple method for heat recovery integration this is similarly advantageous for resource constrained environments common to decentralised sanitation solutions.

Non-sewered sanitation is currently dependant upon pit latrine emptying, the safety of which is compromised by the high costs of faecal sludge transport to centralised treatment facilities. Transport in turn is hindered by the complex rheology of pit latrine sludge. This study therefore characterised the compressional rheology of fresh faeces and modelled the implications for passive (gravity) or mechanical (forced) solid/liquid separation. This informs on the viability of decentralising dewatering for more efficient volume reduction and improving the economics of transportation. The gel point (ϕg) is the solids concentration where the material has a networked structure and signifies the point when mechanical intervention is required for further solid-liquid separation. For fresh faeces, ϕg ranged between 6.3 and 15.6% total solids (TS) concentration. This is significantly higher than the ϕg observed for wastewater sludge at centralised facilities, and it implies that passive gravity driven processes can suffice to improve localised dewatering. The kinetics of passive sedimentation of faecal material were modelled and illustrate thickening from 3 to 10% TS concentration in

Whilst reverse electrodialysis (RED) has been extensively characterised for saline gradient energy from seawater/river water (0.5 M/0.02 M), less is known about RED stack design for high concentration salinity gradients (4 M/0.02 M), important to closed loop applications (e.g. thermal-to-electrical, energy storage). This study therefore focuses on the scale-up of RED stacks for high concentration salinity gradients. Higher velocities were required to attain a maximum Open Circuit Voltage (OCV) for 4 M/0.02 M, which gives a measure of the electrochemical potential of the cell. The experimental OCV was also much below the theoretical OCV, due to the greater boundary layer resistance observed, which is distinct from 0.5 M/0.02 M. However, negative net power density (net produced electrical power divided by total membrane area) was demonstrated with 0.5 M/0.02 M for larger stacks using shorter residence times (three stack sizes tested: 10 × 10cm, 10 × 20cm and 10 × 40cm). In contrast, the highest net power density was observed at the shortest residence time for the 4 M/0.02 M concentration gradient, as the increased ionic flux compensated for the pressure drop. Whilst comparable net power densities were determined for the 10 × 10cm and 10 × 40cm stacks using the 4 M/0.02 M concentration gradient, the osmotic and ionic transport mechanisms are distinct. Increasing cell pair number improved maximum current density. This subsequently increased power density, due to the reduction in boundary layer resistance, and may therefore be used to improve thermodynamic efficiency and power density from RED for high concentrations. Although comparable power densities may be achieved for small and large stacks, large stacks maybe preferred for high concentration salinity gradients due to the comparative benefit in thermodynamic efficiency in single pass. The greater current achieved by large stacks may also be complemented by an increase in cell pair number and current density optimisation to increase power density and reduce exergy losses., Graphical abstract Image 1, Highlights • RED for energy generation from high concentration salinity gradients in studied. • Boundary layer effects require higher velocities to achieve maximum OCV. • Highest power at short residence time with larger stack contrasting sea/riverwater. • Same power density for small and large stacks, but higher current in large stack. • More cell pairs lowers boundary layer resistance and improves power density.

Hollow fibre membrane contactor (HFMC) technology has been developed for CO2 absorption primarily using synthetic gas, which neglects the critical impact that trace contaminants might have on separation efficiency and robustness in industrial gases. This study, therefore, commissioned a demonstration-scale HFMC for CO2 separation at a full-scale anaerobic digester facility to evaluate membrane integrity over six months of operation on real biogas. The CO2 capture efficiency identified using real biogas was benchmarked at comparable conditions on synthetic gas of an equivalent partial pressure, and an equivalent performance identified. Two HFMC were subsequently compared, one with and one without a pre-treatment stage that targeted particulates, volatile organic compounds (VOCs) and humidity. Similar CO2 separation efficiency was again demonstrated, indicating limited impact within the timescale evaluated. However, gas phase pre-treatment is advised in order to ensure robustness in the long term. Over longer-term operation, a decline in CO2 separation efficiency was observed. Membrane autopsy identified shell-side deposition, where the structural morphology and confirmation of amide I and II groups, indicated biofouling. Separation efficiency was reinstated via chemical cleaning, which demonstrated that proactive maintenance could minimise process risk.

In order to obviate the economic issues associated with pit latrine emptying and transport such as high water additions and rheologically difficult sludge properties, the implications of prompt solid/liquid separation were investigated. This was achieved through rheological characterisation of fresh human faeces and synthetic faeces, and comparison with aged faecal sludges. Shear yield stress, thixotropy and post-shear structural recovery were characterised for a total solids (TS) concentration range of 5–35% total solids (TS) and stickiness yield stress was determined for concentrations up to 100% TS. Fresh faeces rheology proved to be favourable when compared to aged matrices, evidenced by a lower shear yield stress and higher gel point solids concentration, suggesting that aging could alter the physico-chemical properties of faecal sludge. Fresh and synthetic faeces exhibited similar shear thinning, thixotropic behaviour with the majority of structural breakdown occurring at a low shear rate of 10 s−1, and the extent increasing with higher solids concentrations. At 32% TS, fresh faeces shear yield stress was permanently reduced by 80%, suggesting that low shear pumping could reduce the energy demand required for faeces transport. The sticky phase, which represents the region to avoid faecal transport and mechanical drying processes, was identified to range from 30 to 50% TS, with 25% TS as ideal to commence dewatering processes. This also coincides with the average solids concentration of faeces, which is achievable by source separation. This study has identified that handling of fresh faeces as opposed to aged faecal sludges would result in economic and environmental benefits, with energy, water and labour savings., Graphical abstract Image 1, Highlights • Early intervention is favourable due to lower shear yield stress and higher gel point. • Fresh faeces shear yield stress can be reduced by low shear structural deformation. • Sticky phase was at 30-50% TS, where transport and mechanical drying should be avoided. • Early intervention can reduce pump head, energy and need for water addition. • Synthetic faeces had similar rheological behaviour to real faeces.

International audience; Previous studies have found difficulties in reconciling mass transfer between membrane contactors of different geometries, which has been attributed to differences in fluid mixing. In this study, we compare the two most commonly adopted geometries (parallel and transverse flow) and use residence time distribution (RTD) analysis to verify the influence of geometry on fluid mixing in addition to developing a generalized correlation that can collectively describe mass transfer for both geometries. Lumen-side mass transfer was well described by the Lévêque solution in well-developed laminar conditions for both parallel and transverse flow modules. However, considerably lower mass transfer was identified for shell-side flow in the parallel fiber configuration, with RTD analysis providing confirmation that this was due to shell-side bypass which reduced mean fluid residence time (τ=v/L) in the contactor to below that of the theoretical residence time. The mean residence time calculated from RTD analysis enabled reconciliation of mass transfer data between both geometries, such that mass transfer could be adequately described for both configurations using: Shs=1.27Re0.793Sc0.33(dh/L). The Reynolds number exponent indicated transitional mass transfer despite operation firmly within the laminar regime, which would indicate an enhancement in mass transfer provided by secondary flow effects within tightly packed fiber bundles. Whilst previously observed, for example in heat transfer analogies, such dependencies are generally more closely associated with parallel flow rather than ‘classical’ cross-flow modules in which fluid flow is explicitly perpendicular to the fiber bundle, and indicates that mass transfer in transverse flow may be better described as parallel flow, which confirms previous assumptions. Importantly, this study demonstrates the capability to reconcile mass transfer between modules of different geometries and permits the opportunity to project process design and scale-up between the two most commonly applied membrane contactor module geometries.

Human faeces (HF) are treated as wastes in many parts of the world, a resource that can be converted to energy and fuels. To enhance the understanding of fuel conversion processes and decomposition characteristics, this study investigated the pyrolysis behaviour and evolved gas profiles of HF using thermogravimetry with gas chromatography–mass spectrometry methods. Kinetic parameters were deduced using model-free kinetic models. Results are compared with simulant faeces (SF), wood biomass (WB) and HF–WB blends. The pyrolysis of HF involved two decomposition peaks — a fronting peak with weight loss of ∼ 51 wt% and a tailing shoulder peak with weight loss of ∼ 15 wt%. The apparent activation energy for HF varied from 122–382 kJ/mol at conversion rates of 10%–90% using Kissinger–Akahira–Sunose model. Some of the key pyrolysis products for HF at 370 °C were 4-methoxy-phenol, n-hexadecanoic acid, phenol, 4-methyl- and indole isomer (pyrrolo[1,2-a]pyridine). At 530 °C, evolved gases were largely fragmented with high proportions of alkanes and alkenes including 3-dodecane, 2-undecane, 6-tridecene, 2-propenylidene-cyclobutene. These products differed to WB that are largely hydroxyphenyls and methoxyphenols with guaiacyl or syringil structures. Blending with WB improved pyrolysis of HF, irrespective of the proportions of blend.

This study has elucidated the mechanisms governing water recovery from blackwater using membrane distillation, and has clarified the role of the organic particle fraction on membrane performance. Whilst fecal pathogen growth was initially observed at lower temperatures, pathogen inactivation was demonstrated over time, due to urea hydrolysis which liberated ammonia in excess of its toxic threshold. During the growth phase, membrane pore size

Three upflow anaerobic sludge blanket (UASB) pilot scale reactors with different configurations and inocula: flocculent biomass (F-UASB), flocculent biomass and membrane solids separation (F-AnMBR) and granular biomass and membrane solids separation (G-AnMBR) were operated to compare start-up, solids hydrolysis and effluent quality. The parallel operation of UASBs with these different configurations at low temperatures (9.7 ± 2.4°C) and the low COD content (sCOD 54.1 ± 10.3 mg/L and pCOD 84.1 ± 48.5 mg/L), was novel and not previously reported. A quick start-up was observed for the three reactors and could be attributed to the previous acclimation of the seed sludge to the settled wastewater and to low temperatures. The results obtained for the first 45 days of operation showed that solids management was critical to reach a high effluent quality. Overall, the F-AnMBR showed higher rates of hydrolysis per solid removed (38%) among the three different UASB configurations tested. Flocculent biomass promoted slightly higher hydrolysis than granular biomass. The effluent quality obtained in the F-AnMBR was 38.0 ± 5.9 mg pCOD/L, 0.4 ± 0.9 mg sCOD/L, 9.9 ± 1.3 mg BOD5/L and

The development of novel, non-sewered sanitation systems like the Nano Membrane Toilet requires thorough investigation of processes that may seem well-understood. For example, unlike the settling of primary sludge, the separation of solids from liquids in a small-volume container at the scale of a household toilet has not been studied before. In two sets of experiments, the settling of real faeces and toilet paper in settling columns and the settling of synthetic faeces in a conical tank are investigated to understand the factors affecting the liquid quality for downstream treatment processes. Toilet paper is found to be a major inhibitor to settling of solids. While a lower overflow point results in better phase separation through displacement of liquid, a higher overflow point and frequent removal of solids may be more advantageous for the liquid quality., Graphical abstract Unlabelled Image, Highlights • Faeces and toilet paper do not settle in urine within small volume tank. • Toilet paper keeps faeces in suspension. • Phase separation can be achieved through displacement of liquid. • Liquid quality decreases over time and with higher solids-liquids ratio in tank.

In this study, membrane crystallization is compared to conventional gas-liquid crystallization for the precipitation of ammonium bicarbonate, to demonstrate the distinction in kinetic trajectory and illustrate the inherent advantage of phase separation introduced by the membrane to crystallization in gas-liquid systems. Through complete mixing of gas and liquid phases in conventional crystallization, high particle numbers were confirmed at low levels of supersaturation. This was best described by secondary nucleation effects in analogy to mixed suspension mixed product removal (MSMPR) crystallization, for which a decline in population density was observed with an increase in crystal size. In contrast, for membrane crystallization, fewer nuclei were produced at an equivalent level of supersaturation. This supported the growth of fewer, larger crystals which is preferred to simplify product recovery and limit occlusions. While continued crystal growth was identified with the membrane, this was accompanied by an increase in nucleation rate, which would indicate the segregation of heterogeneous primary nucleation from crystal growth, and was confirmed by experimental derivation of the interfacial energy for ammonium bicarbonate (?, 6.6 mJ m), which is in agreement with that estimated for inorganic salts. The distinction in kinetic trajectory can be ascribed to the unique phase separation provided by the membrane which promotes a counter diffusional chemical reaction to develop, introducing a region of concentration adjacent to the membrane. The membrane also lowers the activation energy required to initiate nucleation in an unseeded solution. In conventional crystallization, the high nucleation rate was due to the higher probability for collision, and the gas stripping of ammonia (around 40% loss) through direct contact between phases which lowered pH and increased bicarbonate availability for the earlier onset of nucleation. It is this high nucleation rate which has restricted the implementation of gas-liquid crystallization in direct contact packed columns for carbon capture and storage. Importantly, this study evidences the significance of the membrane in governing crystallization for gas-liquid chemical reactions through providing controlled phase separation.

A hollow fibre membrane contactor (HFMC), and two vacuum thermal stripping processes, a rotary evaporator (VTS) and multi-component system (MVTS) were compared for their ability to recover ammonia (NH3) from ion exchange (IEX) regeneration brines. The IEX was a 10 m3/day demonstration scale plant fed with secondary municipal wastewater. The 10% potassium chloride regeneration brine was used multiple times leading to ammonium (NH4+-N) saturation (up to 890 mg N/L). When treating the saturated IEX brine, the highest NH3 mass transfer coefficient for the HFMC, MVTS and VTS were 0.6, 0.7 and 0.1 h−1, respectively, compared to values between 1.7 and 3.5 h−1, when treating a synthetic solution. The highest NH3 recovery was obtained with the HFMC (99.8%) and the ammonium sulphate produced was characterised for impurities, presenting high quality. Concentrated ammonium (NH4+-N) solutions (0.5–3.1 g N/L) were obtained from the MVTS and VTS processes. To further valorise the recovered NH4+-N solution produced from the MVTS process, this was used as a substrate for microbial protein (MP) production. Limited differences were observed for production rate (specific growth rate 0.092–0.40 h−1), protein yield (0.021–0.18 g protein/g acetate-CODconsumed) and protein content (0.073–0.87 g protein/g cell dry weight) between recovered and commercial nitrogen (N) sources, indicating that recovered N from IEX can serve as a substrate for MP production. This study demonstrates a comprehensive N management solution for wastewater applications, leading to a range recovered products. These combined technologies can contribute to the local economy, whilst delivering to the ambitious NET-ZERO and circular economy targets.

Remediation of electronic gas CF4 using commercially available technologies results in another kind of greenhouse gas and corrosive side products. This investigation aimed to develop CF4 removal at room temperature with formation of useful product by attempting an electrogenerated Cu1+[Ni2+(CN)4]1− mediator. The initial electrolysis of the bimetallic complex at the anodized Ti cathode demonstrated Cu1+[Ni2+(CN)4]1− formation, which was confirmed by additional electron spin resonance results. The degradation of CF4 followed mediated electrochemical reduction by electrogenerated Cu1+[Ni2+(CN)4]1−. The removal efficiency of CF4 of 95% was achieved by this electroscrubbing process at room temperature. The spectral results of online and offline Fourier transform infrared analyzer, either in gas or in solution phase, demonstrated that the product formed during the removal of CF4 by electrogenerated Cu1+[Ni2+(CN)4]1− by electroscrubbing was ethanol (CH3CH2OH), with a small amount of trifluoroethane (CF3CH3) intermediate.

Since their inception in larger pond systems, the focus of anaerobic ponds has shifted from solids removal to optimising biogas production and reducing physical footprint to minimise land requirements. In this study, a horizontally baffled (HBAP) and vertically baffled (VBAP) anaerobic pond were compared. Distinct differences in the removal efficiency of COD fractions were observed, with particulate COD removal of 78% and 32%, and soluble COD removal of −26% and 19% in the HBAP and VBAP, respectively. A staged pond (SAP) was constructed through an HBAP placed upstream of a VBAP, with an additional HBAP used as a control (CAP). The SAP demonstrated superior biogas recovery potential over the control: methane production by the conclusion of the study was 6.09 and 9.04 LCH4 m−3 wastewater treated for the CAP and SAP, respectively. Methanogenic activity in the ponds was higher closer to the outlet, and hydrogenotrophic methanogenesis dominated over acetoclastic pathways.

The degradation of CF4 gas using existing technologies produces other types of greenhouse gas (CO2) and corrosive side products. The main aim of this study is to degrade CF4 gas at room temperature into useful products without producing corrosive side products by mediated electrochemical reduction (MER) process using an electrogenerated Cu1+[Ni2+(CN)4]1− mediator. Initial studies on the electrolytic reduction of the hetero-bimetallic complex in catholyte solution at anodized Ti cathode was monitored by oxidation/reduction potential (ORP) variation whether the Cu2+ or Ni2+ was reduced in the Cu2+[Ni2+(CN)4] and confirmed by electron spin resonance (ESR) spectroscopy the Cu1+[Ni2+(CN)4]1− formation. The concentration variation of Cu1+[Ni2+(CN)4]1− during CF4 injection demonstrated the degradation of CF4 followed the MER by electrogenerated Cu1+[Ni2+(CN)4]1−. Maximum removal efficiency of CF4 using electroscrubbing process was 96% at room temperature. Through the variation in gas phase parameters, the gas phase mass transfer coefficient was calculated that can facilitate scale up the developed process. Fourier transform infrared spectroscopy analysis in both the gas and solution phases showed that CH3CH2OH was the main product that formed during the removal of CF4 by electrogenerated Cu1+[Ni2+(CN)4]1− at electroscrubber along with a small amount of CF3CH3 intermediate. Importantly, this mechanism also avoided formation of the corrosive product HF.

In this study, conventional and novel gas sparging regimes have been evaluated for a municipal wastewater granular anaerobic MBR to identify how best to achieve high sustainable fluxes whilst simultaneously conserving energy demand. Using continuous gas sparging in combination with continuous filtration, flux was strongly dependent upon shear rate, which imposed a considerable energy demand. Intermittent gas sparging was subsequently evaluated to reduce energy demand whilst delivering an analogous shear rate. For a flux of 5 L m−2 h−1, a fouling rate below 1 mbar h−1 was sustained with low gas sparging frequency and gas sparging rates. However, to sustain low fouling rates for fluxes above 10 L m−2 h−1, a gas sparging frequency of 50% (i.e. 10 s on/10 s off) and an increase in gas sparging rate is needed, indicating the importance of shear rate and gas sparging frequency. An alternative gas sparging regime was subsequently tested in which filtration was conducted without gas sparging, followed by membrane relaxation for a short period coupled with gas sparging, to create a pseudo dead-end filtration cycle. Fouling characterisation evidenced considerable cake fouling rates of 200–250 mbar h−1 within each filtration cycle. However, long term fouling transient analysis demonstrated low residual fouling resistance, suggesting the cake formed during filtration was almost completely reversible, despite operating at a flux of 15 L m−2 h−1, which was equivalent or higher than the critical flux of the suspension. It is therefore asserted that by operating filtration in the absence of shear, fouling is less dependent upon the preferential migration of the sub-micron particle fraction and is instead governed by the compressibility of the heterogeneous cake formed, which enables higher operational fluxes to be achieved. Comparison of energy demand for the three gas sparging regimes to the energy recovered from municipal wastewater AnMBR demonstrated that only by using dead-end filtration can energy neutral wastewater treatment be realised which is the ultimate ambition for the technology.

In this study, membrane distillation is evaluated as a technology for non-sewered sanitation, using waste heat to enable separation of clean water from urine. Whilst membrane fouling was observed for urine, wetting was not evident and product water quality met the proposed discharge standard, despite concentration of the feed. Fouling was reversible using physical cleaning, which is similar to previous membrane studies operating without pressure as the driving force. High chemical oxygen demand reduction was achieved following faecal contamination, but mass transfer was impeded and wetting occurred which compromised permeate quality, suggesting upstream intervention is demanded to limit the extent of faecal contamination.

This study aimed at developing a simple tool for improving the management of gaseous emissions in UASB-based sewage treatment plants (STPs), considering different scenarios for the management of sludge, biogas and gaseous emissions (especially sulfide and methane). For small STPs (10,000; 100,000 inhab.) STPs, other biogas uses were considered, such as in sludge dryers, boilers or combined heat and power engines for electricity generation and heat recovery. All these possibilities were grouped in an interactive spreadsheet containing an extensive database of factors that affect gaseous emissions and energy balance in STPs. The tool can be important for decision makers choosing the best gaseous emissions management practices in UASB-based STPs. Carbon footprint should be the main decision factor when evaluating alternatives for the management of gaseous emissions.

Highlights • Reverse electrodialysis stack design studied for large salinity gradients in recycle. • Energy efficiency of a Reverse electrodialysis and Electrodialysis stack compared. • Thicker electrodialysis membranes exhibited lower water permeance. • Membrane properties and intermembrane distance critical for high concentrations., In this study, stack design for high concentration gradient reverse electrodialysis operating in recycle is addressed. High concentration gradients introduce complex transport phenomena, which are exacerbated when recycling feeds; a strategy employed to improve system level energy efficiency. This unique challenge indicates that membrane properties and spacer thickness requirements may differ considerably from reverse electrodialysis for lower concentration gradients (e.g. seawater/river water), drawing closer parallels to electrodialysis stack design. Consequently, commercially available electrodialysis and reverse electrodialysis stack design was first compared for power generation from high concentration gradients. Higher gross power densities were identified for the reverse electrodialysis stack, due to the use of thinner membranes characterised by a higher permselectivity, which improved current. However, energy efficiency of the electrodialysis stack was twice that recorded for the reverse electrodialysis stack at low current densities, which was attributed to: (i) an increased residence time provided by the larger intermembrane distance, and (ii) reduced exergy losses of the electrodialysis membranes, which provided comparatively lower water permeance. Further in-depth investigation into membrane properties and spacer thickness identified that membranes characterised by an intermediate water permeability and ohmic resistance provided the highest power density and energy efficiency (Neosepta ACS/CMS), while wider intermembrane distances up to 0.3 mm improved energy efficiency. This study confirms that reverse electrodialysis stacks for high concentration gradients in recycle therefore demand design more comparable to electrodialysis stacks to drive energy efficiency, but when selecting membrane properties, the trade-off with permselectivity must also be considered to ensure economic viability.

In this study, the mechanisms for solids breakthrough in upflow anaerobic sludge blanket (UASB) configured anaerobic membrane bioreactors (AnMBRs) have been described to establish design parameters to limit membrane fouling. As the sludge blanket develops, two periods can be identified: (i) an initial progressive enhancement in solids separation provided through sludge blanket clarification, via depth filtration, which sustains downstream membrane permeability; and (ii) sludge blanket destabilisation, which imposed solids breakthrough resulting in a loss in membrane permeability. The onset of sludge blanket destabilisation was identified earlier in the flocculent AnMBR, which was ascribed to an increased gas production, caused by hydrolysis within the sludge blanket at extended solids residence time. Whilst hydrolysis also induced higher gas productivity within the granular AnMBR, solids breakthrough was not evidently observed during this period, and was instead only observed as the sludge blanket approached the UASB overflow. However, solids breakthrough was observed earlier for both reactors when treating wastewater with lower temperatures. This was explained through characterisation of the settling velocity of discrete particles from the sludge blanket of both MBRs; solids washout was evidenced to be induced by the increase in fluid viscosity with a reduction in temperature, which lowered terminal particle settling velocity. Nevertheless, particle settling velocity was comparable for particles from both sludge blankets. We therefore propose that the enhanced stability imparted by the granular AnMBR is due to the higher inertial force of the dense granular sludge. From this study, we suggest that similarly low levels of membrane fouling can be achieved within flocculent AnMBR by managing solids retention time to constrain sludge bed height and excess hydrolysis, together with adopting an upflow velocity based on particle buoyancy at the lowest expected operating temperature.

Urban sanitation in growing cities of the Global South presents particular challenges, like the speed of their growth, the high population density, and, often, the lack of existing wastewater infrastructure. This led to the Bill & Melinda Gates Foundation’s Reinvent The Toilet Challenge, a call to develop novel, non-sewered sanitation technologies, which sparked the development of various inventions, like the Nano Membrane Toilet. Complex technologies like this entail an extensive product development process, including various iterations of prototype tests. While there is an abundance of literature discussing how to build prototypes, and the optimal number of tests, there has been little focus on how to plan, communicate, and conduct tests, especially in a product development endeavour of this complexity. Multiple aspects of testing prototypes are reviewed. A visual test planning tool is proposed that encompasses the entire product development process and can be used to plan and communicate prototype tests for the Nano Membrane Toilet to ultimately achieve compliance with international standards.

As a waste management technology which offers environmental benefit and renewable energy production, anaerobic digestion (AD) has become the preferred technology for the treatment of organic waste. However, in such waste streams nitrogen contents are likely to be high. There is prevailing literature evidence suggests that high ammonia concentration especially its free molecular form (NH3), derived from nitrogen content in substrates is the cause of inhibition and sudden failure of the AD process. This paper comprehensively reviews previous knowledge from digestion studies using high nitrogen waste streams as feedstocks and critically analysed the considerable variations in the inhibition/toxicity levels reported for ammonia. Literature evidences suggest methanogens, particularly acetoclastic methanogens are most susceptible to ammonia toxicity, and therefore this review has a particular focus on the mechanism of the ‘selective’ inhibition to methanogens and the impact of ammonia toxicity to the overall methanogen population in an AD digester. This population change explains in many reported cases that sufficient acclimatisation can significantly alleviate the phenomenon of inhibition and specific requirement of certain trace nutrients. Currently available mitigation strategies for high nitrogen content feedstock digestion are reviewed and discussed in relation to the population change and trace nutrient requirements.

Ammonia recovery from urine avoids the need for nitrogen removal through nitrification/denitrification and re-synthesis of ammonia (NH3) via the Haber-Bosch process. Previously, we coupled an alkalifying electrochemical cell to a stripping column, and achieved competitive nitrogen removal and energy efficiencies using only electricity as input, compared to other technologies such as conventional column stripping with air. Direct liquid-liquid extraction with a hydrophobic gas membrane could be an alternative to increase nitrogen recovery from urine into the absorbent while minimizing energy requirements, as well as ensuring microbial and micropollutant retention. Here we compared a column with a membrane stripping reactor, each coupled to an electrochemical cell, fed with source-separated urine and operated at 20 A m−2. Both systems achieved similar nitrogen removal rates, 0.34 ± 0.21 and 0.35 ± 0.08 mol N L−1 d−1, and removal efficiencies, 45.1 ± 18.4 and 49.0 ± 9.3%, for the column and membrane reactor, respectively. The membrane reactor improved nitrogen recovery to 0.27 ± 0.09 mol N L−1 d−1 (38.7 ± 13.5%) while lowering the operational (electrochemical and pumping) energy to 6.5 kWhe kg N−1 recovered, compared to the column reactor, which reached 0.15 ± 0.06 mol N L−1 d−1 (17.2 ± 8.1%) at 13.8 kWhe kg N−1. Increased cell concentrations of an autofluorescent E. coli MG1655 + prpsM spiked in the urine influent were observed in the absorbent of the column stripping reactor after 24 h, but not for the membrane stripping reactor. None of six selected micropollutants spiked in the urine were found in the absorbent of both technologies. Overall, the membrane stripping reactor is preferred as it improved nitrogen recovery with less energy input and generated an E. coli- and micropollutant-free product for potential safe reuse. Nitrogen removal rate and efficiency can be further optimized by increasing the NH3 vapor pressure gradient and/or membrane surface area.

Highlights • UF is used as a pre-treatment to reduce membrane distillation fouling. • UF removes particles and colloids from blackwater but low MW fraction increases. • Whilst UF treated blackwater high in organics, flux and water quality is stable. • Without UF pre-treatment, severe fouling reduces flux, which reduces quickly. • With UF pre-treatment, permeate quality consistently meets treatment quality., In this study, the pretreatment of concentrated blackwater using ultrafiltration (UF) was shown to improve the permeability, selectivity and robustness of membrane distillation (MD) for application to wastewater treatment. Concentrated blackwater comprises urine and faeces, with minimal flushwater added. The faecal contribution increased the soluble organic fraction and introduced coarse and colloidal particles into the urine, which increased resistance to filtration during dead-end UF. Ultrafiltration removed the particulate and colloidal fractions (MW > 500 kDa) from the blackwater, which permitted similar permeability and robustness for MD to that observed with urine (29.9 vs 25.9 kg m−2 h−1), which comprises a lower colloidal organic concentration. Without UF pretreatment, a higher density organic layer formed on the MD surface (197 vs 70 gCOD m−2) which reduced mass transfer, and transformed the contact angle from hydrophobic to hydrophilic (144.9° to 49.8°), leading to pore wetting and a dissipation in product water quality due to breakthrough. In comparison, with UF pretreatment, MD delivered permeate water quality to standards satisfactory for discharge or reuse. This is particularly timely as the ISO standard for non-sewered sanitation has been adopted by several countries at a national level, and to date there are relatively few technologies to achieve the treatment standard. Membrane distillation provides a robust means for concentrated blackwater treatment, and since the energy required for separation is primarily heat, this advanced treatment can be delivered into areas with more fragile power networks.

Whilst the efficiency of reverse electrodialysis (RED) for thermal-to-electrical conversion has been theoretically demonstrated for low-grade waste heat, the specific configuration and salinity required to manage power generation has been less well described. This study demonstrates that operating RED by recycling feed solutions provides the most suitable configuration for energy recovery from a fixed solution volume, providing a minimum unitary cost for energy production. For a fixed membrane area, recycling feeds achieves energy efficiency seven times higher than single pass (conventional operation), and with an improved power density. However, ionic transport, water flux and concentration polarisation introduce complex temporal effects when concentrated brines are recirculated, that are not ordinarily encountered in single pass systems. Regeneration of the concentration gradient at around 80% energy dissipation was deemed most economically pragmatic, due to the increased resistance to mass transport beyond this threshold. However, this leads to significant exergy destruction that could be improved by interventions to better control ionic build up in the dilute feed. Further improvements to energy efficiency were fostered through optimising current density for each brine concentration independently. Whilst energy efficiency was greatest at lower brine concentrations, the work produced from a fixed volume of feed solution was greatest at higher saline concentrations. Since the thermal-to-electrical conversion proposed is governed by volumetric heat utilisation (distillation to reset the concentration gradient), higher brine concentrations are therefore recommended to improve total system efficiency. Importantly, this study provides new evidence for the configuration and boundary conditions required to realise RED as a practical solution for application to sources of low-grade waste heat in industry., Highlights • Power dissipation using reverse electrodialysis in recycle is described. • Recycle is more economically and energetically efficient than single-pass. • Water flux, ionic transport and concentration polarisation impactful in recycle. • Control of ionic concentration in dilute feed can improve system efficiency. • Optimum current density is specific to chemical gradient.

Highlights • On dry basis, typical human faeces contain 83 wt.% organic fraction and 17 wt.% ash. • The LHV of dry human faeces ranged from 19 to 22 MJ/kg, values similar to wood biomass. • Syngas from dry human faeces had LHV of 15–17 MJ/kg at equivalence ratio of ∼0.31. • Energy is best recovered from moist human faeces at equivalence ratio above 0.6. • Recoverable exergy potential from moist human faeces can be up to 15 MJ/kg., Non-sewered sanitary systems (NSS) are emerging as one of the solutions to poor sanitation because of the limitations of the conventional flush toilet. These new sanitary systems are expected to safely treat faecal waste and operate without external connections to a sewer, water supply or energy source. The Nano Membrane Toilet (NMT) is a unique domestic-scale sanitary solution currently being developed to treat human waste on-site. This toilet will employ a small-scale gasifier to convert human faeces into products of high energy value. This study investigated the suitability of human faeces as a feedstock for gasification. It quantified the recoverable exergy potential from human faeces and explored the optimal routes for thermal conversion, using a thermodynamic equilibrium model. Fresh human faeces were found to have approximately 70–82 wt.% moisture and 3–6 wt.% ash. Product gas resulting from a typical dry human faeces (0 wt.% moisture) had LHV and exergy values of 17.2 MJ/kg and 24 MJ/kg respectively at optimum equivalence ratio of 0.31, values that are comparable to wood biomass. For suitable conversion of moist faecal samples, near combustion operating conditions are required, if an external energy source is not supplied. This is however at 5% loss in the exergy value of the gas, provided both thermal heat and energy of the gas are recovered. This study shows that the maximum recoverable exergy potential from an average adult moist human faeces can be up to 15 MJ/kg, when the gasifier is operated at optimum equivalence ratio of 0.57, excluding heat losses, distribution or other losses that result from operational activities.

In this study, reactive crystallisation is introduced into a liquid-liquid membrane contactor for the selective separation, purification and recovery of ammonia from concentrated waste. Whilst liquid-liquid membrane contactor technology has been previously demonstrated for ammonia absorption, further process intensification can be achieved by incorporating crystallisation into transmembrane chemisorption to recover the ammonia as crystalline ammonium sulphate. Reactive crystallisation occurred in the draw solution (sulphuric acid) which was supplied to the lumen-side of the polypropylene hollow-fibre. The ammonium sulphate concentration in the draw solution increased through ammonia mass transfer to supersaturation, at which time induction (the onset of nucleation) commenced. Ammonia mass transfer at draw concentrations above the solubility limit was not limited provided sufficient ‘free’ sulphate was available. This resulted in nucleation which occurred at a low level of supersaturation (C/C*, 1.03) to produce small crystals of around 2.5 μm, which indicated that nucleation was favoured. The nucleation rate was found to be proportional to the ammonia flux in the draw solution. As the solution became more saturated, crystal number increased but crystal growth was comparatively small; this is symptomatic of reactive crystallisation, where the rate of reaction exceeds the rate of mass transfer. Due to the large difference in the ratio between the lumen internal diameter and the mean crystal diameter ( d f i b r e / d m e a n , C S D , ~180), no fibre clogging was observed despite facilitating crystallisation on the lumen-side of the membrane. Transmembrane chemisorption crystallisation presents a feasible process intensification for the selective separation of ammonia from environmental applications. For its integration into environmental applications, solutions to wetting and fouling remain due to associative interactions with the complex organic matrix that are practically achievable through engineering intervention. Subsequent transformation of ammonia into a crystalline phase of ammonium sulphate presents a new product which is of commercial interest.

In this study, thermal desorption was developed to separate and concentrate ammonia from return liquor, for use as a chemical absorbent in biogas upgrading, providing process intensification and the production of crystalline ammonium bicarbonate as the final reaction product. Applying modest temperature (50 °C) in thermal desorption suppressed water vapour pressure and increased selective transport for ammonia from return liquor (0.11MNH3) yielding a concentrated condensate (up to 1.7MNH3). Rectification was modelled through second-stage thermal processing, where higher initial ammonia concentration from the first stage increased mass transfer and delivered a saturated ammonia solution (6.4MNH3), which was sufficient to provide chemically enhanced CO2 separation and the simultaneous initiation of ammonium bicarbonate crystallisation, in a hollow fibre membrane contactor. Condensate recovered from return liquor exhibited a reduction in surface tension. We propose this is due to the stratification of surface active agents at the air-liquid interface during primary-stage thermal desorption which carried over into the condensate, ‘salting’ out CO2 and lowering the kinetic trajectory of absorption. However, crystal induction (the onset of nucleation) was comparable in both synthetic and thermally recovered condensates, indicating the thermodynamics of crystallisation to be unaffected by the recovered condensate. The membrane was evidenced to promote heterogeneous primary nucleation, and the reduction in the recovered condensate surface tension was shown to exacerbate nucleation rate, due to the reduction in activation energy. X-ray diffraction of the crystals formed, showed the product to be ammonium bicarbonate, demonstrating that thermal desorption eliminates cation competition (e.g. Ca2+) to guarantee the formation of the preferred crystalline reaction product. This study identifies an important synergy between thermal desorption and membrane contactor technology that delivers biogas upgrading, ammonia removal from wastewater and resource recovery in a complimentary process.

The feasibility of gas-liquid hollow fibre membrane contactors for the chemical absorption of carbon dioxide (CO2) into ammonia (NH3), coupled with the crystallisation of ammonium bicarbonate has been demonstrated. In this study, the mechanism of chemically facilitated heterogeneous membrane crystallisation is described, and the solution chemistry required to initiate nucleation elucidated. Induction time for nucleation was dependent on the rate of CO2 absorption, as this governed solution bicarbonate concentration. However, for low NH3 solution concentrations, a reduction in pH was observed with progressive CO2 absorption which shifted equilibria toward ammonium and carbonic acid, inhibiting both absorption and nucleation. An excess of free NH3 buffered pH suitably to balance equilibria to the onset of supersaturation, which ensured sufficient bicarbonate availability to initiate nucleation. Following induction at a supersaturation level of 1.7 (3.3 M NH3), an increase in crystal population density and crystal size was observed at progressive levels of supersaturation which contradicts the trend ordinarily observed for homogeneous nucleation in classical crystallisation technology, and demonstrates the role of the membrane as a physical substrate for heterogeneous nucleation during chemically reactive crystallisation. Both nucleation rate and crystal growth rate increased with increasing levels of supersaturation. This can be ascribed to the relatively low chemical driving force imposed by the shift in equilibrium toward ammonium which suppressed solution reactivity, together with the role of the membrane in promoting counter-current diffusion of CO2 and NH3 into the concentration boundary layer developed at the membrane wall, which permitted replenishment of reactants at the site of nucleation, and is a unique facet specific to this method of membrane facilitated crystallisation. Free ammonia concentration was shown to govern nucleation rate where a limiting NH3 concentration was identified above which crystallisation induced membrane scaling was observed. Provided the chemically reactive membrane crystallisation reactor was operated below this threshold, a consistent (size and number) and reproducible crystallised reaction product was collected downstream of the membrane, which evidenced that sustained membrane operation should be achievable with minimum reactive maintenance intervention.

Public willingness to use decentralised sanitation facilities or arising water products is discouraged due to malodour, preventing improved sanitation practices or water reuse opportunities in low income countries. Whilst odour is characterised in the gas phase, it originates in the liquid phase. Consequently, controlling odour at source could prevent gas-phase partitioning and limit produced water contamination. This study therefore developed an analytical method for the quantitation of a range of liquid phase volatile organic compounds (VOCs) classified into eight chemical groups, known to be primary indicators of faecal odour, to provide characterisation of real fluids and to permit evaluation of several potential membrane separation technologies for liquid phase odourant separation. The gas chromatography mass spectrometry method provided quantitation in the range of 0.005 mg L−1 to 100 mg L−1 with instrument detection limits ranging from 0.005 mg L−1 to 0.124 mg L−1. Linear calibration curves were achieved (r2 > 0.99) with acceptable accuracy (77-115%) and precision (

The key driver for anaerobic membrane bioreactors (AnMBRs) for municipal wastewater treatment is enabling the transition to energy neutral wastewater treatment. However, municipal wastewater delivers a comparatively constrained methane yield, which means energy conservation must be prioritised to achieve the proposed energy neutral ambition. A critical focus on membrane fouling is therefore warranted, as membrane operation represents the primary energy demand in MBRs. This review seeks to quantify the characteristics of the prevailing AnMBR biological suspension and to ascertain whether knowledge transfer exists between fouling characteristics in aerobic and anaerobic MBRs for municipal applications. Analysis of literature data revealed that the level of extractable extracellular polymeric substrate is slightly higher in aerobic MBRs than in anaerobic MBRs. However, AnMBR comprises considerably higher soluble microbial product concentrations, which have been widely reported to increase fouling propensity in aerobic systems. More distinct is the difference in the colloidal and fine solids fraction (between 1 and 10–15 μm), which is likely to dominate fouling in anaerobic systems and limit knowledge transfer from aerobic MBRs. Literature data on energy production was compared to that employed for membrane operation, and evidences that despite the challenging character of the particle matrix, energy neutral operation is achievable for AnMBR applied to municipal wastewater treatment.

In this study, the impact of peak flow on anaerobic membrane bioreactor operation is investigated to establish how system perturbation induced by diurnal peaks and storm water flows will influence membrane permeability. Good permeability recovery was attained through increasing gas sparging during peak flow, which was explained by the transition in critical flux of the suspension at higher shear rates. However, supra-critical fluxes could also be sustained, provided peak flow was for a short duration. We suggest longer durations of supra-critical operation could be sustained through introduction of reactive fouling control strategies (e.g. TMP set-point control). An initial flux below the critical flux, prior to the introduction of peak flow, was advantageous to permeability recovery, suggesting membrane ‘conditioning’ is important in governing recoverability following peak flow. The importance of conditioning was confirmed through analysis of multiple peak flow events in which the loss of permeability following each peak-flow event was increasingly negligible, and can be ascribed to the arrival of a steady-state in membrane surface deposition. Whilst responding to peak flow with increased gas sparging has been shown effective, the energy demand is considerable, and as such a pseudo dead-end filtration strategy was also evaluated, which required only 0.04 kWh m−3 of energy for gas sparging. Comparison of both filtration modes identified comparable fouling rates, and the feasibility of a low energy gas sparging method for peak flow management that has successfully enabled supra-critical fluxes to be achieved over long-periods in other MBR applications. Importantly, membrane area provides the highest contribution toward capital cost of AnMBR. The potential to turn-up flux in response to peak-flow has been identified in this study, which suggests membrane area can be specified based on average flow rather than peak flow, providing substantial reduction in the capital cost of AnMBR for municipal wastewater treatment.

Highlights • The performance of Stirling engine integrated to a micro-combustor in the NMT system was investigated. • Energy recovery and power generation of 27 Wh/h from combustion of human faeces. • The integrated position of the Stirling engine to the micro-combustor is highly paramount. • Sensitivity of the performance of the Stirling engine to working gas temperature. • Requirements for optimum performance of the Stirling engine for integration with micro-combustor., The demand for better hygiene has increased the need for developing more effective sanitation systems and facilities for the safe disposal of human urine and faeces. Non-Sewered Sanitary systems are considered to be one of the promising alternative solutions to the existing flush toilet system. An example of these systems is the Nano Membrane Toilet (NMT) system being developed at Cranfield University, which targets the safe disposal of human waste while generating power and recovering water. The NMT will generate energy from the conversion of human waste with the use of a micro-combustor; the heat produced will power a Stirling engine connected to a linear alternator to generate electricity. This study presents a numerical investigation of the thermodynamic analysis and operational characteristics of a quasi steady state model of the gamma type Stirling engine integrated into a combustor in the back end of the NMT system. The effects of the working gas, at different temperatures, on the Stirling engine performance are also presented. The results show that with the heater temperature of 390 °C from the heat supply via conduction at 820 W from the flue gas, the Stirling engine generates a daily power output of 27 Wh/h at a frequency of 23.85 Hz.

The individual cost contributions to the mechanical components of a small membrane bioreactor (MBR) (100–2,500 m3/d flow capacity) are itemised and collated to generate overall capital and operating costs (CAPEX and OPEX) as a function of size. The outcomes are compared to those from previously published detailed cost studies provided for both very small containerised plants (

Siloxane-induced damage is responsible for a significant proportion of the cost of producing electricity from biogas. The performance of siloxane removal vessels is currently determined by discrete sampling followed by analysis at an external laboratory, making refined process control difficult to achieve. This article introduces the use of on-line siloxane detection. Siloxane breakthrough curves within this article identified that upon approaching media exhaustion, a concentration of 30 mg/m3 was reached within a short time frame. Consequently, changepoint analysis was evaluated as a method to predict the onset of breakthrough. Breakthrough data were collated from vessels that exhibited both broad-fronted and sharp-fronted breakthrough profiles. When applied to broad-fronted profiles, changepoint analysis provided a 25–45 h early warning of breakthrough. In this case, probabilistic changepoint detection methods facilitated by on-line analysis provide sufficient process lag time to enable duty/standby switch over before the critical siloxane concentration is reached.

Dissolved gases produced within engineered anaerobic processes subsequently create a fugitive emission which can have financial, environmental and health and safety implications. Whilst desorption technology has been used to control dissolved gases in the drinking water sector, there is considerably less understanding of its deployment in wastewater for which there are numerous existing and emerging challenges. This review therefore focuses on existing and proposed technological approaches to gas desorption in engineered anaerobic wastewater processes, with specific emphasis on technology compatibility and downstream gas phase management. Simplified engineered solutions such as diffused aeration and multi-tray aerators appear robust solutions for implementation into wastewater. However, these processes are characterised by a low mass transfer coefficient and require high gas to liquid ratios (G/L) to achieve reasonable separation, which suggests their suitability is limited to small scale applications, in which gas recovery is not a priority. Packed columns and membrane contactors afford process intensification through increasing interfacial area which favours large scale applications; although both will require prefiltration technology to obviate media clogging. Vacuum or steam is the preferred driving force for separation when gas recovery is sought, while sweep-gas is energetically favoured. Sweep-gas has been used for gas recovery by operating at G/L toward the equilibrium value, which somewhat constrains mass transfer. Process selection must therefore be weighted on whole life cost, but will also be dependent upon process scale, financial (e.g. incentivisation) and non-financial (e.g. carbon) instruments, which are strongly influenced by regional policy.

A novel enzymatic membrane reactor (EMR) was explored for continuous removal of two trace organic contaminants (TrOCs) ubiquitously detected in wastewater - namely bisphenol A (BPA) and diclofenac (DCF) - by a commercially available laccase from Aspergillus oryzae. An ultrafiltration membrane prevented washout of the enzyme and allowed continuous removal of BPA and DCF (>85% and >60%, respectively) under a loading rate of 570 ± 70 µg/L d (BPA) and 480 ± 40 µg/L d (DCF). The BPA and DCF removal could be further improved to >95% and >80%, respectively, by dosing to the EMR a natural redox-mediator compound - syringaldehyde (5 µM) - believed to act as an electron shuttle between laccase and the target pollutants. Of particular interest was the significant retention of the TrOCs on the gel layer of enzyme on the membrane surface, and their subsequent biodegradation.

To better understand pharmaceutical fate during wastewater treatment, analysis in both aqueous and particulate phases is needed. Reported herein is a multi-residue method for the determination of ten pharmaceutical drugs and the personal care product triclosan in wastewater matrices. Method quantitation limits ranged from 7.6 to 76.6 ng l − 1 for aqueous phases and from 7.0 to 96.7 ng g − 1 for particulate phases. The analytical method was applied to attain a complete process mass balance of a pilot-scale activated sludge plant (ASP) operated under controlled conditions. The mass balance (inclusive of aqueous and particulate concentrations at all sample points) was used to diagnose removal, revealing pharmaceuticals to be separable into three fate pathways: (a) biological degradation, (b) sorption onto activated sludge and (c) resistant to removal from the aqueous phase. These differences in fate behaviour explained a broad range of secondary removal observed (− 8 to 99%). The ASP was also simultaneously compared to a full-scale trickling filter (TF) works whilst receiving the same influent wastewater. Performance of the ASP and TF was similar, achieving total pharmaceutical removals of 253 and 249 μg g − 1 biochemical oxygen demand (BOD) removed, respectively. This corresponded with reductions in total pharmaceutical load of 91 and 90% (ANOVA, p - value > 0.05). Interestingly, despite low suspended solid concentrations final effluents of both the ASP and TF contained significant concentrations of some chemicals in the particulate phase. Individually, triclosan and the antibiotics ofloxacin and ciprofloxacin were within the particulate phase of effluents at concentrations ranging from 26 to 296 ng l − 1 .

A hollow fibre membrane contactor (HFMC) comprised of nonporous symmetric ultrathin wall polydimethylsiloxane (PDMS) fibres has been studied for biogas upgrading to establish if the ultrathin wall can enable low resistance to mass transfer coupled with enhanced selectivity for carbon dioxide (CO 2 ). For a feed gas CO 2 mole fraction of 80%, a CO 2 flux of 1.25×10 −4 mol m −2 s −1 was recorded which was higher than expected and is ostensibly due to the thin wall and the absence of a support layer which can limit gas transfer due to concentration polarisation. Maximum CO 2 flux was recorded at the highest liquid velocity tested due to a reduction in the thickness of the liquid phase boundary layer. Resistance in series analysis demonstrated that by limiting liquid phase resistance, mass transfer was controlled by the PDMS membrane and selectivity toward CO 2 was analogous to the ideal selectivity imparted by PDMS. In comparison, mass transfer was liquid phase controlled for a microporous HFMC that comprised of fibres with equivalent wall thickness. Whilst PDMS presents a higher theoretical selectivity when compared to the gas filled pore of a microporous fibre, higher selectivity was provided by the microporous fibre due to the solvents selectivity, which established that selectivity is dependent upon the controlling phase boundary. Though higher CO 2 fluxes were achieved with microporous fibres, ultrathin PDMS fibres are potentially beneficial for gases with a low CO 2 mole fraction due to their greater resistance to wetting. However, at higher CO 2 mole fraction, PDMS HFMC are only viable by increasing CO 2 flux through overpressure or reduction in wall thickness, though the feasibility is impingent upon validating the fibres mechanical integrity for both conditions.

Direct catalysis is generally proposed for nitrous oxide (N2O) abatement but catalysis is expensive, requires high temperatures, and suffers from media fouling, which limits its lifetime. In the present study, an ambient temperature electroscrubbing method was developed, coupling wet-scrubbing with an electrogenerated Ni(I) ([Ni(I)(CN)4]3−) mediator, to enable N2O reduction in a single process stage. The initial studies of 10 ppm N2O absorption into 9 M KOH and an electrolyzed 9 M KOH solution showed no removal. However, 95% N2O removal was identified through the addition of Ni(I) to an electrolyzed 9 M KOH. A change in the oxidation/reduction potential from −850 mV to −650 mV occurred following a decrease in Ni(I) concentration from 4.6 mM to 4.0 mM, which confirmed that N2O removal was mediated by an electrocatalytic reduction (MER) pathway. Online analysis identified the reaction product to be ammonia (NH3). Increasing the feed N2O concentration increased NH3 formation, which suggests that a decrease in electrolyzed solution reactivity induced by the increased N2O load constrained the side reaction with the carrier gas. Importantly, this study outlines a new regenerable method for N2O removal to commodity product NH3 at ambient temperature that fosters process intensification, overcomes the limitations generally observed with catalysis, and permits product transformation to NH3.

An ultra-performance liquid chromatography method using a triple quadrupole mass spectrometer was developed and validated for the determination of steroid oestrogens in wastewater matrices. To date, analytical methods established in the literature for 17α-ethinylestradiol have been unable to achieve the proposed predicted no effect concentration of 0.1 ng l−1. The extensive sample pretreatment and analytical methodology proposed herein enable 17α-ethinylestradiol to be determined at very low background concentrations with a theoretical method detection limit of 0.06 ng l−1 which has been applied in real environmental matrices. During the validation process, a trickling filter wastewater treatment works was monitored to demonstrate the method's application. Oestrogen removal across the filters demonstrated good removals of natural free oestrogens (≥62.0%) with lower removals of the synthetic oestrogen 17α-ethinylestradiol (29.2%) from wastewaters at 10°C. The method's application illustrates its capability...

The significance of electrostatic protein–polysaccharide interactions has been studied using bovine serum albumin (BSA) and sodium alginate (Na-alginate) to specifically illustrate the contribution of this form of non-covalent network to membrane fouling. Three physical states were observed: (1) at high pH, repulsive forces dominate yielding a co-soluble phase in which BSA and Na-alginate mutually exist with minimum interaction; (2) at a lower critical pH, BSA:Na-Alginate attraction is initiated enabling formation of soluble complexes; and (3) at a lower threshold pH, advanced BSA:Na-alginate interaction results in the nucleation of insoluble complexes (coacervates) measuring several micrometres in diameter. Soluble complex formation is governed by lowering zeta-potential sufficiently to enable positively charged micro-regions on the protein to bridge between negatively charged carboxyl groups on the alginate. The resultant non-covalent network presented the highest fouling rate and could explain the apparent role of protein in the irreversible fouling fraction previously observed by others. The precise solution conditions required for the growth of coacervates was found to be dependent upon the isoelectric point of the protein, biopolymer concentration and protein–polysaccharide ratio. Lower fouling rates were recorded for coacervates which can be attributed to their coarse diameter enabling a more porous and less cohesive foulant layer. Whilst this example of non-covalent electrostatic interaction was illustrated with BSA (and a low isoelectric point), numerous environmentally relevant proteins exhibit isoelectric points above and within the circum-neutral pH region, typical of membrane bioreactors.

This is the post-print version of the final paper published in TrAC Trends in Analytical Chemistry. The published article is available from the link below. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. Copyright @ 2013 Elsevier B.V. Recent trends in the determination of pharmaceutical drugs in wastewaters focus on the development of rapid multi-residue methods. This review addresses recent analytical trends in drug determination in environmental matrices used to facilitate fate studies. Analytical requirements for further fate evaluation and tertiary process selection and optimization are also discussed. EPSRC, Northumbrian Water, Anglian Water, Severn Trent Water, Yorkshire Water, and United Utilities.