Recent progresses in synthesis and modification of g-C3N4 for improving visible-light-driven photocatalytic degradation of antibiotics.

Graphitic carbon nitride (g-C3N4) is a widely studied visible-light-active photocatalyst for low cost, non-toxicity, and facile synthesis. Nonetheless, its photocatalytic efficiency is below par, due to fast recombination of charge carriers, low surface area, and insufficient visible light absorption. Thus, the research on the modification of g-C3N4 targeting at enhanced photocatalytic performance has attracted extensive interest. A considerable amount of review articles have been published on the modification of g-C3N4 for applications. However, limited effort has been specially contributed to providing an overview and comparison on available modification strategies for improved photocatalytic activity of g-C3N4-based catalysts in antibiotics removal. There has been no attempt on the comparison of photocatalytic performances in antibiotics removal between modified g-C3N4 and other known catalysts. To address these, our study reviewed strategies that have been reported to modify g-C3N4, including metal/non-metal doping, defect tuning, structural engineering, heterostructure formation, etc. as well as compared their performances for antibiotics removal. The heterostructure formation was the most widely studied and promising route to modify g-C3N4 with superior activity. As compared to other known photocatalysts, the heterojunction g-C3N4 showed competitive performances in degradation of selected antibiotics. Related mechanisms were discussed, and finally, we revealed current challenges in practical application.

Novel microbial-electrochemical filter with a computer-feedback pH control strategy for upgrading biogas into biomethane.

A novel microbial-electrochemical filter was designed and operated based on a combined microbial electrolysis cell and bio-trickling filter principles with the aim to maximize gas-liquid mass-transfer efficiency and minimize costs associated with bubbling biogas through liquid-filled reactor. CO2/biogas feed to the MEF was done via a computer-feedback pH control strategy, linking CO2 feed directly to the OH- production. As a result current efficiency was constant at around 100% throughout the period of experiments. CO2 from biogas was almost completely removed at cathodic pH setpoint of 8.5. Maximum CO2 removal rate was 14.6 L/L/day (equivalent to 29.2 L biogas/L/day). Net energy consumption was around 1.28 kWh/Nm3CO2 or 0.64 kWh/m3 biogas (maximum 49% energy efficiency). An ability to maintain a constant pH means elevated pH from increasing applied potential (current) is no longer an issue. The process can potentially be up-scaled and operated at a much higher current and therefore CO2 removal rate.

Review - Bacteria and their extracellular polymeric substances causing biofouling on seawater reverse osmosis desalination membranes.

Biofouling in seawater reverse osmosis (SWRO) membranes is a critical issue faced by the desalination industry worldwide. The major cause of biofouling is the irreversible attachment of recalcitrant biofilms formed by bacteria and their extracellular polymeric substances (EPS) on membrane surfaces. Transparent exopolymer particles (TEP) and protobiofilms are recently identified as important precursors of membrane fouling. Despite considerable amount of research on SWRO biofouling, the control of biofouling still remains a challenge. While adoption of better pretreatment methods may help in preventing membrane biofouling in new desalination setups, it is also crucial to effectively disperse old, recalcitrant biofilms and prolong membrane life in operational plants. Most current practices employ the use of broad spectrum biocides and chemicals that target bacterial cells to disperse mature biofilms, which are evidently inefficient. EPS, being known as the strongest structural framework of biofilms, it is essential to breakdown and disintegrate the EPS components for effective biofilm removal. To achieve this, it is necessary to understand the chemical composition and key elements that constitute the EPS of major biofouling bacterial groups in multi-species, mature biofilms. However, significant gaps in understanding the complexity of EPS are evident by the failure to achieve effective prevention and mitigation of fouling in most cases. Some of the reasons may be difficulty in sampling membranes from fully operational full-scale plants, poor understanding of microbial communities and their ecological shifts under dynamic operational conditions within the desalination process, selection of inappropriate model species for laboratory-scale biofouling studies, and the laborious process of extraction and purification of EPS. This article reviews the novel findings on key aspects of SWRO membrane fouling and control measures with particular emphasis on the key sugars in EPS. As a novel strategy to alleviate biofouling, future control methods may be aimed towards specifically disintegrating and breaking down these key sugars rather than using broad spectrum chemicals such as biocides that are currently used in the industry.

Bioelectrochemical enhancement of anaerobic digestion: Comparing single- and two-chamber reactor configurations at thermophilic conditions.

Bioelectrochemical system (BES) can act as an auxiliary technology for improving organic waste treatment and biogas production in anaerobic digestion (AD). For the first time this study directly compared the performance of a single- and a cation-exchange membrane-equipped two-chamber BES-AD systems at thermophilic conditions. The results indicated that an active glucose-fed thermophilic anaerobic sludge could readily (<3days) increase biogas production in both reactor configurations by inserting a carbon electrode poised at -0.8V (vs. Ag/AgCl). However, after a 3-week operation, the biogas production rates from the single- and two-chamber BES reactor decreased due to volatile fatty acids accumulation. Only the two-chamber configuration could enable methane enrichment (98% CH4v/v) in biogas. Overall, this study suggests that integrating bioelectrodes in-situ could not sustainably improve biogas production in a thermophilic AD reactor, and future studies should be directed towards the use of bioelectrodes for improving biogas quality.

Characterisation and comparison of bacterial communities on reverse osmosis membranes of a full-scale desalination plant by bacterial 16S rRNA gene metabarcoding.

Microbiomes of full-scale seawater reverse osmosis membranes are complex and subject to variation within and between membrane units. The pre-existing bacterial communities of unused membranes before operation have been largely ignored in biofouling studies. This study is novel as unused membranes were used as a critical benchmark for comparison. Fouled seawater reverse osmosis membrane biofilm communities from an array of autopsied membrane samples, following a 7-year operational life-span in a full-scale desalination plant in Western Australia, were characterised by 16S rRNA gene metabarcoding using the bacterial primers 515F and 806R. Communities were then compared based on fouling severity and sampling location. Microbiomes of proteobacterial predominance were detected on control unused membranes. However, fouled membrane communities differed significantly from those on unused membranes, reflecting that operational conditions select specific bacteria on the membrane surface. On fouled membranes, Proteobacteria were also predominant but families differed from those on unused membranes, followed by Bacteriodetes and Firmicutes. Betaproteobacteria correlated with stable, mature and thick biofilms such as those in severely fouled membranes or samples from the feed end of the membrane unit, while Alpha and Gammaproteobacteria were predominantly found in biofilms on fouled but visually clean, and moderately fouled samples or those from reject ends of membrane units. Gammaproteobacteria predominated the thin, compact biofilms at the mid-feed end of membrane units. The study also supported the importance of Caulobacterales and glycosphingolipid-producing bacteria, namely Sphingomonadales, Rhizobiales and Sphingobacteriia, in primary attachment and biofilm recalcitrance. Nitrate-and-nitrite-reducing bacteria such as Rhizobiales, Burkholderiales and some Pseudomonadales were also prevalent across all fouled membranes and appeared to be critical for ecological balance and biofilm maturation.

New method for characterizing electron mediators in microbial systems using a thin-layer twin-working electrode cell.

Microbial biofilms are significant ecosystems where the existence of redox gradients drive electron transfer often via soluble electron mediators. This study describes the use of two interfacing working electrodes (WEs) to simulate redox gradients within close proximity (250µm) for the detection and quantification of electron mediators. By using a common counter and reference electrode, the potentials of the two WEs were independently controlled to maintain a suitable "voltage window", which enabled simultaneous oxidation and reduction of electron mediators as evidenced by the concurrent anodic and cathodic currents, respectively. To validate the method, the electrochemical properties of different mediators (hexacyanoferrate, HCF, riboflavin, RF) were characterized by stepwise shifting the "voltage window" (ranging between 25 and 200mV) within a range of potentials after steady equilibrium current of both WEs was established. The resulting differences in electrical currents between the two WEs were recorded across a defined potential spectrum (between -1V and +0.5V vs. Ag/AgCl). Results indicated that the technique enabled identification (by the distinct peak locations at the potential scale) and quantification (by the peak of current) of the mediators for individual species as well as in an aqueous mixture. It enabled a precise determination of mid-potentials of the externally added mediators (HCF, RF) and mediators produced by pyocyanin-producing Pseudomonas aeruginosa (WACC 91) culture. The twin working electrode described is particularly suitable for studying mediator-dependent microbial electron transfer processes or simulating redox gradients as they exist in microbial biofilms.

A framework for planning sustainable seawater desalination water supply.

A quantitative framework for sustainable desalination planning in metropolitan areas, which integrates the tools of mixed integer linear programming and life cycle assessment, is presented. The life cycle optimisation framework allows for optimal desalination planning by considering choices over intake type, staging and location of the infrastructure under different land-use, environmental and economic policies. Optimality is defined by the decision maker's selected objective function, being either an environmental impact or a levelised cost indicator. The framework was tested for future desalination planning scenarios in the northern metropolitan area of Perth, Western Australia. Results indicate that multi-staged construction and decentralised planning solutions may produce lower life cycle environmental impacts (58%) and at a lower levelised cost (24%) than a centralised desalination solution currently being considered by Western Australian water planners. Sensitivity analysis results suggest that the better environmental and economic performance of decentralised planning over centralised planning is highly sensitive to the proportion of land that can be made available for the siting of decentralised plants near the demand zone. Insight into land use policies is a critical factor to the initiation and success of decentralised solution in developed metropolitan areas.

A bubble column evaporator with basic flat-plate condenser for brackish and seawater desalination.

This paper describes the development and experimental evaluation of a novel bubble column-based humidification-dehumidification system, for small-scale desalination of saline groundwater or seawater in remote regions. A bubble evaporator prototype was built and matched with a simple flat-plate type condenser for concept assessment. Consistent bubble evaporation rates of between 80 and 88 ml per hour were demonstrated. Particular focus was on the performance of the simple condenser prototype, manufactured from rectangular polyvinylchlorid plastic pipe and copper sheet, a material with a high thermal conductivity that quickly allows for conduction of the heat energy. Under laboratory conditions, a long narrow condenser model of 1500 mm length and 100 mm width achieved condensate recovery rates of around 73%, without the need for external cooling. The condenser prototype was assessed under a range of different physical conditions, that is, external water cooling, partial insulation and aspects of air circulation, via implementing an internal honeycomb screen structure. Estimated by extrapolation, an up-scaled bubble desalination system with a 1 m2 condenser may produce around 19 l of distilled water per day. Sodium chloride salt removal was found to be highly effective with condensate salt concentrations between 70 and 135 µS. Based on findings and with the intent to reduce material cost of the system, a shorter condenser length of 750 mm for the non-cooled (passive) condenser and of 500 mm for the water-cooled condenser was considered to be equally efficient as the experimentally evaluated prototype of 1500 mm length.

Novel process of bio-chemical ammonia removal from air streams using a water reflux system and zeolite as filter media.

A novel biofilter that removes ammonia from air streams and converts it to nitrogen gas has been developed and operated continuously for 300 days. The ammonia from the incoming up-flow air stream is first absorbed into water and the carrier material, zeolite. A continuous gravity reflux of condensed water from the exit of the biofilter provides moisture for nitrifying bacteria to develop and convert dissolved ammonia (ammonium) to nitrite/nitrate. The down-flow of the condensed water reflux washes down nitrite/nitrate preventing ammonium and nitrite/nitrate accumulation at the top region of the biofilter. The evaporation caused by the inflow air leads to the accumulation of nitrite to extremely high concentrations in the bottom of the biofilter. The high nitrite concentrations favour the spontaneous chemical oxidation of ammonium by nitrite to nitrogen (N2). Tests showed that this chemical reaction was catalysed by the zeolite filter medium and allowed it to take place at room temperature. This study shows that ammonia can be removed from air streams and converted to N2 in a fully aerated single step biofilter. The process also overcomes the problem of microorganism-inhibition and resulted in zero leachate production.

Potential for energy generation from anaerobic digestion of food waste in Australia.

Published national and state reports have revealed that Australia deposits an average of 16 million Mg of solid waste into landfills yearly, of which approximately 12.6% is comprised of food. Being highly biodegradable and possessing high energy content, anaerobic digestion offers an attractive treatment option alternative to landfilling. The present study attempted to identify the theoretical maximum benefit of food waste digestion in Australia with regard to energy recovery and waste diversion from landfills. The study also assessed the scope for anaerobic process to utilize waste for energy projects through various case study scenarios. Results indicated anaerobic digestion of total food waste generated across multiple sites in Australia could generate 558 453 dam(3) of methane which translated to 20.3 PJ of heating potential or 1915 GWe in electricity generation annually. This would contribute to 3.5% of total current energy supply from renewable sources. Energy contribution from anaerobic digestion of food waste to the total energy requirement in Australia remains low, partially due to the high energy consumption of the country. However its appropriateness in low density regions, which are prevalent in Australia, may allow digesters to have a niche application in the country.

Overcoming sodium toxicity by utilizing grass leaves as co-substrate during the start-up of batch thermophilic anaerobic digestion.

Sodium toxicity is a common problem causing inhibition of anaerobic digestion, and digesters treating highly concentrated wastes, such as food and municipal solid waste, and concentrated animal manure, are likely to suffer from partial or complete inhibition of methane-producing consortia, including methanogens. When grass clippings were added at the onset of anaerobic digestion of acetate containing a sodium concentration of 7.8 gNa(+)/L, a total methane production about 8L/L was obtained, whereas no methane was produced in the absence of grass leaves. In an attempt to narrow down which components of grass leaves caused decrease of sodium toxicity, different hypotheses were tested. Results revealed that betaine could be a significant compound in grass leaves causing reduction to sodium inhibition.

Distribution of methanogenic potential in fractions of turf grass used as inoculum for the start-up of thermophilic anaerobic digestion.

This study aims to investigate thermophilic methanogens in turf used as an inoculum. Results showed that Methanoculleus sp. regarded as hydrogenotrophic and Methanosarcina sp. regarded as acetoclastic methanogens were present in turf tested. However, active acetoclastic methanogens were present in turf soil only. The current study showed that thermophilic methanogens were present in various turf grass species: Stenotaphrum secundatum, Cynodon dactylon, and Zoysia japonica. Severe treatments of grass leaves under oxic conditions, including blending, drying and pulverizing did not affect the thermophilic hydrogenotrophic methanogenic activity of the grass. A dried and pulverized grass extract could be generated that can serve as a readily storable methanogenic inoculum for thermophilic anaerobic digestion. The methanogens could also be physically extracted into an aqueous suspension, suitable as an inoculum. The possible contribution of the presence of methanogens on grass plants to global greenhouse emissions is briefly discussed.

Energy-efficient treatment of organic wastewater streams using a rotatable bioelectrochemical contactor (RBEC).

A membraneless bioelectrochemical system - rotatable bio-electrochemical contactor (RBEC) consists of an array of rotatable electrode disks was developed to convert the chemical energy from wastewater organics (acetate) directly into electricity. Each rotatable electrode disk had an upper-air exposing and a lower-water submerging halves. Intermittent rotation (180°) enabled each halve to alternately serve as anode and cathode. Removal of chemical oxygen demand (COD) was increased by 15% (from 0.79 to 0.91 kg COD m(-3) d(-1)) by allowing electron flow from the lower to the upper disk halves. Coupling with a potentiostat could alleviate cathodic limitation and increased COD removal to 1.32 kg COD m(-3) day(-1) (HRT 5h). About 40% of the COD removed was via current, indicating that the biofilm could use the lower half disk as electron acceptor. The RBEC removed COD more energy-efficiently than conventional activated sludge processes as active aeration is not required (0.47 vs. 0.7-2.0 kW h kg COD(-1)).

Nitrogen removal and ammonia-oxidising bacteria in a vertical flow constructed wetland treating inorganic wastewater.

Nitrogen removal performance and the ammonia-oxidising bacterial (AOB) community were assessed in the batch loaded 1.3 ha saturated surface vertical flow wetland at CSBP Ltd, a fertiliser and chemical manufacturer located in Kwinana, Western Australia. From September 2008 to October 2009 water quality was monitored and sediment samples collected for bacterial analyses. During the period of study the wetland received an average inflow of 1,109 m3/day with NH3-N = 40 mg/L and NO3-N = 23 mg/L. Effluent NH3-N and NO3-N were on average 31 and 25 mg/L, respectively. The overall NH3-N removal rate for the period was 1.2 g/m2/day indicating the nitrifying capacity of the wetland. The structure of the AOB community was analysed using group specific primers for the ammonia monooxygenase gene (amoA) by terminal restriction fragment length polymorphism and by clone libraries to identify key members. The majority of sequences obtained were most similar to Nitrosomonas sp. while Nitrosospira sp. was less frequent. Another two vertical flow wetlands, 0.8 ha each, were commissioned at CSBP in July 2009, since then the wetland in this study has received nitrified effluent from these two new cells.

Water balance modelling of alternate water sources at the household scale.

Alternate water sources are being implemented in urban areas to augment scheme water supplied by a water utility to homes. These sources include residential wells, rainwater tanks and greywater systems. Greater water efficiency can be achieved when these systems are designed to match a water source to a given demand based on both water quantity and quality parameters. In this way the use of an alternate water source can be maximised and the use of the high quality scheme water minimised. This paper examines the use of multiple alternate water sources sequentially to supply the same demand point potentially optimising the use of all available water sources. It also allows correct sizing of such water systems and their components to reduce scheme water demand. A decision support tool based on water balance modelling was developed that considers such water options at the household scale. Application of this tool to eight scenarios for both large and small house lots shows that using alternate water sources individually can result in significant scheme water savings. However by integrating these sources additional scheme water saving can be made.

Rapid start-up of thermophilic anaerobic digestion with the turf fraction of MSW as inoculum.

This study aims to determine suitable start-up conditions and inoculum sources for thermophilic anaerobic digestion. Within days of incubation MSW at 55°C, methane was produced at a high rate. In an attempt to narrow down which components of typical MSW contained the thermophilic methanogens, vacuum cleaner dust, banana peel, kitchen waste, and garden waste were tested as inoculum for thermophilic methanogenesis with acetate as the substrate. Results singled out grass turf as the key source of thermophilic acetate degrading methanogenic consortia. Within 4 days of anaerobic incubation (55°C), anaerobically incubated grass turf samples produced methane accompanied by acetate degradation enabling successful start-up of thermophilic anaerobic digestion. Other essential start-up conditions are specified. Stirring of the culture was not conducive for successful start-up as it resulted specifically in propionate accumulation.

Novel methanogenic rotatable bioelectrochemical system operated with polarity inversion.

A novel membraneless bioelectrochemical system termed rotatable bioelectrochemical contactor (RBEC) was fabricated and evaluated for its ability to recover useful energy (here methane) from a low organic strength wastewater. We studied the operational characteristics of the RBEC by operating it as a three-electrode electrolysis cell. A stack of conductive disks (each subdivided into two half disks), similar to rotating biological contactors, were rotated with one-half disk immersed in the wastewater and the other into the gas headspace. By carrying out regular half rotations (180° rotation) the anode became the cathode and vice versa. This operation resulted in the build-up of a biofilm that could catalyze both an anodic acetate oxidation and a cathode-driven methanogenesis. Methane production rate was directly proportional to the applied electrical energy. Increase in current density (from 0.16 to 4.1 A m(-2)) resulted in a faster COD removal (from 0.2 to 1.38 kg COD m(-3) day(-1)) and methane production (from 0.04 to 0.53 L L(-1) day(-1)). Of the electrons flowing across the circuit, over 80% were recovered as methane. Such methane production was electrochemically driven by the headspace-exposed cathodic half disks, which released the methane directly to the gas-phase. Energy analysis shows that the new design requires less energy for COD removal than what is typically required for oxygen supply in activated sludge processes. Because the system could operate without wastewater recirculation against gravity; additional pH buffer chemicals; ion-exchange membranes or electrochemical catalysts, it has desirable characteristics for process up-scale. Further, the current report shows the first example of a BES with identical biofilm (due to intermittent polarity inversion) on both electrodes.

Ethanol from lignocellulose using crude unprocessed cellulase from solid-state fermentation.

It was desired to study a simplified method of cellulase production using solid-state fermentation for its potential to be used on-site as part of a cellulose to ethanol conversion process, in lieu of expensive and energy intensive commercial enzyme preparations. Crude unprocessed cellulase extracts were produced by solid-state fermentation of Trichoderma reesei on ground wheat straw. While cellulase yields were not high they were sufficient to produce ethanol from wheat straw in simultaneous saccharification and fermentation with Saccharomyces cerevisiae. As little as an additional 5% of the material converted to ethanol may be employed for cellulase production suggesting an inordinate quantity of additional substrate would not be required. These findings suggest a simplified crude cellulase process at the site of ethanol production using a common lignocellulosic substrate may be employed in lieu of commercial enzyme preparations.

Anodophilic biofilm catalyzes cathodic oxygen reduction.

Poor cathodic oxygen reduction and the detrimental buildup of a pH gradient between anode and cathode are the major hurdles in the development of sustainable microbial fuel cells (MFCs). This article describes and tests a concept that can help overcoming both of these limitations, by inverting the polarity of the MFC repeatedly, allowing anodic and cathodic reactions to occur alternately in the same half-cell and hence neutralizing its respective pH effects. For simplicity, we studied polarity inversion exclusively in one half-cell, maintaining its potential at -300 mV (vs Ag/AgCl) by a potentiostat. An alternating supply of acetate and dissolved oxygen to the biofilm resulted in the tested half-cell repeatedly changing from an anode to a cathode and vice versa. This repeated inversion of current direction avoided the detrimental drifting of the electrolyte pH. Control runs without current inversion ceased to produce current, as a result of anode acidification. The presence of the anodophilic biofilm survived the intermittent oxygen exposure and could measurably facilitate the cathodic reaction by reducing the apparent oxygen overpotential. It enabled cathodic oxygen reduction at about -150 mV (vs Ag/AgCl) compared to -300 mV (vs Ag/AgCl) for the same electrode material (granular graphite) without biofilm. Provided that a suitable cathodic potential was chosen, the presence of "anodophilic bacteria" at the cathode could enable a 5-fold increase in power output. Overall, the ability of an electrochemically active biofilm to catalyze both substrate oxidation and cathodic oxygen reduction in a single bioelectrochemical system has been documented. This property could be useful to alleviate both the cathodic oxygen reduction and the detrimental drifting of electrolyte pH in an MFC system. Further research is warranted to explore the application of such bidirectional microbial catalytic properties for sustainable MFC processes.

Heavy metals in a constructed wetland treating industrial wastewater: distribution in the sediment and rhizome tissue.

This study assessed copper and zinc distribution in the surface layer of sediment and rhizome tissue within the saturated surface vertical flow constructed wetland of CSBP Ltd, a fertiliser and chemical manufacturer located in Western Australia. Sediment and Schoenoplectus validus rhizome samples were collected at various distances from the inlet pipe while water samples are routinely collected. Water samples were analysed for nutrients and metals, sediments were analysed for total and bioavailable metals and rhizomes were analysed for total metals only. Mean influent copper and zinc concentrations were 0.19 mg/L and 0.24 mg/L respectively. The distribution of bioavailable Cu and Zn in the top sediment layer follows a horizontal profile. Analysis of variance (ANOVA) showed that the bioavailable fraction of these metals in sediments near the inlet pipe (30.2 mg/kg Cu and 60.4 mg/kg Zn) is significantly higher than in sediments at the farthest location (10.3 mg/kg Cu and 26.1 mg/kg Zn). The average total Cu concentration in the sediment at the 2 m location has reached the 65 mg/kg trigger value suggested by the Interim Sediment Quality Guidelines (ANZEEC 2000). Cu and Zn concentrations in the rhizome of S. validus do not vary significantly among different locations. Whether Cu and Zn concentrations at the CSBP wetland may reach toxic levels to plants and bacteria is still unknown and further research is required to address this issue. The surface component of the wetland favours sedimentation and binding of metals to the organic matter on the top of the sediment, furthermore, the sediment which tends to be anoxic with reducing conditions acts as a sink for metals.