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Purpose of Review In the presented review, we have summarized recent achievements on the use of immobilized oxidoreductases for biodegradation of hazardous organic pollutants including mainly dyes, pharmaceuticals, phenols, and bisphenols. In order to facilitate process optimization and achievement of high removal rates, effect of various process conditions on biodegradation has been highlighted and discussed. Recent Findings Current reports clearly show that immobilized oxidoreductases are capable of efficient conversion of organic pollutants, usually reaching over 90% of removal rate. Further, immobilized enzymes showed great recyclability potential, allowing their reuse in numerous of catalytic cycles. Summary Collected data clearly indicates immobilized oxidoreductases as an efficient biocatalytic tools for removal of hazardous phenolic compounds, making them a promising option for future water purification. Data shows, however, that both immobilization and biodegradation conditions affect conversion efficiency; therefore, process optimization is required to achieve high removal rates. Nevertheless, we have demonstrated future trends and highlighted several issues that have to be solved in the near-future research, to facilitate large-scale application of the immobilized oxidoreductases in wastewater treatment.

The occurrence of emerging contaminants, such as estrogens, in secondary and tertiary treated effluents and in sewage-impacted water bodies is one of the major obstacles to the implementation of water reuse. This review critically evaluates the performance of emerging process of enzymatic degradation of estrogens, and its efficiency. The data collected from peer-review literature show that enzymes have been extensively applied (in both free and immobilized form) in estrogen removal. Amongst others, the use of laccase as a catalyst provides over 90% removal of estrogens. Immobilized enzymes can overcome some limitations of the free biocatalysts, including reusability. Research evidence points to the formation of by-products, such as dimers and trimers. Nevertheless, estrogenic activity assessment indicates a reduction in toxicity after enzyme treatment. The cost and stability of enzymes, as well as their performance in a real wastewater matrix, are the major obstacles to the implementation of enzymatic processes in wastewater treatment. Continued endeavors are required to enhance the successful application of enzymes in the wastewater treatment industry. Highlights: Processes of enzyme-supported conversion of estrogens are reviewed and discussed. Laccase is the most commonly applied enzyme and achieves over 90% estrogen removal. Immobilization is suggested as an effective tool for enhancement of estrogen removal. Dimers and trimers have been identified as main bioconversion products of estrogens. Existing research gaps are highlighted and future recommendations are provided.

This work examined fouling-associated microbial community in a carefully controlled laboratory-scale membrane bioreactor (MBR) at different fouling stages. In agreement with the literature, fouling severity was positively correlated with bound polysaccharide and protein content (indicators) in the mixed liquor. UPGMA clustering analysis with different indices indicated that although the biofouling layer (biofilm) and mixed liquor possessed highly similar microbial identity, important differences between the two communities' structures were also observed. This appears to be the first comprehensive study to apply differential abundance analysis (ANCOM) to identify microbial taxa driven the divergence in microbial structure including Victivallales, Coxiellales, unassigned Microgenomatia and Blastocatellia 11–24 (all presented at 0.6) with fouling indicators, confirming their important contributions to fouling propensity. The biofilm community exhibited a more complex structure with higher level of inter-species interaction and prevalence of positive connections (74.6%) compared to the mixed liquor community (42.2%), reflecting higher stability and synergy between microbial taxa in the biofilm. Results from this comprehensive investigation can support the development of new fouling control strategies.

© 2019 The Royal Society of Chemistry. A hybrid process combining a single compartment aerobic membrane bioreactor (MBR) and a membrane microalgal reactor (MMR) was evaluated for nutrient removal and microalgal biomass production. When operated without biomass extraction, the microalgal biomass in the MMR reached 920 mg L-1 on day 18 and then collapsed, rendering nutrient removal ineffective. Stable operation of the MMR was achieved by regular biomass extraction (i.e. 1/30 of the microalgal biomass in the reactor daily). The biomass production at steady state was approximately 26 g m-3 d-1. The NO3- and PO43- uptake values by microalgae were 4.0 ± 1.1 and 1.5 ± 0.9 g m-3 d-1, respectively. A facile flocculation and separation technique capable of recovering 98% microalgal biomass was demonstrated. Although the hybrid process can significantly enhance nutrient removal and biomass production, further research is needed to intensify the microalgal growth rate. At the current microalgal growth rate, a large MMR volume (37 times that of the MBR) is necessary for synchronous operation.

Chlorhexidine (CHX) is a broad-spectrum antimicrobial, which may pose environmental health risks. This study examined the removal potential and the mechanisms regulating the fate of CHX in activated sludge (AS). Bioreactors inoculated with AS removed 74 ± 8% and 81 ± 6% of CHX at steady state while receiving 0.5 and 1 mg/L CHX, respectively. Analysis of the removal pathways showed that biosorption, rather than biological breakdown or other abiotic losses, largely (>70%) regulated the removal of CHX. 16S rRNA gene-based analysis revealed that CHX selected for Luteolibacter (4.3-10.1-fold change) and Runella (6.2-14.1-fold change) with potential multi-drug resistance mechanisms (e.g., efflux pumps). In contrast, it significantly reduced core members (Comamonadaceae and Flavobacteriaceae) of AS, playing a key role in contaminant removal and floc formation directly associated with the performance of WWTPs (e.g., wastewater effluent quality). Antimicrobial susceptibility testing showed that 0.4-1.3 mg/L of CHX can be sublethal to AS. Our work provided new insights into the fate of CHX in urban waste streams and the potential toxicity and effects on the structure and function of AS, which has practical implications for the management of biological WWTPs treating CHX. This work was supported by a grant from the National Research Foundation of Korea (NRF) funded by the Korea government (MSIP; Ministry of Science, ICT & Future Planning) (No. NRF-2017R1C1B5076367).

© 2018 Elsevier B.V. This study evaluated the removal of diclofenac (DCF) in activated sludge and its long-term exposure effects on the function and structure of the microbial community. Activated sludge could remove

© 2019 This study investigated changes in microbial community structure and composition in response to operational disturbance and subsequent process recovery by inoculum addition. Amplicon sequencing of 16S rRNA and mcrA marker genes on the Illumina Miseq platform was used for microbial community analysis. The results show that imbalance among core microbial groups caused volatile fatty acid accumulation and subsequent deteriorated biogas production (decreased by 45% of daily volume) and methane content (57% of the total abundance) and reduction of acetogenic and methanogenic microbes (they accounted for

Antibiotics in wastewater leads to migration of pollutants and disrupts natural processes of mineralization of organic matter. In order to understand the mechanism of this, research was undertaken on the influence of nitrofurantoin (NFT) and furazolidone (FZD), on the behaviour of a consortium of microorganisms present in a model wastewater in a bioreactor. Our study confirmed biodegradation of the antibiotics by the microbial consortium, with the degradation efficiency within 10 days of 65% for FZD, but only 20% for NFT. The kinetic study proved that the presence of analysed antibiotics had no adverse effect on the microbes, but the consortium behaviour differ significantly with the NFT reducing the consumption of organic carbon in wastewater and increasing the production of extracellular biopolymeric and volatile organic compounds, and the FZD reducing assimilation of other carbon sources to a less extent, at the expense of cellular focus on biodegradation of this antibiotic.

This study demonstrates the proof-of-concept of biogas sparging to control membrane fouling during sludge centrate pre-concentration by forward osmosis (FO). Sludge centrate sparging by biogas reduced membrane fouling (measured by water flux decline) and filtration time by two and eight times, respectively, compared to FO operation without biogas sparging at the same water recovery of 60%. In addition, the water flux was almost fully recovered by physical flushing when biogas sparging was applied. Biogas sparging also resulted in a significant improvement in the enrichment of organic, ammonia, and phosphate to close to the theoretical value based on mass balance calculation. In other words, organic matter and nutrients were retained in the bulk solution for subsequent recovery. Fouling mitigation and nutrient enrichment improvement by biogas sparging could be attributed to carbonate buffering to maintain a near neutral pH for preventing calcium phosphate precipitation on the membrane surface and ammonia volatilisation.

This study aims to evaluate a passive inexpensive process to remove the residual phosphorus (P) from wastewater treatment effluents prior to discharge to the environment. This work also differentiates between surface adsorption and chemical precipitation in the bulk solution as key P removal mechanisms by steel-making slag. Experimental results show that P removal efficiency is governed by steel-making slag particle size, initial P content and ratio of steel-making slag mass to aqueous solution volume. The results demonstrate the potential of steel-making slag for removing dissolved phosphate from wastewater especially as a polishing step. Even at an elevated concentration of P of 5 mg/L, 90% P removal was achieved using 5 kg steel-making slag with particle size of 0.15–0.6 mm for each m3 aqueous solution. Higher removal efficiency was also achievable through process optimisation. In particular, P removal by steel-making slag can be significantly enhanced, and nearly complete removal (>99%) can be achievable by buffering the aqueous solution at pH of 5.6. This study also established the isotherms and kinetics of the adsorption of P to steel-making slag to identify key removal mechanisms. Experimental data systematically indicate that P removal by steel-making slag is governed by both adsorption and chemical precipitation. At the early stage of the removal process, adsorption is the dominating removal mechanism, while the P removal via chemical precipitation can occur once the release of Ca2+ calcium into the aqueous phase is sufficient to form calcium phosphate precipitates. Overall, P removal by chemical precipitation depends on both pH and Ca2+ concentration in aqueous solution.

This study addresses the challenge of microalgae harvesting through the development of flocculants. Two positively charged cationic polymers including poly[2 (acryloyloxy)ethyl]trimethylammonium chloride (PAETAC) and poly(3 acrylamidopropyl)trimethylammonium chloride (PAmPTAC) were synthesized using the UV-induced radical polymerization, for harvesting both freshwater and marine microalgae. The results show that the synthesized polymers have excellent flocculation performance for both freshwater green microalgae (Chlorella vulgaris) and marine red microalgae (Porphyridium purpureum). PAETAC outperformed PAmPTAC for both Chlorella vulgaris and Porphyridium purpureum microalgae. The optimal PAETAC doses for Chlorella vulgaris and Porphyridium purpureum microalgae were 50 and 4.8 mg/g of dry biomass while the optimal PAmPTAC doses were 252 and 35 mg/g of dry biomass respectively. Additionally, the floc formation with the PAETAC was more stable than PAmPTAC, which supported the dewatering step via sieving. The superior performance can be attributed to the higher molecular weight of the PAETAC polymer when compared to the PAmPTAC polymer. In comparison to commercially available polydiallyldimethylammonium chloride (PolyDADMAC), the newly synthesised PAETAC and PAmPTAC polymers demonstrated superior flocculation efficiency at a lower dose. The findings of this study established a platform technology for designing and synthesising cationic flocculants for use in microalgae harvesting.

Flocculation is a low-cost harvesting technique for microalgae biomass production, but flocculation efficiency is species dependent. In this study, we investigated the efficacy of two synthetic (polyacrylamide) and one natural (chitosan) flocculants against three algal species: the cyanobacterium Synechocystis sp., the freshwater Chlorella vulgaris, and the marine Phaeodactylum tricornutum at laboratory and pilot scales to evaluate harvesting efficiency, biomass integrity and media recycling. Growth phase affected the harvesting efficiency of the eukaryotic microalgae. The flocculation was optimal at stationary phase with high flocculation efficiency achieved using polyacrylamides at 24–36 mg/g dry weight. The effect of the flocculants on the harvested biomass was investigated. The flocculated Synechocystis sp. showed a higher proportion of compromised cells compared to C. vulgaris and P. tricornutum likely due to differences in cell walls composition. Compromised cells could lead to the release of valuable products into the surrounding growth media during flocculation. The residual culture media was recycled once with no impact on cell growth for all treatments and algal species. The flocculation technique was demonstrated at pilot-scale using 350 L microalgal suspension, showing an efficiency of 82–90% at a polyacrylamide dosage of 6.5–10 mg/L. This efficiency and the biomass quality are comparable to the laboratory-scale results. Overall, results indicate that polyacrylamide flocculants work on a wide range of species without the need for pre-treatment. The information generated in this study can contribute to making the microalgae industry more competitive.

This study evaluates the feasibility of a novel rumen membrane bioreactor (rumen MBR) to produce volatile fatty acids (VFA) from crop residues (i.e. lignocellulosic biomass). Rumen MBR can provide a sustainable route for VFA production by mimicking the digestive system of ruminant animals. Rumen fluid was inoculated in a reactor coupled with ultrafiltration (UF) membrane and fed with maize silage and concentrate feed at 60:40% (w/w). Continuous VFA production was achieved at an average daily yield of 438 mg VFA/g substrate. The most abundant VFA were acetic (40–80%) and propionic (10–40%) acids. The majority (73 ± 15%) of produced VFA was transferred through the UF membrane. Shifts in dominant rumen microbes were observed upon the transition from in vivo to in vitro environment and during reactor operation, however, stable VFA yield was maintained for 35 days, providing the first proof-of-concept of a viable rumen MBR.

A proof of concept of using steel-making slag to upgrade biogas to biomethane is demonstrated in this study. Biogas is generated from the anaerobic co-digestion of sewage sludge and beverage waste. The CO2 capture capacity of an alkaline liquor derived from the release of calcium from the steel-making slag is comparable to that of the commercial adsorbent monoethanolamine. Although only 5% of Ca in the steel-making slag was released to the alkaline liquor, 1 ton of steel-making slag could be capable of upgrading 10 m3 of biogas to over 90% methane content. The results also show that pH can be used as a surrogate parameter to monitor and control biogas upgrading. Further research to improve the release of calcium is essential for the acceleration of the weathering process of steel-making slag for subsequent construction applications.

Laccase enzyme from white-rot fungi is a potential biocatalyst for the oxidation of emerging contaminants (ECs), such as pesticides, pharmaceuticals and steroid hormones. This study aims to develop a three-step platform to treat ECs: (i) enzyme production, (ii) enzyme concentration and (iii) enzyme application. In the first step, solid culture and liquid culture were compared. The solid culture produced significantly more laccase than the liquid culture (447 vs. 74 &micro, M/min after eight days), demonstrating that white rot fungi thrived on a solid medium. In the second step, the enzyme was concentrated 6.6 times using an ultrafiltration (UF) process, resulting in laccase activity of 2980 &micro, M/min. No enzymatic loss due to filtration and membrane adsorption was observed, suggesting the feasibility of the UF membrane for enzyme concentration. In the third step, concentrated crude enzyme was applied in an enzymatic membrane reactor (EMR) to remove a diverse set of ECs (31 compounds in six groups). The EMR effectively removed of steroid hormones, phytoestrogen, ultraviolet (UV) filters and industrial chemical (above 90%). However, it had low removal of pesticides and pharmaceuticals.

The current work provided an insight into biofouling and enzyme-based mitigating techniques during the application of membrane-based separation for water and wastewater purification. The study emphasized underlying mechanisms of biofouling formation. The roles of extracellular polymeric substances (EPSs) in the interaction with the membrane surface as well as in biofilm stability and diversity that govern biofouling severity were thoroughly discussed herewith. In addition to EPSs, the quorum sensing (QS) process that regulates the bacterial communication process for biofilm formation and subsequent biofouling was also comprehensively reviewed. The relationship among EPS, QS, and biofouling has been systematically described for the first time in this study. The up-to-date enzyme-based techniques to control and remove biofouling that were derived from the appreciation of the above relationship were critically and comprehensively reviewed before future research directions were proposed for further treatment improvement.

This study examined the removal and enantio-specific fate of a suite of eleven chiral 2-arylpropionic acids (2-APAs) during biological wastewater treatment simulated in a laboratory-scale membrane bioreactor (MBR). Using pure (R)- and (S)- enantiomers in the MBR influent, chiral inversion was determined through the increase in the concentration of the non-dominant enantiomer and changes in the enantiomeric fraction (EF) between the two enantiomers during the treatment process. Effective (> 90%) and similar removal rates between (R)- and (S)- enantiomers were confirmed for eight 2-APAs. In this study, 2-APAs exhibited diverse and distinctive chiral inversion behaviours: two 2-APAs showed (R→S) unidirectional inversion, three 2-APAs showed (S→R) unidirectional inversion, and six 2-APAs showed bidirectional inversion. This is the first study to report chiral inversion behaviours of a comprehensive suite of 2-APAs with a variety of functional groups substituted onto the aryl ring. A decrease in effluent EF over time was observed for two 2-APAs. This study shows that chiral inversion of 2-APAs varies significantly from compound to compound, despite the high similarity in their chemical structures.

This study aims to evaluate the performance of C. vulgaris microalgae to simultaneously recover nutrients from sludge centrate and produce biomass in a membrane photobioreactor (MPR). Microalgae growth and nutrient removal were evaluated at two different nutrient loading rates (sludge centrate). The results show that C. vulgaris microalgae could thrive in sludge centrate. Nutrient loading has an indiscernible impact on biomass growth and a notable impact on nutrient removal efficiency. Nutrient removal increased as the nutrient loading rate decreased and hydraulic retention time increased. There was no membrane fouling observed in the MPR and the membrane water flux was fully restored by backwashing using only water. However, the membrane permeability varies with the hydraulic retention time (HRT) and biomass concentration in the reactor. Longer HRT offers higher permeability. Therefore, it is recommended to operate the MPR system in lower HRT to improve the membrane resistance and energy consumption.

A novel membrane distillation – enzymatic membrane bioreactor (MD-EMBR) system was developed for efficient degradation of trace organic contaminants (TrOCs). Degradation of five TrOCs, namely carbamazepine, oxybenzone, diclofenac, atrazine and sulfamethoxazole was examined using two commercially available laccases (from Trametes versicolor and Aspergillus oryzae ). The MD system ensured complete retention (>99%) of both enzyme and TrOCs. Of particular interest was that the complete retention of the TrOCs resulted in high TrOC degradation by both laccases. Oxybenzone and diclofenac degradation in the MD-EMBR ranged between 80 and 99%. Compared to previously developed EMBRs, as much as 40% improvement in the removal of resistant non-phenolic TrOCs ( e.g., carbamazepine) was observed. Laccase from A. oryzae demonstrated better TrOC degradation and enzymatic stability. With the addition of redox mediators, namely 1-hydroxybenzotriazole (HBT) or violuric acid (VA), TrOC degradation was improved by 10–20%. This is the first demonstration of a laccase-based high retention membrane bioreactor for enhanced biodegradation of TrOCs.

Enzymatic treatment can effectively degrade recalcitrant micro-pollutants in wastewater. However, its industrial application is constrained by the high cost of the purified enzyme preparations. This work introduces a novel technique to directly immobilize the in-house crude enzyme extracts (from P. ostreatus ) onto the functionalized TiO 2 nanoparticle surface. Comprehensive investigations were carried out to understand the interactions between complex crude enzyme extracts and the immobilization support. By simple dilution of the crude enzyme extract, the immobilization efficiency can be significantly improved. The resultant biocatalytic nanoparticles had comparable performance to the immobilized purified commercial enzymes. Finally, the micropollutant degradation capability of the biocatalytic nanoparticles was demonstrated with two micro-pollutants, namely, bisphenol-A and carbamazepine, commonly detected in sewage. The efficient laccase extraction and immobilization on biocatalytic nanoparticles show great promise as a cost-effective alternative to conventional wastewater treatment processes for recalcitrant micro-pollutants.

Global water quantity and quality are anticipated to decrease in the coming decades, as a result of both increasing global populations and the effects of climate change. Reusing and recycling water is a key part of reducing the pressure on our existing water supplies and the aquatic environment. However, the occurrence of nonsteroidal anti-inflammatory drugs (NSAIDs) in secondary, and in some tertiary, treated effluents- and sewage-impacted water bodies is one of the major obstacles for the implementation of water reuse. For several decades, NSAIDs have been extensively used for therapeutic purposes in both humans and domestic livestock. The negative effects of NSAIDs on aquatic biota are just beginning to be realized. Currently, intensive treatments are required to remove effectively NSAIDs from recycled treated effluent in order to minimize or eliminate risks to human health and aquatic environment. In this chapter, we focus the discussion on contemporary methods for NSAID removal including biological, physical, chemical, and combined process that may provide a more effective and efficient alternative.

Composite polycaprolactone–chitosan material was produced by an electrospinning method and used as a support for immobilization of tyrosinase by mixed ionic interactions and hydrogen bonds formation. The morphology of the fibers and enzyme deposition were confirmed by SEM images. Further, multivariate polynomial regression was used to model the experimental data and to determine optimal conditions for immobilization process, which were found to be pH 7, temperature 25 °C and 16 h process duration. Under these conditions, novel type of biocatalytic system was produced with immobilization yield of 93% and expressed activity of 95%. Furthermore, as prepared system was applied in batch experiments related to biodegradation of bisphenol A under various remediation conditions. It was found that over 80% of the pollutant was removed after 120 min of the process, in the temperature range 15–45 °C and pH 6–9, using solutions at concentration up to 3 mg/L. Experimental data collected proved that the stability and reusability of the tyrosinase were significantly improved upon immobilization: the immobilized biomolecule retained around 90% of its initial activity after 30 days of storage, and was still capable to remove over 80% of bisphenol A even after 10 repeated uses. By contrast, free enzyme was able to remove over 80% of bisphenol A at pH 7–8 and temperature range 15–35 °C, and retained less than 60% of its initial activity after 30 days of storage.

This chapter provides an overview on the development and application of aerobic membrane bioreactor (MBR) systems for municipal wastewater treatment in recent years (after 2008). Nutrient removal in aerobic MBR could be improved by combining with anoxic and/or anaerobic processes, or adding biomass carriers. Nevertheless, wide application of aerobic MBR is still limited by micropollutants removal and membrane fouling. Aerobic MBR systems coupled with reverse osmosis or with addition of biomass carriers significantly improve removal of micropollutants. On the other hand, membrane fouling propensity varies with bound extracellular polymer substances, sludge supernatant (polysaccharides), and operating conditions. The presence of micropollutants stimulates the production of soluble microbial products, which aggravates membrane fouling. Application of powdered activated carbon and plastic carriers could enhance sludge properties and effectively mitigate membrane fouling. Future research trends are finally given, such as development of new media and novel flocculants, etc.

High concentrations of antibiotics in swine wastewater pose potentially serious risks to the environment, human and animal health. Identifying the mechanism for removing antibiotics during the anaerobic treatment of swine wastewater is essential for reducing the serious damage they do to the environment. In this study, batch experiments were conducted to investigate the biosorption and biodegradation of tetracycline and sulfonamide antibiotics (TCs and SMs) in anaerobic processes. Results indicated that the removal of TCs in the anaerobic reactor contributed to biosorption, while biodegradation was responsible for the SMs' removal. The adsorption of TCs fitted well with the pseudo-second kinetic mode and the Freundlich isotherm, which suggested a heterogeneous chemisorption process. Cometabolism was the main mechanism for the biodegradation of SMs and the process fitted well with the first-order kinetic model. Microbial activity in the anaerobic sludge might be curtailed due to the presence of high concentrations of SMs.

© 2019 Elsevier B.V. A simple, efficient, and fast settling flocculation technique to harvest microalgal biomass was demonstrated using a proprietary cationic polyacrylamide flocculant for a freshwater (Chlorella vulgaris) and a marine (Phaeodactylum tricornutum) microalgal culture at their mid-stationary growth phase. The optimal flocculant doses were 18.9 and 13.7 mg/g of dry algal biomass for C. vulgaris and P. tricornutum, respectively (equivalent to 7 g per m3 of algal culture for both species). The obtained optimal dose was well corroborated with changes in cell surface charge, and culture solution optical density and turbidity. At the optimal dose, charge neutralization of 64 and 86% was observed for C. vulgaris and P. tricornutum algal cells, respectively. Algae recovery was independent of the culture solution pH in the range of pH 6 to 9. Algal biomass recovery was achieved of 100 and 90% for C vulgaris and P. tricornutum respectively, and over 98% medium recovery was achievable by simple decanting.

© 2019 Elsevier Ltd This study investigated the production of biogas, volatile fatty acids (VFAs), and other soluble organic from lignocellulosic biomass by two microbial communities (i.e. rumen fluid and anaerobic sludge). Four types of abundant lignocellulosic biomass (i.e. wheat straw, oaten hay, lurence hay and corn silage)found in Australia were used. The results show that rumen microbes produced four-time higher VFAs level than that of anaerobic sludge reactors, indicating the possible application of rumen microorganism for VFAs generation from lignocellulosic biomass. VFA production in the rumen fluid reactors was probably due to the presence of specific hydrolytic and acidogenic bacteria (e.g. Fibrobacter and Prevotella). VFA production corroborated from the observation of pH drop in the rumen fluid reactors indicated hydrolytic and acidogenic inhibition, suggesting the continuous extraction of VFAs from the reactor. Anaerobic sludge reactors on the other hand, produced more biogas than that of rumen fluid reactors. This observation was consistent with the abundance of methanogens in anaerobic sludge inoculum (3.98% of total microbes)compared to rumen fluid (0.11%). VFA production from lignocellulosic biomass is the building block chemical for bioplastic, biohydrogen and biofuel. The results from this study provide important foundation for the development of engineered systems to generate VFAs from lignocellulosic biomass.

© 2019 Elsevier Ltd Activated sludge (AS) and return activated sludge (RAS) microbial communities from three full-scale municipal wastewater treatment plants (denoted plant A, B and C) were compared to assess the impact of sludge settling (i.e. gravity thickening in the clarifier) and profile microorganisms responsible for nutrient removal and reactor foaming. The results show that all three plants were dominated with microbes in the phyla of Proteobacteria, Bacteroidetes, Verrucomicrobia, Actinobacteria, Chloroflexi, Firmicutes, Nitrospirae, Spirochaetae, Acidobacteria and Saccharibacteria. AS and RAS shared above 80% similarity in the microbial community composition, indicating that sludge thickening does not significantly alter the microbial composition. Autotrophic and heterotrophic nitrifiers were present in the AS. However, the abundance of autotrophic nitrifiers was significantly lower than that of the heterotrophic nitrifiers. Thus, ammonium removal at these plants was achieved mostly by heterotrophic nitrification. Microbes that can cause foaming were at 3.2% abundance, and this result is well corroborated with occasional aerobic biological reactor foaming. By contrast, these microbes were not abundant (

This study compares the effectiveness of seven redox-mediating compounds namely, 1-hydrozybenzotriazole (HBT), N-hydroxyphthalimide (HPI), 2,2,6,6-Tetramethyl-1-piperidinyloxy (TEMPO), violuric acid (VA), syringaldehyde (SA), vanillin (VA), and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS), which follow distinct oxidation pathways, for the degradation of trace organic contaminants (TrOCs). These redox-mediators were investigated for improved degradation of four TrOCs showing resistance to degradation by crude laccase from the white-rot fungus Pleurotus ostreatus. ABTS and VA achieved the highest degradation of the phenolic compounds (i.e., oxybenzone and pentachlorophenol), whereas the non-phenolic compounds (i.e., naproxen and atrazine) were best removed using VA or HBT. This implies that the non-phenolic compounds are more effectively removed by the radical species generated by the [Formula presented] type mediators (i.e., VA and HBT), while removal of the phenolic compounds may depend more on the stability and the redox potential of the radicals generated from the mediator, irrespective of the type. Notably, enzyme stability was greatly affected by the [Formula presented] type mediators but it was compensated by their rapid degradation capacity. Overall, VA and HBT ([Formula presented] type) appear to be the best mediators for enhanced degradation of the selected compounds without causing significant toxicity in the effluent.

This study aims to examine the flocculation efficiency of Porphyridium purpureum (i.e. a red marine microalga with high content of pigments and fatty acids) grown in seawater medium using polyacrylamide polymers and alkaline flocculation. Polymers Flopam™ and FO3801 achieved the highest flocculation efficiency of over 99% at the optimal dose of 21 mg per g of dry biomass through charge neutralisation and bridging mechanism. The addition of sodium hydroxide, potassium hydroxide, and sodium carbonate also achieved flocculation efficiency of 98 and 91%, respectively, but high doses were required (i.e. > 500 mg per g of dry biomass). Calcium hydroxide was not as effective and could only achieve 75% flocculation efficiency. Precipitation of magnesium hydroxide was identified as the major cause of hydroxide-induced flocculation. On the other hand, sodium carbonate addition induced flocculation via both magnesium and calcium carbonate co-precipitation. The large mass of precipitates caused a sweeping effect and enmeshed the microalgal cells to trigger sedimentation. Cell membrane integrity analysis of flocculated P. purpureum indicated that polyacrylamide polymers led to significant compromised cells (i.e. 96%), compared to the alkaline bases (70–96% compromised cells). These results appear to be the first to demonstrate the high efficiency of polyacrylamide polymer and alkaline flocculation of P. purpureum but at the expense of the biomass quality.

Electrospun materials, due to the possibility of design of their properties, are suitable as supports for enzyme immobilization. Produced biocatalytic systems might be then apply in various biocatalytic reactions, including conversion of pollutants. In our study, electrospun fibers made from nylon 6 was produced, modified and applied as a support for laccase immobilization by adsorption and covalent binding. The systems with immobilized laccase were used in decolorization process of selected dyes, azo dye Reactive Black 5 and the anthraquinone dye Reactive Blue 4. It was found that at from dye solution at concentration 1 mg/L at pH 5, temperature 25 °C, after 24 h of process the efficiency of decolorization of Reactive Blue 4 and Reactive Black 5 reached 77% and 63%, respectively. The storage stability studies showed that after 30 days of storage, the relative activities were 60% and 95% for adsorbed and covalently bonded oxidoreductase respectively. Moreover, after 10 consecutive catalytic cycles adsorbed and covalently bonded laccase retained over 60% and 70% respectively, indicating the possibility of application of the obtained systems on a larger scale for removal of phenolic pollutants from wastewaters.

Water contamination by cadmium (Cd), which is a toxic heavy metal widely used in many industrial processes, is a pervasive environmental problem. This study investigated the removal of Cd by dry cyanobacterium Aphanothece sp cultivar in adsorption columns The effect of inlet Cd concentrations (1.00 – 4.85mg/L), flow rates (0.30-0.60 L/h) and bed height (4.6 -7.2 cm) on the breakthrough characteristics of the adsorption column was investigated. The maximum adsorption capacity and efficiency were found to be 8.20 mg/g and 89.07 %, respectively with a flow rate of 0.60 L/h and 4.85 mg/L inlet concentration of Cd. The fixed bed adsorption data were fitted to three well known fixed bed empirical models namely Thomas, Adam–Bohart and Yoon–Nelson. The experimental results well fitted with the models mentioned above with R2 of greater than 0.98 at different conditions. The regeneration efficiency of benthic cyanobacterium Aphanothece sp cultivar based adsorbent was studied using 0.1 M HCl. Repetitive adsorption–regeneration experiment show that, at the end of the fifth cycle, the desorption efficiency decreased by 21%. Thus, further research is necessary to improve the reusability of dried biomass of cyanobacterium Aphanothece sp adsorbent.

In the concept of a circular economy, wastewater is no longer waste but a resource for water, energy and nutrients. In this study, a hybrid system containing an anaerobic membrane bioreactor (AnMBR) and a microalgal membrane reactor (MMR) was developed to harvest energy, nutrients, and microalgal biomass from food and agribusiness industrial wastewater. The AnMBR removed over 97% of chemical oxygen demand (COD) and generated 4.7 ± 0.15 L (n=80) of biogas equivalent to 2.4 kWh kg−1 COD (feed) d−1. Through anaerobic metabolism, the microorganism in AnMBR generated NH 4 + and PO 4 3 − -rich effluent. Their effluent concentrations were 1.9 and 1.4 times of that in the influent, respectively. NH 4 + and PO 4 3 − -rich effluent was directly used (i.e. without filtration or sterilization) to culture microalgae Chlorella vulgaris in the MMR. . Microalgal biomass production reached up to 700 mg/L after 6 days of operation and nutrient removal rates of above 75% were achieved. However, biomass production and nutrient removal declined towards the end of experiment. The generated biomass was completely harvested using cationic polyacrylamide at the dose of 36 mg g−1 dry weight. Overall, the AnMBR has great potential to produce energy. Future research is needed to intensify the microalgal growth (e.g. genetic modification of strains, addition of plant hormones) in the MMR for continuous operation of the hybrid system.

© 2019, Springer Nature B.V. This study investigated the effects and fate of the antibiotic ciprofloxacin (CIP) at environmentally relevant levels (50–500 µg/L) in activated sludge (AS) microbial communities under aerobic conditions. Exposure to 500 µg/L of CIP decreased species diversity by about 20% and significantly altered the phylogenetic structure of AS communities compared to those of control communities (no CIP exposure), while there were no significant changes upon exposure to 50 µg/L of CIP. Analysis of community composition revealed that exposure to 500 µg/L of CIP significantly reduced the relative abundance of Rhodobacteraceae and Nakamurellaceae by more than tenfold. These species frequently occur in AS communities across many full-scale wastewater treatment plants and are involved in key ecosystem functions (i.e., organic matter and nitrogen removal). Our analyses showed that 50–500 µg/L CIP was poorly removed in AS (about 20% removal), implying that the majority of CIP from AS processes may be released with either their effluents or waste sludge. We therefore strongly recommend further research on CIP residuals and/or post-treatment processes (e.g., anaerobic digestion) for waste streams that may cause ecological risks in receiving water bodies.

© 2018 Elsevier Ltd This study evaluated short- and long-term exposure of activated sludge (AS) microbiome to cetylpyridinium chloride (CPC), a quaternary ammonium compound widely used as biocidal additive or cationic surfactant. Toxicity assay in batch mode showed that CPC (50 μg L−1) inhibited cell growth. However, in a continuous reactor, CPC concentration in the range of 50–500 μg L−1 did not result in any observable impact on the biological activities of the AS microbiome. Similarly, 16S rRNA gene-based community profiling revealed that CPC had no observable impact on microbial diversity. At the phylogenetic structure, Rhodobacter (15 ± 7% of the total) and Asticcacaulis (9 ± 3%) were the only two phyla with increasing population in the 500 μg L−1-exposed reactors. This was also supported by an observation of no major change in the community structure. The reactors could remove >60% of CPC at initial concentrations of 50–500 μg L−1, primarily by adsorption and biodegradation. The enrichment of Rhodobacter and Asticcacaulis genus might contribute to CPC biodegradation and emerge as a potential microbial niche for the removal of CPC.

© 2018 Elsevier Ltd Ciprofloxacin (CIP) is an antibiotic that is widely used to treat bacterial infections and is poorly biodegraded during wastewater treatment. In this study, a CIP-degrading bacterial strain (GLC_01) was successfully retrieved from activated sludge by enrichment and isolation. The obtained bacterial strain shares over 99% nucleotide identity of the 16S rRNA gene with Bradyrhizobium spp. Results show that Bradyrhizobium sp. GLC_01 degraded CIP via cometabolism with another carbon substrate following a first-order kinetics degradation reaction. CIP degradation by Bradyrhizobium sp. GLC_01 increased when the concentration of the primary carbon source increased. The biodegradability of the primary carbon source also affected CIP degradation. The use of glucose and sodium acetate (i.e. readily biodegradable), respectively, as a primary carbon source enhanced CIP biotransformation, compared to starch (i.e. relatively slowly biodegradable). CIP degradation decreased with the increase of the initial CIP concentration. Over 70% CIP biotransformation was achieved at 0.05 mg L−1 whereas CIP degradation decreased to 26% at 10 mg L−1. The phylogenetic identification and experimental verification of this CIP-degrading bacterium can lead to a bioengineering approach to manage antibiotics and possibly other persistent organic contaminants during wastewater treatment.

Redox-mediators such as syringaldehyde (SA) can improve laccase-catalyzed degradation of trace organic contaminants (TrOCs) but may increase effluent toxicity. The degradation performance of 14 phenolic and 17 non-phenolic TrOCs by a continuous flow enzymatic membrane reactor (EMR) at different TrOC and SA loadings was assessed. A specific emphasis was placed on the investigation of the toxicity of the enzyme (laccase), SA, TrOCs and the treated effluent. Batch tests demonstrated significant individual and interactive toxicity of the laccase and SA preparations. Reduced removal of resistant TrOCs by the EMR was observed for dosages over 50 μg/L. SA addition at a concentration of 10 μM significantly improved TrOC removal, but no removal improvement was observed at the elevated SA concentrations of 50 and 100 μM. The treated effluent showed significant toxicity at SA concentrations beyond 10 μM, providing further evidence that higher dosage of SA must be avoided.

Laccase-catalysed degradation of 30 trace organic contaminants (TrOCs) with diverse chemical structure was investigated in an enzymatic membrane reactor (EMR) equipped with an ultrafiltration membrane. Compared to the results from batch incubation tests, the EMR could facilitate degradation of some phenolic and a number of non-phenolic TrOCs. Laccase, which was completely retained by the membrane, formed a dynamic gel layer on the membrane surface onto which TrOCs were adsorbed. EMR investigations with active and heat-inactivated laccase confirmed that the TrOCs retained by the active laccase gel layer were eventually degraded. Redox-mediator addition to the EMR significantly extended the spectrum of efficiently degraded TrOCs, but a limited improvement was observed in batch tests. The results demonstrate the important role of TrOC retention by the enzyme gel layer dynamically formed on the membrane in achieving improved degradation of TrOCs by the mediator-assisted laccase system. Despite following the same hydrogen atom transfer pathway, the mediators tested (syringaldehyde and 1-hydroxybenzotriazole) exhibited TrOC-specific degradation improvement capacity.

This study demonstrates continuous enantiomeric inversion and further biotransformation of chiral profens including ibuprofen, naproxen and ketoprofen by an enzymatic membrane bioreactor (EMBR). The EMBR dosed with laccase showed non-enantioselective transformations, with high and consistent transformation of both ( R )- and ( S )-ibuprofen (93 ± 6%, n = 10 ), but lower removals of both enantiomers of naproxen (46 ± 16%, n = 10 ) and ketoprofen (48 ± 17%, n = 10 ). Enantiomeric analysis revealed a bidirectional but uneven inversion of the profens, for example 14% inversion of ( R )- to ( S )- compared to 4% from ( S )- to ( R )-naproxen. With redox-mediator addition, the enzymatic chiral inversion of both ( R )-/( S )-profens remained unchanged, although the overall conversion became enantioselective: except for ( S )-naproxen, the addition of redox mediator promoted the degradation of ( R )-profens only.

© 2020 Elsevier B.V. The flocculation efficiency of microalgae Chlorella vulgaris for subsequent harvesting was investigated using single flocculants of inorganic salts, synthetic polymer, chitosan and dual flocculants of inorganic salts and chitosan. Synthetic polymer (FlopamTM) could achieve over 90% optical density removal (OD680removal) at a low flocculant dose (20 to 40 mg polymer per litre of algal suspension) through the bridging mechanism and charge neutralisation. Inorganic salts (i.e. ferric chloride and aluminium sulphate) and chitosan individually resulted in low flocculation efficiency (80% flocculation efficiency, significantly higher than the sum of each individual flocculation. The improvement in flocculation efficiency was 57 and 24% respectively for ferric chloride/chitosan and aluminium sulphate/chitosan. Charge neutralisation of microalgal cells by ferric chloride or aluminium sulphate combined with bridging by chitosan produced the synergy.

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.

The performance of two redox mediating compounds, namely 1-hydroxybenzotriazole (HBT) and syringaldehyde (SA), was compared in terms of enhancement of enzymatic degradation of a diverse set of 14 phenolic and 16 non-phenolic trace organic contaminants (TrOCs) and the toxicity of the treated media. Extracellular enzyme extract (predominantly containing laccase) from Trametes versicolor culture achieved efficient degradation (70–95%) of nine phenolic and one non-phenolic TrOCs. Mediator dosing extended the spectrum of efficiently degraded TrOCs to 13 phenolic and three non-phenolic compounds, with moderate improvements in removal of a few other non-phenolic compounds. TrOC removal efficiency improved significantly as the HBT dose was increased from 0.1 to 0.5 mM, while SA achieved similar removal over dosage range of 0.1–1 mM. A particular concern was the toxicity of the treated media (1200–2200 times that of the control) for all SA dosages applied. Overall, HBT at a concentration of 0.5 mM achieved the best removal without raising concern regarding toxicity of the treated media. The results are discussed in the light of the redox potential of the enzyme-mediator cocktail, the balance between the stability and reactivity of the radicals generated and their cytotoxic effects.

This study reports the removal of 30 diverse trace organic contaminants (TrOC) by live (biosorption + biodegradation), intracellular enzyme-inhibited and chemically inactivated (biosorption only) whole-cell preparations and the fungal extracellular enzyme extract (predominantly laccase) from Trametes versicolor (ATCC 7731). Because phenolic substrates are amenable to degradation by laccase, all 14 phenolic TrOC were readily biodegraded. On the other hand, only eight of the 16 non-phenolic TrOC were readily biodegraded while the removal of hydrophilic TrOC (log D < 3) was negligible. With the exception of diclofenac, no non-phenolic TrOC were degraded by the extracellular enzyme extract. The whole-cell culture showed considerably higher degradation of at least seven compounds, indicating the importance of biosorption and subsequent degradation by intracellular and/or mycelium associated enzymes. Improvement (20-90%) of enzymatic degradation of four phenolic and seven non-phenolic TrOC was achieved in the presence of a redox mediator. Compared with the whole-cell culture, mediator-amended extracellular extract achieved better removal of six TrOC, but lower removal of six others. A particular concern was the increased toxicity of the treated media when the redox-mediator was used. In addition to reporting the white-rot fungal removal of two UV filters, three phytoestrogens and a few other pharmaceutically active TrOC for the first time, this study provides unique insights into their removal mechanisms.

This study compared the removal efficiency of 22 widespread trace organic contaminants by a laboratory-scale membrane bioreactor (MBR) with and without direct addition of powdered activated carbon (PAC) into the activated sludge reactor over a period of 312 days. The removal of hydrophilic and biologically persistent trace organic contaminants was immediately improved to above 95% after the addition of PAC into MBR. However, a compound-specific gradual decrease in removal underscored the requirement for the addition of fresh PAC. Adsorption onto PAC-added sludge appeared to play a significant role in the relatively more effective aqueous phase removal of a few resistant compounds such as carbamazepine in this study. A slower reduction in removal efficiency of compounds showing extraordinary persistence such as fenoprop and diclofenac was observed after raising the PAC concentration in the MBR from 0.1 to 0.5 g/L. Nevertheless, comparison of extent of removal in terms of PAC usage indicated the suitability of more frequent dosing of smaller amounts of PAC.

The aim of this study was to demonstrate the complementarity of combining membrane bioreactor (MBR) treatment with UV oxidation or high pressure membrane filtration processes such as nanofiltration (NF) or reverse osmosis (RO) for the removal of trace organic contaminants (TrOC). The results suggest that the removal mechanisms of TrOC by either UV oxidation or NF/RO membrane filtration differ significantly from those of an MBR system. Thus, they can complement MBR treatment very well to significantly improve the removal of TrOC. MBR treatment can effectively remove hydrophobic and readily biodegradable hydrophilic TrOC. The remaining hydrophilic and biologically persistent TrOC were shown to be effectively removed by either UV oxidation or NF/RO membrane filtration. The combination of MBR with UV oxidation or NF/RO membrane filtration resulted in a removal ranging from 85% to complete removal (or removal to below the analytical detection limit) of all 22 TrOC selected in this study. In particular, it is noteworthy that although MBR treatment and direct UV oxidation separately achieved low removal of carbamazepine (a widely reported problematic compound), the combination of these two processes resulted in more than 96% removal.

Previous studies have confirmed significant removal of various trace organic contaminants (TrOCs) by white-rot fungal cultures under sterile batch test conditions. However, little is known about TrOC removal in continuous flow fungal reactors in a non-sterile environment. This study reports the removal of two TrOCs, namely, bisphenol A and diclofenac, by a fungal membrane bioreactor (MBR). Sterile batch tests with "active" (biosorption and biodegradation) and "chemically inactivated" (biosorption only) Trametes versicolor (ATCC 7731) confirmed biodegradation as the main mechanism for the removal of both compounds. An MBR inoculated with T. versicolor was operated in non-sterile conditions for a period of three months during which diclofenac and bisphenol A were continuously added to the synthetic wastewater. Relatively stable removal of bisphenol A (80-90%) and diclofenac (similar to 55%) was achieved by applying a hydraulic retention time of two days, at the bisphenol A and diclofenac loadings of 475 +/- 25 and 345 +/- 112 mu g/L.d, respectively.

This study investigated the removal of trace organic contaminants by a combined membrane bioreactor - granular activated carbon (MBR-GAC) system over a period of 196 days. Of the 22 compounds investigated here, all six hydrophilic compounds with electron-withdrawing functional groups (i.e., metronidazole, carbamazepine, ketoprofen, naproxen, fenoprop and diclofenac) exhibited very low removal efficiency by MBR-only treatment. GAC post-treatment initially complemented MBR treatment very well; however, a compound-specific gradual deterioration of the removal of the above-mentioned problematic compounds was noted. While a 20% breakthrough of all four negatively charged compounds namely ketoprofen, naproxen, fenoprop and diclofenac occurred within 1000-3000 bed volumes (BV), the same level of breakthrough of the two neutral compounds metronidazole and carbamazepine did not occur until 11,000 BV. Single-solute isotherm parameters did not demonstrate any discernible correlation individually with any of the parameters that may govern adsorption onto GAC, such as log D, number of hydrogen-bond donor/acceptor groups, dipole moment or aromaticity ratio of the compounds. The isotherm data, however, could differentiate the breakthrough behaviour between negatively charged and neutral trace organic contaminants.

© 2017, © 2017 Informa UK Limited, trading as Taylor & Francis Group. This study investigated the influence of inorganic salts on enzymatic activity and the removal of trace organic contaminants (TrOCs) by crude laccase from the white-rot fungus Pleurotus ostreatus. A systematic analysis of 15 cations and anions from common inorganic salts was presented. Laccase activity was not inhibited by monovalent cations (i.e. Na + , NH 4+ , K + ), while the presence of divalent and trivalent cations showed variable impact–from negligible to complete inhibition–of both laccase activity and its TrOC removal performance. Of interest was the observation of discrepancy between residual laccase activity and TrOC removal in the presence of some ions. Mg 2+ had negligible impact on residual laccase activity but significant impact on TrOC removal. Conversely, F − showed greater impact on residual laccase activity than on TrOC removal. This observation indicated different impacts of the interfering ions on the interaction between laccase and TrOCs as compared to that between laccase and the reagent used to measure its activity, implicating that residual laccase activity may not always be an accurate indicator of TrOC removal. The degree of impact of halides was in the order of F − > I − > Br − > Cl − . Particularly, the tolerance of the tested laccase to Cl − has important implications for a range of industrial applications.

The removal of trace organics by a membrane bioreactor-granular activated carbon (MBR-GAC) integrated system were investigated. The results confirmed that MBR treatment can be effective for the removal of hydrophobic (log D>3.2) and readily biodegradable trace organics. The data also highlighted the limitation of MBR in removing hydrophilic and persistent compounds (e.g. carbamazepine, diclofenac, and fenoprop) and that GAC could complement MBR very well as a post-treatment process. The MBR-GAC system showed high removal of all selected trace organics including those that are hydrophilic and persistent to biological degradation at up to 406 bed volumes (BV). However, over an extended period, breakthrough of diclofenac was observed after 7320 BV. This suggests that strict monitoring should be applied over the lifetime of the GAC column to detect the breakthrough of hydrophilic and persistent compounds which have low removal by MBR treatment.

The effects of controlled temperature variation in the range of 10–45 °C were assessed in a lab-scale MBR that treated synthetic municipal wastewater spiked with selected micropollutants. The effects were evaluated with respect to total organic carbon (TOC) and total nitrogen (TN) removal, micropollutant removal, sludge growth, level of soluble microbial products (SMPs) in the mixed liquor and membrane fouling. Overall, the temperature shifts caused high variation in the TOC and TN levels in the reactor supernatant, however that in membrane-permeate was relatively more stable, substantiating the robustness of the MBR process. Results regarding the removal of micropollutants at ambient temperature (20 °C) demonstrate an apparent correlation between hydrophobicity, chemical structures and the removal of micropollutants. Temperature variation below and above 20 °C, especially the operation under 45 °C appeared to significantly influence the removal of certain less hydrophobic (log D D > 3.2) was stable under the temperature range of 10–35 °C, however, deteriorated at 45 °C. The temperature shifts were also associated with higher levels of SMP in the mixed liquor which appeared to trigger membrane fouling as evidenced by a rapid increase in transmembrane pressure.