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Microalgae photobioreactor (PBR) is a kind of efficient wastewater treatment system for nitrogen removal. However, there is still an urgent need for process optimization of PBR. Especially, the synergistic effect and optimization of light and flow state poses a challenge. In this study, the computational fluid dynamics is employed for simulating the optimization of the number and length of the internal baffles, as well as the aeration rate of PBR, which in turn leads to the optimal growth of microalgae and efficient nitrogen removal. After optimization, the Light/Dark cycle of the reactor B is shortened by 51.6 %, and the biomass increases from 0.06 g/L to 3.94 g/L. In addition, the removal rate of NH 4 + -N increased by 106.0 % to 1.56 mg L -1  h -1 . This work provides a feasible method for optimizing the design and operational parameters of PBR aiming the engineering application., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Microalgal technology holds great promise for both low C/N wastewater treatment and resource recovery simultaneously. Nevertheless, the advancement of microalgal technology is hindered by its reduced nitrogen removal efficiency in low C/N ratio wastewater. In this work, microalgae and waste oyster shells were combined to achieve a total inorganic nitrogen removal efficiency of 93.85% at a rate of 2.05 mg L -1  h -1 in low C/N wastewater. Notably, over four cycles of oyster shell reuse, the reactor achieved an average 85% ammonia nitrogen removal extent, with a wastewater treatment cost of only $0.092/ton. Moreover, microbial community analysis during the reuse of oyster shells revealed the critical importance of timely replacement in inhibiting the growth of non-functional bacteria (Poterioochromonas_malhamensi). The work demonstrated that the oyster shell - microalgae system provides a time- and cost-saving, environmental approach for the resourceful treatment of harsh low C/N wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Conventional microalgal-bacterial consortia have limited capacity to treat low-C/N wastewater due to carbon limitation and single nitrogen (N) removal mode. In this work, indigenous synergetic microalgal-bacterial consortia with high N removal performance and bidirectional interaction were successful in treating rare earth tailing wastewaters with low-C/N. Ammonia removal reached 0.89 mg N L -1 h -1 , 1.84-fold more efficient than a common microalgal-bacterial system. Metagenomics-based metabolic reconstruction revealed bidirectional microalgal-bacterial interactions. The presence of microalgae increased the abundance of bacterial N-related genes by 1.5- to 57-fold. Similarly, the presence of bacteria increased the abundance of microalgal N assimilation by 2.5- to 15.8-fold. Furthermore, nine bacterial species were isolated, and the bidirectional promotion of N removal by the microalgal-bacterial system was verified. The mechanism of microalgal N assimilation enhanced by indole-3-acetic acid was revealed. In addition, the bidirectional mode of the system ensured the scavenging of toxic byproducts from nitrate metabolism to maintain the stability of the system. Collectively, the bidirectional enhancement system of synergetic microalgae-bacteria was established as an effective N removal strategy to broaden the stable application of this system for the effective treatment of low C/N ratio wastewater.

Rare earth element tailings (REEs) wastewater, which has the characteristics of high ammonia nitrogen (NH 4 + -N) and low COD. It can cause eutrophication and biotoxicity in water which is produced in high volumes, requiring treatment before final disposal. Microalgae-Bacteria symbiotic (MBS) system can be applied in REEs wastewater, but its low extent of nitrogen removal and instability limit its application. By adding biodegradable carrier as both carbon source and carrier, the system can be stabilized and the efficiency can be improved. In this work, the extent of NH 4 + -N removal reached 100% within 24 h in a MBS system after adding loofah under optimal conditions, and the removal rate reached 127.6 mg NH 4 + -N·L -1 ·d -1 . In addition, the carbon release from loofah in 3 d reached 408.7 mg/L, which could be used as a carbon source to support denitrification. During 90 d of operation of the MBS system loaded with loofah, the effluent NH 4 + -N was less than 15 mg/L. At phylum level, Proteobacteria were dominant which accounted for 78.2%. Functional gene analysis showed that enhancement of microalgae assimilation was the main factor affecting NH 4 + -N removal. This work expands our understanding of the enhanced role of carbon-based carriers in the denitrification of REEs wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Low C/N municipal wastewater is difficult to be treated effectively via traditional biological methods, leading to concentrations of pollutants in effluent far exceeding increasingly strict standards. In this work, we propose a novel microalgae-bacteria tandem-type process to simultaneously remove ammonia nitrogen (NH 4 + -N) and phosphorus (P) from municipal wastewater. A 4.5 L microalgae-bacteria tandem-type reactor was constructed and operated stably for 40 days. The removal efficiencies of NH 4 + -N and P reached 97.5% and 92.9%, respectively, effluent concentrations were 0.53 and 0.17 mg/L on average, which met the Environmental quality standards for surface water in China (GB 3838-2002). Remarkably, microalgae ponds accounted for 69.3% and 76.3% of the overall NH 4 + -N and P removal via microalgae assimilation. Furthermore, 16 S rRNA gene amplicon sequencing revealed the abundance of bacteria changed, suggesting that the presence of microalgae leads to some species extinction and low-abundance bacteria increase. This work demonstrated that the microalgae-bacteria tandem-type processes can be efficient and widely applied in the advanced treatment of municipal wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Low nitrogen (N) removal efficiency limits the potential of microalgae technology for the treatment of high nitrogen and low carbon rare earth tailings (REEs) wastewater. In this study, waste corncob was utilized as a biocarrier immobilizing Chlamydopodium sp. microalgae to realize high-efficient treatment of the REEs wastewater. In only 2.5 d, corncob-immobilized microalgae allowed the residual concentrations of N lower than the emission standards, and ammonia nitrogen (NH 4 + -N) removal rate is 83.3 mg L -1 ·d -1 , total inorganic nitrogen (TIN) removal rate is 86.7 mg L -1 ·d -1 , which was 18.5 times that of the previously-reported microalgae (4.68 mg L -1 ·d -1 ). Compared with other microalgae immobilization carriers, corncob possesses the ability to release available carbon sources for microalgae. Composition analysis and sugar verification experiments showed that the main content of TOC released by corncob was monosaccharide, and in a certain range, the removal rate of N was positively correlated with the TOC concentration. The utilization of biomass wastes with dual functions as biological carriers has great potential to improve the performance of microalgae, and is conducive to the development of engineering applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Bio-electrochemically assisted anaerobic methanogenic systems (An-BES) are highly effective in wastewater treatment for methane production and degradation of toxic compounds. However, information on the treatment of antibiotic-bearing wastewater in An-BES is still very limited. This study therefore investigated the effect of tetracycline (TC) on the performance, microbial community, as well as functional and antibiotic resistance genes of An-BES. TC at 1 and 5 mg/L inhibited methane production by less than 4.8% compared to the TC-free control. At 10 mg/L TC, application of 0.5 and 1.0 V decreased methane production by 14 and 9.6%, respectively. Under the effect of 1-10 mg/L TC, application of 1.0 V resulted in a decrease of current from 42.3 to 2.8 mA. TC was mainly removed by adsorption; its removal extent increased by 19.5 and 32.9% with application of 0.5 and 1.0 V, respectively. At 1.0 V, current output was not recovered with the addition of granular activated carbon, which completely removed TC by adsorption. Metagenomic analysis showed that propionate oxidizing bacteria and methanogens were more abundant in electrode biofilms than in suspended culture. Antibiotic resistance genes (ARGs) were less abundant in biofilms than in suspended culture, regardless of whether voltage was applied or not. Application of 1.0 V resulted in the enrichment of Geobacter in the anode and Methanobacterium in the cathode. TC inhibited exoelectrogens, propionate oxidizing bacteria, and the methylmalonyl CoA pathway, leading to a decrease of current output, COD consumption, and methane production. These findings deepen our understanding of the inhibitory effect of TC in An-BES towards efficient bioenergy recovery from antibiotic-bearing wastewater, as well as the response of functional microorganisms to TC in such systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Microbial methane oxidation is the major biological methane (CH 4 ) sink in the carbon cycle. Methanotrophs can use various electron acceptors in addition to oxygen; understanding the role and contribution of methanotrophs is thus an important topic. However, anaerobic oxidation of methane (AOM) mediated by methanotrophs is poorly explored and understood. This article summarizes the role aerobic methanotrophic bacteria play in AOM. Though AOM was originally considered to be mediated by anaerobic methanotrophic archaea, intra-aerobic methane-oxidizing bacteria (Candidatus Methylomirabilis oxyfera) appear to be involved in nitrite-dependent AOM. In addition, aerobic methanotrophs of the Methylomonadaceae and Methylocystaceae, are more versatile than previously assumed and can also be involved in nitrate/nitrite- or mineral oxide-dependent AOM under oxygen-limitation. Furthermore, the simultaneous reduction of nitrous oxide and oxidation of CH 4 may be another new metabolic trait of aerobic methanotrophs. We discuss the potential metabolic pathways of CH 4 oxidation under hypoxic conditions. It is of great ecological importance not only for the quantification of CH 4 oxidation and emissions, but also for the definition of a new function of aerobic methanotrophs in anaerobic/hypoxic environments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Peracetic acid (PAA) has been widely used as a disinfectant in many industries. However, information related to the potential inhibitory effect of PAA solutions (PAA and H 2 O 2 ) on biological wastewater treatment processes is very limited. The work reported here assessed the effect of PAA and H 2 O 2 solutions on nitrification kinetics and inhibition, cellular level responses and gene expression of a suspended-growth nitrifying culture. The initial ammonia removal and nitrate production rates significantly decreased at 1/0.14 to 3/0.42 mg/L PAA/H 2 O 2 . H 2 O 2 up to 3 mg/L did not impact nitrification, cell viability or related respiratory activities; thus, the impact of the PAA solution is attributed to PAA alone or in some combination with H 2 O 2 . Nitrification inhibition by PAA was predominantly related to enzyme inhibition, rather than to loss of cell viability and/or cell lysis. PAA and H 2 O 2 negatively affected Nitrosomonas but resulted in Nitrosospira enrichment. Most nitrogen metabolism-related genes (e.g., hydroxylamine oxidoreductase and nitrite oxidoreductase genes) as well as oxidase genes (e.g., cytochrome c oxidase, catalase-peroxidase, and peroxidase genes) were upregulated in PAA- and H 2 O 2 -amended cultures. Major ATPase genes were downregulated while ATP synthase genes upregulated under the effect of PAA and/or H 2 O 2 . Upregulation of ATP-dependent protease genes indicates protein damage predominantly caused by PAA rather than H 2 O 2 . The transcriptional level of genes related to cell division and DNA repair did not show a particular pattern; thus, cell division functionality and DNA integrity were not significantly affected by PAA or H 2 O 2 . The results of this study have significant implications in the design and operation of effective biological nitrogen removal systems for the treatment of PAA-bearing wastewater., (Copyright © 2022. Published by Elsevier Ltd.)

Manganese oxide (MnOx) mediated ammonium (NH 4 + ) oxidation in wetlands is receiving increased interest; however, the biochemical mechanisms of this process are vague due to only few studies have focused on terrestrial ecosystems. In this study, three subsurface flow constructed wetlands (CWs), high/low content of Mn-sand CW (HMn-CW/LMn-CW) and quartz sand CW (C-CWs), were set up to explore the extent of ammonium nitrogen (NH 4 + -N) removal and underlying mechanisms. According to the surface characteristics of Mn-sand, MnOx nanospheres were loaded as birnessite on the sand, while changes of the Mn/N contents indicated involvement of Mn-sand in NH 4 + -N removal. During the 120-day operation, higher extent of NH 4 + -N removal with decreased nitrous oxide (N 2 O) emission was achieved in the HMn-CW (76%) than in the LMn-CW (73%) and C-CW (67%). According to the distribution of nitrogen compounds and Mn 2+ , Mn-sand in the HMn-CW delayed oxidation of NH 4 + and production of nitrate and nitrite. High abundance of Zooloea and Psychrobacter was observed in the Mn-sand layer of HMn-CW, corresponding to a higher observed NH 4 + -N removal. NH 4 + oxidation to hydroxylamine and then to nitrite was enhanced in HMn-CW due to ammonia monooxygenase genes being promoted. The decrease of N 2 O emission was closely related to the genus TM7a, verified by Pearson correlation analysis. Our findings expand the knowledge of MnOx-mediated NH 4 + oxidation in wetlands and support the potential application of manganese oxide for effective nitrogen removal in CWs., (Copyright © 2022. Published by Elsevier Ltd.)

The objective of this study was to investigate the benefits of co-digestion of a sludge-mix of primary sludge (PS)/thickened waste activated sludge (TWAS) with concentrated fat-oil-grease (FOG) over a wide range of FOG/sludge-mix volumetric feed ratios. The biodegradability (i.e., COD to methane conversion) of PS, TWAS, sludge-mix, and FOG was 43.0, 38.6, 41.8, and 97.7%, respectively, with a pseudo first-order rate of 0.13, 0.12, 0.13, and 0.18 d -1 , respectively. Batch co-digestion of sludge-mix and FOG at COD ratios ranging from 93.2:6.8 to 27.3:72.7% resulted in methane production linearly correlated to both the total waste blend and FOG COD feed concentration. An enhanced extent of degradation of the sludge-mix COD to as much as 10.9% (increased from 42.2 to 53.1%) and an increased degradation rate by 17% (increased from 0.12 to 0.14 d -1 ) was observed when the feed FOG COD was 18.5% of the total waste COD feed. Overall, co-digestion of mixed municipal sludge with FOG is feasible and recommended to meet target biogas/methane levels at municipal wastewater treatment facilities taking into account the trade-off between energy production and solids destruction to fit their particular needs., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

The discharge of rare earth element (REE) tailings wastewater results in serious ecological deterioration and health risk, due to high ammonia nitrogen, and strong acidity. The low C/N ratio makes it recalcitrant to biodegradation. Recently it has been shown that microalgal technology has a promising potential for the simultaneous harsh wastewater treatment and resource recovery. However, the low nitrogen removal rate and less biomass of microalgae restricted its development. In this work, Chlorococcum sp. was successfully isolated from the rare earth mine effluent. The microalgae was capable of enhancing nitrogen contaminants removal from REEs wastewater due to the carbonate addition, which simulated the activity increase of carbonic anhydrase (CA). The total inorganic nitrogen (TIN) removal rate reached 4.45 mg/L h -1 , which compared to other microalgal species, the nitrogen removal rate and biomass yield were 7.8- and 4.9-fold higher, respectively. Notably, high lipid contents (mainly triglycerides, 43.85% of dry weight) and a high biomass yield were obtained. Meanwhile, the microalgae had an excellent settleability attributed to higher extracellular polymeric substance (EPS) formation, leading to easier resource harvest. These results were further confirmed in a continuous-flow photobioreactor with a stable operation for more than 30 days, indicating its potential for application., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Greenhouse gas (GHG) emissions from constructed wetlands (CWs) lower the environmental and ecological benefits of CWs and thus have raised increasing environmental concern. To prevent GHGs emissions, it is important to assess and quantify the correlation of GHGs emission and microbial carbon and nitrogen transformations. In this study, two typical wetland substrate samples (mud sampled from Xiaomei River CW and sand sampled from Dongwen River CW) were used to build lab-scale vertical subsurface flow CW microcosms, labeled as XRCW and DRCW, respectively. The mean COD removal rate of the DRCW group (76.1%) was higher than that of XRCW group (60.6%). Both groups achieved a high extent of nitrogen nutrient removal, indicating a higher metabolic activity of nitrifying and denitrifying microorganisms in the system, especially in XRCW. The mean emission fluxes of N 2 O, CH 4 and CO 2 in the XRCW group were 52.7 μg/m 2 -h, 1.6 mg/m 2 -h and 100.4 mg/m 2 -h, which were higher than that in the DRCW group (30.0 μg/m 2 -h, 1.0 mg/m 2 -h and 28.0 mg/m 2 -h, respectively). The relation of GHG emissions to microbial carbon and nitrogen transformation was assessed by genomics and functional analysis. The release of GHGs by the XRCW group had a positive correlation with the relative abundance of Proteobacteria, while for the DRCW group a positive correlation was found with the relative abundance of Cyanobacteria. Nitrogen fixation by Cyanobacteria could be an approach to reduce GHG emissions. The release of CH 4 and CO 2 was positively correlated with glucose metabolism. N 2 O gas emission was affected by the species of denitrifiers. This study is of great importance to clarify the emissions of GHGs in vertical subsurface flow CWs, as it is relating to microbial carbon and nitrogen transformation. The connection is of great significance to control the emission of GHGs in wetlands., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Methanogenic bioelectrochemical systems (BESs) can convert carbon dioxide (CO 2 ) to methane (CH 4 ) and may be used for anaerobic digester biogas upgrading. However, the effect of hydrogen sulfide (H 2 S), a common biogas component, on BES performance is unknown. Thus, the objective of this study was to assess the effect of H 2 S addition to the cathode headspace on BES performance at a range of initial gas-phase H 2 S concentrations (0-6% v/v), as well as its effect on the anode and cathode microbial communities. As the initial cathode headspace H 2 S increased from 0 to 2% (v/v), biocathodic CH 4 production increased by two-fold to 3.56 ± 0.36 mmol/L-d, due to dissolved H 2 S transport from the cathode to the anode where H 2 S was oxidized. Elemental sulfur and sulfate were H 2 S oxidation products detected in the anode. Above 3% initial cathode headspace H 2 S, biocathodic CH 4 production declined due to inhibition. A phylotype most closely related to Methanobrevibacter arboriphilus dominated the cathode archaeal communities. In the sulfide-amended BES, a phylotype similar to the exoelectrogen Ochrobactrum anthropi was enriched in both the anode and cathode, whereas phylotypes related to sulfate-reducing and sulfur oxidizing Bacteria were detected in the bioanode. Thus, sulfide transport and oxidation in the anode play an important role in methanogenic BESs treating sulfide-bearing biogas., (Copyright © 2021 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Hydrothermal treatment (HT) is a promising technology to enhance anaerobic digestion (AD) of municipal sludge. However, the capacity of pre- and inter-stage HT (i.e., HT-AD and AD-HT-AD, respectively) to enhance the digestibility of municipal sludge has not been sufficiently explored. This study compared the efficacy of pre- and inter-stage HT performed from 90 to 185°C to enhance methane production from a mixture of primary sludge and waste activated sludge using mesophilic (35°C) biochemical methane potential tests. In both configurations, sludge solubilization increased with HT temperature. HT-AD, and to a greater extent AD-HT-AD, increased the release of ammonium nitrogen. Even though HT at 185°C dramatically increased sludge solubilization, the overall specific methane yield with HT at 185°C was lower than or comparable to that at lower HT temperatures in the HT-AD and AD-HT-AD configurations, respectively. Up to 155°C HT, the overall specific methane yield with the HT-AD configuration was higher by 4.9%-8.3% compared to the AD-HT-AD configuration. However, when the HT energy was considered, compared to the control (i.e., AD of sludge without HT), the net energy gain (ΔE) decreased as the HT temperature increased, becoming negative at an HT of 185°C. The AD-HT-AD configuration resulted in a higher overall volatile solids destruction (by 8.1 to 20.1%). In conclusion, for municipal sludge with a relatively high ultimate digestibility, as was the case in this study, HT-AD is preferable as it has a smaller footprint and is easier to operate than the AD-HT-AD configuration. However, given the significantly higher volatile solids destruction in the AD-HT-AD configuration, compared to the HT-AD configuration, AD-HT-AD may be more beneficial considering post-AD sludge handling processes. PRACTITIONER POINTS: Hydrothermal treatment (HT) increased the rate and extent of methane production from municipal sludge mixture. 155°C was the optimal temperature for either pre- or inter-stage HT to increase biogas production. Pre- and inter-stage HT resulted in comparable ultimate methane production. Pre-stage HT is preferable to inter-stage HT (smaller footprint, easier to operate). AD-HT-AD resulted in significantly higher volatile solids destruction compared to the HT-AD configuration., (© 2021 Water Environment Federation.)

Methane (CH 4 ) and nitrous oxide (N 2 O) are the most powerful greenhouse gases globally; recent emissions exceed previous estimates. The potential link between N 2 O reduction and CH 4 oxidation in anoxic wetland sediments would be a sink for both gases, which has attracted broad attention. To explore the simultaneous N 2 O and CH 4 biotransformation, wetland sediments were used to inoculate an enrichment reactor, continuously fed with CH 4 and N 2 O for 500 days. After enrichment, the CH 4 oxidation rate reached 2.8 μmol·g - 1 dw ·d - 1 , which was 800-fold higher than the rate of the wetland sediments used as inoculum. Moreover, stable isotopic tracing proved CH 4 oxidation was driven by N 2 O consumption under anoxic conditions. Genomic sequencing showed that the microbial community was dominated by methanotrophs. Species of Methylocaldum genus, belonging to γ-Proteobacteria class, were significantly enriched, and became the predominant methanotrophs. Quantitative analysis indicated methane monooxygenase and nitrous oxide reductase increased by 38- and 8-fold compared to the inoculum. As to the potential mechanisms, we propose that N 2 O-driven CH 4 oxidation was mediated by aerobic methanotrophs solely or along with denitrifying bacteria under hypoxia. Electrons and energy are generated and transferred in the oxidative phosphorylation pathway. Our findings expand the range of electron acceptors associated with CH 4 oxidation as well as elucidate the significant role of methanotrophs relative to both carbon and nitrogen cycles., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021. Published by Elsevier Ltd.)

Peracetic acid (PAA) has been widely used as a disinfectant in many industries; its use in poultry processing is steadily increasing. However, information related to the potential inhibitory effect of PAA solutions (PAA and H 2 O 2 ) on biological wastewater treatment processes used by the poultry processing industry is extremely limited. The work reported here assessed the long-term effect of PAA solution on aerobic degradation and nitrification in three bioreactors fed with poultry processing wastewater by quantifying the extent of COD removal and nitrification rates. Changes in culture viability, intracellular reactive oxygen species (ROS), and microbial community structure were also evaluated. COD removal and nitrification were not affected by H 2 O 2 and PAA solutions added to the wastewater before feeding (indirect addition). However, both processes were significantly affected by high levels of H 2 O 2 (i.e., 27 mg/L) and PAA solution (i.e., 60/8.4 mg/L PAA/H 2 O 2 ) directly added to the reactors. Directly added PAA/H 2 O 2 at 40/5.6 mg/L was the lowest dose resulting in nitrification inhibition. Fast recovery of COD removal and nitrification was observed when direct addition of H 2 O 2 and PAA solution ended. Cell viability measurements revealed that the negative impact on nitrification was predominantly attributed to enzyme inhibition rather than to loss of cell viability. The impact on nitrification was not related to intracellular ROS levels. Microbiome analysis showed major shifts in community composition during the long-term addition of H 2 O 2 and even more with PAA addition. No significant time-trend change in the relative abundance of ammonia-oxidizing bacteria or nitrite-oxidizing bacteria was observed, further supporting the conclusion that the negative impact on nitrification was attributed mainly to enzyme inhibition., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

4-Hydroxybenzoic acid (HBA) is commonly found at high concentrations in waste streams generated by the thermochemical conversion of lignocellulosic biomass to bio-oils and biofuels. The objective of this study was to systematically assess the biotransformation of HBA in the bioanode of a microbial electrolysis cell (MEC) for the production of renewable cathodic H 2 . A mixed, denitrifying culture, enriched with HBA as the sole electron donor, was used as the anode inoculum. MEC electrochemical performance, H 2 yield, HBA biotransformation pathways and products, and the bioanode suspended and biofilm microbial communities were examined. In the absence of nitrate, 60%-100% HBA was converted to phenol, which persisted, resulting in very limited exoelectrogenesis. Under nitrate-reducing conditions, complete HBA degradation was achieved in the MEC bioanode with very low phenol production, resulting in the production of cathodic H 2 . The predominant bacterial genus in the MEC bioanode (relative abundance 33.4%-41.9%) was the denitrifier Magnetospirillum , which uses the benzoyl-CoA pathway to degrade aromatic compounds. Geobacter accounted for 5.9-7.8% of the MEC bioanode community. Thus, active nitrate reduction in the MEC bioanode led to complete HBA degradation, resulting in a higher extent of exoelectrogenesis and cathodic H 2 production. The results of this study provide mechanistic insights into a productive use of HBA and other phenolic compounds typically found in waste streams resulting from the thermochemical conversion of lignocellulosic biomass to biofuels.

Anaerobic digestion (AD) combined with hydrothermal treatment (HT) is an attractive technology for sewage sludge treatment and resource recovery. The fate and distribution of heavy metals in the sludge during combined HT/AD significantly affect the sludge final disposal/utilization options, yet such information is still lacking. This study systematically characterizes the transformation of important heavy metals Cu, Zn, and Cr in sewage sludge during AD with pre- or interstage HT (i.e., HT-AD or AD-HT-AD, respectively). Complementary sequential chemical extraction and X-ray absorption spectroscopy were used to characterize the speciation and mobility of metals. For the HT-AD system, both Cu and Zn predominantly occur as sulfides in HT hydrochars. Subsequent AD favors the formation of Cu 2 S and partial transformation of nano-ZnS to adsorbed and organo-complexed Zn species. HT favors the formation of Cr-bearing silicates in hydrochars, whereas Fe(III)-Cr(III)-hydroxide and Cr(III)-humic complex are the predominant Cr species in AD solids. Similar reaction pathways occur in the AD-HT-AD system with some minor differences in metal species and contents, as the first-stage AD changed the sludge matrix. These findings have important implications for understanding the fate and mobility of heavy metals in sludge-derived hydrochars and AD solids.

Tetracycline (TC) transformation in the anode of an air cathode microbial fuel cell (MFC) and in the cathode of an MFC-Fenton system was investigated. TC at 10 mg/L in the anolyte was removed by 43-74% in 14-d cycles, mainly attributed to adsorption. The electrochemical activity, COD and acetate consumption of the anodic biofilm were inhibited by TC; inhibition was reversed when TC addition was stopped. Over 84 d of MFC operation with TC, Geobacter and Mycobacterium in the anode biofilm decreased, while Janthinobacterium and Comamonas increased. Over 99% of TC at 10-40 mg/L was removed within 8 h in the MFC-Fenton cathode. O 2 - •/HO 2 • and •OH were responsible for the cathodic TC degradation. The maximum current was 0.93 mA (at 250 Ω) and increased by 36.3% by the MFC-Fenton reaction. Cathodic MFC-Fenton is an efficient and energy-saving process for TC removal, compared to slow and problematic anodic TC bio-oxidation., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The individual and combined effects of sulfamethoxazole (SMX) and oxytetracycline (OTC) on an enhanced biological phosphorus removal (EBPR) system was investigated. OTC at 5 mg/L resulted in filamentous bulking with a collapse of EBPR system. P removal decreased to 44.8% and COD was mostly removed during the aerobic phase. SMX and OTC had antagonistic effects in EBPR system. The inhibitory effect of SMX and SMX + OTC on P removal, COD removal, glycogen transformation and extracellular polymeric substances content was reversible with prolonged operation, accompanied with increase of polyphosphate accumulating organisms. The presence of nitrification inhibitor allylthiourea, high pH and low tetX abundance limited the removal of SMX and OTC. The bacterial community structure, antibiotic resistance genes abundances and genes functions were also investigated by metagenomic analysis. The results of this study offer insights into the individual and combined environmental risks of SMX and OTC, and their impact on EBPR., (Copyright © 2020. Published by Elsevier Ltd.)

BES biogas upgrading studies have typically used bicarbonate or commercial gas mixtures as a biocathode substrate instead of anaerobic digester biogas. Therefore, the objective of this study was to (i) compare the performance of a methanogenic BES between CO 2 -fed and biogas-fed cycles; (ii) investigate possible factors that may account for observed performance differences; and (iii) assess the performance of a biogas-fed biocathode at various applied cathode potentials. The maximum 1-d CH 4 production rate in a biogas-fed biocathode (3003 mmol/m 2 -d) was 350% higher than in a CO 2 -fed biocathode (666 mmol/m 2 -d), and the biogas-fed biocathode was capable of maintaining high performance despite a variable biogas feed composition. Anode oxidation of reduced gases (e.g., CH 4 and H 2 S) from biogas may theoretically contribute 4% to 35% of the total charge transfer from anode to cathode at applied cathode potentials of -0.80 to -0.55 V (vs SHE). The introduction of biogas did not significantly change the biocathode archaeal community (dominated by a Methanobrevibacter sp. phylotype), but the bacterial community shifted away from Bacteroidetes and toward Proteobacteria , which may have contributed to the improved performance of the biogas-fed system. This study shows that anaerobic digester biogas is a promising biocathode feedstock for BES biogas upgrading.

Anaerobic digestion (AD) with hydrothermal (HT) pretreatment is an emerging technology for enhanced resource recovery from sewage sludge. This study investigates the speciation of Fe, P, and S during sequential HT-AD treatment of sewage sludge using sequential chemical extraction, X-ray diffraction, and X-ray absorption spectroscopy. Results suggest strong correlations between Fe and P species as well as Fe and S species, affecting the solubility and bioavailability of each other. For instance, much vivianite formed in the hydrochars after HT treatment at low temperature, while more strengite precipitated at higher HT temperature. During the subsequent AD process, microbial reduction of strengite and other Fe(III) species led to the formation of more vivianite, with concurrent P release into the solution and adsorption onto other minerals. HT pretreatment of sewage sludge had a weak effect on the sulfidation of Fe during the AD process. This work has important implications for understanding the nutrient speciation and availability in sludge-derived hydrochars and AD solids. It also provides fundamental knowledge for the selection and optimization of HT pretreatment conditions for enhanced resource recovery through sequential HT-AD process.

Plant-derived materials as environmentally friendly biosorbents to remove heavy metals from wastewater have been extensively studied. However, the chemical oxygen demand (COD) increase caused by the plant-derived biosorbent has not been considered previously. In this study, water hyacinth was used as biosorbent to remove Cd(II) from wastewater. About 66% of Cd(II) was removed by the biosorbent with a maximum biosorption capacity (q max ) of 21.6 mg g -1 . However, the COD of the filtrate increased from 0 to 292 mg L -1 during this process. Subsequently, endophytes, microalgae and the microalgae-endophyte symbiotic system (MESS) were assessed for the simultaneous Cd(II) and COD removal. Among these three systems, the MESS achieved the best performance. After 3 d of inoculation, the extent of total Cd(II) removal increased to 99.2% while COD decreased to 77 mg L -1 . This study provides a new insight into the application of a plant-derived biosorbent in combination with microalgae and endophytes for the effective treatment of heavy metal-bearing wastewater., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Tetracycline (TC) as an emerging contaminant has raised serious concerns about its toxicity and removal in wastewater treatment processes. The more toxic transformation products of TC, 4-epitetracycline (ETC), anhydrotetracycline (ATC) and 4-epianhydrotetracycline (EATC) are also widely detected. This study investigated the antibacterial and bactericidal activity of TC, ETC, ATC, EATC against Shewanella sp, using Escherichia coli and Pseudomonas aeruginosa strains as quality controls. Further, batch assays were conducted to investigate the inhibition of these antibiotics on the phosphorus removal of the Shewanella strain, and removal mechanisms of TC and its transformation products (TCs). The inhibition on phosphorus removal by the Shewanella strain at 20 mg L -1 was in the order of ATC > EATC > TC > ETC. COD removal, poly-P accumulation and glycogen synthesis by the Shewanella strain were also inhibited. Biodegradation was the main removal mechanism of TC and ETC, while adsorption was the main one of ATC and EATC. This study helps to further understand the structure-activity relationship of TC., Competing Interests: Declaration of competing interest The authors declare no financial/commercial conflicts of interest., (Copyright © 2019. Published by Elsevier Ltd.)

Global expectation for sustainability has prompted the transition of practices in wastewater treatment plants toward not only waste management but also energy and nutrient recovery. It has been shown that low-temperature hydrotherm (HT) treatment can enhance downstream biogas production via anaerobic digestion (AD). Yet, because the application of combined HT and AD is still at an early stage, a systematic understanding of the dynamic speciation evolution of important elements is still lacking. This study investigates energy and nutrient recovery from sewage sludge and swine manure via combined HT-AD treatment. Bench-scale investigation was conducted to evaluate biogas production and understand the dynamic evolution of organic carbon (C) and phosphorus (P) speciation. C and P speciations were characterized using complementary chemical and spectroscopic techniques, including 13 C nuclear magnetic resonance (NMR) spectroscopy, P X-ray absorption near edge structure (XANES) spectroscopy, and sequential chemical extraction. Results from this study suggest that low-temperature HT pretreatment can achieve enhanced biogas production for sludge compared to the minimal effect on the biogas production from manure. It also provides guidance for P recovery from liquid digestate and solid residue after the AD process.

Acidic rare earth element tailings (REEs) wastewater with high nitrogen and low COD is the most serious and yet unsolved environmental issue in the rare earth mining industry. The effective and cheap remediation of NH 4 + -N and NO 3 - -N from the REEs wastewater is still a huge challenge. This harsh wastewater environment results in the difficulty for common microbes and microalgae to be survived. In this work, a novel highly tolerant co-flocculating microalgae (the combination of Scenedesmus sp. and Parachlorella sp.) was successfully isolated from the rare earth mine effluent through three-year cultivation. The removal efficiency of total inorganic nitrogen (TIN) by the co-flocculating microalgae cultivation was as high as 90.9%, which is 1.9 times than the average removal efficiency (47.9%) of previously-reported microalgae species in the wastewater with COD/N ratio ranging from 0 to 1. Thus, the residual concentrations of NH 4 + -N and TIN could reach the Emission Standards of Pollutants from Rare Earths Industry (GB 26451-2011). Along with the high N removal performance, other related characteristics of the co-flocculating microalgae were also revealed, such as high tolerance towards high NH 4 + -N and strong acid, rapid growth and sedimentation, and simultaneous removal of NH 4 + -N and NO 3 - -N. These algae characteristics were ascribed to the specific co-flocculating community structure covered by extracellular polymeric substances., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Trial-and-error method is widely used to seek an efficient adsorbent, although it is time- and money-consuming. Rationally design of functional materials via theoretical calculation is an emerging and appealing strategy in material science. However, exploiting of theoretical calculation for assistance of adsorbent design is rarely to be attempted despite it is usually utilized to explore the adsorption mechanism. In this work, density functional theory (DFT) calculation is exploited to design an adsorbent with high adsorption capacity and selectivity. The well-known palladium ion-imprinted polymer (IIP) was used as a model adsorbent. Then, three types of given adsorption configurations (a-Pd-IIP, b-Pd-IIP and c-Pd-IIP) were optimized. Further, their adsorption energies were calculated by DFT, which were -13.978 eV for b-Pd-IIP, -8.764 eV for a-Pd-IIP and -3.587 eV for c-Pd-IIP, respectively. The correlation coefficient (R 2 ) between the theoretical adsorption energy and the experimental adsorption capacity reached to as high as 0.985. In addition, the dynamics and selectivity experimental results further consolidated the tendency of the calculation result. All these results demonstrate that the adsorption energy derived from DFT calculations is an important factor in guiding the design of IIPs., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Bioelectrochemical systems (BESs) possess a great potential for simultaneous wastewater treatment and energy recovery. Rational construction of electrode materials could significantly improve the BESs performance. Three-dimensional macroporous electrode interface with high conductivity is highly desirable but challenging. In this work, we report a hierarchically nanostructured reduced graphene oxide nanosheets-polypyrrole (rGO@PPy) electrode via one-step electrodeposition technique. The prepared electrode was comprehensively studied by scanning/transmission electron microscopy, Raman spectroscopy, X-ray diffraction and electrochemical measurements, which showed that the rGO@PPy possessed a three-dimensional macroporous interconnecting scaffold with superior conductivity. The rGO@PPy electrode was utilized in Geobacter sulfurreducens inoculated BESs, and the maximum current density was 4.10 ± 0.02 mA cm -2 , which is 8-fold higher than that of a rGO electrode (0.51 ± 0.03 mA cm -2 ), and is among the best performance reported for two-dimensional electrodes. The improved performance is ascribed to ultrahigh biomass concentration induced by "best match scale" between rGO@PPy and microbes, excellent extracellular electron transfer, as well as enhanced microbial affinity through the adequate exposure of biocompatible PPy layers. This work demonstrated a synergistic effect between rGO and PPy for the BESs performance improvement, and provided a new insight to design and fabricate a high-performance bioelectrode., (Copyright © 2019. Published by Elsevier B.V.)

Anaerobic oxidation of methane (AOM) coupled to denitrification is becoming the focus of scientific inquiry due to its potential contribution to global carbon and nitrogen cycles. AOM has been previously reported to proceed with nitrate (NO 3 - ) or nitrite (NO 2 - ). However, little research has been conducted on the simultaneous use of methane (CH 4 ) and nitrous oxide (N 2 O). Here, coupled CH 4 and N 2 O biotransformation in a freshwater wetland sediment was obtained in a 7-day anaerobic sediment incubation assay. The significant CO 2 accumulation and decrease of CH 4 emission in sediment microcosms was attributed to two mechanisms: inhibition of methanogenesis and N 2 O-dependent AOM. To further confirm the coupled CH 4 and N 2 O transformation, a 13 C-labelled stable isotope tracer assay after anaerobic incubation was conducted with N 2 O and/or CH 4 amendments. The N 2 O-dependent AOM rate was 3.41 ± 0.13 nmol CO 2  g -1 dry sediment·day -1 . According to metagenomic analysis, addition of N 2 O stimulated AOM by increasing the activity and abundance of methanotrophic bacteria and by increasing enzymatic activities in the electron transport chain. Based on these results, we propose coupled CH 4 and N 2 O biotransformation in the sediment microcosms for the first time, carried out by unidentified methanotroph(s) via intra‑oxygen produced in the presence of N 2 O. Such a process has the potential to reduce the emission of two highly potent greenhouse gases and makes a significant contribution to the link of global carbon and nitrogen cycles in anoxic environments., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Furanic and phenolic compounds are problematic compounds resulting from the pretreatment of lignocellulosic biomass for biofuel production. Microbial electrolysis cell (MEC) is a promising technology to convert furanic and phenolic compounds to renewable H 2 . The objective of the research presented here was to elucidate the processes and electron equivalents flow during the conversion of two furanic (furfural, FF; 5-hydroxymethyl furfural, HMF) and three phenolic (syringic acid, SA; vanillic acid, VA; 4-hydroxybenzoic acid, HBA) compounds in the MEC bioanode. Cyclic voltammograms of the bioanode demonstrated that purely electrochemical reactions in the biofilm attached to the electrode were negligible. Instead, microbial reactions related to the biotransformation of the five parent compounds (i.e., fermentation followed by exoelectrogenesis) were the primary processes resulting in the electron equivalents flow in the MEC bioanode. A mass-based framework of substrate utilization and electron flow was developed to quantify the distribution of the electron equivalents among the bioanode processes, including biomass growth for each of the five parent compounds. Using input parameters of anode efficiency and biomass observed yield coefficients, it was estimated that more than 50% of the SA, FF, and HMF electron equivalents were converted to current. In contrast, only 12 and 9% of VA and HBA electron equivalents, respectively, resulted in current production, while 76 and 79% remained as fermentation end products not further utilized in exoelectrogenesis. For all five compounds, it was estimated that 10% of the initially added electron equivalents were used for fermentative biomass synthesis, while 2 to 13% were used for exoelectrogenic biomass synthesis. The proposed mass-based framework provides a foundation for the simulation of bioanode processes to guide the optimization of MECs converting biomass-derived waste streams to renewable H 2 .

A novel cyclic functional monomer (CFM) was used to develop an As(III)-ion imprinted polymer (As-IIP). CFM possesses a positively charged imidazolium moiety and its specific cyclic size matches that of As(III). Batch adsorption experiments showed that the As-IIP has a maximum As(III) adsorption capacity of 55 mg/g, while that of the control polymer (CP) is only 25 mg As(III)/g. Adsorption isotherms for As(III) agree with the Langmuir model, suggesting monolayer adsorption. Kinetic studies showed that the adsorption process followed pseudo-second-order kinetics. The relative selectivity coefficients of As-IIP compared to CP for Cl - /H 2 AsO 3 - , SO 4 2- /H 2 AsO 3 - , HPO 4 2- /H 2 AsO 3 - , NO 3 - /H 2 AsO 3 - , and Mo 7 O 24 6- /H 2 AsO 3 - are 1.03, 1.95, 2.55, 1.52 and 2.51, respectively. The removal efficiency of As-IIP for As(III) in actual industrial wastewater was nearly 100%, which confirms that As-IIP has a high adsorption capacity as well as selectivity for the removal of As(III) from wastewater., (Copyright © 2018. Published by Elsevier B.V.)

While the misuse of antibiotics has clearly contributed to the emergence and proliferation of resistant bacterial pathogens, with major health consequences, it remains less clear if the widespread use of disinfectants, such as benzalkonium chlorides (BAC), a different class of biocides than antibiotics, has contributed to this problem. Here, we provide evidence that exposure to BAC coselects for antibiotic-resistant bacteria and describe the underlying genetic mechanisms. After inoculation with river sediment, BAC-fed bioreactors selected for several bacterial taxa, including the opportunistic pathogen Pseudomonas aeruginosa , that were more resistant to several antibiotics than their counterparts in a control (no BAC) bioreactor. A metagenomic analysis of the bioreactor microbial communities, confirmed by gene cloning experiments with the derived isolates, suggested that integrative and conjugative elements encoding a BAC efflux pump together with antibiotic resistance genes were responsible for these results. Furthermore, the exposure of the P. aeruginosa isolates to increasing concentrations of BAC selected for mutations in pmrB (polymyxin resistance) and physiological adaptations that contributed to a higher tolerance to polymyxin B and other antibiotics. The physiological adaptations included the overexpression of mexCD-oprJ multidrug efflux pump genes when BAC was added in the growth medium at subinhibitory concentrations. Collectively, our results demonstrated that disinfectants promote antibiotic resistance via several mechanisms and highlight the need to remediate (degrade) disinfectants in nontarget environments to further restrain the spread of antibiotic-resistant bacteria. IMPORTANCE Benzalkonium chlorides (BAC) are biocides broadly used in disinfectant solutions. Disinfectants are widely used in food processing lines, domestic households, and pharmaceutical products and are typically designed to have a different mode of action than antibiotics to avoid interfering with the use of the latter. Whether exposure to BAC makes bacteria more resistant to antibiotics remains an unresolved issue of obvious practical consequences for public health. Using an integrated approach that combines metagenomics of natural microbial communities with gene cloning experiments with isolates and experimental evolution assays, we show that the widely used benzalkonium chloride disinfectants promote clinically relevant antibiotic resistance. Therefore, more attention should be given to the usage of these disinfectants, and their fate in nontarget environments should be monitored more tightly., (Copyright © 2018 American Society for Microbiology.)

The objective of this study was to evaluate the effect of biofilm and external voltage on the performance and microbial community composition of batch-fed, combined anaerobic digestion-bioelectrochemical cell (AD-BEC) systems under different operational conditions. A dextrin/peptone mixture was fed at a range of organic loading rates (0.34 to 1.37g COD/L-d). The hybrid system with both suspended biomass and biofilm without any external potential application achieved a substantially higher initial soluble COD consumption (53.7±2.3% vs. 39.7±3.7) and methane (CH 4 ) production (331 vs. 225mL) within one day of feeding than the conventional AD system (suspended biomass only). Compared to the conventional AD system, the hybrid systems had higher resilience to shock organic loadings. A range of external potential (0.5 to 2.0V vs. Ag/AgCl) was applied to AD-BEC reactors, developed with two different start-up procedures. A potential of 2.0V resulted in water electrolysis leading to a higher CH 4 production rate (105 vs. 84mL/L-d) and biogas CH 4 content (88.5±1.4 vs. 64.5±1.9%) in the AD-BEC reactor (closed vs. open circuit condition, respectively). Application of external potential enriched putative exoelectrogens at the anode biofilm and hydrogenotrophic methanogens at the cathode biofilm, which may have contributed to the observed enhanced CH 4 production in the AD-BEC system. A phylotype related to Methanobacterium formicicum, a hydrogenotrophic methanogen, dominated the archaeal community in the AD-BEC cathode biofilm., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Benzalkonium chlorides (BAC) are commonly used biocides in broad-spectrum disinfectant solutions. How microorganisms cope with BAC exposure remains poorly understood, despite its importance for disinfection and disinfectant-induced antibiotic resistance. To provide insights into these issues, we exposed two isolates of an opportunistic pathogen, Pseudomonas aeruginosa , to increasing concentrations of BAC. One isolate was preadapted to BAC, as it originated from a bioreactor fed with subinhibitory concentrations of BAC for 3 years, while the other originated from a bioreactor that received no BAC. Replicated populations of both isolates were able to survive high concentrations of BAC, up to 1,200 and 1,600 mg/liter for the non- and preadapted strains, respectively, exceeding typical application doses. Transcriptome sequencing (RNA-seq) analysis revealed upregulation of efflux pump genes and decreased expression of porins related to BAC transport as well as reduced growth rate. Increased expression of spermidine (a polycation) synthase genes and mutations in the pmrB (polymyxin resistance) gene, which cause a reduction in membrane negative charge, suggested that a major adaptation to exposure to the cationic surfactant BAC was to actively stabilize cell surface charge. Collectively, these results revealed that P. aeruginosa adapts to BAC exposure by a combination of mechanisms and provided genetic markers to monitor BAC-resistant organisms that may have applications in the practice of disinfection. IMPORTANCE BAC are widely used as biocides in disinfectant solutions, food-processing lines, domestic households, and health care facilities. Due to their wide use and mode of action, there has been rising concern that BAC may promote antibiotic resistance. Consistent with this idea, at least 40 outbreaks have been attributed to infection by disinfectant- and antibiotic-resistant pathogens such as P. aeruginosa However, the underlying molecular mechanisms that bacteria use to deal with BAC exposure remain poorly elucidated. Elucidating these mechanisms may be important for monitoring and limiting the spread of disinfectant-resistant pathogens. Using an integrated approach that combined genomics and transcriptomics with physiological characterization of BAC-adapted isolates, this study provided a comprehensive understanding of the BAC resistance mechanisms in P. aeruginosa Our findings also revealed potential genetic markers to detect and monitor the abundance of BAC-resistant pathogens across clinical or environmental settings. This work contributes new knowledge about high concentrations of benzalkonium chlorides disinfectants-resistance mechanisms at the whole-cell genomic and transcriptomic level., (Copyright © 2018 American Society for Microbiology.)

Development of high capacity material for antimonite (Sb(III)) and antimonate (Sb(V)) removal is the key to solving water antimony contamination. Three-dimensional Cu(II)-specific metallogels (Cu-MG), which are considered to have high density adsorption sites for antimony (Sb), were first applied to adsorb Sb(III) and Sb(V). Batch assays resulted in adsorption capacities of Cu-MG for Sb(III) and Sb(V) at 102.4 mg/g and 264.1 mg/g, respectively. In addition, the adsorption capacity for Sb(III) was up to 225.7 mg/g using in situ oxidation. Kinetic assays resulted in more than 90% removal of Sb in 30 min. X-ray photoelectron spectroscopy (XPS) revealed the adsorption of Sb depended mainly on coordination interactions of vacant orbitals of the Cu atom with the lone-pairs of the O atom of Sb(OH) 3 or Sb(OH) 6 - . Adsorption energy based on density functional theory (DFT) confirmed that Sb(III) adsorbed as a single layer whereas Sb(V) adsorbed as a multi-layer. These findings are consistent with experimental results. In addition, DFT calculations revealed that the Cu-MG theoretical capacity for Sb(V) adsorption is higher than for Sb(III). Cu-MG is a new and promising class of adsorbents for the removal of Sb(III) and Sb(V) from contaminated water., (Copyright © 2017 Elsevier B.V. All rights reserved.)

A dicyclic-type electrode based biofilm electrode reactor (BER) was developed for advanced nitrate removal from saline municipal wastewater. The denitrification efficiency was evaluated with a synthetic feed (NO 3 - -N, 20 mg L -1 ) under different salinity and COD to nitrogen ratios (COD/N). As the salinity increased from 0% to 1.0%, the denitrification performance of both the traditional biofilm reactor (BR) and BER was inhibited; however, the BER showed better adaptation and ability to recover. The BER achieved a high nitrate removal efficiency (≥90%) at a salinity of 1.0% and a low COD/N of 2.5 (theoretical stoichiometric 2.86 ignoring microbial growth). The abundance of Methylotenera mobilis in BR and Clostridium sticklandii in BER was higher than in the initial sludge sample used as inoculum. Likewise, the abundance of napA, nirS and nosZ genes increased as the COD/N further decreased. Under high salinity stress, the BER had a higher denitrification efficiency and the consumption of the organic carbon source (i.e., methanol) was reduced compared to BR. The cooperation between heterotrophic and autotrophic denitrifiers in the BER system provides a more efficient and feasible solution for nitrate removal from saline municipal wastewater., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Methanogenic bioelectrochemical systems (BESs), which convert carbon dioxide (CO 2 ) directly to methane (CH 4 ), promise to be an innovative technology for anaerobic digester biogas upgrading. Zero-valent iron (ZVI), which has previously been used to improve CH 4 production in anaerobic digesters, has not been explored in methanogenic biocathodes. Thus, the objective of this study was to assess the effect of biocathode ZVI on BES performance at 1 and 2 g/L initial ZVI concentrations and at various cathode potentials (-0.65 to -0.80 V versus SHE). The total CH 4 produced during a 7-day feeding cycle with 1 and 2 g/L initial ZVI was 2.8- and 2.9-fold higher, respectively, than the mean CH 4 production in the four prior cycles without ZVI addition. Furthermore, CH 4 production by the ZVI-amended biocathodes remained elevated throughout three subsequent feeding cycles, despite catholyte replacement and no new ZVI addition. The fourth cycle following a single ZVI addition of 1 g/L and 2 g/L yielded 123% and 231% more total CH 4 than in the non-ZVI cycles, respectively. The higher CH 4 production could not be fully explained by complete anaerobic oxidation of the ZVI and utilization of produced H 2 by hydrogenotrophic methanogens. Microbial community analysis showed that the same phylotype, most closely related to Methanobrevibacter arboriphilus, dominated the archaeal community in the ZVI-free and ZVI-amended biocathodes. However, the bacterial community experienced substantial changes following ZVI exposure, with more Proteobacteria and fewer Bacteroidetes in the ZVI-amended biocathode. Furthermore, it is likely that a redox-active precipitate formed in the ZVI-amended biocathode, which sorbed to the electrode and/or biofilm, acted as a redox mediator, and enhanced electron transfer and CH 4 production. Thus, ZVI may be used to increase biocathode CH 4 production, assist in the start-up of an electromethanogenic biocathode, and/or maintain microbial activity during voltage interruptions.

The cathode microbial community of a methanogenic bioelectrochemical system (BES) is key to the efficient conversion of carbon dioxide (CO 2 ) to methane (CH 4 ) with application to biogas upgrading. The objective of this study was to compare the performance and microbial community composition of a biocathode inoculated with a mixed methanogenic (MM) culture to a biocathode inoculated with an enriched hydrogenotrophic methanogenic (EHM) culture, developed from the MM culture following pre-enrichment with H 2 and CO 2 as the only externally supplied electron donor and carbon source, respectively. Using an adjacent Ag/AgCl reference electrode, biocathode potential was poised at -0.8 V (versus SHE) using a potentiostat, with the bioanode acting as the counter electrode. When normalized to cathode biofilm biomass, the methane production in the MM- and EHM-biocathode was 0.153 ± 0.010 and 0.586 ± 0.029 mmol CH 4 /mg biomass-day, respectively. This study showed that H 2 /CO 2 pre-enriched inoculum enhanced biocathode CH 4 production, although the archaeal communities in both biocathodes converged primarily (86-100%) on a phylotype closely related to Methanobrevibacter arboriphilus. The bacterial community of the MM-biocathode was similar to that of the MM inoculum but was enriched in Spirochaetes and other nonexoelectrogenic, fermentative Bacteria. In contrast, the EHM-biocathode bacterial community was enriched in Proteobacteria, exoelectrogens, and putative producers of electron shuttle mediators. Similar biomass levels were detected in the MM- and EHM-biocathodes. Thus, although the archaeal communities were similar in the two biocathodes, the difference in bacterial community composition was likely responsible for the 3.8-fold larger CH 4 production rate observed in the EHM-biocathode. Roles for abundant OTUs identified in the biofilm and inoculum cultures were highlighted on the basis of previous reports.

Monensin is a common antiparasitic drug given to poultry that contaminates poultry manure and bedding material (broiler litter). As broiler litter is commonly applied to agricultural fields as fertilizer, monensin could be released beyond the farm if it is not retained or degraded in the soil. This study aimed to assess the impact of long-term surface application of broiler litter (i.e., 17 years) on the capacity of pasture soil to sorb monensin. The soils were exposed to a range of monensin concentrations (0.18 to 1.81 μmol L -1 ), solution pH (pH 4-9), and temperatures (15, 25, and 35 °C) and monensin was measured as loss from solution (i.e., sorption). Soils receiving long-term litter applications were hypothesized to retain more monensin than unamended soils because they have higher organic matter concentrations. However, soils from broiler litter-amended fields sorbed 46% less monensin than soils from unamended fields, likely because broiler litter also increased soil pH. The sorption of monensin to soil was strongly influenced by pH, with an order of magnitude greater sorption at pH 4 than at pH 9. Both soils had similar capacity to sorb monensin under similar solution pH, despite differences in organic carbon content (with the broiler litter-amended having 25% greater relative to the unamended soil). Temperature did not significantly impact monensin sorption for either soil. Our findings suggest increasing soil pH, for instance through liming, could enhance mobility of monensin.

Bioelectrochemical systems (BESs) may be used to upgrade anaerobic digester biogas by directly converting CO 2 to CH 4 . The objective of this study was to evaluate gas (N 2 , CO 2 , CH 4 , and H 2 ) and carbon transport within a methanogenic BES. Four BES configurations were evaluated: abiotic anode with abiotic cathode (AAn-ACa), bioanode with abiotic cathode (BAn-ACa), abiotic anode with biocathode (AAn-BCa), and bioanode with biocathode (BAn-BCa). Transport of N 2 , a gas commonly used for flushing anoxic systems, out of the anode headspace ranged from 3.7 to 6.2 L/d-atm-m 2 , normalized to the proton exchange membrane (PEM) surface area and net driving pressure (NDP). CO 2 was transported from the cathode to the anode headspace at rates from 3.7 to 5.4 L/d-atm-m 2 . The flux of H 2 from cathode to anode headspace was 48% greater when the system had a biocathode (AAn-BCa) than when H 2 was produced at an abiotic cathode (BAn-ACa), even though the abiotic cathode headspace had 75% more H 2 than the AAn-BCa biocathode at the end of 1 day. A 7-day carbon balance of a batch-fed BAn-BCa BES showed transient microbial carbon storage and a net transport of carbon from anode to cathode. After a 7-day batch incubation, the CH 4 production in the biocathode was 27% greater on a molar basis than the initial CO 2 supplied to the biocathode headspace, indicating conversion of CO 2 produced in the anode. This research expands the current understanding of methanogenic BES operation, which may be used in improving the assessment of BES performance and/or in the development of alternative BES designs and mathematical models. Biotechnol. Bioeng. 2017;114: 961-969. © 2016 Wiley Periodicals, Inc., (© 2016 Wiley Periodicals, Inc.)

Phenolic compounds in hydrolysate/pyrolysate and wastewater streams produced during the pretreatment of lignocellulosic biomass for biofuel production present a significant challenge in downstream processes. Bioelectrochemical systems are increasingly recognized as an alternative technology to handle biomass-derived streams and to promote water reuse in biofuel production. Thus, a thorough understanding of the fate of phenolic compounds in bioanodes is urgently needed. The present study investigated the biotransformation of three structurally similar phenolic compounds (syringic acid, SA; vanillic acid, VA; 4-hydroxybenzoic acid, HBA), and their individual contribution to exoelectrogenesis in a microbial electrolysis cell (MEC) bioanode. Fermentation of SA resulted in the highest exoelectrogenic activity among the three compounds tested, with 50% of the electron equivalents converted to current, compared to 12 and 9% for VA and HBA, respectively. The biotransformation of SA, VA and HBA was initiated by demethylation and decarboxylation reactions common to all three compounds, resulting in their corresponding hydroxylated analogs. SA was transformed to pyrogallol (1,2,3-trihydroxybenzene), whose aromatic ring was then cleaved via a phloroglucinol pathway, resulting in acetate production, which was then used in exoelectrogenesis. In contrast, more than 80% of VA and HBA was converted to catechol (1,2-dihydroxybenzene) and phenol (hydroxybenzene) as their respective dead-end products. The persistence of catechol and phenol is explained by the fact that the phloroglucinol pathway does not apply to di- or mono-hydroxylated benzenes. Previously reported, alternative ring-cleaving pathways were either absent in the bioanode microbial community or unfavorable due to high energy-demand reactions. With the exception of acetate oxidation, all biotransformation steps in the bioanode occurred via fermentation, independently of exoelectrogenesis. Therefore, the observed exoelectrogenic activity in batch runs conducted with SA, VA and HBA was controlled by the extent of fermentative transformation of the three phenolic compounds in the bioanode, which is related to the number and position of the methoxy and hydroxyl substituents., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The objective of this study was to systematically investigate the inhibitory effect of furfural (FF), 5-hydroxymethylfurfural (HMF), syringic acid (SA), vanillic acid (VA), and 4-hydroxybenzoic acid (HBA), which are problematic lignocellulose-derived byproducts, on exoelectrogenesis in the bioanode of a microbial electrolysis cell. The five compound mixture at an initial total concentration range from 0.8 to 8.0 g/L resulted in an up to 91% current decrease as a result of exoelectrogenesis inhibition; fermentative, nonexoelectrogenic biotransformation pathways of the five compounds were not affected. Furthermore, the parent compounds at a high concentration, as opposed to their biotransformation products, were responsible for the observed inhibition. All five parent compounds contributed to the observed inhibition of the mixture. The IC 50 (i.e., concentration resulting in 50% current decrease) of individually tested parent compounds was 2.7 g/L for FF, 3.0 g/L for HMF, 1.9 g/L for SA, 2.1 g/L for VA and 2.0 g/L for HBA. However, the parent compounds, when tested below their respective noninhibitory concentration, jointly resulted in significant inhibition as a mixture. Catechol and phenol, which were persistent biotransformation products, inhibited exoelectrogenesis only at high concentrations, but to a lesser extent than the parent compounds. Exoelectrogenesis recovery from inhibition by all compounds was observed at different rates, with the exception of catechol, which resulted in irreversible inhibition.

Monensin (MON) and salinomycin (SAL), known as polyether ionophore antibiotics (IPAs), are extensively used in livestock industry and can enter the environment via animal manure and agricultural runoff. Although some studies have investigated the environmental fate and transformation of IPAs, the lack of information on IPAs' aqueous-phase chemical properties is a major hindrance for further in-depth research. This study was able to experimentally determine the acidity constants (pKa), metal-complex dissociation constants (Kdiss), and intrinsic aqueous solubility of MON species, and some of these properties of SAL. The pKa value of MON was found to be 4.5, close to other aliphatic carboxylic acids and the predicted value by the computer program ChemAxon. The metal-complex dissociation constants of MON were estimated to be 0.058 and 0.573 with sodium ion (Na(+)) and potassium ion (K(+)), respectively. The Kdiss value of SAL with sodium ion was found to be 1.31. Compared to the previous values determined in organic solvents, the Kdiss of MON in aqueous phase are several orders of magnitude higher but maintain the same relative selectivity toward metal ions (Na(+) versus K(+)). The determined pKa and Kdiss values were also used to assess the aqueous solubility limits of different IPA species under different pH and metal ion concentrations. Results from this study provide more accurate information for the properties of IPAs. The obtained constants can be applied to predict the speciation of IPAs in various aquatic systems and help shed light on the environmental fate of IPAs.

A bench-scale investigation was conducted to select external organic wastes and mixing ratios for co-digestion with municipal sludge at the F. Wayne Hill Water Resources Center (FWHWRC), Gwinnett County, GA, USA to support a combined heat and power (CHP) project. External wastes were chosen and used subject to two constraints: a) digester retention time no lower than 15 d; and b) total biogas (methane) production not to exceed a specific target level based on air permit constraints on CO2 emissions. Primary sludge (PS), thickened waste activated sludge (TWAS) and digested sludge collected at the FWHWRC, industrial liquid waste obtained from a chewing gum manufacturing plant (GW) and dewatered fat-oil-grease (FOG) were used. All sludge and waste samples were characterized and their ultimate digestibility was assessed at 35 °C. The ultimate COD to methane conversion of PS, TWAS, municipal sludge (PS + TWAS; 40:60 w/w TS basis), GW and FOG was 49.2, 35.2, 40.3, 72.7, and 81.1%, respectively. Co-digestion of municipal sludge with GW, FOG or both, was evaluated using four bench-scale, mesophilic (35 °C) digesters. Biogas production increased significantly and additional degradation of the municipal sludge between 1.1 and 30.7% was observed. Biogas and methane production was very close to the target levels necessary to close the energy deficit at the FWHWRC. Co-digestion resulted in an effluent quality similar to that of the control digester fed only with the municipal sludge, indicating that co-digestion had no adverse effects. Study results prove that high methane production is achievable with the addition of concentrated external organic wastes to municipal digesters, at acceptable higher digester organic loadings and lower retention times, allowing the effective implementation of CHP programs at municipal wastewater treatment plants, with significant cost savings., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Furanic and phenolic compounds are problematic byproducts resulting from the breakdown of lignocellulosic biomass during biofuel production. The capacity of a microbial electrolysis cell (MEC) to produce hydrogen gas (H2) using a mixture of two furanic (furfural, FF; 5-hydroxymethyl furfural, HMF) and three phenolic (syringic acid, SA; vanillic acid, VA; and 4-hydroxybenzoic acid, HBA) compounds as the substrate in the bioanode was assessed. The rate and extent of biotransformation of the five compounds and efficiency of H2 production, as well as the structure of the anode microbial community, were investigated. The five compounds were completely transformed within 7-day batch runs and their biotransformation rate increased with increasing initial concentration. At an initial concentration of 1200 mg/L (8.7 mM) of the mixture of the five compounds, their biotransformation rate ranged from 0.85 to 2.34 mM/d. The anode Coulombic efficiency was 44-69%, which is comparable to that of wastewater-fed MECs. The H2 yield varied from 0.26 to 0.42 g H2-COD/g COD removed in the anode, and the bioanode volume-normalized H2 production rate was 0.07-0.1 L/L-d. The biotransformation of the five compounds took place via fermentation followed by exoelectrogenesis. The major identified fermentation products that did not transform further were catechol and phenol. Acetate was the direct substrate for exoelectrogenesis. Current and H2 production were inhibited at an initial substrate concentration of 1200 mg/L, resulting in acetate accumulation at a much higher level than that measured in other batch runs conducted with a lower initial concentration of the five compounds. The anode microbial community consisted of exoelectrogens, putative degraders of the five compounds, and syntrophic partners of exoelectrogens. The MEC H2 production demonstrated in this study is an alternative to the currently used process of reforming natural gas to supply H2 needed to upgrade bio-oils to stable hydrocarbon fuels.

The use of ionophores as antiparasitic drugs plays an important role in US poultry production, especially in the broiler () industry. However, administered ionophores can pass through the bird's digestive system and appear in broiler litter, which, when applied to agricultural fields, can present an environmental hazard. Stacking (storing or stockpiling) broiler litter for some time might decrease the litter ionophore concentrations before land application. Because ionophores undergo abiotic hydrolysis at low pH, decreasing litter pH with acidic aluminum sulfate (alum) might also decrease ionophore concentrations. We assessed the change in ionophore concentrations in broiler litter in response to the length of time broiler litter was stored (stacking time) and alum addition. We spiked broiler litter with monensin and salinomycin, placed alum-amended litter (∼pH 4-5) and unamended litter (∼pH 8-9) into 1.8-m bins, and repeatedly sampled each bin for 112 d. Our findings showed that stacking broiler litter alone did not have an impact on monensin concentration, but it did slowly reduce salinomycin concentration by 55%. Adding alum to broiler litter reduced monensin concentration by approximately 20% relative to unamended litter, but it did not change salinomycin concentration. These results call for continued search for alternative strategies that could potentially reduce the concentration of ionophores in broiler litter before their application to agricultural soils., (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)