Enhancing methane production and interspecies electron transfer of anaerobic granular sludge by the immobilization of magnetic biochar.

Supplementation of conductive materials has been proved to be a promising approach for enhancing microbial interspecies electron transfer (IET) in anaerobic digestion systems. In this study, magnetic bamboo-based biochar was prepared at temperatures of 400-800 °C via a ball milling/carbonization method, and it immobilized in mature anaerobic granular sludge (AGS) aimed to enhance methane production by improving the IET process between syntrophic microbial communities in the AGS. Results showed that the AGS with magnetic biochar immobilization demonstrated increased glucotrophic and acetotrophic methane production by 69.54-77.56 % and 39.96-54.92 %, respectively. Magnetic biochar prepared at 800 °C with a relatively higher Fe content (0.37 g/g magnetic biochar) displayed a stronger electron charge/discharge capacity (36.66 F/g), and its immobilization into AGS promoted methane production most. The conductivity of AGS increased by 52.13-87.32 % after incorporating magnetic biochar. Furthermore, the extracellular polymeric substance (EPS) of AGS showed an increased capacitance and decreased electron transfer resistance possibly due to the binding of magnetic biochar and more riboflavin secretion in EPS, which could contribute to the accelerated IET process in the inner AGS. In addition, the immobilization of magnetic biochar could promote the production of volatile fatty acids by 15.36-22.50 %. All these improvements may jointly lead to the enhanced methane production capacity of AGS. This study provided a fundamental understanding of the role of incorporated magnetic biochar in AGS in promoting anaerobic digestion performance.

Mediating the performance of anaerobic granular sludge by exogenous flavin supplementation: Flavin binding capacity and behavior, interspecies electron transfer, and methane production.

Although flavins are known as effective electron mediators, the binding capacity of exogenous flavins by anaerobic granular sludge (AGS) and their role in interspecies electron transfer (IET) remains unknown. In this study, AGS was mediated by using three exogenous flavins of riboflavin (RF), flavin mononucleotide (FMN), and flavin adenine dinucleotide (FAD). Results showed that the total amounts of flavins associated with extracellular polymeric substance (EPS) of AGS increased by 2.03-2.42 and 3.83-4.94 folds, after exposure to 50 and 200 µM of exogenous flavins, respectively. A large portion of FMN and FAD was transformed into RF by AGS. Exogenous flavin mediation also stimulated the production of EPS and cytochrome c (c-Cyts) as well as cytochrome-bound flavins. The increased abundance of these electron mediators led to a reduced electrochemical impedance of EPS and improved extracellular electron transfer capacity. The methane production of AGS after mediation with exogenous RF, FMN, and FAD increased by 19.03-31.71%, 22.86-26.04%, and 28.51-33.44%, respectively. This study sheds new light on the role of exogenous flavins in promoting the IET process of a complex microbial aggregate of AGS.

Enhancing methanogenesis of anaerobic granular sludge by incorporating Fe/Fe oxides nanoparticles aided with biofilm disassembly agents and mediating redox activity of extracellular polymer substances.

Anaerobic granular sludge (AGS) is a promising technology for organic wastewater treatment and energy recovery. In this study, three different kinds of Fe and Fe oxides nanoparticles (Fe3O4, Fe2O3 and ZVI) were tried to be incorporated into AGS through direct loading or aided with biofilm disassembly agents of norspermidine and D-tyrosine, which was aimed to enhance methane production capacity of AGS via increasing redox activity of extracellular polymer substance (EPS) and interspecies electron transfer. Despite the loading methods, incorporation of Fe and Fe oxides nanoparticles into AGS increased methane production capacity remarkably, with an enhancement of 36.49-85.17%, 20.37-204.95% and 189.71-243.32%, respectively, for the Fe3O4, Fe2O3 and ZVI loaded AGS. Pretreatment of AGS using biofilm disassembly agents helped to incorporate more Fe and Fe oxides into the inner structure of AGS, which further enhanced methane production capacity by 48.68% and 184.58%, respectively, for the Fe3O4 and Fe2O3 loaded AGS. Loading Fe and Fe oxides into AGS not only introduced exogenous conductive substances and Fe(III)/Fe(II) redox couples into EPS matrix of AGS, but also stimulated the production of redox active components of flavins and c-Cyts. All these factors may contribute to the reduced resistance of EPS, enhanced interspecies electron transfer and methane production capacity of AGS. This study provides a novel strategy and facile method to accelerate interspecies electron transfer and enhance methane production for matured AGS.

In-situ formation and self-immobilization of biogenic Fe oxides in anaerobic granular sludge for enhanced performance of acidogenesis and methanogenesis.

Addition of ferric oxides into flocculent anaerobic sludge was reported to enhance methanogenesis due to accelerated direct interspecies electron transfer (DIET) between syntrophic microbial communities. However, it is generally hard to incorporate Fe oxides into already matured anaerobic granular sludge (AGS) due to its special aggregated structure. In this study, a novel method was attempted to fast incorporate Fe oxides into AGS through in-situ microbial formation and immobilization of biogenic Fe oxides. Factors influencing the formation of Fe oxides were investigated and effects of Fe oxides on the acidogenic and methanogenic performance of AGS were assessed. Results showed that AGS could form Fe oxides mainly in the form of magnetite and hematite through biological reduction of Fe(III) oxyhydroxide. A maximum loading amount of 83.9 mg Fe/g MLVSS was obtained at pH 7 after contacting with 60 mM Fe(III) oxyhydroxide. The efficiency of electron donors which supported Fe(III) reduction followed the order of pyruvate > propionate > glucose > acetate > lactate > formate. Addition of electron transfer mediators (ETMs) promoted the formation of Fe oxides and their performance followed the order of AQDS > AQC > humics > FMN > riboflavin. Presence of Fe oxides in AGS (134.6 Fe/g VSS) increased the production of volatile fatty acids (VFAs) and methane by 16.28% and 41.94% respectively, comparing to the control. The enhancement may be attributed to increased conductivity and stimulated growth of exoelectrogens (Clostridium and Anaerolinea) and methanogenic endoelectrogens Methanosaeta in granular sludge which may strengthen direct interspecies electron transfer between syntrophic microbial communities. Overall, this study provides an alternative strategy to improve the digestion performance of AGS through in-situ formation and immobilization of biogenic Fe oxides.

Cytotoxicity of functionalized CeO2 nanoparticles towards Escherichia coli and adaptive response of membrane properties.

The cytotoxicity and mechanisms of cerium oxide nanoparticles (CeO2-NPs) on organisms have attracted great concerns recently, while that of CeO2-NPs with functional groups remains unclear. This study investigated cytotoxic effects and mechanisms of CeO2-NPs with hydroxyl, carboxyl, or amino functional groups towards a strain Escherichia coli (E. Coli). Results showed that CeO2-NPs produced a stronger cytotoxicity in NaCl medium than in PBS medium at the concentrations of 10-400 mg/L. The toxicity followed the order of CeO2-COOH > CeO2-NH2 > CeO2-OH. Exposing to CeO2-NPs increased cell membrane permeability and reduced membrane fluidity. The membrane phospholipid fatty acid compositions also varied greatly as a response to the stress of CeO2-NPs, with the proportion of unsaturated fatty acids increased and saturated fatty acids decreased. Both intracellular reactive oxygen species (ROS) level and malonaldehyde (MDA) level declined, suggesting the oxidative stress from ROS may be not the primary reason for the membrane damage. Other mechanisms such as direct membrane oxidation by Ce4+ or physical penetration based on a close contact between nanoparticles and microbes might contribute to the membrane damages and cell viability loss. The present study provides a significant insight into the influence of functionalized CeO2-NPs on a gram-negative bacterium.

Occurrence and distribution of typical semi-volatile organic chemicals (SVOCs) in paired indoor and outdoor atmospheric fine particle samples from cities in southern China.

Interest in the potential human health of semi-volatile organic chemicals (SVOCs) in indoor and outdoor environments has made the exposure assessment and source appointment a priority. In this study, paired indoor and outdoor atmospheric fine particle (PM2.5) samples were collected from 15 homes representing five typical urban cities in southern China. Four typical SVOCs, including 16 congeners of polycyclic aromatic hydrocarbons (PAHs), 13 congeners of organophosphorus flame retardants (OPFRs) and 8 congeners of polybrominated diphenyl ethers (PBDEs), as well as tetrabromobisphenol A (TBBPA) and its three debrominated congeners were analyzed. The highest total concentrations were found for OPFRs, followed by PAHs, PBDEs, and TBBPA. The indoor concentrations of two alkyl-OPFR isomers, tributylphosphate (TBP) and tris (2-butoxyethyl) phosphate (TBEP), were 4.3 and 11 times higher, respectively, than those of outdoors (p < 0.05). Additionally, the ratios of indoor to outdoor concentrations of alkyl-OPFR isomers varied greatly, suggesting that these compounds originated mainly from different household goods and products used in individual homes. The outdoor concentrations of PAHs and highly brominated PBDEs (BDE-209) typically exceeded the indoor concentrations. Significant correlations were also found between indoor and outdoor PM2.5 samples for PAHs and BDE-209, indicating that outdoor sources such as vehicle exhausts and industrial activities strongly influence their atmospheric occurrence. Additionally, the concentrations of debrominated TBBPA derivatives were higher than those of TBBPA in over 33% of both indoor and outdoor air particle samples. Nevertheless, our results indicated that inhalation exposure to typical SVOCs posed no non-carcinogenic risks to the human body. Although we observed notable differences in the sources, occurrences, and distributions of typical SVOC congeners, more studies using matched samples are still needed to unambiguously identify important indoor and outdoor sources in order to accurately assess the contributions of different sources and the associated human exposure risks.

Phosphate-modified m-Bi2O4 enhances the absorption and photocatalytic activities of sulfonamide: Mechanism, reactive species, and reactive sites.

Widespread usage of the sulfonamide class of antibiotics is causing increasing ecotoxicological concern, as they have the capacity to alter ambient ecosystems. Photocatalytic technology is an attractive yet challenging strategy for the degradation of antibiotics. For this work, the phosphate modification of m-Bi2O4 (Bi2O4-P) was prepared via a one-step hydrothermal process involving sodium bismuthate and sodium phosphate, which was employed for the degradation of sulfamethazine (SMZ) under visible light irradiation. The 0.5% Bi2O4-P exhibited excellent photocatalytic performance, which was 1.9 times that of pure m-Bi2O4. The photocatalytic degradation kinetics and mechanism of SMZ was investigated at different pH, whereupon it was revealed that m-Bi2O4-P exhibited improved SMZ adsorption and photocatalytic activities in contrast to pure m-Bi2O4. Compared with other four sulfonamide antibiotics, structures that contained additional methyl on the pyrimidine could be more easily attacked by phosphate modified m-Bi2O4. Reactive species (RS) scavenging experiments revealed that h+ was primarily responsible for the degradation of SMZ. Further studies of RS by ESR technology, and the results of photoelectrochemical properties showed phosphate-modified m-Bi2O4 could make greater use of photogenerated carriers, thereby producing additional RS. Based on the HRAM LC-MS/MS and the Frontier Molecular Orbital Theory, the degradation pathways of SMZ were proposed.

Chlorinated paraffins in the indoor and outdoor atmospheric particles from the Pearl River Delta: Characteristics, sources, and human exposure risks.

Chlorinated paraffins (CPs) are ubiquitously present in the environment due to their abundant production and consumption. Information on CPs as part of indoor particles is very limited although a significant amount of time is spent in indoor environments. Seventy-two indoor and 66 outdoor TSP/PM10/PM2.5 samples (particulate matters with aerodynamic diameter <100, 10, and 2.5µm) from 24 homes of the Pearl River Delta (PRD), China, were analyzed for CPs. PM2.5 were found to be the dominant particles both indoors and outdoors. CPs were mainly distributed in PM2.5 that accounted for 89.1% and 93.0% of the total particles indoors and outdoors, respectively. The geometric mean (GM) concentrations of medium-chain CPs (MCCPs) exceeded those of short-chain CPs (SCCPs) (22.0 vs. 9.2ng/m3) in all particle samples. Both SCCPs and MCCPs in the indoor particles (GM: 13.4 and 30.9ng/m3) were approximately twice as high as in the outdoor environment (GM: 6.1 and 15.2ng/m3). C11 and C14 carbon chains as well as six and seven chlorine homologues were found to be predominant in all samples with average percentages of 43.0% and 55.4%, respectively. The estimated daily CP intakes via PM2.5 inhalation were 8.1-24.6 and 25.1-76.0ng/kg·bw/day for all age subgroups based on both mean and 95th percentile concentrations of CPs. However, the estimated daily uptakes decreased to 4.4-16.4 and 13.5-50.6ng/kg·bw/day, respectively, when the deposition fractions of PM2.5 in the human lung were considered. Indoor PM2.5 attributed to 93.8% exposure of CPs based on both total estimated daily intakes (EDIs) and estimated daily uptakes (EDUs), indicating that the indoor PM2.5 exposure was very important. Infants and toddlers suffered higher exposure risks of CPs compared to other subgroups, indicating higher potential health risks; however, based on the margin of the exposure analysis these risks could be ignored.