A 20-year shift in China's sewage sludge heavy metals and its feasibility of nutrient recovery in land use.

Recycling resources from wastewater is even more important for developing a more sustainable society. Disposing sewage sludge, which accumulates most pollutants and resources in sewage, is the main challenge in wastewater pollution control and resource utilization. Heavy metals (HMs) are the greatest constraint limiting the application of sewage sludge to land as a sustainable use of this material. We conducted a meta-analysis of the concentrations of HMs in Chinese sewage sludge by combining data from studies published from 2000 to 2019 (N = 8477). Over this period, the reported concentrations of HMs in sewage sludge declined in three stages (a fluctuating stage, a slight decrease stage, and a rapid and stable decrease stage). The results revealed that economic development and environmental policy implementation were the main factors mitigating HM pollution in sewage sludge in China. Moreover, if environmental regulations were strengthened and HM pollution-mitigation strategies were made consistent, such that the proportion of sewage sludge applied to land in China could be increased from 18.6% to 48.0% (the proportion applied to land in the United States), the ecosystem services analysis showed that huge ecological-economic benefits could be realized (3.1 billion Chinese Yuan) and the use of fertilizers could be substantially reduced (the use of nitrogen fertilizers by 8.5% and the use of phosphate fertilizers by 18.1%). This review shows that China should formulate a unified policy and interdepartmental committee for sustainable application of sewage sludge to land and wastewater resource recycling management.

Biomass-Derived Carbonaceous Materials with Graphene/Graphene-Like Structures: Definition, Classification, and Environmental Applications.

Biomass-derived carbonaceous materials with graphene/graphene-like structures (BGS) have attracted tremendous attention in the field of environmental remediation. The introduction of graphene/graphene-like structures into raw biochars can effectively improve their properties, such as electrical conductivity, surface functional groups, and catalytic activity. In 2021, the International Organization for Standardization defined graphene as a "single layer of carbon atoms with each atom bound to three neighbours in a honeycomb structure". Considering this definition, several studies have incorrectly referred to BGS (e.g., biomass-derived few-layer graphene or porous graphene-like nanosheets) as "graphene". The definitions and classifications of BGS and their applications in environmental remediation have not been assessed critically thus far. Comprehensive analysis and sufficient and robust evidence are highly desired to accurately determine the specific structures of BGS. In this perspective, we provide a systematic framework to define and classify the BGS. The state-of-the-art methods currently used to determine the structural properties of BGS are scrutinized. We then discuss the design and fabrication of BGS and how their distinctive features could improve the applicability of biomass-derived carbonaceous materials, particularly in environmental remediation. The environmental applications of these BGS are highlighted, and future research opportunities and needs are identified. The fundamental insights in this perspective provide critical guidance for the further development of BGS for a wide range of environmental applications.

Electron Transfer Mechanism at the Interface of Multi-Heme Cytochromes and Metal Oxide.

Electroactive microbial cells have evolved unique extracellular electron transfer to conduct the reactions via redox outer-membrane (OM) proteins. However, the electron transfer mechanism at the interface of OM proteins and nanomaterial remains unclear. In this study, the mechanism for the electron transfer at biological/inorganic interface is investigated by integrating molecular modeling with electrochemical and spectroscopic measurements. For this purpose, a model system composed of OmcA, a typical OM protein, and the hexagonal tungsten trioxide (h-WO3 ) with good biocompatibility is selected. The interfacial electron transfer is dependent mainly on the special molecular configuration of OmcA and the microenvironment of the solvent exposed active center. Also, the apparent electron transfer rate can be tuned by site-directed mutagenesis at the axial ligand of the active center. Furthermore, the equilibrium state of the OmcA/h-WO3 systems suggests that their attachment is attributed to the limited number of residues. The electrochemical analysis of OmcA and its variants reveals that the wild type exhibits the fastest electron transfer rate, and the transient absorption spectroscopy further shows that the axial histidine plays an important role in the interfacial electron transfer process. This study provides a useful approach to promote the site-directed mutagenesis and nanomaterial design for bioelectrocatalytic applications.

Digested sludge-derived three-dimensional hierarchical porous carbon for high-performance supercapacitor electrode.

Digested sludge, as the main by-product of the sewage sludge anaerobic digestion process, still contains considerable organic compounds. In this protocol, we report a facile method for preparing digested sludge-derived self-doped porous carbon material for high-performance supercapacitor electrodes via a sustainable pyrolysis/activation process. The obtained digested sludge-derived carbon material (HPDSC) exhibits versatile O-, N-doped hierarchical porous framework, high specific surface area (2103.6 m2 g-1) and partial graphitization phase, which can facilitate ion transport, provide more storage sites for electrolyte ions and enhance the conductivity of active electrode materials. The HPDSC-based supercapacitor electrodes show favourable energy storage performance, with a specific capacitance of 245 F g-1 at 1.0 A g-1 in 0.5 M Na2SO4; outstanding cycling stability, with 98.4% capacitance retention after 2000 cycles; and good rate performance (211 F g-1 at 11 A g-1). This work provides a unique self-doped three-dimensional hierarchical porous carbon material with a favourable charge storage capacity and at the same time finds a high value-added and environment-friendly strategy for disposal and recycling of digested sludge.

Denitrification in an integrated bioelectro-photocatalytic system.

Since nitrate causes severe ecological and health risks, nitrate contamination of drinking water sources has become one of the most important water quality concerns all over the world. Photocatalytic reduction of nitrate to molecular nitrogen presents a promising approach to remove nitrate from drinking water sources. However, harmful intermediates like NO2-, NO, NO2 and N2O are usually formed, and metal loading or hole scavengers are generally needed to reduce the recombination of photo-generated electrons and holes, which will cause secondary pollution to drinking water. In this work, an efficient, selective and sustainable bioelectro-photocatalytic nitrate-reducing system by utilizing commercial TiO2 nanoparticles P25 as the photocatalyst and bio-electrons from microbial metabolism as the hole scavenger is reported. In this system, bio-electrons extracted from organic substrates in bioanode are transferred to the photocathode through an external circuit for hole quenching. With the utilization of the residual photogenerated electrons, nitrate is completely reduced to nitrogen without accumulation of harmful nitrite or ammonium. The experimental results and the mechanistic analysis using the first-principles density functional theory calculations demonstrate that toxic by-products like nitrite or ammonium will not be accumulated in this system. Thus, this approach has a great potential for sustainable remediation of nitrate-contaminated drinking water sources.

Facile synthesis of sewage sludge-derived in-situ multi-doped nanoporous carbon material for electrocatalytic oxygen reduction.

Developing efficient, low-cost, and stable carbon-based catalysts for oxygen reduction reaction (ORR) to replace the expensive platinum-based electrocatalysts remains a major challenge that hamper the practical application of fuel cells. Here, we report that N, Fe, and S co-doped nanoporous carbon material, derived via a facile one-step pyrolysis of sewage sludge, the major byproduct of wastewater treatment, can serve as an effective electrocatalyst for ORR. Except for the comparable catalytic activity with commercial 20% Pt/C via a nearly four-electron transfer pathway in both alkaline and acid medium, the as-synthesized co-doped electrocatalyst also exhibits excellent methanol crossover resistance and outstanding long-term operation stability. The organic compounds in sewage sludge act as the carbon source and the in-situ N and S dopant in the fabrication, while the inorganic compounds serve as the in-built template and the in-situ Fe dopant. Our protocol demonstrates a new approach in the economic and eco-friendly benign reuse of sewage sludge, and also provides a straightforward route for synthesizing excellent carbon-based electrocatalysts as promising candidates for ORR directly from a type of waste/pollution.

Rapid isolation of a facultative anaerobic electrochemically active bacterium capable of oxidizing acetate for electrogenesis and azo dyes reduction.

In this study, 27 strains of electrochemically active bacteria (EAB) were rapidly isolated and their capabilities of extracellular electron transfer were identified using a photometric method based on WO3 nanoclusters. These strains caused color change of WO3 from white to blue in a 24-well agar plate within 40 h. Most of the isolated EAB strains belonged to the genera of Aeromonas and Shewanella. One isolate, Pantoea agglomerans S5-44, was identified as an EAB that can utilize acetate as the carbon source to produce electricity and reduce azo dyes under anaerobic conditions. The results confirmed the capability of P. agglomerans S5-44 for extracellular electron transfer. The isolation of this acetate-utilizing, facultative EBA reveals the metabolic diversity of environmental bacteria. Such strains have great potential for environmental applications, especially at interfaces of aerobic and anaerobic environments, where acetate is the main available carbon source.

A plate-based electrochromic approach for the high-throughput detection of electrochemically active bacteria.

Electrochemically active bacteria (EAB) have the ability to transfer electrons to electron acceptors located outside the cell, and they are widely present in diverse environments. In spite of their important roles in geochemical cycles, environmental remediation and electricity generation, so far, only a limited number and types of EAB have been isolated and characterized. Thus, effective and rapid EAB identification methods are highly desirable. In this protocol, we describe a photometric protocol for the visualization and high-throughput identification and isolation of EAB. The protocol relies on the fast electron acquisition and color change ability of an electrochromic material, namely a tungsten trioxide (WO3) nanorod assembly. The extracellular electron transfer (EET) from EAB to the WO3 nanorod assembly probe is accompanied by a bioelectrochromic reaction made evident by the color change of the probe. This protocol enables researchers to rapidly identify EAB and evaluate their EET ability either qualitatively with the naked eye or quantitatively by image analysis. We have also successfully used this protocol to isolate EAB from environmental samples. The time needed to complete this protocol is ∼2 d, with the actual EAB identification process taking about 5 min.

Nitrate formation from atmospheric nitrogen and oxygen photocatalysed by nano-sized titanium dioxide.

The concentration of nitrate in aquatic systems is rising with the development of modern industry and agriculture, causing a cascade of environmental problems. Here we describe a previously unreported nitrate formation process. Both indoor and outdoor experiments are conducted to demonstrate that nitrate may be formed from abundant atmospheric nitrogen and oxygen on nano-sized titanium dioxide surfaces under UV or sunlight irradiation. We suggest that nitric oxide is an intermediate product in this process, and elucidate its formation mechanisms using first-principles density functional theory calculations. Given the expanding use of titanium dioxide worldwide, such a titanium dioxide-mediated photocatalysis process may reveal a potentially underestimated source of nitrate in the environment, which on one hand may lead to an increasing environmental pollution concern, and on the other hand may provide an alternative, gentle and cost-effective method for nitrate production.

Synthesis, characterization and application of a novel starch-based flocculant with high flocculation and dewatering properties.

Flocculation process is one of the most widely used techniques for water and wastewater treatment, and also for sludge dewatering. Synthesis of natural biopolymers or modification of natural biopolymers as environmentally friendly flocculants is highly desired in the field of environmental protection. In this work, a water soluble copolymer flocculant, STC-g-PDMC (starch-graft-poly (2-methacryloyloxyethyl) trimethyl ammonium chloride) was synthesized through grafting a monomer, (2-methacryloyloxyethyl) trimethyl ammonium chloride (DMC), onto starch initiated by potassium persulphate. Acetone and ethanol were used for copolymer precipitation and purification in the synthesis, which diminished the toxicity during the synthesis process. The graft copolymer was characterized using Fourier-transform infrared spectroscopy, (1)H nuclear magnetic resonance, X-ray powder diffraction, thermogravimetric analysis and elemental analysis. The prepared STC-g-PDMC exhibited a highly effective flocculation capability for kaolin suspensions compared with starch and polyacrylamide as control. The charge neutralization effect played an important role in the flocculation process at low flocculant dosages. When it was used as dewatering agent for anaerobic sludge, the conditioned sludge could be easily filtered after the dosage reached 0.696% of the dry weight of sludge. Such a graft copolymer is a promising green agent for wastewater treatment and sludge dewatering applications.

A photometric high-throughput method for identification of electrochemically active bacteria using a WO3 nanocluster probe.

Electrochemically active bacteria (EAB) are ubiquitous in environment and have important application in the fields of biogeochemistry, environment, microbiology and bioenergy. However, rapid and sensitive methods for EAB identification and evaluation of their extracellular electron transfer ability are still lacking. Herein we report a novel photometric method for visual detection of EAB by using an electrochromic material, WO(3) nanoclusters, as the probe. This method allowed a rapid identification of EAB within 5 min and a quantitative evaluation of their extracellular electron transfer abilities. In addition, it was also successfully applied for isolation of EAB from environmental samples. Attributed to its rapidness, high reliability, easy operation and low cost, this method has high potential for practical implementation of EAB detection and investigations.

pH dependence of structure and surface properties of microbial EPS.

The flocculation of microorganisms plays a crucial role in bioreactors, and is substantially affected by pH. However, the mechanism for such an effect remains unclear. In this work, with an integrated approach, the pH dependence of structure and surface property of microbial extracellular polymeric substances (EPS), excreted from Bacillus megaterium TF10, and accordingly its flocculation is elucidated. From the Fourier transform infrared spectra and acid-base titration test results, the main functional groups and buffering zones in the EPS responsible for the microbial flocculation are indentified. The laser light scattering analysis reveals that the deprotonated or protonated states of these functional groups in EPS result in more dense and compact structure at a lower pH because of hydrophobicity and intermolecular hydrogen bonds. The zeta potential measurements identify the isoelectric point and indicate that the electrostatic repulsion action of EPS is controlled by pH. The highest flocculation efficiency is achieved near the isoelectric point (pH 4.8). These results clearly demonstrate that the EPS structure, surface properties, and accordingly the microbial flocculation are dependent heavily on pH in solution.

Optimization of the coagulation-flocculation process for pulp mill wastewater treatment using a combination of uniform design and response surface methodology.

Pulp mill wastewater was treated using the coagulation-flocculation process with aluminum chloride as the coagulant and a modified natural polymer, starch-g-PAM-g-PDMC [polyacrylamide and poly (2-methacryloyloxyethyl) trimethyl ammonium chloride], as the flocculant. A novel approach with a combination of response surface methodology (RSM) and uniform design (UD) was employed to evaluate the effects and interactions of three main influential factors, coagulant dosage, flocculant dosage and pH, on the treatment efficiency in terms of the supernatant turbidity and lignin removals as well as the water recovery. The optimal conditions obtained from the compromise of the three desirable responses, supernatant turbidity removal, lignin removal and water recovery efficiency, were as follows: coagulant dosage of 871 mg/L, flocculant dosage of 22.3 mg/L and pH 8.35. Confirmation experiments demonstrated that such a combination of the UD and RSM is a powerful and useful approach for optimizing the coagulation-flocculation process for the pulp mill wastewater treatment.

Identification of key constituents and structure of the extracellular polymeric substances excreted by Bacillus megaterium TF10 for their flocculation capacity.

Extracellular polymeric substances (EPS), a complex high-molecular-weight mixture of polymers excreted by microorganisms and produced from cell lysis, may have a high bioflocculation activity. In this work, the EPS excreted from Bacillus megaterium TF10, which was isolated from a soil sample, were systematically characterized to give insights into the relationship between their specific constituents and structure with their flocculation capacity. The results of microscopic observation, zeta potential, and TF10 EPS structure analysis show that the bridging mechanism was mainly responsible for the flocculation of the TF10. The constituents with a large molecular weight (1037-2521 kDA) and functional groups had contributed to the flocculation. GC-MS and NMR analyses demonstrate that the polysaccharides had long chain composed of rhamnose as well as glucose and galactose with uronic acids, acetyl amino sugars, and proteins as the side chains. The proteins in TF10 had no flocculation ability because of their special secondary structure and molecular weight diffusion characters. The EPS from Bacillus megaterium TF10 were found to exhibit a high flocculation activity, and the polysaccharides in EPS, which have the structure of the long backbone with active side chains, were identified as the active constituents for the high flocculation activity.

Degradation of organic pollutants in a photoelectrocatalytic system enhanced by a microbial fuel cell.

Photocatalytic oxidation mediated by TiO(2) is a promising oxidation process for degradation of organic pollutants, but suffers from the decreased photocatalytic efficiency attributed to the recombination of photogenerated electrons and holes. Thus, a cost-effective supply of external electrons is an effective way to elevate the photocatalytic efficiency. Here we report a novel bioelectrochemical system to effectively reduce p-nitrophenol as a model organic pollutant with utilization of the energy derived from a microbial fuel cell. In such a system, there is a synergetic effect between the electrochemical and photocatalytic oxidation processes. Kinetic analysis shows that the system exhibits a more rapid p-nitrophenol degradation at a rate two times the sum of rates by the individual photocatalytic and electrochemical methods. The system performance is influenced by both external resistor and electrolyte concentration. Either a lower external resistor or a lower electrolyte concentration results in a higher p-nitrophenol degradation rate. This system has a potential for the effective degradation of refractory organic pollutants and provides a new way for utilization of the energy generated from conversion of organic wastes by microbial fuel cells.

Contribution of extracellular polymeric substances (EPS) to the sludge aggregation.

The contribution of extracellular polymeric substances (EPS), including loosely bound EPS (LB-EPS) and tightly bound EPS (TB-EPS), to the aggregation of both aerobic and anaerobic sludge is explored using the extended DLVO theory. It is observed that the aggregation abilities of both sludge samples decrease with the extraction of LB-EPS and TB-EPS, implying the crucial roles of EPS in sludge aggregation. Furthermore, through analyzing the interaction energy curves of sludge before and after the EPS extraction using the extended DLVO theory, it is found that both LB-EPS and TB-EPS have a substantial contribution to the sludge aggregation. The interaction energy of LB-EPS is always negative, suggesting that the LB-EPS always display a positive effect on the sludge aggregation. On the other hand, the interaction energy of TB-EPS is not always negative, depending on the separation distance between sludge cells. These results imply that the LB-EPS and TB-EPS have different contributions to the sludge aggregation.

Synthesis and characterization of a novel cationic chitosan-based flocculant with a high water-solubility for pulp mill wastewater treatment.

In this work, pulp mill wastewater was treated using a novel copolymer flocculant with a high water-solubility, which was synthesized through grafting (2-methacryloyloxyethyl) trimethyl ammonium chloride (DMC) onto chitosan initiated by potassium persulphate. The experimental results demonstrate that the two main problems associated with the utilization of chitosan as a flocculant, i.e., low molecular weight and low water-solubility, were concurrently sorted out. The physicochemical properties of this flocculant were characterized with Fourier-transform infrared spectroscopy, (1)H nuclear magnetic resonance spectroscopy, X-ray powder diffraction and field emission scanning electron microscopy. Reaction parameters influencing the grafting percentage, such as temperature, reaction time, initiator concentration and monomer concentration, were optimized using an orthogonal array design matrix. With an increase in grafting percentage, the water-solubility of the flocculant was improved, and it became thoroughly soluble in water when the grafting percentage reached 236.4% or higher. Its application for the treatment of pulp mill wastewater indicates that it had an excellent flocculation capacity and that its flocculation efficiency was much better than that of polyacrylamide. The optimal conditions for the flocculation treatment of pulp mill wastewater were also obtained.