Utilizing cost-effective pyrocarbon for highly efficient gold retrieval from e-waste leachate.

Addressing burdens of electronic waste (E-waste) leachate while achieving sustainable and selective recovery of noble metals, such as gold, is highly demanded due to its limited supply and escalating prices. Here we demonstrate an environmentally-benign and practical approach for gold recovery from E-waste leachate using alginate-derived pyrocarbon sorbent. The sorbent demonstrates potent gold recovery performance compared to most previously reported advanced sorbents, showcasing high recovery capacity of 2829.7 mg g-1, high efficiency (>99.5%), remarkable selectivity (Kd ~ 3.1 × 108 mL g-1), and robust anti-interference capabilities within environmentally relevant contexts. The aromatic structures of pyrocarbon serve as crucial electrons sources, enabling a hydroxylation process that simultaneously generates electrons and phenolic hydroxyls for the reduction of gold ions. Our investigations further uncover a "stepwise" nucleation mechanism, in which gold ions are reduced as intermediate gold-chlorine clusters, facilitating rapid reduction process by lowering energy barriers from 1.08 to -21.84 eV. Technoeconomic analysis demonstrates its economic viability with an input-output ratio as high as 1370%. Our protocol obviates the necessity for organic reagents whilst obtaining 23.96 karats gold product from real-world central processing units (CPUs) leachates. This work introduces a green sorption technique for gold recovery, emphasizing its role in promoting a circular economy and environmental sustainability.

Overcoming metals redox rate limitations in spinel oxide-driven Fenton-like reactions via synergistic heteroatom doping and carbon anchoring for efficient micropollutant removal.

The transition metals redox rate limitations of spinel oxides during Fenton-like reactions hinder its efficient and sustainable treatment of actual wastewater. Herein, we propose to optimize the electronic structure of Co-Mn spinel oxide (CM) via sulfur doping and carbon matrix anchoring synergistically, enhancing the radicals-nonradicals Fenton-like processes for efficient water decontamination. Activating peroxymonosulfate (PMS) with optimised spinel oxide (CMSAC) achieved near-complete removal of ofloxacin (10 mg/L) within 6 min, showing 8.4 times higher efficiency than CM group. Significantly higher yields of SO4·- and high-valent metal species in CMSAC/PMS system provided exceptional resistance to co-existing anions, enabling efficient removal of various emerging contaminants in high salinity leachate. Specifically, sulfur coordination and carbon anchoring-induced oxygen vacancy synergistically improved the electronic structure and electron transfer efficiency of CMSAC, thus forming highly reactive Co sites and significantly reducing the energy barrier for Co(IV)=O generation. The reductive sulfur species facilitated the conversion of Co(III) to Co(II), thereby maintaining the stability of the catalytic activity of CMSAC. This work developed a synergistic optimization strategy to overcome the metals redox rate limitations of spinel oxides in Fenton-like reactions, providing deep mechanistic insights for designing Fenton-like catalysts suitable for practical applications.

Low-voltage stimulated denitrification performance of high-salinity wastewater using halotolerant microorganisms.

Nitrate is a common contaminant in high-salinity wastewater, which has adverse effects on both the environment and human health. However, conventional biological treatment exhibits poor denitrification performance due to the high-salinity shock. In this study, an innovative approach using an electrostimulating microbial reactor (EMR) was explored to address this challenge. With a low-voltage input of 1.2 V, the EMR reached nitrate removal kinetic parameter (kNO3-N) of 0.0166-0.0808 h-1 under high-salinities (1.5 %-6.5 %), which was higher than that of the microbial reactor (MR) (0.0125-0.0478 h-1). The mechanisms analysis revealed that low-voltage significantly enhanced microbial salt-in strategy and promoted the secretion of extracellular polymeric substances. Halotolerant denitrification microorganisms (Pseudomonas and Nitratireductor) were also enriched in EMR. Moreover, the EMR achieved a NO3-N removal efficiency of 73.64 % in treating high-salinity wastewater (salinity 4.69 %) over 18-cycles, whereas the MR only reached 54.67 %. In summary, this study offers an innovative solution for denitrification of high-salinity wastewater.

Leachate from municipal solid waste landfills: A neglected source of microplastics in the environment.

Over the past decade or so, microplastics (MPs) have received increasing attention due to their ubiquity and potential risk to the environment. Waste plastics usually end up in landfills. These plastics in landfills undergo physical compression, chemical oxidation, and biological decomposition, breaking down into MPs. As a result, landfill leachate stores large amounts of MPs, which can negatively impact the surrounding soil and water environment. However, not enough attention has been given to the occurrence and removal of MPs in landfill leachate. This lack of knowledge has led to landfills being an underestimated source of microplastics. In order to fill this knowledge gap, this paper collects relevant literature on MPs in landfill leachate from domestic and international sources, systematically summarizes their presence within Asia and Europe, assesses the impacts of landfill leachate on MPs in the adjacent environment, and particularly discusses the possible ecotoxicological effects of MPs in leachate. We found high levels of MPs in the soil and water around informal landfills, and the MPs themselves and the toxic substances they carry can have toxic effects on organisms. In addition, this paper summarizes the potential impact of MPs on the biochemical treatment stage of leachate, finds that the effects of MPs on the biochemical treatment stage and membrane filtration are more significant, and proposes some novel processes for MPs removal from leachate. This analysis contributes to the removal of MPs from leachate. This study is the first comprehensive review of the occurrence, environmental impact, and removal of MPs in leachate from landfills in Asia and Europe. It offers a comprehensive theoretical reference for the field, providing invaluable insights.

Progress of improving waste activated sludge dewaterability: Influence factors, conditioning technologies and implications and perspectives.

Large amounts of waste activated sludge (WAS) as a by-product generated from the biological treatment in wastewater treatment plants (WWTPs) is of high moisture content (MC), organic pollutants, heavy metals and pathogenic bacteria, it may cause serious environmental ecological risk without appropriate disposal. More than one half of the total operation cost is accounted for sludge disposal in a WWTP. Dewatering is an essential and important step during the sludge treatment and disposal process for it could efficiently reduce its volume, and be beneficial to the subsequent treatment and disposal of sludge. However, sludge should be conditioned before mechanical dewatering because of its high hydrophilicity. In this work, it presented a comprehensive review on sludge dewatering including summarizing the dewaterability measurement indexes, affecting factors, conditioning technologies, the improvement mechanisms. Finally, based on the eventual disposal and low carbon emission target, the implications and perspectives development of sludge conditioning were discussed. Based on the above discussion, there is no unified theoretical insight of the improvement mechanism of sludge dewaterability. In addition, the relationship between the microstructure of organic matters in sludge floc and the dewaterability should be deepened. Especially, how to choose the optimal conditioning technology for sludge dewatering lies in the physical and chemical properties of sludge, however, the carbon emission of the conditioning and dewatering process also needs to be considered. Accordingly, green, low-cost and organic conditioning agents are the direction of future research, and the establishment of automatic operating system and real-time evaluation index system is the key challenge.

Target-prepared sludge biochar-derived synergistic Mn and N/O induces high-performance periodate activation for reactive iodine radicals generation towards ofloxacin degradation.

Converting waste activated sludge into catalysts for the removal of antibiotics in water fulfils the dual purpose of waste-to-resource and hazardous pollution elimination. In this study, sludge-derived biochar (SDB) for efficient periodate (PI) activation was first prepared via one-step pyrolysis of potassium permanganate-polyhexamethylenebiguanide conditioned sludge without additional modification. The SDB (750 °C)-PI system degraded 100% ofloxacin (OFL, 41.5 µM) within 6 min and was almost undisturbed by inorganic ions or humic acids. The experimental results confirmed that the predominant role of reactive iodine species (RIS) and the auxiliary involvement of singlet oxygen (1O2) jointly contributed to the OFL degradation. Theoretical calculations further indicated that the synergy between Mn and N/O induced local charge redistribution and improved electron transfer capability of SDB, leading to the formation of electron-rich Mn sites and enhanced Mn(II)↔Mn(III)↔Mn(IV) redox to promote PI activation. More importantly, the enhanced adsorption and charge transfer of PI on the Mn site of the Mn-N/O-C structures induced the I-O bond stretching and the rapid generation of RIS. This study offered a cost-effective strategy for developing SDB-based catalysts, further advancing the comprehension of sludge management and the intricate mechanisms underlying RIS formation in PI-advanced oxidation processes.

Unveiling the occurrence, distribution, removal, and environmental impacts of 65 emerging contaminants in neglected fresh leachate from municipal solid waste incineration plants.

Emerging contaminants (ECs) are commonly found in environmental media. Yet leachate from municipal solid waste incineration plants (MSWIPs), which can serve as a reservoir for various contaminants, including ECs, has received little investigation. To address this gap, 65 ECs were analyzed in the fresh leachate and biological effluent from three major MSWIPs in Shanghai. Results indicated that over half (56%) of the 65 ECs were detected in fresh leachate. Different ECs would be removed to varying degrees after biological treatment, including polycyclic aromatic hydrocarbons (PAHs) (65%), polybrominated diphenyl ethers (PBDEs) (51%), phthalate esters (PAEs) (36%), and organophosphorus pesticides (OPPs) (34%). Notably, for tetrabromobisphenol A (TBBPA), a PBDE substitute, only 2% was removed after biological treatment, while polychlorinated biphenyls (PCBs) were effectively removed at 83%. Water solubility and the octanol-water partition coefficient are key factors influencing the distribution and removal of ECs in leachate. the effluent will still contain refractory ECs even after the biological treatment. These residual ECs discharged to sewers can impact wastewater treatment plants or contaminate surface water and groundwater. These findings provide insights into the leachate contamination by ECs, their environmental fate, factors affecting their behavior, and potential environmental impacts.

Factors affecting the durability of dimethyl dithiocarbamate-stabilized air pollution control (APC) residues derived from municipal solid waste incineration.

Sodium dimethyl dithiocarbamate (SDD) is widely used for stabilizing heavy metals to minimize pollution from air pollution control (APC) residues derived from municipal solid waste incineration. However, the effect of environmental conditions on heavy metal leaching from SDD-stabilized APC residues remains unknown. Therefore, this study aimed to evaluate the durability of SDD-stabilized APC residues and determine the relationship between heavy metal leaching and environmental factors, including pH, temperature, and oxygen. The results revealed that accelerated SDD decomposition and the decline in durability of SDD-stabilized APC residues were caused by acidic and aerated conditions and temperatures above 40 °C. A decrease in pH from 12.25 to 4.69 increased the Cd and Pb concentrations in SDD-stabilized APC residue leachate from below detection (0.002 mg/L) to 1.32 mg/L and 0.04 mg/L to 3.79 mg/L, respectively. Heating at 100 °C for 2 d increased the Cd and Pb concentrations from below detection (0.002 mg/L and 0.01 mg/L) to 2.96 mg/L and 0.47 mg/L, respectively. Aeration for 5 d increased the Cd and Pb concentrations from below detection to 0.09 mg/L and 0.49 mg/L, respectively. The decline in durability was attributed to acid hydrolysis, thermal decomposition, and oxidative damage of SDD, resulting in breakage of the chelated sulfur-metal bond, which was confirmed by the decrease in the oxidizable fraction of heavy metals and the SDD content. This study improves the understanding of the factors contributing to the decline in durability of heavy metals in SDD-stabilized APC residues, which is important for ensuring the long-term stabilization and environmental safety of these residues.

Distribution, removal and ecological risk assessment of antibiotics in leachate from municipal solid waste incineration plants in Shanghai, China.

Leachate from Municipal Solid Waste (MSW) incineration plants contains multiple antibiotics. However, current knowledge of antibiotics in such leachate is very limited compared to landfill leachate. In this study, the distribution, removal and ecological risks of 8 sulfonamides (SAs), 4 quinolones (FQs), and 4 macrolides (MLs) antibiotics in leachate from three MSW incineration plants in Shanghai were investigated. The results showed that 12 types of target antibiotics were detected at high concentrations (7737.3-13,758.7 ng/L) in the fresh leachate, exceeding the concentrations reported for landfill leachate. FQs were the dominant antibiotics detected in all three fresh leachates, accounting for >60 % of the total detected concentrations. The typical "anaerobic-anoxic/aerobic-anoxic/aerobic-ultrafiltration" treatment process removed the target antibiotics effectively (89.0 %-93.4 %), of which the anaerobic unit and the primary anoxic/aerobic unit were the most important antibiotic removal units. Biodegradation was considered to be the dominant removal mechanism, removing 78.11 %-92.37 % of antibiotics, whereas sludge adsorption only removed 1.02 %-10.89 %. Antibiotic removal was significantly correlated with leachate COD, pH, TN, and NH3-N, indicating that they may be influential factors for antibiotic removal. Ecological risk assessment revealed that ofloxacin (OFX) and enrofloxacin (EFX) in the treated leachate still posed high risks to algae and crustaceans. This research provides insights into the fate of antibiotics in leachate.

Optimizing adsorption performance of sludge-derived biochar via inherent moisture-regulated physicochemical properties.

Understanding the impact of abundant inherent moisture in sewage sludge on the physicochemical properties and adsorption applications of sludge-derived biochar (SDB) contributed significantly to promoting economical sludge reuse. The moisture (0-80%) contributed to the development of micropore and mesopore in SDB at 400 °C, resulting in a maximum increase in specific surface area (SSA) and total pore volume (TPV) of SDB by 38.47% (84.811-117.437 m2/g) and 92.60% (0.0905-0.1743 m3/g), respectively. At 600/800 °C, moisture only facilitated mesopore formation, while was exacerbated with increasing moisture content. Despite reduction in SSA during this stage, TPV increased by a maximum of 20.47% (0.1700-0.2048 m3/g). The presence of moisture during pyrolysis led to an increase in the formation of 3-5 thickened benzene rings and defective structures in SDB, along with more C=O, O-C=O/-OH, pyrrole N, pyridine N, and thiophene. As a result, moisture (40%/80%) increased the maximum adsorption capacity (76.2694-88.0448/90.1190 mg/g) of SDB (600 °C) for tetracycline, mainly due to enhanced pore filling effect and hydrogen bonding induced by improved physicochemical properties. This study offered a novel approach for optimizing the performance of SDB adsorption applications by manipulating the sludge moisture, which is critical for practical sludge management.

Exploring into a light-avoided environment: Mechanical-thermal coupled conditions responsible for the aging behavior of plastic waste in landfills.

Plastics in landfills undergo a unique micronization process due to multi-factor and light-avoided conditions, but their aging process in such a typical environment remains unexplored. This study investigated the aging behavior of polyethylene plastics, representative of landfills, under simulated dynamic mechanical forces and high temperature-two prevalent environmental factors in landfills. The study explored the individual and combined contributions of these factors to the aging process. Results indicated that high temperature played a primary role in aging plastics by depolymerization and degradation through ·OH production, while mechanical forces contributed mainly to surface structure breakdown. The combined effect leads to more serious surface damage, creating holes, cracks, and scratches that provide access for free radical reactions to plastic bulk, thereby accelerating the aging and micronization process. The resulting microplastics were found to be 14.25 ± 0.53 µg L-1. Aged plastics exhibit a rapid aging rate of depolymerization and oxidation compared to virgin plastics due to their weak properties, suggesting a higher potential risk of microplastic generation. This study fills a knowledge gap regarding the aging behavior of plastics under complex and light-avoided landfill conditions, emphasizing the need for increased attention to the evolution process of microplastics from aged plastic waste in landfills.

Effect of thermal hydrolysis pretreatment on the stabilization of sludge with different solid contents during autothermal thermophilic aerobic digestion.

Sludge stabilization was affected by solid content during autothermal thermophilic aerobic digestion (ATAD). Thermal hydrolysis pretreatment (THP) could alleviate the issues of high viscosity, slow solubilization and low ATAD efficiency caused by increased solid content. The influence of THP on the stabilization of sludge with different solid contents (5.24%-17.14%) during ATAD was investigated in this study. The results demonstrated that stabilization was achieved with volatile solid (VS) removal of 39.0%-40.4% after 7-9 days of ATAD for sludge with solid content of 5.24%-17.14%. The solubilization of sludge with different solid contents reached 40.1%-45.0% after THP. The rheological analysis indicated that the apparent viscosity of sludge was obviously reduced after THP at different solid contents. The increase in fluorescence intensity of fulvic acid-like organics, soluble microbial by-products and humic acid-like organics in the supernatant after THP and the decrease in fluorescence intensity of soluble microbial by-products after ATAD were detected by excitation emission matrix (EEM). The molecular weight (MW) distribution in the supernatant elucidated that the proportion of 50 kDa < MW < 100 kDa increased to 16%-34% after THP and the proportion of 10 kDa < MW < 50 kDa decreased to 8%-24% after ATAD. High throughput sequencing showed that the dominant bacterial genera shifted from Acinetobacter, Defluviicoccus and Norank_f__norank_o__PeM15 to Sphaerobacter and Bacillus during ATAD. This work revealed that solid content of 13%-17% was appropriate for efficient ATAD and rapid stabilization under THP.

Roles of catalytic ozonation by bimetallic Fe/Ce loading sludge-derived biochar in amelioration of sludge dewaterability: Performance and implementation mechanisms.

In this study, an environmentally friendly alternative was developed using catalytic ozonation by sludge-derived biochar loaded with bimetallic Fe/Ce (O3/SBC-FeCe) for enhanced sludge dewatering. The results indicated that the lowest capillary suction time (CST) of 20.9 s and water content of dewatered sludge cake (Wc) of 64.09% were achieved under the dosage of 40 mg O3/g dry solids (DS) and 0.4 g SBC-FeCe/g DS which were considered as the optimum condition. In view of excellent electron exchanging capacity of SBC-FeCe with rich Lewis acid sites and conversions of valence sates of Fe and Ce, more O3 were decomposed into reactive oxygen species under the catalytic action of SBC-FeCe, which strengthened oxidizing capacity. Enhanced oxidation rendered sludge cells inactivation and compact network structure rupture releasing intracellular water and organic substances. Subsequently, hydrophilic organic matters were attacked and eliminated lessening sludge viscosity and colloidal forces and intensifying hydrophobicity and flowability. In addition, changes of sludge morphology suggested that sludge roughness was alleviated, structural strength and compressibility were raised and porous and retiform structure was constructed providing channels for water outflow by adding skeleton builder of SBC-FeCe. Overall, the synergistic interaction of strengthened oxidation and skeleton construction improved sludge dewaterability.

Antiviral drugs in wastewater are on the rise as emerging contaminants: A comprehensive review of spatiotemporal characteristics, removal technologies and environmental risks.

Antiviral drugs (ATVs) are widely used to treat illnesses caused by viruses. Particularly, ATVs were consumed in such large quantities during the pandemic that high concentrations were detected in wastewater and aquatic environment. Since ATVs are not fully absorbed by the human or animal body, this results in large amounts of them being discharged into the sewage through urine or feces. Most ATVs can be degraded by microbes at wastewater treatment plants (WWTPs), while some ATVs either require deep treatment to reduce concentration and toxicity. Parent and metabolites residing in effluent posed a varying degree of risk when entering the aquatic environment, while increasing the potential of natural reservoirs for environmentally acquired antiviral drug resistance potential. There is a rising research on the behavior of ATVs in the environment has surged since the pandemic. In the context of multiple viral diseases worldwide, especially during the current COVID-19 pandemic, a comprehensive assessment of the occurrence, removal, and risk of ATVs is urgently needed. This review aims to discuss the fate of ATVs in WWTPs from various regions in the world with wastewater as the main analyzing object. The ultimate goal is to focus on ATVs with high ecological impact and regulate their use or develop advanced treatment technologies to mitigate the risk to the environment.

Successive choline addition enhancing the methanogenesis of waste activated sludge anaerobic digestion: Insight from hydrophilicity, electrochemical performance and microbial community.

Anaerobic digestion (AD) is a promising technology to treat waste-activated sludge, previous study proved that methane production could be enhanced with the addition of choline, this work aimed to solve the problem of rapid biodegradability of choline in the AD process by changing its dosing method. With 0.75 g/L as the optimal choline dosing concentration, experimental results showed that successive choline dosing during the first 3-6 days of AD (experimental groups, EGs) performed better than the single dosing. The accumulative biogas production in EGs was increased by 35.55-36.73%, which could be caused by the simultaneous promotion of hydrolysis-acidification and methanogenesis processes. Especially, the electron exchange capacity of digested sludge in EGs was increased by 16.71-34.58%. In addition, the surface Gibbs free energy (△GSL) of sludge in EGs was 105.51-172.21% higher (corresponding to stronger hydrophilicity and repulsion), which might help disperse sludge flocs and improve mass transfer efficiency, and the △GSL values were positively correlated with the accumulative methane production (R2 = 0.7029). Microbiological analysis showed that microbial communities in EGs were richer and Methanosaeta was regarded as the dominant species with 15.93-30.08% higher relative abundance with choline addition. According to Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analysis, EGs were found to be more active in metabolism clusters. Collectively, these findings demonstrated that successive choline dosing during the first 3-6 days is an effective and novel method to enhance methane production in AD process.

Identifying the fate of nitrogenous species during sewage sludge pyrolysis via in-situ tracing of protein-sludge inherent components interactions.

The effect of interactions between different components in sewage sludge on the thermochemical transformation of nitrogenous species is usually neglected, which is important to explain the generation mechanism of some key nitrogenous by-products. Here, we investigated the distribution, form, and chemical properties of the products from sludge-extracted protein (PR) under different pyrolysis scenarios using several in-situ probe techniques, to elucidate the critical role of typical sludge organics/inorganics on the evolution of nitrogenous intermediates and by-products. The results suggested that Ca/Fe/Si/Al-containing inorganics significantly affected the pyrolytic behavior of PR and the thermal transformation of nitrogenous species, while sludge organics, including humic acids and polysaccharides, had limited effects on the temperature-dependent evolution of nitrogenous species in PR. Among them, calcium oxide catalyzed the ring-opening reaction of heterocyclic-N with aromatic-like structures, resulting in a 21.1 %-68.8 % reduction in nitrogen fixation efficiency in the char. At lower temperatures (350-450 °C), calcium oxide caused more nitrogen to be transferred to the gas/tar phases in the form of NH3 and heterocyclic-N, and it also enhanced the conversion of nitrile-N → HCN → NO at temperatures above 450 °C. In contrast, polyferric salts inhibited the devolatilization of mono-heterocyclic-N and enhanced the thermal stability of poly-heterocyclic-N, resulting in a maximum increase of 18.5 mg·g-1 of nitrogen content in the char, while reducing the release of NH3 and HCN by 71.1 % and 32.0 %. This work elucidated the interaction between PR and inherent components in sludge, providing key information for the control of nitrogenous volatiles and NOx.

Low-molecular-weight dissolved organic nitrogen transformation behavior in concentrated leachate by O3 and •OH: Partition, molecular insight, and potential precursor-product relationship.

Low-molecular-weight dissolved organic nitrogen (LMW-DON) is an emerging issue in concentrated leachate (CL). Ozonation is crucial to remove LMW-DON, but selectivity mechanisms of different reactive oxygen species were unknown. Here, reactions of O3 and •OH with LMW-DON at different dosages were determined from composition, unsaturation/redox potential, and precursor-product relationship. The molecular weight of LMW-DON in CL presented a normal distribution and 76.5% was below 450 Da. LMW-DON with 400-1000 Da increased to 55.6%-66.7% and O/Cwa increased by over 40.0% due to electrophilic substitution of O3. LMW-DON with <400 Da and 550-1000 Da were preferentially degraded by •OH at the low and high O3 dosage, respectively. O3 preferred to remove lipid-like (69.1%), protein-like (58.2%), and amino sugars-like (72.8%) LMW-DON, whereas •OH preferred to the refractory LMW-DON, such as carbohydrates-like (71.1%), lignin-like (49.6%), and tannins-like (72.5%) LMW-DON. Forty-three transformation reactions were quantified using mass difference analysis, and O3 preferred to oxygen addition (e.g., +2O) and conversed amino to nitro groups, and saturated LMW-DON increased via unsaturated bonds rupture. •OH attacked the carbon groups (e.g., -CH2) and nitrogen groups (e.g., -NH3+O, -NO2+H). These findings provide molecular evidence for the selectivity of oxidants with LMW-DON and improve the ozonation application in wastewater treatment.

Medium-Low Temperature Conditions Induce the Formation of Environmentally Persistent Free Radicals in Microplastics with Conjugated Aromatic-Ring Structures during Sewage Sludge Pyrolysis.

Medium-low temperature pyrolysis is an effective method of retaining active components in sludge char. However, we found that incomplete cracking reactions resulted in residues of microplastics (MPs) remaining in the char; moreover, high levels of environmentally persistent free radicals (EPFRs) were detected in these MPs. Here, we investigated the temperature-dependent variations in the char-volatile products derived from sludge and MPs under different pyrolysis scenarios using multiple in situ probe coupling techniques and electron paramagnetic resonance spectroscopy, thereby identifying the sources of EPFRs and elucidating the corresponding formation-conversion mechanisms. The temperature was the key factor in the formation of EPFRs; in particular, in the 350-450 °C range, the abundance of EPFRs increased exponentially. Reactive EPFR readily formed in MPs with conjugated aromatic-ring structures (polyethylene terephthalate and polystyrene) at a temperature above 350 °C; EPFR concentrations were 5-17 times higher than those found in other types of polymers, and these radicals exhibited half-lives of more than 90 days. The EPFR formation mechanism could be summarized as solid-solid/solid-gas interfacial interactions between the polymers and the intermediate products from sludge pyrolysis (at 160-350 °C) and the homolytic cleavage-proton transfer occurring in the polymers themselves under the dual action of thermal induction and acid sites (at 350-450 °C). Based on the understanding of the evolution of EPFRs, temperature regulation and sludge components conditioning may be effective approaches to inhibit the formation of EPFRs in MPs, constituting reliable strategies to diminish the environmental risk associated with the byproducts of sludge pyrolysis.

Booming microplastics generation in landfill: An exponential evolution process under temporal pattern.

Landfills are the main plastic sinks and microplastics (MPs) sources in the anthropogenic terrestrial system. Understanding the dynamic process of generating MPs is a prerequisite to reducing their potential risk, which remains unexplored because of the complex stabilization process of landfills. In this study, we investigated the evolution process of MPs generated in a partitioned landfill, with well-recorded disposal ages of over 30 years. Considering the initial plastic proportions in fresh landfilled waste, the occurrence of MPs increased exponentially with the disposal age. A booming generation of MPs occurred from 71.3 ± 17.7 items/(g plastic) to 653.1 ± 191.5 items/(g plastic). The generation rates of MPs varied greatly depending on the individual polymer types, with polyethylene (PE) having the highest generation rate of 28.4 items/(g plastic) per year at 31 years, compared to that of polypropylene (PP) and polystyrene (PS) at 15.0 and 9.6 items/(g plastic) per year, respectively. The variation in the carbonyl index indicated that environmental oxidation might facilitate the fragmentation of plastic waste. The relative abundance of plastic-degrading microbes increased more than three times in the plastisphere after 30 years of landfilling, indicating that the potential biodegradation might be a nonnegligible driver for plastic fragmentation after long-term natural acclimatization. This study revealed the dynamic evolution process of MPs in landfills and predicted the booming stage, which might provide an important guideline for reducing the leakage risk of MPs during the reclamation of old landfills or dumping sites.

Coupling sludge-based biochar and electrolysis for conditioning and dewatering of sewage sludge: Effect of char properties.

The addition of sludge-based biochar during electrochemical pretreatment of sewage sludge, as an efficient hybrid technology, is potentially to be applied in sludge deep-dewatering. The chars functioned as conductors, catalysts and skeleton particles could enhance the sludge dewaterability and increase the calorific value of the dewatered sludge cake. However, the effect of synthesis conditions on the char properties and further on the dewatering performance is still unknown. Herein, the sludge-based particle electrodes (SPEs) under three main synthesis conditions, including liquid-solid ratio, pyrolysis temperature and time, were prepared. The sludge-based biochars (i.e., SPE-400, SPE-600, and SPE-800 pyrolyzed under 400, 600 and 800 °C, respectively) were characterized and utilized as three-dimensional electrodes during sludge electrolysis. The increased pyrolysis temperature (within 400-800 °C) resulted in the enrichment of metallic ions and increment of specific surface area and pore volume of SPE, which led to the increased catalysis and adsorption sites for viscous proteins (PNs). Particularly, the pores of SPE-800 provided more drainage channels as skeleton builders. Compared with raw sludge, the capillary suction time (CST) and the specific resistance of filtration (SRF) of the treated sludge with 3D-SPE-800 were reduced by 58.12% and 81.01%, respectively, but the net sludge solids yield (YN) was increased by 87.05%. The highest decrease of hydrophilic α-Helix content in PNs (from 9.93% to 7.30%) was observed when using SPE-800 as particle electrode, revealing the crucial role of char characteristics on protein reduction and subsequent dewatering enhancement. The synergistic effects of electrolysis and sludge-based biochar provided a new insight for a closed-loop pretreatment of sewage sludge in the wastewater treatment plant.