Is Pyrolysis Treatment a Viable Solution to Detoxify Metal(loid)s in Sewage Sludge toward Land Application? Case Studies of Chromium and Zinc.

Metal(loid)s in sewage sludge (SS) are effectively immobilized after pyrolysis. However, the bioavailability and fate of the immobilized metal(loid)s in SS-derived biochar (SSB) following land application remain largely unknown. Here, the speciation and bioavailability evolution of SSB-borne Cr and Zn in soil were systematically investigated by combining pot and field trials and X-ray absorption spectroscopy. Results showed that approximately 58% of Cr existing as Cr(III)-humic complex in SS were transformed into Fe (hydr)oxide-bound Cr(III), while nano-ZnS in SS was transformed into stable ZnS and ferrihydrite-bound species (accounting for over 90% of Zn in SSB) during pyrolysis. All immobilized metal(loid)s, including Cr and Zn, in SSB tended to be slowly remobilized during aging in soil. This study highlighted that SSB acted as a dual role of source and sink of metal(loid)s in soil and posed potential risks by serving a greater role of a metal(loid) source than a sink when applied to uncontaminated soils. Nevertheless, SSB could impede the translocation of metal(loid)s from soil to crop compared to SS, where coexisting elements, including Fe, P, and Zn, played critical roles. These findings provide new insights for understanding the fate of SSB-borne metal(loid)s in soil and assessing the viability of pyrolyzing SS for land application.

MoS2 coupled with ball milling co-modified sludge biochar to efficiently activate peroxymonosulfate for neonicotinoids degradation: Dominant roles of SO4•-, 1O2 and surface-bound radicals.

An efficient catalyst of molybdenum disulfide (MoS2) coupled with ball milling modified sludge biochar (BMSBC) was prepared to efficiently activate peroxymonosulfate (PMS) for neonicotinoids elimination. As expected, 95.1% of imidacloprid (IMI) was degraded by PMS/BMSBC system within 60 min and it was accompanied by the outstanding mineralization rate of 71.9%. The superior pore structures, rich defects, oxygen-containing functional groups and grafted MoS2 on BMSBC offered excellent activation performance for PMS. The influencing factor experiments demonstrated that PMS/BMSBC system performed high anti-interference to wide pH range and background constituents (e.g., inorganic ions and humic acid). Quenching experiments and electron paramagnetic resonance analysis revealed that SO4•-, 1O2, and surface-bound radicals played critical roles in IMI degradation. Electron donors on biochar activated PMS, producing surface radicals. The lone pair electrons within the Lewis basic site of C=O on BMSBC enhanced PMS decomposition by facilitating the cleavage of the -O-O- bond in PMS to release 1O2. The activation process of PMS by MoS2 accelerated the oxidation of Mo (IV) to Mo (VI) to generate SO4•-. Based on the transformed products (TPs), four degradation pathways of IMI in PMS/BMSBC system were suggested, and all TPs toxicity levels were lower than that of IMI by ECOSAR analysis. Additionally, BMSBC exhibited outstanding sustainable catalytic activity towards PMS activation with the well accepted degradation rate of 71.3% for IMI even after five reuse cycles. PMS/BMSBC system also exhibited satisfactory degradation rates (>71.8%) for IMI in various real waters (e.g., sewage effluent and livestock wastewater). Furthermore, PMS/BMSBC system also offered a favorable broad-spectrum elimination performance for other typical neonicotinoids (e.g., thiamethoxam, clothianidin, thiacloprid) with the degradation rates over 98%. This study has developed a desirable neonicotinoids purification technology in view of its high degradation/mineralization rate, outstanding detoxification performance, satisfied anti-interference to ambient conditions and sustainable sludge management.

Biochar derived from alkali-treated sludge residue regulates anaerobic digestion: Enhancement performance and potential mechanisms.

Biochar produced from bio-wastes has been widely used to promote the performance of anaerobic digestion. Waste activated sludge (WAS) is considered as a kind of popular precursor for biochar preparation, but the abundant resources in WAS were neglected previously. In this study, the roles of biochar prepared from raw, pretreated, and fermented sludge on anaerobic digestion were investigated. That is, parts of carbon sources and nutrients like polysaccharides, proteins, and phosphorus were firstly recovered after sludge pretreatment or fermentation, and then the sludge residuals were used as raw material to prepare biochar. The methane yield improved by 22.1% with adding the biochar (AK-BC) prepared by sludge residual obtained from alkaline pretreatment. Mechanism study suggested that the characteristics of AK-BC like specific surface area and defect levels were updated. Then, the conversion performance of intermediate metabolites and electro-activities of extracellular polymeric substances were up-regulated. As a result, the activity of electron transfer was increased with the presence of AK-BC, with increase ratio of 21.4%. In addition, the electroactive microorganisms like Anaerolineaceae and Methanosaeta were enriched with the presence of AK-BC, and the potential direct interspecies electron transfer was possibly established. Moreover, both aceticlastic and CO2-reducing methanogenesis pathways were improved by up-regulating related enzymes. Therefore, the proposed strategy can not only obtain preferred biochar but also recover abundant resources like carbon source, nutrients, and bioenergy.

Characteristics of nutrients and heavy metals release from sewage sludge biochar produced by industrial-scale pyrolysis in the aquatic environment and its potential as a slow-release fertilizer and adsorbent.

To assess the application potential of sewage sludge biochar produced by industrial-scale pyrolysis (ISB), the release characteristics of nutrients (NH4+, PO43-, K, Ca, Mg and Fe) and heavy metals (Mn, Cu, Zn, Pb, Ni and Cr) were investigated. Their release amounts increased with decreasing initial pH and increasing solid-liquid ratios (RS-L) and temperature. The release types of NH4+, K, Mg, and Mn were diffusion/dissolution, while those of Cu, Zn, Pb, Ni, and Cr were diffusion/resorption. The release types of PO43- and Ca varied with initial pH and RS-L, respectively. The chemical actions played dominant roles in their release, while particle surface diffusion and liquid film diffusion determined the rates of diffusion and resorption phases, respectively. The release of NH4+, PO43-, K, Ca, Mg, Mn and Zn was a non-interfering, spontaneous (except PO43-), endothermic, and elevated randomness process. The release efficiency of NH4+, PO43- and K met the Chinese standard for slow-release fertilizers, while the total risk of ISB was low. The eutrophication and potential ecological risks of ISB were acceptable when the dose was less than 3 g L-1 and the initial pH was no lower than 3. In conclusion, ISB had potential as a slow-release fertilizer and adsorbent.

Vitamin B12 and iron-rich sludge-derived biochar enhanced PFOA biodegradation: Importance of direct inter-species electron transfer and functional microbes.

Owing to the strong C-F bond in nature and the rigidity of the poly-fluoroalkyl chain, perfluorooctanoic acid (PFOA) is difficult to be eliminated by reactive species and microbes in environments, thus posing a serious threat to ecosystems. Vitamin B12 as a cofactor for enzymes, and biochar as the electron providers and conductors, were integrated to enhance PFOA biodegradation. The raw material of biochar was the sludge after dewatering by adding 50 mg/g DS of Fe(III). After pyrolysis under high temperature (800 °C), biochar (SC800) detected high content of Fe(II) (197.64 mg/g) and abundant oxygen-containing functional groups, thus boosting PFOA biodegradation via donating electrons. 99.9% of PFOA could be removed within 60 d as 0.1 g/L SC800 was presented in the microbial systems containing vitamin B12. Moreover, vitamin B12 facilitated the evolution of Sporomusa which behaved the deflorination. Via providing reactive sites and mediating direct inter-species electron transfer (DIET), SC800 boosted PFOA biodegradation. Corresponding novel results in the present study could guide the development of bioremediation technologies for PFOA-polluted sites.

Unveiling the mechanisms of peracetic acid activation by iron-rich sludge biochar for sulfamethoxazole degradation with wide adaptability.

Advanced oxidation processes (AOPs) based on peracetic acid (PAA) has been extensively concerned for the degradation of organic pollutants. In this study, metallic iron-modified sludge biochar (Fe-SBC) was employed to activate PAA for the removal of sulfamethoxazole (SMX). The characterization results indicated that FeO and Fe2O3 were successfully loaded on the surface of the sludge biochar (SBC). Fe-SBC/PAA system achieved 92% SMX removal after 30 min. The pseudo-first-order kinetic reaction constant of the Fe-SBC/PAA system was 7.34 × 10-2 min-1, which was 2.4 times higher than the SBC/PAA system. The degradation of SMX was enhanced with increasing the Fe-SBC dosage and PAA concentration. Apart from Cl-, NO3- and SO42- had a negligible influence on the degradation of SMX. Quenching experiments and electron paramagnetic resonance (EPR) techniques identified the existence of reactive species, of which CH3C(O)OO•, 1O2, and O2•- were dominant reactive species in Fe-SBC/PAA system. The effect of different water matrices on the removal of SMX was investigated. The removal of SMX in tap water and lake water were 79% and 69%, respectively. Four possible pathways for the decay of SMX were presented according to the identification of oxidation products. In addition, following the ecological structure-activity relationship model (ECOSAR) procedure and the germination experiments with lettuce seeds to predict the toxicity of the intermediates. The acute and chronic ecotoxicity of SMX solution was dramatically diminished by processing with Fe-SBC/PAA system. In general, this study offered a prospective strategy for the degradation of organic pollutants.

Heterogeneous Fenton system driven by iron-loaded sludge biochar for sulfamethoxazole-containing wastewater treatment.

In this study, the treatment performance of a heterogeneous Fenton system (Fe-BC + H2O2) driven by iron-loaded sludge biochar (Fe-BC) on wastewater containing sulfamethoxazole (SMX) was investigated using the CODcr removal efficiency (φ) as an indicator. The batch experimental results showed that the optimal operating conditions were as follow: initial pH 3, H2O2 concentration 20 mmol L-1, Fe-BC dose 1.2 g L-1, temperature 298 K. The corresponding φ was as high as 83.43%. The removal of CODcr was better described by BMG model and revised BMG (BMGL) model. According to the BMGL model, the φmax could be 98.37% (298 K). Moreover, the removal of CODcr was a diffusion-controlled process, while liquid film diffusion and intraparticle diffusion together determined its removal rate. The removal of CODcr should be a synergistic effect of adsorption and Fenton oxidation (real heterogeneous Fenton and homogeneous Fenton) and other pathways. Their contributions were 42.79%, 54.01% and 3.20%, respectively. For homogeneous Fenton, there seemed to be two simultaneous SMX degradation pathways: SMX→4-(pyrrolidine-11-sulfonyl)-aniline→N-(4-aminobenzenesulfonyl) acetamide/4-amino-N-ethyl benzene sulfonamides→4-amino-N-hydroxy benzene sulfonamides; SMX→N-ethyl-3-amino benzene sulfonamides→4-methanesulfonylaniline. In summary, Fe-BC had potential for practical application as a heterogeneous Fenton catalyst.

Adsorbed copper on urea modified activated biochar catalyzed H2O2 for oxidative degradation of sulfadiazine：Degradation mechanism and toxicity assessment.

The combined pollution of heavy metals and organic compounds usually occurs simultaneously and induces high toxicity. The technology of simultaneous removal of combined pollution is lacking and the removal mechanism is not clear. Sulfadiazine (SD), a widely used antibiotic, was used as a model contaminant. Urea modified sludge-based biochar (USBC) was prepared and used to catalyze H2O2 to remove the combined pollution of Cu2+ and sulfadiazine (SD) without causing secondary pollution. After 2 h, the removal rates of SD and Cu2+ were 100 and 64.8%, respectively. Cu2+ adsorbed on the surface of USBC accelerated the activation of H2O2 by the USBC catalyzed by CO bond to produce hydroxyl radical (•OH) and single oxygen (1O2) to degrade SD. Twenty-three intermediate products were detected, most of which were completely decomposed into CO2 and H2O. The toxicity was significantly reduced in the combined polluted system. This study highlights the potential of the low-cost technology based on sludge reuse and its inherent significance in reducing the toxic risk of combined pollution in the environment.

The effectiveness of sewage sludge biochar amendment with Boehmeria nivea L. in improving physicochemical properties and rehabilitating microbial communities in mine tailings.

Biochar amendment can be adopted to improve soil substrate, in turn facilitated phytoremediation. However, improvements to the properties of tailings following different feedstocks of biochar amendment in phytoremediation, particularly the impacts on nitrogen cycle and the related nitrogen-fixing microorganisms remain unclear. In this study, a 100-day pot experiment was designed to determine the co-effects of different combinations of woody and non-woody biochar, namely hibiscus cannabinus core biochar (HB), sewage sludge biochar (SB), chicken manure biochar (MB) and two crops (Cassia alata L., Boehmeria nivea L.). It was found that, on the one hand, biochar amendment directly immobilized heavy metal (loid) contamination in the tailings; on the other hand, biochar amendment, particularly non-woody SB, improved soil properties (i.e., the combination of SB with crops increased the total nitrogen content by 4.7-7.5 times). This indirectly improved phytostabilization (i.e., SB increased crop height 1.5-1.8 fold, root length 3.3-3.7 fold, decreased NH4NO3-extractable Pb, Cu, Cd and also increased the relative abundance of nitrogen-fixing bacteria such as Mesorhizobium, Bradyrhizobium, and Rhizobium). Besides this, redundant analysis shown that the carbon, nitrogen sources, and pH provided by the biochar were identified as the key factors associated with the nitrogen-fixing bacteria. Through the comprehensive evaluation of different biochar amendment in phytoremediation, it was found that the non-woody SB got higher comprehensive score (3.1-3.6) in biochar amendment in phytoremediation, especially in Boehmeria nivea L. Thus, the combination of non-woody SB and Boehmeria nivea L. improved microbial function, while the microorganisms in turn promoted crop growth. Our results revealed the prospect of using non-woody SB assisted Boehmeria nivea L. for phytoremediation in multi-metal mine tailings.

Speciation Evolution of Phosphorus and Sulfur Derived from Sewage Sludge Biochar in Soil: Ageing Effects.

Phosphorus (P) and sulfur (S) are usually involved simultaneously in the immobilization of heavy metals in sewage sludge during pyrolysis, and thus their speciation in sewage sludge-derived biochar (SSB) profoundly affects the recycling of the nutrients and the environmental risks of sewage sludge. Here, we investigated the speciation evolution of P and S in SSB induced by ageing processes in soil using X-ray absorption near edge structure spectroscopy. Results showed that Ca-bound compounds like hydroxyapatite dominated the P forms, while over 60% of S existed as reduced inorganic sulfides in the SSB. The stable Ca-associated P species in SSB tended to be transformed gradually into relatively soluble species during ageing in soil. The speciation composition of S in SSB remained almost unaffected when aged in pot soils, whereas about 33.6% of reduced sulfides were transformed into oxidized species after 1-year ageing in field soils. SSB significantly increased the proportion of sulfides and the contents of available P and S in the amended soil but showed relatively weak effects on the speciation distribution of P in the soil because of their similar compositions. These findings provide insights into biogeochemistry of nutrients and behaviors of heavy metals in SSB after its application to the soil environments.

Fate and mechanistic insights into nanoscale zerovalent iron (nZVI) activation of sludge derived biochar reacted with Cr(VI).

While nanoscale zero-valent iron modified biochar (nZVI-BC) have been widely investigated for the removal of heavy metals, the corrosion products of nZVI and their interaction with heavy metals have not been revealed yet. In this paper, nZVI-BC was synthesized and applied for the removal of Cr(VI). Batch experiments indicated that the adsorption of Cr(VI) fit Langmuir isotherm, with the maximum removal capacity at 172.4 mg/g at pH 2.0. SEM-EDS, BET, XRD, FT-IR, Raman and XPS investigation suggested that reduction of Cr(VI) to Cr(III) was the major removal mechanism. pH played an important role on the corrosion of nZVI-BC, at pH 4.5 and 2.0, FeOOH and Fe3O4 were detected as the major iron oxide, respectively. Therefore, FeOOH-BC and Fe3O4-BC were further prepared and their interaction with Cr were studied. Combining with DFT calculations, it revealed that Fe3O4 has higher adsorption capacity and was responsible for the effective removal of Cr(VI) through electrostatic attraction and reduction under acidic conditions. However, Fe3O4 will continue to convert to the more stable FeOOH, which is the key to for the subsequent stabilization of the reduced Cr(III). The results showed that the oxide corrosion products of nZVI-BC were subjected to the environment, which will eventually affect the fate and transport of the adsorbed heavy metal.

Phosphate-lanthanum coated sewage sludge biochar improved the soil properties and growth of ryegrass in an alkaline soil.

The reclamation of alkaline soils remains challenging while the application of biochar has been proposed as a viable measure to rehabilitate soil fertility. The objective of the current pot study was to evaluate the efficacy of various P-La modified sewage sludge biochars (SSBC, La-SSBC, SSBC-P, La-SSBC-P) on soil phosphate-retention and ryegrass (Lolium perenne L.) growth in an alkaline soil (excess CaCO3). The results revealed that germination percentage, plant dry biomass, plant height, and the total amount of P in the ryegrass leaves were significantly (P < 0.05) improved under La-SSBC-P treatment as compared to other treatments. La-SSBC-P treatment significantly altered the chemical characteristics of post-harvest alkaline soil, such as pH, electrical conductivity (EC), cation exchange capacity (CEC), soil organic matter (SOM), limestone (CaCO3), phosphate, and lanthanum contents. In comparison to the SSBC treatment, soil available phosphorous (AP) contents under La-SSBC-P were enhanced by 6.7 times after loading biochar with P and La (La-SSBC-P). After the plantation of ryegrass, concentration of lanthanum in the soil was negligible. The contents of CaCO3 reduced by 76.2% after La-SSBC-P biochar treatment, compared to the cultivated control. This phenomenon clearly indicated that lanthanum was reduced due to the precipitation with limestone, which was proposed based on the data of X-ray diffraction (XRD) analysis. Overall, results showed that the P-loaded lanthanum decorated biochar (La-SSBC-P) could be used as a potential substitute for P-fertilizer under the experimental conditions. However, field experiments are required to confer the efficiency of La-SSBC-P as P fertilizer in different soils.

Chemical speciation and distribution of potentially toxic elements in soilless cultivation of cucumber with sewage sludge biochar addition.

Potentially toxic elements in municipal sewage sludge can be effectively immobilized during biochar production via pyrolysis. However, the bioavailability of these elements when biochar is applied in soilless cultivation to improve substrate quality has yet to be sufficiently established. In this study, we investigated the chemical speciation and cucumber plant uptake of potentially toxic elements in soilless cultivation when the growth substrate was amended with sewage sludge biochar (0, 5, 10, 15, and 20 wt%). It was found that the addition of 10 wt% biochar was optimal with respect to obtaining a high cucumber biomass and achieving low environmental risk considering the occurrence of hormesis. When the substrate was amended with 10 wt% biochar, cucumber fruit contained lower concentrations of As, Cr, and Zn and smaller bioavailable fractions of As, Cd, Cr, Ni, Cu, and Zn compared with the fruit of control plants, thereby meeting national safety requirements (standard GB 2762-2012, China). Most of the As and Cd taken up by cucumbers accumulated in the leaves and fruit, whereas Cr was found primarily in the roots, and most Ni, Cu, and Zn was detected in the fruit. Importantly, only small proportions of the potentially toxic elements in biochar were taken up by cucumber plants (As: 0.0075%; Cd: 0.038%; Ni: 0.0064%; Cu: 0.0016%; and Zn: 0.0015%). Given that the As, Cd, Ni, and Zn speciation in sewage sludge biochar was effectively immobilized after cultivation, the findings of this study indicate that sewage sludge biochar is a suitable substrate amendment in terms of the risk posed by potentially toxic elements.

Iron/zinc and phosphoric acid modified sludge biochar as an efficient adsorbent for fluoroquinolones antibiotics removal.

Iron/zinc (Fe/Zn), phosphoric acid (H3PO4) or in combination (Fe/Zn + H3PO4) modified sludge biochar (SBC) were prepared and tested in this study to adsorb fluoroquinolones antibiotics including ciprofloxacin (CIP), norfloxacin (NOR) and ofloxacin (OFL) from water. Fe/Zn + H3PO4-SBC had an increased surface area (SBET), total pore volume (Vtot), mesoporous volume (Vmes), pore diameter (Dp) and oxygen-containing functional groups. It exhibited superior adsorption performance for CIP, NOR and OFL with the maximum adsorption amount of 83.7, 39.3, 25.4 mg g-1, respectively. Pseudo-second kinetic and Freundlich isotherm model presented the better fitting. The results of models and characterization analysis in combination indicated that physisorption and chemisorption, including pore filling, hydrogen bonding, π-π interaction, electrostatic interaction and functional groups complexation on a heterogeneous surface were the dominant process and mechanism. Liquid film diffusion was the main rate-limiting step. The adsorption process of CIP, NOR and OFL onto Fe/Zn + H3PO4-SBC were a spontaneous endothermic process. This study demonstrated that Fe/Zn + H3PO4 modified SBC exhibited high adsorption capacity, which was a promising adsorbent for fluoroquinolones as well as for other antibiotics effective removal from waters.

Effect of pyrolysis temperature on chemical and physical properties of sewage sludge biochar.

The objective of this study was to evaluate the effects of pyrolysis temperatures (300, 400, 500, 600 and 700°C) on properties of biochar produced from an urban sewage sludge. Biochar yield significantly decreased from 72.5% at 300°C to 52.9% at 700°C, whereas an increase in temperature increased the gas yield. Biochar pH and electrical conductivity increased by 3.8 and 1.4 dS m⁻¹, proportionally to the increment of temperature. Biochar produced at low temperatures had higher total nitrogen and total organic carbon content but a lower C/N ratio, calcium carbonate equivalent, and total P, K and Na contents. Total and diethylene triamine penta acetic acid (DTPA)-extractable concentrations of Fe, Zn, Cu, Mn, Ni, Cr and Pb increased with increment of temperature. Lower DTPA-extractable concentrations of Fe, Zn, Cu, Mn, Ni and Pb were found in biochars compared to the sewage sludge. Pyrolysis decreased bulk density, whereas particle density and porosity increment was observed upon pyrolysis with increment of temperature. Sewage sludge saturated water content (θs ) was 130.4 g 100g⁻¹ and significantly greater than biochar, but biochar θs significantly increased with temperature (95.7 versus 105.4 g 100g⁻¹ at 300 and 700°C, respectively). Pyrolysis decreased the biochar's water repellency, assessed by molarity of ethanol droplet (MED), compared to the sewage sludge. The lowest MED of 0.2 and water repellency rating of 3 were found for the biochar produced at 700°C. Based on our results and considering the energy consumption, pyrolysis temperature in the range of 300-400°C may be suggested for sewage sludge pyrolysis.

Adsorption of Sb(III) and Pb(II) in wastewater by magnetic γ-Fe2O3-loaded sludge biochar: Performance and mechanisms.

Magnetically modified carbon-based adsorbent (BC@γ-Fe2O3) was prepared through facile route using activated sludge biomass and evaluated for the simultaneous removal of Sb(III) and Pb(II). BC@γ-Fe2O3 exhibited outstanding Sb(III) and Pb(II) adsorption capacity when 200 mg of adsorbent was employed at pH 5.0 for 240 min, with the removal efficiency higher than 90%. The experiments demonstrated the excellent reusability and the potent anti-interference properties of the prepared absorbent. Freundlich and pseudo-second-order kinetic were prior to describe the adsorption process. The adsorption of Sb(III) and Pb(II) onto BC@γ-Fe2O3 was spontaneous and endothermic. BC@γ-Fe2O3 with high specific surface area revealed the exceptional competence to absorb Sb(III) and Pb(II) through pore filling, electrostatic adsorption and complexation. The adsorption mechanisms of Sb(III) and Pb(II) showed similarities with slight disparities. The removal of Sb(III) involved the Fe-O-Sb bond and π-π bond, while the adsorption of Pb(II) was closely related to ion exchange. Moreover, Sb(III) was oxidized to Sb(V) in a minor part during adsorption. The Fe-O-Cl active sites on BC allowed for the binding of γ-Fe2O3, guaranteeing the abundant adsorption sites and stability. BC@γ-Fe2O3 provides an efficient and green insight into the simultaneous removal of complex heavy metals with promising application in wastewater treatment.

Removal of sulfonamide antibiotics by non-free radical dominated peroxymonosulfate oxidation catalyzed by cobalt-doped sulfur-containing biochar from sludge.

The reuse of activated sludge as a solid waste is severely underutilized due to the limitations of traditional treatment and disposal methods. Given that, the sulfur-containing activated sludge catalyst doped with cobalt (SK-Co(1.0)) was successfully prepared by one-step pyrolysis and calcinated at 850 â„ƒ. The generation of CoSx was successfully characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), indicating that the sulfur inside the sludge was the anchoring site for the externally doped cobalt. Cobalt (Ⅱ) (Co2+), as the main adsorption site for peroxymonosulfate(PMS), formed a complex (SK-Co(1.0)-PMS* ) and created the conditions for the generation of surface radicals. The SK-Co(1.0)/PMS system showed high degradation efficiency and apparent rate constants for Sulfamethoxazole (SMX) (91.56% and 0.187 min-1) and Sulfadiazine (SDZ) (90.73% and 0.047 min-1) within 10 min and 30 min, respectively. Three sites of generation of 1O2, which played a dominant role in the degradation of SMX and SDZ in the SK-Co(1.0)/PMS system, were summarized as：sulfur vacancies (SVs), the Co3+/Co2+ cycles promoted by sulfur(S) species, oxygen-containing functional groups (C-O). The degradation mechanisms and pathways had been thoroughly investigated using DFT calculations. In view of this, a new idea for the resource utilization of activated sludge solid waste was provided and a new strategy for wastewater remediation was proposed.

Sewage sludge pyrolysis 'kills two birds with one stone': Biochar synergies with persulfate for pollutants removal and energy recovery.

The disposal and resource utilization of sewage sludge (SS) have always been significant challenges for environmental protection. This study employed straightforward pyrolysis to prepare iron-containing sludge biochar (SBC) used as a catalyst and to recover bio-oil used as fuel energy. The results indicated that SBC-700 could effectively activate persulfate (PS) to remove 97.2% of 2,4-dichlorophenol (2,4-DCP) within 60 min. Benefiting from the appropriate iron content, oxygen-containing functional groups and defective structures provide abundant active sites. Meanwhile, SBC-700 exhibits good stability and reusability in cyclic tests and can be easily recovered by magnetic separation. The role of non-radicals is emphasized in the SBC-700/PS system, and in particular, single linear oxygen (1O2) is proposed to be the dominant reactive oxygen. The bio-oil, a byproduct of pyrolysis, exhibits a higher heating value (HHV) of about 30 MJ/kg, with H/C and O/C ratios comparable to those of biodiesel. The energy recovery rate of the SS pyrolysis system was calculated at 80.5% with a lower input cost. In conclusion, this investigation offers a low-energy consumption and sustainable strategy for the resource utilization of SS while simultaneously degrading contaminants.

Sodium hydroxide/magnesium chloride multistage activated sludge biochar: interfacial chemical behavior and Cd(II) adsorption performance.

To enhance the adsorption performance of municipal sludge biochar on Cd(II), modified sludge biochar was prepared by sodium hydroxide/magnesium chloride (NaOH/MgCl2) graded activation, and the Cd(II) adsorption performance on sludge biochar (BC), NaOH-activated sludge biochar (NBC) and NaOH/MgCl2 activated sludge biochar (NBC-Mg) was investigated. The results showed that NaOH/MgCl2 graded activation upgraded the surface structure and enhanced the graphitization of sludge biochar. The adsorption experiments indicated that the adsorption kinetic and adsorption isotherm for Cd(II) were in accordance with the pseudo second-order kinetic and Langmuir model. The adsorption capacity of NBC-Mg (143.49 mg/g) for Cd(II) was higher than that of BC (50.40 mg/g) and NBC (85.20 mg/g). The mechanism of Cd(II) adsorption included ion exchange, complexation, cation-π interaction, and mineral precipitation. After five regeneration, the removal efficiency of Cd(II) by NBC-Mg remained above 90%. This work indicated that sludge biochar prepared by multistage activation could be an effective material for Cd-containing wastewater treatment.

Preparation of Mn-doped sludge biochar and its catalytic activity to persulfate for phenol removal.

In recent years, the increasing prevalence of phenolic pollutants emitted into the environment has posed severe hazards to ecosystems and living organisms. Consequently, there is an urgent need for a green and efficient method to address environmental pollution. This study utilized waste sludge as a precursor and employed a hydrothermal-calcination co-pyrolysis method to prepare manganese (Mn)-doped biochar composite material (Mn@SBC-HP). The material was used to activate peroxydisulfate (PDS) for the removal of phenol. The study investigated various factors (such as the type and amount of doping metal, pyrolysis temperature, catalyst dosage, PDS dosage, pH value, initial phenol concentration, inorganic anions, and salinity) affecting phenol removal and the mechanisms within the Mn@SBC-HP/PDS system. Results indicated that under optimal conditions, the Mn@SBC-HP/PDS system achieved 100% removal of 100 mg/L phenol within 180 min, with a TOC removal efficiency of 82.7%. Additionally, the phenol removal efficiency of the Mn@SBC-HP/PDS system remained above 90% over a wide pH range (3-9). Free radical quenching experiments and electron spin resonance (ESR) results suggested that hydroxyl radicals (·OH) and sulfate radicals (SO4-) yed a role in the removal of phenol through radical pathways, with singlet oxygen (1O2) being the dominant non-radical pathway. The phenol removal efficiency remained above 90%, demonstrating the excellent adaptability of the Mn@SBC-HP/PDS system under the interference of coexisting inorganic anions or increased salinity. This study proposes an innovative method for the resource utilization of waste, creating metal-biochar composite catalysts for the remediation of water environments. It provides a new approach for the efficiency of organic pollutants in water environments.