Ionic liquid catalyzed low-temperature hydrothermal carbonization of sewage sludge to produce hydrochar with low heavy metal content and positive energy recovery.

An ionic liquid (IL, [DMAPA]HSO4) was prepared to facilitate the removal of heavy metals by hydrothermal carbonization (HTC) in sewage sludge (SS) and to obtain a positive energy recovery (ER, (Energyoutput/Energyinput - 1) > 0). The results found that the removal efficiencies of the Fe, Mn, Zn, Co, and Cd from SS exceeded 75 % with positive ER (6 %) at 20 wt% IL dosage (IL:SS). IL promoted the HTC reactions of proteins and polysaccharides to produce fixed carbon and small molecule polymers. The process mainly relies on IL to catalyze the dehydration and graphitization of SS and to destroy the heavy metal binding sites such as carboxyl and hydroxyl groups. Additionally, IL aids in constructing the macropore structures in hydrochar, thereby facilitating the release of heavy metals and water during the HTC process. This discovery holds promise for removing heavy metals from SS by one-pot HTC processes with positive energy recovery.

Deep eutectic solvents pretreatment enhances methane production from anaerobic digestion of waste activated sludge: Effectiveness evaluation and mechanism elucidation.

Anaerobic digestion (AD) is a prevalent waste activated sludge (WAS) treatment, and optimizing methane production is a core focus of AD. Two DESs were developed in this study and significantly increased methane production, including choline chloride-urea (ChCl-Urea) 390% and chloride-ethylene glycol (ChCl-EG) 540%. Results showed that ChCl-Urea mainly disrupted extracellular polymeric substances (EPS) structures, aiding in initial sludge solubilization during pretreatment. ChCl-EG, instead, induced sludge self-driven organic solubilization and enhanced hydrolysis and acidification processes during AD process. Based on the extent to which the two DESs promoted AD for methane production, the AD process can be divided into stage Ⅰ and stage Ⅱ. In stage Ⅰ, ChCl-EG promoted methanogenesis more significantly, microbiological analysis showed both DESs enriched aceticlastic methanogens-Methanosarcina. Notably, ChCl-Urea particularly influenced polysaccharide-related metabolism, whereas ChCl-EG targeted protein-related metabolism. In stage Ⅱ, ChCl-Urea was more dominant than ChCl-EG, ChCl-Urea bolstered metabolism and ChCl-EG promoted genetic information processing in this stage. In essence, this study investigated the microbial mechanism of DES-enhanced sludge methanogenesis and provided a reference for future research.

Enhancing bioavailable carbon sources and minimizing ammonia emissions in distillery sludge and distiller's grains waste co-composting through deep eutectic solvent addition.

This study introduced two deep eutectic solvents, ChCl/oxalic acid (CO) and ChCl/ethylene glycol (CE), into a 34-day co-composting process of distillery sludge and distiller's grains waste to address challenges related to NH3 emissions. The addition of DES increased dissolved organic carbon by 68% to 92%, offering more utilizable carbon for microorganisms. SYTO9/PI staining and enzyme activity tests showed the CE group had higher bacterial activity and metabolic levels during the thermophilic phase than the control. Bacterial community analysis revealed that early dominance of Lactobacillus and Lysinibacillus in CE accelerated the onset of the thermophilic phase, reduced pile pH, and significantly decreased urease production by reducing Ureibacillus. Consequently, CE treatment substantially dropped NH3 emissions by 73% and nitrogen loss by 54%. Besides, CE fostered a more abundant functional microbial community during the cooling and maturation phases, enhancing deep degradation and humification of organic matter.

Removal of low concentration of perchlorate from natural water by quaternized chitosan sphere (CGQS): Efficiency and mechanism research.

In this study, an innovative approach utilizing betaine as a raw material was employed to effectively modify the surface of chitosan with quaternary ammonium groups. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectrometer (FTIR) characterization showed that the quaternary ammonium groups on betaine were successfully loaded on the chitosan surface. The effects of dosage, pH, initial perchlorate concentration, temperature and co-existing anions on the removal efficiency of perchlorate were investigated. The saturated adsorption capacity of CGQS was 35.41 mg/g under natural condition. The impact of initial perchlorate concentrations and column flow rates on the column adsorption experiments were investigated, as well as natural water tests. Sterilizing performance experiments of CGQS were carried out innovatively. Under the condition of initial concentration of 0.5 mg/L, 9 BV/h (bed volume per hour), the effluent natural water was up to standard (≤0.07 mg/L) with a treatment capacity of 210 BV/g, and the sterilizing rate of CGQS was up to 97.02%. The proposed adsorption mechanisms involved surface pore adsorption, electrostatic adsorption of quaternary ammonium groups, and ion exchange between chloride and perchlorate ions. The CGQS prepared in this work had great potential for treating trace perchlorate contamination in natural water.

The impact of dissolved organic matter on the photodegradation of tetracycline in the presence of microplastics.

Microplastics (MPs), an emerging class of pollutants, significantly impact the photoconversion dynamics of tetracycline (TC). But the effect of prevalent dissolved organic matter (DOM) on TC photodegradation in the presence of MPs remains a gap in current research. In this study, the photoconversion behavior and mechanism of TC under simulated sunlight conditions were systematically investigated, both in the presence of DOM and in combination with polystyrene (PS) MPs. The results demonstrated that both DOM and MPs enhanced the photodegradation of TC when compared to its direct degradation. However, DOM, particularly humic acid (HA, 10 mg/L), exhibited a more pronounced enhancing effect on TC photodegradation within 1 h reaction, regardless of the presence or absence of MPs, reaching up to 80%. In reaction systems involving TC-HA and TC-HA-PS, the primary contributors to TC degradation were direct photolysis and HA photosensitization (free radical reactions). Conversely, photosensitization effects were not significant in the presence of fulvic acid (FA). Furthermore, even under dark reaction conditions, HA exhibited a 10% degradation effect on TC. Quenching experiments and electron spin resonance (ESR) results indicate that dark reaction processes involve free radical reactions. Additionally, toxicity test results showed a reduction in the acute toxicity of TC photodegradation products, yet the long-term cumulative risks to organisms deserved attention. In general, this investigation significantly advances our understanding of the intricate photoconversion behavior of TC in the presence of coexisting chemical components.

Differences between reductive defluorination of perfluorooctanoic acid by chlorination, bromination, and iodization in the vacuum-ultraviolet/sulfite process.

The introduction of iodide (I-) has broad perspectives on the decomposition of perfluorocarboxylates (PFCAs, CnF2n+1COO-). However, the iodinated substances produced are highly toxic synthetic chemicals, hence, it is urgent to find a similar alternative with less toxicity. In this work, the defluorination of perfluorooctanoic acid (PFOA) by I-, bromide (Br-) and chlorine (Cl-) was systematically compared in the VUV/sulfite process. Results indicated that the PFOA defluorination rates increased with increasing nucleophilicity of halogens (I > Br > Cl). Meanwhile, the introduction of I-, Br-, and Cl- reduced the interference of the coexisting water matrix on the degrading influence of PFOA. The in situ produced eaq-, SO3•-, H•, and HO• were recognized, among the addition of I- maximized the relative contribution of eaq- but Br- and Cl- decreased that of H• and other radicals. Additionally, HPLC/MS analysis revealed the presence of I-, Br-, and Cl- had a vital impact on the difference in product concentrations, while they had a negligible effect on the change in the pathway of degradation. Overall, this study demonstrated the similarities and differences between I-, Br-, and Cl-, which has significant implications for further understanding VUV/sulfite degradation.

Effect of polystyrene microplastics on tetracycline photoconversion under simulated sunlight: Vital role of aged polystyrene.

Photoconversion of tetracycline (TC) has been widely reported. However, the effect of microplastics (MPs) on TC conversion kinetics and mechanism has rarely been discussed. In this study, we investigated the effect of (aged) MPs on TC degradation under simulated sunlight and elucidated the underlying mechanism. Our findings demonstrated that the physical and chemical properties of polystyrene (PS), such as particle size, surface groups, and morphology, were significantly altered after aging. Moreover, photoconversion efficiency of TC was suppressed with the spiking of aged PS, while virgin PS showed an opposite tendency. The photodegradation reaction for photosensitization of PS involved 1O2 and HO·. The light-screening effect of aged PS occupied predominance, weakening the direct UV-light absorption of TC and resulting in lower TC degradation efficiency. Additionally, triplet-excited state PS was generated after photon acceptance by aged PS, which could transfer energy to O2, leading to the production of 1O2. The toxicity test manifested that the direct impact of TC products on fathead minnow was ignorable, but long-term negative effects on growth deserved observation. This study enhances our understanding of the environmental fate of PS and TC under sunlight, and provides crucial reference information for better evaluating the potential risk of MPs and chemicals.

Interface engineering of Mn3O4/Co3O4 S-scheme heterojunctions to enhance the photothermal catalytic degradation of toluene.

Transition metal oxides have high photothermal conversion capacity and excellent thermal catalytic activity, and their photothermal catalytic ability can be further improved by reasonably inducing the photoelectric effect of semiconductors. Herein, Mn3O4/Co3O4 composites with S-scheme heterojunctions were fabricated for photothermal catalytic degradation of toluene under ultraviolet-visible (UV-Vis) light irradiation. The distinct hetero-interface of Mn3O4/Co3O4 effectively increases the specific surface area and promotes the formation of oxygen vacancies, thus facilitating the generation of reactive oxygen species and migration of surface lattice oxygen. Theoretical calculations and photoelectrochemical characterization demonstrate the existence of a built-in electric field and energy band bending at the interface of Mn3O4/Co3O4, which optimizes the photogenerated carriers' transfer path and retains a higher redox potential. Under UV-Vis light irradiation, the rapid transfer of electrons between interfaces promotes the generation of more reactive radicals, and the Mn3O4/Co3O4 shows a substantial improvement in the removal efficiency of toluene (74.7%) compared to single metal oxides (53.3% and 47.5%). Moreover, the possible photothermal catalytic reaction pathways of toluene over Mn3O4/Co3O4 were also investigated by in situ DRIFTS. The present work offers valuable guidance toward the design and fabrication of efficient narrow-band semiconductor heterojunction photothermal catalysts and provides deeper insights into the mechanism of photothermal catalytic degradation of toluene.

Treatment of sewage sludge hydrothermal carbonization aqueous phase by Fe(II)/CaO2 system: Oxidation behaviors and mechanism of organic compounds.

The Fe(II)/CaO2 system with a stable oxidant and a low-cost homogeneous activating agent has been considered as a prospective process for the disposal of wastewater. The system was constructed to treat sewage sludge hydrothermal carbonization aqueous phase (HTC-AP) in this study. As the hydrothermal temperature increased, the organics in the HTC-AP were first decomposed and then cyclized, while the Maillard reaction occurs throughout the stage. The oxidation efficiency of the Fe(II)/CaO2 system was related to the composition of organics in HTC-AP, and the removal of dissolved organic carbon (DOC) by the system was 38.56 % in the HTC-AP obtained by hydrothermal treatment at 220 °C. Redundancy analysis showed that the low molecular weight organics, hydrophobic acids, and hydrophobic neutral components were beneficial to DOC removal, while Maillard products and cyclization products were hard to be oxidized to CO2 and H2O. The CN functional group of the protein facilitated DOC removal, and some organics in HTC-AP were oxidized to acids and phenols. The energy input to remove DOC in Fe(II)/CaO2 system was 27.74 MJ per kg carbon. This study provides a low-energy consumption Fe(II)/CaO2 system for the post-treatment of HTC-APs and explores the applicability of the system.

Thermal treatment of sewage sludge: A comparative review of the conversion principle, recovery methods and bioavailability-predicting of phosphorus.

Phosphorus is a nutrient that is essential to nature and human life and has attracted attention because of its very limited reserves. Dwindling phosphorus reserves and soaring prices have made the recovery of phosphorus from waste biosolids even more urgent. Waste activated sludge, as the final destination of most of the phosphorus in human domestic and industrial water, has been considered as a reliable source of phosphorus recovery. The thermal treatment method of sewage sludge is currently a relatively environmentally friendly disposal method, which mainly includes incineration, pyrolysis and hydrothermal carbonization. This paper reviews the methods for the recovery of different forms of phosphorus (wet chemical, thermochemical and electrodialysis) from solid products obtained from different sludge thermal treatment methods (incinerated sewage sludge ash, pyrolysis of sewage sludge char and hydrochar) and the bioavailability of the recovered phosphorus products. Incineration of sewage sludge is currently the most established and effective method for recovering phosphorus from the thermal treatment products of sewage sludge. One of the wet chemical methods has been applied on a commercial scale and is expected to be further developed for future industrial applications. Pyrolysis and hydrothermal carbonation still have many research gaps in this field. Based on their principles and laboratory performance, both of them have the potential to recover phosphorus and should be further explored.

Mechanistic insights into enhanced waste activated sludge dewaterability with Cu(II) and Cu(II)/H2O2 treatment: Radical and non-radical pathway.

Without extra adjustment of pH, the effects of cupric ions (Cu(II)) and hydrogen peroxide (H2O2) alone or in combination on sludge dewatering were studied. It showed good dewatering capability after treated by Cu(II) and Cu(II)/H2O2, which indicated by the capillary suction times (CST) decreased from 120.8 ± 4.7 s (control) to about 40 s, and the water content (Wc) of sludge cake dropped by about 10%. The results showed that the extracellular polymeric substances (EPS) were destroyed, which characterized by a significant decrease in the biopolymers' concentrations in tightly-bound EPS. Meanwhile, more rough and porous microstructures and higher zeta potentials were obtained after conditioned. Based on the changes of physicochemical properties of sludge, the variations of EPS, and the identification of reactive species, two distinct mechanisms of improved sludge dewatering were postulated. As for Cu(II) treatment, it was mainly due to the surface charge neutralization, strong cytotoxicity of Cu(I) produced by intracellular reduction of Cu(II), and pH decline caused by Cu(II) hydrolysis that improved sludge dewatering performance, which could be noted as a "non-radical pathway". When in combination with H2O2, hydroxyl radicals (·OH) produced by Cu(II)-catalyzed Fenton-like process played a dominant role in degrading sludge flocs and EPS, which could be regarded as a "radical pathway".

Feasibility and risk assessment of heavy metals from low-temperature magnetic pyrolysis of municipal solid waste on a pilot scale.

Low-temperature magnetic pyrolysis (LMP) of municipal solid waste (MSW) was conducted in a pilot scale continuous reactor to investigate the distribution and transformation of heavy metals (HMs) in biochar. Environmental safety was evaluated by the risk assessment code (RAC) and the modified potential ecological risk index (MRI). Statistical analyses of HMs revealed that the total concentrations of HMs in biochar was higher than that in MSW and the exchangeable fraction of Cd in biochar under 200 °C and 250 °C were at high risk levels. Temperature increment indicates an increase in regular steps not only migrated more HMs into biochar, but also broke the immobilization of HMs, so resulted in higher environmental risks. The lowest direct toxicity to the environment was obtained by LMP at 200 °C. In light of the residual fraction and the high concentration of HMs in biochar produced in this work, it should be mixed with other uncontaminated plant waste for further application in agriculture. The results of economic assessment reveal that the value of net present value (NPV) and the internal rate of return (IRR) can be positive if high quality bio-products are produced with low operating costs. Optimized design of operation, feedstock and the investment are the key factors to improve the economic feasibility of LMP.

Catalytic enhancement of hydrogenation reduction and oxygen transfer reaction for perchlorate removal: A review.

Perchlorate is the main contaminant in surface water and groundwater, and it is of current urgency to remove due to its high water solubility, mobility, and endocrine-disrupting properties. The conversion of perchlorate into harmless chloride ions by using appropriate catalysts is the most promising and effective route to overcome its high activation energy and kinetic stability. Perchlorate is usually reduced in two ways: (1) indirect reduction via oxygen atom transfer (OAT) reaction or (2) hydrodeoxygenation through highly active reducing H atoms. This paper discusses the mechanisms underlying both the OAT reaction catalyzed by homogenous rhenium-oxo complexes or biological Mo-based enzymes and the heterogeneous hydrogenation for perchlorate reduction. Particular emphasis is placed on the factors affecting the catalytic process and the synergy between the (1) and (2) reactions. For completeness, the applicability of different electrolysis devices, electrodes, and bioreactors is also illustrated. Finally, this article gives prospects for the synthesis and application of catalysts in different pathways.

Biowaste hydrothermal carbonization for hydrochar valorization: Skeleton structure, conversion pathways and clean biofuel applications.

Hydrothermal carbonization (HTC), as one of thermal conversion techniques, shows promising commercial potential for hydrochar production from wet biowaste. This technique was re-discovered and regraded as artificial coalification to mimic natural process. In recent years, researchers concern more about hydrochar obtained from HTC, since large amount of organic waste including sludge, algae, food waste, manure etc. are generated with high moisture, which can be directly used as reaction medium, and hydrochar has high carbon density and energy retention. With this regard, application of hydrochar as biofuel is a renewable and sustainable way for biowaste recycling. In this review, HTC process and pathways about hydrochar formation from (N-free/N-rich biowaste), carbon-skeleton structure, critical elements on clean properties, and hydrochar pelletization for biofuel production were presented. Potential applications and challenges for HTC as green and sustainable way were presented, which will provide prospect for hydrochar as clean and renewable biofuel.

Persulfate assisted hydrothermal processing of spirulina for enhanced deoxidation carbonization.

The influence of persulfate assisted hydrothermal carbonization (HTC) (160 °C-220 °C) of spirulina and hydrochar properties was assessed. The elementary composition and proximate analysis of hydrochar were investigated on the carbonization degree and basic fuel properties, and the surface functional groups and morphological characteristics of hydrochar were analyzed as well as thermal stability. Results suggested that persulfate assisted process enhanced the carbonization degree of hydrochar by oxygen reduction (1.53%-2.74%) and increase of C ratio, and HHVs increased 0.81-1.39 MJ/kg at temperature above 180 °C. The -OH and CO on hydrochar surface were significantly reduced, and C-(C, H) and C-(O, N) were weakened by persulfate addition and more C-H peaks was formed. Additionally, the persulfate addition enhanced the thermal stability of hydrochar by lowing the maximum mass loss rate. The result suggested that HTC can be conducted with persulfate at lower temperature for hydrochar biofuel production.

Insight into the effect of SO2 on the Hg0 removal performance over a 1V-8Ce/AC sorbent at low temperatures.

The influences of SO2 on Hg° removal over the 1V-8Ce/AC sorbent were systematically investigated at low temperatures. The experimental results showed that SO2 has a dual effect on Hg° removal, that is, SO2 has both a promoting effect and an inhibiting effect on Hg° removal. The SO2 transient response experiment indicated that SO2 could not only react with Hg° to promote the removal of Hg° but also react with the active components and poison the sorbent. O2 is indispensable for the removal of Hg°, which can offset the adverse effects caused by SO2 and H2O. HCl exhibited an obvious promoting effect on Hg° removal in the presence of SO2. The 1V-8Ce/AC sorbent exhibited good sulfur resistance and excellent stability (EHg = 90.04 %) after a 24 h reaction performed under the 1000 ppm SO2 condition at 150 °C. In addition, the Hg-TPD and XPS methods were used to assist in studying the effect of SO2 on Hg° removal over the 1V-8Ce/AC sorbent. Finally, the mechanism of Hg° removal in an SO2 atmosphere was also explored, which showed that Hg° was removed by two possible pathways over the 1V-8Ce/AC sorbent.

Co-hydrothermal carbonization of food waste-woody sawdust blend: Interaction effects on the hydrochar properties and nutrients characteristics.

The influence of co-hydrothermal carbonization (co-HTC) on the hydrochar properties and nutrients distribution derived from food waste (FW) and woody sawdust (WS) blend was assessed. The carbon retention, surface functional groups and morphology features involved in hydrochar were evaluated to study the interaction effects. Results suggested that hydrochar yield consistently decreased with increase of both FW ratio and HTC temperature. C retention from 260 °C hydrochar was low (approximately 65%), but more microsphere structures was formed due to the enhanced carbonization degree of hydrochar. Hydrochar obtained at high FW blend ratio and temperature resulted in weaken oxygen-containing groups like OH and CO with enhanced CC and C(O, N). 10.43-60.45% of N and 82-94% of P were retained in hydrochar. NH4+-N (6.63%-15.63%) and organic nitrogen (70.4%-87.7%) were identified as main N-containing species in liquid phase, while total P content (14-166 mg/L) depended more on FW ratio.

Catalytic co-pyrolysis of sewage sludge and rice husk over biochar catalyst: Bio-oil upgrading and catalytic mechanism.

In this study, the effects of different biochar catalysts on the quality of bio-oil derived from the co-pyrolysis of sewage sludge (SS) and rice husk (RH) are explored. Catalysts include SS biochar (SWC), RH biochar (RHC), mixed SS and RH biochar (SRC), and RH ash (RHA). The quality of bio-oil was evaluated based on the results of gas chromatography-mass spectrometry (GC-MS; including the contents of hydrocarbons and N-species), oxygen content, higher heating value, and pH. The GC-MS analysis results illustrated that N-species content in the bio-oil reduced with the addition of the biochar catalyst, while the hydrocarbons content increased from 15.51% for co-pyrolysis to 38.74-61.84% for different biochar catalysts at a catalytic temperature of 650 °C. RHC exhibited the best catalytic effect in terms of decreasing the content of N-species by 58.79% and increasing the content of hydrocarbons by nearly four times compared to co-pyrolysis. The higher heating value of bio-oil raised from 25.75 to 34.67 MJ/kg, while oxygen content decreased from 31.1 to 8.81 wt%, and the pH increased from 4.06 to 5.48. Moreover, the catalytic mechanism of catalytic co-pyrolysis over RHC, including the hydrocarbon generation pathway and nitrogen removal, is also discussed here. High specific surface area of RHC provides sufficient active sites (e.g. O-containing and N-containing functional groups) for the catalytic reaction of pyrolytic intermediates.

Sonochemical synthesis of ZnS nanolayers on the surface of microbial cells and their application in the removal of heavy metals.

In order to improve the adsorption performance of microorganisms, we synthesized a novel material - phanerochaete chrysosporium cells covered with a layer of ZnS nanoparticles (ZnS-cells). The preparation of the ZnS-cells is based on the Sonochemical method to synthesize the ZnS nanoparticle layer on the surface of the microbial cells. The ZnS-cells were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) and Fourier transform infrared spectroscopy (FTIR). Characterization results showed that wurtzite ZnS was coated on the cell surface in the form of nanoclusters by sonochemical reaction, and the formation of ZnS was related to the carboxyl group on the cell surface. Batch experiments showed that the ZnS-cells exhibited high adsorption efficiency for Pb2+and Cd2+, the removal rate of Pb2+ and Cd2+ by ZnS-cells was 140 % and 160 % higher than that of pure P. chrysosporium, respectively. Studies on the adsorption mechanism showed that the removal of heavy metals by ZnS-cells mainly depended on the complexation of surface functional groups on the surface of the cells and the ion exchange of ZnS nanofilms.

Ultrafine Re/Pd nanoparticles on polydopamine modified carbon nanotubes for efficient perchlorate reduction and reusability.

This study synthesized nanocomposite catalysts via a modification of Re/Pd codoped carbon nanotubes (CNTs) with different concentrations of polydopamine (PDA), which were used for perchlorate (ClO4-) reduction. The loads, dispersion and reducibility of Re/Pd nanoparticles increased yet their particle sizes significantly decreased with the increase of PDA concentrations. The average diameter of Re/Pd codoped D2CNT (CNT modified by 2 mg/mL PDA) with a narrow size distribution was measured to be 2 nm. The ultrafine Re/Pd codoped D2CNT catalysts represented outstanding catalytic reduction activity for the conversion of ClO4- to Cl- with TOF of 17.34 h-1 under the room H2 atmospheric pressure, which was about 8 times than that of the unmodified catalysts. Furthermore, PDA modification minimized the dissociation of Re by chemical bonding between Re and CNTs carrier and maintained good stability of nanocomposite. This study inspires us to apply green bionic methods to enhance the catalytic reduction of perchlorate by changing the physical properties of Re/Pd nanoparticles.