Syntrophic microbes involved in the oxidation of short-chain fatty acids in continuous-flow anaerobic digesters treating waste activated sludge with hydrochar.

The rapid degradation of short-chain fatty acids (SCFAs) is an essential issue of anaerobic digestion (AD), in which SCFA oxidizers could generally metabolize in syntrophy with methanogens. The dynamic responses of active metagenome-assembled genomes to low concentrations of propionate and acetate were analyzed to identify specific syntrophic SCFA oxidizers and their metabolic characteristics in continuous-flow AD systems treating waste activated sludge with and without hydrochar. In this study, hydrochar increased methane production by 19%, possibly due to hydrochar enhancing acidification and methanogenesis processes. A putative syntrophic propionate oxidizer and two acetate oxidizers contributed substantially to the syntrophic degradation of SCFAs, and hydrochar positively regulated their functional gene expressions. A significant relationship was established between the replication rate of SCFA oxidizers and their stimulation-related transcriptional activity. Acetate was degraded in the hydrochar group, which might be mainly through the syntrophic acetate oxidizer from the genus Desulfallas and methanogens from the genus Methanosarcina.IMPORTANCEShort-chain fatty acid (SCFA) degradation is an important process in the methanogenic ecosystem. However, current knowledge of this microbial mechanism is mainly based on studies on a few model organisms incubated as mono- or co-cultures or in enrichments, which cannot provide appropriate evidence in complex environments. Here, this study revealed the microbial mechanism of a hydrochar-mediated anaerobic digestion (AD) system promoting SCFA degradation at the species level and identified key SCFA oxidizing bacteria. Our analysis provided new insights into the SCFA oxidizers involved in the AD of waste activated sludge facilitated by hydrochar.

Sustainable Biomass Acts as an Electron Donor for Cr(VI) Reduction during the Subcritical Hydrothermal Process: Molecular Insights into the Role of Hydrochar and Liquid Compounds.

Heavy metal pollution is a critical environmental issue that has garnered significant attention from the international community. Subcritical hydrothermal liquefaction (HTL) as an emerging green technology has demonstrated remarkable promise in environmental remediation. However, there is limited research on the remediation of highly toxic Cr(VI) using HTL. This study reveals that the HTL reaction of biomass enables the simultaneous reduction and precipitation of Cr(VI). At 280 °C, the reduction of Cr(VI) was nearly complete, with a high reduction rate of 98.9%. The reduced Cr as Cr(OH)3 and Cr2O3 was primarily enriched in hydrochar, accounting for over 99.9% of the total amount. This effective enrichment resulted in the removal of Cr(VI) from the aqueous phase while simultaneously yielding clean liquid compounds like organic acids and furfural. Furthermore, the elevated temperature facilitated the formation of Cr(III) and enhanced its accumulation within hydrochar. Notably, the resulting hydrochar and small oxygenated compounds, especially aldehyde, served as electron donors for Cr(VI) reduction. Additionally, the dissolved Cr facilitated the depolymerization and deoxygenation processes of macromolecular compounds with lignin-like structures, leading to more small oxygenated compounds and subsequently influencing Cr(VI) reduction. These findings have substantial implications for green and sustainable development.

Hydrochar and Its Dissolved Organic Matter Aged in a 30-Month Rice-Wheat Rotation System: Do Primary Aging Factors Alter at Different Stages?

Hydrochar, recognized as a green and sustainable soil amendment, has garnered significant attention. However, information on the aging process in soil and the temporal variability of hydrochar remains limited. This study delves deeper into the interaction between hydrochar and soil, focusing on primary factors influencing hydrochar aging during a 30-month rice-wheat rotation system. The results showed that the initial aging of hydrochar (0-16 months) is accompanied by the development of specific surface area and leaching of hydrochar-derived dissolved organic matter (HDOM), resulting in a smaller particle size and reduced carbon content. The initial aging also features a mineral shield, while the later aging (16 to 30 months) involves surface oxidation. These processes collectively alter the surface charge, hydrophilicity, and composition of aged hydrochar. Furthermore, this study reveals a dynamic interaction between the HDOM and DOM derived from soil, plants, and microbes at different aging stages. Initially, there is a preference for decomposing labile carbon, whereas later stages involve the formation of components with higher aromaticity and molecular weight. These insights are crucial for understanding the soil aging effects on hydrochar and HDOM as well as evaluating the interfacial behavior of hydrochar as a sustainable soil amendment.

Recent advances in environmental and agricultural applications of hydrochars: A review.

Hydrochar is a carbonaceous material that is generated through the process of hydrothermal carbonization (HTC) from biomass, which has garnered considerable attention in recent years owing to its potential applications in a diverse range of fields, such as environmental remediation and agriculture. Hydrochar is produced from a diverse range of biomass waste materials and retains exceptional properties, including high carbon content, stability, and surface area, making it an optimal candidate for various enviro-agricultural applications. Moreover, it delves into the production process of hydrochar, with explicit emphasis on the optimization of certain properties during the production of hydrochar from bio-waste. Furthermore, the potential of hydrochar as an adsorbent and catalyst support for heavy metals and dyes was extensively explored, along with a soil remediation potential that can improve the physical, chemical and biological properties of soil. This comprehensive review aims to provide a thorough overview of hydrochar with a particular focus on its production, properties, and prospective applications. The significance of hydrochar is accentuated and the growing need for alternative sources of energy and materials that are environmentally sustainable is highlighted in this paper. Besides, the consequence of hydrochar on soil properties such as water-holding capacity, nutrient retention, and total soil porosity, as well as its influence on soil chemical properties such as cation exchange capacity, electrical conductivity, and surface functionality is scrutinized.

Syntrophic propionate degradation in anaerobic digestion facilitated by hydrochar: Microbial insights as revealed by genome-centric metatranscriptomics.

Propionate is a model substrate for studying energy-limited syntrophic communities in anaerobic digestion, and syntrophic bacteria usually catalyze its degradation in syntrophy with methanogens. In the present study, metagenomics and metatranscriptomics were used to study the effect of the supportive material (e.g., hydrochar) on the key members of propionate degradation and their cooperation mechanism. The results showed that hydrochar increased the methane production rate (up to 57.1%) from propionate. The general transcriptional behavior of the microbiome showed that both interspecies H2 transfer (IHT) and direct interspecies electron transfer (DIET) played essential roles in the hydrochar-mediated methanation of propionate. Five highly active syntrophic propionate-oxidizing bacteria were identified by genome-centric metatranscriptomics. H85pel, a member of the family Pelotomaculaceae, was specifically enriched by hydrochar. Hydrochar enhanced the expression of the flagellum subunit, which interacted with methanogens and hydrogenases in H85pel, indicating that IHT was one of the essential factors promoting propionate degradation. Hydrochar also enriched H162tha belonging to the genus of Thauera. Hydrochar induced the expression of genes related to the complete propionate oxidation pathway, which did not produce acetate. Hydrochar and e-pili-mediated DIET were enhanced, which was another factor promoting propionate degradation. These findings improved the understanding of metabolic traits and cooperation between syntrophic propionate oxidizing bacteria (SPOB) and co-metabolizing partners and provided comprehensive transcriptional insights on function in propionate methanogenic systems.

Swine manure management by hydrothermal carbonization: Comparative study of batch and continuous operation.

Hydrothermal carbonization (HTC) is considered a promising technology for biomass waste management without pre-drying. This study explores the potential for swine manure management by comparing batch and continuous processes, emphasizing the benefits of the continuous mode, particularly for its potential full-scale application. The continuous process at low temperature (180 °C) resulted in a hydrochar with a lower degree of carbonization compared to the batch process, but similar characteristics were found in both hydrochars at higher operating temperatures (230-250 °C), such as C content (∼ 52 wt%), fixed carbon (∼ 24 wt%) and higher calorific value (21 MJ kg-1). Thermogravimetric and combustion analyses showed that hydrochars exhibited characteristics suitable as solid biofuels for industrial use. The process water showed a high content of organic matter as soluble chemical oxygen demand (7-22 g L-1) and total organic carbon (4-10 g L-1), although a high amount of refractory species such as N- and O-containing long aromatic compounds were detected in the process water from the batch process, while the process water from the continuous process presented more easily biodegradable compounds such as acids and alcohols, among others. The longer time required to reach operating temperature in the case of the batch system (longer heating time to reach operating temperature) resulted in lower H/C and O/C ratios compared to hydrochar from the continuous process. This indicates that the dehydration and decarboxylation reactions of the feedstock play a more important role in the batch process. This study shows the efficiency of the continuous process to obtain carbonaceous materials suitable for use as biofuel, providing a solution for swine manure management.

Utilization of peanut hull hydrochar /beta cyclodextrin/Fe3O4 magnetic composite for lead ion removal from water solution.

This study involves synthesizing peanut hull hydrochar (PHH) and a PHH/ß-CD/Fe3O4 magnetic composite through hydrothermal and chemical precipitation methods, respectively, to use as effective adsorbents for Pb2+ removal. Vibrating-sample magnetometry (VSM) and Brunauer-Emmett-Teller (BET) analyses revealed that the magnetic saturation value and specific active surface area of PHH/ß-CD/Fe3O4 are 31.543 emu/g and 32.123 m2/g, respectively. The impact of key variables on adsorption efficiency was evaluated using the response surface method - central composite design. ANOVA results (F-value: 166.22 and p-value: <0.05) demonstrated that the model effectively assesses the interaction of variables in the adsorption process. Additionally, R2, Adjusted R2, and Predicted R2 values were 0.999, 0.986, and 0.975, respectively, indicating the model's high adequacy in describing response changes. The maximum efficiency for Pb2+ adsorption was found to be 95.35% using PHH and 99.73% with the PHH/ß-CD/Fe3O4 magnetic composite. These measurements were taken at a temperature of 25 °C, an adsorbent dose of 1 g/L, a pH of 6, and a Pb2+ concentration of 5 mg/L, with respective contact times of 130 min and 50 min. Thermodynamic analysis revealed negative enthalpy and Gibbs free energy values, indicating that the adsorption process is exothermic and spontaneous. The negative entropy parameter suggests a reduction in random interactions during the process. The Pb2+ adsorption data for both PHH (R2: 0.982) and PHH/ß-CD/Fe3O4 (R2: 0.985) were best described by the Pseudo 2nd order kinetic model. Equilibrium data followed the Freundlich model, with R2 values of 0.981 for PHH and 0.990 for PHH/ß-CD/Fe3O4, highlighting the importance of heterogeneous surfaces in the removal process. The maximum adsorption capacities for Pb2+ were 26.72 mg/g for PHH and 33.88 mg/g for PHH/ß-CD/Fe3O4. Reuse and stability tests confirmed the structural stability and reusability of the adsorbents. Therefore, the PHH/ß-CD/Fe3O4 magnetic composite is a promising option for removing Pb2+ from aqueous solutions.

Biocrude extraction from human-excreta-derived hydrochar for sustainable energy and agricultural applications.

Hydrothermal carbonization may be a sustainable sanitary treatment for wet organic waste including human excreta. Human-excreta-derived hydrochar properties differ from those of typical wet biomass due to the formation of a biocrude-like phase at low reaction temperatures. This study characterized the importance of this phase in terms of hydrochar combustion properties and potential agricultural use. Hydrothermal carbonization of raw human excreta was undertaken at 180, 210, and 240 °C, after which the biocrude phase was extracted with dichloromethane. Physicochemical properties, surface-area parameters, combustion profiles, and gas emissions of non-extracted hydrochar, biocrude, and extracted hydrochar were compared. The potential agricultural use of extracted hydrochar was assessed in germination experiments. Biocrude comprised up to 49.5% of hydrochar mass with a calorific value of >60% that of extracted hydrochar. Biocrude combustion properties were better than those of hydrochar, before and after extraction as demonstrated by higher combustion index value (Si). The extracted hydrochar surface area (34.7 m2 g-1) was greater than that of non-extracted hydrochar (<2 m2 g-1), and seeds germinated more readily due to the lower phytotoxin content. Most macro and micronutrients required for plant growth were retained in the extracted hydrochar. The extraction of biocrude from human-excreta-derived hydrochar not only provided a higher-quality fuel with enhanced combustion properties but also improved hydrochar characteristics, suggesting its potential as a soil additive for enhanced plant growth.

Chromium immobilization from wastewater via iron-modified hydrochar: Different iron fabricants and practicality assessment.

The recycling of industrial solid by-products such as red mud (RM) has become an urgent priority, due to their large quantities and lack of reutilization methods can lead to resource wastage. In this work, RM was employed to fabricate green hydrochar (HC) to prepare zero-valent iron (ZVI) modified carbonous materials, and conventional iron salts (IS, FeCl3) was applied as comparison, fabricated HC labeled as RM/HC and IS/HC, respectively. The physicochemical properties of these HC were comprehensively characterized. Further, hexavalent chromium (Cr(VI)) removal performance was assessed (375.66 and 337.19 mg/g for RM/HC and IS/HC, respectively). The influence of dosage and initial pH were evaluated, while isotherms, kinetics, and thermodynamics analysis were also conducted, to mimic the surface interactions. The stability and recyclability of adsorbents also verified, while the practical feasibility was assessed by bok choy-planting experiment. This work revealed that RM can be used as a high value and green fabricant for HC the effective removal of chromium contaminants from the wastewater.

Synthesis of hydrochar from date palm seeds using microwave-enhanced hydrothermal carbonization and its application in dyes removal.

This work reports new findings on the preparation of hydrochar from date palm (Phoenix dactylifera) seeds through the application of the microwave hydrothermal carbonization (HTC) method. Optimization investigations involving temperatures and reaction times were conducted to establish the highest yield, achieving a maximum yield of 60.87%. The prepared material was then impregnated in phosphoric acid and carbonized in the tube furnace at 550 °C for 1.5 h with a nitrogen flow of 50 CCM. The samples were characterized via scanning electron microscopy (SEM), Brunauer-Emmet-Teller (BET) and Fourier transform infrared (FTIR). The samples showed remarkable BET surface areas following activation, reaching up to 992 m2·g-1. The substance was subsequently used to absorb methylene blue with good fitting to the Freundlich and Redlich-Peterson isotherm and achieved a peak adsorption capacity of 196.6 ± 3.9 mg·g-1.

This study involves the preparation of hydrochar through microwave-assisted hydrothermal carbonization (HTC) of date palm seeds. It explores the impact of different process parameters, such as power, reaction temperatures, and timing on the mass yield and BET surface area of the hydrochars. Additionally, the prepared material undergoes chemical activation with phosphoric acid, and its efficacy in extracting methylene blue (MB) from an aqueous solution is assessed. This research is particularly novel as it represents the first comprehensive investigation into the use of microwave-derived and phosphoric acid-activated hydrochar for MB extraction.

Effects of biogas slurry on hydrothermal carbonization of digestate: Synergistic valorization of hydrochars and aqueous phase.

In this study, livestock manure digestate (LMD) was used as feedstock for hydrothermal carbonization (HTC) at different temperature (180-260 °C) and residence time (0-4 h). Nutrient flow and distribution during the HTC process were evaluated by comparing the effects of livestock manure biogas slurry (LBS) and ultrapure water (UW) to determine the optimal reaction conditions for the synergistic production and application of hydrochars (HC) and aqueous phases (AP). Compared with UW, the HC yields derived from LBS as solvent were increased by 27.05-38.24% under the same conditions. The C content, high heating value (HHV), and energy densification of HC obtained from LMD and UW were higher than those obtained from LMD and LBS, and the ash content was lower. While, LBS circumstance improved the porosity, N content and some trace elements e.g. Ca, Fe and Mg in HC that showed excellent fertility potential. In addition, the recovery rate of K, TOC, NH4+-N, and TN concentrations in AP were significantly higher in the LBS circumstance than in UW. The results show that the addition of UW is more favorable for fuel generation, and the HC obtained from LMD and UW at 220 °C has the potential to be used as a fuel. Whereas, the addition of LBS enhanced the potential of HC and AP for agricultural applications simultaneously. It is recommended to use HC and AP obtained from LMD and LBS at 240 °C for using as fertilizer.

Simultaneous synthesis of super-paramagnetic hydrochar in a one-pot using subcritical water medium and evaluation of its photocatalytic activity.

The unregulated release of chemical dyes into the environment presents considerable environmental hazards when left untreated. Photocatalytic degradation, acknowledged as an eco-friendly and cost-effective method, has garnered attention for its efficacy in eliminating organic pollutants like dye. Consequently, the development of multifunctional materials with different applications in environmental and catalytic fields emerges as a promising avenue. Recognizing the significance of integrating catalysts and porous materials for enhancing interactions between pollutants and photo-sensitive substances, magnetic hydrochar emerges as a solution offering heightened efficiency, scalability, recyclability, and broad applicability in various environmental processes, notably wastewater treatment, due to its facile separation capability. In this study, Fe3O4-based, super-paramagnetic hydrochar (SMHC) was simultaneously synthesized in a single step using a coconut shell in the subcritical water medium. A thorough analysis was conducted on both raw hydrochar (RHC) and SMHC to unravel the mechanism of interaction between Fe3O4 nanoparticles and the hydrochar matrix. The synthesized hydrochar exhibited super-paramagnetic characteristics, with a saturation magnetization of 23.7 emu/g and a magnetic hysteresis loop. SMHC displayed a BET surface area of 42.6 m2/g and an average pore size of 26.3 nm, indicating a mesoporous structure according to nitrogen adsorption-desorption isotherms. XRD analysis revealed magnetic crystal sizes in the obtained SMHC to be 13.7 nm. The photocatalytic performance of SMHC was evaluated under visible light exposure in the presence of H2O2 for Astrazon yellow (AY) dye degradation, with optimization conducted using response surface methodology (RSM). The most substantial dye removal, reaching 92.83%, was achieved with 0.4% H2O2 at a 20 mg/L dye concentration and an 80-min reaction duration.

Optimization of two-phase synthesis of Fe-hydrochar for arsenic removal from drinking water: Effect of temperature and Fe concentration.

Arsenic-contaminated water is a global concern that demands the development of cost-effective treatments to ensure a safe drinking water supply for people worldwide. In this paper, we report the optimization of a two-phase synthesis for producing a hydrochar core from olive pomace to serve as support for the deposition of Fe-hydroxide, which is the active component in As(V) removal. The operating conditions considered were the initial concentration of Fe in solution in the hydrothermal treatment (phase I) and the temperature of Fe precipitation (phase II). The obtained samples were characterized for their elemental composition, solid yield, mineral content (Fe and K), phenol release, As(V) sorption capacity, and sorbent stability. Correlation analysis revealed that higher Fe concentrations (26.8 g/L) ensured better carbonization during hydrothermal treatment, increased arsenic removal, reduced concentrations of phenols in the final liquid, and improved stability of the sorbent composite. On the other hand, the temperature during Fe precipitation (phase II) can be maintained at lower levels (25-80 °C) since higher temperatures yielded lower adsorption capacity. Regression analysis demonstrated the significance of the main effects of the parameters on sorption capacity and provided a model for selecting operating conditions (Fe concentration and phase II temperature) to obtain composite sorbents with tailored sorption properties.

Revealing the generation of reactive oxygen species in hydrochar and pyrochar: Insight into rational regulation of free radicals and catalytic mechanism.

The removal of organic pollutants by biochar has been extensively studied. However, the differences in the removal mechanisms of contaminants by biochar obtained from different preparation techniques have not been thoroughly elucidated. In this study, the catalytic performances of hydrochar (HC) and pyrochar (PC) were compared in the dark and light. Owing to more persistent free radicals (PFRs), greater defects and stronger charge transfer ability on the surface, PC could produce a certain concentration of superoxide radicals (•O2-) even in the dark, making its degradation efficiency for benzoic acid (BA) 11% higher than that of HC. On the contrary, when the light was turned on, HC rather than PC can generate a higher amount of hydroxyl radical (•OH), resulting in an 11% higher degradation efficiency of BA compared to PC. The improvement of catalytic performance in HC originated from its oxygen-containing functional groups (OFGs), which was beneficial for its effective production of singlet oxygen (1O2) and ·OH under light exposure. For PC, its photocatalytic activity depended mainly on the formation of 1O2 induced by the triplet of DOM (dissolved organic matter), but the lack of oxidative ·OH in its system leads to a lower degradation efficiency than that of HC. To prove the universal applicability of this rule for biochar materials, HC and PC materials obtained from soybean residue were also prepared for degrading BA. This work is devoted to an in-depth exploration of the catalytic activation mechanism of biochar obtained by different technological methods, and can create conditions for the generation of more dominant reactive oxygen species (ROS) on biochar, thus providing the guidance for environmental remediation.

Unveiling drastic influence of cross-interactions in hydrothermal carbonization of spirulina with cellulose, lignin or poplar on nature of hydrochar and activated carbon.

Spirulina platensis contains abundant nitrogen-containing organics, which might react with derivatives of cellulose/lignin during hydrothermal carbonization (HTC), probably affecting yield, property of hydrochar, and pore development in activation of hydrochar. This was investigated herein by conducting co-HTC of spirulina platensis with cellulose, lignin, and sawdust at 260 °C and subsequent activation of the resulting hydrochars with K2C2O4 at 800 °C. The results showed that cross-condensation of spirulina platensis-derived proteins with cellulose/lignin-derived ketones and phenolics did take place in the co-HTC, forming more π-conjugated heavier organics, retaining more nitrogen species in hydrochar, reducing yields of hydrochar, making the hydrochar more aromatic and increasing the thermal stability and resistivity towards activation. This enhanced the yield of activated carbon (AC) by 7 %-20 % and significantly increased specific surface area of the AC from activation of hydrochar of spirulina platensis + lignin to 2074.5 m2/g (859.3 m2/g from spirulina platensis only and 1170.1 m2/g from lignin only). Furthermore, more mesopores from activation of hydrochar of spirulina platensis + cellulose (47 %) and more micropores from activation of hydrochar of spirulina + sawdust (93 %) was generated. The AC from spirulina platensis + lignin with the developed pore structures generated sufficient sites for adsorption of tetracycline from aqueous phase and minimized steric hindrance for mass transfer with the abundant mesopores (43 %).

Effect of citric acid modification on the properties of hydrochar and pyrochar and their adsorption performance toward methylene blue: crucial roles of minerals and oxygen functional groups.

Modification is widely used to enhance the adsorption performance of pristine hydrochar (HBC) and pyrochar (BC). However, comparisons between modified HBC and BC toward pollutant removal have rarely been reported. In this study, pristine HBC and BC derived from rice straw were first produced, and then citric acid (CA) was used as a modifier to synthesize CA-modified HBC (CAHBC) and CA-modified BC (CABC). Furthermore, the adsorption performance of biochars toward methylene blue (MB) was investigated. The results showed that BC exhibits relatively rough surfaces and contains more minerals (ash), whereas HBC has plentiful O-containing functional groups and fewer minerals. CA modification partially removed minerals from the surface of BC, which weakened the ion exchange, surface complexation, and n-π interaction, resulting in a lower adsorption ability toward MB. By contrast, CA produced more O-containing functional groups on the surface of HBC, which strengthened the hydrogen bonding and electrostatic interaction, thus increasing the adsorption capacity toward MB. The two-compartment model showed a good fit to the adsorption process of MB on CAHBC, and the isotherm data for MB adsorption by HBC and CAHBC are suitable for the Freundlich model. The highest adsorption amount of MB using CAHBC was 80.13 mg·g-1, which was 27.66% higher than that for CABC. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy analysis indicated that the carboxyl groups in the surface functional groups of CAHBC played a crucial role in the MB adsorption process. In addition, CAHBC showed a good performance for a wide range of pH values (4.0-10.0) and under the interference of coexisting ions, and also presented a recycling ability. Furthermore, the adsorption of MB on CAHBC biochar was a spontaneous, exothermic, degree-of-randomness-increasing process. Consequently, CA modification of HBC is a promising strategy and could be used for MB removal from aquatic environments.

Innovative Long-Lasting Catalytic Hydrothermal Reaction for High Efficient Energy Harvest and Carbon Capture from Recalcitrant Wastewater.

Simultaneous recovery of energy and carbon from recalcitrant wastewater has attracted ever-growing interest for water management. However, the existing technologies to break down recalcitrant pollutants are mainly energy and chemical intensive. Here, a novel hydrothermal reaction amended with activated carbon (AC) was demonstrated to enable an unprecedented 99.5% removal of an exemplar difficult-to-degrade contaminant, polyvinyl alcohol (PVA), from wastewater. Meanwhile, an easy-separated hydrochar (C6H7.08O0.99) with an abundance of unsaturated aromatic rings was produced, exhibiting 118.46% of energy yield with a high heating value of 32.9 MJ/kg, outperforming the hydrochar(s) reported to date. The retrieved energy from the hydrochar was able to entirely offset the energy needs for this hydrothermal process. Interestingly, the AC catalyst can sustain in situ reuse over 125 cycles with no evidence of irreversible deactivation. The adjacent carbonyl groups on AC were revealed to provide active sites for dehydrogenation from either the C-H (1.24 Å) or O-H (1.40 Å) bond in PVA, forming hydroxyl groups on AC and highly reactive intermediates (ΔG0 = -11.5 kcal/mol). It was further proved that the free oxygen in the headspace extracted H atoms from the newly formed hydroxyl groups on AC (ΔG0 = -4.7 kcal/mol), thus regenerating the carbonyl sites on AC for the next catalytic hydrothermal dehydrogenation cycles. The long-lasting catalyst reusability and energy self-sufficient approach offer a sustainable route to carbon neutrality in recalcitrant wastewater treatment.

Carbon Sequestration Strategies in Soil Using Biochar: Advances, Challenges, and Opportunities.

Biochar, a carbon (C)-rich material obtained from the thermochemical conversion of biomass under oxygen-limited environments, has been proposed as one of the most promising materials for C sequestration and climate mitigation in soil. The C sequestration contribution of biochar hinges not only on its fused aromatic structure but also on its abiotic and biotic reactions with soil components across its entire life cycle in the environment. For instance, minerals and microorganisms can deeply participate in the mineralization or complexation of the labile (soluble and easily decomposable) and even recalcitrant fractions of biochar, thereby profoundly affecting C cycling and sequestration in soil. Here we identify five key issues closely related to the application of biochar for C sequestration in soil and review its outstanding advances. Specifically, the terms use of biochar, pyrochar, and hydrochar, the stability of biochar in soil, the effect of biochar on the flux and speciation changes of C in soil, the emission of nitrogen-containing greenhouse gases induced by biochar production and soil application, and the application barriers of biochar in soil are expounded. By elaborating on these critical issues, we discuss the challenges and knowledge gaps that hinder our understanding and application of biochar for C sequestration in soil and provide outlooks for future research directions. We suggest that combining the mechanistic understanding of biochar-to-soil interactions and long-term field studies, while considering the influence of multiple factors and processes, is essential to bridge these knowledge gaps. Further, the standards for biochar production and soil application should be widely implemented, and the threshold values of biochar application in soil should be urgently developed. Also needed are comprehensive and prospective life cycle assessments that are not restricted to soil C sequestration and account for the contributions of contamination remediation, soil quality improvement, and vegetation C sequestration to accurately reflect the total benefits of biochar on C sequestration in soil.

Hydrochar-nanoparticle integration for arsenic removal from wastewater: Challenges, possible solutions, and future horizon.

Arsenic (As) contamination poses a significant threat to human health, ecosystems, and agriculture, with levels ranging from 12 to 75% attributed to mine waste and stream sediments. This naturally element is abundant in Earth's crust and gets released into the environment through mining and rock processing, causing ≈363 million people to depend on As-contaminated groundwater. To combat this issue, introducing a sustainable hydrochar system has achieved a remarkable removal efficiency of over 92% for arsenic through adsorption. This comprehensive review presents an overview of As contamination in the environment, with a specific focus on its impact on drinking water and wastewater. It delves into the far-reaching effects of As on human health, ecosystems, aquatic systems, and agriculture, while also exploring the effectiveness of existing As treatment systems. Additionally, the study examines the potential of hydrochar as an efficient adsorbent for As removal from water/wastewater, along with other relevant adsorbents and biomass-based preparations of hydrochar. Notably, the fusion of hydrochar with nanoparticle-centric approaches presents a highly promising and environmentally friendly solution for achieving the removal of As from wastewater, exceeding >99% efficiency. This innovative approach holds immense potential for advancing the realms of green chemistry and environmental restoration. Various challenges associated with As contamination and treatment are highlighted, and proposed solutions are discussed. The review emphasizes the urgent need to advance treatment technologies, improve monitoring methods, and enhance regulatory frameworks. Looking outlook, the article underscores the importance of fostering research efforts, raising public awareness, and fostering interdisciplinary collaboration to address this critical environmental issue. Such efforts are vital for UN Sustainable Development Goals, especially clean water and sanitation (Goal 6) and climate action (Goal 13), crucial for global sustainability.

Hydrothermal synthesis of a photocatalyst based on Byrsonima crassifolia and TiO2 for degradation of crystal violet by UV and visible radiation.

This work presents a one-step synthesis methodology for preparing a hydrochar (HC) doped with TiO2 (HC-TiO2) for its application on the degradation of crystal violet (CV) using UV and visible radiation. Byrsonima crassifolia stones were used as precursors along with TiO2 particles. The HC-TiO2 sample was synthesized at 210 °C for 9 h using autogenous pressure. The photocatalyst was characterized to evaluate the TiO2 dispersion, specific surface area, graphitization degree, and band-gap value. Finally, the degradation of CV was investigated by varying the operating conditions of the system, the reuse of the catalyst, and the degradation mechanism. The physicochemical characterization of the HC-TiO2 composite showed good dispersion of TiO2 in the carbonaceous particle. The presence of TiO2 on the hydrochar surface yields a bandgap value of 1.17 eV, enhancing photocatalyst activation with visible radiation. The degradation results evidenced a synergistic effect with both types of radiation due to the hybridized π electrons in the sp2-hybridized structures in the HC surface. The degradation percentages were on average 20% higher using UV radiation than visible radiation under the following conditions: [CV] = 20 mg/L, 1 g/L of photocatalyst load, and pH = 7.0. The reusability experiments demonstrated the feasibility of reusing the HC-TiO2 material up to 5 times with a similar photodegradation percentage. Finally, the results indicated that the HC-TiO2 composite could be considered an efficient material for the photocatalytic treatment of water contaminated with CV.