Hydrochar Research Articles

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.

Adsorption of Ammonium, Nitrate, and Phosphate on Hydrochars and Biochars

Biochar (BC) and hydrochar (HC) have attracted considerable attention owing to their versatile characteristics and proven effectiveness in diverse technical fields. Solid BC is generated as a result of the dry carbonisation process of pyrolysis, in contrast to the slurry HC, which is produced during the hydrothermal carbonisation process. In this study, we evaluated the adsorption potential of two hydrochar samples (HCs) and three biochar samples (BCs) produced from sugar cane bagasse. The adsorption capacity of these samples was tested for ammonium, nitrate, and phosphate ions under various conditions. The BCs and HCs were subjected to characterisation using a CHNS/O analyser, the zeta potential, and Fourier transform infrared (FTIR). Elevating the pyrolysis temperature of the biochar resulted in changes in the fixed carbon and ash contents, while the volatile matter and H/C and O/C atomic ratios decreased. As the residence time increased, the H/C ratio and volatile matter content of the hydrochars (HCs) decreased. However, the fixed carbon content, ash content, and O/C and C/N ratios exhibited an increase. Thermodynamics, adsorption isotherms, and pH were also taken into consideration. The FTIR spectra analysis indicated that the carboxyl and ester functional groups present in both the BCs and HCs displayed reduced peak intensities subsequent to the adsorption of the three ions. While the adsorption was exothermic, we noticed that the adsorption capacity increased with temperature. The results indicate that sorption was homogenous across all binding sites, as evidenced by the optimal fit to the Langmuir isotherm. The research findings indicate that the adsorption capacity of various BC and HC adsorbents is significantly influenced by the surface area of the adsorbents in the case of nitrate and phosphate, but in the case of ammonia, adsorption is dictated by the functional polar groups present on the adsorbent surface.

Zinc Chloride as a Catalyst in Hydrothermal Carbonization of Cocoa Pods Husk

In this study, we have successfully synthesized a high surface area of activated carbons (ACs) from cocoa pod husk (CPH) by using a combination of hydrothermal carbonization (HTC) and chemical activation in the presence of ZnCl2 as both of catalyst as well as activating agent. During HTC, the effect of HTC temperature (200 and 225 °C) and ZnCl2 to biomass mass ratio (1:1, 2:1, 3:1) as a catalyst to the characteristics of the obtained hydrochar (HC) and ACs were investigated. The obtained hydrochar (HCs) was then processed by using ZnCl2 chemical activation with a fixed HC to ZnCl2 mass ratio of 1:4 and the mixture was pyrolyzed at 600 °C for 1 h under an inert atmosphere. The results showed that the addition of catalyst during HTC presented different AC morphology, where the carbon samples were decorated with carbon microspheres. An increase of surface area was observed, where the ACs synthesized from catalyzed HC at biomass to ZnCl2 ratio of 1:3 at temperature 200 °C gave a higher surface area of 1954 m2/g compared to that of without catalyst (1165 m2/g). The catalysis effect was more profound at the HTC temperature of 200 °C compared to 225 °C, as reflected in the significant increase of AC surface area. The addition of a catalyst creates ACs with narrow pore distribution compared to that of synthesized in the absence of a catalyst. It was also observed that the ACs from catalyzed hydrochar possessed higher oxygenated functional groups (OFG) than those without catalysts.

Metagenomic analysis towards understanding the effects of ammonia on chain elongation process for medium chain fatty acids production

The production of medium chain fatty acids (MCFAs) through chain elongation (CE) from organic wastes/wastewater has attracted much attention, while the effects of a common inhibitor-ammonia has not been elucidated. The mechanism of ammonia affecting CE was studied by metagenomic. The lag phase duration of caproate production was increased, and the maximum caproate production rate was decreased by 43.4 % at 4 g-N/L, as compared to 0 g-N/L. And hydrochar (HC) alleviated the inhibition of ammonia at 4 g-N/L. Metagenomic analysis indicated that ammonia induced UBA4085 sp.FDU78 as the dominant microorganism, and metabolic reconstruction revealed its potential CE ability. Furthermore, ammonia inhibited the reverse β oxidation pathway and Acetyl-CoA production pathway. The tolerance of UBA4085 sp.FDU78 to ammonia was associated with the uptake of inorganic ions, energy conservation, and synthesis of osmoprotectants. The present study provided a deep-insight on the ammonia tolerance mechanism on the CE process.

Insight into using hydrochar to alleviate ammonia nitrogen inhibition during anaerobic digestion of waste activated sludge: Performance, metagenomic and metabolomic signatures

In this study, hydrochar (HCR) was used to alleviate high ammonia inhibition to the anaerobic digestion (AD) of waste activated sludge (WAS) and to elucidate the inner microorganism mechanism. After HCR addition, the cumulative methane yield increased by 73.6 % and 35.6 % under ammonia inhibition levels of 3000 and 6000 mg/L, respectively. Metagenomic analysis showed that HCR enriched the diversity of hydrogenotrophic methanotrophs, and the relative abundances of functional microorganisms with electron transfer capabilities (Geobacteraceae bacterium etc.) were 1.5–7.8 times higher than those without HCR addition. Metabolomics analysis implied that metabolites related to fatty acid degradation, such as glutaric acid and hexadecanal, were downregulated (2.9–15.7 %) under ammonia inhibition conditions and that HCR regulates metabolites in the methane metabolic pathway. Moreover, HCR changed the methanogenic pathway from hydrogenotrophic methanogenesis to multiple pathways under ammonia inhibition conditions, especially methanolic and methylotrophic methanogenesis, which facilitated the methane yield. This study provides valuable information for understanding the inner microbial mechanism of HCR addition on alleviating high ammonia inhibition to AD of WAS, and gives basic knowledge for the application of AD of WAS under ammonia inhibition conditions.

Impacts of kaolinite enrichment on biochar and hydrochar characterization, stability, toxicity, and maize germination and growth

In this study, biochar (BC) and hydrochar (HC) composites were synthesized with natural kaolinite clay and their properties, stability, carbon (C) sequestration potential, polycyclic aromatic hydrocarbons (PAHs) toxicity, and impacts on maize germination and growth were explored. Conocarpus waste was pretreated with 0%, 10%, and 20% kaolinite and pyrolyzed to produce BCs (BC, BCK10, and BCK20, respectively), while hydrothermalized to produce HCs (HC, HCK10, and HCK20, respectively). The synthesized materials were characterized using X-ray diffraction, scanning electron microscope analyses, Fourier transform infrared, thermogravimetric analysis, surface area, proximate analyses, and chemical analysis to investigate the distinction in physiochemical and structural characteristics. The BCs showed higher C contents (85.73–92.50%) as compared to HCs (58.81–61.11%). The BCs demonstrated a higher thermal stability, aromaticity, and C sequestration potential than HCs. Kaolinite enriched-BCs showed the highest cation exchange capacity than pristine BC (34.97% higher in BCK10 and 38.04% higher in BCK20 than pristine BC), while surface area was the highest in kaolinite composited HCs (202.8% higher in HCK10 and 190.2% higher in HCK20 than pristine HC). The recalcitrance index (R50) speculated a higher recalcitrance for BC, BCK10, and BCK20 (R50 > 0.7), minimal degradability for HCK10 and HCK20 (0.5 < R50 < 0.7), and higher degradability for biomass and HC (R50 < 0.5). Overall, increasing the kaolinite enrichment percentage significantly enhanced the thermal stability and C sequestration potential of charred materials, which may be attributed to changes in the structural arrangements. The ∑ total PAHs concentration in the synthesized materials were below the USEPA’s suggested limits, indicating their safe use as soil amendments. Germination indices reflected positive impacts of synthesized charred materials on maize germination and growth. Therefore, we propose that kaolinite-composited BCs and HCs could be considered as efficient and cost-effective soil amendments for improving plant growth.

Activation of hydrochar derived from food waste via hydrothermal carbonization for Cu(II) adsorption

ABSTRACT Currently, heavy metal pollution is a challenge that needs to be solved urgently, and there is a broad prospect for food waste(FW) utilization. In this paper, activated hydrochar (AHC) made from FW according to actual proportion was produced by hydrothermal carbonization (HTC) and activated with K2CO3. The effects of the AHC on Cu(II) adsorption were investigated using static adsorption experiments. The results indicated that the sample fabricated at 160°C (FW-160) for 6 h had the best adsorption performance with the maximum adsorption amount of Cu(II) (36.77 mg/g). The oxygenated functional group on the surface of FW-160 was observed. The pseudo-second-order kinetic model fitted the experimental results better, which proved that chemisorption was the main adsorption mechanism, and the surface complexations, including oxygenated functional groups, were the predominant factors in hydrochar(HC) sorption for Cu(II). The adsorption amount of the sample simulating rotten FW with Aspergillus niger (FW-160A) was 24.82 mg/g. Through the HTC process, the rotten FW can be made into heavy metal absorbents which can be stored for long term, and finally realize the reduction of volume and cost of storage.

Molecular characteristics of organic matter derived from sulfonated biochar.

Sulfonated biochar (SBC), as a functional carbon-based material, has attracted widespread attention due to its excellent adsorption properties. The composition of biochar-derived organic matter (B-DOM) is a key factor influencing the migration and transformation of soil elements and pollutants. However, molecular characteristics of sulfonated biochar-derived organic matter (SBC-DOM) are still unclear. In this study, the molecular composition of derived organic matter (DOM) from SBC prepared via one-step carbonization-sulfonation techniques was investigated by Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and then compared with those of DOMs from rice husk (RH), pyrochar (PYC), and hydrochar (HYC). The results show that the CHOS- and CHONS-containing formulae are predominant in SBC-DOM, accounting for 85% of the total molecular formula number, while DOMs from RH, PYC, and HYC are dominated by CHO-containing formulae. Compared to PYC-DOM and HYC-DOM, SBC-DOM has more unsaturated aliphatic compounds, which make it more labile and easily biodegraded. Additionally, SBC-DOM has higher O/C, (N + O)/C ratios and sulfur-containing compounds. These findings provide a theoretical basis for further research on the application of sulfonated biochar in soil improvement and remediation.

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.

Hydrotreatment of Eucalyptus sawdust: The influence of process temperature and H2SO4 catalyst on hydrochar quality, combustion behavior and related emissions

Hydrothermal carbonization (HTC) presents a promising avenue for waste-to-energy conversion, owing to its cost-effectiveness, low emissions, and adaptability. This study employed HTC to convert Eucalyptus grandis sawdust residues into hydrochars (HC). HTC was conducted for 60 min in a high-pressure steel reactor within glycerin thermal bath equipment under different temperatures (150, 170, 190, and 220 °C) and reaction mediums (water and H2SO4 concentrations of 0.1 and 0.2 mol L–1). The resulting HC underwent thorough analysis, encompassing proximate, ultimate, and morphological assessments and investigations into combustion behavior and potential emissions. Moreover, a new indicator, the hydrotreatment severity index (HSI), is proposed to provide a standardized measure of hydrotreatment severity and property predictions. Higher temperatures and increased H2SO4 concentrations were found to reduce solid yield (ranging from 43.21 % to 90.72 %) and induce morphological changes, including an abundance of carbon microspheres, particularly at higher acid concentrations. These modifications substantially improved higher heating values (HHV), up to 34 % (HHV of 25.72 MJ kg−1 achieved at 220 °C with 0.2 mol L–1 H2SO4) compared to raw feedstock. Interestingly, the intermediate temperature of 190 °C contributed significantly, enhancing HHV by 33 %. All HTC processes greatly enhanced the combustion performance and ignitability of hydrochars. The most favorable reactivity (S = 7.61E7 %2 min−2 °C−3) was observed at 220 °C with 0.2 mol L–1 H2SO4, along with an estimated CO2 emissions of 2,058.46 kg per ton of hydrochar. These results underscore the efficacy of the simplified methodology and reactor system, emphasizing the critical roles of H2SO4 as catalyst and temperature in shaping the characteristics and performance of hydrochars from a representative Brazilian residue, Eucalyptus grandis.

Semi-continuous hydrothermal processing of pine sawdust for integrated production of fuels precursors and platform chemicals

This research reports data for the integrated obtaining of fermentable sugars (FSs), bio-oil (BO), and hydro-char (HC) – all fuel precursors – as well as platform chemicals (PCs – acetic, formic, and levulinic acid, besides furfural, and hydroxymethylfurfural) through semi-continuous hydrothermal processing of sawdust from pine wood. The influence of temperature (260, 300, and 340 °C) and the water-to-biomass ratio (25 and 50 g H2O (g biomass)−1) were the parameters considered to evaluate the mass yields, kinetic profiles, and BO properties. For FSs (and PCs), a detailed analysis considering the kinetic profiles of obtaining cellobiose, glucose, xylose, and arabinose is presented. For the conditions evaluated, a distinct behavior concerning the process parameters was observed, where 7.11 and 9.28 g (100 g biomass)−1 of FSs and PCs were synergistically obtained, respectively, after 30 min, 20 MPa, 260 °C, and 50 g H2O (g biomass)−1. Contextually, 17.59 g (100 g biomass)−1 of BO was obtained at 340 °C and the same water/biomass ratio. FTIR analysis of the BO samples suggested the presence of aldehydes, carboxylic acids, ketones, hydrocarbons, ethers as well as aromatic, alcohols, and nitrogenous compounds. Similar HC yields were achieved among the conditions analyzed, where 24.68 g (100 g biomass)−1 were obtained at 340 °C and 50 g H2O (g biomass)−1 for a higher heating value of 29.14 MJ kg−1 (1.5 times higher than the in natura biomass).

Facile preparation of high-performance hydrochar/TiO2 heterojunction visible light photocatalyst for treating Cr(VI)-polluted water

In order to remedy the shortcomings of narrow absorption wavelength range and low photogenerated carrier separation efficiency of TiO2 photocatalyst, hydrochar (HC) was chosen to modify TiO2 by constructing HC/TiO2 heterojunction composite. HC/TiO2 composites were synthesized from glucose, tetrabutyl titanate and deionized water by a simple one-pot hydrothermal way, and their photocatalytic Cr(VI) reduction properties were studied. The results indicated that HC/TiO2 composites had tremendously improved photocatalytic Cr(VI) reduction activity, in comparison with TiO2, HC and a number of newly reported TiO2-based visible light photocatalysts. When the mass percentage of glucose to tetrabutyl titanate was 14, the obtained HC/TiO2-2 possessed the maximal photocatalytic activity, which was 19 times that of TiO2 and 14.3 times that of HC under visible light (wavelength > 420 nm) irradiation, and 3.2 times that of TiO2 under ultraviolet-visible light (Xenon lamp) irradiation. Furthermore, the photocatalytic stability of HC/TiO2-2 was also excellent. Additionally, proper choice of the photocatalysis experiment parameters could further raise the photocatalytic Cr(VI) reduction efficiency of HC/TiO2-2. The exceptionally elevated photocatalytic activity of HC/TiO2-2 was found to be due to its type-II heterojunction structure, which drastically heightened the separation and transfer efficiencies of photogenerated electrons and holes. Besides, HC/TiO2-2 also showed great potential for practical application in photocatalytic treatment of the Cr(VI) effluents discharged from freezing brine and black chromium plating industries.

Electrochemical Sensor Based on Spent Coffee Grounds Hydrochar and Metal Nanoparticles for Simultaneous Detection of Emerging Contaminants in Natural Water

This research describes the modification of a glassy carbon electrode with spent coffee grounds hydrochar (HDC) and copper nanoparticles (CuNPs) for the simultaneous determination of hydroxychloroquine sulfate (HCS) and bisphenol A (BPA). Scanning electron microscopy, EDS and cyclic voltammetry were used to characterize the nanocomposite. The analytical parameters were optimized and the sensing platform was applied for the determination of HCS and BPA using square-wave voltammetry (SWV). For HCS, the linear range was from 1.0 μmol L−1 to 50 μmol L−1, with an LOD and LOQ of 0.46 and 1.53 μmol L−1, respectively. For BPA, the linear range was from 0.5 μmol L−1 to 10 μmol L−1, with an LOD and LOQ of 0.31 μmol L−1 and 1.06 μmol L−1, respectively. Finally, the developed electrochemical sensor was applied for the quantification of the emerging contaminants in natural water, with recoveries between 94.8% and 106.8% for HCS and 99.6% and 105.2% for BPA. Therefore, HDC-CuNPs demonstrated themselves to be a good alternative as a sustainable and cheaper material for application in electroanalyses.

Cornstalk hydrochar produced by phosphoric acid-assisted hydrothermal carbonization for effective adsorption and photodegradation of norfloxacin

Hydrochars have been widely applied in removing pollutants from aqueous solutions. In this study, hydrochars synthesized by H3PO4-assisted hydrothermal carbonization (HC-xPs) were used to remove norfloxacin (NOR) from water through synergistic adsorption and photodegradation. HC-xPs showed the morphology of carbon microspheres with an average diameter of 0.3 μm. The specific surface area of the hydrochar carbonized with 5 mol/L H3PO4 (HC-5P) was 11.2 times higher than that of the pristine hydrochar (HC). Furthermore, phosphorus-containing functional groups were introduced to HC-5P, beneficial to its adsorption of NOR. The highest NOR adsorption was achieved on HC-5P with the maximum Langmuir capacity of 69.1 mg g−1, owing to multiple mechanisms including electrostatic effects, π-π interactions, hydrophobic interactions, and hydrogen bonding. Compared with HC, HC-5P also demonstrated increased visible light absorption capacity. The first-order rate constant of HC-5P on combined adsorption and photodegradation of NOR was 12.0 times of HC. The photodegradation intermediates were identified by HPLC-MS to understand NOR degradation pathways. This work can be extended to the preparation of low-cost and highly efficient hydrochars for adsorption and photodegradation of pollutants in water.

Engineered hydrochar production methodologies, key factors influencing agriculture wastewater treatment, and life cycle analysis: A critical review

For intensive food production, a range of chemical compounds are used to increase production, reduce the amount of weeds, and prevent pest infestation. Therefore, agricultural wastewater discharge to water bodies creates human health and environmental risks. This highlights the need for technologies to remove organic and inorganic pollutants, where adsorption using carbon-based materials has emerged as a cost-effective and promising alternative for agricultural wastewater treatment with high removal efficacy and alignment with the circular economy concept by generating value-added products, achieving energy conservation and reducing the environmental footprint. Among the different adsorbent materials, hydrochar (HC) has attracted attention because, compared to the thermal processes used for synthesizing other carbon-based materials, it requires relatively milder production conditions and possesses higher adsorption capability for water pollutants. Although HC holds advantages for the adsorption of water pollutants, HC modification using different methods has been found to improve the properties, including adsorption capacity. Accordingly, engineered hydrochar (EHC) has attracted research attention. However, past research publications show that the investigations have focused on material characterization and removal rates, with little knowledge created of the environmental impacts of HC production, application, and disposal. This study reviews current knowledge on EHC synthesis, characteristics, water treatment applications, and life cycle analysis. Initially, production methodologies were investigated to understand their influence on key surface physical and chemical characteristics. This was followed by assessing EHC efficacy for water and wastewater treatment. Finally, the environmental footprint of EHC production, application, and disposal was evaluated to identify critical knowledge gaps and to provide recommendations for future research.

Enhanced energy and nutrient recovery via hydrothermal carbonisation of sewage sludge: Effect of process parameters

Integration of waste management with energy and resource recovery is being widely explored to achieve sustainability. To achieve this, sewage sludge was treated with hydrothermal carbonisation (HTC) at temperatures ranging from 180 °C–260 °C with an increment of 20 °C for three different duration of 1 h, 3 h, and 5 h. The energy and resource recovery potential of the HTC treatment was evaluated through of hydrochar (HC) and process water (PW) properties. Dehydration and decarboxylation reactions resulted in reduced H/C and O/C atomic ratios of 1.35 and 0.45 respectively in HC-260-3, exhibiting peat-like propertied. The calorific value of HC-260-5 was enhanced to 5.9 MJ/kg (increase of 25.8 %) due to the combined effect of H/C and O/C atomic ratios, increased volatile organics and fixed carbon. A maximum energy recovery efficiency of 82.44 % was realised at 240 °C for 3 h rendering it the optimal process condition to ensure energy enrichment. Thermogravimetric analysis (TGA) of HC samples indicated an enhanced combustion behaviour with an increased HTC severity. The elevated levels of volatile fatty acids (VFAs) in PW (maximum 2296 mg/L) made it viable for energy recovery in anaerobic digestion units. Additionally, the PW contains significant concentrations of N and P (2091.68 mg/L and 40.51 mg/L, respectively), indicating enhanced resource/nutrient recovery potential.

Tailoring the porosity of chemically activated carbons derived from the HTC treatment of sewage sludge for the removal of pollutants from gaseous and aqueous phases

The management of sewage sludge is currently an open issue due to the large volume of waste to be treated and the necessity to avoid incineration or landfill disposal. Hydrothermal carbonization (HTC) has been recognized as a promising thermochemical technique to convert sewage sludge into value-added products. The hydrochar (HC) obtained can be suitable for environmental application as fuel, fertilizer, and sorbent. In this study, activated hydrochars (AHs) were prepared from sewage sludge through HTC followed by chemical activation with potassium hydroxide (KOH) and tested for the removal of pollutants in gaseous and aqueous environments, investigating carbon dioxide (CO2) and ciprofloxacin (CIP) adsorption capacity. The effects of activation temperature (550–750 °C) and KOH/HC impregnation ratio (1–3) on the produced AHs morphology and adsorption capacity were studied by Response Surface Methodology (RSM). The results of RSM analysis evidenced a maximum CO2 uptake of 71.47 mg/g for mild activation conditions (600–650 °C and KOH/HC = 1 ÷ 2), whereas the best CIP uptake of 628.61 mg/g was reached for the most severe conditions (750 °C, KOH/HC = 3). The prepared AHs were also applied for the removal of methylene blue (MB) from aqueous solutions, and the MB uptake results were used for estimating the specific surface area of AHs. High surface areas up to 1902.49 m2/g were obtained for the highest activation temperature and impregnation ratio investigated. Predictive models of CO2 and CIP uptake were developed by RSM analysis, and the optimum activation conditions for maximizing the adsorption performance together with high AH yield were identified: 586 °C and KOH/HC ratio = 1.34 for maximum yield (26.33 %) and CO2 uptake (67.31 mg/g); 715 °C and KOH/HC ratio = 1.78 for maximum yield (18.75 %) and CIP uptake (370.77 mg/g). The obtained results evidenced that chemical activation of previously HTC-treated sewage sludge is a promising way to convert waste into valuable low-cost adsorbents.

Surface acidic sites strengthened core-shell HC@MnO2 for enhanced gaseous ammonia adsorption

As a common gaseous pollutant in atmospheric environment, ammonia (NH3) not only contributes to the formation of haze, but also disturb the nitrogen balance in ecosystem through atmospheric nitrogen deposition. Therefore, the control of NH3 emission has important environmental significance. Adsorption is the most commonly used technology for NH3 purification in practice, and efficient adsorbents are the key to adsorption method. Herein, a core-shell structured HC@MnO2 adsorbent was constructed by in-situ growth of layered δ-MnO2 on hydrochar (HC) surface, and its surface acidic sites were further strengthened. The enhancement of surface acidic sites significantly improved the adsorption performance of HC@MnO2 for NH3, reaching 34.49 mg NH3/g, which was superior to commercial carbon-based materials (whose adsorption capacity was 8.47 times that of Coal-based activated carbon, 14.25 times that of Coconut shell activated carbon, and 12.77 times that of Bamboo charcoal). Moreover, the operating parameters and adsorption kinetics were detailly investigated. The adsorption of HC@MnO2 on NH3 was in accordance with pseudo-second-order adsorption kinetics model. Large surface area of core-shell structure and abundant surface acidic sites of δ-MnO2 are the decisive reasons for the excellent adsorption performance of HC@MnO2. Importantly, the enhancement of surface stronger Brønsted acidic sites is the key to improve NH3 adsorption performance of HC@MnO2. Finally, the thermal regeneration and recycling performance of HC@MnO2–H were also investigated. This study provides a suggestive for further research on low-cost composite materials with excellent NH3 adsorption performance.

Research advancements in nutrients and heavy metals, its speciation and behavior during hydrothermal carbonization of sludge – A critical review

Due to rapid increase in urbanization generation rate of sludge is expected to reach over 60 million tonnes hence its proper management has become necessary more than ever. Although, sludge is a complex mixture substance having high moisture content, low energy density and possesses several pollutants but it is also a carbon rich material having potential of resource utilization which attracts many thermochemical techniques to convert it into high value product. Hydrothermal carbonization (HTC) is an efficient pre-treatment technique of converting moisture waste material to high value product with low energy consumption. Phosphorus and nitrogen are major nutrients for agriculture and due to HTC, they can be recovered from hydrochar (HC) as well as process water depending on various conditions. Secondly, the presence of heavy metals is limiting the applicability of sludge-derived HC as soil conditioner and they can be easily transferred to human beings via crops. High ash content in sludge-derived HC is disadvantageous for using it as a fuel. Therefore, this review paper critically discusses transforming mechanism and speciation of nutrients and heavy metals (HMs) for fully utilization of sludge through HTC and how additives (oxides, acids and inorganics) are affecting behavior of nutrients and HMs is systematically discussed. In the end, future perspectives have been discussed for its efficient utilization.

Proteomics coupled with AhR-reporter gene bioassay for human and environmental safety assessment of sewage sludge and hydrochar

Today application of sewage sludge (SL) and hydrochar (HC) in agriculture is a common practice for soil conditioning and crop fertilization, however safety concerns for human and environmental health due to the presence of toxic compounds have recently been expressed.Our aim was to test the suitability of proteomics coupled with bioanalytical tools for unravelling mixture effects of these applications in human and environmental safety assessment. We conducted proteomic and bioinformatic analysis of cell cultures used in the DR-CALUX® bioassay to identify proteins differentially abundant after exposure to SL and the corresponding HC, rather than only using the Bioanalytical Toxicity Equivalents (BEQs) obtained by DR-CALUX®.DR-CALUX® cells exposed to SL or HC showed a differential pattern of protein abundance depending on the type of SL and HC extract. The modified proteins are involved in antioxidant pathways, unfolded protein response and DNA damage that have close correlations with the effects of dioxin on biological systems and with onset of cancer and neurological disorders. Other cell response evidence suggested enrichment of heavy metals in the extracts.The present combined approach represents an advance in the application of bioanalytical tools for safety assessment of complex mixtures such as SL and HC. It proved successful in screening proteins, the abundance of which is determined by SL and HC and by the biological activity of legacy toxic compounds, including organohalogens.