Long-term evaluation of palm oil mill effluent (POME) steam reforming over lanthanum-based perovskite oxides.

To replace the obsolete ponding system, palm oil mill effluent (POME) steam reforming (SR) over net-acidic LaNiO3 and net-basic LaCoO3 were proposed as the POME primary treatments, with promising H2-rich syngas production. Herein, the long-term evaluation of POME SR was scrutinized with both catalysts under the optimal conditions (600 °C, 0.09 mL POME/min, 0.3 g catalyst, & 74-105 µm catalyst particle size) to examine the catalyst microstructure changes, transient process stability, and final effluent evaluation. Extensive characterization proved the (i) adsorption of POME vapour on catalysts before SR, (ii) deposition of carbon and minerals on spent SR catalysts, and (iii) dominance of coking deactivation over sintering deactivation at 600 °C. Despite its longer run, spent LaCoO3 (50.54 wt%) had similar carbon deposition with spent LaNiO3 (50.44 wt%), concurring with its excellent coke resistance. Spent LaCoO3 (6.12 wt%; large protruding crystals) suffered a harsher mineral deposition than spent LaNiO3 (3.71 wt%; thin film coating), confirming that lower reactivity increased residence time of reactants. Transient syngas evolution of both SR catalysts was relatively steady up to 4 h but perturbed by coking deactivation thereafter. La2O2CO3 acted as an intermediate species that hastened the coke removal via reverse Boudouard reaction upon its decarbonation. La2O2CO3 decarbonation occurred continuously in LaCoO3 system but intermittently in LaNiO3 system. LaNiO3 system only lasted for 13 h as its compact ash blocked the gas flow. LaCoO3 system lasted longer (17 h) with its porous ash, but it eventually failed because KCl crystallites blocked its active sites. Relatively, LaCoO3 system offered greater net H2 production (72.78%) and POME treatment volume (30.77%) than LaNiO3 system. SR could attain appreciable POME degradation (>97% COD, BOD5, TSS, & colour intensity). Withal, SR-treated POME should be polished to further reduce its incompliant COD and BOD5.

Van Krevelen diagrams based on machine learning visualize feedstock-product relationships in thermal conversion processes.

Feedstock properties play a crucial role in thermal conversion processes, where understanding the influence of these properties on treatment performance is essential for optimizing both feedstock selection and the overall process. In this study, a series of van Krevelen diagrams were generated to illustrate the impact of H/C and O/C ratios of feedstock on the products obtained from six commonly used thermal conversion techniques: torrefaction, hydrothermal carbonization, hydrothermal liquefaction, hydrothermal gasification, pyrolysis, and gasification. Machine learning methods were employed, utilizing data, methods, and results from corresponding studies in this field. Furthermore, the reliability of the constructed van Krevelen diagrams was analyzed to assess their dependability. The van Krevelen diagrams developed in this work systematically provide visual representations of the relationships between feedstock and products in thermal conversion processes, thereby aiding in optimizing the selection of feedstock and the choice of thermal conversion technique.

Fe-Co Bimetallic Catalysts for Pyrolysis of Disposable Face Masks and Nitrile Gloves: Synthesis and Characterization of N-Doped Carbon Nanotubes.

The global spread of severe acute respiratory syndrome coronavirus 2 has led to a widespread surge in the use of disposable medical face masks (DFMs) and waste nitrile gloves (WNGs). To address the immense disruption in waste management systems, the catalytic pyrolysis of DFMs and WNGs was undertaken to yield multiwalled carbon nanotubes. Two MgO-supported bimetallic catalysts, Fe-Co and Fe-Ni, were synthesized for catalytic pyrolysis. The MgO-supported Fe and Co catalysts showed a good yield of N-doped CNTs (N-CNTs) above 33 wt %, while the percentage of WNGs did not exceed 20 wt %. The pyrolysis process resulted in the formation of Fe-Co microspinels, which were subsequently encapsulated within N-CNTs, ultimately yielding FeCo-NCNTs. The synthesized FeCo-NCNTs were approximately 25 nm in diameter and were extended over several micrometers in length. Subsequent evaluations included testing several acid-washed FeCo-NCNTs as catalysts for the oxygen reduction reaction. The FeCo-NCNTs exhibited remarkable catalytic performance, with a half-wave potential at 0.831 V (vs RHE) and exceptional resistance to methanol poisoning. These remarkable findings have the potential to contribute to the sustainable recycling of waste generated during the COVID-19 pandemic and to the utilization of waste-derived materials.

Improving urban ecosystem holistic sustainability of municipal solid waste-to-energy strategy using extended exergy accounting analysis.

Waste-to-energy technologies play a crucial role in integrated waste management strategies to reduce waste mass and volume, disinfect the waste, and recover energy; different technologies have advantages and disadvantages in treating municipal solid waste under urban conditions. This paper applies the extended exergy accounting method to develop an analytical framework to identify the optimal waste-to-energy strategy from an urban ecosystem holistic sustainability perspective. In the analytical framework, urban ecosystem costs and revenues are formulated as a multi-criteria cost-benefit quantitative model. The urban ecosystem cost is divided into five categories, and the urban ecosystem revenues consist of direct and indirect parts. The direct part is the chemical exergy of the waste-to-energy plants produced product, and the indirect part includes equivalent exergy content of power generation substitution, human health risk elimination, disamenity impact removal and environmental degradation avoidance. Proposing an indicator system to evaluate the waste-to-energy strategy impact on the sustainability of the urban ecosystems and social, economic and environmental sub-ecosystem. Detailed analysis of food waste treatment scenarios of a food center in Singapore was done as a case study to illustrate this analytical framework. Base scenario is current practice that food waste disposal in incineration plant. Anaerobic digestion and gasification are proposed as potential technological solutions for on-site food waste treatment in scenario I and II respectively. In different scenarios, the urban ecosystem costs are estimated to be 71,536.01, 61,854.87 and 74,190.34MJ/year respectively, and the urban ecosystem revenues are estimated to be 135,312.66, 405,442.53 and 298,426.81MJ/year respectively. We show that the scenario where food waste is treated by anaerobic digestion outperforms both the base scenario and scenario II in terms of urban ecosystem costs and revenues, technical energy conversion efficiency, contribution to urban ecosystem holistic sustainability, and natural, social, and economic subsystems improvement, making it the optimal municipal solid waste-to-energy strategy choice.

Green, non-toxic and efficient adsorbent from hazardous ash waste for the recovery of valuable metals and heavy metal removal from waste streams.

As compared to alkali-activated geopolymers with phosphoric acid which may be used in high concentrations resulting in disposal concerns, acid-based geopolymers may have superior properties. A novel green method of converting waste ash to a geopolymer for use in adsorption applications such as water treatment is presented here. We use methanesulfonic acid, a green chemical with high acid strength and biodegradability to form geopolymers from coal and wood fly ashes. The geopolymer is characterized for its physico-chemical properties and tested for heavy metal adsorption. The material specifically adsorbs iron and lead. The geopolymer is coupled to activated carbon forming a composite, which adsorbs silver (precious metal) and manganese (hazardous metal) significantly. The adsorption pattern complies with pseudo-second order kinetics and Langmuir isotherm. Toxicity studies show while activated carbon is highly toxic, the geopolymer and the carbon-geopolymer composite have relatively less toxicity concerns.

Efficient microwave-assisted mineralization of oxytetracycline driven by persulfate and hypochlorite over Cu-biochar catalyst.

Microwave (MW)-assisted catalytic degradation of organic pollutants draws increasing attention owing to its high efficiency in wastewater treatment. This work developed Cu-loaded biochar (CuBC) catalysts for time-efficient mineralization of refractory and high-concentration oxytetracycline (OTC). With only 1 min at 80 °C, Na2S2O8 achieved 100% total organic carbon (TOC) removal over the Cu5BC, while NaClO mineralized 73.3% TOC over the metal-free BC, in contrast to a relatively low mineralization efficiency (< 35%) achieved by H2O2. The high efficiency in MW-assisted oxidation systems could be ascribed to reactive oxidizing species (•SO4- or •ClO), which otherwise were barely detectable in a conventional heating system. The interactions between CuBC and MW were revealed by correlating the physiochemical characteristics to the MW absorption ability. The proposed catalytic systems can contribute to the development of a high-throughput and low-carbon wastewater treatment technology.

Meeting the heavy-metal safety requirements for food crops by using biochar: An investigation using sunflower as a representative plant under different atmospheric CO2 concentrations.

Global warming impacts on plant growth and food safety are emerging topics of concern, while biochar as a soil additive benefits plants. This study investigates (1) sunflower plant growth at various biochar concentrations in a soil-compost growing substrate under both ambient (420 ppm) and elevated (740 ppm) atmospheric CO2 concentrations, and (2) concentrations of heavy metals in the growing substrates and organs of the plants. The elevated CO2 concentration benefits the vegetative parts but harms the reproductive parts of the plants. Additionally, the elevated CO2 concentration inhibits the beneficial effects that biochar confers on the plants at the ambient concentration. The optimum biochar concentration at both CO2 levels was found to be 15%. At the time of harvest, most of the heavy-metal concentrations in the growing substrate increased. It was demonstrated that biochar can reduce the amount of heavy metals that accumulate in the roots and seeds whose heavy-metal concentrations complied with Singapore food safety regulations, while those for the biochar met the proposed Singapore biochar standard's thresholds. Our results show that the proposed Singapore biochar standard is practical and sound.

In-situ vaccination using dual responsive organelle targeted nanoreactors.

The poor translation of nanomedicines from bench to bedside can be attributed to (i) lack of a delivery system with precise drug compositions with no batch-to-batch variations, (ii) off-target or undesirable release of payload, and (iii) lack of a method to monitor the fate of the specific drug of interest, which often has to be modified with a fluorescent tag or replaced with a model drug which can be tracked. To overcome these translation hurdles, we developed dual responsive organelle targeted nanoreactors (DRONEs) with precise drug composition, site specific payload release and which enable accurate in-vivo monitoring. DRONEs consist of a polyprodrug inner core composed of a dual responsive backbone containing a photosensitizer (Protoporphyrin IX) grafted with functionalized polyethylene glycol (PEG) outer shell to prolong blood circulation and a tumour homing pro-apoptotic peptide (CGKRKD[KLAKLAK]2) (THP). DRONEs can significantly reduce the tumour burden in an orthotopic glioblastoma model due to its BBB penetrating and tumour homing capabilities. DRONEs exhibit good safety profile and biocompatibility along with a reliable route of elimination. DRONEs showed great potential as an in-situ vaccine which can not only eliminate the tumour but also trigger an adaptive immune response which would provide long-term anti-tumoural immunity.

Bioengineered immunomodulatory organelle targeted nanozymes for photodynamic immunometabolic therapy.

Intelligent nanomedicines integrated with stimuli-responsive components enable on-demand customizable treatment options which would improve therapeutic outcome and reduce systemic toxicity. In this work, we explore the synergistic therapeutic potential of photodynamic therapy and immunometabolic modulation to achieve tumour regression and to trigger an adaptive immunity to prevent tumour recurrence. The therapeutic potential of the fabricated Bioengineered Immunomodulatory Organelle targeted Nanozymes (BIONs) was tested on 3D printed mini-brains which could effectively recapitulate the biologically relevant interactions between glioblastoma cells and macrophages. In the presence of glioblastoma organotypic brain slices, activated BIONs upregulated the cell surface expression of CD86, a costimulatory molecule and CD83, maturation marker, on monocyte derived dendritic cells, suggesting its ability to elicit a strong immune response. Furthermore, the antigen pulsed dendritic cells by chemotaxis and transendothelial migration readily relocate into the draining lymph node where they present the antigenic cargo to enable the proliferation of T lymphocytes. The stealth and tunable catalytic activity of BIONs prevent ROS mediated diseases such as acute kidney injury by providing environment dependent protection without compromising on its promising anti-cancer activity.

Designer biochar with enhanced functionality for efficient removal of radioactive cesium and strontium from water.

Radioactive elements released into the environment by accidental discharge constitute serious health hazards to humans and other organisms. In this study, three gasified biochars prepared from feedstock mixtures of wood, chicken manure, and food waste, and a KOH-activated biochar (40% food waste + 60% wood biochar (WFWK)) were used to remove cesium (Cs+) and strontium (Sr2+) ions from water. The physicochemical properties of the biochars before and after adsorbing Cs+ and Sr2+ were determined using X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectroscopy, extended X-Ray absorption fine structure (EXAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDX). The WFWK exhibited the highest adsorption capacity for Cs+ (62.7 mg/g) and Sr2+ (43.0 mg/g) among the biochars tested herein. The removal of radioactive 137Cs and 90Sr exceeded 80% and 47%, respectively, in the presence of competing ions like Na+ and Ca2+. The functional groups present in biochar, including -OH, -NH2, and -COOH, facilitated the adsorption of Cs+ and Sr2+. The Cs K-edge EXAFS spectra revealed that a single coordination shell was assigned to the Cs-O bonding at 3.11 Å, corresponding to an outer-sphere complex formed between Cs and the biochar. The designer biochar WFWK may be used as an effective adsorbent to treat radioactive 137Cs- and 90Sr-contaminated water generated during the operation of nuclear power plants and/or unintentional release, owing to the enrichment effect of the functional groups in biochar via alkaline activation.

Bioaugmentation of Methanosarcina thermophila grown on biochar particles during semi-continuous thermophilic food waste anaerobic digestion under two different bioaugmentation regimes.

This study presents the effect of bioaugmentation of thermophilic anaerobic digestion of food waste with Methanosarcina thermophila grown on a wood-derived biochar. Two different supplementation regimes were tested, namely a single bioaugmentation (SBABC) in which 10% v/v of the microbes grown on biochar (1 g/L) is added at setup of the reactors, versus a routine bioaugmentation (RBABC) wherein the same amount of supplements were added over 10 feeding cycles. The optimally performing 'R' and 'S' reactors had increased methane yields by 37% and 32% over their respective controls while reactors SBABC 2 and 3 produced 21.89% and 56.09% higher average methane yield than RBABC 2 and 3, respectively. It appears that a single dose bioaugmentation is advantageous for improving AD as analysed in terms of average methane yield and VFA production. This study provides the basis for understanding how biochar and bioaugmentation can be used for engineering sustainable pilot-scale AD processes.

Copper ferrite and cobalt oxide two-layer coated macroporous SiC substrate for efficient CO2-splitting and thermochemical energy conversion.

CO2-splitting and thermochemical energy conversion effectiveness are still challenged by the selectivity of metal/metal oxide-based redox materials and associated chemical reaction constraints. This study proposed an interface/substrate engineering approach for improving CO2-splitting and thermochemical energy conversion through CuFe2O4 and Co3O4 two-layer coating SiC. The newly prepared material reactive surface area available for gas-solid reactions is characterized by micro-pores CuFe2O4 alloy easing inter-layer oxygen micro mass exchanges across a highly stable SiC-Co3O4 layer. Through a thermogravimetry analysis, oxidation of the thermally activated oxygen carriers exhibited remarkably CO2-splitting capacities with a total CO yield of 1919.33 µmol/g at 1300 °C. The further analysis of the material CO2-splitting performance at the reactor scale resulted in 919.04 mL (788.94 µmol/g) of CO yield with an instantaneous CO production rate of 22.52 mL/min and chemical energy density of 223.37 kJ/kg at 1000 °C isothermal redox cycles. The reaction kinetic behavior indicated activation energy of 30.65 kJ/mol, which suggested faster CO2 activation and oxidation kinetic on SiC-Co3O4-CuFe2O4 O-deficit surfaces. The underlying mechanism for the remarkable thermochemical performances was analyzed by combining experiment and density functional theory (DFT) calculations. The significance of exploiting the synergy between CuFe2O4 and Co3O4 layers and stoichiometric reaction characteristics provided fundamental insights useful for the theoretical modeling and practical application of the solar thermochemical process.

Towards understanding respiratory particle transport and deposition in the human respiratory system: Effects of physiological conditions and particle properties.

Fly ash is a common solid residue of incineration plants and poses a great environmental concern because of its toxicity upon inhalation exposure. The inhalation health impacts of fly ash is closely related to its transport and deposition in the human respiratory system which warrants significant research for health guideline setting and inhalation exposure protection. In this study, a series of fly ash transport and deposition experiments have been carried out in a bifurcation airway model by optical aerosol sampling analysis. Three types of fly ash samples of different morphologies were tested and their respiratory deposition and transport processes were compared. The deposition efficiencies were calculated and relevant transport dynamics mechanisms were discussed. The influences of physiological conditions such as breathing rate, duration, and fly ash physical properties (size, morphology, and specific surface area) were investigated. The deposition characteristics of respiratory particles containing SARS-CoV-2 has also been analyzed, which could further provide some guidance on COVID-19 prevention. The results could potentially serve as a basis for setting health guidelines and recommending personal respiratory protective equipment for fly ash handlers and people who are in the high exposure risk environment for COVID-19 transmission.

Sustainable and Highly Efficient Recycling of Plastic Waste into Syngas via a Chemical Looping Scheme.

Converting plastic waste into valuable products (syngas) is a promising approach to achieve sustainable cities and communities. Here, we propose for the first time to convert plastic waste into syngas via the Fe2AlOx-based chemical looping technology in a two-zone reactor. The Fe2AlOx-based redox cycle was achieved with the pyrolysis of plastic waste in the upper zone, followed by the decomposition and thermal cracking of hydrocarbon vapors, and the oxidation and water splitting in the lower zone (850 °C) enabled a higher carbon conversion (81.03%) and syngas concentration (92.84%) when compared with the mixed feeding process. The iron species could provide lattice oxygen and meanwhile act as the catalyst for the deep decomposition of hydrocarbons into CO and the accumulation of deposited carbon in the reduction step. Meanwhile, the introduced water would be split by the reduced iron and deposited carbon to further produce H2 and CO in the following oxidation step. A high hydrogen yield of 85.82 mmol/g HDPE with a molar ratio of H2/CO of 2.03 was achieved from the deconstruction of plastic waste, which lasted for five cycles. This proof of concept demonstrated a sustainable and highly efficient pathway for the recycling of plastic waste into valuable chemicals.

Hydrodynamics and mass transfer of concentric-tube internal loop airlift reactors: A review.

The concentric-tube internal loop airlift reactor is a typical reactor configuration which has been adopted for a myriad of chemical and biological processes. The reactor hydrodynamics (including mixing) and the mass transfer between the gas and liquid phases remarkably affect the operational conditions and thus are crucial to the overall reactor performance. Hence, this study aims at providing a thorough description of the basic concepts and a comprehensive review of the relevant reported studies on the hydrodynamics and mass transfer of the concentric-tube internal loop airlift reactors, taking microalgae cultivation as an exemplary application. In particular, the reactor characteristics, geometry, CFD modeling, experimental characterization, and scale up considerations are elucidated. The research gaps for future research and development are also identified.

Methanosarcina thermophila bioaugmentation and its synergy with biochar growth support particles versus polypropylene microplastics in thermophilic food waste anaerobic digestion.

Both biochar supplementation as well as bioaugmentation have been shown in literature to improve the methane yield of anaerobic digestion. In this study, the combination of both are evaluated by growing Methanosarcina thermophila on biochar support particles prior to augmentation of thermophilic food waste anaerobic digestion. Biochar stand alone, bioaugmentation solely, a combination of both added separately or grown together, and utilizing polypropylene (PP) microplastics as growth support instead were all tested when starting up a thermophilic process from mesophilic inoculum. Methanosarcina thermophila and biochar supplementation displayed synergy, with 5% M. thermophila on 1 g/L biochar presenting a 32% increase in specific methane yield over the control. Double the bioaugmentation dosage/concentration was also trialled with a thermophilic inoculum, and 10% M. thermophila grown on 2 g/L biochar displayed the best results with a 20% increase specific methane yield from its control standard.

Microbial succession analysis reveals the significance of restoring functional microorganisms during rescue of failed anaerobic digesters by bioaugmentation of nano-biochar-amended digestate.

Nano-biochar application was investigated for anaerobic digestion of orange peel waste. The application for methane production focused on the optimization of biochar feedstock, rescue of failed digesters, and microbial succession analysis. It showed that sewage sludge (SS) derived biochar had the highest performance enhancement among the different feedstocks, which could be ascribed to the improvement of electron transfer, interspecies hydrogen transfer, and supply of trace elements. Subsequently, nano SS biochar-amended digestate was evaluated for rescuing failed digesters, and the experimental results indicated its positive roles through gradual bioaugmentation operation. The dynamic analysis of microbial succession indicated the successful application was through the mechanism of restoring partially the functional microbial communities. The major reconstruction of functional microorganisms included bacteria phyla Hydrogenispora (24.5%) and Defluviitoga (18.8%) as well as methanogenic genera of Methanosarcina (41.5%) and Methanobacterium (27.3%). These findings would contribute to rescuing failed anaerobic digesters by bioaugmentation with biochar-amended digestate.

An innovative accelerated carbonation process for treatment of incineration bottom ash and biogas upgrading.

Incineration is the main technology used for the management of municipal solid waste, in parallel to various recycling programs. However, incineration should not be considered as the final step for waste management as the ash still needs to be treated and disposed properly. In this work, an innovative accelerated carbonation of incineration bottom ash (IBA) using simulated biogas composition from anaerobic digestion processes (a mixture of CH4 and CO2) has been applied to lower the leaching of heavy metals from the carbonated IBA and its associated toxicity. Various temperatures and reaction times were explored for carbonation optimization and it was found that the carbonation at 25 °C for 8 h was the optimal reaction condition by taking into account the degree of carbonation and time constraint. The mineral content, functional groups, thermal stability, leaching patterns and ecotoxicity of both raw IBA and carbonated IBA were tested. It was found that carbonated IBA leached out less heavy metals than the raw IBA due to the locking of heavy metals in the calcite matrix. Cost-benefit analysis was also conducted on the industrial-scale process with a capacity of processing 10 tons of IBA per day. The results indicated that the proposed process had great economic potential.

Sewage sludge ash-based mortar as construction material: Mechanical studies, macrofouling, and marine toxicity.

Incinerated sewage sludge ash is tested here as a cement and aggregate substitute in mortar blocks. It can be used at various percentages to reduce the overall cost of production and promote ash recycling. The compressive strength of the cast blocks was tested at 28 days to determine the optimal combination of ball milled ash (replacing cement) and sewage sludge ash (replacing sand). This was compared with a control block made of cement and sand only. The cast blocks with the optimal ash formulation were tested for their flexural strength and other properties such as surface functional groups, constituent phases and porosity. The control and ash mortars exhibited similar properties. A potential application of these blocks is to use them as part of seawalls. These blocks were thus suspended in the sea for 6 months. Marine organism attachment was observed over time in both control and ash mortar blocks. There was no significant difference between the mortars after 6 months. The mortar blocks were also subjected to leaching tests (NEN-7345). The leachates did not exhibit toxicity to microalgae. In contrast, mild toxicity was observed in the sea urchin embryo development assay. Overall, the study suggests that sewage sludge ash is a potential material to be used for seawall construction as it has the desirable mechanical properties. However, there remain some residual marine toxicity concerns that need to be further addressed.