Enhanced Uranium Extraction via Charge Dynamics and Interfacial Polarization in MoS2/GO Heterojunction Electrodes.

The removal of uranyl ions (UO2 2+) from water is challenging due to their chemical stability, low concentrations, complex water matrix, and technical limitations in extraction and separation. Herein, a novel molybdenum disulfide/graphene oxide heterojunction (MoS2/GO-H) is developed, serving as an effective electrode for capacitive deionization (CDI). By combining the inherent advantages of electroadsorption and electrocatalysis, an innovative electroadsorption-electrocatalysis system (EES) strategy is introduced. This system utilizes interface polarization at the MoS2 and GO interface, creating an additional electric field that significantly influences carrier behavior. The MoS2/GO-H electrode, with its extraordinary adsorption capacity of 805.57 mg g-1 under optimal conditions, effectively treated uranium-laden wastewater from a mine, achieving over 90% removal efficiency despite the presence of numerous competing ions at concentrations significantly higher than UO2 2+. Employing density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations, it is found that the MoS2/GO-H total charge density at the Fermi level, enhanced by interfacial polarization, surpasses that of separate MoS2 and GO, markedly boosting conductivity and electrocatalytic effectiveness.

Corrective protocol to predict interference free sensor response for paper-based solution sampling coupled with heavy metal sensitive ion-selective electrodes.

Paper-based microfluidics combined with potentiometric measurement has emerged as an attractive approach for detecting various chemical ionic moieties. Detection of heavy metal ions, using paper substrates as solution sampling and delivery systems remains challenging despite efforts to introduce several physico-chemical paper substrate modifications to stop adsorption of ions onto the paper substrates. This study quantitatively investigates the adsorption of heavy metal ions on the paper substrates during paper-based potentiometric measurements and explains the super-Nernstian response of potentiometric sensors through local depletion of heavy metal ions from the solution. Consequently, based on the investigated ion adsorption, a corrective potential protocol was established for the electrodes coupled with paper-based solution sampling by predicting interference free sensor response from paper-based measurement. Furthermore, the ion adsorption was also recorded for mixed metal ion solutions to understand competitive primary/interfering ions adsorption onto the paper substrates and establish corrective measures to predict interference free sensor response. In this method, no modifications of the paper substrates are necessary before actual potentiometric measurements. The proposed corrective protocol allows prediction of sensor response based on the paper-based solution sampling potentiometric measurement, providing a simple methodological approach based on correction of potential readout of the potentiometric sensor, thus completely resigning from the need of modifying paper substrate for measurements of heavy metal ions.

Converting ash into reusable slag at lower carbon footprint: Vitrification of incineration bottom ash in MSW-fueled demonstration-scale slagging gasifier.

Globally waste incineration is becoming the predominant treatment method of solid waste. The largest fraction of solid residue of this process is incineration bottom ash (IBA) requiring further treatment before applications such as in the construction industry become feasible. In this study, vitrification of IBA was conducted in a demonstration-scale high-temperature slagging gasification plant fueled with MSW and biomass charcoal as a green auxiliary fuel. High IBA co-feeding rates of up to 491 kg/h (equivalent to 107% of MSW feeding rate) were achieved during the trials. A highly leaching-resistant slag immobilizing heavy metals in the glass-like amorphous structure and recyclable iron-rich metal granules were generated in the process. The heavy metal migration into the solid by-product fractions depended on the IBA feeding rates and process conditions such as cold cap temperature, charcoal-to-ash ratio, and gasifier temperature profile. Slaked lime and activated carbon powder were used in a dry flue gas treatment and stack gas emissions were kept well below Singapore's regulatory limits. Steam from the hot flue gas was generated in a boiler to drive a steam turbine. The application of biomass charcoal instead of fossil fuels or electricity lead to a lower carbon footprint compared to alternative vitrification technologies. The overall results reveal promising application of high temperature slagging gasification process for commercial-scale vitrification of IBA.

Integrating gravity-driven ceramic membrane filtration with hydroponic system for nutrient recovery from primary municipal wastewater.

In this study, a gravity-driven membrane (GDM) filtration system and hydroponic system (cultivating basil and lettuce) were combined for nutrient recovery from primary municipal wastewater. The GDM system was optimized by increasing the periodic air sparging flow rate from 1 to 2 L/min (∼15 hr per 3-4 days), resulting in a ∼52% reduction of irreversible fouling. However, the total fouling was not alleviated, and the water productivity remained comparable. The GDM-filtrated water was then delivered to hydroponic systems, and the effects of hydroponic operation conditions on plant growth and heavy metal uptake were evaluated, with fertilizer- and tap water-based hydroponic systems and soil cultivation system (with tap water) for comparison. It was found that (i) the hydroponic system under batch mode facilitated to promote vegetable growth with higher nutrient uptake rates compared to that under flow-through feed mode; (ii) a shift in nutrient levels in the hydroponic system could impact plant growth (such as plant height and leaf length), especially in the early stages. Nevertheless, the plants cultivated with the GDM-treated water had comparable growth profiles to those with commercial fertilizer or in soils. Furthermore, the targeted hazard quotient levels of all heavy metals for the plants in the hydroponic system with the treated water were greatly lower than those with the commercial fertilizer. Especially, compared to the lettuce, the basil had a lower heavy metal uptake capability and displayed a negligible impact on long-term human health risk, when the treated water was employed for the hydroponic system.

Ion-selective membrane modified microfluidic paper-based solution sampling substrates for potentiometric heavy metal detection.

Paper-based microfluidic solution sampling is a viable option for potentiometric sensors to be used for the determination of analytes in samples with high solid-to-liquid ratios. Unfortunately, heavy metal sensitive electrodes cannot be easily integrated with paper-based solution sampling as heavy metals have strong physicochemical adsorption affinity towards paper substrates. In this work, paper substrates were modified with an ion-selective membrane (ISM) cocktail (used for the preparation of Pb2+-ion-selective electrodes (ISEs)) and coupled with model heavy metal Pb2+-ISEs. It was found that the super-Nernstian response of Pb2+-ISEs was eliminated when 10 to 50 mg ml-1 of the ISM cocktail was used for the modification of paper substrates. The modification of the paper substrates by Pb2+-ISM allowed the elimination of adsorption sites. In addition, it resulted in an improvement of sensor performance in terms of their detection limits to be similar to those for conditioned electrodes in standard beaker-based measurements. It is believed that the elimination of super-Nernstian response of the electrodes and improving the potentiometric responses and detection limits of ISEs were attributed to the compatibility improvement of the paper substrates and Pb2+-ISEs to the same type of ISM.

Impacts of pyrolysis temperatures on physicochemical and structural properties of green waste derived biochars for adsorption of potentially toxic elements.

This study comparatively investigated the influence of changes in pyrolysis temperature on the physicochemical, structural, and adsorptive properties of biochars derived from a green waste (Cynodon dactylon L.). For this purpose, the biophysically dried green wastes were pyrolyzed at 400 °C, 600 °C, and 800 °C under the same pyrolysis conditions. The results revealed that the physicochemical and structural properties were varied, depending upon the pyrolysis temperatures. With the increase of pyrolysis temperature, the surface functional groups were escaped, the structure became more porous (pore volume of 0.089 ± 0.001), the metal oxides were remained consistent, and the biochars turned into more alkaline nature (pH of 11.9 ± 0.2). Furthermore, as referring to the adsorptive performance for potentially toxic elements, with experimental adsorption capacity of up to 33.7 mg g-1 and removal rate up to 96% for a multi-metals containing solution, the biochars pyrolyzed at high temperature (800 °C) was significantly (p < 0.05) higher than those pyrolyzed at low temperature (400 °C). According to the physicochemical and structural properties, and the adsorptive performances of the biochars, the optimal pyrolysis temperature was herein recommended to be 800 °C.

Heavy Metals Detection with Paper-Based Electrochemical Sensors.

This Feature summarizes recent works in paper-based potentiometry and voltammetry in heavy metal determination. Interactions of paper substrates with heavy metals, influence on the sensing response, and modification methods applied to paper substrates to improve the performance of recently developed electrochemical sensors are discussed. Since the rekindling of interest in paper-based analytical devices, methodologies and electrode designs for heavy metal determinations are highlighted. Promising aspects of the use of these sensors for samples containing solids and the increased versatility of the use of paper in analytics offers the possibility of increased acceptance of these low-cost platforms.

PVC-Based Ion-Selective Electrodes with a Silicone Rubber Outer Coating with Improved Analytical Performance.

An outer layer of pure silicone rubber (SR), i.e. SR without any plasticizer, ionophore, or lipophilic anion, was applied on top of a conventional poly(vinyl chloride) (PVC) based K+-selective membrane in a solid-contact ion-selective electrode (SC-ISE). The influence of the outer SR coating on the analytical performance of the K+-ISEs was studied. The presence of the SR coating did not affect the selectivity of the SC-ISE, indicating that the plasticizer, ionophore, and lipophilic anion are spontaneously distributed from the PVC-based membrane into the SR layer. This was confirmed by electrochemical impedance spectroscopy (EIS). Interestingly, the reproducibility of the standard potential of the conditioned SC-ISE was significantly improved from E0 ± 35.3 mV to E0 ± 3.5 mV simply by adding the SR coating on top of the plasticized PVC based K+-selective membrane. Moreover, the adsorption of bovine serum albumin (BSA) was significantly reduced at the SR coated ion-selective membrane. Thus, the addition of a SR coating on a plasticized PVC ion-selective membrane seems to be a feasible method to improve the analytical performance and to reduce the biofouling of potentiometric ion sensors.

A novel real-time monitoring and control system for waste-to-energy gasification process employing differential temperature profiling of a downdraft gasifier.

A novel, cost-effective and real-time process monitoring and control system was developed to maintain stable operation of waste-to-energy gasification process. It comprised a feedback loop control that utilized the differential temperatures of the oxidation and reduction zones in the gasifier to determine the regional heat-flow (endothermic or exothermic), to assess the availability of oxidizing agent (for instance, air or O2) at the char bed and to calculate the fuel feeding rate. Based on the correlations developed, the air-to-fuel ratio or the equivalence air ratio (ER) for air gasification could be instantaneously adjusted to maintain stable operation of the gasifier. This study demonstrated a simplification of complex reaction dynamics in the gasification process to differential temperature profiling of the gasifier. The monitoring and control system was tested for more than 70 h of continuous operation in a downdraft fixed-bed gasifier with refuse-derived fuel (RDF) prepared from municipal solid wastes (MSW). With the system, fuel feeding rate could be adjusted accurately to stabilize the operating temperature and ER in the gasifier and generate syngas with consistent properties. Significant reductions in the fluctuations of temperature profiles at oxidation and reduction zones (from higher than 100 °C to lower than 50 °C), differential temperatures (from ±200 to ±50 °C) in gasifier and the flow rate (from 16 ±â€¯6.5 to 12 ±â€¯1.8 L/min), composition of main gas components, LHV (from 6.2 ±â€¯3.1 to 5.7 ±â€¯1.6 MJ/Nm3) and tar content (from 8.0 ±â€¯9.7 to 7.5 ±â€¯4.2 g/Nm3) of syngas were demonstrated. The developed gasifier monitoring and control system is adaptable to various types (updraft, downdraft, and fluidized-bed) and scales (lab, pilot, large scale) of gasifiers with different types of fuel.

Dualism of Sensitivity and Selectivity of Porphyrin Dimers in Electroanalysis.

This work uncovers the application of porphyrin dimers for the use in electroanalysis, such as potentiometric determination of ions. It also puts in question a current perception of an occurrence of the super-Nernstian response, as a result of the possible dimerization of single porphyrins within an ion-selective membrane. To study that, four various porphyrin dimers were used as ionophores, namely, freebase-freebase, Zn-Zn, Zn-freebase, and freebase-Zn. Since the Zn-freebase and freebase-Zn porphyrin dimers carried both anion- and cation-sensitive porphyrin units, their application in ISEs was utilized in both anion- and cation-sensitive sensors. With respect to the lipophilic salt added, both porphyrins dimers were found anion- and cation-sensitive. This allowed using a single molecule as novel type of versatile ionophore (anion- and cation-selective), simply by varying the membrane composition. All anion-sensitive sensors were perchlorate-sensitive, while the cation-selective sensors were silver-sensitive. The selectivity of the sensors depended primarily on the porphyrin dimers in the ion-selective membrane. Furthermore, the selectivity of cation-sensitive dimer based sensors was found significantly superior to the ones measured for the single porphyrin unit based sensors (precursors of the porphyrin dimers). Thus, the dimerization of single porphyrins may actually be a factor to increase or modulate porphyrin selectivity. Moreover, in the case of cation-sensitive sensors, the selectivity vastly depended on the order of porphyrin units in the dimer. This opens a new approach of regulating and adjusting sensitivity and selectivity of the sensor through the application of complex porphyrin systems with more than one porphyrin units with mix sensitive porphyrins.

In Situ Potentiometry and Ellipsometry: A Promising Tool to Study Biofouling of Potentiometric Sensors.

In situ potentiometry and null ellipsometry was combined and used as a tool to follow the kinetics of biofouling of ion-selective electrodes (ISEs). The study was performed using custom-made solid-contact K(+)-ISEs consisting of a gold surface with immobilized 6-(ferrocenyl)hexanethiol as ion-to-electron transducer that was coated with a potassium-selective plasticized polymer membrane. The electrode potential and the ellipsometric signal (corresponding to the amount of adsorbed protein) were recorded simultaneously during adsorption of bovine serum albumin (BSA) at the surface of the K(+)-ISEs. This in situ method may become useful in developing sensors with minimized biofouling.

Potentiometric sensing utilizing paper-based microfluidic sampling.

A new approach to potentiometric sensing utilizing paper-based microfluidic sampling is studied in this work. A solid-contact ion-selective electrode and a solid-contact reference electrode are pressed against a filter paper into which the sample solution is absorbed. The filter paper acts simultaneously as a sampling unit and as a sample container during potentiometric sensing. The paper substrates containing standard and sample solutions are disposable, while the sensors are used multiple times. The analytical method presented here opens new possibilities for economically and ecologically sound measurements of ions in various samples.

Blue-Emissive Antioxidant Carbon Dots Enhance Drought Resistance of Pea (Pisum sativum L.).

Prolonged drought conditions are a critical challenge for agricultural advancement, threatening food security and environmental equilibrium. To overcome these issues, enhancing plant resilience to drought is essential for plant growth and sustainable agriculture. In this study, blue-emitting antioxidant carbon dots (B-CDs), synthesized from citric acid and ascorbic acid, emerged as a promising solution to enhance the drought resistance of peas (Pisum sativum L.). B-CDs can efficiently scavenge reactive oxygen species (ROS), which are harmful in excess to plants under stress conditions. Through detailed experimental analyses and density functional theory (DFT) studies, it is found that these B-CDs possess structures featuring eight-membered aromatic rings with abundant oxygen-containing functional groups, providing active sites for reactions with ROS. The practical benefits of the B-CDs are evident in tests with pea plants exposed to drought conditions. These plants show a remarkable reduction in ROS accumulation, an increase in photosynthetic efficiency due to improved electron transfer rates, and significant growth enhancement. Compared to untreated controls under drought stress, the application of B-CDs results in an impressive increase in the fresh and dry weights of both the shoots and roots of pea seedlings by 39.5 and 43.2% for fresh weights and 121.0 and 73.7% for dry weights, respectively. This suggests that B-CDs can significantly mitigate the negative effects of drought on plants. Thus, leveraging B-CDs opens a novel avenue for enhancing plant resilience to abiotic stressors through nanotechnology, thereby offering a sustainable pathway to counter the challenges of drought in agriculture.

Polyolefin-derived substrate-grown carbon nanotubes as binder-free electrode for hydrogen evolution in alkaline media.

Switching from a linear mode of waste management to a circular loop by transforming plastic waste into carbon nanotubes (CNTs) is a promising approach to current plastic waste treatment. One of the many applications of CNTs is its use for electrocatalytic water splitting for hydrogen evolution. Existing methods of CNTs-based hydrogen evolution reaction (HER) electrode fabrication involve additives like polymeric binders and additional steps to improve CNT dispersion, which are detrimental to the CNT structure and properties. The in-situ fabrication approach can potentially be a one-pot solution to HER electrode synthesis. In this study, polyolefins pyrolysis gas and a Co:Ni:Mg catalyst were used to fabricate binder-free CNTs-based electrodes on different substrates for HER. The study assessed CNT quality on conductive carbon paper, semiconductive silicon, and dielectric glass substrates, evaluating their HER performance in 1 M KOH. A mixture of hollow-core, bamboo-like, and cup-stacked arrangement nanotubes were synthesized on the substrates, with CNTs on glass and carbon paper substrates possessing better graphitization than CNTs grown on silicon. This is in agreement with HER performance, whereby the as-prepared electrodes required overpotentials of 267 mV, 241 mV, and 216 mV for silicon, glass, and carbon paper, respectively, to achieve 10 mA/cm2. Despite being poorly conductive, the glass substrate electrode achieved a lower overpotential than the silicon electrode. Additionally, the as-prepared silicon electrode faced a delamination issue likely attributed to the lower surface energy of the silicon substrate surface, demonstrating the weaker adhesion between the CNTs and silicon surface. The proposed approach thus showed that the in-situ fabricated electrodes performed better than separately synthesized CNTs prepared into electrodes by 27.4% and 14.2% for carbon paper and glass substrates, respectively. The improved performance of the as-prepared, binder-free electrodes can be linked to the lower charge-transfer resistance and reduced contact resistance between the CNTs and substrate.

A New Discovery on the Potential Stability of Ion-Selective Membranes: The Poison from Tetrahydrofuran.

Ion-selective electrodes (ISEs) have widespread use in the fields of clinical and environmental analyses. Tetrahydrofuran (THF) is the most used solvent for the preparation of modern ISEs, equipped with ion-selective membranes (ISMs). Until now, the influence of impurities in THF toward potentiometric instability of ion-selective membrane based ISEs was probably associated with the presence of either residual water or peroxide. To address this issue, most literature recommends redistilling THF prior to use in the preparation of the potentiometric membranes. Current study reveals that the actual THF impurity that is responsible for potential instability in the ISM includes products from the oxidation of THF, which contains the hydroxyl group and possibly carbonyl group with a boiling point of above 200 °C. The density functional theory calculation supported pathway of the chemical reaction of THF oxidation, hence, the chemical structure of the uncertain impurities was predicted. The underlying reason for the deteriorating potential stability of the ISEs is proposed as the significant hydrophilicity of these impurities that affect the partitioning of the ion sensing components in the membrane, thus enhancing the leaching of the membrane components from the membrane phase. This finding explains why redistillation of aged THF is advised.

Reclaimed seawater discharge - Desalination brine treatment and resource recovery system.

With the proliferation of reverse osmosis technology, seawater reverse osmosis desalination has been heralded as the solution to water scarcity for coastal regions. However, the large volume of desalination brine produced may pose an adverse environmental impact when directly discharged into the sea and result in energy wastage as the seawater pumped out is dumped back into the sea. Recently, zero liquid discharge has been extensively studied as a way to eliminate the aquatic ecotoxicity impact completely, despite being expensive and having a high carbon footprint. In this work, we propose a new strategy towards the treatment of brine to seawater level for disposal, dubbed reclaimed seawater discharge (RSD). This process is coupled with existing resource recovery techniques and waste alkali CO2 capture processes to produce an economically viable waste treatment process with minimal CO2 emissions. In this work, we placed significant focus on the electrolysis of brine, which simultaneously lowers the salinity of the desalination brine (56.0 ± 2.1 g/L) to seawater level (32.0 ± 1.4 g/L), generates alkali brine from seawater (pH 13.6) to remove impurities in brine (Mg2+ and Ca2+ to below ppm level), and recovers magnesium hydroxide, calcium carbonate, chlorine, bromine, and hydrogen gas as valuable resources. The RSD is further chemically dechlorinated and neutralised to pH 7.3 to be safe to discharge into the sea. The excess alkali brine is used to capture additional CO2 in the form of bicarbonates, achieving net abatement in climate change impact (9.90 CO2 e/m3) after product carbon abatements are accounted.

Categorization of leaching behaviors of elements from commercially treated incineration bottom ash in Singapore.

Leaching of potentially hazardous substances, especially the heavy metals from Incineration Bottom Ash (IBA) is a major problem in its recyclable usage. To address this concern, treatment of IBA is indispensable before it can be reused. IBA subjected to laboratory-scale treatment typically yields clearer conclusions in terms of leaching behaviors, benefiting from the controlled laboratory environment. However, the leaching behaviors of commercially treated IBA appear to be more ambiguous due to the complex and comprehensive nature of industrial-scale treatments, where multiple treatment techniques are involved concurrently. Furthermore, treatment efficiencies vary among different plants. In this study, three types of commercially treated IBA were sampled from leading waste treatment companies in Singapore. Characterization and leaching tests were performed on the treated IBAs in both standardized and modified manners to simulate various scenarios. Besides deionized water, artificial seawater was used as a leachant in leaching tests for simulating seawater intrusion. The results reveal the promoting effect of seawater on the leaching levels of several elements from three types of treated IBA, which may require special attention for IBA application and landfill near the coast. Furthermore, the elements examined in these three types of commercially treated IBA generally comply with the non-hazardous waste acceptance criteria outlined in Council Decision, 2003/33/EC (2003), except Sb. By combining two leaching tests, the elements were categorized into different types of leaching behavior, making it possible to prepare and respond to the concerning leaching scenarios in future engineering applications.

Unveiling key impact parameters and mechanistic insights towards activated biochar performance for carbon dioxide reduction.

Chemically activated biochar is effective in supercapacitors and water splitting, but low conductivity hinders its application as a carbon support in carbon dioxide reduction reaction (CO2RR). Based on the observed CO2RR performance from potassium hydroxide (KOH)-activated biochar, increased microporosity was hypothesized to enhance the performance, leading to selection of potassium carbonate (K2CO3) for activation. K2CO3 activation at 600℃ increased microporosity significantly, yielding a total Faradaic efficiency of 72%, compared to 60% with KOH at 800℃. Further refinement of thermal ramping rate enriched micropore content, directly boosting FEC to 82%. Additionally, K2CO3's lower activation temperature could preserve hydroxyl groups to improve ethylene selectivity. These findings demonstrate that optimizing microporosity and surface chemistry is critical for designing activated biochar-based CO2RR electrocatalysts. Despite lower electrical conductivity of activated biochar, selecting the appropriate activating agents and conditions can make it a viable alternative to carbon black-based electrocatalysts.

Ultrasonic aerosol agglomeration: Manipulation of particle deposition and its impact on air filter pressure drop.

Acoustic agglomeration is a technique that leverages on sound waves to promote the collision of aerosol particulate matter, thus leading to the formation of larger particle agglomerates. In this study, this acoustics-driven phenomenon is demonstrated for its usefulness as an aerosol pre-conditioning method to significantly enhance the efficiency of filtration systems in particle treatment processes. Specifically, favorable changes in pressure drop across the filters are observed as a result of receiving less particle mass, for which filters are shown to be able to have their operational life extended remarkably by more than 50%. The involved ultrasonic aerosol agglomeration mechanisms are unveiled through numerical simulations, and the effects of residence time, sound pressure level, and initial particle number concentration on agglomeration performances are experimentally investigated. In addition, validations and measurements of filter pressure drop are obtained through a series of experiments. This study provides a comprehensive overview to the design and performance characterization of acoustics-agglomeration-enhanced filtration systems, which could potentially derive energy savings for fan power in ventilation systems and be scaled up for applications in industrial plants for reducing carbon emissions.

Solid-contact ion-selective electrodes with highly selective thioamide derivatives of p-tert-butylcalix[4]arene for the determination of lead(II) in environmental samples.

Thioamide derivatives of p-tert-butylcalix[4]arene were used as ionophores in the development of solid-contact ion-selective electrodes based on conducting polymer poly(3,4-ethylenedioxythiophene)/polystyrene sulfonate (PEDOT/PSS) which was synthesized by electrodeposition on the glassy carbon electrodes. The typical ion-selective membranes with optionally two different plasticizers [bis(2-ethylhexyl)sebacate (DOS) and 2-nitrophenyl octyl ether (NPOE)] were investigated. The potentiometric selectivity coefficients were determined by separate solution method (SSM) for Pb(2+) over Cu(2+), Cd(2+), Ca(2+), Na(+), and K(+). High selectivity toward Pb(2+) was obtained. By applying two conditioning protocols, a low detection limit log(a(DL)) ≈ -9 was achieved. The fabricated ion-selective electrodes were used to determine Pb(2+) concentration in environmental samples. The obtained results were compared to analysis done by inductively coupled plasma mass spectrometry (ICPMS).