Integration of Digestate-Derived Biochar into the Anaerobic Digestion Process through Circular Economic and Environmental Approaches-A Review.

The growing energy consumption and the need for a circular economy have driven considerable interest in the anaerobic digestion (AD) of organic waste, offering potential solutions through biogas and digestate production. AD processes not only have the capability to reduce greenhouse gas emissions but also contribute to the production of renewable methane. This comprehensive review aims to consolidate prior research on AD involving different feedstocks. The principles of AD are explored and discussed, including both chemical and biological pathways and the microorganisms involved at each stage. Additionally, key variables influencing system performance, such as temperature, pH, and C/N ratio are also discussed. Various pretreatment strategies applied to enhance biogas generation from organic waste in AD are also reviewed. Furthermore, this review examines the conversion of generated digestate into biochar through pyrolysis and its utilization to improve AD performance. The addition of biochar has demonstrated its efficacy in enhancing metabolic processes, microorganisms (activity and community), and buffering capacity, facilitating Direct Interspecies Electron Transfer (DIET), and boosting CH4 production. Biochar also exhibits the ability to capture undesirable components, including CO2, H2S, NH3, and siloxanes. The integration of digestate-derived biochar into the circular economy framework emerges as a vital role in closing the material flow loop. Additionally, the review discusses the environmental benefits derived from coupling AD with pyrolysis processes, drawing on life cycle assessment investigations. Techno-economic assessment (TEA) studies of the integrated processes are also discussed, with an acknowledgment of the need for further TEA to validate the viability of integrating the biochar industry. Furthermore, this survey examines the techno-economic and environmental impacts of biochar production itself and its potential application in AD for biogas generation, aiming to establish a more cost-effective and sustainable integrated system.

Corn Cobs' Biochar as Green Host of Salt Hydrates for Enhancing the Water Sorption Kinetics in Thermochemical Heat Storage Systems.

Heat storage technologies are essential for increasing the use of solar energy in the household sector. Their development can be achieved by designing new storage materials; one way is to impregnate a porous matrix with hygroscopic salts. In this article, the possibility of using biochar-based composite sorbents to develop promising new heat storage materials for efficient thermal storage is explored. Biochar-based composites with defined salt loadings (5, 10, 15, and 20%) were produced by impregnating MgSO4 into a biochar matrix derived from corn cobs. The new materials demonstrated a high water sorption capacity of 0.24 g/g (20MgCC). After six successive charging-discharging cycles (dehydration/dehydration cycles), only a negligible variation of the heat released and the water uptake was measured, confirming the absence of deactivation of 20MgCC upon cycling. The new 20MgCC composite showed an energy storage density of 635 J/g (Tads = 30 °C and RH = 60%), higher than that of other composites containing a similar amount of hydrate salt. The macroporous nature of this biochar increases the available surface for salt deposition. During the hydration step, the water molecules effectively diffuse through a homogeneous layer of salt, as described by the intra-particle model applied in this work. The new efficient biochar-based composites open a low-carbon path for the production of sustainable thermal energy storage materials and applications.

Tomato waste biochar in the framework of circular economy.

Tomato pomace was slowly pyrolyzed at 350 and 550 °C (under an N2 flow of 50 L/h) at a rate of 6 °C/min and a residence time of 1:30 h to produce two biochars named B350 and B550, respectively. In addition, the two biochars were chemically activated with ΚΟΗ (at a ratio of 1:10 w/v) at 800 °C to produce two new materials named BA350 and BA550. The four biochars produced were characterized physically and chemically (pH, yield, calorific value). They were also analyzed by scanning electron microscopy (SEM), Brunauer-Emmett-Teller (B.E.T), elemental analysis (EA), and thermogravimetric analysis (TGA). The results showed that as the pyrolysis temperature increased (350 to 550 °C), the specific surface area (SSA) increased. The latter was also significantly increased by the activation process. EA showed a variation in the mineral content of the produced biochars, resulting in a different content of the biochars after activation. The parameters studied showed that biochars from tomato waste could be used as an organic amendment to improve soil fertility in agricultural. In addition, because of their ability to absorb water, they could be used as a water reservoir in soils in arid areas.

Synthetic beidellite clay as nanocarrier for delivery of antitumor oxindolimine-metal complexes.

Studies on the immobilization of oxindolimine­copper(II) or zinc(II) complexes [ML] in synthetic beidellite (BDL) clay were developed to obtain a suitable inorganic carrier capable of promoting the modified-release of metallopharmaceuticals. Previous investigations have shown that the studied metal complexes are promising antitumor agents, targeting DNA, mitochondria, and some proteins. They can bind to DNA, causing oxidative damage via formation of reactive oxygen species (ROS). In mitochondria they lead to a decrease in membrane potential, acting as decoupling agents, and therefore efficiently inducing apoptosis. Additionally, they inhibit human topoisomerase IB and cyclin dependent kinases, proteins involved in the cell cycle. BDL clays in the sodium form were synthesized under hydrothermal conditions and characterized by a set of physicochemical techniques while the BDL-[ML] hybrid materials were prepared by ion exchange method. The characterization of pristine clay and the obtained hybrids were performed by Infrared, Raman, electron paramagnetic resonance and energy dispersive X-ray spectroscopies, thermogravimetric analysis, scanning electron microscopy, X-ray powder diffraction, specific surface area, zeta potential and surface ionic charge measurements. The [ML] release assays under the same cell incubation conditions were performed monitoring metals by X-ray fluorescence. The BDL-[CuL] hybrid materials were stable and able to derail tumor HeLa cells, with corresponding IC50 values in the 0.11-0.41 mg mL-1 range. By contrast, the analogous hybrid samples of zinc(II) and the pristine BDL proved to be non-toxic facing the same cells. These results indicate a promising possibility of using synthetic beidellite as a carrier of such antitumor metal complexes.

Unveiling the Potential of Corn Cob Biochar: Analysis of Microstructure and Composition with Emphasis on Interaction with NO2.

In the context of sustainable solutions, this study examines the pyrolysis process applied to corn cobs, with the aim of producing biochar and assessing its effectiveness in combating air pollution. In particular, it examines the influence of different pyrolysis temperatures on biochar properties. The results reveal a temperature-dependent trend in biochar yield, which peaks at 400 °C, accompanied by changes in elemental composition indicating increased stability and extended shelf life. In addition, high pyrolysis temperatures, above 400 °C, produce biochars with enlarged surfaces and improved pore structures. Notably, the highest pyrolysis temperature explored in this study is 600 °C, which significantly influences the observed properties of biochars. This study also explores the potential of biochar as an NO2 adsorbent, as identified by chemical interactions revealed by X-ray photoelectron spectroscopy (XPS) analysis. This research presents a promising and sustainable approach to tackling air pollution using corn cob biochar, providing insight into optimized production methods and its potential application as an effective NO2 adsorbent to improve air quality.

New Materials and Technologies for Wastewater Treatment.

This Special Issue (SI) contains the successful submissions [...].

Potential Valorization of Waste Tires as Activated Carbon-Based Adsorbent for Organic Contaminants Removal.

The present study investigates the potential of waste tires to produce a valuable adsorbent material for application in wastewater treatment. In the first stage, the pyrolysis of ground rubber tire was explored using non-isothermal and isothermal thermogravimetric analysis experiments. The effect of operating parameters, such as heating rate and pyrolysis temperature, on the pyrolysis product yields was considered. The slow pyrolysis of ground rubber tire was taken up in a large-scale fixed-bed reactor for enhanced char recovery. Four pyrolysis temperatures were selected by thermogravimetric data. The product yields were strongly influenced by the pyrolysis temperature; at higher temperatures, the formation of more gases and liquid was favored, while at lower pyrolysis temperatures, more char (solid fraction) was formed. The produced chars were characterized in terms of mineral composition, textural properties, proximate analysis, and structural properties to identify the relationships between the pyrolysis temperature and the char properties. In a second step, a series of activated chars were prepared, starting from the pyrolytic chars via chemical and/or physical activation methods. Then, the activated chars were characterized and tested as adsorbents for atrazine and ibuprofen. Adsorption experiments in aqueous media were carried out in a small-scale batch reactor system. Chemical activation seems appropriate to significantly reduce the inorganic compounds initially present in ground rubber tire and contribute to an important increase in the surface area and porosity of the chars. Adsorption experiments indicated that chemically activated chars exhibit high aqueous adsorption capacity for atrazine.

Review: Clay-Modified Electrodes in Heterogeneous Electro-Fenton Process for Degradation of Organic Compounds: The Potential of Structural Fe(III) as Catalytic Sites.

Advanced oxidation processes are considered as a promising technology for the removal of persistent organic pollutants from industrial wastewaters. In particular, the heterogeneous electro-Fenton (HEF) process has several advantages such as allowing the working pH to be circumneutral or alkaline, recovering and reusing the catalyst and avoiding the release of iron in the environment as a secondary pollutant. Among different iron-containing catalysts, studies using clay-modified electrodes in HEF process are the focus in this review. Fe(III)/Fe(II) within the lattice of clay minerals can possibly serve as catalytic sites in HEF process. The description of the preparation and application of clay-modified electrodes in the degradation of model pollutants in HEF process is detailed in the review. The absence of mediators responsible for transferring electrons to structural Fe(III) and regenerating catalytic Fe(II) was considered as a milestone in the field. A comprehensive review of studies investigating the use of electron transfer mediators as well as the mechanism behind electron transfer from and to the clay mineral structure was assembled in order to uncover other milestones to be addressed in this study area.

Biochar production from Cypress sawdust and olive mill wastewater: Agronomic approach.

Olive mill wastewater (OMW) is nowadays considered as a serious source pollution. At the same time, it contains high amounts of nutrients, especially potassium and phosphorus that could be recovered for agricultural purposes. The aim of the current experimental research work is to investigate the agronomic potential use of OMW based biochar produced from the slow pyrolysis at 500 °C of raw cypress sawdust (CS) impregnated with OMW (ICS-OMW-B). In order to understand the contribution of OMW, two additional biochars were produced from raw cypress sawdust (RCS-B) and cypress sawdust pretreated with potassium chloride (ICS-K-B). Results indicated that RCS impregnation by OMW significantly improved the produced biochar's chemical properties, especially its nutrients contents. Furthermore, in comparison with the other biochars, ICS-OMW-B application as an organic fertilizer showed promising results in terms of produced fresh and dry masses, as well as potassium bioavailability as assessed in test experiments with ryegrass. For instance, the dry matter masses of the rye-grass treated with ICS-OMW-B were about 23, 34 and 50 wt% higher than the ones measured for the tests using RCS-B, ICS-K-B and synthetic K-fertilizer as amendments, respectively. Besides, this biochar has a potential effect on the suppression of various pathogens existing in the tested agricultural soil. All these results demonstrated that the biochar generated from the slow pyrolysis of impregnated sawdust with OMW could be considered as attractive and promising organic fertilizer for acidic agricultural soils.

Sustainable metropolitan areas perspectives through assessment of the existing waste management strategies.

Human activities are considered among the main producers of any kind of pollution. This paper, through a Driver-Pressure-State-Impact-Response (DPSIR) model analyses, focuses on the evaluation and assessment of the existing practices, procedures, and results obtained in order to determine whether the municipal solid waste (MSW) management implemented in three major Greek municipalities in the greater urban area of Attica, namely the municipalities of Nea Smirni, Vyronas, and Piraeus, could be considered viable and sustainable. The evaluation indicated that MSW in Greek cities have reduced over the last years, also suggesting a steady downward trend, which could be considered consistent with that of the per capita incomes in Greece due to the extended economic austerity, while at the same time the recycling indicator seems to optimize. The results are very useful for policymakers and local authorities towards taking actions related to the targets set from the circular economy strategies as well as the targets set from United Nation Development Program and the European Green Deal Strategy.

Synthesis, Characterization and Catalytic Activity of Ternary Oxide Catalysts Using the Microwave-Assisted Solution Combustion Method.

Ni-Co-Al, Ni-Cu-Al and Co-Cu-Al ternary oxide catalysts, with a fixed 5 wt% transition metal loading, were prepared by the microwave-assisted solution combustion method and tested in CO oxidation. The bulk and surface properties of the catalysts were investigated, using XRD, N2 adsorption-desorption, SEM, XPS and TEM techniques. XRD, XPS and TEM results revealed that nickel and cobalt were present as spinels on the surface and in the bulk. Differently, copper was preferentially present in "bulk-like" CuO-segregated phases. No interaction between the couples of transition metal species was detected, and the introduction of Cu-containing precursors into the Ni-Al or Co-Al combustion systems was not effective in preventing the formation of NiAl2O4 and CoAl2O4 spinels in the Ni- or Co-containing catalysts. Copper-containing catalysts were the most active, indicating that copper oxides are the effective active species for improving the CO oxidation activity.

Laponites® for the Recovery of 133Cs, 59Co, and 88Sr from Aqueous Solutions and Subsequent Storage: Impact of Grafted Silane Loads.

In this study, silylated Laponites® (LAP) were synthetized with various loads of 3-aminopropyltriethoxysilane (APTES) to evaluate their adsorption properties of 133Cs, 59Co, and 88Sr during single-solute and competitive experiments. The increase in the initial load of APTES increased the adsorbed amount of APTES in the resulted grafted clay. The characterization of LAP-APTES exhibited a covalent binding between APTES and LAP and emphasized the adsorption sites of APTES for each tested load. In comparison with raw LAP, LAP-APTES displayed significantly higher adsorption properties of Co2+, Cs+, and Sr2+. The competitive adsorption of these three contaminants provides a deeper understanding of the affinity between adsorbate and adsorbent. Therefore, Co2+ displayed a strong and specific adsorption onto LAP-APTES. Except for Cs+, the adsorption capacity was improved with increasing the load of APTES. Finally, the desorption behavior of the three contaminants was tested in saline solutions. Cs+ and Sr2+ were significantly released especially by inorganic cations displaying the same valence. Conversely, desorption of Co2+ was very low whatever the saline solution. LAP-APTES, therefore, presented suitable adsorption properties for the removal of radionuclides especially for Co2+, making this material suitable to improve the decontamination of radioactive wastewaters.

Free-standing cellulose film containing manganese dioxide nanoparticles and its use in discoloration of indigo carmine dye.

In this study, we report the production of a free-standing film of non-modified cellulose impregnated with 12 wt.% of MnO2 nanoparticles with less than 100 nm in size. The method here described can be applied to the immobilization of different types of nanoparticles. The film was prepared by dissolving microcrystalline cellulose in an ionic liquid followed by its regeneration by adding water to the former solution. Then, the wet film was impregnated with the nanoparticles by dipping it in a MnO2 dispersion. Electron microscopy images revealed manganese dioxide nanoparticles distributed not only at the film surface but also in its interior. The cellulose film impregnated with MnO2 nanoparticles was capable of efficiently discolouring an Indigo Carmine dye solution in 25 min upon ambient light. The film was easily removed from the dye solution and repeatedly reused for at least 10 times without losing its discolouring efficiency.

Inorganic and Hybrid (Organic⁻Inorganic) Lamellar Materials for Heavy metals and Radionuclides Capture in Energy Wastes Management-A Review.

The energy industry (nuclear, battery, mining industries, etc.) produces a large quantity of hazardous effluents that may contain radionuclides (137Cs and 90Sr in particular) and heavy metals. One of the hardest tasks of environmental safety and sustainable development is the purification of wastewater holding these pollutants. Adsorption is one of the most powerful methods for extracting toxic compounds from wastewater. This study reviews the usefulness of clay minerals as adsorbent for removing these hazardous elements to clean up energy production processes. Phyllosilicates are able to extract several heavy metals from effluent, as widely examined. A particular focus is given to synthetic phyllosilicates and their abilities to entrap heavy metals with a special attention paid to those synthesized by sol-gel route. Indeed, this method is attractive since it allows the development of organic-inorganic hybrids from organosilanes presenting various functions (amino, thiol, etc.) that can interact with pollutants. Regarding these pollutants, a part of this review focuses on the interaction of lamellar materials (natural and synthetic phyllosilicates as well as layered double hydroxide) with heavy metals and another part deals with the adsorption of specific radionuclides, cesium and strontium.

Activated Carbon/Transition Metal (Ni, In, Cu) Hexacyanoferrate Nanocomposites for Cesium Adsorption.

Transition metal hexacyanoferrate/microporous activated carbon composites were obtained using a simple successive impregnation approach. The effect of metal type (nickel, indium, or copper), and the carbon oxidation on the composite characteristics (porosity, metal structure, and particle size), as well as on the removal efficiency of cesium from aqueous solution was investigated. Successful formation of the desired metal hexacyanoferrate phase was achieved and the size of the metallic nanoparticles and their dispersion in the carbon network was found to depend on the metal type, with the indium and nickel-based materials exhibiting the smallest particle size distribution (< 10 nm). Adsorption tests performed under batch conditions demonstrate that the copper hexacyanoferrate/activated carbon composite present the highest cesium removal capacity from aqueous solution (74.7 mg·g-1) among the three studied metal-based nanocomposites. The carbon oxidation treatment leads to the increase in the number of functional groups to the detriment of the porosity but allows for an improvement in the Cs adsorption capacity. This indicates that the Cs adsorption process is governed by the carbon surface chemistry and not its porosity. Moreover, combining oxidized carbon support with copper hexacyanoferrate induces the highest cesium adsorption capacity (101.5 mg·g-1). This could be related to synergistic effects through two absorption mechanisms, i.e., a cation exchange mechanism of Cs with the metallic hexacyanoferrate phase and Cs adsorption via carbon oxygen surface groups, as demonstrated using X-ray photoelectron spectroscopy (XPS) analyses.

Binary Oxides Prepared by Microwave-Assisted Solution Combustion: Synthesis, Characterization and Catalytic Activity.

Three different alumina-based Ni, Cu, Co oxide catalysts with metal loading of 10 wt %, and labeled 10Ni⁻Al, 10Co⁻Al and 10Cu⁻Al, were prepared by microwave-assisted solution combustion. Their morphological, structural and surface properties were deeply investigated by complementary physico-chemical techniques. Finally, the three materials were tested in CO oxidation used as test reaction for comparing their catalytic performance. The 10Cu⁻Al catalyst was constituted of copper oxide phase, while the 10Ni⁻Al and 10Co⁻Al catalysts showed the presence of "spinels" phases on the surface. The well-crystallized copper oxide phase in the 10Cu⁻Al catalyst, obtained by microwave synthesis, allowed for obtaining very high catalytic activity. With a CO conversion of 100% at 225 °C, the copper containing catalyst showed a much higher activity than that usually measured for catalytic materials of similar composition, thus representing a promising alternative for oxidation processes.

Systems for stimuli-controlled release: Materials and applications.

The design and development of delivery controlled systems of molecules of interest has attracted great interest over the last years. pH variation, light irradiation, temperature increasing, variation of the redox potential and the application of a magnetic field are among the most widely used stimuli that can be used to induce the release of an active molecule in a medium. The dominance of pH and photo-controlled release is clearly highlighted by the numerous articles published in these fields as well as all the related applications. In the case of pH-controlled release, two main parameters govern the release: the solubility of the active molecule in the releasing medium and the stability of the carrier materials. In the photo-controlled release, the carrier needs to contain a photosensible functionality; this stimulus can be successfully applied in the medical field when red light, that is able to penetrate the human tissues, is used. A large panel of applications of controlled release can be identified in the pharmaceuticals, agriculture, cosmetics, chemistry and dyes industry fields. More recently, biological, enzymatic, and mechanical (ultrasounds, stretching, shear stress) stimuli have been developed for target applications, in particular for drugs and hormones release. Consequently, many types of materials (polymers, silica, oxides, MOF…) can be used as carrier in relation to their compatibility with the active molecule and the type of releasing medium. This review aims to gives a useful overview on the materials, applications and mechanisms implied in stimuli-controlled release.

Factors Influencing NO2 Adsorption/Reduction on Microporous Activated Carbon: Porosity vs. Surface Chemistry.

The textural properties and surface chemistry of different activated carbons, prepared by the chemical activation of olive stones, have been investigated in order to gain insight on the NO2 adsorption mechanism. The parent chemical activated carbon was prepared by the impregnation of olive stones in phosphoric acid followed by thermal carbonization. Then, the textural properties and surface chemistry were modified by chemical treatments including nitric acid, sodium hydroxide and/or a thermal treatment at 900 °C. The main properties of the parent and modified activated carbons were analyzed by N2-adsorption, scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR) techniques, in order to enlighten the modifications issued from the chemical and thermal treatments. The NO2 adsorption capacities of the different activated carbons were measured in fixed bed experiments under 500 ppmv NO2 concentrations at room temperature. Temperature programmed desorption (TPD) was applied after adsorption tests in order to quantify the amount of the physisorbed and chemisorbed NO2. The obtained results showed that the development of microporosity, the presence of oxygen-free sites, and the presence of basic surface groups are key factors for the efficient adsorption of NO2.

Investigations on phosphorus recovery from aqueous solutions by biochars derived from magnesium-pretreated cypress sawdust.

The ability of biochars, derived from the pyrolysis at 400 °C; 500 °C and 600 °C of pretreated cypress sawdust with 20 wt% magnesium chloride (MgCl2) solutions, in recovering phosphorus from aqueous solutions was investigated under various experimental conditions in batch mode. The experimental results indicated that cypress sawdust pretreatment with MgCl2 induced important modifications of the physical and chemical biochars' properties favoring phosphorus recovery from the used synthetic solutions. Moreover, phosphorus recovery efficiency increased with the increase of the used pyrolysis temperature. Indeed, for an aqueous pH of 5.2 and a phosphorus concentration of 75 mg L-1, the recovered amounts increased from 19.2 mg g-1 to 33.8 mg g-1 when the used pyrolysis temperature was raised from 400 °C to 600 °C. For all the tested biochars, the phosphorus recovery kinetics data were well fitted by the pseudo-second-order model, and the equilibrium state was obtained after 180 min of contact time. Furthermore, the phosphorus recovery data at equilibrium were well described by the Langmuir model with a maximal recovery capacity of 66.7 mg g-1 for the magnesium pretreated biochar at 600 °C. Phosphorus recovery by the used biochars occurred probably through adsorption onto biochars' active sites as well as precipitation with magnesium ions as magnesium phosphates components. All these results suggested that biochars derived from MgCl2 pretreated cypress sawdust could be considered as promising materials for phosphorus recovery from wastewaters for a possible further subsequent use in agriculture as amendments.

Modification of the Selectivity Properties of Tubular Ceramic Membranes after Alkaline Treatment.

This work focuses on the selectivity modification of ceramic membranes after a mild alkaline treatment. Filtration of pure salt-water solutions was carried out with commercial titania membranes before and after the treatment. After treatment, the rejection of NaF significantly decreased, while the rejection of NaCl and NaBr increased. Additionally, NaI and Na2SO4 remained close to zero. Pore size and electrical charge being almost unchanged, only significant modifications in the dielectric effects can explain this modification of selectivity. Therefore, the surface chemistry and the interaction (nature and magnitude) with the solvent and with the species present in the solution appear to be modified by the alkaline treatment. This trend is also illustrated by discussing the electric and the dielectric properties that were numerically identified before and after treatment. The alkaline treatment significantly decreased the apparent dielectric constant of NaCl-water solution in the pore, highlighting the rejection of sodium chloride. Contrariwise, the modification of the surface chemistry increased the apparent dielectric constant of NaF-water solution by promoting fluoride transmission.