Effects of biomass co-pyrolysis and herbaceous plant colonization on the transformation of tailings into soil like substrate.

Enhancing soil organic matter characteristics, ameliorating physical structure, mitigating heavy metal toxicity, and hastening mineral weathering processes are crucial approaches to accomplish the transition of tailings substrate to a soil-like substrate. The incorporation of biomass co-pyrolysis and plant colonization has been established to be a significant factor in soil substrate formation and soil pollutant remediation. Despite this, there is presently an absence of research efforts aimed at synergistically utilizing these two technologies to expedite the process of mining tailings soil substrate formation. The current study aimed to investigate the underlying mechanism of geochemical changes and rapid mineral weathering during the process of transforming tailings substrate into a soil-like substrate, under the combined effects of biomass co-smoldering pyrolysis and plant colonization. The findings of this study suggest that the incorporation of smoldering pyrolysis and plant colonization induces a high-temperature effect and biological effects, which enhance the physical and chemical properties of tailings, while simultaneously accelerating the rate of mineral weathering. Notable improvements include the amelioration of extreme pH levels, nutrient enrichment, the formation of aggregates, and an increase in enzyme activity, all of which collectively demonstrate the successful attainment of tailings substrate reconstruction. Evidence of the accelerated weathering was verified by phase and surface morphology analysis using X-ray diffraction and scanning electron microscopy. Discovered corrosion and fragmentation on the surface of minerals. The weathering resulted in corrosion and fragmentation of the surface of the treated mineral. This study confirms that co-smoldering pyrolysis of biomass, combined with plant colonization, can effectively promote the transformation of tailings into soil-like substrates. This method has can effectively address the key challenges that have previously hindered sustainable development of the mining industry and provides a novel approach for ecological restoration of tailings deposits.

Oxygen atmosphere enhances ball milling remediation of petroleum-contaminated soil and reuse as adsorptive/catalytic materials for wastewater treatment.

Ball milling is an environmentally friendly technology for the remediation of petroleum-contaminated soil (PCS), but the cleanup of organic pollutants requires a long time, and the post-remediation soil needs an economically viable disposal/reuse strategy due to its vast volume. The present paper develops a ball milling process under oxygen atmosphere to enhance PCS remediation and reuse the obtained carbonized soil (BCS-O) as wastewater treatment materials. The total petroleum hydrocarbon removal rates by ball milling under vacuum, air, and oxygen atmospheres are 39.83%, 55.21%, and 93.84%, respectively. The Langmuir and pseudo second-order models satisfactorily describe the adsorption capacity and behavior of BCS-O for transition metals. The Cu2+, Ni2+, and Mn2+ adsorbed onto BCS-O were mainly bound to metal carbonates and metal oxides. Furthermore, BCS-O can effectively activate persulfate (PDS) oxidation to degrade aniline, while BCS-O loaded with transition metal (BCS-O-Me) shows better activation efficiency and reusability. BCS-O and BCS-O-Me activated PDS oxidation systems are dominated by 1O2 oxidation and electron transfer. The main active sites are oxygen-containing functional groups, vacancy defects, and graphitized carbon. The oxygen-containing functional groups and vacancy defects primarily activate PDS to generate 1O2 and attack aniline. Graphitized carbon promotes aniline degradation by accelerating electron transfer. The paper develops an innovative strategy to simultaneously realize efficient remediation of PCS and sequential reuse of the post-remediation soil.

Alternative green application areas for olive pomace catalytic pyrolysis biochar obtained via marble sludge catalyst.

Evaluating industrial wastes in the system with minimum preprocessing and generation economically valuable products from them have critical importance. In this regard, especially cheap, wieldy, and readily available catalysts have been researched to increase variety of useful products in pyrolysis systems, to reduce process time, and to increase quality and diversity of products. Therefore, in this study, marble sludge (named K1) was evaluated as catalyst at different dosages (10%, 20%, 30%, 50%) and pyrolysis temperatures (300, 500, 700 °C) in olive pomace (OP) pyrolysis and; the potential green applications of produced new biochars at new usage areas with different purposes based on characteristics were investigated. ANOVA test results showed that temperature and catalysts ratio had significant effect on pyrolysis product yields since significance value for K1 and temperature was lower than 0.05 for pyrolysis products. OP-K1 biochars had alkaline properties and high earth metal quantities. Moreover, increment in K1 ratio and temperature resulted in decrement of the biochar surface acidity. Therefore, it can be indicated that these biochars can have a potential usage for anaerobic digestion processes, lithium-ion batteries, and direct carbon solid oxide fuel cell (DC-SOFC) but further electrochemical property test should be performed. Moreover, produced biochars can be alternative fuels in some processes instead of coal since they have low S content and high heat values. Consequently, it is foreseen that produced biochars will have an important place in the development of potential usage areas with a new and environmentally friendly approach in different areas apart from the conventional uses of catalytic pyrolysis chars.

Pontederia crassipes utilization for dual phytoremediation and adsorption in greywater treatment: a techno-economic and sustainable approach.

While phytoremediation has been widely employed for greywater treatment, this system suffers from the transfer of considerable amounts of surfactants to the aquatic environment through partially treated effluent and/or exhausted plant disposal. Hence, this study focuses on greywater phytoremediation followed by recycling the spent plant for preparing an adsorbent material used as post-treatment. P. crassipes was used to operate a phytoremediation unit under 23 °C, 60% relative humidity, plant density (5-30 g/L), dilution (0-50%), pH (4-10), and retention time (3-15 days). The optimum condition was 12.7 g/L density, 34.0% dilution, pH 8.4, and 13 days, giving chemical oxygen demand (COD), surfactant, and NH4-N removal efficiencies of 94.62%, 90.45%, and 88.09%, respectively. The exhausted plant was then thermally treated at 550 °C and 40 min to obtain biochar used as adsorbent to treat the phytoremediation effluent. The optimum adsorption process was biochar dosage of 1.51 g/L, pH of 2.1, and 137 min, providing a surfactant removal efficiency of 92.56%. The final discharge of this phytoremediation/adsorption combined process contained 8.30 mg/L COD, 0.23 mg/L surfactant, and 0.94 mg/L NH4+-N. Interestingly, this approach could be economically feasible with a payback period of 6.5 years, 14 USD net present value, and 8.6% internal rate of return.

The research succeeded in treating greywater by phytoremediation followed by recycling the exhausted P. crassipes plant to prepare an adsorbent material used in the post-treatment phase, giving an economically feasible scenario with 6.5-year payback period.

Recycling and reuse of waste agricultural plastics with hydrothermal pretreatment and low-temperature pyrolysis method.

Recycling and reuse of agricultural plastics is an urgent worldwide issue. In this work, it is shown that low-density polyethylene (PE) typically used in mulch films can be converted into high-capacity P and N adsorbents through a two-step method that uses hydrothermal pretreatment (180 °C, 24 h) followed by pyrolysis at 500 °C with Ca(OH)2 additive. CaPE@HC500 materials prepared with the proposed two-step method were found to have high adsorption capacities for phosphate (263.6 mg/g) and nitrogen (200.7 mg/g) over wide ranges of pH (3-11). Dynamic adsorption of phosphate by CaPE@HC500 material in a packed-bed had a half-time breakthrough of 210 min indicating the feasibility of continuous systems. Material stability, cost, environmental-friendliness, and recyclability of the CaPE@HC500 material were determined to be superior to literature-proposed Ca-containing adsorbents. The two-step method for converting waste agricultural plastic mulch films into adsorbents is robust and highly-applicable to industrial settings.

Environmental remediation potential of a pioneer plant (Miscanthus sp.) from abandoned mine into biochar: Heavy metal stabilization and environmental application.

Pyrolysis stands out as an effective method for the disposal of phytoremediation residues in abandoned mines, yielding a valuable by-product, biochar. However, the environmental application of biochar derived from such residues is limited by the potential environmental risks of heavy metals. Herein, Miscanthus sp. residues from abandoned mines were pyrolyzed into biochars at varied pyrolysis temperatures (300-700 °C) to facilitate the safe reuse of phytoremediation residues. The results showed that pyrolysis significantly stabilizes heavy metals in biomass, with Cd exhibiting the most notable stabilization effect. Acid-soluble/exchangeable and reducible fractions of Cd decreased significantly from 69.91 % to 2.52 %, and oxidizable and residue fractions increased approximately 3.24 times at 700 °C. The environmental risk assessment indicated that biochar pyrolyzed over 500 °C pose lower environmental risk (RI < 30), making them optimal for the safe utilization of phytoremediation residues. Additionally, adsorption experiments suggested that biochars prepared at higher temperature (500-700 °C) exhibit superior adsorption capacity, attributed to alkalinity and precipitation effect. This study highlights that biochars produced by pyrolyzing Miscanthus sp. from abandoned mines above 500 °C hold promise for environmental remediation, offering novel insight into the reutilization of metal-rich biomass.

Facing the solid waste of cotton straw and plastic mulch film mixture in China: Centralized or decentralized pyrolysis facility?

The widespread use of plastic mulch film (PMF) has led to significant environmental pollution, with PMF residues dispersed and mixed with straw and soil, posing challenges for recycling. Here, we proposed the mobile pyrolysis facility for the cotton straw and mulch film mixture (CMM) to mitigate the collection, storage, and transportation costs, while the application of co-pyrolysis technology for CMM conversion could improve the added value of products. Additionally, centralized combustion power generation and centralized pyrolysis systems were also established to evaluate and compare their sustainability from economic and environmental perspectives. Results showed that mobile pyrolysis has better economic performance than the centralized scenarios, due to its high internal rate of return (31 %) and significant net present value (29.21 M USD). Meanwhile, the mobile pyrolysis facility achieved a GWP of -1.298 kgCO2-eq/kg, reducing emissions by 70.79 % and 38.82 % compared to the two centralized scenarios. In conclusion, mobile pyrolysis technology provides a promising solution for PMF residue recycling because of its economically competitive approach with a lower carbon footprint.

Conversion and fate of waste Li-ion battery electrolyte in a two-stage thermal treatment process.

Disposal of electrolytes from waste lithium-ion batteries (LIBs) has gained much more attention with the growing application of LIBs, yet handling spent electrolyte is challengeable due to its high toxicity and the lack of established methods. In this study, a novel two-stage thermal process was developed for treating residual electrolytes resulted from spent lithium-ion batteries. The conversion of fluorophosphate and organic matter in oily electrolyte during low-temperature rotation distillation was investigated. The distribution and migration of the concentrated electrolytes were studied and the corresponding reaction mechanisms were elucidated. Additionally, the influence of alkali on the fixation of fluorine and phosphate was further examined. The results indicated that hydrolyzed carbonate esters and lithium in the electrolyte could combine to form Li2CO3 and the hydrolysable hexafluorophosphate was proven to be stable in the concentrated electrolyte (45 rpm/85 °C, 30 min). It was found that CO2, CO, CH4, and H2 were the primary pyrolysis gases, while the pyrolysis oil consisted of extremely flammable substances formed by the dissociation and recombination of chemical bonds in the electrolyte solvent. After pyrolysis at 300 °C, fluorine and phosphate were present in the form of sodium fluoride and sodium phosphate. The stability of the residue was enhanced, and the environmental risk was reduced. By adding alkali (KOH/Ca(OH)2, 20 %), hexafluorophosphate in the electrolyte was transformed into fluoride and phosphate in the residue, thereby reducing the device's corrosion from fluorine-containing gas. This study provides a viable approach for managing the residual electrolyte in the waste lithium battery recovery process.

Bimetal Oxides Anchored on Carbon Nanotubes/Nanosheets as High-Efficiency and Durable Bifunctional Oxygen Catalyst for Advanced Zn-Air Battery: Experiments and DFT Calculations.

To meet increasing requirement for innovative energy storage and conversion technology, it is urgent to prepare effective, affordable, and long-term stable oxygen electrocatalysts to replace precious metal-based counterparts. Herein, a two-step pyrolysis strategy is developed for controlled synthesis of Fe2O3 and Mn3O4 anchored on carbon nanotubes/nanosheets (Fe2O3-Mn3O4-CNTs/NSs). The typical catalyst has a high half-wave potential (E1/2 = 0.87 V) for oxygen reduction reaction (ORR), accompanied with a smaller overpotential (η10 = 290 mV) for oxygen evolution reaction (OER), showing substantial improvement in the ORR and OER performances. As well, density functional theory calculations are performed to illustrate the catalytic mechanism, where the in situ generated Fe2O3 directly correlates to the reduced energy barrier, rather than Mn3O4. The Fe2O3-Mn3O4-CNTs/NSs-based Zn-air battery exhibits a high-power density (153 mW cm-2) and satisfyingly long durability (1650 charge/discharge cycles/550 h). This work provides a new reference for preparation of highly reversible oxygen conversion catalysts.

Sulfur release behavior and sulfur fixation mechanism during biomass microwave co-pyrolysis of Ascophyllum and rice straw.

Co-pyrolysis with low-sulfur biomass is expected to improve the yield and quality of bio-fuels, without the usage of calcium-based desulfurizer. Sulfur transformation during microwave fluidized-bed co-pyrolysis between terrestrial and marine biomass (Ascophyllum, AS; Rice straw, RS) was investigated. Sulfur release was promoted during biomass co-pyrolysis, but it was inhibited during pyrolysis between AS and low-sulfur char. Thermal cracking of biomass was promoted during co-pyrolysis between biomass, accelerating the combination of H atoms and -SH radicals. Introduction of low-sulfur bio-char (CA) inhibited the generation of bio-char and the release of sulfur. Released sulfur was captured by -OH/C = C functional groups on bio-char through dehydration reactions/addition reactions, forming mercaptan in bio-char. Furthermore, introduction of microwave and bio-char promoted the cyclization and aromatization reaction, converting mercaptan to thiophene and improving the thermal stability of solid sulfur, and thus increasing in-situ sulfur fixation rate.

Impact of biochar produced at different pyrolysis conditions on heavy metal contaminated soil.

This study aimed to assess the effectiveness of urban derived biochars such as Sugarcane bagasse (SB), Brinjal Stem (BS), and Citrus Peel (CP) produced at two different pyrolysis conditions (450 and 600 °C for 60 min) for soil heavy metal bioremediation potential. An ex-situ study was conducted to remediate single heavy metal-contaminated SoilRite with lead (Pb), copper (Cu), chromium (Cr) and cadmium (Cd), with biochars applied at different rates. Heavy metal status in soilrite was evaluated using various extraction methods (water-soluble, exchangeable, TCLP (Toxicity Characteristic Leaching Procedure), and PBET (Physiologically Based Extraction Tests)) to determine the biochar treatments' efficacy. The findings show that SB biochar at 450-60 are more effective in immobilizing heavy metals in water-soluble (Cd-100% Pb and Cu-70%), exchangeable (Pb:91%, Cd and Cu by 70-80%) and PBET-extracted forms (Cd-91%, Pb-80%, and Cu-75%), whereas biochar derived from BS (84%) and CP (90%) at 600-60 are more effective in immobilizing TCLP-extracted form of Pb and Cu. Urban derived biochars significantly reduced the toxicity of Pb, Cu, and Cd in various extractable forms and can stabilize and convert them into less accessible forms except for Cr. These extraction methods aid in evaluating environmental risks and influencing remediation strategies for soil heavy metal pollution. Urban biochar, as a cost-effective and eco-friendly solution, significantly solves this issue, facilitating sustainable waste management.

Py-GC-MS analysis for microplastics: Unlocking matrix challenges and sample recovery when analyzing wastewater for polypropylene and polystyrene.

Matrix interference and recovery when using pyrolysis gas chromatography (Py-GC-MS) to analyze wastewater for polystyrene (PS) and polypropylene (PP) microplastics (MP) was studied. Raw wastewater underwent a sample preparation train commonly applied for such matrix. The train consisted of six discrete steps to reduce the organic matter content without affecting MP in the sample. One large wastewater sample was collected, homogenized, and subdivided into 21 subsamples. Three samples were analyzed without further sample preparation. The remaining samples were divided in sets of three, and each set underwent an increasing number of steps of the procedure, up to the last set, which underwent the full treatment. The matrix effect on the determination of PS and PP was statistically evaluated by comparing in-matrix and external calibration curves at each step. Recovery of MP was assessed after each step by adding deuterated PS to the samples. A main finding was that there was no significant matrix effect for these polymers throughout the preparation train, suggesting that matrix components did not interfere with the analytical method. However, a significant loss of polymer mass was found between the steps, which may result in MPs falling below detection limits. Therefore, Py-GC-MS could be used for MP quantification before analysis by other techniques which require more extensive matrix removal. A downside of this approach is that analyzing such samples without matrix reduction will increase the need for instrumental maintenance.

Assessment of carbonized himalayan chir pine biomass as an eco-friendly adsorbent for effective removal of industrial dyes.

This study investigates the use of carbonized Himalayan Chir Pine Biomass, known as Chir Pine Activated Carbon (CPAC), as an eco-friendly and cost-effective adsorbent for efficient industrial dye removal, with a focus on environmental sustainability. By applying different additive treatments, four adsorbents (C1, C2, C3, and C4) were formulated. CPAC was synthesized through pyrolysis and characterized using various analytical techniques including FE-SEM, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC). The adsorption capacity of CPAC was evaluated using Malachite Green (MG) dye as a model contaminant. FE-SEM images revealed high porosity (~ 10 µm) and a high surface area (119.886 m2/g) as confirmed by BET testing. CPAC effectively removed MG dye within 30 min at a solution pH of 7. Langmuir and Freundlich isotherm models indicated both monolayer and multilayer adsorption, while kinetic models suggested chemisorption. The regeneration efficiency was assessed using 0.1 N HCl over five consecutive cycles, with C4 demonstrating a high regeneration tendency of 85% and only a 9% reduction in adsorption ability after the fifth cycle. The developed CPAC shows excellent potential for use in the textile, paper, and leather industries for industrial dye adsorption, contributing to the protection of aquatic ecosystems. Additionally, CPAC can be utilized in other water and air purification applications.

Efficient eco-friendly synthesis of carbon nanotubes over graphite nanosheets from yellow corn: a one-step green approach.

The present work reports the synthesis of multi-wall carbon nanotubes (MWCNTs) over graphite nanosheets by an easy and simple approach without using any external catalyst. Simply, yellow corn seeds were thermally annealed in a hydrogen atmosphere at 1050 °C for 3 h without any pretreatments. Notably, the growth of MWCNTs was observed to preferentially occur on the outer surface of the corn shell. This uncomplicated approach not only emphasizes the feasibility of synthesizing carbon nanomaterials using agricultural by-products but also underscores the potential applications of these synthesized materials in various fields. Samples were examined through a comprehensive analysis employing various techniques, including scanning electron microscopy (SEM), Raman spectroscopy, FTIR, X-ray diffraction (XRD), and high-resolution transmission electron microscopy (HRTEM). The findings unveiled the formation of rolled graphene accompanied by the presence of vertical multi-wall carbon nanotubes (MWCNTs) positioned over stacked graphene sheets. This detailed characterization provides insights into the structural features and arrangement of the synthesized materials, paving the way for a deeper understanding of their potential applications. The pyrolysis temperature is a crucial factor in the morphological characteristics of the synthesized carbon nanostructures. While graphene cage-like structures were obtained at 800 °C, small carbon nanotubes were grafted to larger ones and formed three-dimensional hierarchical morphologies when the annealing temperature increased to 900 °C. The growth mechanism of the carbon nanotubes was explained based on the jet self-extrusion of the generated gases through the inherent pores of the corn seeds. The current technique employed in manufacturing MWCNTs shows significant promise as a green synthesis method for producing catalyst-free MWCNTs suitable for industrial applications including sensors and energy storage materials.

Selective recovery of pyrolyzates of biodegradable (PLA, PHBH) and common plastics (HDPE, PP, PS) during co-pyrolysis under slow heating.

Pyrolytic synergistic interactions, in which the production of pyrolyzates is enhanced or inhibited, commonly occur during the co-pyrolysis of different polymeric materials, such as plastics and biomass. Although these interactions can increase the yield of desired pyrolysis products under controlled degradation conditions, the desired compounds must be separated from complex pyrolyzates and further purified. To balance these dual effects, this study was aimed at examining pyrolytic synergistic interactions during slow heating co-pyrolysis of biodegradable plastics including polylactic acid (PLA) and poly(3-hydroxybutyrate-co-3-hydroxyhexaoate) (PHBH) and petroleum-based plastics including high-density polyethylene (HDPE), polypropylene (PP), and polystyrene (PS). Comprehensive investigations based on thermogravimetric analysis, pyrolysis-gas chromatography/mass spectrometry, and evolved gas analysis-mass spectrometry revealed that PLA and PHBH decompose at lower temperatures (273-378 °C) than HDPE, PP, and PS (386-499 °C), with each polymer undergoing independent decomposition without any pyrolytic interactions. Thus, the independent pyrolysis of biodegradable plastics, such as PLA and PHBH, with common plastics, such as HDPE, PP, and PS, can theoretically be realized through temperature control, enabling the selective recovery of their pyrolyzates in different temperature ranges. Thus, pyrolytic approaches can facilitate the treatment of mixed biodegradable and common plastics.

Characteristics of nutrients and heavy metals release from sewage sludge biochar produced by industrial-scale pyrolysis in the aquatic environment and its potential as a slow-release fertilizer and adsorbent.

To assess the application potential of sewage sludge biochar produced by industrial-scale pyrolysis (ISB), the release characteristics of nutrients (NH4+, PO43-, K, Ca, Mg and Fe) and heavy metals (Mn, Cu, Zn, Pb, Ni and Cr) were investigated. Their release amounts increased with decreasing initial pH and increasing solid-liquid ratios (RS-L) and temperature. The release types of NH4+, K, Mg, and Mn were diffusion/dissolution, while those of Cu, Zn, Pb, Ni, and Cr were diffusion/resorption. The release types of PO43- and Ca varied with initial pH and RS-L, respectively. The chemical actions played dominant roles in their release, while particle surface diffusion and liquid film diffusion determined the rates of diffusion and resorption phases, respectively. The release of NH4+, PO43-, K, Ca, Mg, Mn and Zn was a non-interfering, spontaneous (except PO43-), endothermic, and elevated randomness process. The release efficiency of NH4+, PO43- and K met the Chinese standard for slow-release fertilizers, while the total risk of ISB was low. The eutrophication and potential ecological risks of ISB were acceptable when the dose was less than 3 g L-1 and the initial pH was no lower than 3. In conclusion, ISB had potential as a slow-release fertilizer and adsorbent.

Carbon nanotubes synthesis over coal ash based catalysts using polypropylene waste via CVD process: Influence of catalyst and reaction temperature.

Coal ash containing significant amount of SiO2 and Al2O3 is utilized as a catalyst substrate for carbon nanotubes (CNTs) synthesis. Three different types of catalysts were made by impregnating coal ash with cobalt, iron, and nickel. These catalysts were used to produce CNTs through pyrolysis of waste polypropylene followed by chemical vapor deposition. The influence of catalyst type and reaction temperature (700, 800 and 900 °C) on CNTs yield and its quality was studied in detail. The produced CNTs were characterized by thermogravimetric analysis (TGA), Raman scattering and electron microscopes (FESEM and HRTEM). The TGA results revealed that the Ni catalyst produced CNTs with highest yield (266 %) compared to those synthesized over and Fe (96 %) and Co (95 %). However, the yield of the CNTs from all three metal impregnated coal ash based catalysts was found to have decreased with increase in reaction temperature. The thermal stability of CNTs obtained over different catalysts followed the order of Fe (570 °C) > Ni (550 °C) > Co (530 °C). Further, the Raman analysis demonstrated that the produced CNTs over different catalysts showed increasing degree of graphitization with the rise in reaction temperature. Additionally, the ID/IG ratios indicated that CNTs produced from Fe catalyst showed highest degree of graphitization followed by Co and Ni. FESEM and HRTEM analysis showed that the coal ash based catalysts produced multiwalled CNTs and the diameter of the CNTs was increasing with the rise in catalysis temperature. Therefore, co-utilization of coal ash and waste plastic for production of high value CNTs can be a sustainable approach to waste management while actively contributing in circular economy.

The fate of post-use biodegradable PBAT-based mulch films buried in agricultural soil.

The fate of black biodegradable mulch film (MF) based on starch and poly(butylene-adipate-co-terephthalate) (PBAT) in agricultural soil is investigated herein. Pristine (BIO-0) and UV-aged film samples (BIO-A192) were buried for 16 months at an experimental field in southern Italy. Visual, physical, chemical, morphological, and mechanical analyses were carried out before and after samples burial. Film residues in the form of macro- and micro-plastics in soil were analyzed at the end of the trial. Progressive deterioration of both pristine and UV-aged samples, with surface loss and alterations in mechanical properties, occurred from 42 days of burial. After 478 days, the apparent surface of BIO-0 and BIO-A192 films decreased by 57 % and 66 %, respectively. Burial determined a rapid depletion of starch from the polymeric blend, especially for the BIO-A192, while the degradation of the polyester phase was slower. Upon burial, an enrichment of aromatic moieties of PBAT in the film residues was observed, as well as microplastics release to soil. The analysis of the MF degradation products extracted from soil (0.006-0.008 % by mass in the soil samples) revealed the predominant presence of adipate moieties. After 478 days of burial, about 23 % and 17 % of the initial amount of BIO-0 and BIO-A192, respectively, were extracted from the soil. This comprehensive study underscores the complexity of biodegradation phenomena that involve the new generation of mulch films in the field. The different biodegradability of the polymeric components, the climate, and soil conditions that did not strictly meet the parameters required for the standard test method devised for MFs, have significantly influenced their degradation rate. This finding further emphasizes the importance of implementing field experiments to accurately assess the real effects of biodegradable MFs on soil health and overall agroecosystem sustainability.

Mechanistic Implications of the Varying Susceptibility of PAHs to Pyro-Catalytic Treatment as a Function of Their Ionization Potential and Hydrophobicity.

Transition metal catalysts in soil constituents (e.g., clays) can significantly decrease the pyrolytic treatment temperature and energy requirements for efficient removal of polycyclic aromatic hydrocarbons (PAHs) and, thus, lead to more sustainable remediation of contaminated soils. However, the catalytic mechanism and its rate-limiting steps are not fully understood. Here, we show that PAHs with lower ionization potential (IP) are more easily removed by pyro-catalytic treatment when deposited onto Fe-enriched bentonite (1.8% wt. ion-exchanged content). We used four PAHs with decreasing IP: naphthalene > pyrene > benz(a)anthracene > benzo(g,h,i)perylene. Density functional theory (DFT) calculations showed that lower IP results in stronger PAH adsorption to Fe(III) sites and easier transfer of π-bond electrons from the aromatic ring to Fe(III) at the onset of pyrolysis. We postulate that the formation of aromatic radicals via this direct electron transfer (DET) mechanism is the initiation step of a cascade of aromatic polymerization reactions that eventually convert PAHs to a non-toxic and fertility-preserving char, as we demonstrated earlier. However, IP is inversely correlated with PAH hydrophobicity (log Kow), which may limit access to the Fe(III) catalytic sites (and thus DET) if it increases PAH sorption to soil OM. Thus, ensuring adequate contact between sorbed PAHs and the catalytic reaction centers represents an engineering challenge to achieve faster remediation with a lower carbon footprint via pyro-catalytic treatment.

Modelling and techno-economic assessment of possible pathways from sewage sludge to green energy in India.

Efficient domestic wastewater management is essential for mitigating the impact of wastewater on human health and the environment. Wastewater management with conventional technologies generates sewage sludge. The present study considered a modelling approach to evaluate various processing pathways to produce energy from the sewage sludge. Anaerobic digestion, gasification, pyrolysis, and hydrothermal liquefaction are analysed in terms of their energy generation potentials with the Aspen Plus software. A techno-economic assessment is performed to assess the economic viability of each pathway. It reveals that gasification appears as the most promising method to produce electricity, with 0.76 kWh/kgdrysludge, followed by anaerobic digestion (0.53 kWh/kgdrysludge), pyrolysis (0.34 kWh/kgdrysludge), and hydrothermal liquefaction (0.13 kWh/kgdrysludge). In contrast, the techno-economic analysis underscores the viability of anaerobic digestion with levelized cost of electricity as 0.02 $/kWh followed by gasification (0.11 $/kWh), pyrolysis (0.14 $/kWh), and hydrothermal liquefaction (2.21 $/kWh). At the same time, if the products or electricity from the processing unit is sold, equivalent results prevail. The present study is a comprehensive assessment of sludge management for researchers and policymakers. The result of the study can also assist policymakers and industry stakeholders in deciding on alternative options for energy recovery and revenue generation from sewage sludge.