Complementary roles for mechanical and solvent-based recycling in low-carbon, circular polypropylene.

Plastic recycling presents a vexing challenge. Mechanical recycling offers substantial greenhouse gas emissions savings relative to virgin plastic production but suffers from degraded aesthetic and mechanical properties. Polypropylene, one of the most widely used and lowest-cost plastics, features methyl pendants along the polymer backbone, rendering it particularly susceptible to declining properties, performance, and aesthetics across a succession of mechanical recycles. Advanced processes, such as solvent-assisted recycling, promise near-virgin quality outputs at a greater energy and emissions footprint. Mechanical and advanced recycling are often presented as competing options, but real-world plastic waste streams are likely to require preprocessing regardless of whether they are routed to an advanced process. This study quantifies the life-cycle greenhouse gas implications of multiple recycling strategies and proposes a system in which mechanical and solvent-assisted recycling can be leveraged together to boost recycling rates and satisfy demand for a wider range of product applications. Polypropylene can be recovered from mixed-plastic bales produced at material recovery facilities and processed through mechanical recycling, with a varying fraction sent for further upgrading via solvent-assisted recycling to produce material approved for food packaging and other higher-quality applications. The resulting mechanically recycled rigid polypropylene reduces life-cycle greenhouse gas emissions by 80% relative to the same quantity of virgin material, while the upgraded higher-quality material achieves GHG savings of 30%.

Mechanochemical upcycling of spent LiCoO2 to new LiNi0.80Co0.15Al0.05O2 battery: An atom economy strategy.

The use of strong acids and low atom efficiency in conventional hydrometallurgical recycling of spent lithium-ion batteries (LIBs) results in significant secondary wastes and CO2 emissions. Herein, we utilize the waste metal current collectors in spent LIBs to promote atom economy and reduce chemicals consumption in a conversion process of spent Li1-xCoO2 (LCO) → new LiNi0.80Co0.15Al0.05O2 (NCA) cathode. Mechanochemical activation is employed to achieve moderate valence reduction of transition metal oxides (Co3+→Co2+,3+) and efficient oxidation of current collector fragments (Al0→Al3+, Cu0→Cu1+,2+), and then due to stored internal energy from ball-milling, the leaching rates of Li, Co, Al, and Cu in the ≤4 mm crushed products uniformly approach 100% with just weak acetic acid. Instead of corrosive precipitation reagents, larger Al fragments (≥4 mm) are used to control the oxidation/reduction potential (ORP) in the aqueous leachate and induce the targeted removal of impurity ions (Cu, Fe). After the upcycling of NCA precursor solution to NCA cathode powders, we demonstrate excellent electrochemical performance of the regenerated NCA cathode and improved environmental impact. Through life cycle assessments, the profit margin of this green upcycling path reaches about 18%, while reducing greenhouse gas emissions by 45%.

Double-interpenetrating nanostructured networks of marine polysaccharides possessing properties comparable to synthetic polymers.

Sustainable circular economy requires materials that possess a property profile comparable to synthetic polymers and, additionally, processing and sourcing of raw materials that have a small environmental footprint. Here, we present a paradigm for processing marine biopolymers into materials that possess both elastic and plastic behavior within a single system involving a double-interpenetrating polymer network comprising the elastic phase of dynamic physical cross-links and stress-dissipating ionically cross-linked domains. As a proof of principle, films possessing more than twofold higher elastic modulus, ultimate tensile strength, and yield stress than those of polylactic acid were realized by blending two water-soluble marine polysaccharides, namely alginic acid (Alg) with physically cross-linkable carboxylated agarose (CA) followed by ionic cross-linking with a divalent cation. Dried CAAlg films showed homogeneous nano-micro-scale domains, with yield stress and size of the domains scaling inversely with calcium concentration. Through surface activation/cross-linking using calcium, CAAlg films could be further processed using wet bonding to yield laminated structures with interfacial failure loads (13.2 ± 0.81 N) similar to the ultimate loads of unlaminated films (10.09 ± 1.47 N). Toward the engineering of wood-marine biopolymer composites, an array of lines of CAAlg were printed on wood veneers (panels), dried, and then bonded following activation with calcium to yield fully bonded wood two-ply laminate. The system presented herein provides a blueprint for the adoption of marine algae-derived polysaccharides in the development of sustainable high-performance materials.

Deamination of Polyols from the Glycolysis of Polyurethane.

Methylenedianiline (MDA) is a secondary, undesired, product of the glycolysis process of polyurethane (PU) scraps due to hydrolysis and pyrolysis side reactions. As an aromatic and carcinogen amine, MDA poses different problems in handling, transporting, and labelling recycled polyols derived from glycolysis, hindering the closure of PU recycling loop. Aiming to provide a solution to this issue, in this work different deaminating agents (DAs) were investigated with the purpose of analyzing their reactivity with MDA. A first part of the study was devoted to the analysis of MDA formation as a function of reaction time and catalyst concentration (potassium acetate) during glycolysis. It was observed that the amount of MDA increases almost linearly with the extent of PU depolymerization and catalyst content. Among the DAs analyzed 2-ethylhexyl glycidyl ether (2-EHGE), and acetic anhydride (Ac2 O) showed interesting performance, which allowed MDA content to be diminished below the limit for labelling prescription in 30 minutes. PU rigid foams were, therefore, synthesized from the corresponding recycled products and characterized in terms of thermal and mechanical performance. Ac2 O-deaminated polyols led to structurally unstable foams with poor compressive strength, while 2-EHGE-deaminated products allowed the production of foams with improved mechanical performance and unaltered thermal conductivity.

Immobilizing white-rot fungi laccase: Toward bio-derived supports as a circular economy approach in organochlorine removal.

Despite their high persistence in the environment, organochlorines (OC) are widely used in the pharmaceutical industry, in plastics, and in the manufacture of pesticides, among other applications. These compounds and the byproducts of their decomposition deserve attention and efficient proposals for their treatment. Among sustainable alternatives, the use of ligninolytic enzymes (LEs) from fungi stands out, as these molecules can catalyze the transformation of a wide range of pollutants. Among LEs, laccases (Lac) are known for their efficiency as biocatalysts in the conversion of organic pollutants. Their application in biotechnological processes is possible, but the enzymes are often unstable and difficult to recover after use, driving up costs. Immobilization of enzymes on a matrix (support or solid carrier) allows recovery and stabilization of this catalytic capacity. Agricultural residual biomass is a passive environmental asset. Although underestimated and still treated as an undesirable component, residual biomass can be used as a low-cost adsorbent and as a support for the immobilization of enzymes. In this review, the adsorption capacity and immobilization of fungal Lac on supports made from residual biomass, including compounds such as biochar, for the removal of OC compounds are analyzed and compared with the use of synthetic supports. A qualitative and quantitative comparison of the reported results was made. In this context, the use of peanut shells is highlighted in view of the increasing peanut production worldwide. The linkage of methods with circular economy approaches that can be applied in practice is discussed.

Slags from roasting of antimony ore in the Brioude-Massiac (France) area used as aggregates: An early example of circular economy.

Towards the end of the 19th century and the early 20th century, France was the world's largest producer of antimony, especially due to the rich deposits in the Brioude-Massiac area. Even though all the mining and smelting activities are long gone, there are still some remains of those activities. The most original of those is the use of roasting slags as aggregates in former plant walls or industrial building. They are macroscopically characterised by a black or red colour with a vesicular aspect similar to natural pozzolanas. Common petrography and mineralogy tools have been used to characterise those slags: optical mineralogy, scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS) and X-ray diffraction (XRD). To gain an insight into their mineral complexity, a QEMSCAN map has been produced. The mineralogy is typical of high-temperature slags: cristobalite, quartz, mullite, fayalite-forsterite series and spinel. The antimony content is quite high, up to seven percent, under the form of various antimony oxides and native antimony.

Smart proteins as a new paradigm for meeting dietary protein sufficiency of India: a critical review on the safety and sustainability of different protein sources.

India, a global leader in agriculture, faces sustainability challenges in feeding its population. Although primarily a vegetarian population, the consumption of animal derived proteins has tremendously increased in recent years. Excessive dependency on animal proteins is not environmentally sustainable, necessitating the identification of alternative smart proteins. Smart proteins are environmentally benign and mimic the properties of animal proteins (dairy, egg and meat) and are derived from plant proteins, microbial fermentation, insects and cell culture meat (CCM) processes. This review critically evaluates the technological, safety, and sustainability challenges involved in production of smart proteins and their consumer acceptance from Indian context. Under current circumstances, plant-based proteins are most favorable; however, limited land availability and impending climate change makes them unsustainable in the long run. CCM is unaffordable with high input costs limiting its commercialization in near future. Microbial-derived proteins could be the most sustainable option for future owing to higher productivity and ability to grow on low-cost substrates. A circular economy approach integrating agri-horti waste valorization and C1 substrate synthesis with microbial biomass production offer economic viability. Considering the use of novel additives and processing techniques, evaluation of safety, allergenicity, and bioavailability of smart protein products is necessary before large-scale adoption.

One story as part of the Global Conversation on Sustainability: dye adsorption studies using a novel bio-derived calcite material.

Many of the United Nations' Sustainable Development Goals (SDGs) can be addressed through chemistry. Researchers at Memorial University of Newfoundland, Canada, have been sharing their stories on September 25 for the past two years through the Global Conversation on Sustainability. This article describes the details of one of these stories. As the global population increases, food production including aquaculture is increasing to provide for this. At the same time, this means more waste is produced. Waste from aquaculture is often overlooked as a source of valuable chemicals. By-products from farming blue mussels (Mytilus edulis) is dominated by shells rich in calcite. A 'soft' calcite material prepared from waste mussels, via a combination of heat and acetic acid treatment, was investigated for its adsorptive properties and its possible use in wastewater remediation. The adsorption of two cationic dyes, methylene blue and safranin-O, on this material were evaluated through isothermal and kinetic modelling. The adsorption systems for both methylene blue and safranin-O can best be described using Langmuir isotherms and the respective adsorption capacities were 1.81 and 1.51 mg/g. The adsorption process was dominated by pseudo-second order rate kinetics. Comparisons are made with other mollusc-derived materials reported to date.

Rare Earth Element Adsorption to Clay Minerals: Mechanistic Insights and Implications for Recovery from Secondary Sources.

The energy transition will have significant mineral demands and there is growing interest in recovering critical metals, including rare earth elements (REE), from secondary sources in aqueous and sedimentary environments. However, the role of clays in REE transport and deposition in these settings remains understudied. This work investigated REE adsorption to the clay minerals illite and kaolinite through pH adsorption experiments and extended X-ray absorption fine structure (EXAFS). Clay type, pH, and ionic strength (IS) affected adsorption, with decreased adsorption under acidic pH and elevated IS. Illite had a higher adsorption capacity than kaolinite; however, >95% adsorption was achieved at pH ∼7.5 regardless of IS or clay. These results were used to develop a surface complexation model with the derived binding constants used to predict REE speciation in the presence of competing sorbents. This demonstrated that clays become increasingly important as pH increases, and EXAFS modeling showed that REE can exist as both inner- and outer-sphere complexes. Together, this indicated that clays can be an important control on the transport and enrichment of REE in sedimentary systems. These findings can be applied to identify settings to target for resource extraction or to predict REE transport and fate as a contaminant.

Increasing the Recycling of PVC Flooring Requires Phthalate Removal for Ensuring Consumers' Safety: A Cross-Checked Substance Flow Analysis of Plasticizers for Switzerland.

As our planet grapples with the severe repercussions of plastic pollution, mechanical recycling has been proposed as a potential remedy. However, increasing mechanical recycling may have unintended negative consequences. For example, recycling of PVC flooring containing hazardous plasticizers that were used in the past may lead to continued exposure. Here we propose measures to increase recycling while circumventing adverse health impacts caused by legacy additives. For this, we conduct a dynamic substance flow analysis for Switzerland and the time period from 1950 to 2100, focusing on three plasticizers: di(2-ethylhexyl) phthalate (DEHP), diisononyl phthalate (DiNP), and di(2-ethylhexyl) terephthalate (DEHT). We quantify the uncertainty of results, check their plausibility against measured concentrations in samples representative for the Swiss market, and compare them with modeled substance flows in Germany. Based on the cross-checked model, future average concentrations of DEHP in PVC flooring on the Swiss market are expected to be above the legal limit of 0.1 wt % for several decades if increased recycling rates are implemented without additional measures. Phasing out the potentially concerning DiNP, too, and preventing phthalates from entering recycling would lower their average market concentrations to values below 0.1 wt % and enable increasing recycling rates without compromising product safety. Analogous measures could help achieve this goal across other European countries and product groups.

Toward a Circular Lithium Economy with Electrodialysis: Upcycling Spent Battery Leachates with Selective and Bipolar Ion-Exchange Membranes.

Recycling spent lithium-ion batteries offers a sustainable solution to reduce ecological degradation from mining and mitigate raw material shortages and price volatility. This study investigates using electrodialysis with selective and bipolar ion-exchange membranes to establish a circular economy for lithium-ion batteries. An experimental data set of over 1700 ion concentration measurements across five current densities, two solution compositions, and three pH levels supports the techno-economic analysis. Selective electrodialysis (SED) isolates lithium ions from battery leachates, yielding a 99% Li-pure retentate with 68.8% lithium retention, achieving relative ionic fluxes up to 2.41 for Li+ over transition metal cations and a selectivity of 5.64 over monovalent cations. Bipolar membrane electrodialysis (BMED) converts LiCl into high-purity LiOH and HCl, essential for battery remanufacturing and reducing acid consumption via acid recycling. High current densities reduce ion leakage, achieving lithium leakage as low as 0.03%, though hydronium and hydroxide leakage in BMED remains high at 11-20%. Our analysis projects LiOH production costs between USD 1.1 and 3.6 per kilogram, significantly lower than current prices. Optimal SED and BMED conditions are identified, emphasizing the need to control proton transport in BMED and improve cobalt-lithium separation in SED to enhance cost efficiency.

Rare Earth Element Speciation in Coal and Coal Combustion Byproducts: A XANES and EXAFS Study.

Transitioning to a low-carbon economy, necessary to mitigate the impacts of anthropogenic climate change, will lead to a significant increase in demand for critical minerals such as rare earth elements (REE). Meeting these raw materials requirements will be challenging, so there is increasing interest in new sources of REE including coal combustion byproducts (CCBs). Extraction of REE from CCBs can be advantageous as it involves reusing a waste product, thereby contributing to the circular economy. While a growing body of literature reports on the abundance of REE in CCBs globally, studies examining the key factors which control their recovery, including speciation and mode of occurrence, are lacking. This study employed synchrotron-based X-ray absorption spectroscopy to probe the speciation and local bonding environment of yttrium in coals and their associated CCBs. Linear Combination Fitting identified silicate and phosphate minerals as the dominant REE-bearing phases. Taken together with the results of extended X-ray absorption fine structure (EXAFS) curve fitting, we find there is minimal transformation in the REE host phase during combustion, indicating it is transferred in bulk from the coals to the CCBs. Accordingly, these findings can be incorporated into the development of an efficient, environmentally conscious recovery process.

Data Science Applications in Circular Economy: Trends, Status, and Future.

The circular economy (CE) aims to decouple the growth of the economy from the consumption of finite resources through strategies, such as eliminating waste, circulating materials in use, and regenerating natural systems. Due to the rapid development of data science (DS), promising progress has been made in the transition toward CE in the past decade. DS offers various methods to achieve accurate predictions, accelerate product sustainable design, prolong asset life, optimize the infrastructure needed to circulate materials, and provide evidence-based insights. Despite the exciting scientific advances in this field, there still lacks a comprehensive review on this topic to summarize past achievements, synthesize knowledge gained, and navigate future research directions. In this paper, we try to summarize how DS accelerated the transition to CE. We conducted a critical review of where and how DS has helped the CE transition with a focus on four areas including (1) characterizing socioeconomic metabolism, (2) reducing unnecessary waste generation by enhancing material efficiency and optimizing product design, (3) extending product lifetime through repair, and (4) facilitating waste reuse and recycling. We also introduced the limitations and challenges in the current applications and discussed opportunities to provide a clear roadmap for future research in this field.

Legacy and Emerging Plasticizers and Stabilizers in PVC Floorings and Implications for Recycling.

Hazardous chemicals in building and construction plastics can lead to health risks due to indoor exposure and may contaminate recycled materials. We systematically sampled new polyvinyl chloride floorings on the Swiss market (n = 151). We performed elemental analysis by X-ray fluorescence, targeted and suspect gas chromatography-mass spectrometry analysis of ortho-phthalates and alternative plasticizers, and bioassay tests for cytotoxicity and oxidative stress, and endocrine, mutagenic, and genotoxic activities (for selected samples). Surprisingly, 16% of the samples contained regulated chemicals above 0.1 wt %, mainly lead and bis(2-ethylhexyl) phthalate (DEHP). Their presence is likely related to the use of recycled PVC in new flooring, highlighting that uncontrolled recycling can delay the phase-out of hazardous chemicals. Besides DEHP, 29% of the samples contained other ortho-phthalates (mainly diisononyl and diisodecyl phthalates, DiNP and DiDP) above 0.1 wt %, and 17% of the samples indicated a potential to cause biological effects. Considering some overlap between these groups, they together make up an additional 35% of the samples of potential concern. Moreover, both suspect screening and bioassay results indicate the presence of additional potentially hazardous substances. Overall, our study highlights the urgent need to accelerate the phase-out of hazardous substances, increase the transparency of chemical compositions in plastics to protect human and ecosystem health, and enable the transition to a safe and sustainable circular economy.

Component-Level Residential Building Material Stock Characterization Using Computer Vision Techniques.

Residential building material stock constitutes a significant part of the built environment, providing crucial shelter and habitat services. The hypothesis concerning stock mass and composition has garnered considerable attention over the past decade. While previous research has mainly focused on the spatial analysis of building masses, it often neglected the component-level stock analysis or where heavy labor cost for onsite survey is required. This paper presents a novel approach for efficient component-level residential building stock accounting in the United Kingdom, utilizing drive-by street view images and building footprint data. We assessed four major construction materials: brick, stone, mortar, and glass. Compared to traditional approaches that utilize surveyed material intensity data, the developed method employs automatically extracted physical dimensions of building components incorporating predicted material types to calculate material mass. This not only improves efficiency but also enhances accuracy in managing the heterogeneity of building structures. The results revealed error rates of 5 and 22% for mortar and glass mass estimations and 8 and 7% for brick and stone mass estimations, with known wall types. These findings represent significant advancements in building material stock characterization and suggest that our approach has considerable potential for further research and practical applications. Especially, our method establishes a basis for evaluating the potential of component-level material reuse, serving the objectives of a circular economy.

Recycled Iron Phosphates: A New Phosphorus Fertilizer for Paddy Rice.

The potential of recycled iron phosphates (FePs), e.g., vivianites (Fe3(PO4)2·8H2O) and Fe(III)-rich phosphorus (P) adsorbent materials, as phosphorus fertilizer is limited by the strong interaction between Fe and P. In this study, the efficiency of FePs as P fertilizer was explored by applying them as granules or powder in flooded strongly P-fixing soils (acid and calcareous), thereby taking advantage of increased P release induced by reductive dissolution of P-bearing Fe(III) minerals. First, no P diffusion from granular FeP fertilizers into flooded soils was detectable by the diffusive gradient in thin films (DGT) technique and microfocused X-ray fluorescence (µ-XRF) analysis of thin soil sections, in contrast to detectable P diffusion away from granules of soluble triple superphosphate (TSP) fertilizer. On the contrary, powdered FePs demonstrated an excellent increase in extractable P (1 mM CaCl2) in a 120-day incubation experiment in flooded soils. Second, a pot experiment was performed with rice (Oryza sativa) grown in flooded acid and calcareous soils. The fertilizer value of FePs was remarkable when dosed as powder, as it was even up to 3-fold higher than TSP in the acid soil and similar to TSP in the calcareous soil. The beneficial effect of FeP over TSP in the acid soil is attributed to the slow release of P from FePs, which allows to partly overcome P fixation. The promising results of FePs as P fertilizer applied as powders in flooded soils debunk the generally accepted idea that FePs are poor sources of P while demonstrating the importance of the timing of FeP fertilizer application.

Synthesis and Characterization of ß-Myrcene-Styrene and ß-Ocimene-Styrene Copolymers.

The structure-properties relationships of sustainable materials derived from biomass-based monomers are investigated, focusing on hybrid styrene/terpene-based copolymers with blocky microstructures, such as ß-myrcene- and ß-ocimene-styrene copolymers. The samples show complex glass transition dynamics, as evidenced by the physical aging experienced by the amorphous phase in styrene-rich copolymers. The tendency of styrene- and terpene-rich sequences to give heterogeneous morphologies with correlation strength extending over 10-40 nm is outlined, through small-angle X-ray scattering analysis. A new class of terpene-based hybrid systems, holding promise for applications in surface coating technologies, is identified.

Towards a unified carbon accounting landscape.

The overarching purpose of carbon accounting is to reduce carbon emissions to meet net-zero targets and minimize the impact of climate change. However, the plethora of methods and approaches used means that products and systems sometimes cannot easily be compared. The mix of regional and life cycle-based systems can mean that we lack global oversight of our emissions and impact. In some situations where a regional approach is used, industry/business/regions are incentivized to reduce their own/territorial emissions, which can mean that an optimal global solution is not adopted. Countries where grid emissions are higher can be selected for production because it reduces regional (not global) carbon levels. Furthermore, these can be areas where the climate impact may be felt the most: not the just transition we aspire to. Our work provides an analysis of the current system together with its challenges and limitations, paving the way towards a more unified framework to create climate justice together with transparent and comparable accounting methodology for industry and regions alike. This article is part of the discussion meeting issue 'Green carbon for the chemical industry of the future'.

Contributions of heterogeneous catalysis enabling resource efficiency and circular economy.

Our industry today is predominantly based on linear value chains. Raw materials are extracted from primary sources, processed into products, used, and disposed of at the end of their life cycle. This linear economy causes a wide range of negative environmental impacts owing to the resulting greenhouse gas emissions and pollution of marine and terrestrial ecosystems. Closed carbon cycles and climate-neutral energy production are essential for the production not only of fuels but also of all chemicals, including plastics and fertilizers, to counteract climate change and further damage to the environment. In this regard, this article discusses the importance of heterogeneous catalysts for selected technologies associated with this transformation of the resource base and energy supply. It discusses the technological framework conditions of a net CO2-neutral industry, with a focus on electrocatalytic water-splitting for hydrogen production, as well as the catalytic challenges of production of chemicals for the whole value chain using biomass, CO2 and plastic waste as raw materials. This article is part of the discussion meeting issue 'Green carbon for the chemical industry of the future'.

Green carbon and the chemical industry of the future.

The pressing need to mitigate climate change and drastically reduce environmental pollution and loss of biodiversity has precipitated a so-called energy transition aimed at the decarbonization of energy and defossilization of the chemical industry. The goal is a carbon-neutral (net-zero) society driven by sustainable energy and a circular bio-based economy relying on renewable biomass as the raw material. It will involve the use of green carbon, defined as carbon derived from terrestrial or aquatic biomass or organic waste, including carbon dioxide and methane emissions. It will also necessitate the accompanying use of green hydrogen that is generated by electrolysis of water using a sustainable source of energy, e.g. solar, wind or nuclear. Ninety per cent of the industrial chemicals produced in oil refineries are industrial monomers that constitute the precursors of a large variety of polymers, many of which are plastics. Primary examples of the latter are polyolefins such as polyethylene, polypropylene, polyvinyl chloride and polystyrene. Polyolefins are extremely difficult to recycle back to the olefin monomers and discarded polyolefin plastics generally end up as the plastic waste that is responsible for the degradation of our natural habitat. By contrast, waste biomass, such as the lignocellulose contained in forestry residues and agricultural waste, constitutes a renewable feedstock for the sustainable production of industrial monomers and the corresponding polymers. The latter could be the same polyolefins that are currently produced in oil refineries but a more attractive long-term alternative is to produce polyesters and polyamides that can be recycled back to the original monomers: a paradigm shift to a truly bio-based circular economy on the road to a net-zero chemical industry. This article is part of the discussion meeting issue 'Green carbon for the chemical industry of the future'.