A review on value-addition to plastic waste towards achieving a circular economy.

Plastic and mixed plastic waste (PW) has received increased worldwide attention owing to its huge rate of production, high persistency in the environment, and unsustainable waste management practices. Therefore, sustainable PW management and upcycling approaches are imperative to achieve the objectives of the United Nations Sustainable Development Goals. Numerous recent studies have shown the application and feasibility of various PW conversion techniques to produce materials with better economic value. Within this framework, the current review provides an in-depth analysis of cutting-edge thermochemical technologies such as pyrolysis, gasification, carbonization, and photocatalysis that can be used to value plastic and mixed PW in order to produce energy and industrial chemicals. Additionally, a thorough examination of the environmental impacts of contemporary PW upcycling techniques and their commercial feasibility through life cycle assessment (LCA) and techno-economical assessment are provided in this review. Finally, this review emphasizes the opportunities and challenges accompanying with existing PW upcycling techniques and deliver recommendations for future research works.

In Vitro Evaluation of the Adsorption Efficacy of Biochar Materials on Aflatoxin B1, Ochratoxin A, and Zearalenone.

Mycotoxin sequestration materials are important tools to reduce mycotoxin illness and enable proper handling of mycotoxin-contaminated commodities. Three food-grade bentonite clays and four generally recognized as safe (GRAS) charcoal/biochar carbon materials that are marketed as feed additives and supplements were evaluated for their ability to sequester the mycotoxins aflatoxin B1, ochratoxin A, and zearalenone. The surface area of the clays varied between 32.1 to 51.4 mg2/g, and the surface area of the carbon-based materials varied from 1.7 to 1735 mg2/g. In vitro, gastric fluid studies indicated that certain pine biochar and activated coconut charcoal could sequester high amounts (85+%) of the mycotoxins at 1 ppm levels or below. However, some biochar materials with lower surface area properties lacked binding capacity. The coconut shell charcoal and pine biochar utilize agricultural waste products in a manner that significantly reduces carbon emissions and provides valuable materials to minimize exposure to toxins found in food and feed.

Glycerol Monooleate (GMO): A Valuable Biobased Lubricity and Pour Point Enhancer Blend Component for the ULSD Fuel.

Novel value-added usage of glycerol (biodiesel coproduct) derivatives has been indispensable due to the extensive production of biodiesel. The physical properties of ultralow-sulfur diesel (ULSD) improved with the addition of technical-grade glycerol monooleate (TGGMO) with increasing concentration from 0.01 to 5 wt %. The influence of increasing concentration of TGGMO was studied on the acid value, cloud point, pour point, cold filter plugging point, kinematic viscosity, and lubricity of its blend with ULSD. The results showed improved lubricity for the blended ULSD with TGGMO as shown by the reduced wear scar diameter from 493 to 90 µm. The low-temperature flow properties were also improved as shown by lower pour points of -36 °C for the 1% TGGMO/ULSD blend compared to -25 °C for ULSDTGGMO blends in ULSD of up to 1 wt %, which met the ASTM standard D975 specifications. We also investigated the blending effect of the pure-grade monooleate (PGMO, purity level >99.98%) on the physical properties of ULSD at a blend concentration of 0.5 and 1.0%. Compared to PGMO, TGGMO significantly improved the physical properties of ULSD with increasing concentration from 0.01 to 1 wt %. Nevertheless, PGMO/TGGMO did not significantly affect the acid value, cloud point, or cold filter plugging point of ULSD. A comparison between TGGMO and PGMO showed that TGGMO improves the ULSD fuel lubricity and pour point more effectively than PGMO. PDSC data indicated that although addition of TGGMO will lower the oxidation stability slightly, it is still better than the addition of PGMO. Thermogravimetric analysis (TGA) data showed higher thermal stability and lesser volatility for TGGMO blends compared to those for PGMO blends. The cost effectiveness of TGGMO makes it a better ULSD fuel lubricity enhancer than PGMO.

Interactions of Surfactants with Biomimetic Membranes-2. Generation of Electric Potential with Non-Ionic Surfactants.

It is known that noncharged surfactants lead to electric effects that interact with biomimetic membranes made of nitrocellulose filters, which are impregnated with fatty acid esters. At a surfactant concentration as low as 64 micrometers in one of the solutions, they lead to the transient formation of transmembrane electric potential. Maximum changes of this potential are proportional to the log of noncharged surfactant concentrations when it changes by three orders of magnitude. We explain this new and nontrivial effect in terms of an earlier suggested physicochemical mechanics approach and noncharged surfactants transient changes induced by membrane permeability for inorganic ions. It could be used to imitate the interactions of non-ionic drugs with biological membranes. The effect may also be used in determining the concentration of these surfactants and other non-ionic chemicals of concern, such as pharmaceuticals and personal care products.

Bilayer Films of Poly(lactic acid) and Cottonseed Protein for Packaging Applications.

Poly(lactic acid) (PLA) is a common biobased film-former made from renewable biomass, such as polysaccharides from sugarcane, corn, or cassava. It has good physical properties but is relatively expensive when compared to the plastics used for food packaging. In this work, bilayer films were designed, incorporating a PLA layer and a layer of washed cottonseed meal (CSM), an inexpensive agro-based raw material from cotton manufacturing, where the main component is cottonseed protein. These bilayer films were made through the solvent casting method. The combined thickness of the PLA/CSM bilayer film was between 47 and 83 µm. The thickness of the PLA layer in this film was 10%, 30%, or 50% of the total bilayer film's thickness. Mechanical properties of the films, opacity, water vapor permeation, and thermal properties were evaluated. Since PLA and CSM are both agro-based, sustainable, and biodegradable, the bilayer film may be used as an eco-friendlier food packaging material, which helps reduce the environmental problems of plastic waste and microplastics. Moreover, the utilization of cottonseed meal may add value to this cotton byproduct and provide a potential economic benefit to cotton farmers.

Potential Chemicals from Plastic Wastes.

Plastic is referred to as a "material of every application". From the packaging and automotive industries to the medical apparatus and computer electronics sectors, plastic materials are fulfilling demands efficiently. These plastics usually end up in landfills and incinerators, creating plastic waste pollution. According to the Environmental Protection Agency (EPA), in 2015, 9.1% of the plastic materials generated in the U.S. municipal solid waste stream was recycled, 15.5% was combusted for energy, and 75.4% was sent to landfills. If we can produce high-value chemicals from plastic wastes, a range of various product portfolios can be created. This will help to transform chemical industries, especially the petrochemical and plastic sectors. In turn, we can manage plastic waste pollution, reduce the consumption of virgin petroleum, and protect human health and the environment. This review provides a description of chemicals that can be produced from different plastic wastes and the research challenges involved in plastic waste to chemical production. This review also provides a brief overview of the state-of-the-art processes to help future system designers in the plastic waste to chemicals area.

A Short Review on Polymeric Biomaterials as Additives for Lubricants.

With increasing environmental concerns and the depletion of petroleum resources, the development of lubricant additives from bioresources has attracted much attention recently. In this review, we reported a few polymers and polymer composites that are synthesized from vegetable oils (soybean oil, sunflower oil, rice bran oil, and castor oil) and used as multifunctional additives in the formulation of eco-friendly lubricant compositions. We mentioned the preparation of vegetable oil-based homo- and copolymers and their characterization by different spectral techniques (FTIR/NMR). The average molecular weights of the polymers are determined by gel permeation chromatography (GPC). Performance evaluations of the polymeric materials mainly as a viscosity index improver (VII), pour point depressant (PPD), and most importantly antifriction additives when blended with lubricating base oils are indicated. Standard ASTM methods have been applied to evaluate their performances. The findings have shown that all the additives discussed are non-toxic, biodegradable, and showed excellent performances compared to commercial petroleum-based additives.

Photocatalytic Cleavage of ß-O-4 Ether Bonds in Lignin over Ni/TiO2.

It is of great importance to explore the selective hydrogenolysis of ß-O-4 linkages, which account for 45-60% of all linkages in native lignin, to produce valued-added chemicals and fuels from biomass employing UV light as catalyst. TiO2 exhibited satisfactory catalytic performances in various photochemical reactions, due to its versatile advantages involving high catalytic activity, low cost and non-toxicity. In this work, 20 wt.% Ni/TiO2 and oxidant PCC (Pyridinium chlorochromate) were employed to promote the cleavage of ß-O-4 alcohol to obtain high value chemicals under UV irradiation at room temperature. The Ni/TiO2 photocatalyst can be magnetically recovered and efficiently reused in the following four consecutive recycling tests in the cleavage of ß-O-4 ether bond in lignin. Mechanism studies suggested that the oxidation of ß-O-4 alcohol to ß-O-4 ketone by oxidant PCC first occurred during the reaction, and was followed by the photocatalysis of the obtained ß-O-4 ketone to corresponding acetophenone and phenol derivates. Furthermore, the system was tested on a variety of lignin model substrates containing ß-O-4 linkage for the generation of fragmentation products in good to excellent results.

Effective delignification of lignocellulosic biomass by microwave assisted deep eutectic solvents.

To establish an environmentally friendly and cheaper method to delignify lignocellulosic biomass feedstocks, deep eutectic solvents (DESs) were investigated as a green alternatives to conventional solvents. Six different DESs were facilely prepared and used to delignify miscanthus and birchwood feedstocks, including monocarboxylic acid/choline chloride (ChCl), dicarboxylic acid/ChCl and polyalcohol/ChCl. The enhanced delignification efficiency was evaluated in relation to the nature of the hydrogen bond donors and acid strength of DES. The largest extraction of lignin from the miscanthus and birchwood was achieved using ChCl.formic acid and ChCl.oxalic acid DES, respectively. The TGA and 13C NMR characterization results of the extracted lignin samples indicated that the different types of lignin were produced using different DESs. The reaction optimization results showed an increase in lignin extraction with increasing temperature from 60 to 130 °C. However, the optimal reaction time was different, 30 min for miscanthus and 60 min for birchwood. A convenient and reliable method for the quantification of lignin was developed using UV-Vis spectrophotometry.

Plastic Solid Waste (PSW) in the Context of Life Cycle Assessment (LCA) and Sustainable Management.

Over the past few decades, life cycle assessment (LCA) has been established as a critical tool for the evaluation of the environmental burdens of chemical processes and materials cycles. The increasing amount of plastic solid waste (PSW) in landfills has raised serious concern worldwide for the most effective treatment. Thermochemical post-treatment processes, such as pyrolysis, seem to be the most appropriate method to treat this type of waste in an effective manner. This is because such processes lead to the production of useful chemicals, or hydrocarbon oil of high calorific value (i.e. bio-oil in the case of pyrolysis). LCA appears to be the most appropriate tool for the process design from an environmental context. However, addressed limitations including initial assumptions, functional unit and system boundaries, as well as lack of regional database and exclusion of socio-economic aspects, may hinder the final decision. This review aims to address the benefits of pyrolysis as a method for PSW treatment and raise the limitations and gaps of conducted research via an environmental standpoint.

Pyrolysis biochar has negligible effects on soil greenhouse gas production, microbial communities, plant germination, and initial seedling growth.

Biochar has been promoted as a soil amendment that enhances soil quality and agronomic productivity and reduces greenhouse gas production. However, these benefits are not always realized. A major hurdle to the beneficial use of biochar is our limited knowledge regarding the mechanisms directing its effects on soil systems. This project aimed to eliminate some of this uncertainty by examining the biological responses (plant productivity, greenhouse gas production, soil microbial community structure) of a suite of soils (10) to the addition of biochars produced by different processes (pyrolysis, gasification, burning) from a range of feedstocks (corn stalks, hardwood, grass). Results indicated that these three responses were not significantly impacted by the addition of pyrolysis biochars from different feedstocks at 1 and 5% (w/w) addition levels. On the other hand, both an open-air burned corn stalk (5%) and raw corn stalks (1 and 5%) additions did alter the measured soil functionality. For example, the 5% burnt corn stalks addition reduced total above ground plant biomass (∼30%), increased observed N2O production by an order of magnitude, and altered soil bacterial community structure. The bacterial groups that increased in relative abundance in the burnt corn stalks-amended soils included families associated with cellulose decomposition (Chitinophagaceae), plant pathogens (Xanthomonadaceae), and biochar/charcoal-amended media (Gemmatimonadetes). In contrast, the abundance of these bacterial groups was not impacted by the pyrolysis biochars. Therefore, this research suggests that pyrolysis biochar represents a stabilized form of carbon that is resistant to microbial mineralization and has negligible effects on soil biological responses.

Optimization and mechanism studies on cell disruption and phosphorus recovery from microalgae with magnesium modified hydrochar in assisted hydrothermal system.

Considering the phosphorus (P) reserve state and its value, recovery of P from microalgae has become a popular topic. In this study, an integrated system of a hydrothermal process for microalgae cell disruption to release P and magnesium modified hydrochar adsorption to capture P was set up. Emission scanning electron microscopy with Energy Dispersive X-ray spectroscopy and Three-Dimensional Excitation Emission matrix spectroscopy with parallel factor analysis were applied to evaluate the P release process from microalgae and found the optimal breaking-wall condition (P release 90.5%, hydrothermal digestion mixture of H2O2 and NaOH at 348 K). Parallel factor analysis showed there was a close relationship between P and humic-like substance. Hydrochar loaded with magnesium exhibited a strong affinity for P, with maximum capacity 89.61 mg/g at 318 K. The P adsorption fitted pseudo-second-order kinetic and Langmuir models. X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy were applied to reveal the mechanism of hydrochar modification and adsorption. It showed that Mg is loaded on the surface of hydrochar by electrostatic attraction and electron transfer with the carboxylic acid. P absorption was reached through anion exchange.

α-Amino Acid Rich Photophytonic Nanoparticles of Algal Origin Serendipitously Reveal Antimigratory Property against Cancer.

Spheroidal nanoparticles of algal ("phytonic") origin were synthesized and composed of carbonaceous architectures and surface-rich oxygenated functional groups. Nanoparticles were negatively charged and efficiently luminescent after ultraviolet-range excitation and called as "photophytonic" nanoparticles. A multitude of analytical techniques confirmed the rich profusion of hydroxyl, carboxylate, and amines at the nanoscale, while spectroscopic investigation indicated the presence of α-amines, a signature functionality present in amino acids. Confirmed via a series of biological assays, i.e., growth regression, antimigration, and protein-regression studies, photophytonic nanoparticles serendipitously revealed remarkable anticancer activity against various stages of breast cancer cells, barring the need for an encapsulated drug. We report that nanoparticles derived from algal biomass exhibit intrinsic antimigratory properties against cancer, likely due to the rich abundance of α-amino acids.

Roles of Phosphoric Acid in Biochar Formation: Synchronously Improving Carbon Retention and Sorption Capacity.

Pretreatment of biomass with phosphoric acid (HPO) for biochar production was expected to improve carbon (C) retention, porosity structure, and the sorption ability of biochar. This study investigated the interaction of phosphorus with the C structure to elucidate the mechanisms by which HPO simultaneously captured C and created micropores. Sawdust was soaked in diluted HPO and dried for pyrolytic biochar generation at 350, 500, and 650°C. Results showed that HPO pretreatment resulted in 70 to 80% of biomass C retention in biochar, compared with only about 50% remaining without pretreatment. The specific surface area and total pore volume of the HPO-pretreated biochar were 930 m g and 0.558 cm g, respectively, compared with <51.0 m g and 0.046 cm g in the untreated biochar. The volume of micropores (<10 nm) increased from 59.0% to 78.4-81.9%. The presence of HPO shifted the decomposition temperature to a lower value and decreased the energy required for biomass decomposition. Micropore formation was via the insertion of P-O-P into the C lattice, leading to swelling and amplification of amorphous form and lattice defect of the C structure, as evidenced by Raman spectrum and small-angle X-ray scattering analysis. The crosslinking of P-O-P and C bonds resulted in greater biomass C retention in biochar. This biochar-phosphorus composite had a much higher sorption ability for Pb than the unmodified biochar, which was possibly dominated by phosphate precipitation and surface adsorption. This study provided a simple method to improve biochar properties and explored the multiple benefits of HPO in biomass pyrolysis.

Nanosalina: A Tale of Saline-Loving Algae from the Lake's Agony to Cancer Therapy.

The nanoparticles (NPs) that contain the therapeutic agent within themselves without further modifications can be coined as "self-therapeutic" NPs. The development of these agents especially when derived from natural resources can lead to a paradigm shift in the field of cancer nanotechnology as they can immensely facilitate the complex chemistry procedures and the follow up biological complications. Herein, we demonstrate that inherently therapeutic NPs "integrating" ß-carotene can be synthesized from Dunaliella salina microalgae in a single step without complicated chemistry. The facile synthesis involved microwave irradiation of aqueous suspension of algae which resulted in water dispersible NPs with hydrodynamic diameter of ∼80 nm. Subsequently, extensive physiochemical characterizations were performed to confirm the integrity of the particles. The pro-oxidant activities of the integrated ß-carotene were triggered by photoexcitation under UV lamp (362 nm). It was demonstrated that after UV exposure, the C32 human melanoma cells incubated with NPs experienced extensive cell death as opposed to nonilluminated samples. Further cellular analysis revealed that the significant reactive oxygen species (ROS) and in particular singlet oxygen were responsible for the cells' damage while the mode of cell death was dominated by apoptosis. Moreover, detailed endocytic inhibition studies specified that UV exposure affected NPs' cellular uptake mechanism. These inherently therapeutic NPs can open new avenues for melanoma cancer treatment via ROS generation in vitro.

Multi-Shell Nano-CarboScavengers for Petroleum Spill Remediation.

Increasingly frequent petroleum contamination in water bodies continues to threaten our ecosystem, which lacks efficient and safe remediation tactics both on macro and nanoscales. Current nanomaterial and dispersant remediation methods neglect to investigate their adverse environmental and biological impact, which can lead to a synergistic chemical imbalance. In response to this rising threat, a highly efficient, environmentally friendly and biocompatible nano-dispersant has been developed comprising a multi-shelled nanoparticle termed 'Nano-CarboScavengers' (NCS) with native properties for facile recovery via booms and mesh tools. NCS treated different forms of petroleum oil (raw and distillate form) with considerable efficiency (80% and 91%, respectively) utilizing sequestration and dispersion abilities in tandem with a ~10:1 (oil: NCS; w/w) loading capacity. In extreme contrast with chemical dispersants, the NCS was found to be remarkably benign in in vitro and in vivo assays. Additionally, the carbonaceous nature of NCS broke down by human myeloperoxidase and horseradish peroxidase enzymes, revealing that incidental biological uptake can enzymatically digest the sugar based core.

Effects of hydrothermal liquefaction on the fate of bioactive contaminants in manure and algal feedstocks.

This study investigated the effects of hydrothermal liquefaction (HTL) on the fate of bioactive compounds (BACs) often present with wet biosolids from wastewater, manure, or algae. Tracking radiolabeled (14)C for two BACs showed that 60-79% of the carbon was transferred to the HTL raw oil product, and most of the rest was found in the aqueous product. In the presence of both swine manure and Spirulina biomass feedstocks, HTL provided essentially complete removal of three BACs when operated at 300°C for ≥ 30 min. Experiments with both natural transformation and high-efficiency transformation showed that HTL provided complete deactivation of antibiotic resistant genes for all tested HTL conditions (250-300°C, 15-60 min reaction time). Thus, incorporating HTL into wastewater treatment systems can simultaneously produce valuable bio-crude oil, provide effective removal of BACs and disrupt the natural pathways for antibiotic resistant gene transfer from manure and wastewater biosolids to the environment.

Thermochemical conversion of raw and defatted algal biomass via hydrothermal liquefaction and slow pyrolysis.

Thermochemical conversion is a promising route for recovering energy from algal biomass. Two thermochemical processes, hydrothermal liquefaction (HTL: 300 °C and 10-12 MPa) and slow pyrolysis (heated to 450 °C at a rate of 50 °C/min), were used to produce bio-oils from Scenedesmus (raw and defatted) and Spirulina biomass that were compared against Illinois shale oil. Although both thermochemical conversion routes produced energy dense bio-oil (35-37 MJ/kg) that approached shale oil (41 MJ/kg), bio-oil yields (24-45%) and physico-chemical characteristics were highly influenced by conversion route and feedstock selection. Sharp differences were observed in the mean bio-oil molecular weight (pyrolysis 280-360 Da; HTL 700-1330 Da) and the percentage of low boiling compounds (bp<400 °C) (pyrolysis 62-66%; HTL 45-54%). Analysis of the energy consumption ratio (ECR) also revealed that for wet algal biomass (80% moisture content), HTL is more favorable (ECR 0.44-0.63) than pyrolysis (ECR 0.92-1.24) due to required water volatilization in the latter technique.

Preparation of acetonides from soybean oil, methyl soyate, and fatty esters.

This paper describes the preparation of a new type of branched vegetable oil and its methyl ester that involves the formation of acetonides. A facile and environmentally friendly synthesis has been found to produce acetonides that entails the use of ferric chloride as a catalyst and is conducted at room temperature. The products have been fully characterized with the help of model compounds, including elemental analysis, infrared (IR) spectroscopy, nuclear magnetic resonance (NMR), and gas chromatography-mass spectrometry (GC-MS).

Synthesis of an amine-oleate derivative using an ionic liquid catalyst.

A facile (and environmentally friendly) reaction between epoxidized methyl oleate and aniline to produce an oleate-aniline adduct, without the formation of fatty amide, was discovered. This reaction was carried out neat, with a catalytic amount of an ionic liquid. No solvent was used, no byproducts were produced, and the ionic liquid could be recovered and recycled. The reaction products were fully characterized by NMR and GC-MS.