This work investigated the effects of 3-aminopropyl triethoxy silane (APTES) hydrolysis time on the physicochemical properties of the resulting starch/epoxidized soybean oil (ESO) bioplastics comprehensively. FTIR analysis confirmed that APTES hydrolyzed for 4 h had the best modification effect on starch. The results of XRD and TGA demonstrated the successful silylation of starch by APTES despite hydrolysis time. Silylation treatment reduced the thermal stability of starch slightly, but enhanced the thermal stability of the resultant bioplastics, revealing better interaction between silylated starch and ESO. The interfacial adhesion of starch and ESO in the bioplastics was obviously enhanced when APTES was hydrolyzed for 2-24 h. The bioplastics with APTES hydrolyzed for 2-4 h showed more desirable tensile properties as the silane hydrolysis was complete and self-condensation of hydrolyzed silanes was avoided. The bioplastics containing silylated starch still showed superior opacity and biodegradability.
The occurrence of microplastics (MPs) in saltwater bodies is relatively well studied, but nothing is known about their presence in most of the commercial salts that are widely consumed by humans across the globe. Here, we extracted MP-like particles larger than 149 μm from 17 salt brands originating from 8 different countries followed by the identification of their polymer composition using micro-Raman spectroscopy. Microplastics were absent in one brand while others contained between 1 to 10 MPs/Kg of salt. Out of the 72 extracted particles, 41.6% were plastic polymers, 23.6% were pigments, 5.50% were amorphous carbon, and 29.1% remained unidentified. The particle size (mean ± SD) was 515 ± 171 μm. The most common plastic polymers were polypropylene (40.0%) and polyethylene (33.3%). Fragments were the primary form of MPs (63.8%) followed by filaments (25.6%) and films (10.6%). According to our results, the low level of anthropogenic particles intake from the salts (maximum 37 particles per individual per annum) warrants negligible health impacts. However, to better understand the health risks associated with salt consumption, further development in extraction protocols are needed to isolate anthropogenic particles smaller than 149 μm.
This study investigates the potential of utilizing green chemically treated spent coffee grounds (SCGs) as micro biofiller reinforcement in Poly-3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV) biopolymer composites. The aim is to assess the impact of varying SCG concentrations (1 %, 3 %, 5 %, and 7 %) on the functional, thermal, mechanical properties and biodegradability of the resulting composites with a PHBV matrix. The samples were produced through melt compounding using a twin-screw extruder and compression molding. The findings indicate successful dispersion and distribution of SCGs microfiller into PHBV. Chemical treatment of SCG microfiller enhanced the interfacial bonding between the SCG and PHBV, evidenced by higher water contact angles of the biopolymer composites. Field Emission Scanning Electron Microscopy (FE-SEM) confirmed the successful interaction of treated SCG microfiller, contributing to enhanced mechanical characteristics. A two-way ANOVA was conducted for statistical analysis. Mass losses observed after burying the materials in natural soil indicated that the composites degraded faster than the pure PHBV polymer suggesting that both composites are biodegradable, particularly at high levels of spent coffee grounds (SCG). Despite the possibility of agglomeration at higher concentrations, SCG incorporation resulted in improved functional properties, positioning the green biopolymer composite as a promising material for sustainable packaging and diverse applications.
Fast co-pyrolysis offers a sustainable solution for upcycling polymer waste, including scrap tyre and plastics. Previous studies primarily focused on slow heating rates, neglecting synergistic mechanisms and sulphur transformation in co-pyrolysis with tyre. This research explored fast co-pyrolysis of scrap tyre with polypropylene (PP), low-density polyethylene (LDPE), and polystyrene (PS) to understand synergistic effects and sulphur transformation mechanisms. A pronounced synergy was observed between scrap tyre and plastics, with the nature of the synergy being plastic-type dependent. Remarkably, blending 75 wt% PS or LDPE with tyre effectively eliminated sulphur-bearing compounds in the liquid product. This reduction in sulphur content can substantially mitigate the release of hazardous materials into the environment, emphasizing the environmental significance of co-pyrolysis. The synergy between PP or LDPE and tyre amplified the production of lighter hydrocarbons, while PS's interaction led to the creation of monocyclic aromatics. These findings offer insights into the intricate chemistry of scrap tyre and plastic interactions and highlight the potential of co-pyrolysis in waste management. By converting potential pollutants into valuable products, this method can significantly reduce the release of hazardous materials into the environment.
In recent years, the environmental pollution of microplastics (MPs) has increasingly drawn our attention. MPs are small fragments of plastics that are commonly dispersed in the environment. The accumulation of environmental MPs is due to population growth and urbanization, while natural disasters such as hurricanes, flooding and human activity may influence their distribution. The leaching of chemicals from MPs raises a significant safety problem and environmental approaches aimed at reducing the use and recycling of plastics, with the replacement by bioplastics and wastewater treatment developments are called for. This summary also helps in demonstrating the connection between terrestrial and freshwater MPs and wastewater treatment plants as the major contributors to environmental MPs by discharges of sludge and effluent. More research on the classification, detection, characterization and toxicity of MPs are essential to enable greater options and solutions. Control initiatives need to intensify the comprehensive study of MP waste control and management information programmes in the fields of institutional engagement, technological research and development, legislation and regulation. A comprehensive quantitative analysis approach for MPs should be created in the future, and more reliable traceability analysis methods should be built to examine further its environmental activity and existence, where this should be done to improve scientific research on MP pollution in terrestrial, freshwater and marine environments and hence, develop more scientific and rational control policies.
Hydrothermal processing (HTP) is an efficient thermochemical technology to achieve sound treatment and resource recovery of sewage sludge (SS) in hot-compressed subcritical water. However, microplastics (MPs) and heavy metals can be problematic impurities for high-quality nutrients recovery from SS. This study initiated hydrothermal degradation of representative MPs (i.e., polyethylene (PE), polyamide (PA), polypropylene (PP)) under varied temperatures (180-300 °C) to understand the effect of four ubiquitous metal ions (i.e., Fe3+, Al3+, Cu2+, Zn2+) on MPs degradation. It was found that weight loss of all MPs in metallic reaction media was almost four times of that in water media, indicating the catalytic role of metal ions in HTP. Especially, PA degradation at 300 °C was promoted by Fe3+ and Al3+ with remarkable weight loss higher than 95% and 92%, respectively, which was ca. 160 °C lower than that in pyrolysis. Nevertheless, PE and PP were more recalcitrant polymers to be degraded under identical condition. Although higher temperature thermal hydrolysis reaction induced severe chain scission of polymers to reinforce degradation of MPs, Fe3+ and Al3+ ions demonstrated the most remarkable catalytic depolymerization of MPs via enhanced free radical dissociation rather than hydrolysis. Pyrolysis gas chromatography-mass spectrometry (Py GC-MS) was further complementarily applied with GC-MS to reveal HTP of MPs to secondary MPs and nanoplastics. This fundamental study highlights the crucial role of ubiquitous metal ions in MPs degradation in hot-compressed water. HTP could be an energy-efficient technology for effective treatment of MPs in SS with abundant Fe3+ and Al3+, which will benefit sustainable recovery of cleaner nutrients in hydrochar and value-added chemicals or monomers from MPs.
Recycling is one of the most efficient methods for environmental friendly waste management. Among municipal wastes, plastics are the most common material that can be easily recycled and polyethylene terephthalate (PET) is one of its major types. PET material is used in consumer goods packaging such as drinking bottles, toiletry containers, food packaging and many more. Usually, a recycling process is tailored to a specific material for optimal purification and decontamination to obtain high grade recyclable material. The quantity and quality of the sorting process are limited by the capacity of human workers that suffer from fatigue and boredom. Several automated sorting systems have been proposed in the literature that include using chemical, proximity and vision sensors. The main advantages of vision based sensors are its environmentally friendly approach, non-intrusive detection and capability of high throughput. However, the existing methods rely heavily on deterministic approaches that make them less accurate as the variations in PET plastic waste appearance are too high. We proposed a probabilistic approach of modeling the PET material by analyzing the reflection region and its surrounding. Three parameters are modeled by Gaussian and exponential distributions: color, size and distance of the reflection region. The final classification is made through a supervised training method of likelihood ratio test. The main novelty of the proposed method is the probabilistic approach in integrating various PET material signatures that are contaminated by stains under constant lighting changes. The system is evaluated by using four performance metrics: precision, recall, accuracy and error. Our system performed the best in all evaluation metrics compared to the benchmark methods. The system can be further improved by fusing all neighborhood information in decision making and by implementing the system in a graphics processing unit for faster processing speed.
Waste plastics contain a substantial number of valuable chemicals. The wastes from post-consumer as well as from industrial production can be recycled to valuable chemical feedstock, which can be used in refineries and/or petrochemical industries. This chemical recycling process is an ideal approach in recycling the waste for a better environment. Polymer cracking using a laboratory fluidized bed reactor concentrated on the used highly contaminated catalyst, E-Cat 2. Even though E-Cat 2 had low activity due to fewer acid sites, the products yielded were similar with amorphous ASA and were far better than thermal cracking. The high levels of heavy metals, namely nickel and vanadium, deposited during their lifetime as an FCC catalyst, did not greatly affect on the catalyst activity. It was also shown that E-Cat 2 could be used with and without regeneration. Although there was more deactivation when there was no regeneration step, the yield of gases (C(2)-C(7)) remained fairly constant. For the first time, these results indicate that "waste" FCC catalyst (E-Cat) is a good candidate for future feedstock recycling of polymer waste. The major benefits of using E-Cat are a low market price, the ability to tolerate reuse and regeneration capacity.
Biodegradable materials made from cassava starch and kenaf fibers were prepared using a solution casting method. Kenaf fibers were treated with NaOH, bleached with sodium chlorite and acetic buffer solution, and subsequently acid hydrolyzed to obtain cellulose nanocrystals (CNCs). Biocomposites in the form of films were prepared by mixing starch and glycerol/sorbitol with various filler compositions (0-10 wt%). X-ray diffraction revealed that fiber crystallinity increased after each stage of treatment. Morphological observations and size reductions of the extracted cellulose and CNCs were studied using field emission scanning electron microscopy and transmission electron microscopy. The effects of different treatments and filler contents of the biocomposites were evaluated through mechanical tests. Results showed that the tensile strengths and moduli of the biocomposites increased after each treatment and the optimum filler content was 6%.
In recent years, increasing environmental concerns focused greater attention on the development of biodegradable materials. A thermoplastic starch derived from bioresources, sugar palm tree was successfully developed in the presence of biodegradable glycerol as a plasticizer. Sugar palm starch (SPS) was added with 15-40 w/w% of glycerol to prepare workable bioplastics and coded as SPS/G15, SPS/G20, SPS/G30 and SPS/G40. The samples were characterized for thermal properties, mechanical properties and moisture absorption on exposure to humidity were evaluated. Morphological studies through scanning electron microscopy (SEM) were used to explain the observed mechanical properties. Generally, the addition of glycerol decrease the transition temperature of plasticized SPS. The mechanical properties of plasticized SPS increase with the increasing of glycerol but up to 30 w/w%. Meanwhile, the water absorption of plasticized SPS decrease with increasing of glycerol.
The aim of this paper is to investigate the characteristics of thermoplastic sugar palm starch/agar (TPSA) blend containing Eucheuma cottonii seaweed waste as biofiller. The composites were prepared by melt-mixing and hot pressing at 140°C for 10min. The TPSA/seaweed composites were characterized for their mechanical, thermal and biodegradation properties. Incorporation of seaweed from 0 to 40wt.% has significantly improved the tensile, flexural, and impact properties of the TPSA/seaweed composites. Scanning electron micrograph of the tensile fracture showed homogeneous surface with formation of cleavage plane. It is also evident from TGA results that thermal stability of the composites were enhanced with addition of seaweed. After soil burial for 2 and 4 weeks, the biodegradation of the composites was enhanced with addition of seaweed. Overall, the incorporation of seaweed into TPSA enhances the properties of TPSA for short-life product application such as tray, plate, etc.
Momordica charantia bioactive polysaccharide (MCBP) was used as an alternative source for the production of bio-based plastics (BPs) with choline chloride/glycerol-based deep eutectic solvent (DES) as a plasticizer. In this study, MCBP was initially extracted using 0.1 M citric acid at temperature 80 °C for 2 h, precipitated using ethanol, and then lyophilized. Subsequently, seven BPs were prepared: MCBP without plasticizer (MCBP), with 1% (w/w) of glycerol (MCBP-G), or with 1% (w/w) of DES at different choline chloride/glycerol molar ratios (i.e. 1.5:1, 1:1, 1:1.5, 1:2, and 1:3). The properties of these BPs were then investigated. Results showed that the tensile strains, stresses and moduli were in the range of 1.3-13.3%, 4.8-19.1 MPa and 132-2487 MPa, respectively. The melting temperatures were found in the range of 92.6-111.4 °C whereas the moisture absorptions and water vapour transmission rates (WVTR) of BPs were 1.4-6.5% and 3.6-5.4 mg/m2·s, respectively. The results also showed that these BPs exhibited bioactivities, such as microbial inhibitory activity (19.5-32.3 mm), free radical scavenging activity (10.3-18.3%) and ferric reducing antioxidant power (FRAP, 16.1-20.0 mM). In addition, it was observed that using DES as a plasticizer had improved the properties of BP, such as tensile strain (354.7-937.5%), melting temperature (4.6-20.3%), radical scavenging activity (0.6-88.6%), FRAP (0.9-18.7%) and antimicrobial activity (12.3-33.6%) compared to MCBP, due to the fact DES has caused different degrees of plasticization via hydrogen bonds and ionic bonds with the polymer chains, and induced a lower pH condition. Therefore, it was suggested that these BPs with DES could contribute to food preservation properties.
A comparative field study was conducted to evaluate the ability of subterranean termites to damage a set of four different plastic materials (cable sheathings) exposed below- and above-ground. Eight pest species from six countries were included, viz., Coptotermes formosanus (Shiraki) in China, Japan, and the United States; Coptotermes gestroi (Wasmann) in Thailand and Malaysia; Coptotermes curvignathus (Holmgren) and Coptotermes kalshoveni (Kemner) in Malaysia; Coptotermes acinaciformis (Froggatt) with two forms of the species complex and Mastotermes darwiniensis (Froggatt) in Australia; and Reticulitermes flavipes (Kollar) in the United States. Termite species were separated into four tiers relative to decreasing ability to damage plastics. The first tier, most damaging, included C. acinaciformis, mound-building form, and M. darwiniensis, both from tropical Australia. The second tier included C. acinaciformis, tree-nesting form, from temperate Australia and C. kalshoveni from Southeast Asia. The third tier included C. curcignathus and C. gestroi from Southeast Asia and C. formosanus from China, Japan, and the United States, whereas the fourth tier included only R. flavipes, which caused no damage. A consequence of these results is that plastics considered resistant to termite damage in some locations will not be so in others because of differences in the termite fauna, for example, resistant plastics from the United States and Japan will require further testing in Southeast Asia and Australia. However, plastics considered resistant in Australia will be resistant in all other locations.
The contamination of aquatic environments with microplastics (MPs) has spurred an unprecedented interest among scientific communities to investigate their impacts on biota. Despite the rapid growth in the number of studies on the aquatic toxicology of MPs, controversy over the fate and biological impacts of MPs is increasingly growing mainly due to the absence of standardized laboratory bioassays. Given the complex features of MPs, such as the diversity of constituent polymers, additives, shapes and sizes, as well as continuous changes in the particle buoyancy as a result of fouling and defouling processes, it is necessary to modify conventional bioassay protocols before employing them for MP toxicity testings. Moreover, several considerations including quantification of chemicals on/in the MP particles, choice of test organisms, approaches for renewing the test solution, aggregation prevention, stock solution preparation, and units used to report MP concentration in the test solution should be taken into account. This critical review suggests some important strategies to help conduct environmentally-relevant MP bioassays.
Plastic or microplastic pollution is a global threat affecting ecosystems, with the current generation reaching as much as 400 metric tons per/year. Soil ecosystems comprising agricultural lands act as microplastics sinks, though the impact could be unexpectedly more far-reaching. This is troubling as most plastic forms, such as polyethylene terephthalate (PET), formed from polymerized terephthalic acid (TPA) and ethylene glycol (EG) monomers, are non-biodegradable environmental pollutants. The current approach to use mechanical, thermal, and chemical-based treatments to reduce PET waste remains cost-prohibitive and could potentially produce toxic secondary pollutants. Thus, better remediation methods must be developed to deal with plastic pollutants in marine and terrestrial environments. Enzymatic treatments could be a plausible avenue to overcome plastic pollutants, given the near-ambient conditions under which enzymes function without the need for chemicals. The discovery of several PET hydrolases, along with further modification of the enzymes, has considerably aided efforts to improve their ability to degrade the ester bond of PET. Hence, this review emphasizes PET-degrading microbial hydrolases and their contribution to alleviating environmental microplastics. Information on the molecular and degradation mechanisms of PET is also highlighted in this review, which might be useful in the future rational engineering of PET-hydrolyzing enzymes.
This study aimed to address the pressing issue of plastic pollution in aquatic ecosystems by assessing the prevalence and distribution of microplastics (MPs) in water and riverbank sediments of the Pekalongan River, a vital water source in Indonesia. From the present findings, MP concentrations in water ranged from 45.2 to 99.1 particles/L, while sediment concentrations ranged from 0.77 to 1.01 particles/g. This study revealed that fragment and film MPs constituted 30.1 % and 25.4 % of the total, respectively, with MPs measuring <1 mm and constituting 51.4 % of the total. Colored MPs, particularly blue and black MPs, accounted for 34 % of the total. The primary polymer components, as determined via Fourier transform infrared spectroscopy, were identified as polystyrene, polyester, and polyamide. In response to the escalating plastic waste crisis caused by single-use plastics, Pekalongan's local government implemented refuse segregation and recycling programs as part of its efforts to transition toward zero-waste practices.
Polymer electrolytes were developed by solution casting technique utilizing the materials of cellulose acetate (CA), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and deep eutectic solvent (DES). The DES is synthesized from the mixture of choline chloride and urea of 1:2 ratios. The increasing DES content well plasticizes the CA:LiTFSI:DES matrix and gradually improves the ionic conductivity and chemical integrity. The highest conducting sample was identified for the composition of CA:LiTFSI:DES (28 wt.%:12 wt.%:60 wt.%), which has the greatest ability to retain the room temperature ionic conductivity over the entire 30 days of storage time. The changes in FTIR cage peaks upon varying the DES content in CA:LiTFSI:DES prove the complexation. This complexation results in the collapse of CA matrix crystallinity, observed from the reduced intensity of XRD diffraction peaks. The DES-plasticized sample is found to be more heat-stable compared to pure CA. Nevertheless, the addition of DES diminishes the CA:LiTFSI matrix's heat-resistivity but at the minimum addition the thermal stability is enhanced.
In this work, poly(lactic acid) (PLA) a fully biodegradable thermoplastic polymer matrix was melt blended with three different epoxidized palm oil (EPO). The aim of this research was to enhance the flexibility, mechanical and thermal properties of PLA. The blends were prepared at various EPO contents of 1, 2, 3, 4 and 5 wt% and characterized. The SEM analysis evidenced successful modification on the neat PLA brittle morphology. Tensile tests indicate that the addition of 1 wt% EPO is sufficient to improve the strength and flexibility compared to neat PLA. Additionally, the flexural and impact properties were also enhanced. Further, DSC analysis showed that the addition of EPO results in a decrease in T(g), which implies an increase in the PLA chain mobility. In the presence of 1 wt% EPO, TGA results revealed significant increase in the thermal stability by 27%. Among the three EPOs used, EPO(3) showed the best mechanical and thermal properties compared to the other EPO's, with an optimum loading of 1 wt%. Conclusively, EPO showed a promising outcome to overcome the brittleness and improve the overall properties of neat PLA, thus can be considered as a potential plasticizer.
Plastic debris is widespread and ubiquitous in the marine environment and ingestion of plastic debris by marine organisms is well-documented. Viscera and gills of 110 individual marine fish from 11 commercial fish species collected from the marine fish market were examined for presence of plastic debris. Isolated particles were characterized by Raman spectroscopy, and elemental analysis was assessed using energy-dispersive X-ray spectroscopy (EDX). Nine (of 11) species contained plastic debris. Out of 56 isolated particles, 76.8% were plastic polymers, 5.4% were pigments, and 17.8% were unidentified. Extracted plastic particle sizes ranged from 200 to 34,900 μm (mean = 2600 μm ±7.0 SD). Hazardous material was undetected using inorganic elemental analysis of extracted plastic debris and pigment particles. The highest number of ingested microplastics was measured in Eleutheronema tridactylum and Clarias gariepinus, suggesting their potential as indicator species to monitor and study trends of ingested marine litter.
The present study was aimed to evaluate the suitability of agro-wastes and crude vegetable oils for the cost-effective production of poly-β-hydroxybutyrate (PHB), to evaluate growth kinetics and PHB production in Alcaligenes faecalis RZS4 and Pseudomonas sp. RZS1 with these carbon substrates and to study the biodegradation of PHB accumulated by these cultures. Alcaligenes faecalis RZS4 and Pseudomonas sp. RZS1 accumulates higher amounts of PHB corn (79.90% of dry cell mass) and rice straw (66.22% of dry cell mass) medium respectively. The kinetic model suggests that the Pseudomonas sp. RZS1 follows the Monod model more closely than A. faecalis RZS4. Both the cultures degrade their PHB extract under the influence of PHB depolymerase. Corn waste and rice straw appear as the best and cost-effective substrates for the sustainable production of PHB from Alcaligenes faecalis RZS4 and Pseudomonas sp. RZS1. The biopolymer accumulated by these organisms is biodegradable in nature. The agro-wastes and crude vegetable oils are good and low-cost sources of nutrients for the growth and production of PHB and other metabolites. Their use would lower the production cost of PHB and the low-cost production will reduce the sailing price of PHB-based products. This would promote the large-scale commercialization and popularization of PHB as an ecofriendly bioplastic/biopolymer.