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At least 19 records

Mobility of soil-biodegradable nanoplastics in unsaturated porous media affected by protein-corona

Soil-biodegradable plastic has been increasingly used as mulches in agriculture, which provides not only agronomical benefits but also in situ disposal and biodegradation options. However, soil-biodegradable plastic mulches inevitably fragment into micro- and nanoplastics during biodegradation, which can reside in soils or migrate into deep soils, where they may not degrade readily due to reduced microbial activity. To date, little is known about the transport of soil-biodegradable micro- and nanoplastics in soils. Here, in this study, we studied the transport of soil-biodegradable nanoplastics (∼200 nm) made of polybutylene adipate co-terephthalate (PBAT) in unsaturated sand (proxy for soil). Specifically, we studied the mobility of pristine and weathered PBAT nanoplastics in the absence and presence of proteins (positively charged lysozyme and negatively charged bovine serum albumin, pH = 7.7). We found that (1) both pristine and the weathered PBAT nanoplastics were mobile; (2) positively charged lysozyme formed protein-coronas around PBAT nanoplastics and inhibited the transport; and (3) decreased water saturation promoted the retention of PBAT nanoplastics via physical straining. These results suggest that soil-biodegradable nanoplastics fragmented from soil-biodegradable plastic mulches are mobile and may readily migrate into deep soil layers, but positively charged proteins and unsaturated flow would prevent such transport via formation of protein-corona and physical straining.

Yu, Yingxue

Toward a Circular Bioeconomy: Designing Microbes and Polymers for Biodegradation

Polymer production is rapidly increasing, but there are no large-scale technologies available to effectively mitigate the massive accumulation of these recalcitrant materials. One potential solution is the development of a carbon-neutral polymer life cycle, where microorganisms convert plant biomass to chemicals, which are used to synthesize biodegradable materials that ultimately contribute to the growth of new plants. Realizing a circular carbon life cycle requires the integration of knowledge across microbiology, bioengineering, materials science, and organic chemistry, which itself has hindered large-scale industrial advances. This review addresses the biodegradation status of common synthetic polymers, identifying novel microbes and enzymes capable of metabolizing these recalcitrant materials and engineering approaches to enhance their biodegradation pathways. Design considerations for the next generation of biodegradable polymers are also reviewed, and finally, opportunities to apply findings from lignocellulosic biodegradation to the design and biodegradation of similarly recalcitrant synthetic polymers are discussed.

59 BASIC BIOLOGICAL SCIENCES

Multiscale Modeling and Experimental Insights into High-Temperature Soil Biodegradation Dynamics of Semi-Crystalline Poly(Lactic Acid) Nonwoven Fabrics

This study investigates the biodegradation of semi-crystalline poly(lactic acid) (PLA) nonwovens (NWs) in soil at 58 °C using both experimental and mathematical modeling approaches. The model utilizes a system of parabolic diffusion-reaction partial differential equations (PDEs) to elucidate chemical transformations over time and in space. It accounts for phenomena such as the diffusion of water and lactic acid monomers through the polymer matrix and into the surrounding soil, along with their microbial breakdown. It also accounts for the initial PLA crystallinity and predicts its evolution in time. The model is solved numerically for a single filament, and the results were used to shed light on PLA NW transformations observed in soil over a 180-day incubation period. Various characterization techniques, including scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and Raman spectroscopy, were employed to assess morphological changes, crystallinity, and molecular changes in the NWs throughout the experiment. By comparing the experimental data with the model predictions, the hydrolysis rate coefficient was found to be 3.37 × 10 -7 s -1 , while the rate of microbial degradation of lactic acid monomers was faster, of the order of 9.63 × 10 -7 s -1 . The findings highlight the significant role of crystallinity in the biodegradation process. The PLA degradation ceases when no amorphous material remains, and the crystallinity reaches 0.8, as observed in the experiments by day 120. Furthermore, this research contributes to a deeper understanding of PLA biodegradation dynamics and offers insights for effectively managing biodegradable materials in environmental settings.

Diffusion−reaction modeling

Marine Toxicity, Biodegradability, and Rolling-Sliding Tribological Performance of Ionic Liquid-Enhanced Environmentally-Acceptable Lubricants for Tidal Turbomachinery

Environmentally acceptable lubricants (EALs) are increasingly being recognized in many fields including waterpower, hydraulics, water transport, agricultural machinery, offshore wind turbines, etc. Specifically, high-performance EALs are demanded for tidal turbomachinery to ensure high efficiency and reliability and avoid the significant risk of direct contamination of the marine ecosystem upon leaks. Here we report a new development of ionic liquid (IL)-enhanced EALs for tidal energy. One short-chain phosphonium phosphate and one short-chain ammonium phosphate ILs were used as the candidate additives and the IL-containing EALs demonstrated significantly improved lubricating performance, much lower toxicity, and increased biodegradability compared with commercial baselines. Specifically, in a rolling-sliding test simulating the operation of a model tidal turbine gearbox bearing, an EAL containing the ILs at a 0.5 wt % concentration demonstrated 40% lower friction, 45% less wear loss, substantially reduced rolling contact fatigue-induced surface damage, and one order of magnitude lower vibration noise compared with a commercial gear oil. In an EPA standard toxicity test, 90 and 70% survival of marine biota was observed when exposed to an EAL containing 5 wt % of the short-chain phosphonium phosphate and ammonium phosphate ILs, respectively, while the selected commercial gear oil and bioderived additive killed all marine biota. In a standard biodegradability test, 2 wt % addition of the phosphonium phosphate IL not only retained the EAL’s ready biodegradability but further boosted the oil decomposition from a range of 60–80% to a higher level of 80–95%. Conversely, adding the commercial bioderived additive downgraded the EAL from readily to inherently biodegradable. Furthermore, this work offers scientific insights for development of ILs as potential EAL additives for marine energy and broader applications.

additives

Tailoring High Hardness and Rigidity in Biodegradable Thermoplastic Polyurethanes

In response to escalating environmental concerns, there is a pressing demand for materials capable of delivering both sustainability and robust mechanical properties, thereby substituting nonrenewable counterparts in various applications. This study presents a comprehensive investigation into the synthesis and characterization of biobased aliphatic thermoplastic polyurethanes (TPUs) that exhibit impressive mechanical properties, including tensile strength in the range of 48–41 MPa and flexural modulus up to 2.2 GPa. These biodegradable TPUs displayed high shore A and D hardness between 95 and 98 and 51–42, respectively, and thus can be categorized as “extra hard” plastics according to the durometer scale for PUs. Herein, we have prepared a series of four 100% biobased polyester polyols from biobased diacid and chain-extender as precursors with molecular weights varying from 500 to 1400 g/mol. The corresponding TPUs that were prepared by using an aliphatic diisocyanate were evaluated for their thermal stability, microphase separation, mechanical properties, and biodegradation. By leveraging renewable feedstocks, these TPUs offer a sustainable alternative to petroleum-derived materials, with their mechanical performance meeting conventional benchmarks. Furthermore, postcomposting analysis revealed significant surface degradation, affirming their biodegradability and environmental compatibility.

36 MATERIALS SCIENCE

Stereomicrostructure-regulated biodegradable adhesives

Commercial adhesives are petroleum-based thermoset networks or nonbiodegradable thermoplastic hot melts, making them ideal targets for replacement by biodegradable alternatives. Poly(3-hydroxybutyrate) (P3HB) is a biorenewable and biodegradable alternative to conventional plastics, but microbial P3HB, which has a stereoperfect stereomicrostructure, exhibits no adhesion. Here, in this study, by elucidating the fundamental relationship between chemocatalytically engineered P3HB stereomicrostructures and adhesion properties, we found that biodegradable syndio-rich P3HB exhibits high adhesion strength and outperforms common commercial adhesives, whereas syndiotactic, isotactic, or iso-rich P3HB shows no measurable adhesion. The syndio-rich stereomicrostructure brings about desired thermomechanical and viscoelastic properties of P3HB that enable strong adhesion to a range of substrates tested, including aluminum, steel, glass, and wood, and its performance is insensitive to molar mass and reprocessing or reuse.

36 MATERIALS SCIENCE

Eroding Permafrost Coastlines Release Biodegradable Dissolved Organic Carbon to the Arctic Ocean

Coastal erosion mobilizes large quantities of organic matter (OM) to the Arctic Ocean where it may fuel greenhouse gas emissions and marine production. While the biodegradability of permafrost-derived dissolved organic carbon (DOC) has been extensively studied in inland soils and freshwaters, few studies have examined dissolved OM (DOM) leached from eroding coastal permafrost in seawater. To address this knowledge gap, we sampled three horizons from bluff exposures near Drew Point, Alaska: seasonally thawed active layer soils, permafrost containing Holocene terrestrial and/or lacustrine OM, and permafrost containing late-Pleistocene marine-derived OM. Samples were leached in seawater to compare DOC yields, DOM composition (chromophoric DOM, Fourier transform ion cyclotron resonance mass spectrometry), and biodegradable DOC (BDOC). Holocene terrestrial permafrost leached the most DOC compared to active layer soils and Pleistocene marine permafrost. However, DOC from Pleistocene marine permafrost was the most biodegradable (33 ± 6% over 90 days), followed by DOC from active layer soils (23 ± 5%) and Holocene terrestrial permafrost (14 ± 3%). Permafrost leachates contained relatively more aliphatic and peptide-like formulae, whereas active layer leachates contained relatively more aromatic formulae. BDOC was positively correlated with nitrogen-containing and aliphatic formulae, and negatively correlated with polyphenolic and condensed aromatic formulae. Using estimates of eroding OM, we scale our results to estimate DOC and BDOC inputs to the Alaska Beaufort Sea. While DOC inputs from coastal erosion are relatively small compared to rivers, our results suggest that erosion may be an important source of BDOC to the Beaufort Sea when river inputs are low.

Bristol, Emily M.

Polylactic acid (PLA)-based multifunctional and biodegradable nanocomposites and their applications

Polylactic acid (PLA)-based nanocomposites are emerging as multifunctional, biodegradable materials, offering sustainable alternatives to petroleum-based plastics. This review examines recent advancements in PLA nanocomposites, focusing on enhanced mechanical strength, thermal stability, and biodegradability achieved through nanofillers like metallic particles, carbon-based materials, and ceramics. Techniques such as in situ polymerization, melt mixing, and electrospinning enable application-specific improvements. PLA's limitations, including brittleness and low barrier properties, are addressed to support diverse applications: in packaging (e.g., extended shelf life), biomedicine (e.g., degradable implants), and electronics (e.g., flexible devices). Despite challenges with filler dispersion and thermal resistance, continued innovations expand PLA's potential across multiple industries, contributing to a sustainable, circular economy.

Biodegradable polymers

Soil Sensors in Agriculture: From Unsustainable to Biodegradable

Commercially available bi-metallic temperature sensors have long exploited differential thermal expansions between materials to produce an actuation-induced readout from a bi-metal helix. When dispersed in agricultural land, electronic components are used to transmit information at the cost of an increased environmental footprint. This paper briefly recaps the proposed sensor, which employs a biodegradable bi-material helix composed of a polymer and metal. Proposed polymer sheetings of cellulose acetate and polylactic acid are characterized via TGA, DMA, and DSC to evaluate plasticizer content, shrinkage, and an appropriate sensor work-use range. Finally, the deflection of non-biodegradable bi-polymer strips is quantified for various combinations to determine if bi-polymer deflection is possible.

47 OTHER INSTRUMENTATION

Biodegradable Biocomposite Development for Large Scale Additive Manufacturing

Oak Ridge National Laboratory (ORNL) worked with Mitsubishi Chemical America, Inc. to develop a highly biodegradable ~100% biobased feedstock for large format additive manufacturing (AM). Together, they developed an AM feedstock based on the biobased polyester, polybutylene succinate (PBS), that is typically used in agriculture and packaging projects. The motivation for this work was to leverage the high degradability of this polymer in AM to create a new avenue for end-of-life disposal of the product. A composite feedstock was developed from PBS, polylactic acid (PLA), and wood flour (WF). While WF improves printability, reduces feedstock cost, and can improve stiffness, it also often results in a loss in tensile strength which can inhibit/limit applications of the material. To recover the loss in tensile strength suffered by including large quantities, up to 30 wt.% WF in the composite, a chain extender was used to compatibilize the different composite constituents with each other. The feedstock was used to 3D-print a demonstration mold for precast concrete catch basins and was tested by casting 750 lbs of concrete. The mold survived the demonstration. Aerobic degradation testing of the composite feedstock showed that it was highly degradable, 40% biodegradation after 90 days, compared to other incumbent biobased feedstocks.

100% biobased feedstock for large format additive

Biodegradable Biocomposite Development for Large Scale Additive Manufacturing

Oak Ridge National Laboratory (ORNL) worked with Mitsubishi Chemical America, Inc. to develop a highly biodegradable ~100% biobased feedstock for large format additive manufacturing (AM). Together, they developed a AM feedstock based on the biobased polyester, polybutylene succinate (PBS), that is typically used in agriculture and packaging projects. The motivation for this work was to leverage the high degradability of this polymer in AM to create a new avenue for end-of-life disposal of the product. A composite feedstock was developed from PBS, polylactic acid (PLA), and wood flour (WF). While WF improves printability, reduces feedstock cost, and can improve stiffness, it also often results in a loss in tensile strength which can inhibit/limit application of the material. To recover the loss in tensile strength suffered by including large quantities, up to 30 wt%, WF in the composite a chain extender was used to compatibilze the different composite constituents with each other. The feedstock was used to 3D-print demonstration mold for precast concrete catch basins and was tested by casting 750 lbs of concrete. The mold survived the demonstration. Aerobic degradation testing of the composite feedstock showed that it was highly degradable, 40% biodegradation after 90 days, compared to other incumbent biobased feedstocks.

36 MATERIALS SCIENCE

Production of high-performance biodegradable polyurethane products made from algae precursors

We successfully developed and scaled the production of high-performance, fully biodegradable thermoplastic polyurethanes (TPUs) derived from algae-based precursors. By employing innovative flow chemistry and chemo-enzymatic methodologies, the research team produced materials with up to 100% bio-based content that match or exceed the mechanical properties of traditional petroleum-based plastics. These algae-derived TPUs were proven to be fully home-compostable, achieving over 90% decomposition within 110 to 120 days while demonstrating practical advantages such as reduced solvent requirements in fabric coating applications.

36 MATERIALS SCIENCE

Upcycling of Waste Plastics into Carboxylic Acids for Biodegradable Surfactants

This work outlines a process for producing high‐purity (>95%) carboxylate surfactants from post‐consumer recycled high‐density polyethylene (PCR‐HDPE). The approach involves the thermal depolymerization of PCR‐HDPE via pyrolysis, followed by fractional distillation to isolate C9–C14 olefins. These olefins undergo hydroformylation using cobalt carbonyl catalysts to generate aldehydes, which are subsequently oxidized to carboxylic acids using Pinnick oxidation under mild aqueous‐phase conditions. Neutralization of the resulting carboxylic acids with sodium hydroxide produces plastic‐derived carboxylate surfactants (PDCs) in the form of sodium carboxylates. Subsequent purification steps ensure surfactant‐grade purity and enable accurate assessment of physicochemical properties. The resulting PDCs are evaluated for critical micelle concentration (CMC), foamability, surface tension reduction, and calcium ion tolerance, demonstrating competitive behavior with conventional anionic carboxylate surfactants. This route provides a sustainable alternative for surfactant production, reducing reliance on fossil‐derived feedstocks and valorizing plastic waste streams through chemical upcycling.

Biodegradable surfactants

Elucidating biodegradation of dimethyl terephthalate by two Rhodococcus strains for its valorization applications

Dimethyl terephthalate (DMT) serves as the precursor in the production of polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate. The widespread use of DMT in the polymer industry and its ubiquitous existence in end products raise alarms about its potential harm to humans and animals. DMT can enter the environment through the degradation of polymers and their end products, and cause endocrine disruption, oxidative stress, and an elevated risk of cancer. In recent years, DMT has also gained renewed interest in its potential for plastic recycling and upcycling. In this study, we identified two strains of Rhodococcus that possess DMT-degrading capabilities and utilized transcriptomic analysis and gene knockout to elucidate the mechanisms of DMT degradation. R. opacus PD630 and R. jostii RPET were found to convert up to 1 g/L DMT into mono-methyl terephthalate (MMT). A putative DMTase (RS34275) was identified for this conversion. R. jostii RPET also demonstrates the ability to convert DMT into MMT and to utilize MMT for its cellular growth via the terephthalate pathway. A putative MMTase (RS21885) as the sole enzyme was identified for the conversion of MMT into terephthalate in the RPET strain. In addition, we successfully produced lycopene and lipids from an engineered RPET strain using DMT as a substrate. Our findings will facilitate future DMT bioremediation and bio-upcycling of DMT-associated plastics, enabling the production of value-added products.

Biodegradation