Chemically Recyclable and Biodegradable Vulcanized Rubber.

The cross-linked nature of vulcanized rubbers as used in tire and many other applications prohibits an effective closed-loop mechanical or chemical recycling. Moreover, vulcanization significantly retards the material's biodegradation. Here, we report a recyclable and biodegradable rubber that is generated by the vulcanization of amorphous, unsaturated polyesters. The elastic material can be broken down via solvolysis into the underlying monomers. After removal of the vulcanized repeat units, the saturated monomers, constituting the major share of the material, can be recovered in overall recycling rates exceeding 90%. Respirometric biodegradation experiments by 13CO2 tracking under environmental conditions via the polyesters' diol monomer indicated depolymerization and partial mineralization of the vulcanized polyester rubbers.

Polymers from Plant Oils Linked by Siloxane Bonds for Programmed Depolymerization.

The increased production of plastics is leading to the accumulation of plastic waste and depletion of limited fossil fuel resources. In this context, we report a strategy to create polymers that can undergo controlled depolymerization by linking renewable feedstocks with siloxane bonds. α,ω-Diesters and α,ω-diols containing siloxane bonds were synthesized from an alkenoic ester derived from castor oil and then polymerized with varied monomers, including related biobased monomers. In addition, cyclic monomers derived from this alkenoic ester and hydrosiloxanes were prepared and cyclized to form a 26-membered macrolactone containing a siloxane unit. Sequential ring-opening polymerization of this macrolactone and lactide afforded an ABA triblock copolymer. This set of polymers containing siloxanes underwent programmed depolymerization into monomers in protic solvents or with hexamethyldisiloxane and an acid catalyst. Monomers afforded by the depolymerization of polyesters containing siloxane linkages were repolymerized to demonstrate circularity in select polymers. Evaluation of the environmental stability of these polymers toward enzymatic degradation showed that they undergo enzymatic hydrolysis by a fungal cutinase from Fusarium solani. Evaluation of soil microbial metabolism of monomers selectively labeled with 13C revealed differential metabolism of the main chain and side chain organic groups by soil microbes.

Synthesis and Deconstruction of Polyethylene-type Materials.

Polyethylene deconstruction to reusable smaller molecules is hindered by the chemical inertness of its hydrocarbon chains. Pyrolysis and related approaches commonly require high temperatures, are energy-intensive, and yield mixtures of multiple classes of compounds. Selective cleavage reactions under mild conditions (

Degradable and Recyclable Polyesters from Multiple Chain Length Bio- and Waste-Sourceable Monomers.

Monomers sourced from waste or biomass are often mixtures of different chain lengths; e.g. catalytic oxidation of polyethylene waste yields mixtures of dicarboxylic acids (DCAs). Yet, polyesters synthesized from such monomer mixtures have rarely been studied. We report polyesters based on multiple linear aliphatic DCAs, present in chain length distributions that vary in their centers and ranges. We demonstrate that these materials can adopt high-density polyethylene-like solid state structures, and are ductile (e.g. Et 610 MPa), allowing for injection molding, or film and fiber extrusion. Melting and crystallization points of the polyesters show no odd-even effects as dipoles cannot favorably align in the crystal, similar to traditional odd carbon numbered, long-chain DCA polyesters. Biodegradation studies of 13 C-labelled polyesters in soil reveal rapid mineralization, and depolymerization by methanolysis indicates suitability for closed-loop recycling.

Diffusion-Ordered Spectroscopy for Rapid and Facile Determination of Consumer Plastic Molecular Weight.

Molecular weight (MW) is a key control of plastic polymer properties and their fate in the environment. However, the primary tool used to determine plastic MW, gel permeation chromatography (GPC), has major limitations, such as low precision and accuracy, requirements for dedicated instrumentation, production of high volumes of hazardous waste, and large sample sizes. In this study, we describe, validate, and apply a diffusion-ordered spectroscopy (DOSY) method for polymer MW determinations, with a focus on applications for consumer plastics. Several experimental conditions were systematically optimized and tested to validate the DOSY method, including the selection of pulse sequences, the effect of sample concentration, cross-validation with multiple sets of external standards, and long-term instrumental stability. Validation was performed for a wide range of polymers, solvents, and temperatures, highlighting its potential for broad applicability. A preliminary screening of polystyrene and polyethylene terephthalate consumer products revealed widely varying MWs (up to two-fold) for products made of the same polymer type. A preliminary experiment was also conducted to track the decrease in polystyrene MW via photochemical chain scission reactions, finding a 20% reduction in MW after less than 1 week of irradiation. Collectively, our results demonstrate the potential for DOSY to provide high-throughput, accurate, and precise measures of polymer MW, as well as the evolution of polymer MW during environmental weathering processes, such as photochemical degradation. We conclude with a discussion of (i) the many advantages of DOSY compared to GPC, (ii) future developments to enhance the depth of information obtained from DOSY, and (iii) approaches to broaden the accessibility of this promising analytical method to the research community.

Synergy between Sunlight, Titanium Dioxide, and Microbes Enhances Cellulose Diacetate Degradation in the Ocean.

Sunlight chemically transforms marine plastics into a suite of products, with formulation─the specific mixture of polymers and additives─driving rates and products. However, the effect of light-driven transformations on subsequent microbial lability is poorly understood. Here, we examined the interplay between photochemical and biological degradation of fabrics made from cellulose diacetate (CDA), a biobased polymer used commonly in consumer products. We also examined the influence of ∼1% titanium dioxide (TiO2), a common pigment and photocatalyst. We sequentially exposed CDA to simulated sunlight and native marine microbes to understand how photodegradation influences metabolic rates and pathways. Nuclear magnetic resonance spectroscopy revealed that sunlight initiated chain scission reactions, reducing CDA's average molecular weight. Natural abundance carbon isotope measurements demonstrated that chain scission ultimately yields CO2, a newly identified abiotic loss term of CDA in the environment. Measurements of fabric mass loss and enzymatic activities in seawater implied that photodegradation enhanced biodegradation by performing steps typically facilitated by cellulase. TiO2 accelerated CDA photodegradation, expediting biodegradation. Collectively, these findings (i) underline the importance of formulation in plastic's environmental fate and (ii) suggest that overlooking synergy between photochemical and biological degradation may lead to overestimates of marine plastic persistence.

Biodegradation of poly(butylene succinate) in soil laboratory incubations assessed by stable carbon isotope labelling.

Using biodegradable instead of conventional plastics in agricultural applications promises to help overcome plastic pollution of agricultural soils. However, analytical limitations impede our understanding of plastic biodegradation in soils. Utilizing stable carbon isotope (13C-)labelled poly(butylene succinate) (PBS), a synthetic polyester, we herein present an analytical approach to continuously quantify PBS mineralization to 13CO2 during soil incubations and, thereafter, to determine non-mineralized PBS-derived 13C remaining in the soil. We demonstrate extensive PBS mineralization (65 % of added 13C) and a closed mass balance on PBS-13C over 425 days of incubation. Extraction of residual PBS from soils combined with kinetic modeling of the biodegradation data and results from monomer (i.e., butanediol and succinate) mineralization experiments suggest that PBS hydrolytic breakdown controlled the overall PBS biodegradation rate. Beyond PBS biodegradation in soil, the presented methodology is broadly applicable to investigate biodegradation of other biodegradable polymers in various receiving environments.

Product Formulation Controls the Impact of Biofouling on Consumer Plastic Photochemical Fate in the Ocean.

The photodegradation rates of floating marine plastics govern their environmental lifetimes, but the controls on this process remain poorly understood. Photodegradation of these materials has so far been studied under ideal conditions in the absence of environmental factors such as biofouling, which may slow photochemical transformation rates through light screening. To investigate this interaction, we incubated different plastics in continuous flow seawater mesocosms to follow (i) the extent of biofilm growth on the samples and (ii) decreases in light transmittance through the samples over time. We used consumer products with high relevance (e.g., shopping bags, water bottles, and packaging materials) and with different formulations, referring to primary polymers (polyethylene (PE) and polyethylene terephthalate (PET)) and inorganic additives (titanium dioxide (TiO2)). The behavior of consumer-relevant formulations was compared to those of pure PE and PET films, revealing that the relative effects of UV- and, to a lesser extent, visible-light screening differ based on the formulation of the product. Pure PE showed greater relative UV-transmittance decreases (Δ = -34% through the entire sample, accounting for biofilm on both sides of the plastic film) than PET (Δ = -20%) and PE products with TiO2 (Δ = < -10%). Our results demonstrate that even with biofouling, photodegradation remains a highly relevant process for the fate of marine plastics. However, we expect photodegradation rates of plastics in the ocean to be slower than those measured in laboratory studies, due to light screening by biofilms, and the specific formulation of plastic products is a key determinant of the extent of this effect.

Quantification of Synthetic Polyesters from Biodegradable Mulch Films in Soils.

Soil biodegradable mulch films composed of the polyester polybutylene adipate-co-terephthalate (PBAT) are being increasingly used in agriculture. Analytical methods to quantify PBAT in field soils are needed to assess its soil occurrence and fate. Here, we report an analytical method for PBAT in soils that couples Soxhlet extraction or accelerated solvent extraction (ASE) with quantitative protonnuclear magnetic resonance (q-1H NMR) spectroscopy detection. The 1H NMR peak areas of aromatic PBAT protons increased linearly with PBAT concentrations dissolved in deuterated chloroform (CDCl3), demonstrating accurate quantitation of PBAT by q-1H NMR. Spike-recovery experiments involving PBAT addition to model sorbents and soils showed increased PBAT extraction efficiencies into chloroform (CHCl3) with methanol (MeOH) as cosolvent, consistent with MeOH competitively displacing PBAT from H-bond donating sites on mineral surfaces. Systematic variations in solvent composition and temperatures in ASE revealed quantitative PBAT extraction from soil with 90/10 volume % CHCl3/MeOH at 110-120 °C. Both Soxhlet extraction and ASE resulted in the complete recovery of PBAT added to a total of seven agricultural soils covering a range of physicochemical properties, independent of whether PBAT was added to soils dissolved in CHCl3, as film, or as particles. Recovery was also complete for PBAT added to soil in the form of a commercial soil biodegradable mulch film with coextractable polylactic acid (PLA). The presented analytical method enables accurate quantification and biodegradation monitoring of PBAT in agricultural field soils.

Oxidation of Reduced Peat Particulate Organic Matter by Dissolved Oxygen: Quantification of Apparent Rate Constants in the Field.

Peat particulate organic matter (POM) is an important terminal electron acceptor for anaerobic respiration in northern peatlands provided that the electron-accepting capacity of POM is periodically restored by oxidation with O2 during peat oxygenation events. We employed push-pull tests with dissolved O2 as reactant to determine pseudo-first-order rate constants of O2 consumption ( kobs) in anoxic peat soil of an unperturbed Swedish ombrotrophic bog. Dissolved O2 was rapidly consumed in anoxic peat with a mean kobs of 2.91 ± 0.60 h-1, corresponding to an O2 half-life of ∼14 min. POM dominated O2 consumption, as evidenced from approximately 50-fold smaller kobs in POM-free control tests. Inhibiting microbial activity with formaldehyde did not appreciably slow O2 consumption, supporting abiotic O2 reduction by POM moieties, not aerobic respiration, as the primary route of O2 consumption. Peat preoxygenation with dissolved O2 lowered kobs in subsequent oxygen consumption tests, consistent with depletion of reduced moieties in POM. Finally, repeated oxygen consumption tests demonstrated that anoxic peat POM has a high reduction capacity, in excess to 20 µmol electrons donated per gram POM. This work demonstrates rapid abiotic oxidation of reduced POM by O2, supporting that short-term oxygenation events can restore the capacity of POM to accept electrons from anaerobic respiration in temporarily anoxic parts of peatlands.