The effect of additives on the biodegradation of polyhydroxyalkanoate (PHA) in marine field trials.

The persistence of conventional fossil fuel-derived plastics in marine ecosystems has raised significant environmental concerns. Biodegradable plastics are being explored as an alternative. This study investigates the biodegradation behaviour in two marine environments of melt-extruded sheets of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) bioplastic as well as blends of PHBV with a non-toxic plasticiser (triethyl citrate, TEC) and composites of PHBV with wood flour. Samples were submerged for up to 35 weeks in two subtropical marine conditions: on the sandy seabed in the sublittoral benthic zone and the sandy seabed of an open air mesocosm with pumped seawater. Rates of biodegradation, lag times and times to 95 % mass loss (T95) were determined through mass loss data and Gompertz modelling. Mechanisms of biodegradation were studied through changes in molecular weight, mechanical properties and surface features. Results reveal a rapid biodegradation rate for all PHBV samples, demonstrating a range of specific biodegradation rates relative to exposed surface area of 0.03 ± 0.01 to 0.09 ± 0.04 mg.d-1.cm-2. This rapid rate of biodegradation meant that the subtle variations in biodegradation mechanisms across different sample thicknesses and additive compositions had little effect on overall lifetimes, with the T95 for most samples being around 250-350 days, regardless of site, highlighting the robust biodegradability of PHBV in seawater. It was only the PHBV-wood flour composite that showed faster biodegradation, and that was only in the exposed ocean site. The mesocosm site was otherwise shown to be a good model for the open ocean, with very comparable biodegradation rates and changes in mechanical properties over time.

Synthesis and physical properties of polyhydroxyalkanoate (PHA)-based block copolymers: A review.

Polyhydroxyalkanoates (PHAs) are a group of natural polyesters that are synthesised by microorganisms. In general, their thermoplasticity and (in some forms) their elasticity makes them attractive alternatives to petrochemical-derived polymers. However, the high crystallinity of some PHAs - such as poly(3-hydroxybutyrate) (P3HB) - results in brittleness and a narrow processing window for applications such as packaging. The production of copolymeric PHA materials is one approach to improving the mechanical and thermal properties of PHAs. Another solution is the manufacture of PHA-based block copolymers. The incorporation of different polymer and copolymer blocks coupled to PHA, and the resulting tailorable microstructure of these block copolymers, can result in a step-change improvement in PHA-based material properties. A range of production strategies for PHA-based block copolymers has been reported in the literature, including biological production and chemical synthesis. Biological production is typically less controllable, with products of a broad molecular weight and compositional distribution, unless finely controlled using genetically modified organisms. By contrast, chemical synthesis delivers relatively controllable block structures and narrowly defined compositions. This paper reviews current knowledge in the areas of the production and properties of PHA-based block copolymers, and highlights knowledge gaps and future potential areas of research.

Synthesis and Characterisation of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)-b-poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Multi-Block Copolymers Produced Using Diisocyanate Chemistry.

Bacterially derived polyhydroxyalkanoates (PHAs) are attractive alternatives to commodity petroleum-derived plastics. The most common forms of the short chain length (scl-) PHAs, including poly(3-hydroxybutyrate) (P3HB) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), are currently limited in application because they are relatively stiff and brittle. The synthesis of PHA-b-PHA block copolymers could enhance the physical properties of PHAs. Therefore, this work explores the synthesis of PHBV-b-PHBV using relatively high molecular weight hydroxy-functionalised PHBV starting materials, coupled using facile diisocyanate chemistry, delivering industrially relevant high-molecular-weight block copolymeric products. A two-step synthesis approach was compared with a one-step approach, both of which resulted in successful block copolymer production. However, the two-step synthesis was shown to be less effective in building molecular weight. Both synthetic approaches were affected by additional isocyanate reactions resulting in the formation of by-products such as allophanate and likely biuret groups, which delivered partial cross-linking and higher molecular weights in the resulting multi-block products, identified for the first time as likely and significant by-products in such reactions, affecting the product performance.

Effect of Toxic Phthalate-Based Plasticizer on the Biodegradability of Polyhydroxyalkanoate.

While new biodegradable materials are being rapidly introduced to address plastic pollution, their end-of-life impacts remain unclear. Biodegradable plastics typically comprise a biopolymer matrix with functional additives and/or solid fillers, which may be toxic. Here, using an established method for continuous biodegradation monitoring, we investigated the impact of a commonly used plasticizer, dibutyl phthalate (DBP), on the biodegradation of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) in soil. The presence of DBP delayed the initial stage of PHBV biodegradation but then accelerated subsequent rates of biodegradation. Furthermore, it led to significant increases in total bacterial and fungal biomass and altered the composition of microbial communities with significant increases in the relative abundances of Thauera (gammaproteobacterial) and Mucor circinelloides (fungal) populations. It is proposed, with evidence from biodegradation behavior and microbial analysis, that the presence of DBP likely stimulated a microbial community shift, introduced higher proportions of more readily degradable amorphous regions from the plasticizing effect, and facilitated access to the bulk polymer matrix for microorganisms or at least their associated enzymes. These effects in combination overcame the initial inhibition effect of the DBP and resulted in a net increase in the rate of biodegradation of PHBV.

Utilisation of Paunch Waste as a Natural Fibre in Biocomposites.

Paunch is a fibrous solid residue consisting of partially digested feed from the stomachs of processed cattle. It is the largest untapped solid waste stream from animals at meat processing plants, and potentially a valuable source of fibres for the production of sustainable and potentially higher-value natural biocomposite materials. Paunch was obtained from the waste effluent of a red meat processing plant, and the fibre characteristics of the as-obtained material were studied and benchmarked against wood flour and ground buffel grass, with a view to evaluating the potential of paunch as a fibre for polymer composites. The ground paunch possessed a rough fibrous surface and fibre-like characteristics that were comparable to both wood flour and ground buffel grass, demonstrating their potential for use in composites. Without any pre-treatment or compatibilisation, composites of a representative biopolymer, poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and ground paunch were successfully produced for the first time via extrusion, with up to 50 wt% paunch content. Mechanical property analysis showed that, at 30 wt% content, PHBV/ground paunch composites yielded mechanical properties that were comparable to those of composites with ground buffel grass.

Identification and Quantification of Micro-Bioplastics in Environmental Samples by Pyrolysis-Gas Chromatography-Mass Spectrometry.

Bioplastics are materials that are biobased and/or biodegradable, but not necessarily both. Concerns about environmental plastic pollution are constantly growing with increasing demand for substituting fossil-based plastics with those made using renewable resource feedstocks. For many conventional bioplastics to completely decompose/degrade, they require specific environmental conditions that are rarely met in natural ecosystems, leading to rapid formation of micro-bioplastics. As global bioplastic production and consumption/use continue to increase, there is growing concern regarding the potential for environmental pollution from micro-bioplastics. However, the actual extent of their environmental occurrence and potential impacts remains unclear, and there is insufficient mass concentration-based quantitative data due to the lack of quantitative analytical methods. This study developed and validated an analytical method coupling pressurized liquid extraction and pyrolysis-gas chromatography-mass spectrometry combined with thermochemolysis to simultaneously identify and quantify five targeted micro-bioplastics (i.e., polylactic acid (PLA), polyhydroxyalkanoate, polybutylene succinate, polycaprolactone, and polybutylene adipate terephthalate (PBAT)) in environmental samples on a polymer-specific mass-based concentration. The recovery of spiked micro-bioplastics in environmental samples (biosolids) ranged from 74 to 116%. The limits of quantification for the target micro-bioplastics were between 0.02 and 0.05 mg/g. PLA and PBAT were commonly detected in wastewater, biosolids, and sediment samples at concentrations between 0.07 and 0.18 mg/g. The presented analytical method enables the accurate identification, quantification, and monitoring of micro-bioplastics in environmental samples. This study quantified five micro-bioplastic types in complex environmental samples for the first time, filling in gaps in our knowledge about bioplastic pollution and providing a useful methodology and important reference data for future research.

Experimental data for extrusion processing and tensile properties of poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) polymer and wood fibre reinforced PHBV biocomposites.

This article features a large database on different extrusion processing conditions and the resulting tensile properties of poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) and wood fibre reinforced biocomposites. The data presented here corresponds to a comprehensive design of experiments conducted separately for both neat PHBV polymer and wood-PHBV composites, in which the effects of temperature profile, screw speed, feeding rate, feeding method, screw configuration, and wood contents (wood-PHBV composites only) of 10, 20, 30, and 40 wt% wood content were examined. For each processing condition, 5 specimens were tested under uniaxial tensile loading. Here we provide the complete set of extrusion parameters, including the observed screw torque, residence time and material output. Individual stress-strain curves for each specimens are provided, along with their calculated elastic modulus, strength, and strain at maximum load. The data is also provided as support material for the research article: "Extrusion of wood fibre reinforced Poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) biocomposites: statistical analysis of the effect of processing conditions on mechanical performance" (Vandi et al., 2018).

Wood-PHA Composites: Mapping Opportunities.

Polyhydroxyalkanoate (PHA) biopolymers are emerging as attractive new sustainable polymers due to their true biodegradability and highly tuneable mechanical properties. However, despite significant investments, commercialisation barriers are hindering the capacity growth of PHA. In this work, we investigated the market potential for wood plastic composites (WPCs) based on PHAs. We considered the latest global production capacity of PHAs, estimated at 66,000 tonnes/year, and examined the implications of using PHAs for WPC production on the WPC market. Results indicate that a hypothetical usage of the current global PHA production for WPC manufacture would only represent the equivalent of 4.4% of the global WPC market, which is currently experiencing a 10.5% compounded annual growth rate. An economic assessment revealed that a wood-PHA composite as a drop-in alternative WPC product could cost as little as 37% of the cost of its neat PHA counterpart. Thus, WPCs with PHA offer a means to access benefits of PHA in engineering applications at reduced costs; however, further developments are required to improve strain at failure. The successful adoption of wood-PHA composites into the market is furthermore reliant on support from public sector to encourage biodegradable products where recycling is not a ready solution.