Environmentally Benign Fast-Degrading Conductive Composites.

An environmentally benign conductive composite that rapidly degrades in the presence of warm water via enzyme-mediated hydrolysis is described. This represents the first time that hydrolytic enzymes have been immobilized onto eco-friendly conductive carbon sources with the express purpose of degrading the encapsulating biodegradable plastic. Amano Lipase (AL)-functionalized carbon nanofibers (CNF) were compounded with polycaprolactone (PCL) to produce the composite film CNFAL-PCL (thickness ∼ 600 µm; CNFAL = 20.0 wt %). To serve as controls, films of the same thickness were also produced, including CNF-AL5-PCL (CNF mixed with AL and PCL; CNF = 19.2 wt % and AL = 5.00 wt %), CNF-PCL (CNF = 19.2 wt %), ALx-PCL (AL = x = 1.00 or 5.00 wt %), and PCL. The electrical performance of the CNF-containing composites was measured, and conductivities of 14.0 ± 2, 22.0 ± 5, and 31.0 ± 6 S/m were observed for CNFAL-PCL, CNF-AL5-PCL, and CNF-PCL, respectively. CNFAL-PCL and control films were degraded in phosphate buffer (2.00 mg/mL film/buffer) at 50 °C, and their average percent weight loss (Wtavg%) was recorded over time. After 3 h CNFAL-PCL degraded to a Wtavg% of 90.0% and had completely degraded after 8 h. This was considerably faster than CNF-AL5-PCL, which achieved a total Wtavg% of 34.0% after 16 days, and CNF-PCL, which was with a Wtavg% of 7.00% after 16 days. Scanning electron microscopy experiments (SEM) found that CNFAL-PCL has more open pores on its surface and that it fractures faster during degradation experiments which exposes the interior enzyme to water. An electrode made from CNFAL-PCL was fabricated and attached to an AL5-PCL support to form a fast-degrading thermal sensor. The resistance was measured over five cycles where the temperature was varied between 15.0-50.0 °C. The sensor was then degraded fully in buffer at 50 °C over a 48 h period.

A spatio-temporal analysis of marine diatom communities associated with pristine and aged plastics.

Complex microbial communities colonize plastic substrates over time, strongly influencing their fate and potential impacts on marine ecosystems. Among the first colonizers, diatoms play an important role in the development of this 'plastiphere'. We investigated 936 biofouling samples and the factors influencing diatom communities associated with plastic colonization. These factors included geographic location (up to 800 km apart), duration of substrate submersion (1 to 52 weeks), plastics (5 polymer types) and impact of artificial ageing with UV light. Diatom communities colonizing plastic debris were primarily determined by their geographic location and submersion time, with the strongest changes occurring within two weeks of submersion. Several taxa were identified as early colonizers (e.g. Cylindrotheca, Navicula and Nitzschia spp.) with known strong adhesion capabilities. To a lesser extent, plastic-type and UV-ageing significantly affected community composition, with 14 taxa showing substrate-specificity. This study highlights the role of plastics types-state for colonization in the ocean.

Leaching and transformation of chemical additives from weathered plastic deployed in the marine environment.

Plastic pollution causes detrimental environmental impacts, which are increasingly attributed to chemical additives. However, the behaviour of plastic additives in the marine environment is poorly understood. We used a marine deployment experiment to examine the impact of weathering on the extractables profile, analysed by liquid chromatography-mass spectrometry, of four plastics at two locations over nine months in Aotearoa/New Zealand. The concentration of additives in polyethylene and oxo-degradable polyethylene were strongly influenced by artificial weathering, with deployment location and time less influential. By comparison, polyamide 6 and polyethylene terephthalate were comparatively inert with minimal change in response to artificial weathering or deployment time. Non-target analysis revealed extensive differentiation between non-aged and aged polyethylene after deployment, concordant with the targeted analysis. These observations highlight the need to consider the impact of leaching and weathering on plastic composition when quantifying the potential impact and risk of plastic pollution within receiving environments.

An investigation into the stability and degradation of plastics in aquatic environments using a large-scale field-deployment study.

The fragmentation of plastic debris is a key pathway to the formation of microplastic pollution. These disintegration processes depend on the materials' physical and chemical characteristics, but insight into these interrelationships is still limited, especially under natural conditions. Five plastics of known polymer/additive compositions and processing histories were deployed in aquatic environments and recovered after six and twelve months. The polymer types used were linear low density polyethylene (LLDPE), oxo-degradable LLDPE (oxoLLDPE), poly(ethylene terephthalate) (PET), polyamide-6 (PA6), and poly(lactic acid) (PLA). Four geographically distinct locations across Aotearoa/New Zealand were chosen: three marine sites and a wastewater treatment plant (WWTP). Accelerated UV-weathering under controlled laboratory conditions was also carried out to evaluate artificial ageing as a model for plastic degradation in the natural environment. The samples' physical characteristics and surface microstructures were studied for each deployment location and exposure time. The strongest effects were found for oxoLLDPE upon artificial ageing, with increased crystallinity, intense surface cracking, and substantial deterioration of its mechanical properties. However, no changes to the same extent were found after recovery of the deployed material. In the deployment environments, the chemical nature of the plastics was the most relevant factor determining their behaviours. Few significant differences between the four aquatic locations were identified, except for PA6, where indications for biological surface degradation were found only in seawater, not the WWTP. In some cases, artificial ageing reasonably mimicked the changes which some plastic properties underwent in aquatic environments, but generally, it was no reliable model for natural degradation processes. The findings from this study have implications for the understanding of the initial phases of plastic degradation in aquatic environments, eventually leading to microplastics formation. They can also guide the interpretation of accelerated laboratory ageing for the fate of aquatic plastic pollution, and for the testing of aged plastic samples.

Ligno-Cellulosic Fibre Sized with Nucleating Agents Promoting Transcrystallinity in Isotactic Polypropylene Composites.

The mechanical performance of composites made from isotactic polypropylene reinforced with natural fibres depends on the interface between fibre and matrix, as well as matrix crystallinity. Sizing the fibre surface with nucleating agents to promote transcrystallinity is a potential route to improve the mechanical properties. The sizing of thermo-mechanical pulp and regenerated cellulose (Tencel™) fibres with α- and ß-nucleating agents, to improve tensile strength and impact strength respectively, was assessed in this study. Polarised microscopy, electron microscopy and differential scanning calorimetry (DSC) showed that transcrystallinity was achieved and that the bulk crystallinity of the matrix was affected during processing (compounding and injection moulding). However, despite substantial changes in crystal structure in the final composite, the sizing method used did not lead to significant changes regarding the overall composite mechanical performance.