Designing for degradation: the importance of considering biotic and abiotic polymer degradation

Considering the increasing global plastic demand, there is a critical need to gain insight into environmental processes that govern plastic degradation in order to inform novel design of sustainable polymers. Current biological degradation testing standards focus on formation of CO₂ (<i>i.e.</i>, mineralization) alone as a diagnostic, ultimately limiting identification of structure-degradation relationships in a timely fashion. This work developed a sequential abiotic (<i>i.e.</i>, photodegradation and hydrolysis) and biotic degradation test and applied it to a suite of 18 polymers, including ten lab produced, novel polyhydroxyalkanoate polyesters, and eight commercially available, bio-based (<i>i.e.</i>, polylactic acid and poly-3-hydroxybutyrate) and fossil-derived (<i>i.e.</i>, polystyrene, polypropylene, low density polyethylene, poly(ethylene terephthalate) and tire rubber) polymers. Biomineralization alone following standard methods (<i>i.e.</i>, ASTM 6691-17, ISO 23977-1 2020) underestimated polymer degradation up to two-fold over 28 days. Simulated sunlight enhanced the overall polymer degradation by mobilizing dissolved organic carbon (DOC). After photoirradiation, up to 100% of released dissolved organic carbon was bioavailable for marine microbes over 14 days. Photodegradation and hydrolysis could be explained by structural drivers in the commodity polymers, and the lab-synthesized polymers illustrated a limit to total degradation beyond which no enhancements in degradation were achieved. Taken together, this workflow allows for relatively fast experimental determination of environmentally relevant stimuli to help support eventual elucidation of structure-property relationships for enhanced <i>a priori</i> design of degradable polymers.