Plastics are known sources of chemical exposure and few, prominent plastic-associated chemicals, such as bisphenol A and phthalates, have been thoroughly studied. However, a comprehensive characterization of the complex chemical mixtures present in plastics is missing. In this study, we benchmark plastic consumer products, covering eight major polymer types, according to their toxicological and chemical signatures using in vitro bioassays and nontarget high-resolution mass spectrometry. Most (74%) of the 34 plastic extracts contained chemicals triggering at least one end point, including baseline toxicity (62%), oxidative stress (41%), cytotoxicity (32%), estrogenicity (12%), and antiandrogenicity (27%). In total, we detected 1411 features, tentatively identified 260, including monomers, additives, and nonintentionally added substances, and prioritized 27 chemicals. Extracts of polyvinyl chloride (PVC) and polyurethane (PUR) induced the highest toxicity, whereas polyethylene terephthalate (PET) and high-density polyethylene (HDPE) caused no or low toxicity. High baseline toxicity was detected in all “bioplastics” made of polylactic acid (PLA). The toxicities of low-density polyethylene (LDPE), polystyrene (PS), and polypropylene (PP) varied. Our study demonstrates that consumer plastics contain compounds that are toxic in vitro but remain largely unidentified. Since the risk of unknown compounds cannot be assessed, this poses a challenge to manufacturers, public health authorities, and researchers alike. However, we also demonstrate that products not inducing toxicity are already on the market.

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Plastic products contain complex mixtures of extractable chemicals that can be toxic. However, humans and wildlife will only be exposed to plastic chemicals that are released under realistic conditions. Thus, we investigated the toxicological and chemical profiles leaching into water from 24 everyday plastic products covering eight polymer types. We performed migration experiments over 10 days at 40 °C and analyzed the migrates using four in vitro bioassays and nontarget high-resolution mass spectrometry (UPLC-QTOF-MS E ). All migrates induced baseline toxicity, 22 an oxidative stress response, 13 antiandrogenicity, and one estrogenicity. Overall, between 17 and 8681 relevant chemical features were present in the migrates. In other words, between 1 and 88% of the plastic chemicals associated with one product were migrating. Further, we tentatively identified ∼8% of all detected features implying that most plastic chemicals remain unknown. While low-density polyethylene, polyvinyl chloride, and polyurethane induced most toxicological endpoints, a generalization for other materials is not possible. Our results demonstrate that plastic products readily leach many more chemicals than previously known, some of which are toxic in vitro. This highlights that humans are exposed to many more plastic chemicals than currently considered in public health science and policies.

Flame retardants (FR) are inevitable additives to many plastics. Halogenated organics are effective FRs but are controversially discussed due to the release of toxic gases during a fire or their persistence if landfilled. Phosphorus-containing compounds are effective alternatives to halogenated FRs and have potential lower toxicity and degradability. In addition, nitrogen-containing additives were reported to induce synergistic effects with phosphorus-based FRs. However, no systematic study of the gradual variation on a single phosphorus FR containing both P–O and P–N moieties and their comparison to the respective blends of phosphates and phosphoramides was reported. This study developed general design principles for P–O- and P–N-based FRs and will help to design effective FRs for various polymers. We synthesized a library of phosphorus FRs that only differ in their P-binding pattern from each other and studied their decomposition mechanism in epoxy resins. Systematic control over the decomposition pathways of phosphate (PO­(OR)3), phosphoramidate (PO­(OR)2(NHR)), phosphorodiamidate (PO­(OR)­(NHR)2), phosphoramide (PO­(NHR)3), and their blends was identified, for example, by reducing cis-elimination and the formation of P–N-rich char with increasing nitrogen content in the P-binding sphere. Our FR epoxy resins can compete with commercial FRs in most cases, but we proved that the blending of esters and amides outperformed the single-molecule amidates/diamidates due to distinctively different decomposition mechanisms acting synergistically when blended.