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The rapidly growing concern over the hazardous impact of phthalates on the environment and public health has led to a critical need for alternative and environmentally friendly plastics. Plasticizers developed from natural materials represent one possible solution. This paper explores four types of renewable feedstocks (sorbitol/polyols, glycerin, cardanol from cashew nutshell liquid, and limonene from citrus peels) as sources for developing alternative plasticizer systems. Key areas explored include the type of feedstock utilized, the methods used for extracting or processing the feedstocks, the nature of the chemical modification processes (e.g., esterification, epoxidation, etherification, or reactive grafting) applied to generate the respective plasticizers, and the resultant physical and mechanical properties. The performance of each plasticizer system in polymers such as PVC, PLA, and polysaccharide-based bioplastics is evaluated, alongside the compatibility with biological tissues, toxicological properties, biodegradability, and chemical migration into food simulants. The feasibility of each family of plasticizers is also assessed from an economic perspective, including availability of the feedstocks, economies of scale associated with large-volume production, and competitive pricing relative to established petroleum-derived plasticizers. Overall, sorbitol/polyol and glycerin derivative families have reached a level of maturity that provides a good balance of processability, food-contact safety, and biodegradability. Cardanol-based systems provide an attractive option where aromatic functional groups and combined plasticization–stabilization effects are needed. Limonene-derived plasticizer systems appear promising for use in PLA, but their broader utility may be limited by volatility, strong odors, and susceptibility to oxidation. Common issues identified across all four families include chemical migration into food products, regulatory approval, and the need for detailed life-cycle assessments.

To date, the toxicity of organophosphate esters has primarily been studied regarding their use as pesticides and their effects on the neurotransmitter acetylcholinesterase (AChE). Currently, flame retardants and plasticizers are the two largest market segments for organophosphate esters and they are found in a wide variety of products, including electronics, building materials, vehicles, furniture, car seats, plastics, and textiles. As a result, organophosphate esters and their metabolites are routinely found in human urine, blood, placental tissue, and breast milk across the globe. It has been asserted that their neurological effects are minimal given that they do not act on AChE in precisely the same way as organophosphate ester pesticides. This commentary describes research on the non-AChE neurodevelopmental toxicity of organophosphate esters used as flame retardants and plasticizers (OPEs). Studies in humans, mammalian, nonmammalian, and models are presented, and relevant neurodevelopmental pathways, including adverse outcome pathways, are described. By highlighting this scientific evidence, we hope to elevate the level of concern for widespread human exposure to these OPEs and to provide recommendations for how to better protect public health. Collectively, the findings presented demonstrate that OPEs can alter neurodevelopmental processes by interfering with noncholinergic pathways at environmentally relevant doses. Application of a pathways framework indicates several specific mechanisms of action, including perturbation of glutamate and gamma-aminobutyric acid and disruption of the endocrine system. The effects may have implications for the development of cognitive and social skills in children. Our conclusion is that concern is warranted for the developmental neurotoxicity of OPE exposure. We thus describe important considerations for reducing harm and to provide recommendations for government and industry decision makers. https://doi.org/10.1289/EHP9285.

The deficiencies of popular phthalate plasticizers (ready migration from a polymer matrix into which they have been incorporated, flammability, environmental pollution, human health risks) have stimulated efforts to develop new effective, nonmigrating, low-cost, nontoxic replacements. In the main, these have been based on readily-available, nontoxic biobased precursors. Some, including those prepared from plant oils, have been generated from biomaterials themselves. However, the more numerous and generally more effective have been generated from discrete compounds produced from various biomaterials. Several structural features of effective plasticizers have been recognized. Polar functionality is required to assure compatibility with a wide range of polymeric materials, including poly(vinyl chloride) (PVC), the most heavily plasticized polymer. A branched structure greatly enhances the effectiveness of compounds used as plasticizers. An oligomeric structure may strongly limit or prevent migration from a polymer matrix. Hyperbranched oligomers of defined structure derived from the readily-available, inexpensive, nontoxic biomonomers, glycerol and adipic acid contain all these features and are excellent plasticizers. They contain ester functionality, are highly branched, and display a large number of end groups, all of which contribute to their effectiveness as plasticizers.

BackgroundMany phthalates are environmental pollutants and toxic to humans. Following phthalate regulations, human exposure to phthalates has globally decreased with time in European countries, the US and Korea. Conversely, exposure to their substitutes DEHT and/or DINCH has increased. In other countries, including China, little is known on the time-trends in human exposure to these plasticizers.ObjectiveWe aimed to estimate time-trends in the urinary concentrations of phthalates, DEHT, and DINCH metabolites, in general population from non-European countries, in the last decade.MethodsWe compiled human biomonitoring (HBM) data from 123 studies worldwide in a database termed “PhthaLit”. We analyzed time-trends in the urinary concentrations of the excreted metabolites of various phthalates as well as DEHT and DINCH per metabolite, age group, and country/region, in 2009–2019. Additionally, we compared urinary metabolites levels between continents.ResultsWe found solid time-trends in adults and/or children from the US, Canada, China and Taiwan. DEHP metabolites decreased in the US and Canada. Conversely in Asia, 5oxo- and 5OH-MEHP (DEHP metabolites) increased in Chinese children. For low-weight phthalates, the trends showed a mixed picture between metabolites and countries. Notably, MnBP (a DnBP metabolite) increased in China. The phthalate substitutes DEHT and DINCH markedly increased in the US.SignificanceWe addressed the major question of time-trends in human exposure to phthalates and their substitutes and compared the results in different countries worldwide.ImpactPhthalates account for more than 50% of the plasticizer world market. Because of their toxicity, some phthalates have been regulated. In turn, the consumption of non-phthalate substitutes, such as DEHT and DINCH, is growing. Currently, phthalates and their substitutes show high detection percentages in human urine. Concerning time-trends, several studies, mainly in Europe, show a global decrease in phthalate exposure, and an increase in the exposure to phthalate substitutes in the last decade. In this study, we address the important question of time-trends in human exposure to phthalates and their substitutes and compare the results in different countries worldwide.

Di(2-ethylhexyl)phthalate (DEHP) is a widely used plasticizer to render poly(vinyl chloride) (PVC) soft and malleable. Plasticized PVC is used in hospital equipment, food wrapping, and numerous other commercial and industrial products. Unfortunately, plasticizers can migrate within the material and leach out of it over time, ending up in the environment and, frequently, the human body. DEHP has come under increased scrutiny as its breakdown products are believed to be endocrine disruptors and more toxic than DEHP itself. DEHP and its breakdown products have been identified as ubiquitous environmental contaminants, and daily human exposure is estimated to be in the microgram per kilogram level. The objective of this review is to summarize and comment on published sources of DEHP exposure and to give an overview of its environmental fate. Exposure through bottled water was examined specifically, as this concern is raised frequently, yet only little exposure to DEHP occurs through bottled water, and DEHP exposure is unlikely to stem from the packaging material itself. Packaged food was also examined and showed higher levels of DEHP contamination compared to bottled water. Exposure to DEHP also occurs in hospital environments, where DEHP leaches directly into liquids that passed through PVC/DEHP tubing and equipment. The latter exposure is at considerably higher levels compared to food and bottled water, specifically putting patients with chronic illnesses at risk. Overall, levels of DEHP in food and bottled water were below current tolerable daily intake (TDI) values. However, our understanding of the risks of DEHP exposure is still evolving. Given the prevalence of DEHP in our atmosphere and environment, and the uncertainty revolving around it, the precautionary principle would suggest its phaseout and replacement. Increased efforts to develop viable replacement compounds, which necessarily includes rigorous leaching, toxicity, and impact assessment studies, are needed before alternative plasticizers can be adopted as viable replacements.

This paper reviews the current trends in replacing commonly used plasticizers in poly(vinyl chloride), PVC, formulations by new compounds with reduced migration, leading to the enhancement in mechanical properties and better plasticizing efficiency. Novel plasticizers have been divided into three groups depending on the replacement strategy, i.e., total replacement, partial replacement, and internal plasticizers. Chemical and physical properties of PVC formulations containing a wide range of plasticizers have been compared, allowing observance of the improvements in polymer performance in comparison to PVC plasticized with conventionally applied bis(2-ethylhexyl) phthalate, di-n-octyl phthalate, bis(2-ethylhexyl) terephthalate and di-n-octyl terephthalate. Among a variety of newly developed plasticizers, we have indicated those presenting excellent migration resistance and advantageous mechanical properties, as well as those derived from natural sources. A separate chapter has been dedicated to the description of a synergistic effect of a mixture of two plasticizers, primary and secondary, that benefits in migration suppression when secondary plasticizer is added to PVC blend.

Acetyl tributyl citrate (ATBC) and epoxidized soybean oil (ESBO) are widely used emerging plasticizers, but their potential to induce lipid metabolism disorders remains poorly understood. In this study, we explored their toxicological mechanisms using a network toxicology framework combined with molecular docking and molecular dynamics simulations. Potential targets of ATBC and ESBO were predicted from multiple databases and compared with genes associated with lipid metabolism disorders. Core targets were identified through protein–protein interaction network analysis. Gene Ontology (GO), Kyoto Encyclopedia of Genes and Genomes (KEGG), and Disease Ontology (DO) enrichment analyses were performed to infer relevant biological processes and pathways. Molecular docking and dynamics simulations were further applied to evaluate the binding affinity and stability between the compounds and key targets. Five core targets—epidermal growth factor receptor (EGFR), signal transducer and activator of transcription 3 (STAT3), toll-like receptor 4 (TLR4), JUN proto-oncogene (JUN), and androgen receptor (AR)—were identified, mainly involved in immune regulation, hormone signaling, and the hypoxia-inducible factor 1 (HIF-1) pathway. Enrichment analyses suggested that the emerging plasticizers ATBC and ESBO may disturb lipid metabolism and contribute to diseases such as non-alcoholic fatty liver disease (NAFLD) and hormone-sensitive cancers. Docking results confirmed strong and specific interactions between the compounds and core targets. Overall, these findings support the hypothesis that ATBC and ESBO may disrupt hepatic lipid metabolism through HIF-1 activation and immune–endocrine pathway interference, providing insight into their potential health risks.

Non-targeted analysis (NTA) and suspect screening analysis (SSA) are powerful techniques that rely on high-resolution mass spectrometry (HRMS) and computational tools to detect and identify unknown or suspected chemicals in the exposome. Fully understanding the chemical exposome requires characterization of both environmental media and human specimens. As such, we conducted a review to examine the use of different NTA and SSA methods in various exposure media and human samples, including the results and chemicals detected. The literature review was conducted by searching literature databases, such as PubMed and Web of Science, for keywords, such as “non-targeted analysis”, “suspect screening analysis” and the exposure media. Sources of human exposure to environmental chemicals discussed in this review include water, air, soil/sediment, dust, and food and consumer products. The use of NTA for exposure discovery in human biospecimen is also reviewed. The chemical space that has been captured using NTA varies by media analyzed and analytical platform. In each media the chemicals that were frequently detected using NTA were: per- and polyfluoroalkyl substances (PFAS) and pharmaceuticals in water, pesticides and polyaromatic hydrocarbons (PAHs) in soil and sediment, volatile and semi-volatile organic compounds in air, flame retardants in dust, plasticizers in consumer products, and plasticizers, pesticides, and halogenated compounds in human samples. Some studies reviewed herein used both liquid chromatography (LC) and gas chromatography (GC) HRMS to increase the detected chemical space (16%); however, the majority (51%) only used LC-HRMS and fewer used GC-HRMS (32%). Finally, we identify knowledge and technology gaps that must be overcome to fully assess potential chemical exposures using NTA. Understanding the chemical space is essential to identifying and prioritizing gaps in our understanding of exposure sources and prior exposures.Impact statementThis review examines the results and chemicals detected by analyzing exposure media and human samples using high-resolution mass spectrometry based non-targeted analysis (NTA) and suspect screening analysis (SSA).

Plasticizers are added to diverse consumer products including children’s products. Owing to their potential for endocrine disruption, the use of phthalate plasticizers is restricted in many children’s products. In this study, exposure to five phthalate esters (dibutylphthalate, di(2-ethylhexyl) phthalate (DEHP), diethyl phthalate, di-isobutyl phthalate, and diisononyl phthalate (DINP)) and an alternative (di-ethylhexyl adipate) was assessed by the use of children’s products based on chemical analysis of 3345 products purchased during 2017 and 2019 in Korea. Plasticizers were found above the detection limits in 387 products, and DEHP and DINP were the two most predominantly detected plasticizers. Deterministic and probabilistic estimation of the margin of exposure at a screening level revealed that the use of children’s products might be an important risk factor. However, it is also highly likely that the exposure could be overestimated, because the migration rate was estimated based solely on the content of plasticizers in children’s products. Chemical migration is a key process determining the absorption of plasticizers from products; thus, further refinements in experimental determination or model estimation of the migration rate are required.

What do bisphenol A, phthalates, alkylphenols, triclosan, and perfluorinated compounds have in common? Aside from their somewhat hermetic nomenclature, they are all synthetic polymers that have definitively infiltrated the human body. Cleaning products, cosmetics, perfumes, clothing, cookware, and food packaging: everything around us contains plastics. The unsurpassed consistency of their molecular profiles combined with nominal production costs made plastics the holy grail of twentieth-century industry, the raw material of advanced capitalism.