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.
Due to the restricted use and ban of brominated flame retardants, organophosphorus compounds (OPs), extensively used as flame retardants and plasticizers, are ubiquitous in various environmental ...compartments worldwide. The present study shows that the release of OPs from a wide variety of commercial products and wastewater discharge might be considered as primary emission sources and that high potential of long-range atmospheric transport and persistence of OPs would be responsible for their presence in various matrices on a global scale. The occurrence and environmental behaviors of OPs in diverse matrices (e.g., dust, air, water, sediment, soil and biota) are reviewed. Human exposures to OPs via dermal contact, dust ingestion, inhalation and dietary intake are comprehensively evaluated. Finally, this study identifies gaps in the existing issues and generates a future agenda for the emerging contaminants OPs.
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•Organophosphorus compounds (OPs) are ubiquitous in various environmental matrices worldwide.•Release of OPs from products and wastewater discharge are treated as primary emission sources.•High potentials of LRAT and persistence of OPs account for their global occurrence.•Dust intake is more important than inhalation and food intake for human, especially for toddlers.•Research gaps are concluded to define the directions and the primary emphasis of future studies.
The emission sources, environmental occurrence, toxicity and human exposure of organophosphorus flame retardants and plasticizers are fully reviewed.
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.
Polymer contamination is a major pollutant in all waterways and a significant concern of the 21st Century, gaining extensive research, media, and public attention. The polymer pollution problem is so ...vast; plastics are now observed in some of the Earth's most remote regions such as the Mariana trench. These polymers enter the waterways, migrate, breakdown; albeit slowly, and then interact with the environment and the surrounding biodiversity. It is these biodiversity and ecosystem interactions that are causing the most nervousness, where health researchers have demonstrated that plastics have entered the human food chain, also showing that plastics are damaging organisms, animals, and plants. Many researchers have focused on reviewing the macro and micro-forms of these polymer contaminants, demonstrating a lack of scientific data and also a lack of investigation regarding nano-sized polymers. It is these nano-polymers that have the greatest potential to cause the most harm to our oceans, waterways, and wildlife. This review has been especially ruthless in discussing nano-sized polymers, their ability to interact with organisms, and the potential for these nano-polymers to cause environmental damage in the marine environment. This review details the breakdown of macro-, micro-, and nano-polymer contamination, examining the sources, the interactions, and the fates of all of these polymer sizes in the environment. The main focus of this review is to perform a comprehensive examination of the literature of the interaction of nanoplastics with organisms, soils, and waters; followed by the discussion of toxicological issues. A significant focus of the review is also on current analytical characterisation techniques for nanoplastics, which will enable researchers to develop protocols for nanopolymer analysis and enhance understanding of nanoplastics in the marine environment.
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•Polymer contamination has reached a breaking point.•Contamination has now been observed in the Earth's most remote oceans.•Macro and micro plastics have been discussed comprehensively.•Nanoplastics are an overlooked issue, this review focuses on nanoplastics.•Sources, breakdown, fates, uptake, and characterisation will be discussed.
Many 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.
We 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.
We 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.
We 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.
We addressed the major question of time-trends in human exposure to phthalates and their substitutes and compared the results in different countries worldwide.
Phthalates 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.
Phthalate esters are substances mainly used as plasticizers in various applications. Some have been restricted and phased out due to their adverse health effects and ubiquitous presence, leading to ...the introduction of alternative plasticizers, such as DINCH. Using a comprehensive dataset from a Norwegian study population, human exposure to DMP, DEP, DnBP, DiBP, BBzP, DEHP, DINP, DIDP, DPHP and DINCH was assessed by measuring their presence in external exposure media, allowing an estimation of the total intake, as well as the relative importance of different uptake pathways. Intake via different uptake routes, in particular inhalation, dermal absorption, and oral uptake was estimated and total intake based on all uptake pathways was compared to the calculated intake from biomonitoring data. Hand wipe results were used to determine dermal uptake and compared to other exposure sources such as air, dust and personal care products. Results showed that the calculated total intakes were similar, but slightly higher than those based on biomonitoring methods by 1.1 to 3 times (median), indicating a good understanding of important uptake pathways. The relative importance of different uptake pathways was comparable to other studies, where inhalation was important for lower molecular weight phthalates, and negligible for the higher molecular weight phthalates and DINCH. Dietary intake was the predominant exposure route for all analyzed substances. Dermal uptake based on hand wipes was much lower (median up to 2000 times) than the total dermal uptake via air, dust and personal care products. Still, dermal uptake is not a well-studied exposure pathway and several research gaps (e.g. absorption fractions) remain. Based on calculated intakes, the exposure for the Norwegian participants to the phthalates and DINCH was lower than health based limit values. Nevertheless, exposure to alternative plasticizers, such as DPHP and DINCH, is expected to increase in the future and continuous monitoring is required.
•Diet is the major route of human exposure to phthalates and DINCH.•Human risk related to phthalates and DINCH is low for the adult study population.•Indoor environmental concentrations can be successfully linked to human body burden.•Dermal uptake of phthalates needs further investigation.
Poly(lactic acid) (PLA), so far, is the most extensively researched and utilized biodegradable aliphatic polyester in human history. Due to its merits, PLA is a leading biomaterial for numerous ...applications in medicine as well as in industry replacing conventional petrochemical-based polymers. The main purpose of this review is to elaborate the mechanical and physical properties that affect its stability, processability, degradation, PLA-other polymers immiscibility, aging and recyclability, and therefore its potential suitability to fulfill specific application requirements. This review also summarizes variations in these properties during PLA processing (i.e. thermal degradation and recyclability), biodegradation, packaging and sterilization, and aging (i.e. weathering and hygrothermal). In addition, we discuss up-to-date strategies for PLA properties improvements including components and plasticizer blending, nucleation agent addition, and PLA modifications and nanoformulations. Incorporating better understanding of the role of these properties with available improvement strategies is the key for successful utilization of PLA and its copolymers/composites/blends to maximize their fit with worldwide application needs.
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•Human urinary excretion kinetics of di(2-ethylhexyl) adipate (DEHA) after oral dose.•New specific DEHA metabolite: mono-5-carboxy-2-ethylpentyl adipate (5cx-MEPA).•Urinary excretion fractions (FUE) ...for three specific DEHA metabolites.•Calculation of metabolite-based daily DEHA intakes for pilot populations.•Highest FUE and detection rates for 5cx-MEPA.
Di(2-ethylhexyl) adipate (DEHA) is used as a substitute for the reprotoxic phthalate plasticizer di(2-ethylhexyl) phthalate (DEHP). This study reports the first quantitative data on human in vivo DEHA metabolism and urinary metabolite excretion with the aim of providing tools for DEHA exposure and risk assessments. After DEHA was administered to four healthy volunteers (107−164 μg/kg body weight (bw)), urine samples were continuously and completely collected for 48 h and analyzed for the specific oxidized monoester metabolites mono-2-ethyl-5-hydroxyhexyl adipate (5OH-MEHA), mono-2-ethyl-5-oxohexyl adipate (5oxo-MEHA), and mono-5-carboxy-2-ethylpentyl adipate (5cx-MEPA), as well as for the non-specific hydrolysis product adipic acid (AA) using stable isotope dilution analysis. AA was confirmed as a major (urinary excretion fraction (FUE): 10–40%), yet non-specific DEHA metabolite. 5cx-MEPA was the major specific DEHA metabolite with an FUE of 0.20% (range: 0.17–0.24%). FUEs for 5OH-MEHA and 5oxo-MEHA were 0.07% (0.03–0.10%) and 0.05% (0.01–0.06%), respectively. The three specific metabolites were excreted with two concentration maxima (tmax1 = 1.5–2.3 h, tmax2 = 3.8–6.4 h). Elimination half-lives (t1/2, calculated after the second tmax) for 5cx-MEPA were calculated between 2.1–3.8 h. The majority (98–100%) of metabolites was excreted within 24 h. The FUE of 5cx-MEPA was applied to demonstrate its applicability for calculating daily intakes based on urinary metabolite levels from three pilot populations. Daily intakes were generally far below the tolerable daily intake (TDI) for DEHA (300 μg/kg bw/day). The highest daily intake (114 μg/kg bw/day) was calculated in individuals after consuming food that had been wrapped in DEHA containing cling film.
Alternative plasticizers to phthalate esters have been used for over a decade, but data regarding emissions, human exposure and health effects are limited. Here we review 20 alternative plasticizers ...in current use and their human exposure, hazard and risk. Physicochemical properties are collated for these diverse alternatives and log KOW values range over 15 orders of magnitude and log KAW and log KOA values over about 9 orders of magnitude. Most substances are hydrophobic with low volatility and are produced in high volumes for use in multiple applications. There is an increasing trend in the total use of alternative plasticizers in Sweden compared to common phthalate esters in the last 10years, especially for DINCH. Evaluative indoor fate modeling reveals that most alternatives are distributed to vertical surfaces (e.g. walls or ceilings). Only TXIB and GTA are predicted to be predominantly distributed to indoor air. Human exposure data are lacking and clear evidence for human exposure only exists for DEHT and DINCH, which show increasing trends in body burdens. Human intake rates are collected and compared with limit values with resulting risk ratios below 1 except for infant's exposure to ESBO. PBT properties of the alternatives indicate mostly no reasons for concern, except that TEHPA is estimated to be persistent and TCP toxic. A caveat is that non-standard toxicological endpoint results are not available and, similar to phthalate esters, the alternatives are likely “pseudo-persistent”. Key data gaps for more comprehensive risk assessment are identified and include: analytical methods to measure metabolites in biological fluids and tissues, toxicological information regarding non-standard endpoints such as endocrine disruption and a further refined exposure assessment in order to consider high risk groups such as infants, toddlers and children.
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•Alternative plasticizers are generally low-volatile, hydrophobic substances•High production volumes with increasing trend in use•More refined human exposure assessments necessary•Data gaps exist regarding non-standard toxicological endpoints•Human risks are low although exposure to DINCH and DEHT are increasing
Plasticizers have long been known for their effectiveness in producing flexible plastics for applications ranging from the automotive industry to medical and consumer products. The plasticizer ...industry has grown with the use of plastics worldwide. Recent plasticizer research has focused on technological challenges including leaching, migration, evaporation and degradation of plasticizers, each of which eventually lead to deterioration of thermomechanical properties in plastics. Human exposure to certain plasticizers has been debated recently because di(2-ethylhexyl) phthalate, used in medical plastics, has been found at detectable levels in the blood supply and potential health risks may arise from its chronic exposure. The current paper presents a brief history and an overview of the traditional plasticizers currently available in the world market, discusses some of the problems associated with the end uses of these plasticizers and reviews recent scientific approaches to resolve these problems. The definition of an ideal plasticizer changes with each application; thus, this paper addresses technical issues first from a broad perspective, and then with a focus on leaching, migration, evaporation and degradation issues. Several approaches to reduce leaching and migration of plasticizers are discussed, including surface modification of plasticized polymers and the application of alternative plasticizers and oligomers to meet technological requirements. New approaches to reduce evaporation and degradation of plasticizers are discussed, with the aim of formulating long-lasting flexible plastics and minimizing the ultimate environmental impact of these chemicals. The development of fire-retardant plasticizers and novel plasticizers for use in biodegradable plastics are also included.
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