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International Journal of Hygiene and... Jul 2021The population is constantly exposed to potentially harmful substances present in the environment, including inter alia food and drinking water, consumer products, and... (Review)
Review
The population is constantly exposed to potentially harmful substances present in the environment, including inter alia food and drinking water, consumer products, and indoor air. Human biomonitoring (HBM) is a valuable tool to determine the integral, internal exposure of the general population, including vulnerable subgroups, to provide the basis for risk assessment and policy advice. The German HBM system comprises of five pillars: (1) the development of suitable analytical methods for new substances of concern, (2) cross-sectional population-representative German Environmental Surveys (GerES), (3) time trend analyses using archived samples from the Environmental Specimen Bank (ESB), (4) the derivation of health-based guidance values as a risk assessment tool, and (5) transfer of data into the European cooperation network HBM4EU. The goal of this paper is to present the complementary elements of the German HBM system and to show its strengths and limitations on the example of plasticizers. Plasticizers have been identified by EU services and HBM4EU partners as priority substances for chemical policy at EU level. Using the complementary elements of the German HBM system, the internal exposure to classical phthalates and novel alternative plasticizers can be reliably monitored. It is shown that market changes, due to regulation of certain phthalates and the rise of substitutes, are rapidly reflected in the internal exposure of the population. It was shown that exposure to DEHP, DiBP, DnBP, and BBzP decreased considerably, whereas exposure to the novel substitutes such as DPHP, DEHTP, and Hexamoll®DINCH has increased significantly. While health-based guidance values for several phthalates (esp. DnBP, DiBP, DEHP) were exceeded quite often at the turn of the millennium, exceedances today have become rarer. Still, also the latest GerES reveals the ubiquitous and concurrent exposures to many plasticizers. Of concern is that the youngest children showed the highest exposures to most of the investigated plasticizers and in some cases their levels of DiBP and DnBP still exceeded health-based guidance values. Over the last years, mixture exposures are increasingly recognized as relevant, especially if the toxicological modes of action are similar. This is supported by a cumulative risk assessment for four endocrine active phthalates which confirms the still concerning cumulative exposure in many young children. Given the adverse health effects of some phthalates and the limited toxicological knowledge of substitutes, exposure reduction and surveillance are needed on German and EU-level. Substitutes need to be monitored, to intervene if exposures are threatening to exceed acceptable levels, or if new toxicological data question their appropriateness. It is strongly recommended to reconsider the use of plastics and plasticizers.
Topics: Biological Monitoring; Child; Child, Preschool; Cross-Sectional Studies; Environmental Exposure; Environmental Pollutants; Humans; Phthalic Acids; Plasticizers; Surveys and Questionnaires
PubMed: 34126298
DOI: 10.1016/j.ijheh.2021.113780 -
Molecules (Basel, Switzerland) Sep 2021Poly(lactic acid) (PLA) is an attractive candidate for replacing petrochemical polymers because it is fully biodegradable. This study investigated the potential of PLA...
Poly(lactic acid) (PLA) is an attractive candidate for replacing petrochemical polymers because it is fully biodegradable. This study investigated the potential of PLA as a sustainable and environmentally friendly alternative material that can be developed into commercially viable wearable mosquito repellent devices with desirable characteristics. PLA strands containing DEET and IR3535 were prepared by twin screw extrusion compounding and simultaneously functioned as plasticizers for the polymer. The plasticizing effect was investigated by thermal and rheological studies. DSC studies showed that the addition of DEET and IR3535 into PLA strands reduced the glass transition temperature consistent with predictions of the Fox equation, thus proving their efficiency as plasticizers. The rheology of molten samples of neat PLA and PLA/repellents blends, evaluated at 200 °C, was consistent with shear-thinning pseudoplastic behaviour. Raman studies revealed a nonlinear concentration gradient for DEET in the PLA strand, indicating non-Fickian Type II transport controlling the desorption process. Release data obtained at 50 °C showed initial rapid release followed by a slower, near constant rate at longer times. The release rate data were fitted to a novel modification of the Peppas-Sahlin desorption model.
Topics: Animals; Culicidae; Insect Repellents; Plasticizers; Polyesters; Polymers; Rheology; Temperature
PubMed: 34641433
DOI: 10.3390/molecules26195890 -
European Journal of Pharmaceutical... Sep 2023The in-situ formation of nanoparticles from polymer-based solid medicines, although previously described, has been overlooked despite its potential to interfere with...
The in-situ formation of nanoparticles from polymer-based solid medicines, although previously described, has been overlooked despite its potential to interfere with oral drug bioavailability. Such polymeric pharmaceuticals are becoming increasingly common on the market and can become even more popular due to the dizzying advance of 3D printing medicines. Hence, this work aimed to study this phenomenon during the dissolution of 3D printed tablets produced with three different polymers, hydroxypropylmethylcellulose acetate succinate (HPMCAS), polyvinyl alcohol (PVA), and Eudragit RL PO® (EUD RL) combined with plasticizers and the model drug naringenin (NAR). The components' interaction, dissolution behavior, and characteristics of the formed particles were investigated employing thermal, spectroscopic, mechanical, and chromatographic assays. All the systems generated stable spherical-shaped particles throughout 24 h, encapsulating over 25% of NAR. Results suggest encapsulation efficiencies variations may depend on interactions between polymer-drug, drug-plasticizer, and polymer-plasticizer, which formed stable nanoparticles even in the drug absence, as observed with the HPMCAS and EUD RL formulations. Additionally, components solubility in the medium and previous formulation treatments are also a decisive factor for nanoparticle formation. In particular, the treatment provided by hot-melt extrusion and FDM 3D printing affected the dissolution efficiency enhancing the interaction between the components, reverberating on particle size and particle formation kinetics mainly for HPMCAS and EUD RL. In conclusion, the 3D printing process influences the in-situ formation of nanoparticles, which can directly affect oral drug bioavailability and needs to be monitored.
Topics: Drug Liberation; Plasticizers; Polymers; Solubility; Tablets; Printing, Three-Dimensional; Technology, Pharmaceutical
PubMed: 37406970
DOI: 10.1016/j.ejps.2023.106517 -
Journal of Exposure Science &... Mar 2023Many phthalates are environmental pollutants and toxic to humans. Following phthalate regulations, human exposure to phthalates has globally decreased with time in...
BACKGROUND
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.
OBJECTIVE
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.
METHODS
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.
RESULTS
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.
SIGNIFICANCE
We addressed the major question of time-trends in human exposure to phthalates and their substitutes and compared the results in different countries worldwide.
IMPACT
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.
Topics: Adult; Child; Humans; Diethylhexyl Phthalate; Phthalic Acids; Environmental Pollutants; Plasticizers; North America; Environmental Exposure
PubMed: 35513587
DOI: 10.1038/s41370-022-00441-w -
Microbial Biotechnology Feb 2023Global economies depend on the use of fossil-fuel-based polymers with 360-400 million metric tons of synthetic polymers being produced per year. Unfortunately, an... (Review)
Review
Global economies depend on the use of fossil-fuel-based polymers with 360-400 million metric tons of synthetic polymers being produced per year. Unfortunately, an estimated 60% of the global production is disposed into the environment. Within this framework, microbiologists have tried to identify plastic-active enzymes over the past decade. Until now, this research has largely failed to deliver functional biocatalysts acting on the commodity polymers such as polyethylene (PE), polypropylene (PP), polyvinylchloride (PVC), ether-based polyurethane (PUR), polyamide (PA), polystyrene (PS) and synthetic rubber (SR). However, few enzymes are known to act on low-density and low-crystalline (amorphous) polyethylene terephthalate (PET) and ester-based PUR. These above-mentioned polymers represent >95% of all synthetic plastics produced. Therefore, the main challenge microbiologists are currently facing is in finding polymer-active enzymes targeting the majority of fossil-fuel-based plastics. However, identifying plastic-active enzymes either to implement them in biotechnological processes or to understand their potential role in nature is an emerging research field. The application of these enzymes is still in its infancy. Here, we summarize the current knowledge on microbial plastic-active enzymes, their global distribution and potential impact on plastic degradation in industrial processes and nature. We further outline major challenges in finding novel plastic-active enzymes, optimizing known ones by synthetic approaches and problems arising through falsely annotated and unfiltered use of database entries. Finally, we highlight potential biotechnological applications and possible re- and upcycling concepts using microorganisms.
Topics: Plastics; Polymers; Polyurethanes; Fossil Fuels; Biodegradation, Environmental
PubMed: 36099200
DOI: 10.1111/1751-7915.14135 -
Molecules (Basel, Switzerland) Oct 2022Since the outbreak of COVID-19, face masks have been introduced in the complex strategy of infection prevention and control. Face masks consist of plastic polymers and...
Since the outbreak of COVID-19, face masks have been introduced in the complex strategy of infection prevention and control. Face masks consist of plastic polymers and additives such as phthalates. The aim of this study was to evaluate the migration of microplastics (MP) and phthalates from face masks to water. Four types of masks including FFP2 masks and surgical were studied. Masks were first characterized to determine the different layers and the material used for their fabrication. Then, masks were cut into 20 pieces of 0.5 cm, including all their layers, placed in water, and the migration of MP and phthalates was evaluated according to the conditions stated in EU Regulation No 10/2011 on plastic materials and articles intended to come into contact with food. For MP, the morphological analysis (shape, dimension, particle count) was performed using a stereomicroscope, while the identification of both masks and MP released was conducted using μ-Fourier-transform infrared spectroscopy (µ-FT-IR). Migration of phthalates was assessed by ultra-high-performance liquid chromatography coupled to triple quadrupole mass spectrometer (UPLC-MS/MS). Face masks analyzed in the present study were made of atactic polypropylene (PP) as stated by the manufacturer. The μ-FT-IR confirmed that PP and polyamide (PA) were released as fragments, while both PP and polyester (PES) were released as fibers. In addition, 4 phthalates were identified at concentrations between 2.34 and 21.0 µg/mask. This study shows that the migration study can be applied to evaluate the potential release of MP and phthalates from face masks to water and could give a hint for the potential impact of their incorrect disposal on the aquatic resources.
Topics: Humans; Microplastics; Plastics; Masks; Water; Spectroscopy, Fourier Transform Infrared; Polypropylenes; Nylons; Chromatography, Liquid; COVID-19; Tandem Mass Spectrometry; Polyesters
PubMed: 36296451
DOI: 10.3390/molecules27206859 -
Journal of Exposure Science &... May 2022Fast food consumption is associated with biomarkers of ortho-phthalates exposures. However, the chemical content of fast food is unknown; certain ortho-phthalates (i.e.,...
BACKGROUND
Fast food consumption is associated with biomarkers of ortho-phthalates exposures. However, the chemical content of fast food is unknown; certain ortho-phthalates (i.e., di-n-butyl phthalate (DnBP) and di(2-ethylhexyl) phthalate (DEHP)) have been phased out and replaced with other plasticizers (e.g., dioctyl terephthalate (DEHT)).
OBJECTIVE
We conducted a preliminary study to examine ortho-phthalate and replacement plasticizer concentrations in foods and food handling gloves from U.S. fast food restaurants.
METHODS
We obtained hamburgers, fries, chicken nuggets, chicken burritos, cheese pizza (n = 64 food samples) and gloves (n = 3) from restaurants and analyzed them for 11 chemicals using gas chromatography mass spectrometry.
RESULTS
We found DEHT at the highest concentrations in both foods (n = 19; median = 2510 µg/kg; max = 12,400 µg/kg) and gloves (n = 3; range: 28-37% by weight). We detected DnBP and DEHP in 81% and 70% of food samples, respectively. Median DEHT concentrations were significantly higher in burritos than hamburgers (6000 µg/kg vs. 2200 µg/kg; p < 0.0001); DEHT was not detected in fries. Cheese pizza had the lowest levels of most chemicals.
SIGNIFICANCE
To our knowledge, these are the first measurements of DEHT in food. Our preliminary findings suggest that ortho-phthalates remain ubiquitous and replacement plasticizers may be abundant in fast food meals.
IMPACT STATEMENT
A selection of popular fast food items sampled in this study contain detectable levels of replacement plasticizers and concerning ortho-phthalates. In addition, food handling gloves contain replacement plasticizers, which may be a source of food contamination. These results, if confirmed, may inform individual and regulatory exposure reduction strategies.
Topics: Dibutyl Phthalate; Diethylhexyl Phthalate; Fast Foods; Food Contamination; Humans; Phthalic Acids; Plasticizers
PubMed: 34702987
DOI: 10.1038/s41370-021-00392-8 -
Chemosphere May 2024Plastic pollution has become a major global concern, posing numerous challenges for the environment and wildlife. Most conventional ways of plastics degradation are... (Review)
Review
Plastic pollution has become a major global concern, posing numerous challenges for the environment and wildlife. Most conventional ways of plastics degradation are inefficient and cause great damage to ecosystems. The development of biodegradable plastics offers a promising solution for waste management. These plastics are designed to break down under various conditions, opening up new possibilities to mitigate the negative impact of traditional plastics. Microbes, including bacteria and fungi, play a crucial role in the degradation of bioplastics by producing and secreting extracellular enzymes, such as cutinase, lipases, and proteases. However, these microbial enzymes are sensitive to extreme environmental conditions, such as temperature and acidity, affecting their functions and stability. To address these challenges, scientists have employed protein engineering and immobilization techniques to enhance enzyme stability and predict protein structures. Strategies such as improving enzyme and substrate interaction, increasing enzyme thermostability, reinforcing the bonding between the active site of the enzyme and substrate, and refining enzyme activity are being utilized to boost enzyme immobilization and functionality. Recently, bioengineering through gene cloning and expression in potential microorganisms, has revolutionized the biodegradation of bioplastics. This review aimed to discuss the most recent protein engineering strategies for modifying bioplastic-degrading enzymes in terms of stability and functionality, including enzyme thermostability enhancement, reinforcing the substrate binding to the enzyme active site, refining with other enzymes, and improvement of enzyme surface and substrate action. Additionally, discovered bioplastic-degrading exoenzymes by metagenomics techniques were emphasized.
Topics: Plastics; Ecosystem; Biodegradable Plastics; Biopolymers; Biodegradation, Environmental; Bioengineering
PubMed: 38521099
DOI: 10.1016/j.chemosphere.2024.141749 -
Pediatric Research Nov 2023Phthalates exposure might affect children's intelligence development. This study aimed to determine (1) whether sex and age affect cognitive function and (2) whether sex... (Meta-Analysis)
Meta-Analysis
BACKGROUND
Phthalates exposure might affect children's intelligence development. This study aimed to determine (1) whether sex and age affect cognitive function and (2) whether sex differences in cognitive performance are wider with higher phthalate concentrations.
METHODS
Data were collected from PubMed (1998-2022), PROQUEST (1997-2022), and SpringerLink (1995-2022). The study followed the PRISMA process. The included articles were followed by PECO framework. The GRADE applied to assess the certainty of evidence. Of 2422 articles obtained, nine were selected using inclusion criteria. The random-effects model was used to estimate the pooled effects.
RESULTS
Our meta-regression indicated a significant difference between sex differences with age at phthalate concentration assessment (β = -0.25; 95% CI = -0.47, -0.03) and MEHP concentration (β = -0.20; 95% CI = -0.37, -0.03).
CONCLUSIONS
The limitation of the current article is it only provides information on intelligence level rather than other aspects of cognitive function. Thus, the sequelae of phthalate exposure on attention and executive function are still unclear. Our analysis shows significant difference between sex differences in cognitive function scores associated with age at phthalate concentration assessment. Girls might be more resilient in cognitive function at a younger age or during lower concentrations of phthalates metabolites.
IMPACT
This is the first meta-analysis to evaluate the pooled estimates of sex differences in objective cognitive functions among children with phthalate exposure. The female might be a protective factor when exposed to toxic plasticizers while the concentration is low. This study captures the possible role of sex in cognitive functioning and plasticizer exposure through a meta-analysis of children's sex, cognitive scores, and plasticizer exposure.
Topics: Humans; Child; Male; Female; Plasticizers; Sex Characteristics; Cognition; Phthalic Acids; Environmental Exposure; Environmental Pollutants
PubMed: 37264138
DOI: 10.1038/s41390-023-02672-5 -
International Journal of Molecular... Jun 2023A [3 + 2] cycloaddition reaction using dialkyne and diazide comonomers, both bearing explosophoric groups, to synthesize energetic polymers containing furazan and...
A [3 + 2] cycloaddition reaction using dialkyne and diazide comonomers, both bearing explosophoric groups, to synthesize energetic polymers containing furazan and 1,2,3-triazole ring as well as nitramine group in the polymer chain have been described. The developed solvent- and catalyst-free approach is methodologically simple and effective, the comonomers used are easily available, and the resulting polymer does not need any purification. All this makes it a promising tool for the synthesis of energetic polymers. The protocol was utilized to generate multigram quantities of the target polymer, which has been comprehensively investigated. The resulting polymer was fully characterized by spectral and physico-chemical methods. Compatibility with energetic plasticizers, thermochemical characteristics, and combustion features indicate the prospects of this polymer as a binder base for energetic materials. The polymer of this study surpasses the benchmark energetic polymer, nitrocellulose (NC), in a number of properties.
Topics: Polymers; Triazoles; Plasticizers; Aniline Compounds
PubMed: 37298596
DOI: 10.3390/ijms24119645