Search Results (55)

As a commonly present organophosphorus flame retardant and persistent organic pollutant, 2-ethylhexyl diphenyl phosphate (EHDPP) has been observed to be genotoxic in cultured human hepatoma (HepG2) cells which depends on CYP activities. Yet, its impacts on hepatic Cyp expression, hepatotoxicity and genotoxicity in intact mammalians remain unidentified. In this study, adult male C57BL/6J mice received EHDPP by gastric gavage at doses of 50, 100, and 150 mg/kg (b.w.)/d for 7 d, then the hepatic expression of several Cyp proteins, aryl hydrocarbon receptor (AhR) and pregnane X receptor (PXR) was analyzed by Western blotting; hepatoxicity was determined by serum ALT/AST activities and hepatic histological examination, while genotoxicity by comet assay, phosphorylated histone (γ-H2AX) protein, micronucleus test, and Pig-a assay. A micronucleus test in mouse hepatoma (Hepa1-6) cells in vitro was employed to observe the modulating effect of PCB 126 (100 nM)/BAY-218 (700 nM) (Ahr-Cyp1a1 activator/inhibitor). The results indicated that EHDPP induced hepatic Cyp1a1, 2e1, AhR, Cyp1a2, Cyp3a4 and PXR proteins and histologic liver damage at 50 mg/kg/d and/or higher doses, while at the highest dose (150 mg/kg/d) with hepatic DNA damage and micronucleus formation in bone marrow polychromatic erythrocytes. The result of Pig-a assay (at 14 and 28 d) was negative. In Hepa1-6 cells EHDPP induced micronucleus marginally; however, this effect was enhanced by PCB 126, while abolished by BAY-218. This study suggests that EHDPP may enhance protein expression of hepatic Cyp1a1, Cyp2e1, AhR and PXR and induce liver damage and DNA/chromosome damage in mice; Cyp1a1 might be a major activating enzyme. Full article

Fish gut microbiota is essential for maintaining host physiological health but is constantly threatened by environmental chemicals. Diphenyl phosphate (DPhP), a major degradation product of organophosphate flame retardants and an environmental pollutant widely detected in aquatic ecosystems, is a chemical of emerging concern; however, few studies have addressed its effects on the gut microbiota. In this study, zebrafish were exposed to environmentally relevant concentrations of DPhP (0.8, 3.9, or 35.6 μg/L) from the embryonic stage to adulthood over 120 days. Using V3-V4 region 16S rRNA gene sequencing and functional gene prediction, we systematically analyzed the sex-specific responses of the gut microbiota. The results showed that life-cycle DPhP exposure exerts markedly different effects on the gut microbiota of male and female zebrafish. In females, DPhP induced concentration-dependent, stepwise Tax4Fun2 predicted functional shifts suggestive of compensation: at the low concentration (0.8 μg/L), energy metabolism and cofactor/vitamin metabolism functions were predicted to be enhanced; at the medium concentration (3.9 μg/L), Fusobacteria (mainly Cetobacterium ceti) became dominant, accompanied by structural remodeling; at the high concentration (35.6 μg/L), genetic information processing and amino acid biosynthesis pathways were upregulated, suggesting active substance synthesis. In contrast, the gut microbiota of male zebrafish did not exhibit significant changes in diversity but showed widespread predicted functional impairment. Core energy metabolism and cofactor/vitamin metabolism functions were significantly suppressed, while taxa associated with pro-inflammatory phyla (Proteobacteria, Verrucomicrobia) expanded. Functional compensation in males was limited to xenobiotic degradation and fatty acid metabolism, suggesting a potential pathological shift. These findings suggest a sex-differential response of DPhP from the perspective of the gut microbiota, providing new evidence for the environmental risk assessment of organophosphorus flame retardants. Full article

Organophosphorus esters (OPEs), widely utilized as flame retardants and plasticizers, are physically incorporated into those products and exhibit semi-volatility, resulting in release throughout their lifecycle. The ocean serves as a significant sink and plays a pivotal role in the global distribution and environmental fate of OPEs. However, the OPEs’ behavior and ecological effects in marine systems are not well understood. This review systematically examines recent advances in the sources, transport pathways, transformation mechanisms, and distributions of OPEs in the marine environment, and it also addresses current research limitations and suggests directions for future work. It is found that OPEs predominantly enter the marine environment through terrestrial input and in situ release; the transportation means include river input, long-range atmospheric transport, air–sea exchange, and oceanic circulation; and the degradation processes of OPEs are recognized as hydrolysis, photodegradation, and biodegradation. The distributions of OPEs in marine environments vary in different media, with their concentrations observed to range from pg m⁻³ to ng m⁻³ in marine air, ng L⁻¹ to hundreds of ng L⁻¹ in seawater, and pg g⁻¹ dw to ng g⁻¹ dw in sediments. The distributions of different species of OPEs are affected by many factors, such as compound properties, environmental conditions, and policy regulations. Comparisons between different regions and different seasons need to be further studied, and predictive models should be developed to better assess ecological risks and exposure pathways of OPEs. Full article

Organophosphorus flame retardants (OPFRs) are emerging alternatives to halogenated compounds, yet their environmental toxicity remains underexplored. This study evaluated the developmental toxicity of two aryl-OPFRs, triphenyl phosphate (TPP) and tricresyl phosphate (TCP), in zebrafish (Danio rerio) from 2 h to 5 days post fertilization (hpf–dpf). Survival, hatching rate, and malformations were assessed across concentrations of 250–1000 µg/L, alongside with gene expression analysis at 5 dpf (250 and 500 µg/L) targeting detoxification (ces2), immune responses (il1β, casp9), and epigenetic markers (dnmt1, dnmt3). In vitro enzymatic assays evaluated interactions of both aryl-OPFRs with carboxylesterase (CE) and acetylcholinesterase (AChE) enzymes. While no significant morphological effects were observed, TPP showed higher toxicity than TCP. Notably, TCP (500 µg/L) downregulated genes linked to metabolism and immunity. CE activity and ces2 modulation may suggest CE as a potential biomarker for aryl-OPFR exposure. These findings, although at concentrations above the environmental ones, may be valuable for mechanistic purposes and underscore the need for further investigation in developmental toxicity given their lipophilic nature and distinct molecular responses. Full article

Halogenated flame retardants have been amongst the most widely used and effective solutions for enhancing fire resistance. However, their use is currently strictly regulated due to serious health and environmental concerns. In this context, phosphorus-based and mineral flame retardants have emerged as promising alternatives. Despite this, their combined use is neither straightforward nor guaranteed to be effective. This study scrutinizes the interactions between these two classes of flame retardants (FR) through a systematic analysis aimed at elucidating the antagonistic pathways that arise from their coexistence. Specifically, this study focuses on two inorganic fillers, mineral huntite and chemically precipitated magnesium hydroxide, both of which produce basic oxides upon thermal decomposition. These fillers were incorporated into a poly(butylene terephthalate) (PBT) matrix to be utilized as advanced-mattress FR coating fabric and were subjected to a series of flammability tests. The pyrolysis products of the prepared polymeric composite compounds were isolated and thoroughly characterized using a combination of analytical techniques. Thermogravimetric analysis (TGA) and differential thermogravimetric analysis (dTGA) were employed to monitor decomposition behavior, while the char residues collected at different pyrolysis stages were examined spectroscopically, using FTIR-ATR and Raman spectroscopy, to identify their structure and the chemical reactions that led to their formation. X-ray diffraction (XRD) experiments were also conducted to complement the spectroscopic findings in the chemical composition of the resulting char residues and to pinpoint the different species that constitute them. The morphological changes of the char’s structure were monitored by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS). Finally, the Limited Oxygen Index (LOI) and UL94 (vertical sample mode) methods were used to assess the relative flammability of the samples, revealing a significant drop in flame retardancy when both types of flame retardants are present. This reduction is attributed to the neutralization of acidic phosphorus species by the basic oxides generated during the decomposition of the basic inorganic fillers, as confirmed by the characterization techniques employed. These findings underscore the challenge of combining organophosphorus with popular flame-retardant classes such as mineral or basic metal flame retardants, offering insight into a key difficulty in formulating next-generation halogen-free flame-retardant composite coatings. Full article

To understand the effect of the hydroxyl group and processing temperatures on dielectric losses of flame retardants and flame-retardant polymers, the performance difference between 6-methyldibenzo[c,e][1,2]oxaphosphinine 6-oxide (DOPO-Me) and 6-(hydroxymethyl)dibenzo[c,e][1,2]oxaphosphinine 6-oxide (DOPO-HM) has been investigated, respectively, in non-polar and polar polymers at 7–20 GHz. DOPO-HM and DOPO-Me differ by only one OH group. The former demonstrates a lower dissipation factor (Df) than the latter, owing to hydrogen bonds. In polystyrene and crosslinked polyphenylene oxide, both flame retardants increase a dielectric loss of flame-retardant polymers, with DOPO-HM being less detrimental because of its higher crystallizability and lower plasticization. In polar poly(methyl methacrylate) (PMMA), conformational changes in PMMA main chains caused by flame retardants and high processing temperatures lead to an early Df drop of PMMA at low loadings of the flame retardants. At high loadings, a change in the physical form of flame retardants from a primitive crystalline state to an amorphous state increases a dielectric loss of flame retardant PMMA, with DOPO-HM resulting in a slightly higher dielectric loss than DOPO-Me. These results prove that the effect of a hydroxyl group in organophosphorus structures on the dielectric loss of flame-retardant polymers is crucially dependent on its interaction with the polymer matrix. Full article

Polyurethane (PUR)-based artificial leathers are often used as interior materials in public area, making flame retardants (FRs) necessary. The mode of action of different FRs varies depending on the chemical class and the structure of the supplied material. Usually, FRs are designed for bulk materials like foams, e.g., for upholstery, the main application of PUR. However, in thin materials, FRs act differently, thus leaving the PUR without sufficient flame resistance. In this study, PUR films and artificial leathers were equipped with twelve commercially available, halogen-free FRs in various concentrations and combinations. Fire resistance was tested with LOI measurements, cone calorimetry, horizontal burning behavior, and thermogravimetric analyses. An organophosphorus FR proved to be the most suited for flame-resistant artificial leather. The LOI was increased from 20 to 24.2%, the peak heat release rate was reduced by about 30%, and the sample was self-extinguishing in horizontal burning behavior. Phosphinates and aluminum trihydroxide were the least efficient FRs. Combinations of bentonite with phosphorus-based FRs showed synergistic effects in reducing the probability of igniting the material. The results demonstrate that sufficient flame retardancy for PUR-based thin materials can be achieved with commercially available halogen-free FRs, paving the way for more sustainable and greener materials by substituting ecologically harmful and health-damaging FRs. Full article

Background/Objectives: It is estimated that gestational diabetes mellitus (GDM) affects approximately 14% of pregnant women. This is due to the inability of the body to produce enough insulin for gestation. With greater appearance during the second and third trimesters, GDM has a multifactorial cause including hypertension, cardiovascular issues (CVD), family history both or either type two diabetes mellitus (T2DM) or GDM, obesity, advanced maternal age, and polycystic ovarian syndrome (PCOS). However, it has been suggested that except for genetic predisposition, environmental factors can increase the risk of GDM development to a great extent. The aim of this systematic review and meta-analysis is the examination of different environmental contributors that play a significant role in the development of GDM. Methods: The databases used were PubMed and ScienceDirect. The inclusion criteria were a 10-year duration (2014–2024), English language, research articles, and only humans included. Afterwards, tables were created to summarize the most important information from each article. Forest and funnel plots were created to assess the possibility of a greatly significant difference between each environmental contributor. Results: Initially, 9361 articles were found. After the automation tools were applied, 706 were left. The total number of articles used in the study after the screening process was 26. Through the systematic review analysis, the following risk factors were stated to play a contributing role with GDM: extreme temperatures (both high and low), organophosphorus flame retardants (OFRs), bisphenol A (BPA), selenium (Se), metallic elements, urinary antimony (Sb), trace elements, thiamine and riboflavin, and fine particulate matter PM_2.5. Conclusions: Through this meta-analysis, it can be concluded that there is statistical significance for fine particulate matter PM_2.5, especially in the first (p < 0.001) and second (p < 0.001) trimesters, proving the acknowledged connection between PM_2.5 and GDM pathogenesis during pregnancy. Apart from that, fetal sex can play an important role in the development of GDM, as there is the greatest risk in males (p < 0.001), whereas no correlation between maternal smoking habit and bisphenol A with GDM was found. In conclusion, it can be stated that environmental factors can have a great impact on the development of GDM during the gestational period, but more studies must be carried out to reinforce our outcomes. Full article

Currently, postulated trends and law regulations tend to direct polymer technology toward sustainability and environmentally friendly solutions. These approaches are expressed by keeping materials in a loop aimed at the circular economy and by reducing the environmental burdens related to the production and use of polymers and polymer-based materials. The application of recycled or waste-based materials often deals efficiently with the first issue but at the expense of the final products’ performance, which requires various additives, often synthetic and petroleum-based, with limited sustainability. Therefore, a significant portion of research is often required to address the drawbacks induced by the application of secondary raw materials. Herein, the presented study aimed to investigate the fire performance of polymer composites containing highly flammable matrix polyurethane (PU) foam and filler ground tire rubber (GTR) originating from car tire recycling. Due to the nature of both phases and potential applications in the construction and building or automotive sectors, the flammability of these composites should be reduced. Nevertheless, this issue has hardly been analyzed in literature and dominantly in our previous works. Herein, the presented work provided the next step and investigated the input of nanoclays to the synergistic flammability reduction in flexible, foamed PU/GTR composites. Hybrid compositions of organophosphorus FRs with expandable graphite (EG) in varying proportions and with the addition of surface-modified nanoclays were examined. Changes in the parameters obtained during cone calorimeter tests were determined, discussed, and evaluated with the fire performance index and flame retardancy index, two parameters whose goal is to quantify the overall fire performance of polymer-based materials. Full article

Jute is an inherent lignocellulosic fiber, consisting of hemicellulose, α-cellulose, and lignin. Industrial ventilation, automotive composites, upholstery, carpets, military uniforms, hospital furnishings, and curtains necessitate the integration of flame-retardance properties into jute fibers. In this investigation, seven weave-structured jute fabrics were treated using an organophosphorus-based flame-retardant (FR) chemical (ITOFLAM CPN) and a crosslinking agent (KNITTEX CHN) by the pad–dry–cure method. The thermal stability, degradation and pyrolysis behavior of jute was measured using a thermogravimetric analyzer (TGA). Surface morphology and element distribution were scrutinized utilizing a scanning electron microscope (SEM) and an energy-dispersive spectrometer (EDS). The ATR-FTIR (Attenuated Total Reflection-Fourier Transform Infrared Spectrometer) technique has been employed for analyzing the composition of chemicals in the jute fabrics. According to the protocols specified in ISO 14184-1, free formaldehyde detection was carried out on the jute fabrics. The flame-retardance property was significantly improved on all of the jute fabrics after FR treatment. FTIR and SEM-EDS studies revealed the presence of FR chemical deposition on the surface of the jute fabrics. TGA analysis indicated that the fabrics treated with FR exhibited premature degradation, leading to the generation of more char compared to untreated samples. The jute fabrics specifically demonstrated a notable enhancement in residual mass, exceeding 50% after FR treatment. However, it is noteworthy that the FR-treated fabrics exhibited an elevated level of free formaldehyde content, surpassing the permissible limit of formaldehyde in textiles intended for direct skin contact. The residual mass loss percentage after ten washes of FR-treated fabrics remained in a range from 32% to 36%. Twill weave designed fabrics (FRD4 and FRD5) clearly showed a lower thermal degradation temperature than the other weaves used in this study. Full article

The aim of the research was to investigate the influence of calcium phosphinate (HPCA) and aluminum phosphinate (HPAL) in synergistic systems with organophosphorus compounds, i.e., diphenylcresyl phosphate (CDP) and trichloropropyl phosphate (TCPP), on the thermal stability, flammability, smoke density, and emission of toxic gases during the thermal decomposition of polyurethane (PUR) foams. Thermogravimetric analysis (TGA), along with cone calorimetry and microcalorimetry, were used to assess the influence of fillers on the thermal stability and flammability of PUR foams. The analysis of toxic gas products was performed with the use of a coupled TG–gas analyzer system. The optical density of gases was measured with the use of a smoke density chamber (SDC). The obtained results showed an increase in thermal stability and a decrease in the flammability of the PUR composites. However, the results regarding smoke and gas emissions, as well as toxic combustion by-products, present ambiguity. On one hand, the applied flame retardant systems in the form of PUR-HPCA-CDP and PUR-HPCA-TCPP led to a reduction in the concentration of CO and HCN in the gas by-products. On the other hand, they clearly increased the concentration of CO₂, NOx, and smoke emissions. Microbiological studies indicated that the obtained foam material is completely safe for use and does not exhibit biocidal properties. Full article

Organophosphorus flame retardants (OPFRs) are abundant and persistent in the environment but have limited toxicity information. Their similarity in structure to organophosphate pesticides presents great concern for developmental neurotoxicity (DNT). However, current in vivo testing is not suitable to provide DNT information on the amount of OPFRs that lack data. Over the past decade, an in vitro battery was developed to enhance DNT assessment, consisting of assays that evaluate cellular processes in neurodevelopment and function. In this study, behavioral data of small model organisms were also included. To assess if these assays provide sufficient mechanistic coverage to prioritize chemicals for further testing and/or identify hazards, an integrated approach to testing and assessment (IATA) was developed with additional information from the Integrated Chemical Environment (ICE) and the literature. Human biomonitoring and exposure data were identified and physiologically-based toxicokinetic models were applied to relate in vitro toxicity data to human exposure based on maximum plasma concentration. Eight OPFRs were evaluated, including aromatic OPFRs (triphenyl phosphate (TPHP), isopropylated phenyl phosphate (IPP), 2-ethylhexyl diphenyl phosphate (EHDP), tricresyl phosphate (TMPP), isodecyl diphenyl phosphate (IDDP), tert-butylphenyl diphenyl phosphate (BPDP)) and halogenated FRs ((Tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), tris(2-chloroethyl) phosphate (TCEP)). Two representative brominated flame retardants (BFRs) (2,2′4,4′-tetrabromodiphenyl ether (BDE-47) and 3,3′,5,5′-tetrabromobisphenol A (TBBPA)) with known DNT potential were selected for toxicity benchmarking. Data from the DNT battery indicate that the aromatic OPFRs have activity at similar concentrations as the BFRs and should therefore be evaluated further. However, these assays provide limited information on the mechanism of the compounds. By integrating information from ICE and the literature, endocrine disruption was identified as a potential mechanism. This IATA case study indicates that human exposure to some OPFRs could lead to a plasma concentration similar to those exerting in vitro activities, indicating potential concern for human health. Full article

Organic phosphoester (OPE) antioxidants are currently required due to their contribution to enhancing the quality of polymers, including polypropylene (PP). In this research, an integral methodology is presented for the efficient extraction of bis(2,4-dicumylphenyl) pentaerythritol diphosphite from industrial wastewater. Upon employing the solid-phase extraction (SPE) technique, the recovered compound is subjected to a comprehensive analysis of the recovered compound using high-performance liquid chromatography (HPLC), mass spectrometry (MS), thermal analysis (TGA), Fourier transforms infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC). Subsequently, purified Bis(2,4-dicumylphenyl) pentaerythritol diphosphite was evaluated as a thermo-oxidative stabilizer after incorporation into PP resins. The relative standard deviation (RSD), Error (Er), linearity (R²), and percentage (%) recovery were less than 2.6, 2.5, more significant than 0.9995, and greater than 96%, respectively, for the inter-day and intra-day tests of the chromatographic method and the SPE. Except for chloroform, which was necessary due to the solubility properties of the investigated analyte, the use of environmentally friendly solvents, such as methanol and acetonitrile, was considered during the development of this research. The OPE extracted from industrial wastewater was characterized by FTIR, UV–Vis, DSC, TGA, and MS, allowing the elucidation of the structure of Bis(2,4-dicumylphenyl) pentaerythritol diphosphite (BDPD). The recovered OPE was mixed with PP resins, allowing it to improve its thermal properties and minimize its thermo-oxidative degradation. Organophosphorus flame retardant (OPE)’ concentration in wastewater is alarming, ranging from 1179.0 to 4709.6 mg L⁻¹. These exceed toxicity thresholds for aquatic organisms, emphasizing global environmental risks. Using a validated solid-phase extraction (SPE) technique with over 94% recovery, the study addresses concerns by removing organic contaminants and supporting circular economy principles. The high economic and environmental significance of recovering BDPD underscores the need for urgent global attention and intervention. Full article

Understanding the interplay among organophosphorus flame retardants (OPFRs), microplastics, and freshwater organisms is crucial for unravelling the dynamics within freshwater environments and foreseeing the potential impacts of organic pollutants and plastic contamination. For that purpose, the present research assessed the exposure impact of 10 mg L⁻¹ flame-retardant aluminium diethylphosphinate (ALPI), 10 μg mg⁻¹_liver microplastics polyurethane (PU), and the combination of ALPI and PU on the freshwater planarian Girardia tigrina. The exposure to both ALPI and PU revealed a sequential effect, i.e., a decrease in locomotor activity, while oxidative stress biomarkers (total glutathione, catalase, glutathione S-transferase, lipid peroxidation) and metabolic responses (cholinesterase activity, electron transport system, and lactate dehydrogenase) remained unaffected. Despite this fact, it was possible to observe that the range of physiological responses in exposed organisms varied, in particular in the cases of the electron transport system, cholinesterase activity, glutathione S-transferase, catalase, and levels of total glutathione and proteins, showing that the energetic costs for detoxification and antioxidant capacity might be causing a lesser amount of energy allocated for the planarian activity. By examining the physiological, behavioural, and ecological responses of planarians to these pollutants, insights can be gained into broader ecosystem-level effects and inform strategies for mitigating environmental risks associated with OPFRs and microplastic pollution in freshwater environments. Full article

Cyclodextrins (CDs) were used as green char promoters in the formulation of organophosphorus flame retardants (OPFRs) for polymeric materials, and they could reduce the amount of usage of OPFRs and their release into the environment by forming [host:guest] inclusion complexes with them. Here, we report a systematic study on the inclusion complexes of natural CDs (α-, β-, and γ-CD) with a representative OPFR of DOPO using computational methods of molecular docking, molecular dynamics (MD) simulations, and quantum mechanical (QM) calculations. The binding modes and energetics of [host:guest] inclusion complexes were analyzed in details. α-CD was not able to form a complete inclusion complex with DOPO, and the center of mass distance [host:guest] distance amounted to 4–5 Å. β-CD and γ-CD allowed for a deep insertion of DOPO into their hydrophobic cavities, and DOPO was able to frequently change its orientation within the γ-CD cavity. The energy decomposition analysis based on the dispersion-corrected density functional theory (sobEDAw) indicated that electrostatic, orbital, and dispersion contributions favored [host:guest] complexation, while the exchange–repulsion term showed the opposite. This work provides an in-depth understanding of using CD inclusion complexes in OPFRs formulations. Full article