Organophosphate Flame Retardants Research Articles

Global Trends and Hotspots in Research on the Health Risks of Organophosphate Flame Retardants: A Bibliometric and Visual Analysis

Background: Organophosphate flame retardants (OPFRs) are compounds with a wide range of industrial and commercial applications and are mainly used as flame retardants and plasticizers. The global consumption of OPFRs has risen rapidly in recent decades, and they have been widely detected in environmental media. Unfortunately, OPFRs have been associated with many adverse health outcomes. The issue of the health risks of OPFRs is attracting increasing attention. Therefore, there is a need to review the current state of research and trends in this field to help researchers and policymakers quickly understand the field, identify new research directions, and allocate appropriate resources for further development of the OPFR health risk research field. Methods: This study statistically analyzed 1162 relevant publications included in the Web of Science Core Collection from 2003–2023. The internal and external features of the literature, such as publication trends, countries, authors, journals, and keywords, were quantitatively analyzed and visually presented to identify the research hotspots, compositions, and paradigms of the field and to horizontally and vertically analyze the development trends and structural evolution of the field. Results: The development of the field can be divided into three stages, and the field entered a period of rapid development in 2016. China (649 papers) is the most prolific country, followed by the United States (188 papers). The authors STAPLETON HM and WANG Y have the highest combined impact. International collaboration between countries and researchers still needs to be strengthened. Science of The Total Environment is the most frequently published journal (162 papers), and Environmental Science and Technology is the most frequently cited journal (5285 citations). Endocrine disruption, developmental toxicity, and neurotoxicity are the health effects of greatest interest. Conclusions: Future research is expected to be multidisciplinary, and research hotspots may involve a comprehensive assessment of OPFR exposure in the population, exploration of the mechanisms of endocrine-disrupting effects and in vivo metabolic processes, and examination of the health effects of OPFR metabolites.

GC/MS-Based Metabolomic Analysis of A549 Cells Exposed to Emerging Organophosphate Flame Retardants

Emerging organophosphate flame retardants (eOPFRs) have attracted attention in recent times and are expected to gain extensive usage in the coming years. However, they may have adverse effects on organisms. Due to their novel nature, there are few relevant articles dealing with toxicological studies of the above eOPFRs, especially their information on the perturbation of cellular metabolism, which is, thus far, marginally understood. Our research initially assessed the cytotoxicity of eOPFRs, which include compounds like cresyl diphenyl phosphate (CDP), resorcinol bis(diphenyl phosphate) (RDP), triallyl phosphate (TAP), and pentaerythritol phosphate alcohol (PEPA). This evaluation was conducted using the methyl thiazolyl tetrazolium (MTT) assay. Subsequently, we utilized a gas chromatography/mass spectrometry (GC/MS)-based metabolomic approach to investigate the metabolic disruptions induced by these four eOPFRs in A549 cells. The MTT results showed that, at high concentrations of 1 mM, their cytotoxicity was ranked as CDP > TAP > RDP > PEPA. In addition, metabolic studies at low concentrations of 10 μM showed that the metabolic interference of CDP, TAP, and PEPA focuses on oxidative stress, amino acid metabolism, and energy metabolism, while RDP mainly affects energy metabolism—galactose metabolism and gluconeogenesis. Therefore, from the perspective of cytotoxicity and metabolic analysis, RDP may be a more promising alternative. Our experiments provide important insights into the possible metabolic effects of potential toxic substances and complement the evidence on the human health risks of eOPFRs.

Occurrence, Fate, and Mass Balance Analysis of Organophosphate Flame Retardants in a Municipal Wastewater Treatment Plant in Hunan Province, China

The occurrence, distribution, removal, and mass loadings of common organophosphate flame retardants (OPFRs) in an advanced municipal wastewater treatment plant (WWTP) were comprehensively investigated. The OPFRs were mainly partitioning in the dissolved phase, and the total concentrations ranged from 1364 to 1701 ng/L in influent, 678~1064 in effluent, and 177~470 ng/g dw in residual sludge. Tributoxyethyl phosphate and tris(2-chloroethyl) phosphate were the abundant compounds in both the dissolved phase and adsorbed phase. The removal frequencies and mechanisms of the OPFRs were highly associated with the properties of compounds. According to the mass balance analysis, 14.9%, 13.0%, and 11.2% of the total OPFR loads were removed in the traditional treatment, tertiary treatment, and to the sludge, respectively. The mass loadings and environmental emissions of the OPFRs were 0.67~291 μg/d/person and 0.57~107 μg/d/person, respectively. The effluent discharged from the WWTP posed ecological risks to the receiving river, which requires being paid more attention.

OPFR removal by white rot fungi: screening of removers and approach to the removal mechanism

The persistent presence of organophosphate flame retardants (OPFRs) in wastewater (WW) effluents raises significant environmental and health concerns, highlighting the limitations of conventional treatments for their remotion. Fungi, especially white rot fungi (WRF), offer a promising alternative for OPFR removal. This study sought to identify fungal candidates (from a selection of four WRF and two Ascomycota fungi) capable of effectively removing five frequently detected OPFRs in WW: tributyl phosphate (TnBP), tributoxy ethyl phosphate (TBEP), trichloroethyl phosphate (TCEP), trichloro propyl phosphate (TCPP) and triethyl phosphate (TEP). The objective was to develop a co-culture approach for WW treatment, while also addressing the utilization of less assimilable carbon sources present in WW. Research was conducted on carbon source uptake and OPFR removal by all fungal candidates, while the top degraders were analyzed for biomass sorption contribution. Additionally, the enzymatic systems involved in OPFR degradation were identified, along with toxicity of samples after fungal contact. Acetate (1.4 g·L-1), simulating less assimilable organic matter in the carbon source uptake study, was eliminated by all tested fungi in 4 days. However, during the initial screening where the removal of four OPFRs (excluding TCPP) was tested, WRF outperformed Ascomycota fungi. Ganoderma lucidum and Trametes versicolor removed over 90% of TnBP and TBEP within 4 days, with Pleorotus ostreatus and Pycnoporus sanguineus also displaying effective removal. TCEP removal was challenging, with only G. lucidum achieving partial removal (47%). A subsequent screening with selected WRF and the addition of TCPP revealed TCPP’s greater susceptibility to degradation compared to TCEP, with T. versicolor exhibiting the highest removal efficiency (77%). This observation, plus the poor degradation of TEP by all fungal candidates suggests that polarity of an OPFR inversely correlates with its susceptibility to fungal degradation. Sorption studies confirmed the ability of top-performing fungi of each selected OPFR to predominantly degrade them. Enzymatic system tests identified the CYP450 intracellular system responsible for OPFR degradation, so reactions of hydroxylation, dealkylation and dehalogenation are possibly involved in the degradation pathway. Finally, toxicity tests revealed transformation products obtained by fungal degradation to be more toxic than the parent compounds, emphasizing the need to identify them and their toxicity contributions. Overall, this study provides valuable insights into OPFR degradation by WRF, with implications for future WW treatment using mixed consortia, emphasizing the importance of reducing generated toxicity.

Rapid and Comprehensive Analysis of 41 Harmful Substances in Multi-Matrix Products by Gas Chromatography-Mass Spectrometry Using Matrix-Matching Calibration Strategy.

Harmful substances in consumer goods pose serious hazards to human health and the environment. However, due to the vast variety of consumer goods and the complexity of their substrates, it is difficult to simultaneously detect multiple harmful substances in different materials. This paper presents a method for the simultaneous determination of 41 harmful substances comprising 17 phthalates (PAEs), 8 organophosphate flame retardants (OPFRs), and 16 polycyclic aromatic hydrocarbons (PAHs) in five types of products using the matrix-matching calibration strategy. The method employs an efficient ultrasonic extraction procedure using a mixture of dichloromethane and methylbenzene, followed by dissolution-precipitation and analysis through gas chromatography-mass spectrometry. Compared with previous experiments, we established a universal pretreatment method suitable for multi-matrix materials to simultaneously determine multiple harmful substances. To evaluate the effects of the matrix on the experimental results, we compared neat standard solutions and matrix-matching standard solutions. The results demonstrated that all compounds were successfully separated within 30 min with excellent separation efficiency. Additionally, the linear relationships of all analytes showed strong correlation coefficients (R2) of at least 0.995, ranging from 0.02 mg/L to 20 mg/L. The average recoveries of the target compounds (spiked at three concentration levels) were between 73.6 and 124.1%, with a relative standard deviation (n = 6) varying from 1.2% to 9.9%. Finally, we tested 40 different materials from consumer products and detected 16 harmful substances in 31 samples. Overall, this method is simple and accurate, and it can be used to simultaneously determine multiple types of hazardous substances in multi-matrix materials by minimizing matrix effects, making it an invaluable tool for ensuring product safety and protecting public health.

Dust dynamics: distribution patterns of semi-volatile organic chemicals across particle sizes in varied indoor microenvironments.

An extensive analysis of the distribution patterns of three distinct classes of semi-volatile organic chemicals (SVOCs)-phthalates (PAEs), organophosphate flame retardants (OPFRs), and polycyclic aromatic hydrocarbons (PAHs)-across four distinct size fractions of dust (25, 50, 100, and 200μm) was conducted. The dust samples were sourced from AC filter, covered car parking lots, households, hotels, mosques, and car floors. To generate the four fractions, ten dust samples from each microenvironment were pooled and sieved utilizing sieving apparatus with the appropriate mesh size. Selected SVOCs were quantified utilizing gas chromatography-mass spectrometry in electron impact (EI) mode. Results unveiled diverse contamination levels among dust fractions, showcasing car parking lot dust with the lowest chemical contamination, while car floor dust displayed the highest levels of PAHs and OPFRs, peaking at 28.3µg/g and 43.2µg/g, respectively. In contrast, mosque and household floor dust exhibited the highest concentrations of phthalates, with values of 985µg/g and 846µg/g, respectively. Across the analyzed microenvironments, we observed a trend where concentrations of SVOCs tended to rise as dust particles decreased in size, forming a visually striking pattern. This phenomenon was particularly pronounced in dust samples collected from car floors and parking lots. Among SVOCs, PAEs emerged as the predominant contributors with > 90% followed by OPFRs and PAHs. The high levels of OPFRs in car floor dust align logically with the fact that numerous interior components of cars are treated with OPFRs, within a compact indoor microenvironment, to comply to fire safety regulations. Furthermore, petroleum products are a major source of PAHs in the environment and all the sampled cars in the study had combustion engines. Consequently, car dust is more likely to be polluted with PAHs stemming from petroleum combustion. Although previous investigations have noted an increase in heavy metals and brominated flame retardants with decreasing dust particles, this is the first study analyzing these SVOCs in different fractions of dust from various microenvironments. However, aside from two specific microenvironments, the observed pattern of escalating SVOC concentrations with smaller dust particle sizes was not corroborated among the examined microenvironments. This divergence in concentration trends suggests the potential involvement of supplementary variables in influencing SVOC distributions within dust particles.

Occurrence and seasonal variations of organophosphate flame retardants in air and dust from college microenvironments at Qingdao, China: Implications for student's exposure and risk assessment

Organophosphorus flame retardants (OPFRs) are widely used as alternatives to brominated flame retardants in a variety of consumer products and their consumption has continuously increased in recent years. However, their concentration and human exposure in indoor microenvironments, particularly in a college environment, have received limited attention. In this study, the concentration and seasonal variation of 15 OPFRs were assessed in microenvironments typical of college students, including dormitories, offices, public microenvironments (PMEs: classroom, dining hall, gymnasium and library), and laboratories in two universities on the northern coast of China.Analysis of the OPFRs in both air and dust samples indicated widespread distribution on college campuses. The concentration of OPFRs in the winter (12,774.4 ng/g and 5.3 ng/m3 for dust and air, respectively) was higher than in the summer (2460.4 g/g and 4.6 ng/m3 for dust and air, respectively). The dust and air samples collected from PMEs and laboratories exhibited higher concentrations of OPFRs, followed by offices and dormitories. An equilibrium was reached between dust and air in all collected microenvironments. TBOEP, TDCP, and TPHP were more likely to partition in dust, while TEP, TIPP, TCEP, and TCPP were more likely to be in the air. The daily intakes of OPFRs were significantly lower than the reference dose. Dust ingestion was the primary intake pathway in the winter, while inhalation and dust ingestion were the main intake pathways in the summer. The non-carcinogenic hazard quotients fell within the range of 10−7–10−3 in both the summer and winter, which are below the theoretical risk threshold. For the carcinogenic risk, the LCR values ranged from 10−10 to 10−8, indicating no elevated carcinogenic risk due to TnBP, TCEP, and TDCP in indoor dust and air.

Eco-toxicological and climate change effects of sludge thermal treatments: Pathways towards zero pollution and negative emissions

The high moisture content and the potential presence of hazardous organic compounds (HOCs) and metals (HMs) in sewage sludge (SS) pose technical and regulatory challenges for its circular economy valorisation. Thermal treatments are expected to reduce the volume of SS while producing energy and eliminating HOCs. In this study, we integrate quantitative analysis of SS concentration of 12 HMs and 61 HOCs, including organophosphate flame retardants (OPFRs) and per- and poly-fluoroalkyl substances (PFAS), with life-cycle assessment to estimate removal efficiency of pollutants, climate change mitigation benefits and toxicological effects of existing and alternative SS treatments (involving pyrolysis, incineration, and/or anaerobic digestion). Conventional SS treatment leaves between 24 % and 40 % of OPFRs unabated, while almost no degradation occurs for PFAS. Thermal treatments can degrade more than 93% of target OPFRs and 95 % of target PFAS (with the rest released to effluents). The different treatments affect how HMs are emitted across environmental compartments. Conventional treatments also show higher climate change impacts than thermal treatments. Overall, thermal treatments can effectively reduce the HOCs emitted to the environment while delivering negative emissions (from about −56 to −111 kg CO2-eq per tonne of sludge, when pyrolysis is involved) and producing renewable energy from heat integration and valorization.

Organophosphorus Flame Retardant TPP-Induced Human Corneal Epithelial Cell Apoptosis through Caspase-Dependent Mitochondrial Pathway.

A widely used organophosphate flame retardant (OPFR), triphenyl phosphate (TPP), is frequently detected in various environmental media and humans. However, there is little known on the human corneal epithelium of health risk when exposed to TPP. In this study, human normal corneal epithelial cells (HCECs) were used to investigate the cell viability, morphology, apoptosis, and mitochondrial membrane potential after they were exposed to TPP, as well as their underlying molecular mechanisms. We found that TPP decreased cell viability in a concentration-dependent manner, with a half maximal inhibitory concentration (IC50) of 220 μM. Furthermore, TPP significantly induced HCEC apoptosis, decreased mitochondrial membrane potential in a dose-dependent manner, and changed the mRNA levels of the apoptosis biomarker genes (Cyt c, Caspase-9, Caspase-3, Bcl-2, and Bax). The results showed that TPP induced cytotoxicity in HCECs, eventually leading to apoptosis and changes in mitochondrial membrane potential. In addition, the caspase-dependent mitochondrial pathways may be involved in TPP-induced HCEC apoptosis. This study provides a reference for the human corneal toxicity of TPP, indicating that the risks of OPFR to human health cannot be ignored.

Personal environmental exposure to plasticizers and organophosphate flame retardants using silicone wristbands and urine: Patterns, comparisons, and correlations

Plasticizers (PLs) and organophosphate flame retardants (OPFRs) are ubiquitous in the environment due to their widespread use and potential for leaching from consumer products. Environmental exposure is a critical aspect of the human exposome, revealing complex interactions between environmental contaminants and potential health effects. Silicone wristbands (SWBs) have emerged as a novel and non-invasive sampling device for assessing personal external exposure. In this study, SWBs were used as a proxy to estimate personal dermal adsorption (EDdermal) to PLs and OPFRs in Belgian participants for one week; four morning urine samples were also collected and analyzed for estimated daily intake (EDI). The results of the SWBs samples showed that all the participants were exposed to these chemicals, and the exposure was found to be highest for the legacy and alternative plasticizers (LP and AP), followed by the legacy and emerging OPFRs (LOPFR and EOPFR). In urine samples, the highest levels were observed for metabolites of diethyl phthalate (DEP), di-isobutyl phthalate (DiBP) and di-n-butyl phthalate (DnBP) among LPs and di(2-ethylhexyl) terephthalate (DEHT) for APs. Outliers among the participants indicated that there were other sources of exposure that were not identified. Results showed a significant correlation between EDdermal and EDI for DiBP, tris (2-butoxyethyl) phosphate (TBOEP) and triphenyl phosphate (TPhP). These correlations indicated their suitability for predicting exposure via SWB monitoring for total chemical exposure. The results of this pilot study advance our understanding of SWB sampling and its relevance for predicting aggregate environmental chemical exposures, while highlighting the potential of SWBs as low-cost, non-invasive personal samplers for future research. This innovative approach has the potential to advance the assessment of environmental exposures and their impact on public health.

Pervasive environmental chemicals impair oligodendrocyte development.

Exposure to environmental chemicals can impair neurodevelopment, and oligodendrocytes may be particularly vulnerable, as their development extends from gestation into adulthood. However, few environmental chemicals have been assessed for potential risks to oligodendrocytes. Here, using a high-throughput developmental screen in cultured cells, we identified environmental chemicals in two classes that disrupt oligodendrocyte development through distinct mechanisms. Quaternary compounds, ubiquitous in disinfecting agents and personal care products, were potently and selectively cytotoxic to developing oligodendrocytes, whereas organophosphate flame retardants, commonly found in household items such as furniture and electronics, prematurely arrested oligodendrocyte maturation. Chemicals from each class impaired oligodendrocyte development postnatally in mice and in a human 3D organoid model of prenatal cortical development. Analysis of epidemiological data showed that adverse neurodevelopmental outcomes were associated with childhood exposure to the top organophosphate flame retardant identified by our screen. This work identifies toxicological vulnerabilities for oligodendrocyte development and highlights the need for deeper scrutiny of these compounds' impacts on human health.

Bioactivity assessment of organophosphate flame retardants via a dose-dependent yeast functional genomics approach

Organophosphate flame retardants (OPFRs) have been widely detected in multiple environment media and have many adverse effects with complex toxicity mechanisms. However, the early molecular responses to OPFRs have not been fully elucidated, thereby making it difficult to assess their risks accurately. In this work, we systematically explored the point of departure (POD) of biological pathways at genome-wide level perturbed by 14 OPFRs with three substituents (alkyl, halogen, and aryl) using a dose-dependent functional genomics approach in Saccharomyces cerevisiae at 24 h exposure. Firstly, our results demonstrated that the overall biological potency at gene level (PODDRG20) ranged from 0.013 to 35.079 μM for 14 OPFRs, especially the tributyl phosphate (TnBP) exhibited the strongest biological potency with the least PODDRG20. Secondly, we found that structural characteristics of carbon number and logKow were significantly negatively correlated with POD, and carbon number and logKow also significantly affected lipid metabolism associated processes. Thirdly, these early biological pathways of OPFRs toxification were found to be involved in lipid metabolism, oxidative stress, DNA damage, MAPK signaling pathway, and amino acid and carbohydrate metabolism, among which the lipid metabolism was the most sensitive molecular response perturbed by most OPFRs. More importantly, we identified one resistant mutant strain with knockout of ERG2 (YMR202W) gene participated in steroid biosynthesis pathway, which can serve as a key yeast strain of OPFRs toxification. Overall, our study demonstrated an effective platform for accurately assessing OPFRs risks and provided a basis for further green OPFRs development.

Association between organophosphate flame retardant exposure and lipid metabolism: data from the 2013-2014 National Health and Nutrition Examination Survey.

Organophosphate flame retardants (OPFRs) are emerging environmental pollutants that can be detected in water, dust, and biological organisms. Certain OPFRs can disrupt lipid metabolism in animal models and cell lines. However, the effects of OPFRs on human lipid metabolism remain unclear. We included 1,580 participants (≥20 years) from the 2013-2014 National Health and Nutrition Examination Survey (NHANES) to explore the relationship between OPFR exposure and lipid metabolism biomarkers. After adjusting for confounding factors, results showed that one-unit increases in the log levels of diphenyl phosphate (DPhP) (regression coefficient = -5.755; S.E. = 2.289; p = 0.023) and log bis-(1-chloro-2-propyl) phosphate (BCPP) (regression coefficient = -4.637; S.E. = 2.019; p = 0.036) were negatively associated with the levels of total cholesterol (TC) in all participants. One-unit increases in the levels of DPhP (regression coefficient = -2.292; S.E. = 0.802; p = 0.012), log bis (1,3-dichloro-2-propyl) phosphate (BDCPP) (regression coefficient = -2.046; S.E. = 0.825; p = 0.026), and log bis-2-chloroethyl phosphate (BCEP) (regression coefficient = -2.604; S.E. = 0.704; p = 0.002) were negatively associated with the levels of high-density lipoprotein cholesterol (HDL-C). With increasing quartiles of urine BDCPP levels, the mean TC levels significantly decreased in all participants (p value for trend = 0.028), and quartile increases in the levels of DPhP (p value for trend = 0.01), BDCPP (p value for trend = 0.001), and BCEP (p value for trend<0.001) were negatively corelated with HDL-C, with approximately 5.9, 9.9, and 12.5% differences between the upper and lower quartiles. In conclusion, DPhP, BDCPP, and BCEP were negatively related to HDL-C concentration, whereas DPhP and BCPP levels were negatively associated with TC level. Thus, exposure to OPFRs may interfere with lipid metabolism.

Semi-volatile organic compounds and trace metals in air cleaner captured house dust

Semi-volatile organic compounds (SVOCs) and trace metals are found anywhere in indoor environments. This study aimed to characterize phthalates, alternative plasticizers (APs), organophosphate flame retardants (OPFRs), and trace metals in air cleaner-captured house dust (ACCD) and to identify the determinants of contaminant levels in ACCD. In total, 120 ACCD samples were collected from 120 houses in Korea that had used air cleaners for over 1 year. All study participants completed a housing, behavior, and lifestyle-related factors questionnaire. The samples were analyzed for 16 phthalates, five APs, 18 OPFRs, and seven trace metals. There were seven chemicals in phthalates, three in APs, and in OPFRs, with 80 % or more detection rates. None of trace metals were found with the detection rate above 65 %. Among the three chemical groups, phthalates were detected at the highest concentrations (geometric mean [GM] (geometric standard deviation [GSD]): 575 (4.6) μg/g in total), followed by APs (389 (5.3) μg/g in total) and OPFRs (290 (3.6) μg/g in total). Among the trace metals, lead and manganese in the ACCD showed the highest concentrations (GM (GSD): 24.8 (8.1) and 24.2 (7.6) μg/g, respectively) with a detection rate of ∼60 %, followed by arsenic (2.9 (17.7) μg/g). The phthalates and Aps measured in the ACCD were comparable to those found in previous investigations of settled dust collected from houses in Korea. Butylbenzyl phthalate and acetyl tributyl citrate concentrations were significantly higher in homes with diffusers, and di-isobutyl phthalate concentrations were higher in homes with air fresheners(p ≤ 0.05). No other determinants were associated with contaminant levels. As residents are persistently exposed to these ubiquitous contaminants through inhalation, appropriate measures are required to reduce potential exposures.

The flame retardant triphenyl phosphate alters the epigenome of embryonic cells in an aquatic in vitro model.

Triphenyl phosphate (TPhP) is an organophosphate flame retardant and plasticizer that is added to a wide variety of consumer and industrial products. It is also a ubiquitous environmental pollutant. Exposure to TPhP has been shown to alter gene expression in metabolic and estrogenic signaling pathways in in vitro and in vivo models of a variety of species, and as such, is considered to be an endocrine disrupting chemical. Exposure to endocrine disrupting chemicals is increasingly being associated with changes to the epigenome, especially during embryonic development. The aim of this study was to evaluate whether TPhP exposure in aquatic ecosystems has the ability to alter the epigenome in two immortal cell lines derived from trout (Oncorhynchus mykiss). This study assessed whether 24 h exposure to TPhP resulted in changes to histone modification and DNA methylation profiles in steelhead trout embryonic cells and rainbow trout gill epithelial cells. Results show that several epigenetic modifications on histone H3 and DNA methylation are altered in the embryonic cells following TPhP exposure, but not in the gill epithelial cells. Specifically, histone H3 acetylation, histone H3 mono-methylation and global DNA methylation were found to be reduced. The alterations of these epigenetic modification profiles in the embryonic cells suggest that exposure to TPhP during fetal development may alter gene expression in the developing embryo, likely in metabolic and estrogenic pathways. The impacts to the epigenome determined in this study may even carry multigenerational detrimental effects on human and ecosystem health, which requires further investigation.

Efficient Discrimination of Hazardous Organophosphate Flame Retardants via Cataluminescence-Based Multidimensional Ratiometric Sensing.

Emerging contaminants have recently evolved into a severe worldwide environmental issue. Organophosphate flame retardants (OPFRs) with neurotoxicity, genotoxicity, and reproductive and developmental toxicity are a class of notorious emerging contaminants that cause great concern. The development of high-efficiency and portable sensors for rapid online monitoring of OPFRs has become the primary demand for the exploration of the environmental migration and transformation of OPFRs. In this work, interestingly, the cataluminescence (CTL) phenomenon of OPFRs is first observed, and an ingenious multidimensional ratiometric CTL sensing strategy is developed for the recognition of multiple OPFRs. Three characteristic ratios are extracted from the multipeak CTL spectral curves based on energy transfer of single Tb/Eu-modified MgO sensing material, and thus a novel three-dimensional (3D) code recognition could be mapped out. This obtained 3D coordinate is found to be a unique characteristic for a given OPFR, just like an exclusive person's ID number, which can successfully discriminate and detect 10 kinds of OPFR vapors, including homologous series and isomers. More importantly, CTL mechanism investigations for OPFRs demonstrate that OPFRs undergo a series of chemical reaction processes, e.g., oxidative pyrolysis and hydroxylation, and different high-energy excited intermediates are generated, which trigger discrepant energy-transfer efficiency toward rare earth ions, leading to multipeak spectral profiles. Briefly, this proposed CTL analytical platform for OPFRs recognition initiates a new sensing principle for the efficient identification of emerging contaminants and shows significant prospects on rapid on-site detection.

Investigation of alkyl, aryl, and chlorinated OPFRs in sediments from estuarine systems: Seasonal variation, spatial distribution and ecological risks assessment

Estuaries in South Africa are very important for biodiversity conservation and serve as focal points for leisure and tourism activities. The organophosphate flame retardants (OPFRs) levels in these aquatic systems haven't been documented in any studies as of yet. Due to the negative effects of persistent organic pollutants in South African estuaries, we examined the occurrence of eight OPFRs in sediments of two estuaries by studying their spatiotemporal distribution, season variation, and ecological risks. The Sundays Estuary (SDE), a semi-urbanized agricultural surrounding system, recorded an ∑8OPFR concentration in sediments that ranged from 0.71 to 22.5 ng/g dw, whereas Swartkops Estuary, a largely urbanized system, recorded a concentration that ranged from 0.61 to 119 ng/g dw. Alkyl-OPFRs were the prevalent homologue in both estuaries compared to the chlorinated and aryl groups. While TBP, TCPP, and TCrP were the most abundant compounds among the homologue groups. There was no distinct seasonal trend of ∑8OPFR concentration in either estuary, with summer and autumn seasons recording the highest concentrations in SDE and SWE, respectively. Ecological risks in the majority of the study sites for the detected compounds were at low (RQ < 0.1) and medium levels (0.1 ≤ RQ < 1) for certain species of fish, Daphnia magna and algae. However, the cumulative RQs for all the compounds had ∑RQs ≥1 for most sites in both estuaries, indicating that these organisms, if present in both estuaries, may be exposed to potential ecological concerns due to accumulated OPFR chemicals. The scope of future studies should be broadened to include research areas that are not only focus on the bioaccumulation patterns of these compounds but also find sustainable ways to reduce them from these estuarine environments.

In Vitro Toxicity Screening of Fifty Complex Mixtures in HepG2 Cells.

To develop the risk prediction technology for mixture toxicity, a reliable and extensive dataset of experimental results is required. However, most published literature only provides data on combinations containing two or three substances, resulting in a limited dataset for predicting the toxicity of complex mixtures. Complex mixtures may have different mode of actions (MoAs) due to their varied composition, posing difficulty in the prediction using conventional toxicity prediction models, such as the concentration addition (CA) and independent action (IA) models. The aim of this study was to generate an experimental dataset comprising complex mixtures. To identify the target complex mixtures, we referred to the findings of the HBM4EU project. We identified three groups of seven to ten components that were commonly detected together in human bodies, namely environmental phenols, perfluorinated compounds, and heavy metal compounds, assuming these chemicals to have different MoAs. In addition, a separate mixture was added consisting of seven organophosphate flame retardants (OPFRs), which may have similar chemical structures. All target substances were tested for cytotoxicity using HepG2 cell lines, and subsequently 50 different complex mixtures were randomly generated with equitoxic mixtures of EC10 levels. To determine the interaction effect, we calculated the model deviation ratio (MDR) by comparing the observed EC10 with the predicted EC10 from the CA model, then categorized three types of interactions: antagonism, additivity, and synergism. Dose-response curves and EC values were calculated for all complex mixtures. Out of 50 mixtures, none demonstrated synergism, while six mixtures exhibited an antagonistic effect. The remaining mixtures exhibited additivity with MDRs ranging from 0.50 to 1.34. Our experimental data have been formatted to and constructed for the database. They will be utilized for further research aimed at developing the combined CA/IA approaches to support mixture risk assessment.

Organophosphate flame retardants in food matrices and their analytical methods

Organophosphate flame retardants in food matrices and their analytical methods

Organophosphate flame retardants and their metabolites in the Pearl River Estuary: Occurrence, influencing factors, and ecological risk control strategies based on a mass balance model

Estuaries serve as crucial filters for land-based pollutants to the open sea, but there is a lack of information on the migration and fate of organophosphate flame retardants (OPFRs) within estuaries. This study focused on the Pearl River Estuary (PRE) by examining the co-occurrence of OPFRs and their metabolites and quantifying their transport fluxes using a mass balance model. The seawater concentrations of OPFRs and their metabolites exhibited significant seasonal variations (p < 0.01), while the sediment concentrations of OPFRs reflected the long-term distributional equilibrium in the PRE. The concentration of Σ9OPFRs in seawater showed a relentless dilution from the entrance to the offshore region in the normal and wet seasons, which was significantly in accordance with the gradients of pH, dissolved oxygen (DO), and salinity (p < 0.05). Furthermore, horizontal migration dominated the transport of OPFRs, and the inventory assessment revealed that both the water column and sediment were important reservoirs in the PRE. According to the estimated fluxes from the mass balance model, riverine input emerged as the principal pathway for OPFR entry into the PRE (1.55 × 105, 6.28 × 104, and 9.00 × 104 kg/yr in the normal, dry and wet seasons, respectively), whereas outflow to the open sea predominantly determined the main fates of the OPFRs. The risk quotient (RQ) results showed that EHDPHP (0.835) in water posed medium ecological risk, while other OPFRs and metabolites presented relatively lower risk (RQ < 0.1). The risk control effects were evaluated through scenario simulations of mathematical fitting between controllable source factors and the RQ of risky OPFR. The risk of EHDPHP in the PRE could be effectively reduced by restricting its concentrations in entrance region (<9.31, 8.67, and 12.7 ng/L in the normal, dry and wet seasons, respectively) of the PRE. This research offers foundational insights into environmental management and pollution control strategies for emerging pollutants in estuaries.