Phthalate Research Articles

Urinary phthalate metabolites associated with bone mineral density in adults: Data from the NHANES 2011–2018

Phthalates (PAEs) are common environmental endocrine disruptors and environmental bone poisons that can reduce bone mineral density (BMD). The purpose of this study is to investigate whether the concentration of PAE metabolites in urine is related to BMD in many parts of adult bones. We examined a series of cross-sectional data of male (n = 1835) and female (n = 1756) participants aged 18 to 59 years old in the National Health and Nutrition Examination Survey from 2011 to 2018 and measured urine PAE metabolites and dual-energy X-ray absorption to determine BMD (total body, lumbar spine, and pelvis). We used linear regression to test the correlation between a single phthalate biomarker and BMD. After adjusting all confounding variables, MEHP was positively correlated with BMD of total body, lumbar spine and pelvis, and BMD levels of the total body, lumbar spine and pelvis decreased with the increase of MECPP concentration. We used the restricted cubic spline function to test the nonlinear correlation between PAE biomarkers and BMD. The results show that urinary PAE metabolites have a nonlinear relationship with total body BMD, lumbar spine BMD, and pelvic BMD. With the increase in the PAE concentration, the BMD level first increased and then decreased, showing an inverted U-shaped trend (P < 0.05). Gender stratification also shows the same related trend. PAEs may be related to the BMD of adults. When the concentration of PAEs increases to a certain threshold, it will lead to a significant decrease in BMD.

Marangoni flow-guided molecular accumulation for sensitive and rapid SERS detection of phthalates

Public attention has been emerging for the prevention and assessment of healthcare risks from phthalate esters (PAEs) in daily life. For the effective detection of small environmentally hazardous materials, we suggest two major points: i) the formation of high-density hotspots and ii) the delivery of molecules to the activated plasmonic regions. In this study, we developed a method for laser-induced Marangoni flow in cotton fabric (CF) nanopillars (NPs) deposited with Au (Au/CFNPs) for the detection of PAEs by surface-enhanced Raman spectroscopy (SERS). We optimized the performance of the Au/CFNP platforms by adjusting both the maskless plasma etching time and the Au deposition thickness. Narrow (∼8 nm) and populated hotspots were achieved at an Ar plasma treatment time of 30 s and a Au thickness of 150 nm. The molecular behaviors were observed via real-time monitoring of SERS signals. Under continuous laser illumination, Marangoni radial convection flow became predominant over the outward capillary force, resulting in molecular accumulation in the detection areas. For small probe dyes and PAEs, the maximum intensities were achieved within 80 s after the injection of analytes and their signal fluctuations were estimated to have a relative standard deviation of < 10 %, which indicated sensitive and reproducible sensing. The prediction of PAEs extracted from the actual samples was investigated on the basis of a model used to quantitatively fit reference samples and the results were compared with those obtained by high-performance liquid chromatography. The results demonstrated that the combination of densified hotspots on three-dimensional porous substrates and laser-induced Marangoni flow is highly desirable for on-site early screening assays for low-quantity harmful materials present in surrounding environments.

Distribution characteristics and relationship of microplastics, phthalate esters, and bisphenol A in the Beiyun River basin of Beijing

Distribution characteristics and relationship of microplastics, phthalate esters, and bisphenol A in the Beiyun River basin of Beijing

Exploring the use of gull eggs as bioindicators of phthalate esters exposure

Plastic pollution and associated plasticizers are a global threat affecting aquatic environments. Phthalates are among the most used plasticizers that can impact on fauna due to their endocrine-disrupting properties. The aim of this study was to investigate the use of eggs of Audouin’s gull (Larus audouinii) and yellow-legged gull (Larus michahellis) as biomonitors of phthalate exposure. Sixteen phthalates were studied and the extraction and purification steps were optimized using various sorbents and clean-up processes to efficiently recover these contaminants in gull eggs. Analysis was performed using ultra-high-performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) using multiple reaction monitoring to obtain high selectivity and sensitivity. Quality control parameters and a comprehensive analysis of blank contribution are provided. The best performance was obtained with Oasis PRiME HLB cartridges with recoveries from 61 to 138% for most of the compounds. Pooled gull-egg samples from seven breeding colonies collected over the period 2016 – 2021 within the Iberian Peninsula revealed the presence of dibutoxyethyl phthalate (DBEP), hexyl 2-ethylhexyl phthalate (HEHP), dimethyl phthalate (DMP), diethyl phthalate (DEP), and dibutyl phthalate (DBP) at mean concentrations ranging from 2.27 to 1330 ng/g ww in Audouin's gull and from 2.74 to 487 ng/g ww in yellow-legged gull (DBP not detected). The absence of other phthalates is likely attributable to their metabolism and excretion by female adults. Overall, this study provides an accurate method to analyse phthalates in gull eggs and supports their use as bioindicators of phthalate contamination.

Isolation and identification of the main components of garlic, Allium sativum, volatiles and their determination of repellent or toxic activities on green peach aphid, Myzus persicae

AbstractTo determine the control mechanism of garlic on Myzus persicae, volatiles from garlic plants were collected, and the components were determined by GC–MS. Then, the volatile extracts and standard components were screened by electroantennogram (EAG) apparatus and Y‐tube olfactometer, and the toxic effects were determined by the immersion method. The results showed the main components from garlic plant volatile were 2‐methoxyphenol, 2,4‐di‐tert‐butylphenol, diallyl disulfide, butyl phthalate esters, (1‐hydroxycyclohexyl) phenyl ketone, and 2,6‐di‐tert‐butylp‐cresol. The volatile extracts and the standard components had significant repellent effects (P ≤ 0.05) on M. persicae when the volume ratio was 1:100. The relative values of EAG from volatile extracts and diallyl disulfide were significantly higher than those of the other substances (P ≤ 0.05) when the volume ratio was 1:100. The toxicity of garlic volatile extracts to M. persicae significantly (P ≤ 0.05) increased with increasing concentration. After 72 h (treated), the adjusted mortality of the extract to M. persicae was 36.99% at 90 ml/L. The standard components had the significant toxic effect on M. persicae at 30 mg/mL, and the rates of mortality were over 78.95%. Thus, the results suggested that the volatile extracts and the four standard components from garlic plants had significant repellent effects and electroantennogram responses for M. persicae, and the toxic effects were stronger than the repellent effects for M. persicae.

Phthalate Exposure and Pediatric Asthma: A Case Control Study Among Egyptian Children

Background: Phthalates, which are diesters of phthalic acid, are commonly used as plasticizers and additives in various consumer products. Several phthalates have been identified as substances of high concern. Exposure to phthalate esters (PAEs) has been linked to asthma in children, but the specific impacts of PAEs on asthmatic children were not well understood. Objective: The objective of this study was to compare urinary phthalate concentrations in asthmatic and non-asthmatic children and to identify potential sources of exposure as risk factors for asthma. Methods: A case control study was conducted for 100 Egyptian children aged 8-16 years (50 asthmatics and 50 healthy controls). Asthma was identified using GINA guidelines. Socio-demographic and probable risk factors were assessed, in addition to measuring phthalate levels in urine samples using high-performance liquid chromatography. Results and conclusion: Mean urinary Mono-methyl as well as Mono-benzyl levels were highly significant in asthmatic children compared to control group (895.26ng/ mL vs 548.55 ng/mL and 13.5 ng/mL vs 2.07 ng/mL respectively) (p= 0.001). The number of asthmatic children living in houses painted with non-plastic paint was significantly lower (P&lt;0.05) than children living in houses painted with other paints. No association between floor type and asthma was reported. The frequent use of personal care products and plastic painting of walls were identified by multiple logistic regression analysis as the highly significant predictors of asthma in the studied subjects. The declared higher levels of urinary phthalate metabolites (Mono-methyl and Mono-benzyl) in Egyptian asthmatic children may reveal the probable risk of phthalate exposure in triggering bronchial asthma.

Investigation of interaction mechanism between polyvinyl chloride microplastics and phthalate acid esters using APGC-MS/MS

Phthalate acid esters (PAEs) are a kind of typical endocrine disruptors chemicals (EDCs). PAEs can be enriched, migrated and released into organisms through microplastics (MPs), causing high toxicological risks. This study presented an atmospheric pressure gas chromatography-tandem mass spectrometry (APGC-MS/MS) method for 10 PAEs trace analysis. Based on this method, the interaction mechanism between polyvinyl chloride microplastics (PVC MPs) and PAEs was explored. The established APGC-MS/MS method achieved 10 PAEs analysis in 14 min with the satisfied detection limit as low as 0.0025 μg/L and excellent linearity (R2 = 0.99868–0.99996). The interaction mechanism investigation showed that PVC MPs had high adsorption and desorption capacities for PAEs. The adsorption mechanism involves adsorption distribution, surface adsorption, hydrophobic interaction and intermolecular van der Waals force. Temperature, diffusion channels, pore filling, hydrophobicity and solubilization may be potential desorption mechanisms. Moreover, the intestinal environment of warm-blood organisms has the highest bioavailability of PAEs. Overall, this APGC-MS/MS method of PAEs had the virtue of simplicity, efficiency, reliability and sensitivity, and could serve as a potential tool for risk analysis of MPs and PAEs exposure.

Composite biopolymer foams fabricated from natural aldehyde functionalized chitosan-whey protein amyloid fibrils: Application for removal of phthalate esters from water

In this work, composite biopolymer foams from chitosan and whey isolate protein amyloid fibrils were prepared for the removal of phthalate esters from water. Natural aldehyde functionalization enhanced the affinity for dibutyl phthalate (DBP), with citral being the most effective. The citral-grafted foams (WCGC) had tunable hydrophobicity, strong mechanical properties, and good water stability. WCGC1.5 foam exhibited a high removal efficiency (96.06 %) of DBP. The adsorption process reached adsorption equilibrium rapidly within 8 h and could be described by pseudo-second-order kinetic and Freundlich isotherm models, indicating a non-homogeneous and chemisorptive sorption process. The maximum adsorption capacity for DBP reached 332.42 mg/g. Moreover, DBP adsorption could be enhanced in alkaline environment and the removal efficiency increased to 98.27 % at pH 10. The removal efficiency of DBP by WCGC1.5 remained above 85 % after the five adsorption-desorption cycles. WCGC1.5 also showed broad-spectrum adsorption behavior, with strong affinity and removal efficiency for six common plasticizers, including DIBP (85.97 %), DPP (91.7 %), DHXP (99.1 %), DEHP (99.09 %), DNOP (91.6 %) and BBP (89.88 %).

Exploring the pyrolytic degradation of seventeen phthalate esters using the non-targeted regions of interest-multivariate curve resolution (ROIMCR) chemometric method

The global use of phthalate esters (PAEs) in plastic production entails a need for developing effective remediation strategies to minimize exposure and health risks. In this study, pyrolysis degradation processes are evaluated for 17 different PAEs that were analyzed by high-resolution gas chromatography-mass spectrometry (Pyr-GC-Orbitrap-MS) at different temperatures (300 °C, 400 °C, 500 °C, 600 °C, 700 °C, 800 °C) both in electron ionization (EI) and positive chemical ionization (PCI) mode. All the analytical data generated have been processed with the Regions of Interest Multivariate Curve Resolution (ROIMCR) chemometrics method. A preliminary selection of the Mass Spectrometry Regions of Interest (ROIs) coupled to a bilinear factor decomposition method (MCR-ALS) allowed the identification of 4 principal components, which were used to define the thermal degradation process. ROIMCR method is a powerful tool for non-targeted analysis which allows the resolution of the elution and spectral profiles of the different constituents present in the analyzed samples, which were confirmed using PCI. Moreover, ROIMCR was used to resolve and identify the different products generated during the studied degradation processes. As a result, 10 new thermal degradation products were identified in the analysis of the different sample sets. Finally, the degradation efficiencies higher than 99.8 % were obtained for all the PAEs at 800 °C, except for benzoic acid-benzyl ester, whose removal efficiency decreased to 94.8 %. As phthalates are widespread and toxic compounds for the environment and for humans, there is a need for new remediation technologies. This study provides new knowledge to understand their elimination through thermal processes. We combine mass spectrometric data with powerful chemometric processing to determine the removal efficiency, to understand the degradation process and to identify the degradation compounds formed through thermal decomposition.

Plasticizers levels in four fish species from the Ligurian Sea and Central Adriatic Sea (Mediterranean Sea) and potential risk for human consumption

Plastic materials contain additives such as plasticizers and flame retardants, which are not covalently bound to plastic polymers and can therefore be unintentionally released into the marine environment. This study investigated three families of compounds, phthalates (PAEs), organophosphate esters (OPEs), and non-phthalate plasticizers (NPPs) currently used as plastic additives, in 48 muscle samples of bogue (Boops boops), European hake (Merluccius merluccius), red mullet (Mullus barbatus), and European pilchard (Sardina pilchardus) sampled in the Central Adriatic and the Ligurian Seas. The additional goal of this study is to assess the potential risk to human health from fish consumption with the objective of determining whether the detected levels might potentially pose a concern. PAEs represent the majority of the plastic additives detected in the selected species, with ubiquitous distribution across the study areas, whereas for OPEs and NPPs, there is a more pronounced difference between the two study areas, suggesting that these compounds may represent different exposure levels in the two seas. Among PAEs, bis(2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DBP), and diisobutyl phthalate (DIBP) were the most abundant compounds, reaching levels up to 455 ng/g ww. OPEs were detected at higher concentrations in samples from the Ligurian Sea, and triethyl phosphate (TEP) was the most abundant compound. Among the NPPs, acetyl tributyl citrate (ATBC) was most frequently detected. From the results obtained, fish consumption may not pose a risk to human health (Hazard Quotient<1) but needs to be considered in future studies. Given the limited number of studies on PAEs, OPEs and NPPs in the Mediterranean Sea, further research is necessary to understand their potential bioaccumulation in marine organisms.

Association between phthalates exposure and all-cause mortality among diabetic cases: A prospective study

The aim of this study was to explore the association between phthalates (PAEs) exposure and all-cause mortality among diabetic cases, and potential molecular mechanisms of the effect. We followed 2806 diabetes cases from 2008 to the end of 2018 based on the Dongfeng-Tongji study, of which 446 cases died. We measured serum levels of six PAEs (DMP, DEP, DiBP, DnBP, BBP, and DEHP). Cox models were used to investigate the associations between PAEs and all-cause mortality. Genes related to PAEs are obtained from the Comparative Toxicogenomics Database. We constructed polygenic scores for sex hormone-binding globulin (SHBG) and testosterone, and functional SNPs for IL-6, PPARG, and GPX1 from genotyping data, and further analyzed the environment-gene interactions. The positive associations of PAEs (DMP, DiBP, DnBP, DEHP) with mortality were only observed in males but not in females. Comparing with the extreme quartile 1, the HRs (95% CI) for quartile 4 were 1.63 (0.17, 2.26) for DMP, 1.82 (1.29, 2.56) for DiBP, 1.68 (1.18, 2.40) for DnBP, 1.66 (1.17, 2.36) for DEHP. Enrichment analysis showed that PAEs-related genes were mainly associated with hormones and IL-6-related pathways. Genetic variants of SHBG, testosterone, and IL-6 modified the association between PAEs mixture and all-cause mortality. PAEs exposure are associated with all-cause mortality among diabetic cases, and PAE exposure increases the risk of all-cause mortality only in males. Effects on the hormonal system and IL6-related pathways may be potential mechanisms.

Single-step template-free synthesis of fluoro-functionalized covalent organic frameworks with a tunable hollow structure for extraction of phthalate acid esters from human urine

Phthalate acid esters (PAEs) are recognized as endocrine disruptors, exhibit carcinogenic characteristics, and have the potential to impair fertility, thereby posing significant risks to both the environment and human health. Consequently, biomonitoring and exposure assessment of PAEs are of paramount importance. Presently, the majority of detection methods for PAEs are centered on aqueous matrices, and the development of techniques for the identification of PAEs in complex matrices remains an area of active research. This paper designed and synthesized a novel fluoro-functionalized hollow covalent organic framework (F-HCOF), characterized by a tunable hollow spherical structure and enriched with fluorine functional groups, through a one-step self-template approach, which effectively regulated the formation of the hollow structure. The synthesized F-HCOF with tunable hollow structures and abundant F functional groups provided efficient diffusion pathways and adsorption sites, facilitating robust and selective adsorption of the target PAEs. Using F-HCOF as a coating, a solid-phase microextraction method was developed to extract PAEs from complex matrices. The method exhibited limits of detection ranging from 0.0108 to 0.0581 ng L−1, with enrichment factors spanning from 2535.3 to 8985.3. The self-made F-HCOF fibers demonstrated the capability to effectively enrich PAEs under various interference conditions, further verifying their feasibility for practical sample analysis. This work provided a strategic approach for the synthesis of F-functionalized hollow COF adsorbents and explored the formation process of hollow spheres. It enables matrix interference-resistant analysis of PAEs, and offers a practical method for studying PAEs exposure and metabolism within the human body.

Comparison of the presence of high production volume chemicals in farmed and wild fish highly consumed in catalonia and their risk assessment

The decline in fish populations and the depletion of marine resources have sparked concerns about sustainable fish production, driving the innovation of new aquaculture methods. While some argue that wild fish are healthier than farmed fish due to less exposure to contaminants and pathogens, wild fish can accumulate contaminants from more contaminated water sources. The slower growth of wild fish and their longer exposure to the environment may contribute to higher pollutant levels in fish tissues. In this study, we focus on 25 contaminants considered as high production volume chemicals (HPVCs), such as organophosphate esters (OPEs), benzothiazoles (BTs), benzosulfonamides (BSAs) and phthalates (PAEs). The compounds were extracted from the edible part of the fish using the QuEChERS method and analysed by gas chromatography-tandem mass spectrometry.A total of 74 samples were analysed from three of the most commonly consumed species in Catalonia, Spain (turbot, sea bass and sea bream). Two samples of each species were collected each month, one form farmed and one from wild origin. In general, the compounds were found in all the samples in a wide concentrations range, although no significant differences were observed between the mean concentration of wild and farmed samples. Although similar mean concentrations for the OPEs, BTs and BSAs were found between farmed and wild origin samples, PAEs were more frequently detected in farmed samples. Di-n-octyl phthalate and diethyl phthalate showed the highest concentrations in all fish samples, with values up to 19505 and 17605 ng g−1 (d.w.), in sea bass and sea bream, respectively. Di-(2-ethylexyl)-adipate proved to be the most relevant carcinogenic compound, with no associated health risk. Despite the detection of the studied HPVCs, no health risk was associated with the consumption of these three fish species.

Bioaccessibility of plastic-related compounds from polymeric particles in marine settings: Are microplastics the principal vector of phthalate ester congeners and bisphenol A towards marine vertebrates?

Marine vertebrates are known to ingest significant amounts of microplastics (MPs). Once ingested, MPs might cause gastrointestinal injuries and serve as a path of harmful plastic components, such as phthalate esters (PAEs) and bisphenol A (BPA) in the food chain. However, there is a lack of standardized in-vitro methods capable of simulating fish uptake of chemicals from MPs in the environment as potential vectors of such contaminants. In this work, leaching and in-vitro oral bioaccessibility testing of PAEs and BPA from MPs were conducted batchwise using artificial seawater and gut fluids mimicking gastric, intestinal, and gastrointestinal compartments of marine vertebrates at physiological temperature. The environmental and physiologically relevant extraction tests were applied to medium-density polyethylene (PE) and polyvinyl chloride (PVC) certified reference materials containing eight PAEs of varying hydrophobicity, namely, dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate, benzylbutyl phthalate, diethylhexyl phthalate, di-n-octyl phthalate, diisononyl phthalate and diisodecyl phthalate, and BPA (only in PE) as MP surrogates with realistic analyte concentrations of additives for primary MPs. The analysis of the leachates/gut fluid extracts was performed via dilute-and-shoot by ultra-high performance liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). Only the most hydrophilic compounds, i.e. DMP, DEP and BPA, were found to get released significantly in saline waters, and exhibited the highest oral bioaccessibility rates (34–83 %). Based on our results, a dual-compartment physiologically relevant gastrointestinal test is recommended for appropriate estimation of fish bioaccessibility. The fish daily intakes of DMP, DEP and BPA from MPs, and seawater ingestion as well were estimated using several contamination scenarios (10th percentile as the low level, 50th percentile as the medium level and 90th percentile as the high level) based on probabilistic distributions and cumulative probability curves of measured environmental concentrations of (i) MPs in seawater throughout the world, (ii) DMP, DEP and BPA in beached MPs and those sampled in the open ocean (including both incurred and adsorbed contaminants), and (iii) DMP, DEP and BPA in seawater as reported in recent literature. Under a medium-level concentration scenario (50th percentile) in marine settings, and taking the gastrointestinal bioaccessibility factor into account, the daily intake of DMP, DEP and BPA from MPs accounted for a mere 0.02 % of the waterborne contribution. Hence, the ingestion of MPs should not be considered the primary route of fish exposure to BPA and the most polar PAEs in marine environments. However, more studies on the local and the global scales for mass concentrations of MPs and additives in marine settings are needed for further confirmation of our findings.

Relationship between mixed exposure to phenyl hydroxides, polycyclic aromatic hydrocarbons, and phthalates and the risk of arthritis

BackgroundTo determine the relationship between mixed exposure to three types of endocrine-disrupting chemicals (EDCs), namely phenyl hydroxides, polycyclic aromatic hydrocarbons (PAHs), and phthalates (PAEs), and risk of arthritis.MethodsParticipants were selected from National Health and Nutrition Examination Survey (NHANES). The relationships between the urinary concentrations of phenyl hydroxides, PAHs, and PAEs and the risk of arthritis were analyzed by generalized linear regression model. The mixed exposure to these EDCs and the risk of arthritis was analyzed by weighted quantile sums (WQSs) and Bayesian kernel machine regression (BKMR) model.ResultsOur analysis showed that participants with urinary benzophenone-3 and methylparaben concentrations in the highest quartile (Q4) had an increased risk of arthritis compared with those in Q1. For each one-unit increase in the natural logarithm-converted urinary concentrations of 1-hydroxynapthalene and 2-hydroxynapthalene, the risk of arthritis increased by 5% and 8%, respectively. Chemical mixing index coefficients were significantly associated with risk of arthritis in both WQS positive- and negative-constraint models. In the BKMR model, there was a significant positive correlation between mixed exposure and the risk of arthritis.ConclusionMixed exposure to phenyl hydroxides, PAHs, and PAEs increased the risk of arthritis, with exposure to PAHs being the key factor.

Screening of Characteristic Pollutants and Risk Pollutants in Different Media in the Yangtze River Basin Using Comprehensive Evaluation and Risk Quotient Methods

A variety of pollutants have frequently been detected in the Yangtze River Basin with the rapid economic development, the population increase, and the acceleration of urbanization, which threaten the aquatic ecosystem and human health. A multi-criteria comprehensive evaluation method was developed to identify the characteristic pollutants, and the risk quotient method was used to derive the risk pollutants in water and sediment samples in this article. A total of 155 pollutants from 11 categories were detected in the Yangtze River Basin according to the literature research. Then, the K-means method was used to analyze the cluster of pollutant comprehensive scores. All pollutants were graded based on their scores and recorded as Ⅰ-Ⅵ according to the number of cases in each cluster. A total of 43 pollutants with high scores of Ⅰ and Ⅱ were listed as the characteristic pollutants, which included 11 polycyclic aromatic hydrocarbons, 11 organochlorine pesticides, 10 polychlorinated biphenyls, eight dioxins, two heavy metals, and one phthalate ester. The top five median concentrations of contaminants in water and sediment samples were heavy metals, polycyclic aromatic hydrocarbons, phthalates esters, bisphenols, and pharmaceuticals and personal care products. According to the principle of risk maximization, the risk entropy value （RQ） was calculated based on the highest pollutant concentration. A total of 38 risky pollutants were screened in the water samples （RQ ≥ 0.1）. There were eight high-risk pollutants with RQ ≥ 1, which included benzo[a,h]-anthracene, anthracene, benzo[a]anthracene, pyrene, methoxychlor, aldrin, 2,4'-dichlorodiphenyl, and cadmium. There were 15 high-risk contaminants in the sediment, which included benzo[b]fluoranthene, anthracene, acenaphthene, fluoranthene, cadmium, lead, chromium, arsenic, selenium, dibutyl phthalate, dimethyl phthalate, diisobutyl phthalate, norfloxacin, perfluorobutyric acid, and bisphenol A. The risk pollutants contained emerging pollutants, which included ten pollutants in water samples and nine pollutants in sediments. Antibiotic pollutants accounted for the largest proportion of these emerging pollutants. The information provided in this article may be useful for the relevant departments to monitor the pollutants and propose management programs for the Yangtze River Basin. Additionally, it is of great significance for the ecological environmental protection and management of the Yangtze River Basin.

Toxicity of Dibutyl phthalate (DBP) toward isolated human blood lymphocytes: Apoptosis initiated from intracellular calcium enhancement and mitochondrial/lysosomal cross talk

Dibutyl phthalate (DBP) is a phthalate ester with wide application in industrial products, so human exposure can happen in workplaces and environment. Conflicting results have been acquired in researches which measured the influences of phthalates contact on immune responses in laboratory animals. Nevertheless, the straight influence of DBP on human lymphocytes and entire mechanisms of its effect against these cells continue to be unexplored. The major purpose of present research was to evaluate the mechanisms which lead to the DBP toxicity on human lymphocytes using accelerated cytotoxicity mechanisms screening (ACMS) technique. Cell viability was determined following12h incubation of lymphocytes with 0.05–1 mM DBP, and mechanistic parameters were assessed after 2, 4 and 6 h of lymphocyte treatment with ½ the IC5012h (0.3 mM), the IC5012h (0.6 mM) and twice the IC5012h (1.2 mM) of DBP. The IC5012 h of a chemical/toxicant is defined as concentration that kills 50 % of cells after 12 h of exposure. The results indicate that DBP exerts toxic effects on isolated human lymphocytes, probably through mitochondrial and lysosomal damage induced by glutathione depletion and oxidative stress. In this study, suppression of cytokines (IL2, INF-gamma and TNF-alpha) production and increase in intracellular calcium were also related to DBP induced lymphocyte toxicity.

Analysis of phthalate esters from vegetable oils by gas chromatography-mass spectrometry coupled with headspace solid-phase microextraction using cyclodextrin-based hypercrosslinked polymer coated fiber

Phthalate esters (PAEs) are used as additives to enhance the pliability and malleability of plastics. These substances frequently migrate from packaging materials to vegetable oils because of the absence of covalent bonds. Over time, this migration could result in the accumulation of PAEs in the human body through ingestion, contributing to various diseases. Therefore, accurate qualitative and quantitative analyses of PAEs in vegetable oils are imperative to assess the origins of contamination and investigate their toxicity, degradation, migration, and transformation patterns. However, the concentration of PAEs in most samples is low, and the composition of vegetable oils is complex. Thus, PAEs must be enriched and purified using appropriate sample pretreatment procedures before analysis. Common methods for pretreating PAEs in oil include solid-phase extraction (SPE), dispersive SPE, and magnetic SPE. These techniques require time-consuming and labor-intensive procedures such as oil dissolution, solvent extraction, and degreasing. These approaches also require numerous solvents and containers, increasing the risk of sample cross-contamination. Solid-phase microextraction (SPME) integrates sampling, extraction, purification, concentration, and injection into a single process, significantly accelerating analytical testing and reducing the potential for sample cross-contamination. In headspace (HS) mode, the analytes achieve equilibrium on the coating and are extracted in the gas phase. The fibers are shielded from nonvolatile and high-relative molecular mass substances in the sample matrix. Thus, SPME is an ideal method for extracting volatile compounds in vegetable oils. When HS-SPME coupled with gas chromatography-mass spectrometry (GC-MS), it can achieve the rapid screening of PAEs in vegetable oil. In this study, an SPME with cyclodextrin-based hypercrosslinked polymers (BnCD-HCP) coated on stainless steel fibers was employed to extract PAEs from vegetable oil. The structure and morphology of the polymers were characterized using Fourier-transform infrared spectroscopy, nuclear magnetic spectroscopy, and scanning electron microscopy. BnCD-HCP exhibited high stability and diverse interactions, including π-π, hydrophobic, and host-guest interactions. The oil samples were incubated with methanol, and the PAEs were extracted from the headspace using the probe. The optimal extraction parameters included an extraction time of 20 min, extraction temperature of 50 ℃, desorption time of 4 min, and desorption temperature of 275 ℃. The BnCD-HCP/HS-SPME method was evaluated under optimized experimental conditions. The limits of detection (LODs) and quantification (LOQs) were determined by applying signal-to-noise ratios (S/N) of 3 and 10, respectively. Method accuracy was evaluated using relative standard deviations (RSDs). Single-needle precision was evaluated by conducting three consecutive analyses at 3 h intervals within a day. Inter-needle precision was assessed by conducting the same analyses (three replicates) with differently coated fibers. The 12 PAE compounds exhibited good linearity with correlation coefficients (R2) of at least 0.99. The LODs and LOQs ranged from 0.21 to 3.74 μg/kg and from 0.69 to 12.34 μg/kg, respectively. The RSDs were in the range of 1.8%-11.4% and 5.1%-13.9% for the single-needle and needle-to-needle methods, respectively. The proposed method was applied to soybean, peanut, and sunflower oils, and two PAEs were found in all three oils. Moreover, the method demonstrated good precision (RSD=1.17%-11.73%) and recoveries (72.49%-124.43%). Compared with other methods, the developed method was able to extract many target analytes and had a low or comparable LOD and high recovery. More importantly, this method does not require tedious operations such as solvent extraction and purification. Consequently, the developed method can be used to extract not only PAEs in oils but also other substances with a high lipid content.

Occurrence, distribution and risk assessment of phthalate esters in dust deposited in the outdoor environment of Yazd industrial park using Monte Carlo simulation

In this study, the distribution of eight phthalate esters (PAEs), namely (dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), butyl benzyl phthalate (BBP), bis (2-ethylhexyl) phthalate (DEHP), and di-n-octyl phthalate (DnOP)) were examined across fifteen sampling stations in Yazd industrial Park. All the PAEs in dust deposited in the outdoor environment were analyzed using a Gas-mass chromatography (GC-MS/MS) device. Both probabilistic and deterministic approaches were utilized to assess the non-carcinogenic and carcinogenic health risks for adult occupational population groups. These risks were associated with three exposure pathways: inhalation, ingestion, and dermal exposure to six phthalates in the dust samples. The findings revealed, among the fifteen sampling stations, highest and lowest concentrations of the PAEs in dust deposited in the outdoor environment were observed in S8 and S6, with BEHP (326.21 ± 4.35) μg/g and DMP (0.00 ± 0.02) μg/g, respectively. The total hazard index (HI) values were below one in all samples, indicating that the combined non-carcinogenic health risk from exposure to phthalates via inhalation, ingestion, and dermal pathways is within acceptable levels in each studied area. The total cancer risk (CR) values for BBP across all exposure routes were consistently low, with magnitudes ranging from 10- x 10−15to 10 x 10−11. The order of cancer risk from phthalate exposure in outdoor environments was ingestion > dermal > inhalation. The sensitivity analysis (SA) results indicated that the influential parameters in the carcinogenic risk in adult occupational population groups were concentration for inhalation and dermal pathways, as well as ingestion rate for the ingestion pathway. The result of this study provides new insight in to PAEs pollution and risk assessments related to the dust deposited in the outdoor environment of industrial Park. Furthermore, this finding is beneficial to the controlling the exposure and promoting steps to reduce PAEs contamination and manage health in the industrial area.

Thermo‐Assisted Deep Eutectic Solvent Based on Dispersive Liquid‐Liquid Microextraction for Preconcentration of Phthalate Esters in Water Samples and Determination by Gas Chromatography With Flame Ionization Detection

ABSTRACTA thermo‐assisted deep eutectic solvent (DES) based on dispersive liquid‐liquid microextraction followed by gas chromatography with flame ionization detection was developed for the analysis of five phthalate esters in different water samples. In the procedure involved, a DES composed of lidocaine, an amphiphilic amine, and oleic acid, was mixed with the sample assisted by ultrasound, and phase separation was achieved with increasing temperature. The heating of the extraction system induced the change of acid‐base properties of the DES components. Thus, the formation of microdroplets of DES in the sample was provided, and two phases were separated. The structure of the upper hydrophobic layer was characterized by Fourier‐transform infrared spectroscopy. Also, the amount of water in the DES phase was analyzed by mass spectrometer and Karl Fischer titration. Some critical variables on the extraction yield were assessed. The proposed method achieved 1.2–1.3 and 4.1–4.3 µg/L for limits of detection and limits of quantification, respectively. The intra‐day and inter‐day percentage relative standard deviations (n = 5) were determined to be in the range of 4.2–6.2% and 5.1–7.2%, respectively. Ultimately, this method analyzed the five phthalate esters in different water samples with high recoveries.