Insights into pollution characteristics and human health risks of plasticizer phthalate esters in shellfish species.

The ubiquitous application of phthalate esters (PAEs) as plasticizers contributes to high levels of marine pollution, yet the contamination patterns of PAEs in various shellfish species remain unknown. The objective of this research is to provide the first information on the pollution characteristics of 16 PAEs in different shellfish species from the Pearl River Delta (PRD), South China, and associated health risks. Among the 16 analyzed PAEs, 13 were identified in the shellfish, with total PAE concentrations ranging from 23.07 to 3794.08 ng/g dw (mean = 514.35 ng/g dw). The PAE pollution levels in the five shellfish species were as follows: Ostreidae (mean = 1064.12 ng/g dw) > Mytilus edulis (mean = 509.88 ng/g dw) > Babylonia areolate (mean = 458.14 ng/g dw) > Mactra chinensis (mean = 378.90 ng/g dw) > Haliotis diversicolor (mean = 335.28 ng/g dw). Dimethyl phthalate (DMP, mean = 69.85 ng/g dw), diisobutyl phthalate (DIBP, mean = 41.39 ng/g dw), dibutyl phthalate (DBP, mean = 130.91 ng/g dw), and di(2-ethylhexyl) phthalate (DEHP, mean = 226.23 ng/g dw) were the most abundant congeners. Notably, DEHP constituted the most predominant fraction (43.98 %) of the 13 PAEs detected in all shellfish from the PRD. Principal component analysis indicated that industrial and domestic emissions served as main sources for the PAE pollution in shellfish from the PRD. It was estimated that the daily intake of PAEs via shellfish consumption among adults and children ranged from 0.004 to 1.27 µg/kgbw/day, without obvious non-cancer risks (< 0.034), but the cancer risks raised some alarm (2.0 × 10-9-1.4 × 10-5). These findings highlight the necessity of focusing on marine environmental pollutants and emphasize the importance of ongoing monitoring of PAE contamination in seafood.

Ecotoxicity assessment of additives in commercial biodegradable plastic products: Implications for sustainability and environmental risk.

Biodegradable plastics have gained popularity as environmentally friendly alternatives to conventional petroleum-based plastics, which face recycling and degradation challenges. Although the biodegradability of these plastics has been established, research on their ecotoxicity remains limited. Biodegradable plastics may still contain conventional additives, including toxic and non-degradable substances, to maintain their functionality during production and processing. Despite degrading the polymer matrix, these additives can persist in the environment and potentially harm ecosystems and humans. Therefore, this study aimed to assess the potential ecotoxicity of biodegradable plastics by analyzing the phthalate esters (PAEs) leaching out from biodegradable plastics through soil leachate. Sixteen commercial biodegradable plastic products were qualitatively and quantitatively analyzed using gas chromatography-mass spectrometry to determine the types and amounts of PAE used in the products and evaluate their ecotoxicity. Among the various PAEs analyzed, non-regulated dioctyl isophthalate (DOIP) was the most frequently detected (ranging from 40 to 212 µg g-1). Although the DOIP is considered one of PAE alternatives, the detected amount of it revealed evident ecotoxicity, especially in the aquatic environment. Other additives, including antioxidants, lubricants, surfactants, slip agents, and adhesives, were also qualitatively detected in commercial products. This is the first study to quantify the amounts of PAEs leached from biodegradable plastics through water mimicking PAE leaching out from biodegradable plastics to soil leachate when landfilled and evaluate their potential ecotoxicity. Despite their potential toxicity, commercial biodegradable plastics are currently marketed and promoted as environmentally friendly materials, which could lead to indiscriminate public consumption. Therefore, in addition to improving biodegradable plastics, developing eco-friendly additives is significant. Future studies should investigate the leaching kinetics in soil leachate over time and toxicity of biodegradable plastics after landfill disposal.

Distribution, seasonal variation and ecological risk assessment of phthalates in the Yitong River, a typical urban watercourse located in Northeast China.

Phthalates (PAEs) are a typical class of endocrine disruptors (EEDs). As one of the most commonly used plasticizers, they have received widespread attention due to their wide application in various countries and high detection rates in various environmental media. To be able to clarify the contamination status of PAEs pollutants in a typical northern cold-temperate urban river, 30 water samples from Yitong River in Changchun City, northern China were collected, during the 2023 dry season (March), normal season (May) and wet season (July). Using these samples, a total of 16 target PAEs are investigated. The resulting total PAEs concentrations are: dry season 408 to 1494 ng/L, wet season 491 to 1299 ng/L, and normal season 341 to 780 ng/L. The average concentration of the 16 PAEs over the three seasons is 773 ng/L. Di-2-ethylhexyl phthalate (DEHP) and Dibutyl phthalate (DBP) have the highest concentrations, ranging from 12 to 403 ng/L and 28-680 ng/L respectively. The ecological risks within the Yitong River Basin are evaluated based on the degree of PAEs contamination. DBP and DEHP pose higher risk assessment levels for algae, crustaceans and fish than the other target PAEs. The accurate determination of PAEs provided baseline data on PAEs for the management of the Yitong River, which is of great significance for the prediction of ecological risk assessment and the development of corresponding control measures, supported further research on PAEs in the cold-temperate zone aquatic environments, and shed light on the seasonal variations of PAEs in the Northeast region in the future. Moreover, considering the bioaccumulation and persistence of PAEs, it is necessary to continue to pay attention to the pollution status of cold-temperate zones rivers and the changes in ecological risks in the future.

Influencing factors and risk assessment of phthalate ester pollution in the agricultural soil on a tropical island.

Phthalate esters (PAEs) are widely prevalent in agricultural soil and pose potential risks to crop growth and food safety. However, the current understanding of factors influencing the behavior and fate of PAEs is limited. This study conducted a large-scale investigation (106 sites in 18 counties with 44 crop types) of 16 types of PAEs on a tropical island. Special attention was given to the impacts of land use type, soil environmental conditions, agricultural activity intensity, and urbanization level. The health risks to adults and children from soil PAEs via multiple routes of exposure were also evaluated. The results showed that the mean concentration of PAEs was 451.87 ± 284.08 µg kg-1 in the agricultural soil. Elevated agricultural and urbanization activities contributed to more pronounced contamination by PAEs in the northern and southern regions. Land use type strongly affected the concentration and composition of PAEs in agricultural soils, and the soil PAE concentration decreased in the order of vegetable fields, orchards, paddy fields, and woodlands. In paddy fields, di-isobutyl phthalate and di-n-butyl phthalate made more substantial contributions to the process through which the overlying water inhibited volatilization. Soil microplastic abundance, pesticide usage, crop yield, gross domestic product, and distance to the nearest city were calculated to be the major factors influencing the concentration and distribution of PAEs. Soil pH, organic matter content, microplastic abundance and the fertilizer application rate can affect the adsorption of PAEs by changing the soil environment. A greater risk was detected in the northern region and paddy fields due to the higher soil PAE concentrations and the dietary structure of the population. This study reveals important pathways influencing the sources and fate of PAE pollution in agricultural soils, providing fundamental data for controlling PAE contamination.

A systematic review of global distribution, sources and exposure risk of phthalate esters (PAEs) in indoor dust.

Phthalate esters (PAEs) are a class of plasticizers that are readily released from plastic products, posing a potential exposure risk to human body. At present, much attention is paid on PAE concentrations in indoor dust with the understanding of PAEs toxicity. This study collected 8187 data on 10 PAEs concentrations in indoor dusts from 26 countries and comprehensively reviewed the worldwide distribution, influencing factors, and health risks of PAEs. Di-(2-ethylhexyl) phthalate (DEHP) is the predominant PAE with a median concentration of 316 µg·g-1 in indoor dust. Polyvinyl chloride wallpaper and flooring and personal care products are the main sources of PAEs indoor dust. The dust concentrations of DEHP show a downward trend over the past two decades, while high dust concentrations of DiNP are found from 2011 to 2016. The median dust contents of 8 PAEs in public places are higher than those in households. Moreover, the concentrations of 9 PAEs in indoor dusts from high-income countries are higher than those from upper-middle-income countries. DEHP in 69.8% and 77.8% of the dust samples may pose a potential carcinogenic risk for adults and children, respectively. Besides, DEHP in 16.9% of the dust samples may pose a non-carcinogenic risk to children. Nevertheless, a negligible risk was found for other PAEs in indoor dust worldwide. This review contributes to an in-depth understanding of the global distribution, sources and health risks of PAEs in indoor dust.

Chemical uptake into silicone wristbands over a five day period.

Silicone wristbands are a noninvasive personal exposure assessment tool. However, despite their utility, questions remain about the rate at which chemicals accumulate on wristbands when worn, as validation studies utilizing wristbands worn by human participants are limited. This study evaluated the chemical uptake rates of 113 organic pollutants from several chemical classes (i.e., polychlorinated biphenyls (PCB), organophosphate esters (OPEs), alkyl OPEs, polybrominated diphenyl ethers (PBDEs), brominated flame retardants (BFR), phthalates, pesticides, and polycyclic aromatic hydrocarbons (PAHs) over a five-day period. Adult participants (n = 10) were asked to wear five silicone wristbands and then remove one wristband each day. Several compounds were detected in all participants' wristbands after only one day. The number of chemicals detected frequently (i.e. in at least seven participants wristbands) increased from 20% of target compounds to 26% after three days and more substantially increased to 34% of target compounds after four days of wear. Chemicals detected in at least seven participants' day five wristbands (n = 24 chemicals) underwent further statistical analysis, including estimating the chemical uptake rates over time. Some chemicals, including pesticides and phthalates, had postive and significant correlations between concentrations on wristbands worn five days and concentrations of wristbands worn fewer days suggesting chronic exposure. For 23 of the 24 compounds evaluated there was a statistically significant and positive linear association between the length of time wristbands were worn and chemical concentrations in wristbands. Despite the differences that exist between laboratory studies using polydimethylsiloxane (PDMS) environmental samplers and worn wristbands, these results indicate that worn wristbands are primarily acting as first-order kinetic samplers. These results suggest that studies using different deployment lengths should be comparable when results are normalized to the length of the deployment period. In addition, a shorter deployment period could be utilized for compounds that were commonly detected in as little as one day.

Non-target screening and prioritization of organic contaminants in seawater desalination and their ecological risk assessment.

The impact of desalination brine on the marine environment is a global concern. Regarding this, salinity is generally accepted as the major environmental factor in desalination concentrate. However, recent studies have shown that the influence of organic contaminants in brine cannot be ignored. Therefore, a non-targeted screening method based on comprehensive two-dimensional gas chromatography-quadrupole mass spectrometry (GC × GC-qMS) was developed for identifying organic contaminants in the desalination brine. A total of 404 compounds were tentatively identified from four seawater desalination plants (three reverse osmosis plants and one multiple effect distillation plant) in China. The identified compounds were prioritized based on their persistence, bioaccumulation, ecotoxicity, usage, and detection frequency. Twenty-one (21) compounds (seven phthalates, ten pesticides, four trihalomethanes) were then selected for further quantitative analysis and ecological risk assessment, including compounds from the priority list along with substances from the same chemical classes. Ecologically risky substances in brine include diisobutylphthalate and bis(2-Ethylhexyl) phthalate, atrazine and acetochlor, and bromoform. Most of the contaminants come from raw seawater, and no high risk contaminants introduced by the desalination process have been found except for disinfection by-products. In brine discharge management, people believed that all pollution in raw seawater was concentrated by desalination process. This study shows that not all pollutants are concentrated during the desalination process. In this study, the total concentration of pesticide in the brine increased by 58.42%. The concentration of ∑PAEs decreased by 13.65% in reverse osmosis desalination plants and increased by 10.96% in the multi-effect distillation plant. The concentration of trihalomethane increased significantly in the desalination concentrate. The change in the concentration of pollutants in the desalination concentrate was related to the pretreatment method and the chemical characteristics of the contaminants. The method and results given in this study hinted a new idea to identify and control the environmental impact factors of brine.

Landfill leachates as a significant source for emerging pollutants of phthalic acid esters: Identification, occurrence, characteristics, fate, and transport.

Phthalic acid esters (PAEs) are byproducts released from various sources, including microplastics, cosmetics, personal care products, pharmaceuticals, waxes, inks, detergents, and insecticides. This review article provides an overview of the literature on PAEs in landfill leachates, exploring their identification, occurrence, characteristics, fate, and transport in landfills across different countries. The study emphasizes the influence of these substances on the environment, especially on water and soil. Various analytical techniques, such as GC-MS, GC-FID, and HPLC, are commonly employed to quantify concentrations of PAEs. Studies show significant variations in levels of PAEs among different countries, with the highest concentration observed in landfill leachates in Brazil, followed by Iran. Among the different types of PAE, the survey highlights DEHP as the most concentrated PAE in the leachate, with a concentration of 89.6 µg/L. The review also discusses the levels of other types of PAEs. The data shows that DBP has the highest concentration at 6.8 mg/kg, while DOP has the lowest concentration (0.04 mg/kg). The concentration of PAEs typically decreases as the depth in the soil profile increases. In older landfills, concentrations of PAE decrease significantly, possibly due to long-term degradation and conversion of PAE into other chemical compounds. Future research should prioritize evaluating the effectiveness of landfill liners and waste management practices in preventing the release of PAE and other pollutants into the environment. It is also possible to focus on developing efficient physical, biological, and chemical methods for removing PAEs from landfill leachates. Additionally, the effectiveness of existing treatment processes in removing PAEs from landfill leachates and the necessity for new treatment processes can be considered.

Occurrence and Health Risk Assessment of Phthalates in Municipal Drinking Water Supply of a Central Indian City.

In this study, the occurrence of phthalates in the municipal water supply of Nagpur City, India, was studied for the first time. The study aimed to provide insights into the extent of phthalate contamination and identify potential sources of contamination in the city's tap water. We analyzed fifteen phthalates and the total concentration (∑15phthalates) ranged from 0.27 to 76.36 µg L-1. Prominent phthalates identified were di-n-butyl phthalate (DBP), di-isobutyl phthalate (DIBP), benzyl butyl phthalate (BBP), di (2-ethylhexyl) phthalate (DEHP), di-n-octyl phthalate (DNOP), and di-nonyl phthalate (DNP). Out of the fifteen phthalates analyzed, DEHP showed the highest concentration in all the samples with the median concentration of 2.27 µg L-1, 1.39 µg L-1, 1.83 µg L-1, 2.02 µg L-1, respectively in Butibori, Gandhibaag, Civil Lines, and Kalmeshwar areas of the city. In 30% of the tap water samples, DEHP was found higher than the EPA maximum contaminant level of 6 µg L-1. The average daily intake (ADI) of phthalates via consumption of tap water was higher for adults (median: 0.25 µg kg-1 day-1) compared to children (median: 0.07 µg kg-1 day-1). The hazard index (HI) calculated for both adults and children was below the threshold level, indicating no significant health risks from chronic toxic risk. However, the maximum carcinogenic risk (CR) for adults (8.44 × 10-3) and children (7.73 × 10-3) was higher than the threshold level. Knowledge of the sources and distribution of phthalate contamination in municipal drinking water is crucial for effective contamination control and management strategies.

A Hazard-Based Framework for Identifying Safer Alternatives to Classes of Chemicals: A Case Study on Phthalates in Consumer Products.

BACKGROUND: Humans are exposed to hazardous chemicals found in consumer products. In 2019, the Pollution Prevention for Healthy People and Puget Sound Act was passed in Washington State. This law is meant to reduce hazardous chemicals in consumer products and protect human health and the environment. The law directs the Washington State Department of Ecology to assess chemicals and chemical classes found in products, determine whether there are safer alternatives, and make regulatory determinations. OBJECTIVES: To implement the law, the Department of Ecology developed a hazard-based framework for identifying safer alternatives to classes of chemicals. METHODS: We developed a hazard-based framework, termed the "Criteria for Safer," to set a transparent bar for determining whether new chemical alternatives are safer than existing classes of chemicals. Our "Criteria for Safer" is a framework that builds on existing hazard assessment methodologies and published approaches for assessing chemicals and chemical classes. DISCUSSION: We describe implementation of our criteria using a case study on the phthalates chemical class in two categories of consumer products: vinyl flooring and fragrances used in personal care and beauty products. Additional context and considerations that guided our decision-making process are also discussed, as well as benefits and limitations of our approach. This paper gives insight into our development and implementation of a hazard-based framework to address classes of chemicals in consumer products and will aid others working to build and employ similar approaches. https://doi.org/10.1289/EHP13549.

Naked-eye sensitive detection of nanoPET by pH-responsive colorimetric method based on dual-enzyme catalysis.

A pH-responsive colorimetric method based on dual-enzyme catalysis for rapid and facile detection and quantification of nanoPET at environment-dependent concentration is proposed. The nanoPET was hydrolyzed by the synergistic catalysis of cutinase and lipase to terephthalic acid which can be sensitive detected using bromocresol purple as the indicator. The color changed from purple to bright yellow as the nanoPET detection concentration increased from 0 mg/mL to 2 mg/mL which can be detected by UV-Vis. This naked-eye method has a high sensitivity for nanoPET detection with the visual detection cutoff of 31.00 µg/mL, and has a good linearity in the range of 0 âˆ¼ 1 mg/mL with LOD of 22.84 µg/mL. The reliability of this method is verified in the detection of nanoPET in lake water and beer samples, with an average recovery of 87.1 %. The as-developed dual-enzyme colorimetric chemosensor holds promising potential as a robust and effective platform for the sensitive detection of nanoPET.

Evidence of economic development revealed in centennial scale sedimentary records of organic pollutants in Huguangyan Marr Lake.

Sedimentary records of polycyclic aromatic hydrocarbons (PAHs) and phthalates could reflect energy consumption and industrial production adjustment. However, there is limited knowledge about their effects on variations of PAH and phthalate compositions in the sediment core. The PAH and phthalate sedimentary records in Huguangyan Maar Lake in Guangdong, China were constructed, and random forest models were adopted to quantify the associated impact factors. Sums of sixteen PAH (∑16 PAH) and seven phthalate (∑7 PAE) concentrations in the sediment ranged from 28.8 to 1110 and 246-4290 µg/kg dry weight in 1900-2020. Proportions of 5-6 ring PAHs to the ∑16 PAHs increased from 32.0 %-40.7 % in 1900-2020 with increased coal and petroleum consumption, especially after 1980. However, those of 2-3 ring PAHs decreased from 30.7 % to 23.6 % due to the biomass substitution with natural gas. The proportions of bis (2-ethylhexyl) phthalate to the ∑7 PAEs decreased from 52.3 %-29.1 % in 1900-2020, while those of di-isobutyl phthalate increased (13.7 % to 42.3 %). The shift from traditional plasticizers to non-phthalates drove this transformation, though the primary plastic production is increasing. Our findings underscore the effectiveness of optimizing energy structures and updating chemical products in reducing organic pollution in aquatic environments.

Temporal evolution of plastic additive contents over the last decades in two major European rivers (Rhone and Rhine) from sediment cores analyses.

Although global plastic distribution is at the heart of 21st century environmental concerns, little information is available concerning how organic plastic additives contaminate freshwater sediments, which are often subject to strong anthropogenic pressure. Here, sediment core samples were collected in the Rhone and the Rhine watersheds (France), dated using 137Cs and 210Pbxs methods and analysed for nine phthalates (PAEs) and seven organophosphate esters (OPEs). The distribution of these organic contaminants was used to establish a chronological archive of plastic additive pollution from 1860 (Rhine) and 1930 (Rhone) until today. Sediment grain size and parameters related to organic matter (OM) were also measured as potential factors that may affect the temporal distribution of OPEs and PAEs in sediments. Our results show that OPE and PAE levels increased continuously in Rhone and Rhine sediments since the first records. In both rivers, ∑PAEs levels (from 9.1 ± 1.7 to 487.3 ± 27.0 ng g-1 dry weight (dw) ± standard deviation and from 4.6 ± 1.3 to 65.2 ± 11.2 ng g-1 dw, for the Rhine and the Rhone rivers, respectively) were higher than ∑OPEs levels (from 0.1 ± 0.1 to 79.1 ± 13.7 ng g-1 dw and from 0.6 ± 0.1 to 17.8 ± 2.3 ng g-1 dw, for Rhine and Rhone rivers, respectively). In both rivers, di(2-ethylhexyl) phthalate (DEHP) was the most abundant PAE, followed by diisobutyl phthalate (DiBP), while tris (2-chloroisopropyl) phosphate (TCPP) was the most abundant OPE. No relationship was found between granulometry and additives concentrations, while organic matter helps explain the vertical distribution of PAEs and OPEs in the sediment cores. This study thus establishes a temporal trajectory of PAEs and OPEs contents over the last decades, leading to a better understanding of historical pollution in these two Western European rivers.

Analysis and remediation of phthalates in aquatic matrices: current perspectives.

Phthalic acid esters (PAEs) are high production volume chemicals used extensively as plasticizers, to increase the flexibility of the main polymer. They are reported to leach into their surroundings from plastic products and are now a ubiquitous environmental contaminant. Phthalate levels have been determined in several environmental matrices, especially in water. These levels serve as an indicator of plasticizer abuse and plastic pollution, and also serve as a route of exposure to different species including humans. Reports published on effects of different PAEs on experimental models demonstrate their carcinogenic, teratogenic, reproductive, and endocrine disruptive effects. Therefore, regular monitoring and remediation of environmental water samples is essential to ascertain their hazard quotient and daily exposure levels. This review summarises the extraction and detection techniques available for phthalate analysis in water samples such as chromatography, biosensors, immunoassays, and spectroscopy. Current remediation strategies for phthalate removal such as adsorption, advanced oxidation, and microbial degradation have also been highlighted.

Optimization of a fast and sensitive method based on matrix solid-phase dispersion-LC-ms/ms for simultaneous determination of phthalates and bisphenols in mussel samples.

Bisphenols and phthalates are wide classes of endocrine disrupting chemicals (EDCs) extensively used as additives in plastic products. In this study, a fast and reliable analytical method based on matrix solid-phase dispersion (MSPD) coupled with LC-MS/MS was developed and optimized for simultaneous determination of 8 bisphenols and 7 phthalates in raw mussel extract. The LC-MS/MS method was tested for linearity (R2), inter- and intra-day repeatability, limit of detection and quantification, both for matrix-free and matrix-matched solutions. The MSPD method was optimized in terms of ratio between sample and sorbent, and the type and quantity of the eluents in order to maximize the recoveries and to minimize matrix effects. The obtained recoveries (values between 75% and 113%), limits of detection (values between 0.048 and 0.36 µg kg-1), limits of quantification (values between 0.16 and 1.28 µg kg-1), repeatability (RSD% between 1.30% and 8.41%) and linearity (R2 > 0.998) were satisfactory and suitable for the determination of target micropollutants in food samples. In addition, the low solvent consumption and fast execution make this method ideal for routinely determinations of bisphenols and phthalates in mussels.

Hepatotoxic effects of chronic exposure to environmentally relevant concentrations of Di-(2-ethylhexyl) phthalate (DEHP) on crucian carp: Insights from multi-omics analyses.

Di-(2-ethylhexyl) phthalate (DEHP) is an extensively used phthalate esters (PAEs) that raise growing ecotoxicological concerns due to detrimental effects on living organisms and ecosystems. This study performed hepatotoxic investigations on crucian carp under chronic low-dosage (CLD) exposure to DEHP at environmentally relevant concentrations (20-500 µg/L). The results demonstrated that the CLD exposure induced irreversible damage to the liver tissue. Multi-omics (transcriptomics and metabolomics) analyses revealed the predominant toxicological mechanisms underlying DEHP-induced hepatotoxicity by inhibiting energy production pathways and the up-regulation of the purine metabolism. Disruption of metabolic pathways led to excessive reactive oxygen species (ROS) production and subsequent oxidative stress. The adverse metabolic effects were exacerbated by an interplay between oxidative stress and endoplasmic reticulum stress. This study not only provides new mechanistic insights into the ecotoxicological effects of DEHP under chronic low-dosage exposure, but also suggests a potential strategy for further ecological risk assessment of PAEs.

[Microbial Mechanisms of Removal of Phthalic Acid Esters in Purple Soils Revealed Using Metagenomic Analysis].

The removal mechanisms of phthalic acid esters (PAEs) have attracted much attention because of their endocrine-disrupting properties and persistence in environmental media. In order to reveal the removal mechanism of PAEs and involved keystone taxa and functional genes, purple soils were polluted by di-n-butyl phthalate (DBP) and di-2-ethylhexyl phthalate (DEHP), respectively, along a gradient of 0, 5, 10, and 20 mg·kg-1 and cultured for 90 days in the dark. The results showed that the degradation dynamics of DBP and DEHP were well-fitted by the first-order kinetic model, and the half-life of DBP and DEHP ranged from 17.0 to 38.2 days. The degradation rate of DBP (5 mg·kg-1) was the fastest, and that of DEHP (20 mg·kg-1) was the slowest. The soil samples of the seventh day and the fifteenth day were analyzed using metagenomic sequencing. NMDS and cluster analysis showed that there was a significant difference between the bacterial community structure of soil samples from the seventh day and the fifteenth day. The relative abundance of Actinobacteria increased from the seventh day to the fifteenth day. The smaller the half-life of DBP or DEHP, the higher the relative abundance of Actinobacteria in the different treatments. In addition, Streptomyces was the dominant genus in all polluted soils. Co-occurrence network analysis elucidated that Pandoraea was a keystone genus of the soil bacterial communities, which could be used to indicate the pollution levels of DBP and DEHP. The results of KEGG annotation demonstrated that Pandoraea was responsible for benzoate degradation, quorum sensing, ABC transporters, and the two-component system and could promote the intercellular communications and the microbial growth and proliferation and maintain the stability of the community structure. Therefore, the degradation rate of DBP and DEHP in purple soils depended on their initial content and their own properties. Actinobacteria played an important role in the PAEs degradation, and Pandoraea played a major part in promoting PAEs degradation and regulating the stability of the structure and function of degrading bacterial communities.

Phthalate ester levels in agricultural soils of greenhouses, their potential sources, the role of plastic cover material, and dietary exposure calculated from modeled concentrations in tomato.

Soil samples collected from 50 greenhouses (GHs) cultivated with tomatoes (plastic-covered:24, glass-covered:26), 5 open-area tomato growing farmlands, and 5 non-agricultural areas were analyzed in summer and winter seasons for 13 PAEs. The total concentrations (Σ13PAEs) in the GHs ranged from 212 to 2484 ng/g, wheeas the concentrations in open-area farm soils were between 240 and 1248 ng/g. Σ13PAE in non-agricultural areas was lower (35.0 - 585 ng/g). PAE exposure through the ingestion of tomatoes cultivated in GH soils and associated risks were estimated with Monte Carlo simulations after calculating the PAE concentrations in tomatoes using a partition-limited model. DEHP was estimated to have the highest concentrations in the tomatoes grown in both types of GHs. The mean carcinogenic risk caused by DEHP for tomato grown in plastic-covered GHs, glass-covered GHs, and open-area soils were 2.4 × 10-5, 1.7 × 10-5 and 1.1 × 10-5, respectively. Based on Positive Matrix Factorization results, plastic material usage in GHs (including plastic cover material source for plastic-GHs) was found to be the highest contributing source in both types of GHs. Microplastic analysis indicated that the ropes and irrigation pipes inside the GHs are important sources of PAE pollution. Pesticide application is the second highest contributing source.

Development and validation of a GC Orbitrap-MS method for the analysis of phthalate esters (PAE) and bis(2-ethylhexyl)adipate (DEHA) in atmospheric particles and its application for screening PM2.5 from Curitiba, Brazil.

Phthalates or phthalic acid esters (PAE) and bis(2-ethylhexyl)adipate (DEHA) are ubiquitous chemicals often used as plasticisers and additives in many industrial products and are classified as both persistent organic pollutants (POPs) and new emerging pollutants (NEPs). Exposure to these chemicals, especially through inhalation, is linked to a wide range of negative health effects, including endocrine disruption. Air particulate matter (PM) with an aerodynamic diameter ≤ 2.5 µm can be enriched with PAEs and DEHA and if inhaled can cause multi-system human toxicity. Therefore, proper monitoring of PAEs and DEHA in PM is required to assess human exposure to these pollutants. In this work, we developed and validated a new and sensitive gas-chromatography high-resolution mass spectrometry (GC-HRMS) method for targeted analysis of PAEs including dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), benzyl butyl phthalate (BBP), bis(2-ethylhexyl)adipate (DEHA), bis(2-ethylhexyl)phthalate (DEHP), di-n-octyl phthalate (DOP), in PM. Analytical aspects including sample preparation steps and GC-HRMS parameters, e.g., quadrupole isolation window, to enhance method sensitivity have been assessed. The estimated limit of detection (LODs) of target PAEs and DEHA ranged from 5.5 to 17 pg µL-1, allowing their trace-level detection in PM. Extraction efficiencies of 78-101% were obtained for the target compounds. Low DMP and DEP extraction efficiencies from the spiked filter substrates indicated that significant losses of higher volatility PAEs can occur during the sample collection when filter-based techniques are used. This work is the first targeted method based on GC-Orbitrap MS for PAEs and DEHA in environmental samples. The validated method was successfully applied for the targeted analysis of PAEs and DEHA in PM2.5 samples from the eighth most populous city in Brazil, Curitiba. This work is the first to report DBP, DEHA, DEHP, and DOP in urban PM from Brazil. The observed concentrations of PAEs (up to 29 ng m-3) in PM2.5 from Curitiba may not represent the extent of pollution by these toxic compounds since the analysed samples were collected during a COVID-19 restriction when anthropogenic activities were reduced.

Pollution characteristics, sources, and health risks of phthalate esters in ambient air: A daily continuous monitoring study in the central Chinese city of Nanchang.

In recent years, the atmospheric pollution caused by phthalate esters (PAEs) has been increasing due to the widespread use of PAE-containing materials. Existing research on atmospheric PAEs lacks long-term continuous observation and samples from cities in central China. To investigate the pollution characteristics, sources, and health risks of PAEs in the ambient air of a typical city in central China, daily PM2.5 samples were collected in Nanchang from November 2020 to October 2021. In this study, the detection and quantification of six significant PAE contaminants, namely diethyl phthalate (DEP), di-n-butyl phthalate (DnBP), diisobutyl phthalate (DIBP), Di-2-ethylhexyl phthalate (DEHP), di-n-octyl phthalate (DnOP), and diisodecyl phthalate (DIDP), were accomplished using gas chromatography and mass spectrometry. The results revealed that the concentrations of DEP, DnBP, DEHP, and DnOP were relatively high. Higher temperatures promote the volatilization of PAEs, leading to an increase in the gaseous and particulate PAE concentrations in warm seasons and winter pollution scenarios. The results of principal component analysis show that PAEs mainly come from volatile products and polyvinylchloride plastics. Using positive matrix factorization analysis, it is shown that these two sources contribute 67.0% and 33.0% in atmosphere PAEs, respectively. Seasonally, the contribution of volatile products to both gaseous and particulate PAEs substantially increases during warm seasons. The residents in Nanchang exposed to PAEs have a negligible non-cancer risk and a potential low cancer risk. During the warm seasons, more PAEs are emitted into the air, which will increase the toxicity of PAEs and their impact on human health.