Diisobutyl Phthalate Research Articles

Pigmentiphaga kullae CHJ604 improved the growth of tobacco by degrading allelochemicals and xenobiotics in continuous cropping obstacles

Plant autotoxicity is considered to be one of the important causes of continuous cropping obstacles in modern agriculture, which accumulates a lot of allelochemicals and xenobiotics and is difficult to solve effectively. To overcome tobacco continuous obstacles, a strain Pigmentiphaga kullae CHJ604 isolated from the environment can effectively degrade these compounds in this study. CHJ604 strain can degrade 11 types of autotoxicity allelochemicals and xenobiotics (1646.22 μg/kg) accumulated in the soil of ten-years continuous cropping of tobacco. The 11 allelochemicals and xenobiotics significantly reduced Germination Percentage (GP), Germination Index (GI), and Mean Germination Time (MGT) of tobacco seeds, and inhibited the development of leaves, stems, and roots. These negative disturbances can be eliminated by CHJ604 strain. The degradation pathways of 11 allelochemicals and xenobiotics were obtained by whole genome sequence and annotation of CHJ604 strain. The heterologous expression of a terephthalate 1,2-dioxygenase can catalyze 4-hydroxybenzoic acid, 4-hydroxy-3-methoxybenzoic acid, 4-hydroxybenzaldehyde, and 4-hydroxy-3-methoxy-benzaldehyde, respectively. The phthalate 4,5-dioxygenase can catalyze phthalic acid, diisobutyl phthalate, and dibutyl phthalate. These two enzymes are conducive to the simultaneous degradation of multiple allelochemicals and xenobiotics by strain CHJ604. This study provides new insights into the biodegradation of autotoxicity allelochemicals and xenobiotics as it is the first to describe a degrading bacterium of 11 types of allelochemicals and xenobiotics and their great potential in improving tobacco continuous obstacles.

Active substances of myxobacteria against plant diseases and their action mechanisms.

Myxobacteria have a complex life cycle and unique social behavior, and obtain nutrients by preying on bacteria and fungi in soil. Chitinase, β-1,3 glucanase and β-1,6 glucanase produced by myxobacteria can degrade the glycosidic bond of cell wall of some plant pathogenic fungi, resulting in a perforated structure in the cell wall. In addition, isooctanol produced by myxobacteria can lead to the accumulation of intracellular reactive oxygen species in some pathogenic fungi and induce cell apoptosis. Myxobacteria can also perforate the cell wall of some plant pathogenic oomycetes by β-1,3 glucanase, reduce the content of intracellular soluble protein and protective enzyme activity, affect the permeability of oomycete cell membrane, and aggravate the oxidative damage of pathogen cells. Small molecule compounds such as diisobutyl phthalate and myxovirescin produced by myxobacteria can inhibit the formation of biofilm and lipoprotein of bacteria, and cystobactamids can inhibit the activity of DNA gyrase, thus changing the permeability of bacterial cell membrane. Myxobacteria, as a new natural compound resource bank, can control plant pathogenic fungi, oomycetes and bacteria by producing carbohydrate active enzymes and small molecular compounds, so it has great potential in plant disease control.

The role of organoaluminum and electron donors in propene insertion on the Ziegler-Natta catalyst.

Alkyl aluminium plays a primary role in activating Ti within Ziegler-Natta (ZN) catalysts for propylene polymerization. We performed density functional calculations to explore the additional roles of AlEt3 and AlEt2Cl, in conjunction with diisobutyl phthalate (DIBP) internal donor and dicyclopentyl dimethoxysilane (DCPDMS) external donor, to enhance the stereoselectivity of propene insertion. Based on our calculated adsorption energies on the (MgCl2)13/TiCl2iBu cluster model for the ZN catalyst, the presence of DIBP on the cluster essentially facilitated AlEt2Cl adsorption while AlEt2Cl also promoted the adsorption of DIBP. The reaction between AlEt3 and DIBP on the cluster led to the extraction of DIBP, creating an available site for DCPDMS adsorption. While the stereoselectivity, represented by the difference in the activation energies between 1,2-re and 1,2-si insertions of propene, was negligible on the cluster containing only DIBP, it became significant on the clusters containing both AlEt2Cl and DIBP (and DCPDMS). AlEt2Cl plays a pivotal role in imposing steric effects near the Ti active site, thereby increasing stereoselectivity. Our findings suggest the importance of including AlEt2Cl alongside DIBP (and DCPDMS) in the ZN cluster model to investigate stereoselective propene insertion. Considering AlEt2Cl adsorption and AlEt3 reaction with internal donors is essential in developing Ziegler-Natta catalysts.

Facile fabrication of carbon nanotube hollow microspheres as a fiber coating for ultrasensitive solid-phase microextraction of phthalic acid esters in tea beverages.

The efficient extraction of phthalic acid esters (PAEs) is challenging due to their extremely low concentration, complicated matrices and hydrophilicity. Herein, hollow microspheres, as an ideal coating, possess significant potential for solid-phase microextraction (SPME) due to their fascinating properties. In this study, multiwalled carbon nanotube hollow microspheres (MWCNT-HMs) were utilized as a fiber coating for the SPME of PAEs from tea beverages. MWCNT-HMs were obtained by dissolving the polystyrene (PS) cores with organic solvents. Interestingly, MWCNT-HMs well maintain the morphology of the MWCNTs@PS precursors. The layer-by-layer (LBL) assembly of MWCNTs on PS microsphere templates was achieved through electrostatic interactions. Six PAEs, di-ethyl phthalate (DEP), di-iso-butyl phthalate (DIBP), di-n-butyl phthalate (DBP), benzyl butyl phthalate (BBP), di-2-ethylhexyl phthalate (DEHP) and di-n-octyl phthalate (DOP), were selected as target analytes for assessing the efficiency of the coating for SPME. The stirring rate, sample solution pH and extraction time were optimized by using the Box-Behnken design. Under optimal working conditions, the proposed MWCNT-HMs/SPME was coupled with gas chromatography-tandem mass spectrometry (GC-MS/MS) to achieve high enrichment factors (118-2137), wide linearity (0.0004-10 μg L-1), low limits of detection (0.00011-0.0026 μg L-1) and acceptable recovery (80.2-108.5%) for the detection of PAEs. Therefore, the MWCNT-HM coated fibers are promising alternatives in the SPME method for the sensitive detection of PAEs at trace levels in tea beverages.

Characterizing Chemical Exposure Trends from NHANES Urinary Biomonitoring Data.

Xenobiotic metabolites are widely present in human urine and can indicate recent exposure to environmental chemicals. Proper inference of which chemicals contribute to these metabolites can inform human exposure and risk. Furthermore, longitudinal biomonitoring studies provide insight into how chemical exposures change over time. We constructed an exposure landscape for as many human-exposure relevant chemicals over as large a time span as possible to characterize exposure trends across demographic groups and chemical types. We analyzed urine data of nine 2-y cohorts (1999-2016) from the National Health and Nutrition Examination Survey (NHANES). Chemical daily intake rates (in milligrams per kilogram bodyweight per day) were inferred, using the R package bayesmarker, from metabolite concentrations in each cohort individually to identify exposure trends. Trends for metabolites and parents were clustered to find chemicals with similar exposure patterns. Exposure variation by age, gender, and body mass index were also assessed. Intake rates for 179 parent chemicals were inferred from 151 metabolites (96 measured in five or more cohorts). Seventeen metabolites and 44 parent chemicals exhibited fold-changes between any two cohorts (deltamethrin, di--octyl phthalate, and di-isononyl phthalate had the greatest exposure increases). Di-2-ethylhexyl phthalate intake began decreasing in 2007, whereas both di-isobutyl and di-isononyl phthalate began increasing shortly before. Intake for four parabens was markedly higher in females, especially reproductive-age females, compared with males and children. Cadmium and arsenobetaine exhibited higher exposure for individuals years of age and lower for individuals years of age. With appropriate analysis, NHANES indicates trends in chemical exposures over the past two decades. Decreases in exposure are observable as the result of regulatory action, with some being accompanied by increases in replacement chemicals. Age- and gender-specific variations in exposure were observed for multiple chemicals. Continued estimation of demographic-specific exposures is needed to both monitor and identify potential vulnerable populations. https://doi.org/10.1289/EHP12188.

Multi-source exposure and health risks of phthalates among university students in Northeastern China

The endocrine disruptor phthalates (PAEs) are widely used as important chemical additives in a variety of areas around the globe. PAEs are toxic to reproduction and development and may adversely affect the health of adolescents. Risk assessments of exposure to PAEs from different sources are more reflective of actual exposure than single-source assessments. We used personal exposure parameters to estimate the dose of PAEs to 107 university students from six media (including dormitory dust, dormitory air, clothing, food, disposable food containers, and personal care products (PCPs)) and three exposure routes (including ingestion, inhalation, and dermal absorption). Individual factors and lifestyles may affect PAE exposure to varying degrees. Based on a positive matrix factorization (PMF) model, the results indicated that the main sources of PAEs in dust were indoor building materials and plastics, while PCPs and adhesives were the major sources of airborne PAEs. The relative contribution of each source to PAE exposure showed that food and air were the primary sources of dimethyl phthalate (DMP) and dibutyl phthalate (DBP). Air source contributed the most to diethyl phthalate (DEP) exposure, followed by PCPs. Food was the most significant source of diisobutyl phthalate (DiBP), benzyl butyl phthalate (BBP), and bis(2-ethylhexyl) phthalate (DEHP) exposure. Additionally, the exposure of DEHP to dust was not negligible. The ingestion pathway was the most dominant among the three exposure pathways, followed by dermal absorption. The non-carcinogenic risk of PAEs from the six sources was within acceptable limits. DEHP exhibits a low carcinogenic risk. We suggest university students maintain good hygienic and living habits to minimize exposure to PAEs.

Phthalate contamination in marine mammals off the Norwegian coast

Phthalates are used in plastics, found throughout the marine environment and have the potential to cause adverse health effects. In the present study, we quantified blubber concentrations of 11 phthalates in 16 samples from stranded and/or free-living marine mammals from the Norwegian coast: the killer whale (Orcinus orca), sperm whale (Physeter macrocephalus), long-finned pilot whale (Globicephala melas), white-beaked dolphin (Lagenorhynchus albirostris), harbour porpoise (Phocoena phocoena), and harbour seal (Phoca vitulina). Five compounds were detected across all samples: benzyl butyl phthalate (BBP; in 50 % of samples), bis(2-ethylhexyl) phthalate (DEHP; 33 %), diisononyl phthalate (DiNP; 33 %), diisobutyl phthalate (DiBP; 19 %), and dioctyl phthalate (DOP; 13 %). Overall, the most contaminated individual was the white-beaked dolphin, whilst the lowest concentrations were measured in the killer whale, sperm whale and long-finned pilot whale. We found no phthalates in the neonate killer whale. The present study is important for future monitoring and management of these toxic compounds.

Comparing the removal efficiency of diisobutyl phthalate by Bacillariophyta, Cyanophyta and Chlorophyta

The utilization of microalgae for both removing phthalate esters (PAEs) from wastewater and producing bioenergy has become a popular research topic. However, there is a lack of studies comparing the effectiveness of different types of microalgae in removing these harmful compounds. Therefore, the present study aimed to evaluate and compare the efficiency of various processes, such as hydrolysis, photolysis, adsorption, and biodegradation, in removing diisobutyl phthalate (DiBP) using six different species of microalgae. The study indicated that the average removal efficiency of DiBP (initial concentrations of 5, 0.5, and 0.05 mg L−1) by all six microalgae (initial cell density of 1 × 106 cells mL−1) was in the order of Scenedesmus obliquus (95.39 %) > Chlorella vulgaris (94.78 %) > Chroococcus sp. (91.16 %) > Cyclotella sp. (89.32 %) > Nitzschia sp. (88.38 %) > Nostoc sp. (84.33 %). The results of both hydrolysis and photolysis experiments revealed that the removal of DiBP had minimal impact, with respective removal efficiencies of only 0.89 % and 1.82 %. The adsorption efficiency of all six microalgae decreased significantly with increasing initial DiBP concentrations, while the biodegradation efficiency was elevated. Chlorella vulgaris and Chroococcus sp. demonstrated the highest adsorption and biodegradation efficiencies among the microalgae tested. Scenedesmus obliquus was chosen for the analysis of the degradation products of DiBP due to its exceptional ability to remove DiBP. The analysis yielded valuable results, identifying monoisobutyl phthalate (MiBP), phthalic acid (PA), and salicylic acid (SA) as the possible degradation products of DiBP. The possible degradation pathways mainly included dealkylation, the addition of hydroxyl groups, and decarboxylation. This study lays a theoretical foundation for the elimination of PAEs in the aquatic environment.

Diisobutyl phthalate (DiBP)-induced male germ cell toxicity and its alleviation approach

Diisobutyl phthalate (DiBP) is a commonly used plasticizer in manufacturing consumer and industrial products to improve flexibility and durability. Despite of the numerous studies, however, the direct mechanism underlying the male reproductive damage of DiBP is poorly understood. In this study, we investigated the male germ cell toxicity of DiBP using GC-1 spermatogonia (spg) cells. Our results indicated that DiBP exposure causes oxidative stress and apoptosis in GC-1 spg cells. In addition, DiBP-derived autophagy activation and down-regulation of phosphoinositide 3-kinase (PI3K)-AKT and extracellular signal-regulated kinase (ERK) pathways further inhibited GC-1 spg cell proliferation, indicating that DiBP can instigate male germ cell toxicity by targeting several pathways. Importantly, a combined treatment of parthenolide, N-acetylcysteine, and 3-methyladenine significantly reduced DiBP-induced male germ cell toxicity and restored proliferation. Taken together, the results of this study can provide valuable information to the existing literature by enhancing the understanding of single phthalate DiBP-derived male germ cell toxicity and the therapeutic interventions that can mitigate DiBP damage.

Single-run gas chromatography-mass spectrometry method for the analysis of phthalates, polycyclic aromatic hydrocarbons, and pesticide residues in infant formula based on dispersive microextraction techniques

For the first time, three important contaminant groups (phthalates, polycyclic aromatic hydrocarbons, and pesticides), traditionally monitored by separated methods, were simultaneously analyzed in complex infant formula matrices. An accurate and sensitive analytical method based on gas chromatography-mass spectrometry (GC–MS) was developed for 45 food contaminants. Dispersive solid-phase extraction and low-density solvent-based dispersive liquid–liquid microextraction techniques were combined for clean-up and analyte enrichment purposes. Distinct GC–MS injection conditions were studied with the highest analytical responses obtained at high temperatures in pulsed splitless mode at high pulse pressures. Low matrix effects were observed for the majority of analytes under study, indicating a possible relation of these effects with the physicochemical parameters of the analytes. Adequate method performance characteristics were achieved, covering limits of detection and quantification sufficiently low to monitor the regulated compounds at the maximum limits fixed for infant formula. Furthermore, the greenness and practicality of the proposed method were evaluated through the AGREE and BAGI metric tools, respectively. In summary, the application of the proposed method to commercial infant formulas, with the identification and quantification of benzo[a]pyrene, benz[a]anthracene, dibutyl phthalate, di(2-ethylhexyl) phthalate, dimethyl phthalate, and diisobutyl phthalate at levels between 1.4 and 47.1 µg kg−1 in a total of 30.0 % samples, demonstrates their suitability for routine analysis as well as contributes to the first data on the co-occurrence of PAHs and phthalates in infant formula.

Phthalates in marine sediment, water and the cockle Anadara antiquata on the coast of Tanzania

Phthalates are a group of chemicals used as plasticisers, and are easily released into the environment, where they degrade over time. We investigated the concentrations of phthalates in sediments, seawater, and the cockle Anadara antiquata from beaches at Dar es Salaam, Mtwara, Tanga and Zanzibar in Tanzania. A dispersive liquid-liquid microextraction method was used to extract analytes from samples, whereafter they were analysed with a gas chromatograph coupled to a mass spectrophotometer. Concentrations of diisobutyl phthalate (DiBP), dibutyl phthalate (DBP) and Bis(2-ethylhexyl) phthalate (DEHP) were determined. DiBP concentrations were highest at Dar es Salaam (11.5 - 12.4 ng/mL in seawater; 11.5 - 13.6 ng/g dry weight in sediments), compared to the other three sites, where minimum and maximum concentrations in sediments were 3.5 ng/g dw (Mtwara) and 10.7 ng/g dw (Tanga). DBP concentrations were also highest at Dar es Salaam (12.4 - 20.6 ng/mL in seawater; 12.1 - 18.7 ng/g dw in sediments) compared to 2.7 (minimum, Mtwara) and 11.2 ng/g dw (maximum, Tanga). DEHP at Dar es Salaam ranged from un-detected to 12.6 ng/mL in seawater and to 12.6 ng/g dw in sediments. It was further revealed that A. antiquata from Kawe Beach (Dar es Salaam) had higher concentrations of DiBP, DBP, and DEHP compared to other sites. Monitoring of phthalate concentrations will indicate pollution hotspots and trends in the region.

Characterization of Biodiesel and Diesel Combustion Particles: Chemical Composition, Lipid Metabolism, and Implications for Health and Environment.

Biodiesel, derived from alkyl esters of vegetable oils or animal fats, has gained prominence as a greener alternative to diesel due to its reduced particle mass. However, it remains debatable whether biodiesel exposure has more severe health issues than diesel. This study performed high-resolution mass spectrometry to examine the detailed particle chemical compositions and lipidomics analysis of human lung epithelial cells treated with emissions from biodiesel and diesel fuels. Results show the presence of the peak substances of CHO compounds in biodiesel combustion that contain a phthalate ester (PAEs) structure (e.g., n-amyl isoamyl phthalate and diisobutyl phthalate). PAEs have emerged as persistent organic pollutants across various environmental media and are known to possess endocrine-disrupting properties in the environment. We further observed that biodiesel prevents triglyceride storage compared to diesel and inhibits triglycerides from becoming phospholipids, particularly with increased phosphatidylglycerols (PGs) and phosphatidylethanolamines (PEs), which potentially could lead to a higher probability of cancer metastasis.

Reducing Transdermal Uptake of Semivolatile Plasticizers from Indoor Environments: A Clothing Intervention.

Models and laboratory studies suggest that everyday clothing influences the transdermal uptake of semivolatile organic compounds, including phthalate plasticizers, from indoor environments. However, this effect has not been documented in environmental exposure settings. In this pilot study, we quantified daily excretion of 17 urinary metabolites (μg/day) for phthalates and phthalate alternatives in nine participants during 5 days. On Day 0, baseline daily excretion was determined in participants' urine. Starting on Day 1, participants refrained from eating phthalate-heavy foods and using personal care products. On Days 3 and 4, participants wore precleaned clothing as an exposure intervention. We observed a reduction in the daily excretion of phthalates during the intervention; mono-n-butyl phthalate, monoisobutyl phthalate (MiBP), and monobenzyl phthalate were significantly reduced by 35, 38, and 56%, respectively. Summed metabolites of di(2-ethylhexyl)phthalate (DEHP) were also reduced (27%; not statistically significant). A similar reduction among phthalate alternatives was not observed. The daily excretion of MiBP during the nonintervention period strongly correlated with indoor air concentrations of diisobutyl phthalate (DiBP), suggesting that inhalation and transdermal uptake of DiBP from the air in homes are dominant exposure pathways. The results indicate that precleaned clothing can significantly reduce environmental exposure to phthalates and phthalate alternatives.

Phthalate Concentration Estimation and Exposure Assessment and Health Risk Assessment in Indoor Organic Film

Organic films act as passive air samplers and can be employed to assess the concentration of semivolatile organic compounds (SVOCs), such as phthalates, in the gas phase over a defined period using the kinetic adsorption model. Consequently, indoor organic films have been identified as effective media for evaluating human exposure to SVOCs. This study proposed an organic film-based method for assessing SVOC exposure in the indoor environment. Exposure assessments of various phthalate pathways were conducted on children and adults. Organic films were collected for analysis from 110 residential dwellings in metropolitan areas over a two-month period. The exposure assessments were categorized into inhalation, oral, and dermal exposure pathways. Diethyl phthalate was highest in inhalation exposure, dibutyl phthalate represented the highest dermal exposure, and bis(2-ethylhexyl) phthalate was identified as the highest contributor to oral exposure. For children, the primary exposure pathways included dermal absorption of DBP, DEP, diisobutyl phthalate (DiBP), butylbenzyl phthalate (BBP), and di-n-hexyl phthalate (DNHP); dust ingestion of DEHP and di-n-octyl phthalate (DNOP); and inhalation of dimethyl phthalate (DMP). The ECR and HQ for inhalation, dermal, and ingestion did not exceed the threshold in children and adults at all pollutants, suggesting no potential health impact. In contrast, the primary routes of exposure for adults were dermal absorption of DBP, DMP, DEP, DiBP, BBP, and DNHP, along with dust ingestion of DEHP and DNOP. The findings of this study provide valuable baseline data for future research in health risk and SVOC exposure assessments utilizing indoor organic films.

Assessment of the UV/DCCNa and UV/NaClO oxidation process for the removal of diethyl phthalate (DEP) in the aqueous system

In this work, the removal and transformation process of diethyl phthalate (DEP) in UV/dichloroisocyanurate (UV/DCCNa) and UV/sodium hypochlorite (UV/NaClO) systems were compared to evaluate the application potential of UV/DCCNa technology. Compared with UV/NaClO, UV/DCCNa process has the advantage of DEP removal and caused a higher degradation efficiency (93.8%) within 45 min of oxidation in ultrapure water due to the sustained release of hypochloric acid (HOCl). Fourteen intermediate products were found by high-resolution mass spectrometry, and the transformation patterns including hydroxylation, hydrolysis, chlorination, cross-coupling, and nitrosation were proposed. The oxidation processes were also performed under quasi-realistic environmental conditions, and it was found that DEP could be effectively removed in both systems, with yields of disinfection byproduct meeting the drinking water disinfection standard (<60.0 μg/L). Comparing the single system, the removal of DEP decreased in the mixed system containing five kinds of PAEs, which could be attributed to the regeneration of DEP and the competitive effect of •OH occurred among the Dimethyl phthalate (DMP), DEP, Dipropyl phthalate (DPrP), Diallyl phthalate (DAP) and Diisobutyl phthalate (DiBP). However, a greater removal performance presented in UV/DCCNa system compared with UV/NaClO system (69.4% > 62.1%). Further, assessment of mutagenicity and developmental toxicity by Toxicity Estimation Software Tool (T.E.S.T) software indicated that UV/DCCNa process has fewer adverse effects on the environment and is a more environmentally friendly chlorination method. This study may provide some guidance for selecting the suitable disinfection technology for drinking water treatment.

Phthalate acid ester release from microplastics in water environment and their comparison between single and competitive adsorption.

The ability of microplastics (MPs) to adsorb environmental pollutants has been extensively studied. However, little is known about the ability of MPs to release inherent additives and the interaction between them. This paper explored the effects of environmental factors on the release of phthalic acid esters (PAEs) from three different types of microplastics (polyethylene microplastics (PE-MPs), polypropylene microplastics (PP-MPs), and polystyrene microplastics (PS-MPs)) by simulating water environments, as well as the differences in the adsorption of one or more PAEs by MPs. The results showed that the types of MPs, single environmental factors, and combined environmental factors had a great influence on the release of di(2-ethylhexyl) phthalate (DEHP). In the influence of a single environmental factor, the releasing amount of DEHP increased significantly. When the pH value increased from 5 to 9, the release of three PAEs from all MPs decreased. Moreover, under the combined influence of three environmental factors, the DEHP release from PP-MPs was most affected by environmental factors, and the order of influence of the three environmental factors was ionic strength > organic matter > pH. The DEHP release of PS-MPs was the highest (0.058 ± 0.023 μg/L), followed by PP-MPs (0.038 ± 0.010 μg/L) and PE-MPs (0.035 ± 0.008 μg/L). Adsorption kinetics and isotherm fitting showed that the adsorption process of the three MPs was suitable for the pseudo-second-order kinetic model, and the Freundlich adsorption isotherm had a higher fitting degree. Compared with single adsorption, the competitive adsorption of three PAEs increased the adsorption capacity of DEHP and decreased the adsorption capacity of dibutyl phthalate (DBP) and diisobutyl phthalate (DIBP). These findings help predict the potential of MPs to release toxic additives under different environmental conditions.

Method development of stir bar sportive extraction coupled with thermal desorption-gas chromatography-mass spectrometry for the analysis of phthalates in Peruvian pisco

In this work, for the first time, a stir bar sorptive extraction (SBSE) coupled with thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS) was developed and validated for the determination of seven phthalates in Peruvian pisco. The phthalate compounds considered were dimethyl phthalate (DMP), diethyl phthalate (DEP), bis(2-ethylhexyl) hexahydrophthalate (BEHP), benzyl butyl phthalate (BBP), di-n-butyl phthalate (DBP), di-isodecyl phthalate (DIDP) and di-isobutyl phthalate (DIBP). The best overall analytical conditions obtained from the optimization were as follow: extraction time of 120 min, size of polydimethylsiloxane (PDMS) twister (20 mm length x 1 mm thickness), NaCl content (20 %) and sample volume (40 mL). The in-house validation of SBSE/TD–GC–MS method was performed taking into account the ISO/IEC 17,025 requirements and EURACHEM/CITAC guideline. Under optimal conditions, very low limits of detection of 1.3–0.21 µg L−1 were obtained. Furthermore, the limits of quantification ranged from 4.2–70 µg L−1, and the correlation coefficients were found to be ≥ 0.991. The method was precise, with relative standard deviations (RSD, %) for inter twister repeatability and the inter day repeatability precisions from 1.1 to 11 and from 6.2 to 15.9, respectively. The pisco samples were analysed with recoveries between 91–124.4%, and DBP, BEHP, and BBP were the most commonly found compounds in the samples. The optimized methodology was also evaluated in terms of green character, and it obtained almost the best AGREE score when it was compared with other previous methods for the analysis of phthalates in alcoholic beverages. Therefore, the SBSE/TD–GC–MS method has proved to be suitable for routine practice because it is simple, less laborious, economical, precise, accurate and green, and it would be applicable for pisco safety regulations.

Concentration identification and endpoint-oriented health risk assessments on a broad-spectrum of organic compounds in atmospheric fine particles: A sampling experimental study in Beijing, China

Understanding the complicate chemical components in atmospheric fine particulate matter (PM2.5) helps policy makers for pollutants control track progress and identify disparities in overall health risks. However, till now, information on accurate component detection, source identification, and effect-oriented risk assessment is scarce, especially for the simultaneous analysis of a broad-spectrum of compounds. In this study, a high-throughput target method was employed to distinguish the occurrence and characteristics of 152 chemicals: phthalate esters (PAEs), organophosphate esters (OPEs), carboxylic acid esters (CAEs), nitrophenols (NPs), nitrogen heterocyclic compounds (NHCs), per- and poly-fluoroalkyl substances (PFASs), triclosan and its derivatives (TCSs), and organosulfates (OSs) in ambient PM2.5 collected from Beijing, China. Detection frequencies of 77 targeted compounds were >50 %. Total concentrations of all compounds ranged from 33.1 to 745 ng/m3. The median concentration of ∑PAEs (108 ng/m3) was the highest, followed by ∑CAEs (12.2 ng/m3) and ∑NPs (10.1 ng/m3). Organophosphate diesters (di-OPEs) and TCSs were reported for the first time in ambient PM2.5. The pollutants mainly originated from the local industrial production, release of building materials, and environmental degradation of parent compounds. Based on absorption, distribution, metabolism, excretion, and toxicity (ADMET)-oriented risk evaluations, we found that bis (2-ethylhexyl) phthalate, diisobutyl phthalate, dibutyl phthalate, and di (2-ethylhexyl) adipate have high health risks. Additionally, the high oxidative stress potential of 4-nitrocatechol and the strong blood-brain barrier penetration potential of triclosan cannot be ignored. Our study will facilitate the evaluations of specific health outcomes and mechanisms of pollutants, and suggestion of pollutants priority control to reduce human health hazards caused by atmospheric particles.

Reproductive toxicity following in utero and lactational exposure to a human-relevant phthalate mixture in rats.

This rodent (Wistar rats) study examined reproductive effects of in utero/lactational exposure to a mixture of 6 antiandrogenic phthalates (PMix): diisobutyl phthalate, di-n-butyl phthalate, diisopentyl phthalate, butylbenzyl phthalate, di-2-ethylhexyl phthalate, and diisononyl phthalate. The PMix was defined based on exposure data from pregnant women in Brazil. Experimental groups were established by extrapolating the estimated human dose to rats (0.1 mg/kg/day), followed by up to 3 additional doses corresponding to 5, 1000, and 5000 times the starting rat dose: 0 (control), 0.1, 0.5, 100, and 500 mg/kg/day. The fetal experiment assessed gestational exposure effects on fetal gonads, whereas the postnatal experiment evaluated reproductive parameters in males and females after in utero and lactational exposure. Prenatal exposure decreased fetal testicular testosterone production at 0.5 and 500 mg/kg/day. PMix 500 also reduced mRNA expression of steroidogenesis-related genes, upregulated transcript expression of the retinoic acid-degrading enzyme Cyp26b1, and increased multinucleated gonocytes incidence in fetal testes. Postnatal assessment revealed antiandrogenic effects at the highest dose, including reduced anogenital distance, nipple retention, and decreased weight of reproductive organs. Early puberty onset (preputial separation) was observed at the lowest dose in males. In contrast, females did not show significant changes in fetal and adult endpoints. Overall, the PMix recapitulated early and late male rat phthalate syndrome phenotypes at the highest dose, but also induced some subtle changes at lower doses, which warrant confirmation and mechanistic assessments. Our data support the use of epidemiologically defined mixtures for exposure risk assessments over traditional toxicological approaches.

Investigation on molecular characteristics of organic compounds during a full-scale landfill leachate treatment process based on non-targeted analysis

In this study, a new methodology for evaluating full-scale landfill leachate treatment processes by non-targeted analysis using comprehensive two-dimensional gas chromatography quadrupole time-of-flight mass spectrometry (GC × GC-QTOF-MS) was proposed. The method revealed the chemical complexity of organic compounds in landfill leachate samples at the molecular level and evaluated the removal efficiency of the anaerobic-anoxic-oxic (A2O) - membrane bioreactor (MBR) - nanofiltration (NF) treatment process in conjunction with multi-level classification of organic compounds. Results showed that the results of non-targeted analysis combined with multi-level classification of organic compounds had a significant correlation with the conventional water quality parameters and can be used to evaluate the treatment process. A total of 2508 organic compounds were detected in 6 samples. 17 emerging contaminants (ECs) with known potentially hazards were detected, including Diisobutyl Phthalate (DIBP), which is toxic to male reproduction and development, and 4-Tert-Butylphenol, which causes endocrine disruption in animals. The removal rate of organic compounds by this full-scale landfill leachate treatment processes reached 79.14%. The anaerobic tank played a crucial role with 64.98% contribution. For compounds, the removal rate of heterocyclics was as high as 94.67%, and the removal rate of aliphatics was poor, only 63.49%. This treatment process had almost perfect removal effect on the steroids in alicyclics and phenols in aromatics, but poor treatment effect on saturated alkanes in aliphatics and naphthenes in alicyclics. This study provides a methodology for accurate assessment of the molecular level of treatment processes, new insights for process optimization in waste treatment plants, and data support for the detection of emerging contaminants. The environmental hazards of landfill leachate can be further evaluated in the future in conjunction with ecotoxicity assessment studies.