Cloud point extraction coupled with HPLC-UV for the determination of phthalate esters in environmental water samples

A method based on cloud point extraction was developed to determine phthalate esters including di-ethyl-phthalate （DEP）, di- （2-ethylhexyl）-phthalate （DEHP） and di-cyclohexyl-phthalate （DCP） in environmental water samples using high-performance liquid chromatography separation and ultraviolet detection （HPLC-UV）. The non-ionic surfactant Triton X-114 was chosen as extraction solvent. The parameters affecting extraction efficiency, such as concentrations of Triton X-114 and Na2SO4, equilibration temperature, equilibration time and centrifugation time were evaluated and optimized. Under the optimum conditions, the method can achieve preconcentration factors of 35, 88, 111 and detection of limits of 2.0, 3.8, 1.0 ng/ml for DEP, DEHP and DCP in 10-ml water sample, respectively. The proposed method was successfully applied to the determination of trace amount of phathalate esters in effluent water of the wastewater treatment plant and the lixivium of plastic fragments.

Analysis of Phthalate Esters in Air, Soil and Plants in Plastic Film Greenhouse

The phthalate esters such as DMP, DEP, DBP and DEHP in air, soil and plant samples in plastic film greenhouse were clean up with fine silica gel column and determined with HPLC. It was found that the concentrations of PEs in air and soil samples in plastic film greenhouse are much higher than those of contrast samples. But concentrations of PEs in plants in plastic film greenhouse are not remarkably affected by the pollution of air and soil.

Determination of phthalate esters in physiological saline solution by monolithic silica spin column extraction method

Monolithic silica spin column extraction （MonoSpin-SPE） was developed as a simple, sensitive, and eco-friendly pretreatment method which combined with ultra-fast liquid chromatography-mass spectrometry （UFLC-MS） to determine the levels of six phthalate esters, dimethyl- （DMP）, diethyl- （DEP）, dipropyl- [ DPrP], butyl-benzyl- （BBP）, dicyclohexyl- （DcHP）, and di-n-octyl-（DOP） phthalate in physiological saline samples. Under optimized experimental conditions, the method was linear in the following ranges： 0.2- 50 μg/L for DMP, DEP, DPrP, DcHP and DOP; 5- 100 μg/L for BBP. The correlation coefficients （R2 ） were in the range of 0. 9951 - 0. 9995 for all the analytes and the limits of detection （LODs） and limits of quantification （LOQs） were in the ranges of 0.02 - 0.9 μg/L and 0.08 - 2.7μg/L, respectively. The pretreatment process showed good reproducibility with inter-day and intra-day relative standard deviations （RSDs） below 8.5% and 11.2%, respectively. This method was used to determine the levels of six phthalate esters in physiological saline samples and the recoveries ranged from 71.2% to 107.3%. DMP and DEP were found in actual physical saline samples （brand A and brand B）.

Occurrence and distribution of phthalate esters (PAEs) in wetland sediments

This study investigated the occurrence and distribution of 15 phthalate esters (PAEs) in sediments collected from Qixinghe wetlands, northeast China. Total concentration of PAEs in all sediments ranged from 128.41 to 502.79 mu g kg(-1), with the mean value of 284.61 mu g kg(-1). PAEs significantly differed among wetland types; the average PAEs concentration of surface sediments were as follows: Phragmites australis wetland (PAW, 419.87 +/- 73.61 mu g kg(-1)) > Carex lasiocarpa wetland (CLW, 304.18 +/- 56.47 mu g kg(-1)) > Deyeuxia angustifolia wetland (DAW, 129.78 +/- 18.24 mu g kg(-1)). Dimethyl phthalate (DMP), diisobutyl phthalate, di-n-butyl phthalate, and di-(2-ethylhexyl) phthalate (DEHP) were found in all sediments, DEHP was the most abundant PAEs congeners with concentrations varying from 37.62 to 294.9 mu g kg(-1). DMP and DEHP exhibited relatively higher concentrations in CLW and PAW wetlands than in DAW, indicating that the different deoxidization and biodegradation conditions could have important implications for the distribution patterns of PAEs in wetland sediments. The variation of PAEs concentrations in horizontal and vertical sediments with wetland types could be attributed to the migration of contaminants by surface water, groundwater and atmospheric deposition. The occurrence and distribution of PAEs in wetlands also suggests that contamination in natural ecosystems should not be overlooked.

Study on Phthalate Esters Pollution in the Soil of Facility Vegetable Base in Yangling District of Xianyang City

[Objectives]To evaluate the pollution status of phthalate esters(PAEs)in the soil of facility vegetable base in Yangling District of Xianyang City.[Methods]A total of 15 kinds of PAEs in soil samples were detected and analyzed by gas chromatography-mass spectrometry.[Results]A total of 12 kinds of PAEs were detected in analyzed soil samples,with a total content of 53.4-3524.1μg/kg and an average of 602.7μg/kg.Specifically,DEHP,DBP,DIBP,DMEP,BBP and DNOP were the main PAEs pollutants in the soil,with the detection rates of 100%,100%,100%,73.3%,63.3%and 53.3%,and the average content were 286.3,167.3,123.1,157.6,121.3,and 130.5μg/kg,respectively.[Conclusions]Compared with the soil in other regions,the pollution level of PAEs in the soil of facility vegetable base in Yangling District is lower,but such compounds are widespread in the facility vegetable base,and their potential environmental risks should attract close attention.

Advances in application of sensors for determination of phthalate esters

Phthalates esters(PAEs) are extensively used as additives for polymers in plastic, particularly in polyvinyl chloride(PVC) and polyethylene terephthalate(PET). These compounds are not part of the polymer chains and can be released easily from products and migrate into beverages and foods that come into direct contact, causing environmental and human health impacts. Simple and rapid detection of such substances is of great significance for ensuring environmental food safety and consumer health. At present, optical sensor and electrochemical sensor detection technologies have been applied to PAEs detection due to their advantages, such as simple, rapid, low cost, high sensitivity, simple operation, portability and high specificity. They can make up for the shortcomings of chromatographic detection technology, such as expensive equipment, cumbersome operation, the need for professional and technical personnel, and difficulty in achieving a large number of sample screening objectives. In this paper, research progress on optical sensors and electrochemical sensors for the detection of phthalates in recent ten years is reviewed and discussed. This is helpful to better understand preparation methods for sensors and their detection mechanisms for phthalates. The review will also be used in developing a more effective trace detection sensor for phthalates.

Research Progress on Distribution,Sources and Ecological Effects of Phthalate in Soil

Phthalate esters(PAEs)are widely used as main plasticizers in plastic products,agricultural regulators,toys,and other fields.This paper reviewed the research progress on the distribution,sources,and ecological effects of PAEs.The effects of PAEs on soil microorganisms,animals,plants and soil properties were explored in sequence,providing effective theoretical basis for future research on PAEs.

Pollution levels and characteristics of phthalate esters in indoor air of offices

The pollution status and characteristics of PAEs（phthalate esters） were investigated in indoor air of offices, and PAEs of both gas-phase and particulate-phase were detected in all the samples. The concentration（sum of the gas phase and the particulate phase） was4748.24 ng/m3, ranging between 3070.09 and 6700.14 ng/m3. Diethyl phthalate, dibutyl phthalate, and di（2-ethylhexyl） phthalate were the most abundant compounds, together accounting for 70% of the ∑ 6PAEs. Dividing the particulate-phase PAEs into four size ranges（〈 2.5, 2.5–5, 5–10, 〉 10 μm）, the result indicated that PAEs in PM2.5were the most abundant,with the proportion of 72.64%. In addition, the PAE concentration in PM2.5correlated significantly with the total particulate-phase PAEs（R2= 0.85）. Thus, the amount of PAEs in PM2.5can be estimated from the total amount of particulate-phase PAEs using this proportion. In a comparison between the offices and a newly decorated study room, it was found that pollution characteristics were similar between these two places. Thus, it is implied that the PAE concentration decreased by 50% 2 yr after decorating.

Occupational exposure assessment of phthalate esters in indoor and outdoor microenvironments

Phthalate esters（PAEs） are widely used as plasticizers in consumer products. PAEs are a group of environmental hormone which disrupts human and animals＇ endocrine systems. Different occupational groups are exposed to various levels of PAEs. In the present study, four typical occupational groups were chosen, including doctors, college teachers, college students, and drivers who worked in public traffic system. In order to understand the exposure levels to PAEs via inhalation, air samples were collected from multiple microenvironments including indoor and outdoor in Hangzhou to measure the gas and particle concentrations of six PAEs, together with time spent in different microenvironments of these four groups. A comprehensive PAEs exposure model was built to estimate the daily PAEs exposure through inhalation, oral and dermal pathways. The Monte Carlo simulation results show that doctors were exposed to the highest level of PAEs, and consequently had the highest health risk among these four occupational groups. In contrast, college students had the lowest health risk. By setting the exposure level of staying in residences as the baseline, doctors and drivers were two occupations exposed to high PAEs health risk. Di-（2-ethylhexyl） phthalate（DEHP） was the largest contributor among the six phthalates, posing moderate health risk（10-5–10-6） to every occupation. For traffic microenvironments alone, the total exposure levels for different transportation modes were in the descending order of busses, cars, cabs, tubes, motor bikes, and walking.

Determination of 15 phthalate esters in air by gas-phase and particle-phase simultaneous sampling

Based on previous research, the sampling and analysis methods for phthalate esters （PAEs） were improved by increasing the sampling flow of indoor air from 1 to 4 L/min, shortening the sampling duration from 8 to 2 hr. Meanwhile, through the optimization of chromatographic conditions, the concentrations of 9 additional PAE pollutants in indoor air were measured. The optimized chromatographic conditions required a similar amount of time for analysis as before, but gave high responsivity, the capability of simultaneously distinguishing 15 kinds of PAEs, and a high level of discrimination between individual sample peaks, as well as stable peak generation. The recovery rate of all gas-phase and particle-phase samples of the 15 kinds of PAEs ranged from 91.26% to 109.42%, meeting the quantitative analysis requirements for indoor and outdoor air sampling and analysis. For the first time, investigation of the concentration levels as well as characteristics of 15 kinds of PAEs in the indoor air from four different traffic micro-environments （private vehicles, busses, taxis and subways） was carried out, along with validation of the optimized sampling and analytical method. The results show that all the 9 additional PAEs could be detected at relatively high pollution levels in the indoor air from the four traffic micro-environments. As none of the pollution levels of the 15 kinds of PAEs in the indoor air from the 4 traffic micro-environments should be neglected, it is of great significance to increase the types of PAEs able to be detected in indoor air.

Detection of Phthalate Esters in Environmental Water Samples -Comparison of Nylon6 Nanofibers Mat-based Solid Phase Extraction and Other Conventional Extraction Methods

In this article, a new method for simultaneous determination of six phthalate esters was developed by a combination of electrospun nylon6 nanofibers mat-based solid phase extraction with high performance liquid chromatography-ultraviolet detector （HPLC-UV）. The six phthalate esters were dimethyl phthalate （DMP）, diethyl phthalate （DEP）, butyl benzyl phthalate （BBP）, di-n-butyl phthalate （DBP）, di-（2-ethylhexyl） phthalate （DEHP） and dioctyl phthalate （DOP）. Under optimized conditions, all target analytes in 50 mL environmental water samples could be completely extracted by 2.5 mg nylon6 nanofibers mat and eluted by 100 μL solvent. Compared with C18 cartridges solid phase extraction, C 18 disks solid phase extraction and national standard method （China）, nylon6 nanofibers mat-based solid phase extraction was advantageous in aspects of simple and fast operation, low consumption of extraction materials and organic solvents. The four methods were applied to analysis of environment water samples. All the results indicated that the determination values of target compounds with the proposed method were consistent with C18 cartridges and C18 disks solid phase extraction method, and the new method was better than the national standard method in aspects of recovery, LOD and precision. Therefore, nylon6 nanofibers mat has great potential as a novel material for solid phase extraction.

Ultrasound-assisted Low Density Solvent Based Dispersive Liquid-liquid Microextraction for Determination of Phthalate Esters in Bottled Water Samples

A technique of ultrasound-assisted low density solvent based dispersive liquid-liquid microextraction was developed for the determination of four phthalate esters, including dimethyl phthalate（DMP）, diethyl phthalate（DEP）, di-n-butyl phthalate（DnBP） and di（2-ethylhexyl） phthalate（DEHP） in bottled water samples. A low density solvent, toluene, was selected as extraction solvent. In the extraction process, a mixture of 15 μL of toluene（extraction solvent） and 100 μL of methanol（disperser solvent） was rapidly injected into 1.0 mL of water samples. A cloudy solution was formed after ultrasounded for 5 min, and then centrifuged at 5000 r/min for 5 min. The enriched analytes in the floa- ting phase were determined by means of gas chromatograph. Under the optimum conditions, the enrichment factors were found to be in a range of 29--67, and the recoveries were ranged from 81.2% to 103.9%. The limits of the detection were in a range of 3.8--5.6 μg/L. The proposed method was applied to the extraction and determination of phthalate esters in bottled water samples, and the concentrations of phthalate esters found in the water samples were below the allowable levels.

Sorption and desorption kinetics of phthalates and phenol on water/sediment interface

The sorption and desorption kinetics of dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP) and phenol on water and sediment interface were studied using two compartment model in this paper. The results showed that the sorption coefficients of DMP, DEP, DBP and phenol measured by batch equilibrium method were 16.79, 24.55, 132 and 0.65μg 1-1/n · g -1 · ml -1/n , the sorption and desorption kinetic constants of DMP, DEP, DBP, phenol were 0.0248, 0.0357, 0.0727, 0.014ml·cm -2 ·h -1 and 0.000512, 0.000754, 0.00127, 0 000899h -1 at static condition respectively; and the sorption and desorption kinetics constants of above chemicals were 0 279, 0.382, 0.496, 0.0904ml·cm -2 ·h -1 and 0.0442, 0.0031, 0.00116, 0.00247h -1 at flow water condition respectively.

Recent Advances of Sensitive Electrochemical Sensing Platforms for Rapid Detection of Phthalate Acid Esters

As a kind of plasticizer,phthalic acid esters(PAEs)are often added to plastics to enhance elasticity,transparency,durability and prolong service life.However,it does not chemically bind to plastics and is easy to migrate to the environment.It is difficult to degrade in the environment,and it is also enriched in the human body through the food chain and respiration,which will lead to obvious adverse reactions such as decreased learning and memory function and neurobehavioral disorders.Due to the toxicity,universality and low concentration limitations of PAEs in the environment and food,it is essential to achieve rapid and sensitive detection of PAEs in soil,atmosphere,water and food.Electrochemical(EC)sensors have the advantages of simplicity,fast,low cost,portability,easy operation,high specificity and high sensitivity,so they are applied for the detection of PAEs.Although there are a large number of studies on the detection of PAEs by EC sensors,there is no review on this aspect.In this review,we introduce the detection of PAEs from classical EC sensors,electrochemiluminescence(ECL)sensors and photo-electrochemical(PEC)sensors in the past five years.This review is beneficial to understanding the construction of EC sensors and the detection mechanism of PAEs.We also propose that the development of rapid,accurate and real-time detection methods of PAEs is key to assessing risk and preventing related diseases.

Prediction model on hydrolysis kinetics of phthalate monoester:A density functional theory study

As primary degradation products of phthalate esters,phthalate monoesters(MPEs)have been widely detected in various aquatic environments and drawn growing toxicological concerns.Hydrolysis kinetics that is of importance for assessing environmental persistence of chemicals remain elusive for MPEs.Herein,kinetics of base-catalyzed and neutral hydrolysis for 18 MPEs with different leaving groups was investigated by density functional theory calculation.Results indicate that MPEs with leaving groups having p Kaof<10 prefer dissociative transition states.MPEs are more persistent than their parents,and their hydrolysis half-lives were calculated to vary from 3.4 min to 79.2 years(p H=7–9).A quantitative structure-activity relationship model was developed for predicting the hydrolysis kinetics parameters.It was found that p Kaof the leaving groups and electronegativity of the MPEs are key factors determining the hydrolysis kinetics.This work may lay a theoretical foundation for better understanding the chemical process that governs MPE persistence in aquatic environments.

Perspectives on ecological risks of microplastics and phthalate acid esters in crop production systems

Microplastics(MPs)and phthalate acid esters(PAEs)co-occur as emerging contaminants of global importance.Their abundance in soil is of increasing concern as plastic-intensive practices continue.Mulching with plastic films,inclusion in fertilizers,composts,sludge application,and wastewater irrigation are all major and common sources of MPs and PAEs in soil.Here,we review studies on the concentration and effects of MPs and PAEs in soil.While there is limited research on the interactions between MPs and PAEs in agroecosystems,there is evidence to suggest they could mutually affect soil ecology and plant growth.Therefore,we propose new research into 1)establishing an efficient,accurate,and simple method to quantify different types of microplastics in soils and plants;2)exploring the behavior and understanding the mechanisms of co-transfer,transformation,and interactions with soil biota(especially in vegetable production systems);3)assessing the risk and consequences of combined and discreet impacts of MPs and PAEs on plants and soil biota,and 4)preventing or reducing the transfer of MPs and PAEs into-and within-the food chain.

Role of inflammatory lipid and fatty acid metabolic abnormalities induced by plastic additives exposure in childhood asthma

Lipid metabolism play an essential role in occurrence and development of asthma,and it can be disturbed by phthalate esters(PAEs)and organophosphate fame retardants(OPFRs).As a chronic infammatory respiratory disease,the occurrence risk of childhood asthma is increased by PAEs and OPFRs exposure,but it remains not entirely clear how PAEs and OPFRs contribute the onset and progress of the disease.We have profiled the serum levels of PAEs and OPFRs congeners by liquid chromatography coupled with mass spectrometry,and its relationships with the dysregulation of lipid metabolism in asthmatic,bronchitic(acute infammation)and healthy(non-infammation)children.Eight PAEs and nine OPFRs congeners were found in the serum of children(1–5 years old)from Shenzhen,and their total median levels were 615.16 ng/m L and 17.06 ng/m L,respectively.Moreover,the serum levels of mono-methyl phthalate(MMP),tri-propyl phosphate(TPP)and tri-n-butyl phosphate(TNBP)were significant higher in asthmatic children than in healthy and bronchitic children as control.Thirty-one characteristic lipids and fatty acids of asthma were screened by machine-learning random forest model based on serum lipidome data,and the alterations of infammatory characteristic lipids and fatty acids including palmitic acids,12,13-Di HODE,14,21-Di HDHA,prostaglandin D2 and Lyso PA(18:2)showed significant correlated with high serum levels of MMP,TPP and TNBP.These results imply PAEs and OPFRs promote the occurrence of childhood asthma via disrupting infammatory lipid and fatty acid metabolism,and provide a novel sight for better understanding the effects of plastic additives on childhood asthma.

Pollution characteristics of 15 gas- and particle-phase phthalates in indoor and outdoor air in Hangzhou

Phthalate esters(PAEs),typical pollutants widely used as plasticizers,are ubiquitous in various indoor and outdoor environments.PAEs exist in both gas and particle phases,posing risks to human health.In the present study,we chose four typical kinds of indoor and outdoor environments with the longest average human residence times to assess the human exposure in Hangzhou,including newly decorated residences,ordinary residences,offices and outdoor air.In order to analyze the pollution levels and characteristics of 15 gasand particle-phase PAEs in indoor and outdoor environments,air and particulate samples were collected simultaneously.The total PAEs concentrations in the four types of environments were 25,396,25,466.8,15,388.8 and 3616.2 ng/m^3,respectively.DEHP and DEP were the most abundant,and DMPP was at the lowest level.Distinct variations in the distributions of indoor/outdoor,gas/particle-phase and different molecular weights of PAEs were observed,showing that indoor environments were the main sources of PAEs pollution.While most PAEs tended to exsit in indoor sites and gas-phase,the high-molecular-weight chemicals tended to exist in the particle-phase and were mainly found in PM2.5.PAEs were more likely adsorbed by small particles,especially for the indoor environments.There existed a good correlation between the particle matter concentrations and the PAEs levels.In addition,neither temperature nor humidity had obvious effects on the distributions of the PAEs concentrations.

Nano Fe_(2)O_(3)embedded in montmorillonite with citric acid enhanced photocatalytic activity of nanoparticles towards diethyl phthalate

Nano-Fe_(2)O_(3)embedded in montmorillonite particles(Fe-Mt)were prepared to degrade diethyl phthalate(DEP)with citric acid(CA)under xenon light irradiation.Compared to pristine montmorillonite(Na-Mt),the embedding process increased 14.5-fold of iron content and 1.8-fold of specific surface area.The synthesized Fe-Mt have more oxygen vacancies than Fe_(2)O_(3)nanoparticles(nFe_(2)O_(3)),which could induce more reactive oxygen species(ROSs)generation in the presence of CA under xenon lamp irradiation.Fe-Mt with CA enhanced photo-assisted degradation of DEP 2.5 times as compared to nFe_(2)O_(3)with CA.Quenching experiments,electron paramagnetic resonance(EPR)spectroscopy and identification of products confirmed that surface-bound·OH was the main radical to degrade DEP.Common anions(i.e.,NO_(3)-,CO_(3)^(2-),Cl^-)and humic acid could compete·OH with DEP and cause slower degradation of DEP.The removal efficiency of DEP was more than 56%with Fe-Mt after three recycles,and the dissolved Fe concentration from Fe-Mt was below 75μmol/L,indicating Fe-Mt had a good stability as a catalyst.Fe-Mt together with CA appeared to be a promising strategy to remove organic pollutants in surface water,or topsoil under solar irradiation.

Analysis of the influencing factors of PAEs volatilization from typical plastic products

The primary emphasis of this research was to investigate the foundations of phthalate（PAEs） pollutant source researches and then firstly confirmed the concept of the coefficient of volatile strength, namely phthalate total content in per unit mass and unit surface area of pollutant sources. Through surveying and evaluating the coefficient of volatile strength of PAEs from typical plastic products, this research carried out reasonable classification of PAEs pollutant sources into three categories and then investigated the relationship amongst the coefficient of volatile strength as well as other environmental factors and the concentration level of total PAEs in indoor air measured in environment chambers.Research obtained phthalate concentration results under different temperature, humidity,the coefficient of volatile strength and the closed time through the chamber experiment. In addition, this study further explored the correlation and ratio of influencing factors that affect the concentration level of total PAEs in environment chambers, including environmental factors, the coefficient of volatile strengths of PAEs and contents of total PAEs in plastic products. The research created an improved database system of phthalate the coefficient of volatile strengths of each type of plastic goods, and tentatively revealed that the volatile patterns of PAEs from different typical plastic goods, finally confirmed that the coefficient of volatile strengths of PAEs is a major factor that affects the indoor air total PAEs concentration, which laid a solid foundation for further establishing the volatile equation of PAEs from plastic products.