Insight into the effect of geographic location and intercropping on contamination characteristics and exposure risk of phthalate esters(PAEs)in tea plantation soils

Phthalate esters(PAEs)are an emerging pollutant due to widespread distribution in environmental mediums that have attracted widespread attention over recent years.However,there is little information about tea plantation soil PAEs.A total of 270 soil samples collected from 45 tea plantations in the major high-quality tea-producing regions of Jiangsu,Zhejiang,and Anhui provinces in China were analyzed for seven PAEs.The detection frequency of PAEs in tea plantation soil was 100%.DBP,DEHP,and DiBP were the main congeners in tea plantation soil.The PAEs concentrations in the upper soil were significantly higher than those in the lower soil.The concentration of tea plantation soil PAEs in Jiangsu Province was significantly lower than those in Zhejiang and Anhui provinces.Intercropping with chestnuts can effectively reduce the contamination level of PAEs in tea plantation soil.Correlation analysis,redundancy analysis,partial correlation analysis,and structural equation modeling methods further confirmed the strong direct influence of factors such as chestnut–tea intercropping,temperature,and agricultural chemicals on the variation of PAEs in tea plantation soil.The health and ecological risk assessments indicated that non-carcinogenic risk was within a safe range and that there was a high carcinogenic risk via the dietary pathway,with DBP posing the highest ecological risk.

Determination of phthalate esters in fat-containing foods by packed nanofiber solid-phase extraction column and gas chromatography

A new method for simultaneous determination of four phthalate esters （ PAEs） in commercial fat-containing foods was developed by the combination of a packed nanofibers column based on solid-phase extraction with gas chromatography-flame ionization detector （ GC-FID ）. Conditions for obtaining optimum extraction efficiency such as extraction solvents, morphologies of adsorbent, ion strength and pH were investigated and optimized in detail. Under the optimized conditions, the limits of detection （LODs） found for dibutyl phthalate （DBP） , butyl benzyl phthalate （BBP）, diethyl hexyl phthalate （DEHP） and di-n-octyl phthalate （DNOP） were 50, 25, 50 and 25 ng/g, respectively. Good linearity of four PAEs was achieved in the range of 50 to 4 000 ng/g. The proposed method was applied for analyzing different kinds of fat-containing samples. PAEs in commercial fat-containing samples can be highly extracted by a packed solid-phase extraction column of 5 mg polystyrene （ PS） nanofibers. The satisfactory average recoveries were obtained in the range of 96. 7% to 102. 3% , and the relative standard deviations （RSDs） below 5% were achieved. The proposed method reduces the organic solvent consumption, the complex and tedious procedures for sample pretreatment, and achieves high sensitivity and reproducibility for the investigated PAEs.

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.

Toxic effects of several phthalate esters on the embryos and larvae of abalone Haliotis diversicolor supertexta

As the most widely used plasticizers in the world, phthalate esters （PAEs） are potential endocrine disruption compounds （EDCs）. In the present study, the toxicity of dimethyl phthalate （DMP）, diethyl phthalate （DEP）, dibutyl phthalate （DBP）, di （2-ethylhexyl） phthalate （DEHP） on embryogenesis and larvae development of the marine univalve Haliotis diversicolor supertexta was examined in laboratory. The results show that the malformation of embryos appeared during the experiment, such as embryos died or lysed, small transparent flocculent rings studded on the periphery of the embryo, and the larvae could failed to hatch. In embryo toxic test, embryos incubated at the highest concentration of DMR DEP and DBP solutions showed significantly high abnormal rate compared with the control, while DEHP solutions displayed no significant difference. In larval toxic test, in all concentrations of DMP, DEP and DBP solutions, larval settlement rates were low significantly than that of the control. Similarly, DEHP solutions show nearly no effect on the larval settlement. The order of toxicity on embryos and larvae is DBP〉DEP〉DMP〉DEHE Being a simple and easy stimulation to indoor spawn, sensitive to environmental factors, and short culture time, the embryos of H. diversicolor supertexta can be used to indicate toxicity of the PAEs.

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.

Magnetic Solid-Phase Extraction of Phthalate Esters from Environmental Water Samples using Fibrous Phenyl-functionalized Fe3O4@SiO2@KCC-1

A new kind of phenyl-functionalized magnetic fibrous mesoporous silica(Fe3 O4@Si O2@KCC-1-phenyl) was prepared by copolymerization as an efficient adsorbent for the magnetic extraction of phthalate esters from environmental water samples. The obtained Fe3 O4@Si O2@KCC-1-phenyl showed monodisperse fibrous spherical morphology, fairly strong magnetic response(29 emu/g), and an abundant π-electron system, which allowed rapid isolation of the Fe3 O4@Si O2@KCC-1-phenyl from solutions upon applying an appropriate magnetic field. Several variables that affect the extraction efficiency of the analytes,including the type of the elution solvent, amount of adsorbent, extraction time and reusability, were investigated and optimized. Under optimum conditions, the Fe3 O4@Si O2@KCC-1-phenyl was used for the extraction of four phthalate esters from environmental water samples followed by high-performance liquid chromatographic analysis. Validation experiments indicated that the developed method presented good linearity(0.1-20 ng/m L), low limit of detection(7.5-29 μg/L, S/N =3). The proposed method was applied to the determination of phthalate esters in different real water samples, with relative recoveries of 93%-103.4%and relative standard deviation of 0.8%-8.3%.

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）.

Microwave Extraction Followed by Solid-phase Extraction for the Determination of Phthalate Esters in Fish Samples by Gas Chromatography

A new analytical procedure based on solid-phase extraction method coupled to GC-FID has been developed and validated for the determination of five phthalate esters （PAEs） （dimethyl-（DMP）, diethyl-（DEP）, di-n-butyl-（DBP）, di-2-ethylhexyl- （DEHP）, di-n-octyl-（DOP）） in fish samples. There was a good linear relationship in the range of 0.05-10μg with the detection limits of 0.09-0.16ng .The recoveries obtained for PAEs ranged from 88.6% to 96.4%with RSD of 4.2%-10.2%.The applicability of the developed method was demonstrated for real fish samples.

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.

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.

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.

Isolation, Identification and Biodegradation Characteristics of a Phthalate Ester Degrading Bacterium

By using plate screening techniques with five phthalate esters （DMP, DEP, DBP, DEHP and DOP） as energy and carbon sources, an active strain was isolated from the sediments of Chaohu Lake, which was identified as Burkholderia pickettil and named B. pickettii.z-1. The biodegradation of five phthalate esters by B. pick- ettii.z-1 strain was in accordance with the pseudo first-order kinetic equation： Ct = C0.e-kt. As the concentration of phthalate esters increased, the degradation rate of phthalate esters was reduced. B. pickettii.z-1 strain exhibited remarkably different degradation effects on various PAEs. Specifically, short-side-chain DMP and DEP were degraded rapidly, while long-side-chain DBP and DEHP were degraded slowly.

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.