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.

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.

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.

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.

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.

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.

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.

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）.

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%.

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.

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.

湖库型饮用水水源地水体PAEs变化特征及风险评价

为探究湖库型饮用水水源地水体邻苯二甲酸酯(phthalate esters,PAEs)的季节变化特征和健康风险状况,以玉溪市城区东风水库和飞井海水库水体为研究对象,基于2021~2023年逐月水质监测数据,分析了研究水体PAEs质量浓度水平、季节变化规律及分布特征,并开展了成人和儿童的健康风险评估。结果表明:①2021~2023年,研究水体中邻苯二甲酸二丁酯(dibutyl phthalate,DBP)和邻苯二甲酸二(2-乙基己基)酯(di-2-ethylhexyl phthalate,DEHP)的检出率较高(≥94.4%),其中DBP检出质量浓度的平均值和最大值分别为0.48μg/L和2.91μg/L,DEHP的平均值和最大值分别为1.12μg/L和3.94μg/L,均未超过中国水质卫生标准(GB 5749-2022)和水质量标准(GB 3838-2002)规定限值。②研究水体DBP和DEHP质量浓度的月均值分布具有显著的季节性差异,两者质量浓度大小随季节变化规律具有一致性,均表现为夏、秋两季>春、冬两季,从不同水量期来看,两者质量浓度大小表现为丰水期>枯、平水期,且研究水体中DEHP质量浓度月均值普遍高于同期DBP。③经饮水和皮肤渗入途径,DBP对成人和儿童的最大非致癌健康风险值处于10-3水平,为无风险,而DEHP对成人和儿童的最大致癌健康风险值达到1.57×10^(-6)和2.07×10^(-6)水平,存在潜在致癌健康风险,应予以重视。饮水是致癌和非致癌健康风险的主要暴露途径,须重点关注由其引起的致癌风险。

茅洲河清淤后表层底泥及水体中PAEs的分布特征及风险评价

为查明茅洲河清淤后表层底泥及水体中酞酸酯类物质(PAEs)的污染情况和风险水平,从茅洲河前期相关研究的采样断面中优选了36个采样点,分析了6种PAEs的污染水平,探讨了PAEs污染来源,并开展了健康风险评价。结果表明,清淤后表层底泥未检测出DMP,底泥中Σ6PAEs含量为450~890μg/kg,水体中Σ6PAEs含量为0.56~1.75mg/L,从检出率及检出量来看,DEHP、DBP是清淤后底泥及水体中PAEs主要组成部分。主成分分析结果表明,PAEs污染主要来源于个人护理品、塑料制品、生活垃圾和电路板制造行业废弃物;茅洲河底泥PAEs的污染水平相对较低,为低风险级别;水体中PAEs的HI均远远小于1,不会对人体健康产生明显的危害,但PAEs会在河道底泥中长期积存,仅一次彻底清淤无法根除,需要建立长效清淤工作机制,高度重视城市河道中新污染物的危害。

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.

住宅室内温湿度及颗粒物浓度对降尘中PAEs浓度分布的耦合影响

深入了解室内邻苯二甲酸酯(PAEs)化合物浓度分布及其影响因素对污染控制具有重要意义。本研究对266户上海住宅进行了室内降尘采集,对PAEs的种类及含量进行了测试分析,采用逻辑回归方法分析了室内温度、湿度和颗粒物浓度与3种典型PAEs浓度分布的关联性,揭示了环境参数对PAEs浓度分布的相乘交互作用和影响。结果显示:温度与邻苯二甲酸二(2-乙基)己酯(DEHP)呈显著负相关性,湿度与邻苯二甲酸二异丁酯(DiBP)呈显著负相关性;将温度、颗粒物浓度作为混淆因素调整后,湿度和DEHP呈显著正相关性;在低温和低湿度条件下,颗粒物浓度与DEHP、高分子量PAEs(HMW-PAEs)、总PAEs(TPAEs)的浓度呈显著负相关性;温度和颗粒物浓度对DEHP浓度分布存在正向相乘交互作用。因此,室内温度、湿度和颗粒物浓度均在不同程度上影响PAEs浓度分布,PAEs浓度的变化是由多个影响因素共同作用引起的。

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.

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.

Data Analysis for High Throughput Detection of 18 Phthalates in Textiles Based on High Resolution Mass Spectrometry

Liquid chromatography coupled to high resolution mass spectrometry(LC-HRMS)was used to establish a high throughput and sensitive method for 18 phthalic acid esters(PAEs)in textiles.The method was applied to screen PAEs in 413 textile samples and 7 434 pieces of test data were analyzed.Further discussion was conducted about specific compounds,textile materials,detected value distribution and positive rate of samples.Twenty-nine percent of samples were detected with PAEs,and no samples were detected beyond regulations.Diisobutyl phthalate(DiBP),Dibutyl phthalate(DBP)and Di-2-ethylhexyl phthalate(DEHP)were detected with high frequency,and most samples were fabrics with coating and printing.This study can be used to reflect distribution of phthalate residues in textiles on the market and provide data support for risk assessment of PAEs for textile producers and consumers.

土壤中邻苯二甲酸酯成分分析标准物质研制

邻苯二甲酸酯类化合物(Phthalates,PAEs)作为一类持续释放并存在于环境中的有机污染物,被列入优先控制污染物名单。土壤是PAEs在环境中的最后归宿之一,中国对土壤中PAEs的污染调查和防控已全面展开。分析测试是环境监测和科学研究的基础,土壤基体标准物质是保证实验数据的准确性和可靠性的重要手段,然而,目前现有的相关标准物质无法满足实际需要。本文针对中国土壤中PAEs污染特征及实际样品分析质量控制需求,采用多家实验室联合定值的方式,研制了4种适用于土壤中不同污染水平PAEs分析的标准物质。候选物样品主要采自农田土壤、地膜覆盖土壤、塑料垃圾回收站周围土壤和塑料制品加工厂周围土壤,经过均匀性、长期稳定性和短期稳定性检验,结果表明均匀性和稳定性均满足要求;在定值过程中,针对PAEs分析空白不易控制的难点,对空白的污染源进行识别和确认,制定严格的质量控制措施,保证了全流程空白值稳定在一定范围内;9家实验室采用气相色谱-质谱法(GC-MS)对候选物中4种PAEs进行协作定值,并评估其不确定度,特性量值范围在36~2870µg/kg,同时邀请权威实验室采用同位素稀释质谱法对定值结果进行验证,确保定值结果的准确性。该系列标准物质已被批准为国家一级标准物质(编号GBW07595~GBW07598),可以满足PAEs分析质量保证与质量控制的要求,为生态地质调查评价提供技术支撑。