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.

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.

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.

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。

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.

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。

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.

环境中邻苯二甲酸酯类(PAEs)污染物研究进展

邻苯二甲酸酯(PAEs)是一种环境激素类化合物,在生物体内有极强的富集作用,对环境安全和人体健康的威胁极大,目前已引起了人们的广泛关注。本文从PAEs有机污染物在环境中的分布特征、分析与检测方法、生物富集与迁移以及生物与非生物降解等方面综述了国内外最新研究进展,认为环境中的PAEs大部分来源于人工合成途径,可被土壤、沉积物及一些悬浮泥沙中的有机物质所吸附。PAEs进入土壤或大气环境后,通过作物吸收作用会在作物体内有一定残留,环境中的PAEs可通过生物与非生物两种方式进行降解,生物降解被认为是PAEs降解的主要形式。文章指出了已有研究中存在的不足之处并对未来的研究进行展望,认为今后应着重从PAEs的环境行为、PAEs健康风险评价、PAEs污染的治理与削减技术以及PAEs替代产品开发等方面开展相关研究。

广州、深圳地区蔬菜生产基地土壤中邻苯二甲酸酯(PAEs)研究

对广州 (含增城、花都 )和深圳地区的 9个代表性蔬菜生产基地进行调查采样 ,利用超声波提取 -硅胶柱净化 -气相色谱 /质谱联机检测技术 (GC/ MS) ,分析了土壤中属于 U.S.EPA优控污染物的 6种邻苯二甲酸酯 (PAEs)化合物。结果表明 ,6种PAEs化合物总含量 (Σ PAEs)在 3.0 0～ 4 5 .6 7mg/ kg之间 ,其中 37%样品的Σ PAEs在 10～ 2 0 mg/ kg,2 2 %样品的Σ PAEs在2 0～ 30 m g/ kg。各蔬菜基地中以联兴基地的 Σ PAEs平均值最高 (35 .6 2 m g/ kg) ;广清基地的 Σ PAEs平均值最低 (10 .31m g/kg)。各 PAEs化合物中以 DEHP的含量最高 ,Dn BP次之 ,两者共占 Σ PAEs的 90 %以上。BBP、DEP、DMP和 Dn OP的含量均在 2 .0 mg/ kg以下。与美国土壤 PAEs控制标准相比 ,除了 Dn OP外 ,其余 5个化合物均不同程度超标 ,其中 DEP、Dn OP、DEHP超标较普遍且较严重。但所有 PAEs化合物的含量均低于美国土壤 PAEs治理标准。总体上看 ,上述蔬菜基地土壤中PAEs的含量较高 。

水稻土施用城市污泥盆栽通菜土壤中邻苯二甲酸酯(PAEs)的残留

应用GC MS联机检测技术对水稻土施用城市污泥盆栽通菜 (Ipomoeaaquatic)后土壤中 6种邻苯二甲酸酯化合物 (PAEs)进行分析 .结果表明 ,盆载通菜土壤中 6种PAEs的总含量 (∑ PAEs)在 7 6 6 7— 4 0 0 2 5mg kg之间 ,平均为 2 6 137mg kg ,其高低次序为 :佛山污泥 >广州污泥 >佛山污泥加化肥 >广州污泥 +化肥 >空白 >化肥 .与空白对照相比 ,施用污泥和污泥 +化肥处理的土壤中 ∑ PAEs含量显著提高 ,但单施化肥的土壤中 ∑ PAEs含量降低 .不同处理土壤中的PAEs化合物是以一种或两种化合物为主 ,主要是DnBP和 或DEHP ,显示了不同的PAEs分布特征 .

汕头市蔬菜产区土壤-蔬菜中邻苯二甲酸酯(PAEs)污染分布特征研究

在广东省汕头市蔬菜产区共采集63个表层土壤样品和26个蔬菜样品,采用GC-FID检测方法分析了样品中被美国国家环保署(EPA)优先控制的6种邻苯二甲酸酯(PAEs)化合物含量,并对其污染分布、污染程度进行了评价。结果表明,汕头市蔬菜产区土壤样品中6种PAEs化合物总浓度(∑PAEs)范围为0.018~9.303 mg·kg-1,平均含量为0.721 mg·kg-1,检出率为100%,5个蔬菜产区土壤中∑PAEs的平均含量大小顺序依次为潮阳区>龙湖区>澄海区>潮南区>金平区,与美国土壤6种优控的PAEs控制标准相比,邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二正丁酯(DBP)和邻苯二甲酸丁基苄基酯(BBP)含量均超过控制标准,超标率分别为38.1%、6.3%、6.3%和3.2%。蔬菜样品中∑PAEs含量范围为0.454~19.193 mg·kg-1,平均含量7.158 mg·kg-1,不同产区内蔬菜中∑PAEs的平均含量顺序依次为潮阳区>澄海区>潮南区>金平区>龙湖区,潮阳区和潮南区蔬菜中DBP含量均高于美国和欧洲建议标准,存在健康风险。DBP在土壤-蔬菜样品中占∑PAEs总量的百分比较高,是汕头市PAEs污染物的主要组成部分;蔬菜-土壤中的∑PAEs、邻苯二甲酸二(2-乙基)己酯(DEHP)和邻苯二甲酸二正辛酯(Dn OP)存在显著正相关性,Pearson相关系数(r)分别为0.7(P=0.016)、0.825(P=0.002)和0.813(P=0.002)。不同蔬菜对土壤中6种PAEs化合物的富集能力存在明显差异,但对∑PAEs的富集系数均大于1。因此,在蔬菜产区土壤质量评价过程中,应重视蔬菜自身特性对PAEs吸收和富集的影响。

菜心对邻苯二甲酸酯(PAEs)吸收途径的初步研究

采用玻璃室处理和污染土壤覆盖原土壤来控制PAEs来源进行盆栽试验,应用GC/MS联机检测技术初步研究了菜心对PAEs的吸收途径。结果表明污染土壤处理与污染土壤上覆盖原土壤处理相比,前者菜心茎叶中DBP和DEHP的含量均高于后者,但相差不大,表明菜心茎叶可以吸收污染土壤中挥发出来的DBP和DEHP,而根系吸收运移是菜心茎叶中DBP和DEHP的主要来源途径。玻璃室处理增加了菜心茎叶和根系中DBP的含量,而对DEHP的影响趋势不明显。DBP与DEHP相比,前者更易被菜心根系吸收并向地上部(茎叶)运移,后者主要滞留在根部。