植物油中邻苯二甲酸酯来源和检测方法研究进展

旨在为植物油中塑化剂的污染防控提供参考,对邻苯二甲酸酯(PAEs)种类和性质,植物油中PAEs的来源以及植物油中PAEs的检测方法进行了综述。PAEs是脂溶性物质,易迁移到植物油中。植物油中PAEs的来源主要有植物油原料、植物油加工过程以及植物油包装材料。测定植物油中PAEs的前处理方法有液液萃取法、凝胶渗透色谱法、固相萃取法、分散固相萃取法、固相微萃取法,常用的植物油PAEs检测方法有气相色谱法、气相色谱-质谱联用法、高效液相色谱法以及液相色谱-质谱联用法。PAEs是植物油的风险因素之一,建立植物油中PAEs快速、便捷、重现性好的检测方法对于实现植物油中PAEs的实时监控具有重要意义。

邻苯酸二甲酯(塑化剂)对大鼠肾脏及生殖系统的影响

目的探索邻苯酸二甲酯(塑化剂)对大鼠肾脏及生殖系统的影响。方法 Wistar清洁级雄性大鼠60只,随机数字表法分为低剂量组、中剂量组、高剂量组和对照组,每组15只,用药组分别给予剂量100、500、1 000 mg/(kg·d)的邻苯酸二甲酯,对照组仅给予植物油。6周后检测血清肌酐(Cr)、尿素氮(BUN)、黄体生成素(LH)、卵泡刺激素(FSH)、睾酮(T)、胱抑素C(Cys-C),β2-微球蛋白(β-Mg)水平。HE染色观察肾脏组织形态学变化。组间比较采用单因素方差分析。结果高剂量组Cr、BUN明显升高(F=11.70,4.16;P<0.05),而Cys-C、β2-微球蛋白在低、中、高剂量组均明显升高(F=31.16,8.05;P<0.05)。高剂量组中血清睾酮水平降低;低剂量组LH水平升高,而中剂量组、高剂量组血清LH水平降低;低、中、高剂量组血清FSH水平升高(F=4.82,59.34,6.91;P<0.05)。对照组和低剂量组大鼠肾脏组织结构未见明显改变;中剂量组大鼠肾脏中肾小球出现萎缩,高剂量组大鼠肾小球出现萎缩,变性,坏死。结论邻苯酸二甲酯可引起大鼠生殖内分泌激素水平的变化和肾小球病变。

邻苯二甲酸二丁酯致自身免疫性甲状腺炎大鼠肝组织氧化损伤研究

邻苯二甲酸二丁酯(DBP)是一种广泛使用的增塑剂,应用于多种塑料制品中。课题组前期研究显示DBP可以诱发自身免疫性甲状腺炎,但是否可诱导肝组织损伤仍不清楚。我们将雌性Wiatar大鼠随机分为7个实验组:生理盐水(Saline)组,DBP组(5mg/kg/day)组,甲状腺球蛋白(TG)组,TG+DBP组,TG+DBP +维生素C(VitC)(100mg/kg/day)组,TG+VitC组,VitC组。研究结果显示,口服暴露DBP可致肝组织中活性氧(ROS)、丙二醛(MDA)、8-羟基脱氧鸟苷(8-OHdG)水平显著增加,还原型谷胱甘肽(GSH)水平显著降低;补充维生素C对上述物质水平变化有明显拮抗作用。表明DBP可以致使自身免疫性甲状腺炎大鼠肝组织氧化损伤的发生,维生素C对该毒性起拮抗作用。

Analysis of the major components of root exudates released from several economic forest tree using GC-MS

In 2000 and 2001, 1-year-old seedlings of 7 economic tree species including chestnut, apricot, persimmon, peach, walnut, pear and apple were cultured in garden pots that had a diameter of 40 cm and were filled with clean sand. The major components of exudates released from their roots were isolated and analysed by GC-MS. Totally 200 kinds of organic chemicals were isolated, of which 3 kinds i.e. naphthalene, dimethylbenzene and dibutyl phthalate were principally controlled pollutants according to 'Blacklist of Principal Environment Pollutants in China' and the standard of U.S. Environmental Protection Agency (EPA). The research result provided theoretical evidence for selecting low-pollution economic forest crops in the water source protection area in Miyun Reservoir.

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.

Characterization of V_2O_5/MoO_3 composite photocatalysts prepared via electrospinning and their photodegradation activity for dimethyl phthalate

Vanadium pentoxide（V2O5）/molybdenum trioxide（MoO 3） composites with different molar ratios of vanadium（V） to molybdenum（Mo） were synthesized via a simple electrospinning technique. The photocatalytic activity of the composites were evaluated by their ability to photodegrade methylene blue and dimethyl phthalate（DMP） under visible-light irradiation. Compared with pure V2O5 and MoO 3,the V2O5/MoO 3 composites showed enhanced visible-light photocatalytic activity because of a V 3d impurity energy level and the formation of heterostructures at the interface between V2O5 and MoO 3. The optimal molar ratio of V to Mo in the V2O5/MoO 3 composites was found to be around 1/2. Furthermore,high-performance liquid chromatographic monitoring revealed that phthalic acid was the main intermediate in the photocatalytic degradation process of DMP.

Mechanistic studies on peroxymonosulfate activation by g-C3N4 under visible light for enhanced oxidation of light-inert dimethyl phthalate

Excitation of metal-free graphitic carbon nitride(g-C3N4) under visible light can successfully achieve efficient activation of peroxymonosulfate(PMS). Synergistic effects and involved mechanism were systematically investigated using a light-inert endocrine disrupting compound, dimethyl phthalate(DMP), as the target pollutant. Under visible light irradiation, DMP could not be degraded by direct g-C3 N4-mediated photocatalysis, while in the presence of PMS, the dominant radicals were converted from ·O2 to SO4·– and ·OH, resulting in effective DMP degradation and mineralization. Results showed that higher dosage of PMS or g-C3 N4 could increase the activation amount of PMS and corresponding DMP degradation efficiency, but the latter approach was more productive in terms of making the most of PMS. High DMP concentration hindered effective contact between PMS and g-C3 N4, but could provide efficient use of PMS. Higher DMP degradation efficiency was achieved at p H lower than the point of zero charge(5.4). Based on intermediates identification, the DMP degradation was found mainly through radical attack(·OH and SO4·–) of the benzene ring and oxidation of the aliphatic chains.

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.

Aerobic biodegradation of diethyl phthalate by Acinetobacter sp. JDC-16 isolated from river sludge

A gram negative bacterium,named JDC-16,which can grow well on the substrate of phthalic acid esters(PAEs) as the sole source of carbon and energy,was isolated from river sludge.Based on the morphology,physiological and biochemical properties and analysis of 16S rRNA gene sequence,it was preliminarily identified belonging to the genus Acinetobacter.The result of substrates utilization range indicates that strain JDC-16 can utilize a variety of phthalates except for diisononyl phthalate(DINP) .The degradation tests using diethyl phthalate(DEP) as the model compound show that the optimal pH and temperature for DEP degradation by Acinetobacter sp.JDC-16 is 8.0 and 35℃,respectively.Meanwhile,degradation kinetics under various initial concentrations of DEP reveals that substrate depletion curves fit well with the modified Gompertz model with high correlation coefficient(R 2 >0.99) .Furthermore,the substrate induction test indicates that DEP-induction can apparently shorten the lag phase and enhance the degradation rate.This work highlights the potential of this isolate for bioremediation of phthalates-contaminated environments.

Isolation and characteristics of Arthrobacter sp.strain CW-1 for biodegradation of PAEs

Isolation of new bacterial strains and recognition of their metabolic activities are highly desirable for sustainability of natural ecosystems. Biodegradation of dimethyl phthalate （DMP） under anoxic conditions has been shown to occur as a series of sequential steps using strain CW-1 isolated from digested sludge of Sibao Wastewater Treatment Plant in Hangzhou, China. The microbial colony on LB medium was yellowish, 3-5 mm in diameter, convex in the center, and embedded in mucous externally. The individual cells of strain CW-1 are irregular rods, measuring （0.6-0.7）×（0.9-1.0） pm, V-shaped, with clubbed ends, Gram positive and without any filaments. 16S rDNA （ 1438 bp） sequence analysis showed that the strain was related to Arthrobacter sp. CW-1 and can degrade PAEs utilizing nitrate as electron acceptor, but cannot mineralize DMP completely. The degradation pathway was recommended as： dimethyl phthalate （DMP）→monomethyl phthalate （MMP）--,phthalic acid （PA）. DMP biodegradation was a first order reaction with degradation rate constant of 0.3033 d 1 and half-life 2.25 d. The DMP conversion to PA by CW-1 could be described by using sequential kinetic model.

Removal of Di-n-butyl Phthalate Using Immobilized Microbial Cells

The biodegradation of di-n-butyl phthalate （DBP） using immobilized microbial cells was carded out in an internal airlift loop reactor with ceramic honeycomb supports. A strain that is capable of degrading DBP was isolated from the activated sludge and identified as Bacillus sp. using 16S rDNA sequential analysis. Bacillus sp. could be rapidly attached onto the ceramic honeycomb supports. The immobilized cells could effectively degrade DBP in batch and continuous experiments. When the influent concentration of DBP was 50mg·L^-1, the effluent DBP reached less than lmg.L i with 6h hydraulic retention time （HRT） in continuous experiment. The immobilized microbial cells could grow and accumulate through the biodegradation of DBP, and the rate of degradation is accordingly increased. The possible pathway of DBP biodegradation using immobilized cells was tentatively proposed.

Effect of Arbuscular Mycorrhizal Inoculation on Plant Growth and Phthalic Ester Degradation in Two Contaminated Soils

A 60-day pot experiment was carried out using di-(2-ethylhexyl) phthalate (DEHP) as a typical organic pollutant phthalic ester and cowpea (Vigna sinensis) as the host plant to determine the effect of arbuscular mycorrhizal inoculation on plant growth and degradation of DEHP in two contaminated soils, a yellow-brown soil and a red soil. The air-dried soils were uniformly sprayed with different concentrations of DEHP, inoculated or left uninoculated with an arbuscular mycorrhizal (AM) fungus, and planted with…

Uncertainty Evaluation for the Determination of Dibutyl Phthalate(DBP) Concentration in Liqueur by GC-MS

The dibutyl phthalate （DBP） concentration in liqueur was measured by gas chromatography-mass spectrometry （GC-MS）, and the uncertainty during the mea-surement was evaluated in this study. The results showed that the combined stan-dard uncertainty was determined as 0.028 and the expanded uncertainty was 0.056 at confidence probability p=95%, coverage factor k=2, by fol owing the methods de-scribed in GB/T 21911-2008 ＂Determination of Phthalate Esters in Foods＂. The av-erage DBP concentration in the liqueur of eight repeated measurements was（0.985＆#177; 0.056） mg/kg finaly.

Aerobic biodegradation of di-n-butyl phthalate by Xiangjiang River sediment and microflora analysis

Di-n-butyl phthalate (DBP),one of phthalate acid esters (PAEs),was investigated to determine its biodegradation rate using Xiangjiang River sediment and find potential DBP degraders in the enrichment culture of the sediment. The sediment sample was incubated with an initial concentration of DBP of 100 mg/L for 5 d. The biodegradation rate of DBP was detected using HPLC and the degraded products were analyzed by GC/MS. Subsequently,the microbial diversity of the enrichment culture was analyzed by polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP). The results reveal that almost 100% of DBP is degraded after merely 3 d,generating two main degraded products:mono-butyl phthalate (MBP) and 9-octadecenoic acid. After a six-month enrichment period under the pressure of DBP,the dominant family in the final enrichment culture is clustered with the Comamonas sp.,the remaining are affiliated with Sphingomonas sp.,Hydrogenophaga sp.,Rhizobium sp.,and Acidovorax sp. The results show the potential of these bacteria to be used in the bioremediation of DBP in the environment.

Long-term effects of di-octyl phthalate on the expression of immune-related genes in Tegillarca granosa

Di-octyl phthalate(DOP) is widely used as a plasticizer in the plastics industry.As a result,DOP is often found in marine water ecosystems where many species are exposed to it.Our objective was to evaluate the effect of long-term(14 d) DOP exposure(2.6,7.8,or 31.2 mg/L) on the expression of immunerelated genes in Tegillarca granosa.The expression of small heat shock protein(sHSPs) and tissue inhibitor of metalloproteinase(TIMP) were highest in clams exposed to 31.2 mg/L DOP on days 7 and 14.The relative expression of Tg-ferritin,superoxide dismutase(SOD),and metallothionein(MT) increased initially then decreased as the concentration of DOP increased.The hemoglobin of T.granosa(Tg-Hb I) exhibited two distinct expression patterns at two time points.Our results suggest that the immune response of T.granosa against DOP pollution varies depending on the dose.Additionally,we identified some immune-related genes that are promising candidates for biomarkers of DOP.

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.

Phthalate Esters Biodegradation by Fusarium Oxysporum in Vegetable Soil

In this research, soil samples were frst polluted with 6 PAEs （i.e. DMP, DEP, DIBP, DBP, DEHP, and BBP） at 3 different concentration gradients （0, 10, and 20 mg/kg） and then treated with a highly-efficient degradation fungus, Fusarium oxysporum （PO-Yi）, to investigate the biodegradation of PAEs in pepper and eggplant soil. The findings revealed that PO-Yi can accelerate the degradation of PAEs in vegetable soils including pepper and eggplant soil to varying degrees. The highest absolute degradation rate （up to 39.5%） was observed in DEP-treated soils at the high pollution level （20 mg/kg）, which was 14.2% higher than that at the middle pollution level （10 mg/kg）. The degradation effect in the pepper soil was superior to that in the eggplant soil. Vegetable soil, either pepper soil or eggplant soil, which was polluted by various PAEs at different pollution gradients and then treated with PO-Yi fungus presented good bioremediation results. In the pepper and eggplant soil, 76.8% and 63.1% of the PAEs with a total volume of 60 mg/kg were degraded within 30 d respectively. PO-Yi, indigenous microorganisms, and the vegetables, i.e. pepper and eggplant had good synergistic effects on the degradation of compound PAEs in PAE-polluted pot soil.

Photocatalytic Degradation of Diethyl Phthalate with Surfactant Addition

This paper studies the adsorption of diethyl phthalate （DEP,an environmental hormone） on the surface of nanoscale TiO2, effects of pH value of solutions, initial concentrations of DEP and additive surfactant on photocatalytic degradation and dynamics of DEP. Under ultra violet illumination, the interaction between DEP and surfactants including DBS （sodium dodecylbenzenesulfonate）, CTAB （cetyltrimethylammonium bromide）, and OP-10 （nonylphenol polyoxyethylene ether） was exploited from the perspective of degradation speed calculated by the data of high pressure liquid chromatography （HPLC） and UV-Vis spectra, respectively. Photocatalytic degradation of DEP followed pseudo first-order reaction kinetics. DEP as substrate degraded fast when its initial concentration was 130 mg/L. TiO2 had certain adsorption ability of DEP. TiO2 could adsorb the most DEP at the approximately neutral pH of 6.91. Degradation of DEP was not affected obviously by additives OP-10 and DBS. Degradation rate of DEP was not enhanced greatly in the presence of surfactants, but degradation of DBS was sped up. Degradation rate of DEP was depressed in the presence of additive CTAB. The more CTAB was added, the less DEP was degraded. Degradation rate of CTAB became slow with the increase of initial CTAB concentration. The possible adsorption models among TiO2, DEP and surfactants were given.