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.     

Enhanced degradation of bioremediation residues in petroleum-contaminated soil using a two-liquid-phase bioslurry reactor

A study was performed to determine the potential of two-liquid-phase (TLP) bioslurry reactors using silicon oil as solvent for degradation of residual contaminants in petroleum-contaminated soil. The residues were characterized by gas chromatography–mass spectrometry and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. This allowed for the identification of a mixture of residual biomarkers, metabolic byproducts, oxygenated and hetero-polynuclear aromatic hydrocarbons in the contaminated soil. The removal amount of total extractable organics (TEO) was 15 900 mg kg⁻¹ soil in the TLP reactor within 12 weeks. However, TEO remained intact in the bioslurry reactor without the addition of silicon oil for the duration of the experiment, due to high toxicity of metabolites to the microorganisms. The availability of TEO was calculated using a mild extraction with Triton X-100, and the amount of TEO extracted was in accord with the amount of biodegraded TEO. Significantly reduced toxicity in soil was observed at week 12 through TLP remediation. Dehydrogenase activity in the bioslurry reactor was strongly suppressed. Fluorescein diacetate was significantly hydrolyzed by the composition of bioremediation residues in the contaminated soil. Microbial adhesion to the solvent was revealed by the determination of microbial activity in the water-immiscible-liquid.     

表面活性剂去除土壤和地下水中LNAPLs作用机制研究

去除多孔介质中滞留的LNAPLs,表面活性剂对LNAPLs的增溶和降低界面张力是关键.在实验测得不同浓度Triton X-100溶液对正十六烷的增溶以及它们之间界面张力的基础上,通过平衡清洗实验和砂柱冲洗实验分析了不同形态正十六烷的产生规律和机制.结果表明,正十六烷溶解能力与Triton X-100浓度成正比,当Triton X-100浓度大于临界胶束浓度CMC时,计算得摩尔增溶比MSR=1.680 4,胶束相/水相分配系数对数值lgK_mc=1.715 8;正十六烷-Triton X-100溶液之间界面张力与Triton X-100浓度成反比,其变化规律符合高斯模型（R₂=0.996 4）;溶解态正十六烷和自由态正十六烷与增溶和降低界面张力分别有较好的对应关系,表明增溶和降低界面张力都对多孔介质中正十六烷去除有影响,其中降低界面张力可以有效增加多孔介质中正十六烷的流动性,在正十六烷去除过程中起主要作用.     

Effects of nonionic surfactant Triton X-100 on the laccase-catalyzed conversion of bisphenol A

The laccase-catalyzed conversion of bisphenol A (BPA) in aqueous solutions was studied in the absence and presence of nonionic surfactant Triton X-100. It was found that the addition of Triton X-100 into the reaction system increased the conversion of BPA, especially near the critical micelle concentration of Triton X-100. Also it was found that the stability of laccase was greatly improved in the presence of TritonX-100. Studies on the endogenous fluorescence emission of laccase indicated that there existed an interaction between Triton X-100 and laccase, which was beneficial to folding and stabilizating of laccase. The binding of Triton X-100 to the laccase surface also mitigated the inactivation e ect caused by the free radicals and polymerization products. Under otherwise identical conditions, a lower dosage of laccase was needed for the higher conversion of BPA in the presence of Triton X-100.     

Triton X-100在土壤颗粒上的吸附特征研究

采用平衡振荡法,研究了砂土对非离子表面活性剂Triton X-100的吸附特征。结果表明,砂颗粒对Triton X-100的吸附能力总体较低,单位吸附含量均＜1.1 mg/g;砂颗粒吸附Triton X-100过程中存在显著的吸附剂浓度效应,砂颗粒上Triton X-100含量随着固液比（吸附剂浓度）的增大而减小;吸附容量q_m与平衡常数K_L值随固液比变化而变化,Langmuir方程适用范围是起始浓度C₀相对较小的固液吸附体系;0.5～1 mm石英砂的吸附能力略＞0.2～0.5 mm石英砂,0.5～1 mm和0.2～0.5 mm石英砂吸附Triton X-100变化特征具有显著的一致性,采用高斯拟合模型可以反映出石英砂吸附Triton X-100的变化规律,相关系数R²均＞0.98。     

Efficient removal of polybrominated diphenyl ethers from soil washing effluent by dummy molecular imprinted adsorbents: Selectivity and mechanisms

Surfactant enhanced elution is an effective method for removing hydrophobic organic pollutants from soils. The key to the development of leaching technology is selective removal of targeted pollutants in soil washing effluent and recycling of surfactant solutions. In this study, a molecular imprinting technique was applied to selectively sorb polybrominated diphenyl ethers (PBDEs) in soil washing effluent. The novel molecular imprinted polymers (MIPs) using different template molecules were synthesized by precipitation polymerization. Adsorption behaviors and mechanisms of MIPs were studied through experiments and theoretical calculations. The results show that 4-bromo-4′-hydroxybiphenyl and toluene can be effective imprinting molecule for MIPs synthesis. The maximal adsorption capacity of selected dummy molecular imprinted polymer (D₁-MIP) was 1032.36 µmol/g, and that of part molecular imprinted polymer (P-MIP) was 981.13 µmol/g. Their imprinting factors in 5 PBDEs adsorption ranged from 2.13 to 5.88, the recovery percentage of Triton X-100 can reach 99.09%, confirming the feasibility of reusing surfactant. Various PBDEs could be removed by MIPs, and Quantitative Structure Property Relationship analysis revealed that PBDEs’ molecular volume, planarity, polarity, and hydrophobicity have major influences on their adsorption performance. DFT calculation revealed that Van der Waals force and hydrogen bonding played important roles during selective adsorption. These results can provide effective theoretical guidance for surfactant enhanced soil elution in practical engineering applications.     

A fast and reliable method for quantitative determination of total mercury in vegetables

A cloud-point extraction (CPE) process using the nonionic surfactant, polyethylene glycol tert octylphenyl ether (Triton X-114) was employed for determination of Hg(II) ions in aqueous solutions. The method is based on the ion-pairing reaction of Hg(II) with Pyronin B (PyrB⁺) in the presence of excess iodide at pH 6.0 and extraction of the complex formed. The chemical variables affecting CPE efficiency were studied, and the analytical characteristics of the method were obtained. The calibration curves were linear in the range of 1–40 μg L^?1 with the detection limits of 0.35 and 0.30 μg L^?1 at 556 and 521 nm. Selectivity was also tested. The coefficients of variation of the method are 2.4% and 5.2% for five replicate measurements of mercury at levels of 10 and 25 μg L^?1, respectively. The results obtained for two certified reference samples were in a good agreement with the certified values. The method was applied to the determination of total mercury in vegetable samples.     

Triton X-100在黄土上的吸附行为及影响因素

水土体系下,应用批实验法研究了Triton X-100在天然黄土上的吸附行为与平衡时间、Triton X-100浓度、溶液离子强度和pH值的关系.结果表明,Triton X-100在黄土中的吸附平衡时间约为30 min,其吸附动力学符合一级动力学模型,相应拟合参数Qe、k1、r2分别为3.041 mg·g-1、0.102 min-1、0.993 4.吸附等温线明显为非线性,在利用的4种等温吸附模型中,Sips模型对实验数据提供了最佳的拟合,其拟合参数Qmax和r2分别为3.202 mg·g-1和0.998 7.溶液离子强度和pH值对Triton X-100在黄土上的吸附有显著的影响,其吸附量随NaCl浓度的增加而明显增加,随pH增加而降低.