微塑料对环境中有机污染物吸附解吸的研究进展

微塑料已成为新的全球性环境污染问题。作为强吸附剂,微塑料可以吸附共存的有机污染物,进而改变其环境行为和毒性;也可以通过解吸作用促进污染物在不同介质中的迁移。因而,微塑料与有机污染物的相互作用强度和机理是全面评估两者的环境风险和深度研究微塑料毒性机制的必要信息。目前微塑料研究处于快速发展的起始阶段,加之微塑料本身成分、粒径、表面风化情况的复杂性及共存有机污染物的多样性使两者的相互作用十分复杂,亟需理清微塑料吸附解吸作用的影响因素和相关机制。因而,本文详细综述了微塑料对有机污染物吸附解吸作用的研究进展,并着重从微塑料性质(成分、粒径和表面风化)、有机污染物性质和水环境介质性质方面探讨了吸附的影响因素和相互作用机制,希望为微塑料吸附有机污染物及吸附的后续影响研究提供借鉴与参考。     

双酚A在湘江沉积物上的吸附特征

探讨了双酚A(BPA)在湘江沉积物上的吸附/解吸特征.结果表明,BPA在湘江沉积物上的吸附主要以快速吸附为主,Freundlich模型能较好地描述其吸附等温线,沉积物有机质中的碳黑物质和孔隙填充相引起了BPA的非线性吸附和解吸滞后行为;沉积物对BPA的吸附是一个放热过程,主要是自发的焓推动的物理吸附;随着沉积物浓度的增大,单位沉积物上的BPA吸附量减少;随着离子强度的增大,单位吸附量也随之增大;在酸性条件下,单位沉积物上的BPA吸附量随着pH值的增大而减少,在碱性条件下这种影响不显著.     

Ignition temperatures of dust layers and bulk storages in hot environments

In many industrial installations, particulate solids (cereals, agri-food products, coal, plants, etc.) are stored or processed. Self-heating of these products, which can lead to fires and explosions, can occur in a variety of situations. Examples include large storage at room temperature, formation of a layer on a hot surface, layer deposited on a surface – insulating or conductive – in a hot environment or even storage of product exposed to heating on one side.The main parameters that determine the occurrence of self-heating are the size of the container, the temperature, the residence time and the characteristics of the product. Depending on the type of situation encountered and these implementation conditions, the analysis of self-heating risks must be based on specific models and/or parameters.This paper presents the different variants and combinations of the theoretical model from the theory of thermal runaway to represent self-heating, taking into account in particular the symmetry or asymmetry of heating, reagent consumption and boundary conditions. It also discusses their adaptation to the previous identified industrial situations.Nine products were chosen to be representative of those used in the different considered industrial situations. They were subjected to self-heating basket tests in isothermal ovens in order to determine the parameters for applying the described theoretical models. These results were compared with the results of self-heating tests in layers of different thicknesses in a hot environment, on an insulating or conductive plate, using a specially developed test protocol, as well as with the results of standardized tests of minimum ignition temperature in 5 mm layers.This led to the proposal of the most appropriate theoretical model to represent the self-heating phenomenon for each of the four identified industrial situations.This analysis can promote better design of industrial equipment and production conditions (temperatures, volumes or product flows …) in order to prevent fires and explosions.     

Thermal and hydrometallurgical recovery methods of heavy metals from municipal solid waste fly ash

Heavy metals in fly ash from municipal solid waste incinerators are present in high concentrations. Therefore fly ash must be treated as a hazardous material. On the other hand, it may be a potential source of heavy metals. Zinc, lead, cadmium, and copper can be relatively easily removed during the thermal treatment of fly ash, e.g. in the form of chlorides. In return, wet extraction methods could provide promising results for these elements including chromium and nickel. The aim of this study was to investigate and compare thermal and hydrometallurgical treatment of municipal solid waste fly ash. Thermal treatment of fly ash was performed in a rotary reactor at temperatures between 950 and 1050 °C and in a muffle oven at temperatures from 500 to 1200 °C. The removal more than 90% was reached by easy volatile heavy metals such as cadmium and lead and also by copper, however at higher temperature in the muffle oven. The alkaline (sodium hydroxide) and acid (sulphuric acid) leaching of the fly ash was carried out while the influence of temperature, time, concentration, and liquid/solid ratio were investigated. The combination of alkaline-acidic leaching enhanced the removal of, namely, zinc, chromium and nickel.     

酸性紫色水稻土颗粒有机质对镉的吸附特性

采集典型的酸性紫色水稻土（APPS）,从中分离出颗粒有机质（POM）,通过批量试验研究POM及其来源土壤Cd²⁺的吸附动力学、等温吸附和热力学特征,通过扫描电镜-能谱仪、傅里叶红外光谱仪等手段及吸附前后镉的形态变化的测定,研究了POM对Cd²⁺的吸附机制.结果表明：POM对Cd²⁺的亲和力远高于其来源土壤.POM及土壤对Cd²⁺的吸附动力学最优模型均为准二级动力学.Langmuir、Freundlich方程均能较好地描述其等温吸附特征,其中对POM,以Freundlich方程更优,表明POM对Cd²⁺的吸附属于多分子层的非均质吸附.吸附热力学参数△G^θ均小于0、△H^θ和△S^θ均大于0,表明吸附属于自发吸热过程.根据△H^θ值及解吸试验判定POM对Cd²⁺的吸附以化学吸附为主,土壤对Cd²⁺的吸附过程以物理吸附为主.吸附平衡后,土壤中可交换态镉比例提高,而POM中交换态和络合态镉比例增加.综上及吸附前后POM的表征结果说明,POM对Cd²⁺的吸附机制包括含氧官能团的络合、离子交换、阳离子-π键、沉淀作用和静电吸附.     

Sorption and Desorption Behavior of Chloroanilines and Chlorophenols on Montmorillonite and Kaolinite

The bioavailability of pollutants, pesticides and/or their degradation products in soil depends on the strength of their sorption by the different soil components, particularly by the clay minerals. This study reports the sorption-desorption behavior of the environmentally hazardous industrial pollutants and certain pesticides degradation products, 3-chloroaniline, 3,4-dichloroaniline, 2,4,6-trichloroaniline, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on the reference clays kaolinite KGa-1 and Na-montmorillonite SWy-l. In batch studies, 2.0 g of clay were equilibrated with 100.0 mL solutions of each chemical at concentrations ranging from 10.0 to 200.0 mg/L. The uptake of the compounds was deduced from the results of HPLC-UV-Vis analysis. The lipophilic species were best retained by both clay materials. The most lipophilic chemical used in the study, 2,4,6-trichloroaniline, was also the most strongly retained, with sorption of up to 8 mg/g. In desorption experiments, which also relied on HPLC-UV-Vis technique, 2,4,6-trichloroaniline was the least desorbed from montmorillonite. However, on kaolinite all of the compounds under study were irreversibly retained. The experimental data have been modelled according to the Langmuir and Freundlich isotherms. A hypothesis is proposed concerning the sorption mechanism and potential applications of the findings in remediation strategies have been suggested.     

大孔树脂吸附—Fenton试剂氧化法预处理含邻苯二甲酸二异丁酯废水

采用大孔树脂吸附—Fenton试剂氧化法预处理含邻苯二甲酸二异丁酯(DIBP)废水。大孔树脂吸附工段的最佳实验条件为:以树脂NDA88为吸附剂,废水pH为2。NDA88经过10批次的连续使用,COD去除率基本稳定在58%左右,脱附率可达96%以上,吸附后废水COD为12 000 mg/L左右。Fenton试剂氧化工段的最佳实验条件为:H2O2加入量70 mL/L,n(H2O2):n(Fe2+)=4,废水pH 4。在此最佳条件下进行实验,Fenton试剂氧化工段COD去除率达65%,处理后废水COD为4 200 mg/L。     

黄泥土微团聚体颗粒组对Cu2+的吸附与解吸研究

采用低能量超声波分散和冷冻机干燥法提取太湖地区黄泥土不同粒径微团聚体颗粒组样品,用平衡液吸附法和CaCl2与HCl溶液的连续解吸法研究原土和不同粒径微团聚体颗粒组对重金属Cu2 的吸附和解吸特征。结果表明,对于Cu2 的吸附,原土用Langmuir方程拟合最佳,而不同粒径微团聚体颗粒组用Freundlich方程拟合最佳。原土和不同粒径微团聚体颗粒组吸附量大小顺序为粘粒级>砂粒级>原土>粉砂级>粗粉砂级,这与其游离氧化铁和有机质含量呈显著正相关。原土和不同粒径微团聚体颗粒组对Cu2 的专性吸附质量分数随吸附量增加而减少,而非专性吸附质量分数则相反。不同粒径微团聚体颗粒组吸附总量小于原土,所以传统风干磨细的研究方法可能高估了土壤对铜固持能力。     

Effective removal of Cobalt(II) ions from aqueous solutions and nuclear industry wastewater using sulfhydryl and carboxyl functionalised magnetite nanocellulose composite: batch adsorption studies

A new adsorbent sulfhydryl and carboxyl functionalized magnetite nanocellulose composite [(MB-IA)-g-MNCC] was synthesized by graft co-polymerization of itaconic acid onto magnetite nanocellulose (MNCC) using EGDMA as cross linking agent and K₂S₂O₈ as free radical initiator. The adsorption occurs maximum in the pH 6.5. The best fitted kinetic model was found to be pseudo-second-order kinetics. Therefore the mechanism of Co(II) adsorption onto (MB-IA)-g-MNCC follows ion exchange followed by complexation. The Langmuir model was the best fitted isotherm model for the adsorption of Co(II) onto the (MB-IA)-g-MNCC. Simulated nuclear power plant coolant water samples were also treated with (MB-IA)-g-MNCC to demonstrate its efficiency for the removal of Co(II) from aqueous solutions in the presence of other metal ions. To recover the adsorbed Co(II) ions and also to regenerate the adsorbent to its original state 0.1?M HCl was used as suitable desorbing agent. Six cycles of adsorption-desorption experiments were conducted and was found that adsorption capacity of (MB-IA)-g-MNCC has been decreased from 97.5% in the first cycle to 84.7% in the sixth cycle. Recovery of Co(II) using 0.1?M HCl decreased from 93.2% in the first cycle to 79.3% in the sixth cycle.

Abbreviations: T: absolute temperature; q_e: amount adsorbed at equilibrium; q_t: amount adsorbed at time t; CELL: cellulose; Co: cobalt; C_e: concentration at equilibrium; C_HCl: concentration of HCl; C_NaOH: concentration of NaOH; C_A: concentrations of acid; C_B: concentrations of base; W_g: dry weight of composite; W_i: dry weight of MNCC; DS: energy dispersive spectra; EGDMA: ethylene glycol dimethacrylate; Ce: equilibrium concentration; K_L: equilibrium constant; F: Faradays constant; FTIR: Fourier transform infrared spectra; ΔG^o: free energy change; K_F: Freundlich adsorption capacity; 1/n: Freundlich constant; R: gas constant; D: grafting density; EC_o: initial concentration; IA: itaconic acid; IA-g-MNCC: itaconic acid-grafted-magnetite nanocellulose composite; b: Langmuir constant; MNCC: magnetite nanocellulose composite; Q⁰: Maximum adsorption capacity; (MB-IA)-g-MNCC: 2-mercaptobenzamide modified itaconic acid-grafted-magnetite nanocellulose composite; NC: nanocellulose; pH_pzc: Point of zero charge; K₂S₂O₈: potassium peroxy sulphate; k₁: pseudo-first-order rate constant; k₂: pseudo-second-order rate constant; SEM: scanning Electron Microscope; b_s: Sips adsorption capacity; Q_s: Sips maximum adsorption capacity; ΔH°: standard enthalpy change; ΔS°: standard entropy change; A: surface area; σ₀: surface charge density; 1/n_s: surface heterogeneity factor; VSM: vibrating sample magnetometer; V: volume of solution; W: weight of (MB-IA)-g-MNCC; M_composite: weight of the composite; XRD: X-ray diffraction     

采用跟踪控温近似绝热系统测定火炸药热爆炸参数的探讨

本文针对以往在火炸药热爆炸参数测试过程中，因试样与加热介质之间的热交换所带来的较大测试误差，建立了跟踪控温下的近似绝热测试系统，研制了本测试系统的中枢仪器──四通道数显温度调节自动跟踪仪。通过本测试系统的建立，使得对热爆炸参数的测试更具有科学性和实用性。