改性聚乙烯醇吸附镍离子的动力学与热力学研究

研究了自制改性聚乙烯醇对Ni~(2+)的吸附行为,在不同的吸附条件下,探讨相关因素的影响,并对实验数据进行动力学与热力学的拟合。结果表明,室温下,在溶液p H=6.0,NaNO_3的浓度为0.1 mol/L,吸附时间为60 min,液固比为250 m L/g,改性聚乙烯醇对浓度为0.1 mol/L Ni2+的吸附效果好,去除率达到98.05%;当干扰因子设定为0.1 mol/L的Ca(NO_3)_2,对Ni2+的去除率降到59.29%。改性聚乙烯醇对Ni2+的吸附动力学符合准二级动力学方程;Langmuir等温模型的拟合度较高,推测改性聚乙烯醇表面是均一的等质体,计算的最大吸附量为1.35 mmol/g,与实验结果一致;D-R等温模型的拟合度次之,在各温度下,E16 k J/mol,说明改性聚乙烯醇对Ni2+的吸附是以化学吸附为主。通过Van’t Hoff方程的拟合,计算得到的吉布斯自由能以及熵变和焓变表明该吸附过程为吸热化学反应。     

Kinetic and isotherm error optimization studies for adsorption of atrazine and imidacloprid on bark of Eucalyptus tereticornis L.

The aim of this study was to establish the bark of Eucalyptus tereticornis L. (EB) as a low cost bio-adsorbent for the removal of imidacloprid and atrazine from aqueous medium. The pseudo-first-order (PFO), pseudo-second-order (PSO), Elovich and intra-particle diffusion (IPD) models were used to describe the kinetic data and rate constants were evaluated. Adsorption data was analysed using ten 2-, 3- and 4-parameter models viz. Freundlich, Jovanovic, Langmuir, Temkin, Koble–Corrigan, Redlich–Peterson, Sips, Toth, Radke–Prausnitz, and Fritz-Schluender isotherms. Six error functions were used to compute the best fit single component isotherm parameters by nonlinear regression analysis. The results showed that the sorption of atrazine was better explained by PSO model, whereas the sorption of imidacloprid followed the PFO kinetic model. Isotherm model optimization analysis suggested that the Freundlich along with Koble–Corrigan, Toth and Fritz-Schluender were the best models to predict atrazine and imidacloprid adsorption onto EB. Error analysis suggested that minimization of chi-square (χ²) error function provided the best determination of optimum parameter sets for all the isotherms.     

Adsorption du chlorfenvinphos et du methidathion sur argiles saturees par differents cations

Summary

Adsorption of chlorfenvinphos and methidathion from dissolutions on H⁺, Ca⁺⁺, Na⁺ and K⁺ are studied. In all cases the saturating cation distinctly influenced the Freundlich‐type adsorption, with adsorption decreasing in the following sequence: H⁺> Ca⁺⁺> Na⁺ > K⁺. Chlorfenvinphos adsorption was slightly greater than methidathion in two clays, and the adsorption extent for them in kaolinite is slower that bentonite.     

Contamination and bioaccumulation of benzotriazole ultraviolet stabilizers in fish from Manila Bay, the Philippines using an ultra-fast liquid chromatography-tandem mass spectrometry

Methyl methacrylate (MMA) is grafted on multiwalled carbon nanotubes (MWCNTs) by using N₂ plasma technique. The MMA grafted MWCNTs (MWCNT-g-pMMA) are characterized by using Raman spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, thermo gravimetric analysis-differential thermal analysis (TGA-DTA), and potentiometric acid-base titration method. The application of MWCNT-g-pMMA in the removal of 4,4′-dichlorinated biphenyl (4,4′-DCB) from large volumes of aqueous solutions is investigated under ambient conditions. The results indicate that the adsorption of 4,4′-DCB on MWCNT-g-pMMA is much higher than that of 4,4′-DCB on MWCNTs, and the adsorbed 4,4′-DCB is difficult to be thermally decomposed from MWCNT-g-pMMA according to the TGA-DTA analysis. MWCNT-g-pMMA are suitable materials in the preconcentration and immobilization of polychlorinated biphenyls (PCBs) from large volumes of aqueous solutions in environmental pollution cleanup.     

Treatment of dynamic mixture of hexane and benzene vapors in a Trickle Bed Air Biofilter integrated with cyclic adsorption/desorption beds

One of the main challenges that face successful biofiltration is the erratic loading pattern and long starvation periods. However, such patterns are common in practical applications. In order to provide long-term stable operation of a biofilter under these conditions, a cyclic adsorption/desorption beds system with flow switching was installed prior to a biofilter. Different square waves of a mixture containing n-hexane and benzene at a 2:1 ratio were applied to the cyclic adsorption/desorption beds and then fed to a biofilter. The performance of this integrated system was compared to a biofilter unit receiving the same feed of both VOCs. The cyclic adsorption/desorption beds unit successfully achieved its goal of stabilizing erratic loading even with very sharp peaks at the influent concentration equalizing influent concentrations ranging from 10-470 ppmv for n-hexane to 30-1410 ppmv for benzene. The study included different peak concentrations with durations ranging from 6 to 20 min. The cyclic beds buffered the fluctuating influent load and the followed biofilter had all the time a continuous stable flow. Another advantage achieved by the cyclic adsorption/desorption beds was the uninterrupted feed to the biofilter even during the starvation where there was no influent in the feed. The results of the integrated system with regard to removal efficiency and kinetics are comparable to published results with continuous feed studies at the same loading rates. The removal efficiency for benzene had a minimum of 85% while for n-hexane ranged from 50% to 77% according to the loading rate. The control unit showed very erratic performance highlighting the benefit of the utilization of the cyclic adsorption/desorption beds. The biofilter was more adaptable to concentration changes in benzene than n-hexane.     

Transfer functions for solid-solution partitioning of cadmium for Australian soils

To assess transport and ecotoxicological risks of metals, such as cadmium (Cd) in soils, models are needed for partitioning and speciation. We derived regression-based “partition-relations” based on adsorption and desorption experiments for main Australian soil types. First, batch adsorption experiments were carried out over a realistic range of dissolved Cd concentrations in agricultural soils in Australia. Results showed linear sorption relationships, implying the adequacy of using Kd values to describe partitioning. Desorption measurements were then carried out to assess in-situ Kd values and relate these to soil properties The best transfer functions for solid-solution partitioning were found for Kd values relating total dissolved Cd concentration to total soil Cd concentrations, accounting for the variation in pH, SOM contents and DOC concentrations. Model predictions compared well with measurements of an independent data set, but there was a tendency to underestimate dissolved Cd concentrations of highly polluted soils.     

Enhancement of chlorophenol sorption on soil by geophagous earthworms (Metaphire guillelmi)

Earthworms are the dominant soil biomass of many terrestrial ecosystems and markedly influence the physico-chemical and biological properties of soil; however, little is known about the effects of earthworm activities on the environmental behavior of micropollutants in soil. We studied the sorption and desorption of 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol on geophagous earthworm (anecic Metaphire guillelmi) casts of various aging times and on the parent soil. The casts were characteristic of lower pH and higher content of fine particles (silt and clay) than the parent soil. The sorption of the chlorophenols on the soil and casts were well fitted to linear isotherms, with sorption capacity in the order of pentachlorophenol > 2,4-dichlorophenol > 2,4,6-trichlorophenol. The sorption on the cast with different aging time was quite similar and was higher than on the parent soil. The sorption on the soil did not change between pH 7.07 of the soil and pH 6.76 of the casts. The desorption hysteresis of the chlorophenols on the soil and casts was compound specific and 2,4,6-trichlorophenol showed the highest hysteresis. The higher sorption capacity of the casts was not owing to the lowered pH of the casts, but mainly to the higher fine particles in the casts and the possible changes of nature of the soil organic matter through the earthworm gut passage. Our results indicate that geophagous earthworms may change sorption behavior and thus the bioavailability and transport of chlorophenols in soil. Earthworm effects should be considered when evaluating the environmental behavior and risk of organic pollutants in the ecosystems where earthworms are abundant.     

铋和石墨烯改性金属有机框架对碘离子的吸附性能

采用一步法制备石墨烯(GO)和铋[Bi(Ⅲ)]改性沸石咪唑酯骨架结构(ZIF-8),得到GZIF和Bi@GZIF吸附剂,并用X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)及扫描电镜(SEM)对制备的吸附剂进行表征。结果显示,改性后ZIF-8晶体结构没有被破坏,表面形态及表面基团发生了变化,对碘离子的吸附能力增强,吸附速度加快,尤其是Bi@GZIF在5 min内完成吸附88.3%,最大吸附容量达197.2 mg/g。     

The effect of soil organic matter on fate of polycyclic aromatic hydrocarbons in soil: A microcosm study

A microcosm study was conducted to address the influences of air-soil partition and sequestration on the fate of polycyclic aromatic hydrocarbons (PAHs) in soil. Sterilized and unsterilized soils with soil organic carbon (SOC) content ranging from 0.23 to 7.06% were incubated in a chamber with six PAHs supplied through air. After 100 d of incubation when the system approached pseudo-steady state, the PAHs concentrations in the unsterilized soils still correlated with SOC significantly, while the association did not exist for those sterilized. The lower degradation rate in the soil with higher SOC was likely the major reason for the association between SOC and PAHs concentrations, while the decreased surface porosity likely suppressed such correlation for the sterilized samples. The results indicated that the sequestration was likely the major mechanism for the accumulation of PAHs in soils, while both of the soil porosity and PAHs properties had observed influences.     

Removal of uranium (VI) from aqueous solution by adsorption of hematite

Hematite, a type of inorganic-sorptive medium, was used for the removal of U (VI) from aqueous solutions. Variables of the batch experiments including solution pH, contact time, initial concentration, temperature, calcium and magnesium ions were studied. The results indicated that the adsorption capacities are strongly affected by the solution pH, contact time and initial concentration. A higher pH favors higher U (VI) removal. The adsorption was also affected by temperature and calcium and magnesium ions, but the effect is very weak. The maximum adsorption capacity (q_m) only increased from 3.36 mg g⁻¹ to 3.54 mg g⁻¹ when the temperature was increased from 293 K to 318 K. A two-stage kinetic behavior was observed in the adsorption of uranium (VI): very rapid initial adsorption in a few minutes, followed by a long period of slower uptake. It was found that an increase in temperature resulted in a higher uranium (VI) loading per unit weight of the sorbent. The adsorption of uranium by hematite had good efficiency, and the equilibrium time of adsorbing uranium (VI) was about 6 h. The isothermal data were fitted with both Langmuir and Freundlich equations, but the data fitted the former better than the latter. The pseudo-first-order kinetic model, pseudo-second-order kinetic model and intraparticle diffusion model were used to describe the kinetic data, but the pseudo-second-order kinetic model was the best. The thermodynamic parameter ΔG⁰ were calculated, the negative ΔG⁰ values of uranium (VI) at different temperatures confirmed the adsorption processes were spontaneous.