原油在土壤中的吸附和解吸研究

用振荡平衡法研究了原油在土壤中的吸附和解吸行为，测得了吸附常数，给出了吸附等温线。结果表明，Linear吸附关系可较好地描述原油在土壤中的吸附状况；土壤有机质含量影响原油的吸附量；其解吸行为则明显受到溶液pH的影响，表面活性剂的加入有助于原油解吸。     

On equilibration of pore water in column leaching tests

Column leaching tests are closer to natural conditions than batch shaking tests and in the last years have become more popular for assessing the release potential of pollutants from a variety of solids such as contaminated soils, waste, recycling and construction materials. Uncertainties still exist regarding equilibration of the percolating water with the solids, that might potentially lead to underestimation of contaminant concentrations in the effluent. The intention of this paper is to show that equilibration of pore water in a finite bath is fundamentally different from release of a certain fraction of the pollutant from a sample and that equilibrium is reached much faster at low liquid-to-solid ratios typical for column experiments (<0.25) than in batch tests with much higher liquid-to-solid ratios (e.g. 2–10). Two mass transfer mechanisms are elucidated: First-order type release (film diffusion) and intraparticle diffusion. For the latter, mass transfer slows down with time and sooner or later non-equilibrium conditions are observed at the column outlet after percolation has been started. Time scales of equilibrium leaching can be estimated based on a comparison of column length with the length of the mass transfer zone, which is equivalent to a Damköhler number approach. Mass transfer and diffusion coefficients used in this study apply to mass transfer mechanisms limited by diffusion in water, which is typical for release of organic compounds but also for dissolution of soluble minerals such as calcite, gypsum or similar. As a conclusion based on these theoretical considerations column tests (a) equilibrate much faster than batch leaching tests and (b) the equilibrium concentrations are maintained in the column effluent even for slow intraparticle diffusion limited desorption for extended periods of time (>days). Since for equilibration the specific surface area is crucial, the harmonic mean of the grain size is relevant (small grain sizes result in high concentrations even after short pre-equilibration of a column). The absolute time scales calculated with linear sorption and aqueous diffusion aim at organic compounds and are not valid for sparingly soluble mineral phases (e.g. metal oxides and silicates). However, the general findings on how different liquid-to-solid ratios and specific surface area influence equilibration time scales also apply to other mass transfer mechanisms.     

毒死蜱在不同土壤腐殖酸上的吸附/解吸特征

通过平衡振荡法研究毒死蜱在不同来源土壤腐殖酸(Has)上的吸附/解吸行为.结果表明,毒死蜱在Has上的等温吸附行为用Freundlich模型描述相对更合理;它们的吸附等温线在实验范围内基本呈直线,且吸附能力很强,顺序为:紫色潮土Has＞黄壤Has＞中性紫色土Has＞酸性紫色土Has＞腐殖土Has;但毒死蜱的解吸率较小,其值均小于26.70%,有明显的滞后现象,尤其是腐殖土Has和紫色潮土Has,固定能力顺序为:紫色潮土Has＞腐殖土Has＞中性紫色土Has＞酸性紫色土Has＞黄壤Has.由于不同来源土壤中Has的组成结构差异明显,它们对毒死蜱的吸附/解吸规律表现出不同的特征.土壤Has对毒死蜱的吸附/解吸行为的影响是多种因素综合作用的结果,具体作用机理尚待进一步研究.     

Impact of crystalline and amorphous iron- and aluminum hydroxides on mechanisms of phosphate adsorption and desorption

Fourier-transform infrared(FT-IR) spectroscopic experiments were carried out during phosphate adsorption on highly crystalline gibbsite, poorly crystalline 2-line-ferrihydrite and amorphous iron–aluminum–hydroxide mixtures in the molar ratio 1:0, 10:1, 5:1, 1:1, 1:5, 1:10 and 0:1. The OH stretching vibrational bands were utilized to analyze changes in structural and surface OH groups during adsorption, because the position of characteristic P\O vibrational bands can shift depending on reaction conditions, pH or adsorbed phosphate content.Adsorption and desorption kinetics were studied at pH6 and different initial phosphate concentrations to achieve varying phosphate coverage on the mineral surfaces. For gibbsite the formation of AlHPO_4 and Al_2HPO_4 can be assumed, while for ferrihydrite, a FeHPO_4 or Fe_2PO_4 complex and the precipitation of FePO_4 with longer equilibration time were proposed.Fe_2HPO_4 or a Fe_2PO_4 surface complex was deduced for Fe-hydroxides, an AlH_2PO_4 surface complex was identified for Al-hydroxide, and both displayed either hydrogen bonds to neighboring hydroxyl groups or hydrogen bonds to outer-sphere complexes. Fe:Al-hydroxide mixtures with high Al ratios showed a low phosphate desorption rate, while ferrihydrite and the Fe:Al-hydroxide mixtures with high Fe ratios had almost negligible desorption rates. It was concluded that within the weakly associated amorphous FeO(OH) materials, FePO_4 precipitated, which was bound by outer-sphere hydrogen bonds. With high Al ratios, desorption increased, which indicated weaker phosphate binding of both inner-sphere and outer-sphere complexes and hence, either no or minor quantities of precipitate. Ferrihydrite showed a more rigid structure and a lower extent of precipitation compared to amorphous Fe-hydroxide.     

Na-Ba/γ-Al2O3的NO和SO2吸附性能研究

研究了Na-Ba/γ-Al2O3吸附催化剂上NO和SO2的吸附-脱附性能.Na、Ba质量分数分别为6.2%、5.4%,焙烧温度和焙烧时间分别为600 ℃和10 h,吸附温度为100 ℃,其对NO、SO2的最大吸附量分别为0.052 4、0.344 mmol/g.同时考察了添加第三活性组份的影响,结果表明,Fe最为有效,Na-Ba/Fe/γ-Al2O3的NO、SO2最大吸附量分别为0.062 4、0.486 mmol/g.漫反射红外光谱研究结果表明,Fe降低了硫酸盐分解温度,促进吸附催化剂的再生.     

活性炭吸附硫化氢及微波辐照解吸研究

研究了两种活性炭对硫化氢的平衡吸附性能力,并对活性炭床层的穿透性进行了考察;吸附饱和和活性炭在微波辐射的作用下进行解吸。实验表明,解吸效率与微波作用时间及温度有关,在本实验条件下H2S解吸效率达90．1％。     

Exploitation of Trichoderma harzianum mycelial waste for the removal of rhodamine 6G from aqueous solution

The harvested mycelial waste of Trichoderma harzianum was used as an adsorbent for the removal of rhodamine 6G and was studied in batch mode. The effects of agitation time and initial dye concentration, adsorbent dosage and pH were examined. The study revealed that the amount of dye adsorbed (mgg(-1)) increased with increase in agitation time and reached equilibrium after 120 min, for dye concentrations of 10-50 mg L(-1). The adsorbent dosage of 1.0 g/50 mL and pH of 8.0 were found to be optimum for maximum dye removal. The batch mode adsorption data followed both the Langmuir and Freundlich isotherms. The pseudo first- and second-order rate kinetics were applied to the adsorbent system. The adsorption kinetics of rhodamine 6G showed that the pseudo-second-order kinetic model provided the best correlation of the equilibrium data. The study implies that it is possible to develop a dye removal system by using T. harzianum biomass, which occurs as sludge in waste stream of fermentation industries.     

Biosorption of heavy metals by activated sludge and their desorption characteristics

The biosorption of different metals (Cu2+, Cd2+, Zn2+, Ni2+ and Pb2+) was investigated using activated sludge. The optimum pH was 4 for Cd, Cu and Pb sorption and 5 for Ni and Zn. Biomass metal uptake clearly competed with protons present in the aqueous medium, making pH an important variable in the process. Protons consumed by biomass in control tests versus protons exchange in biosorption tests confirmed a maximum exchange between metal cations and protons at pH 2. The study of the influence of biomass concentration revealed that the amount of protons released from biomass increased with biomass concentration. This would confirm the hypothesis of ion exchange between both types of ions. The application of the Langmuir and Freundlich models showed a better fitting of experimental data to the first model. The maximum sorption uptake of the studied metals by the activated sludge showed the following decreasing order: Pb>Cu>CdZn>Ni. Desorption experiments showed that HCl was a good eluent for the five metals tested, particularly at low pH values (1 and 2). At pH 3 or 4 the desorption yield was significantly lower. However, its use did not allow the reuse of biomass in subsequent loading and unloading cycles. EDTA was also a good desorption agent, achieving the total recovery for the five metals tested at a concentration of 1mM, with the advantage that biomass could be reused for three sorption-desorption cycles.     

Comparative sorption and desorption behaviors of PFHxS and PFOS on sequentially extracted humic substances

The sorption and desorption behaviors of two perfluoroalkane sulfonates（PFSAs）, including perfluorohexane sulfonate（PFHx S） and perfluorooctane sulfonate（PFOS） on two humic acids（HAs） and humin（HM）, which were extracted from a peat soil, were investigated. The sorption kinetics and isotherms showed that the sorption of PFOS on the humic substances（HSs） was much higher than PFHx S. For the same PFSA compound, the sorption on HSs followed the order of HM 〉 HA2 〉 HA1. These suggest that hydrophobic interaction plays a key role in the sorption of PFSAs on HSs. The sorption capacities of PFSAs on HSs were significantly related to their aliphaticity, but negatively correlated to aromatic carbons,indicating the importance of aliphatic groups in the sorption of PFSAs. Compared to PFOS,PFHx S displayed distinct desorption hysteresis, probably due to irreversible pore deformation after sorption of PFHx S. The sorption of the two PFSAs on HSs decreased with an increase in p H in the solution. This is ascribed to the electrostatic interaction and hydrogen bonding at lower p H. Hydrophobic interaction might also be stronger at lower p H due to the aggregation of HSs.     

被动采样/热脱附/GC-MS法测定环境空气中挥发性有机物暴露量

建立了吸附管被动采样-热脱附解吸气相色谱质谱联用测定环境空气中挥发性有机物暴露量的采样、分析方法。14种挥发性有机物的检出限为0.002~0.005 ng/h。该法采样无需动力,具有简单、方便、灵敏度高等特点,可广泛应用于环境气体的监测。