黄壤表面电场作用下Cu~(2+)与Zn~(2+)的吸附/解吸动力学研究

利用静态恒流法研究了黄壤表面电场作用下Cu2+与Zn2+的吸附/解吸动力学.结果发现:考虑黄壤表面电场作用下,Cu2+和Zn2+的吸附实验呈现初期强吸附作用下的零级动力学过程和一定时间之后弱吸附作用下的一级动力学过程,与理论预期一致;在Cu2+和Zn2+的解吸实验中,只有前期出现了弱吸附作用下的一级动力学过程,实验结果与理论预期存在差别,原因在于专性吸附的Cu2+、Zn2+很难被解吸下来;在交换/吸附实验中,Cu2+的吸附速率值和平衡吸附量均大于Zn2+,且Cu2+-K+体系的表面电化学参数φ0、σ0、E0均大于Zn2+-K+体系中的对应值,证明了黄壤颗粒表面对Cu2+的吸附作用强于Zn2+;在交换/解吸实验中,Zn2+的解吸速率值和平衡解吸量均大于Cu2+,Zn2+-K+体系的表面电化学参数φ0、σ0、E0均大于Cu2+-K+体系中的对应值,证明Zn2+-K+体系中Zn2+的解吸作用比Cu2+-K+体系中的Cu2+解吸作用强.     

硒对菜地土壤镉微区分布及其吸附解吸特性的影响

以南方酸性黄棕壤为研究对象,采用根箱进行小白菜种植,研究了不同剂量的外源硒(0、0.25、1.00 mg·kg-1,以Se计)处理下,小白菜根际与非根际土壤Cd的含量变化;同时,通过Langmuir和Freundlich吸附模型进一步分析了经Se(0、0.25、1.00 mg·kg-1)预处理并经历过小白菜生长的根际与非根际土壤对Cd的吸附与解吸特性.结果表明,在Cd含量较低(0.50 mg·kg-1)的土壤中,低剂量的Se处理(0.25 mg·kg-1)根际土壤与非根际土壤的Cd含量均高于Se剂量为0、1.00 mg·kg-1的两个处理;在Cd含量较高(5.00 mg·kg-1)的土壤中,不同剂量的Se处理未能对土壤中Cd含量造成显著差异.通过吸附解吸试验及Langmuir和Freundlich两种吸附模型的模拟,发现根际土壤对Cd的吸附容量和吸附能力均小于非根际土壤,且根际土壤Cd的非专性吸附比率大于非根际土壤,表明小白菜的生长能够改变根际土壤对重金属Cd的吸附解吸特性,增加土壤中Cd的环境风险;然而,在本实验剂量范围内,外源Se预处理并未显著改变小白菜土壤Cd的吸附解吸特性,尚不足以证明Se通过影响小白菜根系分泌物等微域环境进而改变土壤重金属Cd的吸附解吸等环境化学行为.     

铁盐浸渍强化污泥活性炭-甲醇热质传递特性

针对以市政污泥为核心的炭素前驱体开展原位铁盐浸渍磁修饰,通过响应曲面试验设计优化并制备了新型原位浸渍炭IM-WNC;以成品炭的后浸渍磁修饰炭PM-WNC为参比,考察了原位浸渍与后浸渍磁修饰过程对污泥活性炭-甲醇工质对的吸附/解吸速率、吸附等温线、吸附床传热性能、制冷量及制冷功率等方面的影响。结果表明:与后浸渍过程相比,原位铁盐浸渍有利于保持污泥炭总孔容积(0.6608cm³/g)及比表面积(1122m²/g)水平,能显著提升致密化污泥炭IM-WNC的导热系数(600kg/m³,4.586W/(m·K))、甲醇Sokoda&Suzuki平衡吸附量((528.74±15.86)mg/g)和Langmuir最大吸附量((673.99±13.52)mg/g)。升温脱附与冷却吸附循环体系内,IM-WNC致密化吸附床中心温度峰谷差值可达到69.07℃。当循环时间为76min,解吸温度为100℃时,IM-WNC吸附制冷床的制冷量和制冷功率分别达到501.43kJ/kg和799.06kJ/(kg·h),较PM-WNC分别提升了15.61%和18.69%。     

气相色谱法测定室内空气中挥发性卤代烃

建立了活性炭吸附-溶剂解吸-气相色谱测定室内空气中7种挥发性卤代烃的分析方法。样品经活性炭采样管富集后,用二硫化碳解吸,Agilent HP-1色谱柱分离,使用带有电子捕获检测器的气相色谱仪测定,以保留时间定性,外标法定量。当采样体积为10 L时,方法检出限范围是0.03~0.18 g/m3,加标回收率在72%~114%之间,相对标准偏差小于15%。结果表明,该方法可以应用于室内空气中痕量挥发性卤代烃样品的检测分析。     

Effect of lipids on sorption/desorption hysteresis in natural organic matter

The chemical composition and physical conformation of natural organic matter (NOM) play a major role in regulating its capacity to retain hydrophobic organic compounds. Naphthalene and phenanthrene were used to study the correlations between sorption/desorption isotherm nonlinearity and compositional data obtained from quantitative ¹³C solid-state DPMAS NMR spectroscopy for soil and peat organic matter with or without lipids. Sorption experiments were conducted using a batch equilibration method. Desorption experiments were carried out immediately following the sorption experiments by three successive decant-refill cycles. Hysteresis was observed in all samples. Nonlinear sorption behavior was increased by removal of lipids from the NOM. The hysteresis index, obtained from the ratio of the Freundlich exponents (N values) for the desorption and sorption isotherms, was lower in the lipid-extracted NOM samples than in the same samples without lipid extraction. The relationship between the extent of hysteresis and the characteristics of the ¹³C DPMAS NMR spectra indicates that altering NOM composition through lipid extraction not only increased the proportion of aromatic-C content, but also increased sorption/desorption hysteresis. Our data also suggest that the hysteresis index is negatively related to aromaticity.     

热解吸对土壤中POPs农药的去除及土壤理化性质的影响

为探索土壤热解吸修复技术对POPs污染土壤的修复效果及修复后土壤可耕作性,选择北京某农药厂旧址的POPs农药污染土壤,研究了不同温度下热解吸处理后土壤中滴滴涕(DDTs)和六六六(HCHs)各组分的去除率以及土壤理化性质的变化。结果表明,热解吸修复技术可有效去除土壤中POPs农药,其中,p,p’-DDE与α-HCH组分去除率受热解吸温度的影响比其他组分更为明显。∑HCH与∑DDT在310℃、340℃时分别达到97%、99%的去除率,且此时土壤中的污染物含量低于我国《展览会用地土壤环境质量评价标准》,此后去除率受温度的影响不明显。热解吸温度对修复后土壤的理化性质有一定的影响,不同温度影响的程度各不相同,其中,有机质含量与全氮含量分别由0.78%、0.0352%降至0.14%、0.0107%;pH波动幅度较小,由7.80变至8.25;阳离子交换量变化存在波动,但呈整体下降趋势,由7.87 mg/kg降至5.00mg/kg;土壤中速效磷显著增加,由7.59 mg/kg升至21.8 mg/kg。而在最优温度条件下,土壤理化性质受热解吸温度的影响较小。由此可以说明,热解吸技术可以用于POPs污染土壤的修复,选择适当的热解吸温度对土壤的可耕作性影响有限,因而是一种潜在的绿色修复技术。     

CPB改性沸石对磷酸盐的吸附-解吸性能研究

采用溴化十六烷基吡啶(CPB)对天然沸石进行改性,并考察了CPB改性沸石对磷酸盐的吸附-解吸性能。结果表明,CPB改性沸石对磷酸盐具备一定的吸附能力,且吸附行为满足Langmuir等温吸附模型;粒径、改性剂投加量、反应温度、pH值及共存阴离子等因素均会影响CPB改性沸石对磷酸盐的吸附能力;减小粒径和降低反应温度均有利于CPB改性沸石对磷酸盐的吸附去除;粒径≤0.18 mm CPB改性沸石吸附磷酸盐较优的改性剂投加量为250 mmol/kg;当溶液的初始pH值位于4~10之间时CPB改性沸石对磷酸盐的吸附能力随pH值的增加而增强;SO42-的存在会明显降低CPB改性沸石对磷酸盐的吸附效率,而提高溶液的pH值有助于消除SO42-存在对CPB改性沸石吸附磷酸盐的负面影响;HCO3-的存在会一定程度上抑制CPB改性沸石对磷酸盐的吸附去除,而提高溶液的pH值无法消除HCO3-存在对CPB改性沸石吸附磷酸盐的负面影响;CPB改性沸石吸附磷酸盐后一定条件下可以重新解吸出来,且随着解吸液SO42-浓度的增加解吸率明显增大。     

新型吸附材料AGS在油气回收中的应用

考查了自制疏水性硅胶吸附材料AGS在加油站模拟油气回收装置及某油库现场油气回收装置的应用效果，并与常用的柱状活性炭进行了比较。实验结果表明：与活柱状性炭相比，AGS对油气的吸附速率和吸附量较小，但是油气脱附效果更好；将二者混合得到的吸附材料同时具备二者的优点，既具有较高的油气吸附量又具有良好的脱附性能，使油气回收装置具有更大的油气吸附量和更好的回收效果。     

Evaluation of solubility of polycyclic aromatic hydrocarbons in ethyl lactate/water versus ethanol/water mixtures for contaminated soil remediation applications

Solubility data of recalcitrant contaminants in cosolvents is essential to determine their potential applications in enhanced soil remediation. The solubilities of phenanthrene, anthracene, fluoranthene and benzo[a]pyrene in ethyl lactate/water and ethanol/water mixtures were measured using equilibrium techniques. The cosolvency powers derived from solubility data were then applied to the model developed from the solvophobic approach to predict the capability of ethyl lactate and ethanol in enhancing the desorption of contaminants from soils. Both ethyl lactate and ethanol cosolvents were shown to be able to enhance the solubilisation of the tested four polycyclic aromatic hydrocarbons by > 4 orders of magnitude above the levels obtained with water alone. However, ethyl lactate demonstrated a greater capacity to enhance PAH solubility than ethanol. The cosolvency powers of ethyl lactate/water system obtained from the end-to-end slope (σ) and the end-to-half slope (σ_0.5) of the solubilisation curve were 1.0--1.5 and 2.0--2.9 higher than ethanol/water system respectively. In line with this, ethyl lactate/water was demonstrated to enhance the desorption of contaminants from soil by 20%--37% and 18%--61% higher compared to ethanol/water system in low organic content and high organic content soils respectively, with a 2:1 (V/W) ratio of solution:soil and with cosolvent fraction as low as 0.4. With the exception of benzo[a]pyrene, the experimental desorption results agreed fairly with the predicted values, under an applied solution:soil ratio that was enough to hold the capacity of released contaminants.     

金属离子对长期污染土壤中多环芳烃解吸的影响

研究了离子强度、不同金属离子对土壤中PAHs表观解吸水平的影响.根据Pearson原理计算了菲、荧蒽、芘和苯并[k]荧蒽等几种PAHs的碱性特征参数并据此分析了其酸碱性类型.结果表明:实验条件下,解吸液中离子强度并非影响土壤中PAHs解吸的控制要素;不同硬度酸性金属离子与PAHs之间的酸碱作用是影响土壤中PAHs解吸水平变化的关键.硬酸性金属离子Ba2+、Al3+、Ca2+对土壤中PAHs的解吸具有促进作用,软酸性离子Hg2+、Ag+则具有抑制作用,比较而言交界酸性金属离子Cu2+、Fe2+、Zn2+在提高土壤中PAHs解吸上作用更加明显.