Redox potential and uranium sorption onto sediments: kinetic and thermodynamic characteristics

ABSTRACT

The effects of the flooding and initial Eh of sediments on the sorption of uranium onto the sediments were analysed by flooding and static experiments. The changes in uranium species with Eh and kinetic and thermodynamic characteristics of the uranium sorption onto the sediments were investigated. The flooding experiment indicates that the initial Eh of the sediment gradually decreased with the increase in flooding time. Based on the redox potential in the flooding experiment, simulation results obtained using the geochemical simulation software PHREEQC show that the concentration of U (VI) decreased. In contrast, the concentrations of U (III), U (IV), and U (V) gradually increased. The pseudo-second-order kinetic model well fitted the experimental data, which shows that the sorption was mainly chemical sorption. The thermodynamic parameters suggest that the entropy and enthalpy under the used conditions were positive and that ΔG^θ was negative. A thermodynamic analysis shows that the sorption was endothermic and spontaneous. These results are useful for the understanding of the sorption mechanism and migration of uranium onto the sediment under different initial sediment redox potentials and provide a good theoretical foundation for radioactive pollution remediation.     

FORUM: A Context for Participation in Sustainable Development

sustainability, but the most meaningful definition is set within an evolutionary framework. Mechanistic and evolutionary frameworks for sustainable development are discussed. Evolution and adaptation are characteristics of complex adaptive systems, and a new understanding of sustainable development can be gleaned by using the complex adaptive systems framework. This approach to sustainable development issues implicitly requires proactive involvement by the public. This paper supports that bottom-up participation needs to be nurtured. Appropriate processes to enable participation need to be designed and implemented.     

黑曲霉对弱酸性艳兰RAWL的吸附动力学和热力学研究

借助吸附等温线比较了不同pH以及完整细胞与单细胞壁染料生物的吸附性能差异,化学修饰研究了菌体表面不同官能团对染料吸附的贡献,考察了不同温度下染料生物的吸附动力学,并进行了模型拟合.结果表明,黑曲霉的染料吸附较好地符合Freundlich方程( R2 ＞0.99),低pH值有利于染料吸附;染料吸附不仅发生在细胞壁,细胞内部也可发生;表面氨基作为主要的吸附官能团,其质子化导致的菌体正电荷和染料负离子间的静电引力作用是染料吸附的重要机理;吸附动力学可用拟二级速率方程描述( R2 =0.999 9);吸附活化能 Ea=5.21 kJ/mol,表明吸附具一定的活化性.     

CTMAB-膨润土从水中吸附氯苯类化合物的机理--吸附动力学与热力学

采用批量平衡实验,研究了CTMAB-膨润土从水中吸附4种氯苯类化合物（CBs）的吸附特性,并从动力学及热力学角度探讨了CBs的吸附作用机理．结果表明,吸附过程符合伪二级动力学方程,吸附活化能较小,反应速率较快,达到平衡的时间较短．CBs在CTMAB-膨润土上的吸附符合Linear方程,吸附过程主要由分配作用所致;CBs的辛醇-水分配系数越大,其在CTMAB-膨润土中的分配系数Kd也越大．另外,CTMAB-膨润土的有机碳含量越高,其对CBs的Kd也越大．CBs在CTMAB-膨润土上的吸附是一个放热过程,同时伴随着熵值的增加,在288—308K范围内,反应的吉布斯自由能变小,表明主要吸附作用力为疏水键力,吸附反应为自发过程．     

有机修饰塿土对苯酚的吸附及其热力学特征

研究了用十六烷基三甲基溴化铵（CTMAB）单一修饰和十六烷基三甲基溴化铵＋十二烷基磺酸钠（CTMAB＋SDS）混合修饰填土耕层、粘化层后土样对苯酚的吸附及其热力学特征,并对其吸附机理进行探讨．结果表明,填土两层次土样表面修饰后均能显著增强对苯酚的吸附能力,耕层土样对苯酚吸附呈现100GCB（100％CTMAB修饰耕层土样）〉120GCS（100％CTMAB＋20％SDS修饰耕层土样）〉50GCB（50％CTMAB修饰耕层土样）〉GCK（耕层原土）的趋势,粘化层土样相应地呈现100NCB（100％CTMAB修饰粘化层土样）〉50NCB（50％CTMAB修饰粘化层土样）〉120NCS（100％CTMAB＋20％SDS修饰粘化层土样）〉NCK（粘化层原土）的变化趋势;耕层原土吸附苯酚能力高于粘化层原土,但修饰后粘化层土样对苯酚的吸附能力超过耕层;两层次原土对苯酚的吸附呈现增温效应,但修饰后耕层土样转变为随温度上升吸附量下降的增温负效应特征,而粘化层修饰土样呈现增温效应特征,证实耕层修饰土样对苯酚以物理吸附为主,而粘化层修饰土样以化学吸附为主;Henry模型可用于描述苯酚在供试土样中的吸附;供试土样对苯酚的吸附属自发性反应,耕层修饰土样的吸附属焙减、熵减过程,自发性取决于焙减,而粘化层的吸附属焓增、熵增过程,自发性主要取决于熵增．     

天然菱铁矿去除水中磷的性能研究

采用批次试验研究菱铁矿对水溶液中磷的吸附特性,考察了初始磷浓度、p H值、菱铁矿投加量、粒径、共存离子对吸附的影响,并探讨了吸附动力学和吸附热力学特征.结果表明,当磷溶液初始浓度为20 mg·L-1,初始p H为6.0时,菱铁矿对磷的吸附效果较好,吸附平衡时间为48h.菱铁矿投加量为0.5~10 g时,随着投加量的增加,菱铁矿对磷的吸附效能逐渐提高.相对于NO-3、Cl-而言,SO2-4、HCO-3对菱铁矿去除磷有微弱的抑制作用.动力学研究发现,菱铁矿对磷的吸附过程更符合准二级动力学模型,吸附平衡可由Freundlich等温线方程描述,饱和吸附量为83.5μg·g-1.最后分别计算了288、303和318 K下的吸附热力学参数,发现吉布斯自由能(ΔG)均为负,焓变(ΔH)及熵变(ΔS)为正,表明该吸附过程为自发的吸热反应.     

氮氧化物减排博弈行为研究

针对我国氮氧化物减排的严峻形势,文章借鉴瑞典氮氧化物减排的税收返还制度,运用进化博弈的理论和方法,建立了政府与企业关于氮氧化物减排的进化博弈模型,并进行了求解分析。结果表明:策略(减排,税收返还制度)和策略(减排,标准减排制度)都可以是稳定均衡策略,即无论政府采取税收返还制度还是标准减排制度,只要对惩罚系数、税率等参数进行调整都能迫使企业进行氮氧化物减排。但通过模拟可知税收返还制度对企业的激励作用更大,可以促使企业长期持续的进行氮氧化物减排。     

Optimum Heat Conductance Distribution for Power Optimization of a Regenerated Closed Brayton Cycle

In this paper, the power output of the cycle is taken as objective for performance optimization of an irreversible regenerated closed Brayton cycle coupled to constant-temperature thermal energy reservoirs in the viewpoint of finite time thermodynamics (FTT) or entropy generation minimization (EGM). The analytical formulae about the relations between power output and pressure ratio are derived with the heat resistance losses in the hot- and cold-side heat exchangers and the regenerator, the irreversible compression and expansion losses in the compressor and turbine, and the pressure drop loss in the piping. The maximum power output optimization is performed by searching the optimum heat conductance distribution corresponding to the optimum power output among the hot- and cold-side heat exchangers and the regenerator for the fixed total heat exchanger inventory. The influence of some design parameters, including the temperature ratio of the heat reservoirs, the total heat exchanger inventory, the efficiencies of the compressor and the turbine, and the pressure recovery coefficient, on the optimum heat conductance distribution and the maximum power output are provided. The power plant design with optimization leads to smaller size including the compressor, turbine, and the hot- and cold-side heat exchangers and the regenerator.     

Postautotomy tail activity in the Balearic lizard, Podarcis lilfordi

Caudal autotomy is an effective antipredator strategy widespread among lizards. The shed tail thrashes vigorously for long periods to distract the predator and facilitate the lizard's escape. This movement is maintained by energy supplied by the anaerobic conversion of glycogen into lactate. It has been suggested that lactate accumulation serves as an index for the vigor of tail thrashing. We made three predictions: (1) tail loss frequency should be higher under heavier predation regime, (2) the duration of postautotomy tail movement should be extended in populations under heavy predation pressure as an adaptation to the higher risk and the increased need for defense, and (3) as result, lactate in these tail tissues should be concentrated at higher levels. To eliminate the impact of phylogeny and environmental factors on the interpretation of our result, we focused exclusively on one species, the Balearic lizard (Podarcis lilfordi). We studied three populations under different predation pressure but sharing the same climatic conditions. We found no differences among the studied populations either in postautotomy duration of tail movement or in levels of final lactate accumulation while autotomy frequency was higher where predation pressure was more intense. Tail loss effectiveness is directly influenced by the level of predation, while secondary features of the trait appear to remain independent from the impact of environment.     

表面活性剂对DDT在胶州湾沉积物上吸附行为的影响

采用批量定时取样法和批量平衡法,研究了低浓度阴离子表面活性剂十二烷基苯磺酸钠（SDBS）和阳离子表面活性剂十六烷基三甲基溴化铵（CTAB）存在下胶州湾沉积物对DDT的吸附特性及机制.结果表明,吸附过程符合伪二级动力学方程,吸附等温线可用Freundlich等温式较好地描述.在实验浓度范围内,SDBS和CTAB均利于DDT在沉积物上的吸附,且吸附速率和吸附能力均随SDBS和CTAB初始浓度的增加而增大,其中CTAB的影响更为显著.以p,p＇-DDT为例,当SDBS的浓度为10mg.L-1时,吸附速率常数k2由1.232×10-2 g.（μg.min）-1提高到4.193×10-2 g.（μg.min）-1,KF由2.866（μg.g-1）（L.μg-1）1/n增加到7.932（μg.g-1）（L.μg-1）1/n.另外本研究还分析了SDBS存在下温度对吸附过程的影响,结果表明,在283～308 K范围内,较低的温度有利于DDT的吸附,该吸附是一个自发的、放热的、熵增加的物理吸附过程,SDBS的存在使DDT在吸附过程中的ΔG0、ΔH0值更负,ΔS0值更小.该研究可为DDT在胶州湾中的迁移转化及其归宿提供一定的理论基础.