Sorption mechanism of naphthalene by diesel soot: Insight from displacement with phenanthrene/p-nitrophenol

The nonlinear sorption of hydrophobic organic contaminants (HOCs) could be changed to linear sorption by the suppression of coexisting solutes in natural system, resulting in the enhancement of mobility, bioavailability and risks of HOCs in the environment. In previous study, inspired from the competitive adsorption on activated carbon (AC), the displaceable fraction of HOCs sorption to soot by competitor was attributed to the adsorption on elemental carbon fraction of soot (EC-Soot), while the linear and nondisplaceable fraction was attributed to the partition in authigenic organic matter of soot (OM-Soot). In this study, however, we observed that the linear and nondisplaceable fraction of HOC (naphthalene) to a diesel soot (D-Soot) by competitor (phenanthrene or p-nitrophenol) should be attributed to not only the linear partition in OM-Soot, but also the residual linear adsorption on EC-Soot. We also observed that the competition on the surface of soot dominated by external surface was different from that of AC dominated by micropore surface, i.e., complete displacement of HOCs by p-nitrophenol could occur for the micropore surface of AC, but not for the external surface of soot. These observations were obtained through the separation of EC-Soot and OM-Soot from D-Soot with organic-solvent extraction and the sorption comparisons of D-Soot with an AC (ACF300) and a multiwalled carbon nanotube (MWCNT30). The obtained results would give new insights to the sorption mechanisms of HOCs by soot and help to assess their environmental risks.     

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.     

Potential nitrogen enrichment of soil and surface water by atmospheric ammonia sorption in intensive livestock production areas

Elevated atmospheric NH₃ levels near intensive livestock operations can add significant N to local agroecosystems. In this study, the potential atmospheric NH₃ sorbed by soil and water was assessed over a 2-year period starting October 2000 in an intensive livestock production area in southern Alberta, Canada. Fifty-two uneven grid sampling sites were selected in the 53,905 ha study area. The sorption rate of atmospheric NH₃ was estimated weekly by exposing distilled water and air-dried soil samples to the atmosphere at the sampling sites. The increases in NH₄–N content in the samples after 1-week exposure was regarded as an index of the atmospheric NH₃ sorbed for that week. The NH₃ sorption rates were highly variable across the 52 sites, with water ranging from 4 to 125 kg ha⁻¹ year⁻¹ with a mean of 22 kg N ha⁻¹ year⁻¹ and soil from 5 to 84 kg N ha⁻¹ year⁻¹ with a mean of 20 kg N ha⁻¹ year⁻¹. Considerable variation in NH₃–N sorption across the study area reflects the effects of size, direction (upwind or downwind) and proximity of nearby livestock operations or other NH₃ sources and operators’ activities around the sampling sites. The NH₃ sorption rate at each site also varied considerably in response to weather conditions. The high rate of NH₃ input poses a direct risk of surface water eutrophication in intensive livestock operation areas. If fertilizer recommendations are not reduced to account for NH₃ sorption by soil, excess N may also contribute to eutrophication through runoff and leaching.     

应用量子化学参数预测多氯有机物的分配性质

应用量子化学AM1算法求得多氯有机物的量化参数，以此来构建定量结构－性质相关（QSPR）模型。该模型能较好地预测多氯有机物的正辛醇／水分配系数（Kow)和沉积物吸附系数（Koc).Kow和Koc平均误差分别为0．31和0．33个对数单位。模型的稳健性检验结果表明：模型中自变量不存在相关关系；残差呈正态分布；对Koc来说，PCB和PCDD／F在构建模型中起核心作用，剔除该类化合物导致模型相关系数明显下降，农药类及氯硝基苯类化合物的存在降低了模型的精度。     

Behavior of the herbicide dimepiperate with homoionic clays in aqueous solution

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Characteristics of the natural organic matter sorption affects of organic contaminants

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阳离子改型蛭石的铵离子交换平衡特性

对经Na^＋，Ca^2＋、Mg^2＋等不同离子处理的改型蛭石在不同pH和温度条件下进行了铵离子交换性能的研究。结果表明，交换反应均在前60min速率最快，约120min就趋向于平衡：铵离子交换总量均随pH变化而波动，在pH=7点上取最大值，且全交换容量按镁型蛭石、钙型蛭石，钠型蛭石顺序依次增大，每100g蛭石分别为59.32，71.89、92.85mmol；改型蛭石对NH^＋4等温交换吸附与Langmuir方程相符。表明改型蛭石对NH^＋4的吸附主要是单分子层的化学吸附。     

模拟酸化下水稻土微团聚体Cu2+吸附与解吸的影响

采用低能量超声波分散和冷冻机干燥法提取太湖地区水稻土(黄泥土)微团聚体颗粒,用平衡液吸附法和CaCl2与HCl溶液的连续解吸法研究了它们在pH2～6范围内pH对Cu2 的静电吸附和专性吸附的影响。结果表明,不同粒径的微团聚体颗粒对Cu2 的吸附等温线可都用Freundlich模型来描述。Cu2 吸附量大小以下序递减,粘粒级、砂粒级、粉砂级、粗粉砂级;吸附量受其中游离氧化铁、氧化铝和有机质含量的控制。吸附量随pH升高而增加。低pH条件下利于静电吸附,吸附过程H 减少使平衡液pH上升;高pH条件下主要是专性吸附所控制,释放H 使平衡液pH下降。     

Effects of lipids on the sorption of hydrophobic organic compounds on geosorbents: a case study using phenanthrene

The impact of the lipid fraction of natural geosorbents on the sorption of a polycyclic aromatic hydrocarbon was assessed using several experiments. In the first set of experiments phenanthrene was sorbed on a coastal sediment as well as on its humin and humic acid fractions before and after lipid extraction. Before lipid extraction, sorption shows dominantly partitioning characteristics. However, the extraction of lipids from sediment and humin drastically increases, by up to one order of magnitude, their sorption affinity for phenanthrene at low sorbate concentrations, resulting in increased isotherm nonlinearity. This effect is less pronounced for humic acids. One mechanism proposed for the increasing sorption is that lipids, despite their very low relative abundance in the sediments, can compete with phenanthrene for specific high affinity sorption sites (e.g., matrix pores and adsorption sites). This competition is not surprising considering the similar hydrophobic nature of lipids and phenanthrene. Lipids, or any non-polar molecules, could also act like plasticizers by swelling rigid domains and disrupting high affinity sites. In both cases, the removal of lipids (and extraction solvents) makes those sites available for phenanthrene. These provide alternative explanations to the previously proposed “solvent conditioning effect” believed to occur when geosorbents are treated with non-polar solvents modifying the matrix structure, an effect yet to be proven at molecular scale. To further investigate the impact of lipids on sorption, other independent experiments were performed. In a second experiment, re-addition of lipids to the extracted sediment restored the sorption isotherm linearity observed in the native material supporting the absence of irreversible extraction artifacts. However, high addition of lipids (i.e., after saturation of high affinity sites) seems to also enlarge the low affinity partitioning domain. These results are consistent with dual-mode, hole-filling, sorption models involving diffusion. In the final set of experiments, solid-state ¹⁹F-NMR using F-labeled lipids sorbed onto the sediments confirmed that lipids may be in different domains (mobile or rigid) that interact or not with phenanthrene. The possible effects of lipid removal on sorption have been overlooked and should be considered when geosorbents are pretreated.     

模拟环境老化对PE微塑料吸附Zn(II)的影响

探讨了酸处理（1mol/L HCl）、碱处理（1mol/L NaOH）、氧化处理（30% H₂O₂）和高温-冻融处理（70℃和-22℃交替）4种老化方式对聚乙烯（PE）微塑料表面性质和Zn（II）吸附行为的影响.结果表明,4种老化方式均使PE微塑料表面出现大量的粗糙褶皱结构,但未改变表面化学结构.4种老化方式均导致PE微塑料Zn（II）吸附量的增加,其顺序为：碱处理 > 酸处理 > 氧化处理 > 高温-冻融处理 > 原样.PE微塑料吸附Zn（II）的动力学过程符合Lagrange准二级吸附动力学和W-M颗粒扩散模型,说明吸附过程是多个吸附阶段共同作用的结果,吸附等温线符合Langmuir和D-R模型,证实PE微塑料对Zn（II）的吸附属于物理吸附,老化使PE微塑料表面出现的大量褶皱是其Zn（II）吸附量增加的主要原因.