复合污染中Triton X-100在膨润土/水界面上的吸附行为

研究了水溶液中膨润土对非离子表面活性剂Triton X-100(X-100)的吸附,重点探讨了阳离子表面活性剂CPC、阴离子表面活性剂SDBS、中性无机盐NaCl及温度对膨润土吸附TX-100的影响.结果表明,Na基膨润土吸附TX-100的效果好于Ca基膨润土;低浓度CPC对膨润土吸附TX-100具有增强作用,当CPC初始浓度大于l0000 mg·L-1(平衡浓度Ce约为1CMC)时具有抑制作用,当CPC浓度低于3000 mg·L-1(Ce约为0.03CMC)时,TX-100吸附量与CPC浓度成线性正相关.SDBS能显著降低膨润土对TX-100的吸附,原因是溶液中SDBS与TX-100混合胶束的形成能阻止TX-100与膨润土硅氧表面间的氢键作用及在其表面形成胶束.NaCl的存在可以大大提高膨润土对TX-100的吸附,去除率由56%提高到99%以上.膨润土对TX-100的吸附随温度升高吸附量增大,其吸附热为12.68 kJ·mol-1,标准自由能的减小和熵值的增大是TX-100在膨润土上吸附的推动力.实验结果对用膨润土处理含表面活性剂废水具有一定的理论价值.     

苹果角质层的组分特征及其对甲萘酚的吸附作用

为能够准确预测有机污染物在植物角质层上的吸附行为,用化学方法(脱蜡、皂化、酸解)分离得到7种苹果角质层组分,探讨了角质组分对甲萘酚的吸附特征及其与结构组成之间的关系.结果表明.苹果角质层由44.7%蜡质、34.6%角质单体、13.6%糖类、7.5%生物高聚物(cutan)组成,脱蜡、皂化脱角质单体后角质组分的极性指数((O N)/C)增大,而酸解脱糖后(O N)/C则减小.角质层组分对甲萘酚的等温吸附曲线均呈非线性(N=0.551～0.918),而高浓度时的等温吸附曲线则呈线性,表明植物角质与有机物的相互作用除了分配作用之外,还存在其它的特殊作用.苹果角质层(ACI)对甲萘酚的吸附系数(Knc)为442,脱蜡、脱糖后角质组分的KDC.值增大,而脱角质单体后Kuc值则大大减小,表明角质单体是主要的吸附介质;蜡质、角质单体、糖类组分对角质层吸附行为的影响存在交互作用.角质组分的Koc值随其(O N)/C变化出现"峰值",意味着甲萘酚与角质组分之间的相互作用存在最佳的极性匹配.     

新型树脂对氯酚类物质的吸附研究

合成了乙酰氯修饰树脂NDA-O,与Purolite公司的MN-200相比,合成的树脂比表面积较小,但酸性官能团较多.用两种树脂吸附2-氯酚、4-氯酚和2,4-二氯酚发现,吸附结果可以用Langmuir和Freundlich等温吸附方程很好地模拟,合成的NDA-O对3种氯酚类物质的吸附能力优于MN-200.两种树脂对氯酚类物质的吸附量随着温度的升高而减少,表明吸附是放热过程,同时对氯酚类物质的吸附焓变随着吸附量的增大而减小.对同一种树脂来说,吸附量随着氯代程度的增加而增加,取代氯数相同的时候,吸附量与吸附质的K..成正相关.进一步研究了pH对吸附的影响,在pH大于9时,3种氯酚类物质的吸附量均急剧减少.     

红壤和黄泥土对不同浓度六氯苯的吸附与解吸特征

采用批量平衡试验的方法,研究了不同初始浓度的六氯苯在红壤和黄泥土表面的吸附与解吸特征. 结果表明,六氯苯在红壤和黄泥土表面的吸附与解吸行为均可用Freundlich方程进行很好的拟合,其相关系数(R2)在0.97-0.99之间,并表现为非线性特征. 六氯苯在红壤和黄泥土上吸附的KadsF值均小于其解吸的KdesF值,说明六氯苯在这两种土壤表面的解吸表现为一定的滞后效应. 随着初始浓度的升高,其滞后效应增强,两者呈线性相关. 用不同方程对滞后系数H,ω和λ进行量化,发现不同浓度的六氯苯在土壤表面的解吸过程表现出正滞后效应.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

Thermodynamics and kinetics of cadmium adsorption onto oxidized granular activated carbon

Cadmium sorption behavior of granular activated carbon oxidized with nitric acid was systematically studied by sets of the equilibrium and time-based experiments under various conditions.The cadmium adsorption capacity of oxidized granular activated carbon enlarged with an increase in pH,and reduced with an increase in ionic strength.Experimental data were evaluated to find out kinetic characteristics.Adsorption processes were found to follow pseudo-second order rate equation.Adsorption isotherms correlate well with the Langmuir isotherm model and the maximum sorption capacity of cadmium evaluated is 51.02μmol/g.Thermodynamic parameters were calculated based on Van't Hoff equation.Equilibrium constant Kd was evaluated from Freundlich isotherm model constants,Langmnir isotherm model constants,and isotherms,respectively.The average change of standard adsorption heatΔH~0 was -25.29 kJ/mol.NegativeΔH~0 andΔG~0 values indicate the adsorption process for cadmium onto the studied activated carbon is exothermic and spontaneous.The standard entropyΔS~0 was also negative,which suggests a decrease in the freedom of the system.     

Influence of fertilizing on the Cs soil–plant transfer in a spruce forest of Southern Germany

Fertilization with 2.5 t/ha limestone: (83% CaCO₃, 8% MgO, 6% K₂O, 3% P₂O₅) reduces the ¹³⁷Cs transfer from spruce forest soil into plants like fern (Dryopteris carthusiana) and blackberry (Rubus fruticosus) by a factor of 2–5 during at least 11 years as measured by the aggregated transfer factor T_ag. In 1997 and 2006 these results were confirmed by additional measurements of the ¹³⁷Cs transfer factor TF, related to the root zone (O_h horizon), which were explained by the selective sorption of ¹³⁷Cs in the root zone by measurements of the Radiocaesium Interception Potential (RIP) in fertilized (RIP > 179 meq/kg) and non-fertilized soils (RIP < 74 meq/kg).     

Biosorption of nickel(II) from aqueous solution by Aspergillus niger: Response surface methodology and isotherm study

In the present study, the effects of biosorbent Aspergillus niger dosage, initial solution pH and initial Ni(II) concentration on the uptake of Ni(II) by NaOH pretreated biomass of A. niger from aqueous solution were investigated. Batch experiments were carried out in order to model and optimize the biosorption process. The influence of three parameters on the uptake of Ni(II) was described using a response surface methodology (RSM) as well as Langmuir and Freundlich isotherm models. Optimum Ni(II) uptake of 4.82 mg Ni(II) g⁻¹ biomass (70.30%) was achieved at pH 6.25, biomass dosage of 2.98 g L⁻¹ and initial Ni(II) concentration of 30.00 mg L⁻¹ Ni(II). Langmuir and Freundlich were able to describe the biosorption isotherm fairly well. However, prediction of Ni(II) biosorption using Langmuir and Freundlich isotherms was relatively poor in comparison with RSM approaches. The biosorption mechanism was also investigated by using Fourier transfer infrared (FT-IR) analysis of untreated, NaOH pretreated, and Ni(II) loaded A. niger biomass.     

Part V—sorption of pharmaceuticals and personal care products

Background, aim, and scope  Pharmaceuticals and personal care products (PPCPs) including antibiotics, endocrine-disrupting chemicals, and veterinary pharmaceuticals are emerging pollutants, and their environmental risk was not emphasized until a decade ago. These compounds have been reported to cause adverse impacts on wildlife and human. However, compared to the studies on hydrophobic organic contaminants (HOCs) whose sorption characteristics is reviewed in Part IV of this review series, information on PPCPs is very limited. Thus, a summary of recent research progress on PPCP sorption in soils or sediments is necessary to clarify research requirements and directions. Main features  We reviewed the research progress on PPCP sorption in soils or sediments highlighting PPCP sorption different from that of HOCs. Special function of humic substances (HSs) on PPCP behavior is summarized according to several features of PPCP–soil or sediment interaction. In addition, we discussed the behavior of xenobiotic chemicals in a three-phase system (dissolved organic matter (DOM)–mineral–water). The complexity of three-phase systems was also discussed. Results  Nonideal sorption of PPCPs in soils or sediments is generally reported, and PPCP sorption behavior is relatively a more complicated process compared to HOC sorption, such as the contribution of inorganic fractions, fast degradation and metabolite sorption, and species-specific sorption mechanism. Thus, mechanistic studies are urgently needed for a better understanding of their environmental risk and for pollution control. Discussion  Recent research progress on nonideal sorption has not been incorporated into fate modeling of xenobiotic chemicals. A major reason is the complexity of the three-phase system. First of all, lack of knowledge in describing DOM fractionation after adsorption by mineral particles is one of the major restrictions for an accurate prediction of xenobiotic chemical behavior in the presence of DOM. Secondly, no explicit mathematical relationship between HS chemical–physical properties, and their sorption characteristics has been proposed. Last but not least, nonlinear interactions could exponentially increase the complexity and uncertainties of environmental fate models for xenobiotics. Discussion on proper simplification of fate modeling in the framework of nonlinear interactions is still unavailable. Conclusions  Although the methodologies and concepts for studying HOC environmental fate could be adopted for PPCP study, their differences should be highly understood. Prediction of PPCP environmental behavior needs to combine contributions from various fractions of soils or sediments and the sorption of their metabolites and different species. Recommendations and perspectives  More detailed studies on PPCP sorption in separated soil or sediment fractions are needed in order to propose a model predicting PPCP sorption in soils or sediments based on soil or sediment properties. The information on sorption of PPCP metabolites and species and the competition between them is still not enough to be incorporated into any predictive models.     

Transport of simazine in unsaturated sandy soil and predictions of its leaching under hypothetical field conditions

The potential contamination of groundwater by herbicides is often controlled by processes in the vadose zone, through which herbicides travel before entering groundwater. In the vadose zone, both physical and chemical processes affect the fate and transport of herbicides, therefore it is important to represent these processes by mathematical models to predict contaminant movement. To simulate the movement of simazine, a herbicide commonly used in Chilean vineyards, batch and miscible displacement column experiments were performed on a disturbed sandy soil to quantify the primary parameters and processes of simazine transport. Chloride (Cl(-)) was used as a non-reactive tracer, and simazine as the reactive tracer. The Hydrus-1D model was used to estimate the parameters by inversion from the breakthrough curves of the columns and to evaluate the potential groundwater contamination in a sandy soil from the Casablanca Valley, Chile. The two-site, chemical non-equilibrium model was observed to best represent the experimental results of the miscible displacement experiments in laboratory soil columns. Predictions of transport under hypothetical field conditions using the same soil from the column experiments were made for 40 years by applying herbicide during the first 20 years, and then halting the application and considering different rates of groundwater recharge. For recharge rates smaller than 84 mm year(-1), the predicted concentration of simazine at a depth of 1 m is below the U.S. EPA's maximum contaminant levels (4 microg L(-1)). After eight years of application at a groundwater recharge rate of 180 mm year(-1) (approximately 50% of the annual rainfall), simazine was found to reach the groundwater (located at 1 m depth) at a higher concentration (more than 40 microg L(-1)) than the existing guidelines in the USA and Europe.