Resistant sorption of in situ chlorobenzenes and a polychlorinated biphenyl in river Rhine suspended matter

The desorption kinetics of in situ chlorobenzenes (dichlorobenzenes, pentachlorobenzene and hexachlorobenzene) and 2,4,4^′-trichlorobiphenyl (PCB-28) were measured with a gas-purge technique for river Rhine suspended matter sampled in Lobith, The Netherlands. This suspended matter is the main source of sediment accumulation in lake Ketelmeer. In lake Ketelmeer sediment earlier observations showed that slow and very slow fractions dominate the desorption profile.

For the river Rhine suspended matter, only for PCB-28 a fast desorbing fraction of around 1.6% could be detected. The observed rate constants were on the average 0.2 h⁻¹ for fast desorption, 0.004 h⁻¹ for slow desorption, and 0.00022 h⁻¹ for very slow desorption. These values are in agreement with previous findings for the sediment from lake Ketelmeer and with available literature data on fast, slow, and very slow desorption kinetics.

The results from this study show the similarity of desorption profiles between river Rhine suspended matter, and the top layer sediment from lake Ketelmeer. This indicates that slow and very slow fractions are already present in material forming the top layer of lake Ketelmeer, and were not formed after deposition of this material in the lake. The absence of detectable fast fractions for most compounds could be caused by the absence of recent pollution of the suspended matter. But, the observations may also be explained by a rapid disappearance of compounds from the fast fraction due to a combination of a high affinity of very slow sites for these compounds, and their relatively high volatility.     

水溶性巯基壳聚糖对污染土壤吸附态汞的解吸作用研究

用两种巯基化试剂半胱氨酸(Cys)和硫代乙醇酸(Thi)与壳聚糖(CTS)反应,制备了两种水溶性巯基壳聚糖,即Cys-CTS和Thi-CTS,对比研究了这两种巯基壳聚糖与CTS对被染毒土壤中吸附态汞的提取能力.结果表明,Thi-CTS在pH=3、质量浓度为0.5g/L、用量为20 mL的条件下.对汞的提取率为59.44%,相同条件下CTS和cys-CTS对汞的最高提取率只有31.81%和10.15%.     

Surface complexation modeling of Yb(III) sorption and desorption on hematite and alumina

Sorption and desorption of Yb(III) were studied on hematite and on alumina using a surface complexation model. The experimental methodology was conceived to allow an analysis of the data using a constant capacitance model. The FITEQL code was used for the calculations.The experimental results tend to show reversibility of sorption when the surface loading is small, and irreversibility when the surface loading is high. Surface complexation modeling gives a good interpretation of these two phenomena, taking into account hydroxylation of the surface complexes. In these two cases, it is possible to describe sorption and desorption curves with the same surface stoichiometries and the same surface complexation constants. The existence of these surface complexes depends on the pH of the solution, surface loading, and reaction direction.     

Modelling of diffusion-limited retardation of contaminants in hydraulically and lithologically nonuniform media

A new reactive transport modelling approach and examples of its application are presented, dealing with the impact of sorption/desorption kinetics on the spreading of solutes, e.g. organic contaminants, in groundwater. Slow sorption/desorption is known from the literature to be strongly responsible for the retardation of organic contaminants. The modelling concept applied in this paper quantifies sorption/desorption kinetics by an intra-particle diffusion approach. According to this idea, solute uptake by or release from the aquifer material is modelled at small scale by a "slow" diffusion process where the diffusion coefficient is reduced as compared to the aqueous diffusion coefficient due to (i) the size and shape of intra-particle pores and (ii) retarded transport of solutes within intra-particle pores governed by a nonlinear sorption isotherm. This process-based concept has the advantage of requiring only measurable model parameters, thus avoiding fitting parameters like first-order rate coefficients.In addition, the approach presented here allows for modelling of slow sorption/desorption in lithologically nonuniform media. Therefore, it accounts for well-known experimental findings indicating that sorptive properties depend on (i) the grain size distribution of the aquifer material and (ii) the lithological composition (e.g. percentage of quartz, sandstone, limestone, etc.) of each grain size fraction. The small-scale physico-chemical model describing sorption/desorption is coupled to a large-scale model of groundwater flow and solute transport. Consequently, hydraulic heterogeneities may also be considered by the overall model. This coupling is regarded as an essential prerequisite for simulating field-scale scenarios which will be addressed by a forthcoming publication.This paper focuses on mathematical model formulation, implementation of the numerical code and lab-scale model applications highlighting the sorption and desorption behavior of an organic contaminant (Phenanthrene) with regard to three lithocomponents exhibiting different sorptive properties. In particular, it is shown that breakthrough curves (BTCs) for lithologically nonuniform media cannot be obtained via simple arithmetic averaging of breakthrough curves for lithologically uniform media. In addition, as no analytical solutions are available for model validation purposes, simulation results are compared to measurements from lab-scale column experiments. The model results indicate that the new code can be regarded as a valuable tool for predicting long-term contaminant uptake or release, which may last for several hundreds of years for some lithocomponents. In particular, breakthrough curves simulated by pure forward modelling reproduce experimental data much better than a calibrated standard first-order kinetics reactive transport model, thus indicating that the new approach is of high quality and may be advantageously used for supporting the design of remediation strategies at contaminated sites where some lithocomponents and/or grain size classes may provide a long-term pollutant source.     

Behaviors and kinetics of toluene adsorption‐desorption on activated carbons with varying pore structure

This work was undertaken to investigate the behaviors and kinetics of toluene adsorption and desorption on activated carbons with varying pore structure. Five kinds of activated carbon from different raw materials were selected. Adsorption isotherms and breakthrough curves for toluene were measured. Langmuir and Freundlich equations were fitted to the equilibrium data, and the Freundlich equation was more suitable for simulating toluene adsorption. The process consisted of monolayer, multilayer and partial active site adsorption types. The effect of the pore structure of the activated carbons on toluene adsorption capacity was investigated. The quasi-first-order model was more suitable for describing the process than the quasi-second-order model. The adsorption data was also modeled by the internal particle diffusion model and it was found that the adsorption process could be divided into three stages. In the external surface adsorption process, the rate depended on the specific surface area. During the particle diffusion stage, pore structure and volume were the main factors affecting adsorption rate. In the final equilibrium stage, the rate was determined by the ratio of meso-and macro-pores to total pore volume. The rate over the whole adsorption process was dominated by the toluene concentration. The desorption behavior of toluene on activated carbons was investigated,and the process was divided into heat and mass transfer parts corresponding to emission and diffusion mechanisms, respectively. Physical adsorption played the main role during the adsorption process.     

废FCC催化剂对水中铅离子的连续吸附及脱附

通过测定吸附等温线，考察了Ｐｂ２＋在废ＦＣＣ（流化催化裂化）催化剂上的吸附性能及规律，结果表明，Ｐｂ２＋在废ＦＣＣ催化剂上的吸附规律可用Ｌａｎｇｍｕｉｒ和Ｆｒｕｎｄｌｉｃｈ模式描述，吸附呈单分子层形式且容易进行。又通过填充床吸附试验，对Ｐｂ２＋的连续吸附及脱附情形作了考察。结果表明，在温度为１５℃、ｐＨ为５．１３、过柱速率为３．０ｍＬ／ｍｉｎ、径高比为２．２５．０条件下，吸附柱具备适宜的生产周期，连续吸附操作可行，柱效率可达７５．９％；在温度为１５℃、采用２ｍｏｌ／Ｌ稀盐酸作脱附剂，过柱速率为５．０ｍＬ／ｍｉｎ的条件下，吸附剂易于脱附再生，脱附效率可达７８．１％     

不同给水管材对管壁附着生物膜铅、镉的解吸动力学研究

给水管壁生物膜会吸附水中的重金属元素积累在管壁生物膜中,在受到扰动时释放回到水体,危害饮用水水质安全。试验以上海管网末梢水为实验对象,研究了PVC、铸铁和紫铜等三种管材上生物膜对铅、镉的解吸特性。结果表明,PVC、铸铁和紫铜附着生物膜对铅的解吸容量qe分别为:5.92211μmol·m^-2、128.3051μmol·m^-2和21.1808,解吸速率常数k分别为:0.001060 m^2·μmol^-1·min^-1、0.000041 m^2·μmol^-1·min^-1和0.000503 m^2·μmol^-1·min^-1,对于镉元素三种材质的解吸容量qe分别为:14.71519μmol·m^-2、18.50481μmol·m^-2和2.25225μmol·m^-2;解吸速率常数k分别为:0.000102 m^2·μmol^-1·min^-1、0.001070 m^2·μmol^-1·min^-1和0.000103 m^2·μmol^-1·min^-1。     

Mapping of tritium emissions using absorption vapour samplers

Püspökszilágy Radioactive Waste Treatment and Disposal Facility (RWTDF) is a typical near-surface engineered repository designated to store low- and intermediate-level wastes from various institutes, research facilities and hospitals in Hungary. Two automatic combined ¹⁴C–tritium sampling units installed at the facility sample the air 2 m above surface. The one installed near the vaults detects tritium (T) activities two orders of magnitude higher than the far reference sampling unit. To localize the T emissions, 19 small absorption vapour samplers filled with silica gel were settled onto the ground surface. After the saturation of the silica gel, the water was recovered and its T concentration was measured with a low-background liquid scintillation counter. The absorption vapour samplers are cheap, simple and easy-to-use. We present the samplers and the T distribution map constructed from the data, which helps to localize the T emission.     

Sorption of alpha and beta hydrophobic endosulfan in a Vertisol from southeast region of Turkey

Endosulfan has been applied to control numerous insects in a variety of food and non-food crops. Limited information is available on dynamics of this pesticide in the soil. The objective of this research was to determine the adsorption–desorption behavior of the alpha (α) and beta (β) endosulfan in a Vertisol from the southeast region of Turkey, where cotton is the main crop in the large irrigated lowlands. The α and β endosulfan were adsorbed considerably and Freundlich adsorption–desorption isotherms fitted the α and β endosulfan data (R² > 0.98). Freundlich adsorption coefficients (K_f) for the α endosulfan ranged between 21.63 and 16.33 while for the β endosulfan they were between 14.01 and 17.98 for the Ap and Bw2 horizons. The difference of K_f values of α and β endosulfan for two horizons were explained with the slight difference in the amount of organic matter and clay, but considerable difference in Fe contents of the two horizons. Alpha and β endosulfan K_fd values were 118.03 and 45.81 for the Ap and 48.08 and 68.71 for the Bw2 horizons. Higher adsorption and desorption behavior of the endosulfan isomers for the same horizon was attributed to poor physical bonding between the endosulfan molecule and the surfaces of fundamental soil particles. This fact is thought to increase the effective use of endosulfan in agriculture with a possibility of its movement to the surface and groundwater in the Vertisol studied.     

Competition between phenanthrene, chrysene, and 2,5-dichlorobiphenyl for high-energy adsorption sites in a sediment

We determined the maximum amounts of added phenanthrene, chrysene, and 2,5-dichlorobiphenyl sorbed onto high-energy adsorption sites in a sediment on bi-solute experiments. The bi-solute pairs were phenanthrene/chrysene and phenanthrene/2,5-dichlorobiphenyl. On the bi-solute sorption experiments, one solute was introduced and equilibrated with sediment prior to addition of the second solute. The values for the maximum amounts adsorbed onto high-energy sites revealed that, after equilibration of the first solute, still some high-energy sites could be occupied by the second solute. Phenanthrene, chrysene, and 2,5-dichlorobiphenyl seem to share about 30% of the accessible high-energy adsorption sites in the sediment employed.