Sorption-desorption behavior of polybrominated diphenyl ethers in soils

Polybrominated diphenyl ethers (PBDEs) are flame retardants that are commonly found in commercial and household products. These compounds are considered persistent organic pollutants. In this study, we used 4,4′-dibromodiphenyl ether (BDE-15) as a model compound to elucidate the sorption and desorption behavior of PBDEs in soils. The organic carbon-normalized sorption coefficient (K_OC) of BDE-15 was more than three times higher for humin than for bulk soils. However, pronounced desorption hysteresis was obtained mainly for bulk soils. For humin, increasing concentration of sorbed BDE-15 resulted in decreased desorption. Our data illustrate that BDE-15 and probably other PBDEs exhibit high sorption affinity to soils. Moreover, sorption is irreversible and thus PBDEs can potentially accumulate in the topsoil layer. We also suggest that although humin is probably a major sorbent for PBDEs in soils, other humic materials are also responsible for their sequestration.     

活性炭吸附硫化氢及微波辐照解吸研究

研究了两种活性炭对硫化氢的平衡吸附性能力,并对活性炭床层的穿透性进行了考察;吸附饱和和活性炭在微波辐射的作用下进行解吸。实验表明,解吸效率与微波作用时间及温度有关,在本实验条件下H2S解吸效率达90．1％。     

Desorption characteristics of kaolin clay contaminated with zinc from electrokinetic soil processing

A number of bench scale laboratory column tests were carried out using a newly designed and developed electrokinetic cell to investigate the fundamental behavior of zinc-spiked kaolin clay subjected to an electric field. Laboratory investigations focused on (i) zinc migration by the combined effects of electromigration and electro-osmosis and (ii) the electrically induced desorption characteristics of zinc-contaminated kaolin that occurred during processing. The correlations of the applied voltage gradient, electro-osmotic flow rate, and the development of a pH gradient were examined and evaluated. The results showed that the removal efficiency was high during the early stage of processing due to rapid desorption by electrokinetic effects in the cathode region. However, the majority of zinc migrating from the anode was precipitated due to the high pH environment in the cathode region.     

Resuspension of contaminated field and formulated reference sediments Part I: Evaluation of metal release under controlled laboratory conditions

In aquatic systems where metal contaminated sediments are present, the potential exists for metals to be released to the water column when sediment resuspension occurs. The release and partitioning behavior of sediment-bound heavy metals is not well understood during resuspension events. In this study, the release of Cd, Cu, Hg, Ni, Pb and Zn from sediments during resuspension was evaluated using reference sediments with known physical and chemical properties. Sediment treatments with varying quantities of acid volatile sulfide (AVS), total organic carbon (TOC), and different grain size distributions were resuspended under controlled conditions to evaluate their respective effects on dissolved metal concentrations. AVS had the greatest effect on limiting release of dissolved metals, followed by grain size and TOC. Predictions of dissolved concentrations of Cd, Ni, Pb and Zn were developed based on the formulated sediment Σ_metal/AVS ratios with Σ_metal being the total sediment metal concentration. Predicted values were compared to measured dissolved metal concentrations in contaminated field sediments resuspended under identical operating conditions. Metal concentrations released from the field sediments were low overall, in most cases lower than predicted values, reflecting the importance of other binding phases. Overall, results indicate that for sulfidic sediments, low levels of the study metals are released to the dissolved phase during short-term resuspension.     

被动采样/热脱附/GC-MS法测定环境空气中挥发性有机物暴露量

建立了吸附管被动采样-热脱附解吸气相色谱质谱联用测定环境空气中挥发性有机物暴露量的采样、分析方法。14种挥发性有机物的检出限为0.002~0.005 ng/h。该法采样无需动力,具有简单、方便、灵敏度高等特点,可广泛应用于环境气体的监测。     

Sorption, desorption, and degradation of (4-chloro-2-methylphenoxy)acetic acid in representative soils of the Danubian Lowland, Slovakia

Herbicide leaching through soil into groundwater greatly depends upon sorption-desorption and degradation phenomena. Batch adsorption, desorption and degradation experiments were performed with acidic herbicide MCPA and three soil types collected from their respective soil horizons. MCPA was found to be weakly sorbed by the soils with Freundlich coefficient values ranging from 0.37 to 1.03 mg^1−1/n kg⁻¹ L^1/n. It was shown that MCPA sorption positively correlated with soil organic carbon content, humic and fulvic acid carbon contents, and negatively with soil pH. The importance of soil organic matter in MCPA sorption by soils was also confirmed by performing sorption experiments after soil organic matter removal. MCPA sorption in these treated soils decreased by 37-100% compared to the original soils. A relatively large part of the sorbed MCPA was released from soils into aqueous solution after four successive desorption steps, although some hysteresis occurred during desorption of MCPA from all soils. Both sorption and desorption were depth-dependent, the A soil horizons exhibited higher retention capacity of the herbicide than B or C soil horizons. Generally, MCPA sorption decreased in the presence of phosphate and low molecular weight organic acids. Degradation of MCPA was faster in the A soil horizons than the corresponding B or C soil horizons with half-life values ranging from 4.9 to 9.6 d in topsoils and from 11.6 to 23.4 d in subsoils.     

Contributions of adsorption,bioreduction and desorption to uranium immobilization by extracellular polymeric substances

● EPS immobilizes U(VI) via adsorption, bioreduction and desorption. ● This work provides a framework to quantify the three immobilization processes. ● The non-equilibrium adsorption of U follows pseudo-second-order kinetics. ● The equilibrium adsorption of U followed Langmuir and Freundlich isotherms. Hexavalent uranium (U(VI)) can be immobilized by various microbes. The role of extracellular polymeric substances (EPS) in U(VI) immobilization has not been quantified. This work provides a model framework to quantify the contributions of three processes involved in EPS-mediated U(VI) immobilization: adsorption, bioreduction and desorption. Loosely associated EPS was extracted from a pure bacterial strain, Klebsiella sp. J1, and then exposed to H₂ and O₂ (no bioreduction control) to immobilize U(VI) in batch experiments. U(VI) immobilization was faster when exposed to H₂ than O₂ and stabilized at 94% for H₂ and 85% for O₂, respectively. The non-equilibrium data from the H₂ experiments were best simulated by a kinetic model consisting of pseudo-second-order adsorption (k_a = 2.87 × 10⁻³ g EPS·(mg U)⁻¹·min⁻¹), first-order bioreduction (k_b = 0.112 min⁻¹) and first-order desorption (k_d = 7.00 × 10⁻³ min⁻¹) and fitted the experimental data with R² of 0.999. While adsorption was dominant in the first minute of the experiments with H₂, bioreduction was dominant from the second minute to the 50^th min. After 50 min, adsorption was negligible, and bioreduction was balanced by desorption. This work also provides the first set of equilibrium data for U(VI) adsorption by EPS alone. The equilibrium experiments with O₂ were well simulated by both the Langmuir isotherm and the Freundlich isotherm, suggesting multiple mechanisms involved in the interactions between U(VI) and EPS. The thermodynamic study indicated that the adsorption of U(VI) onto EPS was endothermic, spontaneous and favorable at higher temperatures.     

On equilibration of pore water in column leaching tests

Column leaching tests are closer to natural conditions than batch shaking tests and in the last years have become more popular for assessing the release potential of pollutants from a variety of solids such as contaminated soils, waste, recycling and construction materials. Uncertainties still exist regarding equilibration of the percolating water with the solids, that might potentially lead to underestimation of contaminant concentrations in the effluent. The intention of this paper is to show that equilibration of pore water in a finite bath is fundamentally different from release of a certain fraction of the pollutant from a sample and that equilibrium is reached much faster at low liquid-to-solid ratios typical for column experiments (<0.25) than in batch tests with much higher liquid-to-solid ratios (e.g. 2–10). Two mass transfer mechanisms are elucidated: First-order type release (film diffusion) and intraparticle diffusion. For the latter, mass transfer slows down with time and sooner or later non-equilibrium conditions are observed at the column outlet after percolation has been started. Time scales of equilibrium leaching can be estimated based on a comparison of column length with the length of the mass transfer zone, which is equivalent to a Damköhler number approach. Mass transfer and diffusion coefficients used in this study apply to mass transfer mechanisms limited by diffusion in water, which is typical for release of organic compounds but also for dissolution of soluble minerals such as calcite, gypsum or similar. As a conclusion based on these theoretical considerations column tests (a) equilibrate much faster than batch leaching tests and (b) the equilibrium concentrations are maintained in the column effluent even for slow intraparticle diffusion limited desorption for extended periods of time (>days). Since for equilibration the specific surface area is crucial, the harmonic mean of the grain size is relevant (small grain sizes result in high concentrations even after short pre-equilibration of a column). The absolute time scales calculated with linear sorption and aqueous diffusion aim at organic compounds and are not valid for sparingly soluble mineral phases (e.g. metal oxides and silicates). However, the general findings on how different liquid-to-solid ratios and specific surface area influence equilibration time scales also apply to other mass transfer mechanisms.     

Impact of crystalline and amorphous iron- and aluminum hydroxides on mechanisms of phosphate adsorption and desorption

Fourier-transform infrared(FT-IR) spectroscopic experiments were carried out during phosphate adsorption on highly crystalline gibbsite, poorly crystalline 2-line-ferrihydrite and amorphous iron–aluminum–hydroxide mixtures in the molar ratio 1:0, 10:1, 5:1, 1:1, 1:5, 1:10 and 0:1. The OH stretching vibrational bands were utilized to analyze changes in structural and surface OH groups during adsorption, because the position of characteristic P\O vibrational bands can shift depending on reaction conditions, pH or adsorbed phosphate content.Adsorption and desorption kinetics were studied at pH6 and different initial phosphate concentrations to achieve varying phosphate coverage on the mineral surfaces. For gibbsite the formation of AlHPO_4 and Al_2HPO_4 can be assumed, while for ferrihydrite, a FeHPO_4 or Fe_2PO_4 complex and the precipitation of FePO_4 with longer equilibration time were proposed.Fe_2HPO_4 or a Fe_2PO_4 surface complex was deduced for Fe-hydroxides, an AlH_2PO_4 surface complex was identified for Al-hydroxide, and both displayed either hydrogen bonds to neighboring hydroxyl groups or hydrogen bonds to outer-sphere complexes. Fe:Al-hydroxide mixtures with high Al ratios showed a low phosphate desorption rate, while ferrihydrite and the Fe:Al-hydroxide mixtures with high Fe ratios had almost negligible desorption rates. It was concluded that within the weakly associated amorphous FeO(OH) materials, FePO_4 precipitated, which was bound by outer-sphere hydrogen bonds. With high Al ratios, desorption increased, which indicated weaker phosphate binding of both inner-sphere and outer-sphere complexes and hence, either no or minor quantities of precipitate. Ferrihydrite showed a more rigid structure and a lower extent of precipitation compared to amorphous Fe-hydroxide.     

Biosorption of heavy metals by activated sludge and their desorption characteristics

The biosorption of different metals (Cu2+, Cd2+, Zn2+, Ni2+ and Pb2+) was investigated using activated sludge. The optimum pH was 4 for Cd, Cu and Pb sorption and 5 for Ni and Zn. Biomass metal uptake clearly competed with protons present in the aqueous medium, making pH an important variable in the process. Protons consumed by biomass in control tests versus protons exchange in biosorption tests confirmed a maximum exchange between metal cations and protons at pH 2. The study of the influence of biomass concentration revealed that the amount of protons released from biomass increased with biomass concentration. This would confirm the hypothesis of ion exchange between both types of ions. The application of the Langmuir and Freundlich models showed a better fitting of experimental data to the first model. The maximum sorption uptake of the studied metals by the activated sludge showed the following decreasing order: Pb>Cu>CdZn>Ni. Desorption experiments showed that HCl was a good eluent for the five metals tested, particularly at low pH values (1 and 2). At pH 3 or 4 the desorption yield was significantly lower. However, its use did not allow the reuse of biomass in subsequent loading and unloading cycles. EDTA was also a good desorption agent, achieving the total recovery for the five metals tested at a concentration of 1mM, with the advantage that biomass could be reused for three sorption-desorption cycles.