Removal of basic dye (Astrazon Blue FGRL) using macroalga Caulerpa lentillifera

The macroalga Caulerpa lentillifera was found to have adsorption capacity for a basic dye, Astrazon Blue FGRL. For the whole range of concentrations employed in this work (20-1280 mgl(-1)), the adsorption reached equilibrium within the first hour. The kinetic data corresponded well with the pseudo second-order kinetic model where the rate constants decreased as initial dye concentrations increased. At low dye concentrations (20-80 mgl(-1)), an increase in the adsorbent dosage resulted in a higher removal percentage of the dye, but a lower amount of dye adsorbed per unit mass (q). The adsorption isotherm followed both the Langmuir and Freundlich models within the temperature range employed in this work (18-70 degrees C). The highest maximum adsorption capacity (q(m)) was obtained at 50 degrees C. The enthalpy of adsorption was estimated at 14.87 kJmol(-1) suggesting a chemical adsorption mechanism.     

Kinetic characterizing of soil trace metal availability using Soil/EDTA/Chelex mixture

The kinetic aspects are not usually tackled when mimicking the soil trace metal mobilization. In this work, a simple procedure is developed for measuring the kinetics of Pb, Cu and Cd transfer from the soil solid phase towards a resin sink. A ternary system of Soil/EDTA/Chelex was employed for mimicking the metal transfer from two agricultural soil samples into the Chelex. Two different kinetic regimes (P₁ and P₂) were observed. The kinetic profile of Pb was distinctly different from those of Cd and Cu. Basing on kinetic principles, two kinetic models were proposed for estimating the apparent rate constants of leaching and removal processes in, respectively, two binary mixtures of soil/EDTA and EDTA extracts/Chelex. Contrary to Pb, solid phase pools of Cd and Cu exchanged with the solution on short time scales. The kinetic rate of desorption occurred in following order: Pb < Cu ? Cd. Comparing the kinetics of binary systems, the desorption process was hypothesized to control the metal transfer. The parameters related to the desorption process were extended to the kinetic regimes of Soil/EDTA/Chelex and revealed that the soil to Chelex transfer of Pb is under kinetics control whereas the bulk concentration (affected by the size of particulate reservoir) is likely to control the Cd transfer. Cu presents an intermediate case.     

Advanced oxidation of alkylphenol ethoxylates in aqueous systems

Alkylphenols and alkylphenol ethoxylates are ubiquitous wastewater contaminants. In this study the oxidation of nonylphenol ethoxylates (NPEO) and octylphenol ethoxylates (OPEO) by oxidant systems generating hydroxide radicals was evaluated. The reaction of each oxidant with a technical mixture of NPEO (Tergitol™) and OPEO (Triton X-100™) in ultrapure laboratory water and four aqueous environmental matrices was carried out in order to develop an understanding of reaction kinetics. The oxidation of APEOs was evaluated by hydroxyl radical generated by (1) hydrogen peroxide in the presence of ultraviolet light, (2) Fenton’s reagent, and (3) a photo-Fenton’s process. The second order kinetic rate constant for both NPEO and OPEO with hydroxyl radical was calculated to be 1.1 × 10¹⁰ M⁻¹ s⁻¹. The efficacy of the AOPs within an aqueous environmental matrix was dependent on the rate of formation of hydroxyl radical and the scavenging capacity of the matrix. A model based on the hydroxyl radical formation, scavenging capacity and the kinetic rate constant of target APEO was developed from the existing literature and applied to predict the concentration of APEOs in solution during advanced oxidation in different aqueous environmental matrices.     

Sorption of dissolved lead from shooting range soils using hydroxyapatite amendments synthesized from industrial byproducts as affected by varying pH conditions

For immobilization technologies to be successful, the use of readily available and cost advantageous amendment is important when the remediation targets vast amounts of contaminated soils. The objectives of this study were to investigate whether the byproduct-synthesized hydroxyapatite can be used as an immobilizing amendment for dissolved Pb from a shooting range soil, and to model the kinetic data collected from dissolution experiments. A soil–solution kinetic experiment was conducted under fixed pH conditions as a function of time. A Pb-contaminated soil was reacted with various hydroxyapatite amendments to determine the dissolution rate and mineral products of soil Pb. Three types of amendments used were pure hydroxyapatite (HA), and poorly crystalline hydroxyapatites synthesized from gypsum waste (CHA), and synthesized from incinerated poultry litter (PHA). The dissolved Pb concentration decreased with the addition of amendments at pH 3–7. Both CHA and PHA were more effective than HA for attenuating Pb dissolution at pH 6 and above. According to the thermodynamic calculation at pH 6, the dissolved Pb concentration for CHA and PHA treatments was predicted to be 66% and 50% lower than that of HA treatment, respectively. A better Pb immobilization effect demonstrated by CHA and PHA resulted in their greater solubility at higher pH, which may promote the formation of chloropyromorphite precipitates. Dissolution kinetics of soil Pb was adequately explained by pseudo-first order and pseudo-second order equations in acid pH ranges. According to the ion exchange model, an adequate agreement between the experimental data and regression curves was shown in the initial 40 min of the reaction process, but the accuracy of model predictability decreased thereafter. According to kinetic models and dissolution phenomena, CHA and PHA amendments had better Pb sorption capacity with rapid kinetics than pure hydroxyapatite at weak acid to neutral pH.     

Cesium and strontium sorption by selected tropical and subtropical soils around nuclear facilities

The dynamics of Cs and Sr sorption by soils, especially in the subtropics and tropics, as influenced by soil components are not fully understood. The rates and capacities of Cs and Sr sorption by selected subtropical and tropical soils in Taiwan were investigated to facilitate our understanding of the transformation and dynamics of Cs and Sr in soils developed under highly weathering intensity. The Langmuir isotherms and kinetic rates of Cs and Sr sorption on the Ap1 and Bt1 horizons of the Long-Tan (Lt) and the A and Bt1 horizons of the Kuan-Shan (Kt), Mao-Lin (Tml) and Chi-Lo (Cl) soils were selected for this study. Air-dried soil (<2 mm) samples were reacted with of 7.5 × 10⁻⁵ to 1.88 × 10⁻³ M of CsCl (pH 4.0) or 1.14 × 10⁻⁴ to 2.85 × 10⁻³ M of SrCl₂ (pH 4.0) solutions at 25 °C. The sorption maximum capacity (q_m) of Cs by the Ap1 and Bt1 horizons of the Lt soil (62.24 and 70.70 mmol Cs kg⁻¹ soil) were significantly (p < 0.05) higher than those by the A and Bt1 horizons of the Kt and Cl soils (26.46 and 27.49 mmol Cs kg⁻¹ soil in Kt soil and 34.83 and 29.96 mmol Cs kg⁻¹ soil in Cl soil, respectively), however, the sorption maximum capacity values of the Lt and Tml soils did not show significant differences. The amounts of pyrophosphate extractable Fe (Fe_p) were correlated significantly with the Cs and Sr sorption capacities (for Cs sorption, r² = 0.97, p < 1.0 × 10⁻⁴; for Sr sorption, r² = 0.82, p < 2.0 × 10⁻³). The partition coefficient of radiocesium sorbed on soil showed the following order: Cl soil ? Kt soil > Tml soil > Lt soil. It was due to clay minerals. The second-order kinetic model was applied to the Cs and Sr sorption data. The rate constant of Cs or Sr sorption on the four soils was substantiality increased with increasing temperature. This is attributable to the availability of more energy for bond breaking and bond formation brought about by the higher temperatures. The rate constant of Cs sorption at 308 K was 1.39-2.09 times higher than that at 278 K in the four soils. The activation energy of Cs and Sr sorbed by the four soils ranged from 7.2 to 16.7 kJ mol⁻¹ and from 15.2 to 22.4 kJ mol⁻¹, respectively. Therefore, the limiting step of the Cs⁺ or Sr²⁺ sorption on the soils was diffusion-controlled processes. The reactive components, which are significantly correlated with the Langmuir sorption maxima of Cs and Sr by these soils, substantially influenced their kinetic rates of Cs and Sr sorption. The data indicate that among components of the subtropical and tropical soils studied, short-range ordered sesquioxides especially Al- and Fe-oxides complexed with organics play important roles in influencing their capacity and dynamics of Cs and Sr sorption.     

Reactivity of cycloxydim toward singlet oxygen in solution and on wax film

The reactivity of the herbicide cycloxydim (CD) toward singlet oxygen was studied in organic solution and on wax films to mimic the leaf surface. Experiments in solution were conducted in acetonitrile using phenalenone as a sensitizer. For the experiments in the solid state, phenalenone was included in paraffinic wax films and CD deposited at the film surface. By laser flash photolysis we observed that the triplet of phenalenone reacts with CD with a bimolecular rate constant of (9.6 ± 1)×10⁶ M⁻¹ s⁻¹. However, scavenging experiments using β-carotene as a singlet oxygen quencher showed that the observed CD degradation in aerated acetonitrile involves singlet oxygen essentially. The bimolecular rate constant of reaction of CD with singlet oxygen was evaluated to (1.0 ± 0.2)×10⁷ M⁻¹ s⁻¹. Phenalenone included in the wax films also significantly increased the rate of CD photodegradation, the involvement of singlet oxygen being very likely. The photoproducts formed via the singlet oxygen pathway resulted from the oxidation of the thiol group and/or the cyclohexene ring. This study should help to better understand the fate of CD after its spraying on crops.     

Kinetics of natural oxidant demand by permanganate in aquifer solids

During in situ chemical oxidation with permanganate, natural organic matter and other reduced species in the subsurface compete with the target compounds for the available oxidant and can exert a significant natural oxidant demand. This competition between target and nontarget compounds can have a significant impact on the permeation, dispersal, and persistence of permanganate in the subsurface. The kinetics of natural oxidant demand by permanganate was investigated using a composite sample made up of aquifer material collected from three different sites. The study found that although the depletion of organic carbon increased with increased permanganate dosage and increased reaction period, the mass ratio of MnO(4)(-):OC (wt/wt) was relatively constant over time (11.4+/-0.9). The reaction order and rate with respect to permanganate were found to decrease with time suggesting a continuum of reactions with the slower reactions becoming more controlling with time. However, the data also suggests that this continuum of reactions can be simplified into short- and long-term kinetic expressions representing fast and slow reactions. An independent first-order kinetic model with separate fast and slow reaction rate constants was used to successfully describe the complete kinetic expression of natural oxidant demand. The kinetic parameters used in the model are easily determined and can be used to better understand the complex kinetics of natural oxidant demand.     

Metal toxicity in a sediment-dwelling polychaete: Threshold body concentrations or overwhelming accumulation rates?

We followed the net accumulation of As, Cu and Zn in the deposit-feeding polychaete Arenicola marina exposed in the laboratory to natural metal-contaminated sediments, one exposure leading to mass mortality between day 10 and 20, and the other not causing lethality over a period of 60 days of exposure. The worms showed lower total accumulated metal concentrations just before mortality occurred (<20 days) at the lethal exposure, than after 30 days of exposure to sediments not causing mortality. Moreover rates of accumulation of As, Cu and Zn were significantly higher in the lethal exposure than in the sublethal exposure. Our results show that it is not possible to link mortality to a critical total body concentration, and we add to a growing body of literature indicating that metal toxicity occurs when organisms cannot cope with overwhelming influx and subsequent accumulation rates.     

电解浮选用于活性污泥固液分离及其动力学研究

在装有Ti/RuO2-IrOz-TiO2阳极、Ti阴极的电解浮选槽中进行了活性污泥固液分离的研究.考察了水力停留时间对浮选效果的影响,研究了电解产生的微气泡对悬浮物浮选的动力学.研究表明,电解浮选是高效的固液分离单元,悬浮物的去除遵循一级动力学模型.