Physicochemical aspects of using natural scavengers in removing methylene blue (basic dye) from solution

Effluent from dyeing and finishing processes is an important source of water pollution. The effectiveness of bentonite, kaolinite and sediment from a local deposit in removing methylene blue as a cationic dye from aqueous solutions has been investigated. The adsorption equilibrium (isotherm) has been determined according to Freundlich and Langmuir equations. The optimum amount is 0.5 g for all adsorbents, and the optimum pH ranges are 2-8 for bentonite and 2-6 for kaolinite and sediment. With respect to kinetic modelling, the adsorption of methylene blue on various adsorbents was fitted to a second-order equation. Also, the thermodynamic parameters were determined. The negative free energy values indicate the feasibility of the process and spontaneous nature of adsorption. The positive ΔH° values indicate the endothermic nature of the process. Thus, Egyptian clay minerals and sediments have a great tendency to remove the dye from solutions.     

Body fluid analog chlorination: Application to the determination of disinfection byproduct formation kinetics in swimming pool water

Disinfection by-products(DBPs) are formed in swimming pools by the reactions of bather inputs with the disinfectant.Although a wide range of molecules has been identified within DBPs,only few kinetic rates have been reported.This study investigates the kinetics of chlorine consumption,chloroform formation and dichloroacetonitrile formation caused by human releases.Since the flux and main components of human inputs have been determined and formalized through Body Fluid Analogs(BFAs),it is possible to model the DBPs formation kinetics by studying a limited number of precursor molecules.For each parameter the individual contributions of BFA components have been quantified and kinetic rates have been determined,based on reaction mechanisms proposed in the literature.With a molar consumption of 4 mol Cl_2/mol,urea is confirmed as the major chlorine consumer in the BFA because of its high concentration in human releases.The higher reactivity of ammonia is however highlighted.Citric acid is responsible for most of the chloroform produced during BFA chlorination.Chloroform formation is relatively slow with a limiting rate constant determined at 5.50 × 10~(-3) L/mol/sec.L-histidine is the only precursor for dichloroacetonitrile in the BFA.This DBP is rapidly formed and its degradation by hydrolysis and by reaction with hypochlorite shortens its lifetime in the basin.Reaction rates of dichloroacetonitrile formation by L-histidine chlorination have been established based on the latest chlorination mechanisms proposed.Moreover,this study shows that the reactivity toward chlorine differs whether L-histidine is isolated or mixed with BFA components.     

生物滴滤池法处理废气动力学模式研究

基于物料平衡和微生物降解废水中污染物的动力学模式,以丙酮、甲苯为处理对象提出了生物滴滤池处理废气的模式。当入口浓度C_(in)较低,小于临界浓度C_(crit),时,C=C_(in)EXP((-B/V_g)·H);当人口浓度C_(in)较高,大于临界浓度C_(crit)时,C=C_(in)-(K_0X/V_g)·H。研究表明,实验结果与模式计算结果吻合较好。     

Modified Fenton reaction for trichlorophenol dechlorination by enzymatically generated H2O2 and gluconic acid chelate

Glucose oxidase is a well-known enzyme that catalyzes the oxidation of β-d-glucose to produce gluconic acid and hydrogen peroxide. Fenton reaction is a powerful oxidation technology used for the oxidation of groundwater pollutants. For the application of Fenton reaction in groundwater remediation, successful operation of Fenton reaction near neutral pH, and on-site generation of both H₂O₂ and chelate will be beneficial. The focus of this experimental study was to couple the glucose oxidation reaction with chelate-based Fenton reaction. The idea was to use the hydrogen peroxide and chelate gluconic acid generated during glucose oxidation for the dechlorination of 2,4,6-trichlorophenol (TCP) by Fenton reaction. The oxidation of glucose was achieved using the enzyme in free and immobilized forms. The rate of production of hydrogen peroxide was determined for each system, and was used to estimate the time required for complete consumption of glucose during the process, thus avoiding any traces of glucose in the Fenton reaction. In the case of free enzyme reaction, separation of the enzyme was achieved using an ultrafiltration membrane before initiating the Fenton reaction. The oxidation of TCP by Fenton reaction was performed at varying ratios of gluconic acid/Fe, and its effect on the decomposition of TCP and H₂O₂ was studied. TCP degradation was studied both in terms of parent compound degradation and free chloride generation.     

Kinetic extractions to assess mobilization of Zn, Pb, Cu, and Cd in a metal-contaminated soil: EDTA vs. citrate

Kinetic EDTA and citrate extractions were used to mimic metal mobilization in a soil contaminated by metallurgical fallout. Modeling of metal removal rates vs. time distinguished two metal pools: readily labile (QM1) and less labile (QM2). In citrate extractions, total extractability (QM1+QM2) of Zn and Cd was proportionally higher than for Pb and Cu. Proportions of Pb and Cu extracted with EDTA were three times higher than when using citrate. We observed similar QM1/QM2 ratios for Zn and Cu regardless of the extractant, suggesting comparable binding energies to soil constituents. However, for Pb and Cd, more heterogeneous binding energies were hypothesized to explain different kinetic extraction behaviors. Proportions of citrate-labile metals were found consistent with their short-term, in-situ mobility assessed in the studied soil, i.e., metal amount released in the soil solution or extracted by cultivated plants. Kinetic EDTA extractions were hypothesized to be more predictive for long-term metal migration with depth.     

Characterization of Ti powders mixed with TiO2 powders: Thermal and kinetic studies

The fire and explosion risks of metal powders admixed with solid inertants have been extensively investigated for many years. However, it remains unclear why such solid mixtures have high potential fire and explosion risk even when mixed with high percentages of non-combustible solids. This paper investigates how to interpret these risks, from a microscopic perspective, with thermal and kinetic parameters including initial ignition temperature, mass unit exothermic energy, activation energy and risk index of spontaneous combustion. The results show that the initial ignition temperature based on TG (Thermogravimetry) analysis is related to ignition sensitivity, and increased with percentage of admixed solid inertant. The unit mass exothermic energy based on DSC (Differential scanning calorimetry) analysis is related to flame spread velocity. Activation energy and the risk index of spontaneous combustion can be used to explain the reactivity and spontaneous combustion hazard, respectively, of metal powders. We conclude that thermal and kinetic parameters may provide another way to describe the fire and explosion risk of combustible powders, especially for nano metal powders due to the laboratory safety in the normative tests for explosion parameter determination.     

应用线性和非线性法求解有机物生物降解动力学参数

根据苯甲酸类化合物在水体中不同时间的生化需氧量，用线性和非线性合法对化合物生物降解随时间变化的动力学过程进行曲线拟合，得到各化合物2个数值不同的安全生化需氧量、生物降解速率常数和生物降解滞后期。根据各化合物2种不同的生物降解动力学模型所得到的生化需氧量拟合值与实测值的误差相比较，发现用非线性法拟合得到的有机物生物降解动力学模型，更符合化合物真实生物降解规律，因此用非线性法拟合化合物的生物降解动态变化，比用线性方法更精确。     

Carry-over of dietary organochlorine pesticides, PCDD/Fs, PCBs, and brominated flame retardants to Atlantic salmon (Salmo salar L.) fillets

Information on carry-over of contaminants from feed to animal food products is essential for appropriate human risk assessment of feed contaminants. The carry-over of potentially hazardous persistent organic pollutants (POPs) from feed to fillet was assessed in consumption sized Atlantic salmon (Salmo salar). Relative carry-over (defined as the fraction of a certain dietary POP retained in the fillet) was assessed in a controlled feeding trial, which provided fillet retention of dietary organochlorine pesticides (OCPs), dioxins (PCDD/Fs), polychlorinated biphenyls (PCBs), and brominated flame retardants (BFRs). Highest retention was found for OCPs, BFRs and PCBs (31-58%), and the lowest retentions were observed for PCDD/Fs congeners (10-34%). National monitoring data on commercial fish feed and farmed Atlantic salmon on the Norwegian market were used to provide commercially relevant feed-to-fillet transfer factors (calculated as fillet POP level divided by feed POP level), which ranged from 0.4 to 0.5, which is a factor 5-10 times higher than reported for terrestrial meat products. For the OCP with one of the highest relative carry-over, toxaphene, uptake and elimination kinetics were established. Model simulations that are based on the uptake and elimination kinetics gave predicted levels that were in agreement with the measured values. Application of the model to the current EU upper limit for toxaphene in feed (50 μg kg⁻¹) gave maximum fillet levels of 22 μg kg⁻¹, which exceeds the estimated permissible level (21 μg kg⁻¹) for toxaphene in fish food samples in Norway.     

Synthesis and kinetics investigation of meso-microporous Cu-SAPO-34 catalysts for the selective catalytic reduction of NO with ammonia

A series of meso-microporous Cu-SAPO-34 catalysts were successfully synthesized by a one-pot hydrothermal crystallization method, and these catalysts exhibited excellent NH_3-SCR performance at low temperature. Their structure and physic chemical properties were characterized by means of X-ray diffraction patterns(XRD), Scanning electron microscopy(SEM), Transmission electron microscopy(TEM), N_2 sorption-desorption, nuclear magnetic resonance(NMR), Inductively Coupled Plasma-Atomic Emission spectrometer(ICP-AES), X-ray absorption spectroscopy(XPS),Temperature-programmed desorption of ammonia(NH_3-TPD), Ultraviolet visible diffuse reflectance spectroscopy(UV-Vis DRS) and Temperature programmed reduction(TPR).The analysis results indicate that the high activities of Cu-SAPO-34 catalysts could be attributed to the enhancement of redox property, the formation of mesopores and the more acid sites. Furthermore, the kinetic results verify that the formation of mesopores remarkably reduces diffusion resistance and then improves the accessibility of reactants to catalytically active sites. The 1.0-Cu-SAPO-34 catalyst exhibited the high NO conversion( 90%) among the wide activity temperature window in the range of 150–425℃.     

Cesium migration in saturated silica sand and Hanford sediments as impacted by ionic strength

Large amounts of 137Cs have been accidentally released to the subsurface from the Hanford nuclear site in the state of Washington, USA. The cesium-containing liquids varied in ionic strengths, and often had high electrolyte contents, mainly in the form of NaNO3 and NaOH, reaching concentrations up to several moles per liter. In this study, we investigated the effect of ionic strengths on Cs migration through two types of porous media: silica sand and Hanford sediments. Cesium sorption and transport was studied in 1, 10, 100, and 1000 mM NaCl electrolyte solutions at pH 10. Sorption isotherms were constructed from batch equilibrium experiments and the batch-derived sorption parameters were compared with column breakthrough curves. Column transport experiments were analyzed with a two-site equilibrium-nonequilibrium model. Cesium sorption to the silica sand in batch experiments showed a linear sorption isotherm for all ionic strengths, which matched well with the results from the column experiments at 100 and 1000 mM ionic strength; however, the column experiments at 1 and 10 mM ionic strength indicated a nonlinear sorption behavior of Cs to the silica sand. Transport through silica sand occurred under one-site sorption and equilibrium conditions. Cesium sorption to Hanford sediments in both batch and column experiments was best described with a nonlinear Freundlich isotherm. The column experiments indicated that Cs transport in Hanford sediments occurred under two-site equilibrium and nonequilibrium sorption. The effect of ionic strength on Cs transport was much more pronounced in Hanford sediments than in silica sands. Effective retardation factors of Cs during transport through Hanford sediments were reduced by a factor of 10 when the ionic strength increased from 100 to 1000 mM; for silica sand, the effective retardation was reduced by a factor of 10 when ionic strength increased from 1 to 1000 mM. A two order of magnitude change in ionic strength was needed in the silica sand to observe the same change in Cs retardation as in Hanford sediments.