塿土表面铜吸附解吸的动力学特征及滞后效应

采用间歇法发现土娄土及不同处理土样对铜离子的吸附过程遵循二级反应动力学方程 ,吸附速率常数ka 呈 :土娄土 >去OM土娄土 >去Ca土娄土 >去Ca、OM土娄土 ;解吸过程符合两点位一级动力学方程 ,第一点位解吸速率常数kd1大于第二点位解吸速率常数kd2 ;各土样解吸速率常数的大小顺序与ka相反 ;吸附 解吸之间的滞后效应用ka/kd来衡量 ,滞后程度大小与ka大小顺序一致     

Kinetics of Copper Desorption from Highly Calcareous Soils

Abstract

Desorption of copper (Cu) is an important factor in determining Cu availability in calcareous soils. Kinetics of native and added Cu desorption by DTPA (diethylene‐triaminepentaacetic‐acid) from 15 highly calcareous soils of southern Iran were studied in a laboratory experiment. Our results showed that two constant‐rate, Elovich, simple Elovich, and parabolic‐diffusion equations were the best‐fitted equations among eight kinetic models used. The copper desorption pattern based on the parabolic‐diffusion equation revealed that the rate of native Cu desorption was higher in the first 2 h followed by a slower release rate, which suggests that two different mechanisms are involved. The trend may describe why the DTPA soil test has been considerably successful in predicting Cu availability in calcareous soils. Stepwise multiple regression equations indicated that CCE (calcium carbonate equivalent), CEC (cation exchange capacity), and clay content are the most important soil characteristics that predict the rate constants of the kinetic models. Mean extractant recovery percentage (ERP) of the soils was only 20%, which indicated that after 20 days, DTPA extracted only one‐fifth of added Cu. Regression equations indicated that as soil OM (organic matter) content increased, the value of ERP decreased. From results reported herein it seems that CCE, CEC, and clay are the most important factors controlling Cu release from highly calcareous soils of southern Iran. However, the initial soil Cu desorption rate is probably controlled by CEC.     

Copper Release Behavior in Two Calcareous Soils Amended with Three Organic Materials

Understanding time-dependent copper (Cu) desorption behavior is critical for improving the prediction of Cu availability in soils. This study was conducted to evaluate the influence of municipal waste compost, sheep manure, and wheat straw on desorption characteristics of Cu and to evaluate the suitability of different kinetic models to describe the Cu release pattern in two calcareous soils. Diethylenetriaminepentaacetic acid (DTPA) and ethylenediaminetetraacetic acid (EDTA) were employed to extract Cu from soils. Best-fitted kinetic models including Elovich, simple Elovich, two-constant rate, and parabolic diffusion were selected based on their low standard error and high coefficient of determination. Extractable copper significantly decreased with increasing rates of sheep manure and wheat straw but increased with increasing rates of municipal waste compost amendment. Results revealed that copper was more readily desorbed from clay soil compared to silt loam soil. The copper desorption patterns were almost similar for both extractants; however, EDTA extracted more Cu from soils.     

Copper Biosorption by Biomass of Marine Alga: Study of Equilibrium and Kinetics in Batch System and Adsorption/Desorption Cycles in Fixed Bed Column

Copper biosorption onto chemically modified biomass of marine alga Sargassum filipendula was investigated in a batch reactor and a fixed bed column. Experiments were carried out in the batch reactor to obtain kinetic and equilibrium data and to assess the copper desorption efficiency of different eluent solutions. The pseudo-first-order, pseudo-second-order, and Langmuir kinetic models were used to correlate kinetic data. The experimental data fitted well to the pseudo first order and Langmuir kinetic models. Langmuir and Freundlich models were applied to describe the equilibrium data obtained at a fixed temperature of 30°C and at pH values of 3.0, 4.0, 5.0, and 6.0. The maximum capacities of copper biosorption onto the algal biomass were 1.43, 1.59, 2.40, and 2.36 mequiv./g at pH 3.0, 4.0, 5.0, and 6.0, respectively. The efficiencies of two eluent solutions (calcium chloride and hydrochloric acid) for copper removal from the biomass were evaluated at different concentrations (0.1, 0.2, 0.5, and 1.0 mol/L). The efficiencies of the calcium chloride solutions varied from 1% to 14%, while efficiencies varying from 95% to 99% were obtained when hydrochloric acid solutions were applied. Three adsorption/desorption cycles were carried out in a fixed bed column using 0.1 mol/L hydrochloric acid as eluent solution. The results showed that an increase in the number of cycles led to a reduction in the adsorption capacity of the alga. The desorbed copper fraction presented no significant variation, remaining around 63% in the three adsorption/desorption cycles.     

羊栖菜粉对水溶液中Cu2+的吸附效果

以羊栖菜粉为吸附剂,研究羊栖菜粉对水溶液中Cu²⁺的吸附特性及吸附机理,考察羊栖菜对重金属铜的吸附能力,以扩展羊栖菜的综合利用范围。采用控制变量法考察pH值、吸附剂浓度、金属离子初始浓度和离子强度等环境因素对水溶液中Cu²⁺去除效果的影响,通过模拟吸附动力学和热力学试验考察羊栖菜粉对Cu²⁺的吸附特性,并采用SEM、FTIR等方法初步分析了羊栖菜粉对Cu²⁺的吸附机理。结果表明,在吸附温度35℃、初始浓度50 mg·L^-1、吸附剂浓度1 g·L^-1条件下,羊栖菜粉对Cu²⁺的去除率可达89.27%。当吸附时间为10 min时,Cu²⁺去除率达总去除率的90%以上;当吸附时间为60 min时,基本达到吸附平衡。羊栖菜粉吸附Cu²⁺的动力学数据符合准二级动力学模型,相关系数均在0.999 0以上。Langmuir可以很好地拟合热力学试验得到的平衡数据,理论最大吸附容量为71.17 mg·g^-1。羊栖菜粉对Cu²⁺的吸附有多种反应参与,参与络合反应的官能团主要有-OH、-NH、-COO^-。羊栖菜粉对Cu²⁺的去除率较高,吸附性能良好,可通过解吸实现吸附剂的再生。     

Polydopamine Nanoparticles as a New and Highly Selective Biosorbent for the Removal of Copper (II) Ions from Aqueous Solutions

The adsorption and desorption of copper (II) ions from aqueous solutions were investigated using polydopamine (PD) nanoparticles. The nanoscale PD nanoparticles with mean diameter of 75?nm as adsorbent were synthesized from alkaline solution of dopamine and confirmed using scanning electron microscopy and X-ray diffraction analysis. The effects of pH (2?C6), adsorbent dosage (0.2?C0.8?g?L^?1), temperature (298?C323?K), initial concentration (20?C100?mg?L^?1), foreign ions (Zn²⁺, Ni²⁺, Cd²⁺, Fe²⁺, and Ag⁺), and contact time (0?C360?min) on adsorption of copper ions were investigated through batch experiments. The isotherm adsorption data were well described by the Langmuir isotherm model. The maximum uptake capacity of Cu²⁺ ions onto PD nanoparticles was found to 34.4?mg/g. The kinetic data were fitted well to pseudo-second-order model. Moreover, the thermodynamic parameters of the adsorption (the Gibbs free energy, entropy, and enthalpy) were studied.     

Copper micronutrient fixation kinetics and interactions with soil constituents in semi-arid alkaline soils

This study examined the fixation pattern and kinetics of plant-available [diethylene triamine pentaacetic acid (DTPA)-extractable] copper (Cu), as well as basic soil properties that influence Cu availability in selected semi-arid soils. Soil samples from six different series were used and data obtained from Cu extraction experiments fitted to various kinetic models. Soils were also characterized for a suite of chemical and physical properties. The majority (80%) of the plant-available Cu fixed over the experimental period of 90 d occurred within the first 14 d. The amount of plant-available Cu fixed within the first 14 d tended to be influenced by the combination of organic matter (OM) and pH. The total amount of Cu fixed at the end of the experimental period of 90 d was influenced by pH and a combination of pH and calcium carbonate. The fixation of plant-available Cu over the experimental period was better described by the power function model [R² = 0.90, Standard Error (SE) = 0.099] but poorly by the other models (R²: 0.58 to 0.59), while reactions within the first 35 d were better described by the second-order model (R² = 0.98, SE = 0.008), suggesting a different fixation pattern. Findings from this study provide a basis for a more mechanistic approach to evaluating and comparing the fixation of Cu micronutrient compounds in these semi-arid soils for more scientific management decision making.     

Evaluation of the sorption process for imidacloprid and diuron in eight agricultural soils from southern Europe using various kinetic models

Kinetic studies are of great concern for understanding the processes and parameters involved in the sorption of pollutants by soils. Sorption kinetics of imidacloprid and diuron in eight soils of different characteristics, with very low organic carbon content were investigated. Pseudosecond-order kinetic reactions closely correlate with the experimental kinetic (R(2) > 0.98) in all soils. The sorbed amount of diuron was higher than that for imidacloprid. The low OC content of these soils correlated neither with the sorbed amount nor with the kinetic parameters for both pesticides. Imidacloprid sorption was correlated with silt and sand content and cation exchange capacity (CEC); meanwhile for diuron, no correlation was found. Thus, sorption kinetics take place throughout different mechanisms related mainly to the chemical character of the pesticides. Sorption kinetic parameters determined using three of the four models selected (pseudosecond-order kinetic reactions, Elovich equation, and Weber-Morris models) have been shown to be worthy to distinguish the process controlling the sorption kinetic of both pesticides.     

Variation in Copper Accumulation at the Tissue Level of Five Hybrid Poplars Subjected to Copper Stress

Heavy metal contamination causes significant environmental problems around the world and poses a threat to human health. Poplar hybrids present features for potential uses in phytoremediation systems in areas with heavy metal contamination. The purpose of this study was to assess the copper (Cu) accumulation level in five poplar inter-species hybrids [(Populus trichocarpa × Populus deltoides) × P. deltoides; P. deltoides × Populus nigra; P. trichocarpa × Populus maximowiczii; P. trichocarpa × P. nigra; and (P. trichocarpa × P. deltoides) × (P. trichocarpa × P. deltoides)] grown in a hydroponic system. The treatments entailed the application of low and high doses of Cu of 8.0 and 16.0 μM, respectively. Cu accumulation was observed in roots, stems, and leaves, which was determined using flame atomic absorption spectroscopy, prior acid digestion of each sample. The methodology was validated according to certified reference material (Cypress BIMEP 432). Significant differences in Cu accumulation were found among genotypes for both roots and leaves, but not for stems. In roots, the genotype P. deltoides × P. nigra had a Cu accumulation level of 169.8% higher than the average accumulation found in the other genotypes. The (P. trichocarpa × P. deltoides) × P. deltoides hybrid showed the least Cu accumulation in leaves. The results of this study can potentially be used for proper crossovers and hybrids selection within the genus Populus for phytoremediation of Cu contaminated land.     

Kinetic compensation and the role of cations in pectinesterase catalysis

The catalytic rate constant of thermostable pectinesterase (TS-PE) from Marsh grapefruit pulp was determined at pH 7 at temperatures between 25 and 60 degrees C. TS-PE activity was measured at NaCl concentrations of 0.05, 0.10, 0.15, and 0.20 M and at CaCl(2) concentrations of 0.005, 0.010, 0.015, and 0.020 M. For sodium- and calcium-added conditions, the kinetic functions of this reaction agreed with kinetic compensation relations. The isokinetic temperatures for sodium- and calcium-added conditions were 327.8 and 312.4 K, respectively. Different isokinetic temperatures and compensation parameters suggest that sodium and calcium uniquely affect TS-PE catalysis. This is the first demonstration of kinetic compensation in an enzyme-catalyzed reaction.     

Refinement and re-evaluation of the drop-shatter soil fragmentation method

The drop-shatter method was re-evaluated since data were reported of degrees of soil fragmentation, obtained by using this method, showing a dependence on the total specific energy input, defined as the cumulative drop height. A new definition of the specific energy input based on the kinetic energy of the soil clods available for fragmentation upon impact is presented. The kinetic energy is calculated from the air-resistance dependent falling velocity of the soil units upon impact. Better correlations were found for the median aggregate diameter and specific surface area with the kinetic energy than with specific energy input. Notwithstanding that improvement, a drop height dependence of the degree of soil fragmentation was found for drop heights > 1.5 m. Compression stress loading rate as the stress-fracturing mechanism is suggested as a possible explanation for that dependence. It is concluded that (a) drop heights should not exceed 1.5 m, and (b) in analyzing soil fragmentation-energy input relationships obtained by the drop-shatter method, the refined method for calculating the kinetic energy available for fragmentation should be used instead of the cumulative height.     

全射流喷头喷洒水滴动能分布规律

喷灌动能是评价喷头水力性能优劣的重要指标之一。该文在0.15、0.20、0.25、0.30和0.35 MPa工作压力下,采用激光雨滴谱仪测量技术(laser precipitation monitor,LPM)对全射流喷头的水滴直径、速度和水量分布等参数进行试验,研究了单个水滴动能、单位体积水滴动能、动能强度分布规律及动能强度均匀性系数与组合间距之间的关系。结果表明:全射流喷头的单个水滴动能分布与水滴直径之间的关系与该文所建立的模型拟合较好,呈幂函数关系;单位体积水滴动能沿径向呈一次函数关系增大,与压力的-0.556次方呈正比关系;动能强度沿径向逐渐增大,而在射程末端迅速减小至0,随压力增大而减小,且沿径向距离的增大而动能强度减小程度越大;在各工作压力下,全射流喷头的矩形最佳组合间距分别为1.2、1.0、1.1、1.0、1.1倍喷头射程;所对应的动能强度均匀性系数分别为56.6%、71.1%、76.2%、77.2%、72.9%。该结果对研究喷头外特性、优化喷头结构、喷灌系统优化配置提供了一定的理论价值。     

阻尼喷头动能分布试验及模型

针对阻尼喷头外流场水力学特性研究较少的问题,该文研究了单位体积动能、动能强度与有无散水齿、不同喷嘴直径之间的关系。在工作压力分别为175、200、250和300 k Pa,喷嘴直径分别为3.6、4.0、4.4和4.8 mm下,采用激光雨滴谱仪对Nelson R33阻尼喷头的水滴直径、速度和数目等参数进行试验测试,并对试验结果分析及模型建立。结果表明:有无散水齿条件下的单位体积动能均有逐渐增大的趋势;距喷头相同测点处,单位体积动能随喷嘴直径的增大而减小;给出了有无散水齿下不同喷嘴阻尼喷头单位体积水滴动能分布模型,相关系数均在0.94以上;在距喷头0~4 m,不同喷嘴直径的动能强度较小且差值不超过0.002 W/m2,在距喷头较远处,不同喷嘴直径的动能强度差值较大,最大差值达到0.006 W/m2。有散水齿时,动能强度在不同压力下波动均比较小,差值不超过5%。该结果为进一步研究阻尼喷头外流场水力学特性提供理论依据。     

Preliminary study on mechanics-based rainfall kinetic energy

A raindrop impact power observation system was employed to observe the real-time raindrop impact power during a rainfall event and to analyze the corresponding rainfall characteristics. The experiments were conducted at different simulated rainfall intensities. As rainfall intensity increased, the observed impact power increased linearly indicating the power observation system would be satisfactory for characterizing rainfall erosivity. Momentum is the product of mass and velocity (Momentum=MV), which is related to the observed impact power value. Since there is no significant difference between momentum and impact power, observed impact power can represent momentum for different rainfall intensities. The relationship between momentum and the observed impact power provides a convenient way to calculate rainfall kinetic energy. The value of rainfall kinetic energy based on the observed impact power was higher than the classic rainfall kinetic energy. The rainfall impact power based kinetic energy and the classic rainfall kinetic energy showed linear correlation, which indicates that the raindrop impact power observation system can characterize rainfall kinetic energy. The article establishes a preliminary way to calculate rainfall kinetic energy by using the real-time observed momentum, providing a foundation for replacing the traditional methods for estimating kinetic energy of rainstorms.     

A new splash cup to measure the kinetic energy of rainfall

Splash cups have long been successfully used for both the quantification of kinetic energy of rainfall and the detachability of soil particles by rainfall impact, the so‐called “splash erosion”. Measurements of kinetic energy, however, have been difficult to operate in the field especially in remote areas, on steep slopes, and in forests since boundary conditions need to be controlled precisely. This paper introduces a new splash cup based on Ellison's archetype that reliably and accurately measures kinetic energy as a function of sand loss under a large variety of conditions. The Tübingen splash cup (T splash cup) is relatively easy to operate under harsh field conditions, and it can be used in experimental designs with a large number of plots and replications at reasonably low costs. The cup is constructed from plastic laboratory flasks and plastic pipes from water‐supply equipments. The unit sand is held by a removable carrier system that can easily be replaced in the field. The splash cups have been calibrated in combination with a laser distrometer using a linear regression function with r² = 0.98. They measure kinetic energy over a wide range of rainfall intensities from 0.6 to 40 L m^–2 h^–1. Kinetic energy per area varies between 10 and 250 J m^–2. Two years of field test measurements in a subtropical forest ecosystem in China proved the reliability, durability, and usability of our new splash cups and allowed detecting differences in kinetic energy between different tree species and biodiversity levels.     

Kinetics of the stability of broccoli (Brassica oleracea Cv. Italica) myrosinase and isothiocyanates in broccoli juice during pressure/temperature treatments

The Brassicaceae plant family contains high concentrations of glucosinolates, which can be hydrolyzed by myrosinase yielding products having an anticarcinogenic activity. The pressure and temperature stabilities of endogenous broccoli myrosinase, as well as of the synthetic isothiocyanates sulforaphane and phenylethyl isothiocyanate, were studied in broccoli juice on a kinetic basis. At atmospheric pressure, kinetics of thermal (45-60 degrees C) myrosinase inactivation could be described by a consecutive step model. In contrast, only one phase of myrosinase inactivation was observed at elevated pressure (100-600 MPa) combined with temperatures from 10 up to 60 degrees C, indicating inactivation according to first-order kinetics. An antagonistic effect of pressure (up to 200 MPa) on thermal inactivation (50 degrees C and above) of myrosinase was observed indicating that pressure retarded the thermal inactivation. The kinetic parameters of myrosinase inactivation were described as inactivation rate constants (k values), activation energy (Ea values), and activation volume (Va values). On the basis of the kinetic data, a mathematical model describing the pressure and temperature dependence of myrosinase inactivation rate constants was constructed. The stability of isothiocyanates was studied at atmospheric pressure in the temperature range from 60 to 90 degrees C and at elevated pressures in the combined pressure-temperature range from 600 to 800 MPa and from 30 to 60 degrees C. It was found that isothiocyanates were relatively thermolabile and pressure stable. The kinetics of HP/T isothiocyanate degradation could be adequately described by a first-order kinetic model. The obtained kinetic information can be used for process evaluation and optimization to increase the health effect of Brassicaceae.     

坚果壳类生物质慢速热解动力学分析

为研究坚果壳生物质的慢速热解动力学过程，对两类坚果壳类生物质(花生壳和葵花瓜子壳)进行了低升温速率下惰性气氛的热重分析实验。采用竞争型热解反应动力学模型描述它们的热解过程。在原有动力学机理函数的基础上，提出了一种新的经验动力学机理函数。利用现代优化技术——模式搜索法，对实验数据进行了动力学分析，结果表明：新动力学机理函数能有效描述坚果壳类生物质的慢速热解动力学过程。     

鲜带鱼不同贮藏温度的货架期预测模型（简报）

为了研究鲜带鱼在冷链流通中的品质变化与货架期,通过不同温度下的贮藏试验研究了鲜带鱼的货架期预测模型。将鲜带鱼贮藏在268、273、278、283和293 K条件下,测定了鲜带鱼的总菌落数、总挥发性盐基氮（T-VBN）、鲜度指标（K值）与感官品质指标的变化。在Arrhenius动力学方程基础之上,建立了菌落总数、总挥发性盐基氮和鲜度指标（K值）与贮藏时间及贮藏温度之间的动力学模型。试验表明一级化学反应动力学模型和Arrhenius方程对总菌落数、总挥发性盐基氮（T-VBN）及鲜度指标（K值）的变化具有较高的拟合精度。菌落总数变化预测模型中的活化能（EA）及速率常数（k0）分别为：71.26 kJ/mol和3.987×1013,挥发性盐基氮变化的活化能（EA）及速率常数（k0）分别为：68.86 kJ/mol和2.159×1012,鲜度指标（K值）变化的活化能（EA）及速率常数（k0）分别为：41.26 kJ/mol和2.539×107。结果表明,鲜带鱼的总菌落数、总挥发性盐基氮（T-VBN）、鲜度指标（K值）随着贮藏时间的延长而增加,且随着贮藏温度的升高而增加迅速,其感官品质指标随着贮藏时间的延长而下降,且随着贮藏温度的升高而下降迅速。该试验建立的带鱼货架期预测模型所获得货架期预测值准确率达到±10%以内,可根据菌落总数、T-VBN值及K值在268～293 K范围内,对带鱼的剩余货架期进行预测。     

蘑菇培养废料的土壤培肥增产效果研究

蘑菇培养后的废料做水稻基肥 1～4t/亩 ,可增加土壤有机质 ,有效磷和有效钾 ;提高水稻产量 .     

Kinetic study of the acid hydrolysis of various oligofructose samples

The kinetic of acid hydrolysis of five commercially available oligofructose samples used as food ingredients has been investigated as a function of the dry matter concentration, reaction pH, and temperature. The initial fructose release rate is found to be roughly proportional to the inverse of the average polymerization degree in number. A pseudo first order kinetic is found with respect to the fructosyl chain end concentration and to the proton concentration. Arrhenius plot is found to reasonably fit the data in a relatively wide temperature range (7-130 degrees C). The results allow the estimation of the fructose release rate in many foodstuff processing conditions.