Evaluation of sorption-desorption processes for metalaxyl in natural and artificial soils

The main process controlling soil-pesticide interaction is the sorption-desorption as influenced by active soil surfaces. The sorption phenomena can influence translocation, volatility, persistence and bioactivity of a pesticide in soil. The present investigation was conducted on natural and artificial soils in order to enumerate the effect of soil components such as montmorillonite and ferrihydrite on the sorption behaviour of the fungicide metalaxyl and if sorption-desorption of the chiral pesticide affects the enantiomeric ratio. The sorption-desorption characteristics of metalaxyl were investigated by batch equilibration technique in a natural soil, two artificial soils, and in pure montmorillonite and ferrihydrite. After extraction, pesticide residues were analyzed by conventional and chiral chromatography using tandem mass spectrometry. A K_dSorp (2.3–6.5) suggests low level sorption of metalaxyl with an appreciable risk of run-off and leaching. Thus, metalaxyl poses a threat to surface and ground water contamination. Furthermore, desorption tests revealed a hysteretic effect (H ≤ 0.8) in natural and artificial soils. Significant amount of metalaxyl was found tightly bound to the adsorbents without desorbing readily after desorption cycle. Desorption of 22–56% of the total amount of the retained metalaxyl was determined. This study reveals that an artificial soil derived from different soil constituents can be used to assess their influence on sorption/desorption processes. The present investigation showed that both montmorillonite and ferrihydrite play a significant role in the sorption of metalaxyl. The sorption doesn't influence the enantiomeric ratio of racemic metalaxyl.     

活性炭纤维的改性及其微孔结构

采用微波辐射、硝酸回流、微波-硝酸处理和氢氧化钠水溶液浸渍改性了粘胶基活性炭纤维,并对其改性机制进行了探讨.利用氮吸附对改性活性炭纤维的孔隙结构进行了表征.结果表明,除碱改性活性炭纤维外,其余改性活性炭纤维的BET表面积增加、微孔容量增大、对氮气的亲和力增强,而且微波辐射改性可使活性碳BET表面积大大增加.活性炭纤维表面呈双重分维特征.     

Influence of particle size and salinity on adsorption of basic dyes by agricultural waste： dried Seagrape （Caulerpa lentiUifera）

Green macroalga Caulerpa lentillifera was found to have reasonable adsorption capacity for basic dyes, Astrazon Blue FGRL （AB）, Astrazon Red GTLN （AR）, and Astrazon Golden Yellow GL-E （AY）. The initial dye concentration was in the range of 100-1,800 mg/L. The dried algal sorbent was ground and sieved into 3 sizes： S （0.1-0.84 mm）, M （0.84-2.0 mm）, and L sizes （larger than 2.0 mm）. For all conditions examined in this work （at 25℃ in batch systems）, the adsorption reached equilibrium within the first hour. The kinetic data corresponded well with the pseudo second order kinetic model where the rate constant, k2, decreased as the sorbent size increased for all dyes. The adsorption isotherms followed both Langmuir and Freundlich models. Among three sorbent sizes, S size gave the highest adsorption capacity followed by M and L sizes. A reduction of sorbent size increased the specific surface area for mass transfer, and also increased the total pore volume, thus providing more active sites for adsorption. The adsorption of AB was adversely influenced by the protonation of algal surface at low pH. On the other hand, the adsorption of AR and AY could be due to weak electrostatic interaction, which was not significantly affected by pH. Increasing salinity of the system caused a decrease in adsorption capacity possibly due to the competition between Na^＋ and the dye cations for the binding sites on algal surface. Moreover, an increase in salinity generated a compressed electrical double layer on the algal surface which exerted repulsive force, retarding the adsorption of positive charged molecules such as the basic dyes.     

Biosorption of Cu(II) on extracellular polymers from Bacillus sp. F19

Biosorption can be an effective process for the removal of heavy metals from aqueous solutions. The adsorption of Cu(Ⅱ) from aqueous solution on the extracellular polymers (EPS) from Bacillus sp. (named MBFF19) with respect to pH, incubation time,concentration of initial Cu(Ⅱ), and biosorbent dose was studied. Biosorption of Cu(Ⅱ) is highly pH dependent. The maximum uptake of Cu(Ⅱ) (89.62 mg/g) was obtained at pH 4.8. Biosorption equilibrium was established in approximately 10 min. The correlation coefficient of more than 0.90 turned out that the adsorption process of Cu(Ⅱ) on MBFF19 was in accordance with both Langmuir and Freundlich isotherms. The pseudo-first and second order models were applied to examine the kinetics of the adsorption, whereas the latter was found to be in harmony with the kinetic data better. Because of the outstanding uptake capacity of Cu(Ⅱ), MBFF19 produced by Bacillus sp. was proved to be an excellent biosorbent for removing Cu(Ⅱ) from aqueous solutions.     

北京地区石灰性土壤对锰的吸附

本文研究了北京地区４种类型５个石灰性土壤样品对锰的吸附、及其与土壤各理化性质的关系。在每克土壤加入２５ｍｌ１０～２００ｇＭｎ／ｍｌ的剂量范围内，土壤对锰的吸附极好的遵从Ｆｒｅｕｎｄｒｉｃｈ等温方程，而是否符合Ｌａｎｇｍｕｉｒ等温方程则与加入的锰溶液浓度有关，当其小于１２０　ｇＭｎ／ｍｌ时，则能较好地符合Ｌａｎｇｍｕｉｒ方程；这一现象说明，土壤具有两种或两种以上的吸附位。在土壤各理化性质中主要是粘粒含量和阳离于交换总量（ＣＥＣ）影响到锰的吸附。但在锰溶液浓度较低时，各土壤理化性质均与土壤吸附锰量无显著相关。平衡溶液的ｐＨ强烈影响土壤吸附锰的能力，当ｐＨ由４上升至７左右时，土壤对锰的吸附急剧增加，ｐＨ值再上升，土壤吸附锰量的增加趋于平缓。     

2,4-二氯苯酚在黄土中的吸附-解吸行为研究

本以自制的模拟系统研究了溶液浓度、离子强度、pH值和常见金属离子对2，4-二氯苯酚在黄土中迁移行为的影响，并对实验数据用Freudlich和Langmuir经验公式进行了拟合。结果表明，2，4-二氯苯酚在黄土中的吸附／解吸过程包括两个阶段：渗滤液浓度在初始阶段降低迅速，在第二阶段变化缓慢逐渐达到平衡。用分布活性模型能很好地解释这一结果。在实验条件下，离子强度对迁移行为影响不显。在实验的pH范围内，随着pH的升高，吸附量降低，相应的解吸量加大；与碱金属离子Mg^2 、Ca^2 相比，过渡金属离子Zn^2 、Mn^2 和Cd^2 的存在能显促进黄土对2，4-二氯苯酚的滞留能力。但滞后因子尺始终较低，表明天然黄土对如2，4-二氯苯酚这样的水溶性有机物染物的滞留能力较差。在对被这类有机物污染的土壤进行修复过程中，有机物对地下水可能造成的影响是必须予以考虑的因素。     

厌氧与缺氧污泥对17β-雌二醇吸附性能的研究

雌二醇浓度为500～10 000　ng/L,采用活性污泥灭活吸附,考察了吸附平衡时间和pH值对吸附的影响.在10、20、30℃不同温度下建立了Freundlich吸附等温线,并计算了分配系数K_d.结果表明,厌氧与缺氧失活污泥对雌二醇的吸附都在30 min以内达到平衡;pH值在6～9范围内对吸附没有影响,pH大于9时随着pH值增加吸附量减少;两者在不同温度下对雌二醇的吸附都符合Freundlich吸附,都呈线性吸附,分配系数随温度升高而降低,厌氧失活污泥的分配系数K_d为629.2(10℃)＞534.9(20℃)＞405.6(30℃),缺氧失活污泥的分配系数K_d为601.2(10℃)＞491.3(20℃)＞360.1(30℃).另外,研究了厌氧与缺氧活性污泥的吸附等温线与分配系数,厌氧活性污泥的K_d大于缺氧活性污泥.厌氧(缺氧)活性污泥与灭活污泥对雌二醇的吸附未出现明显差别,厌氧污泥的吸附性能强于缺氧污泥.     

Statistical optimization of adsorption processes for removal of 2,4-dichlorophenol by activated carbon derived from oil palm empty fruit bunches

The adsorption capacity of activated carbon produced from oil palm empty fruit bunches through removal of 2,4-dichlorophenol from aqueous solution was carried out in the laboratory. The activated carbon was produced by thermal activation of activation time with 30 min at 800℃. The adsorption process conditions were determined with the statistical optimization followed by central composite design. A developed polynomial model for operating conditions of adsorption process indicated that the optimum conditions for maximum adsorption of phenolic compound were： agitation rate of 100 r/min, contact time of 8 h, initial adsorbate concentration of 250 mg/L and pH 4. Adsorption isotherms were conducted to evaluate biosorption process. Langmuir isotherm was more favorable （R^2=0.93） for removal of 2,4-dichlorophenol by the activated carbon rather than Freundlich isotherm （R^2=0.88）.     

Particle concentration effect in adsorption/desorption of Zn（Ⅱ） on anatase type nano TiO2

Adsorption/desorption in a new Zn(II)-TiO2 adsorption system was investigated at different particle concentrations (Cp). TEM, SEM and XRD analyses revealed that the TiO2 particles were an aggregation of nano-sized (approximately 10 nm) pure anatase-type TiO2. Adsorption experiments were carried out with particle concentrations of 100, 400 and 1000 mg/L, and their adsorption isotherms were found to decline successively, showing an obvious Cp effect. Desorption experiments indicated that adsorption in this system was irreversible, and the irreversibility increased with increasing Cp. These phenomena could be explained by the MEA (metastable equilibrium adsorption) theory and the Cp effect could be modeled well with an MEA-Freundlich-type Cp effect isotherm equation. This study may help understand environmental behavior of contaminants on ultrafine natural particles.     

Sorption of 2,4-dinitroanisole (DNAN) on lignin

The present study describes the use of two commercially available lignins, namely, alkali and organosolv lignin, for the removal of 2,4-dinitroanisole (DNAN), a chemical widely used by the military and the dye industry, from water. Sorption of DNAN on both lignins reached equilibrium within 10 hr and followed pseudo second-order kinetics with sorption being faster with alkali than with organosolv lignin, i.e. k₂ 10.3 and 0.3 g/(mg hr), respectively. In a separate study we investigated sorption of DNAN between 10 and 40°C and found that the removal of DNAN by organosolv lignin increased from 0.8 to 7.5 mg/g but reduced slightly from 8.5 to 7.6 mg/g in the case of alkali lignin. Sorption isotherms for either alkali or organosolv lignin best fitted Freundlich equation with enthalpy of formation, ΔH⁰ equaled to 14 or 80 kJ/mol. To help understand DNAN sorption mechanisms we characterized the two lignins by elemental analysis, BET nitrogen adsorption-desorption and ³¹P NMR. Variations in elemental compositions between the two lignins indicated that alkali lignin should have more sites (O- and S-containing functionalities) for H-bonding. The BET surface area and calculated total pore volume of alkali lignin were almost 10 times greater than that of organosolv lignin suggesting that alkali lignin should provide more sites for sorption. ³¹P NMR showed that organosolv lignin contains more phenolic -OH groups than alkali lignin, i.e., 70% and 45%, respectively. The variations in the type of OH groups between the two lignins might have affected the strength of H-bonding between DNAN and the type of lignin used.