Modelling the biphasic sorption of simazine,imidacloprid, and boscalid in water/soil systems

The sorption kinetics of simazine (6-chloro-N,N′-diethyl-1,3,5-triazine-2,4-diamine), imidacloprid (1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine), and boscalid (2-chloro-N-(4′-chlorobiphenyl-2-yl)nicotinamide), three pesticides of wide use in agriculture, was determined in five different water/soil systems over a time interval from the initial few seconds to about 1 month. In all the experiments, sorption kinetics showed a biphasic pattern characterized by an initial, relatively short phase with a high sorption rate and a later phase with much a lower sorption rate. Initial sorption capacity increased with soil organic carbon content and with sorbate hydrophobicity. We postulate that the first phase of the process involves a fast second-order sorption reaction on superficial sites of soil particles, whereas the second phase depends on diffusion-controlled migration to internal binding sites. A kinetic equation based on this hybrid model accurately fitted all data sets. Less satisfactory results were obtained employing the pseudo-first order, pseudo-second order, Elovich, two site non-equilibrium, or Weber-Morris equation. The superior performance of the hybrid model for describing boscalid sorption probably reflects the high hydrophobic character and consequent low diffusion rates of this compound. The accuracy of modelling was in any case strongly dependent on the time interval considered.     

Dissipation and sorption of six commonly used pesticides in two contrasting soils of New Zealand

We investigated dissipation and sorption of atrazine, terbuthylazine, bromacil, diazinon, hexazinone and procymidone in two contrasting New Zealand soils (0–10 cm and 40–50 cm) under controlled laboratory conditions. The six pesticides showed marked differences in their degradation rates in both top- and subsoils, and the estimated DT₅₀ values for the compounds were: 19–120 (atrazine), 10–36 (terbuthylazine), 12–46 (bromacil), 7–25 (diazinon), 8–92 (hexazinone) and 13–60 days for procymidone. Diazinon had the lowest range for DT₅₀ values, while bromacil and hexazinone gave the highest DT₅₀ values under any given condition on any soil type. Batch derived effective distribution coefficient (K _d ^eff) values for the pesticides varied markedly with bromacil and hexazinone exhibiting low sorption affinity for the soils at either depth, while diazinon gave high sorption values. Comparison of pesticide degradation in sterile and non-sterile soils suggests that microbial degradation was the major dissipation pathway for all six compounds, although little influence of abiotic degradation was noticeable for diazinon and procymidone.     

Hydrotalcites and organo‐hydrotalcites as sorbents for removing pesticides from water

Abstract

This paper reports on the adsorption of different organic pesticides by hydrotalcite, hydrotalcite heated to 500°C and organo‐hydrotalcite in aqueous medium by employing adsorption isotherms, and using X‐ray diffraction and infrared spectroscopy techniques. The results suggest that the adsorption capacity of the different materials depends on their nature as well as on the structure, polarity and hydrophobic or anionic nature of the pesticides. The results also show that hydrotalcite, both natural and after calcination at 500°C, is not a good sorbent of hydrophobic pesticides. The data demonstrated that both types of hydrotalcite, however, are very good sorbents of glyphosphate. Furthermore, the organo‐hydrotalcites may be as good sorbents as organo‐montmorillonites for hydrophobic pesticides.     

Enhanced Desorption of Phenanthrene from Soils Using Hydroxypropyl‐β‐cyclodextrin: Experimental Results and Model Predictions

Objective of this study was to evaluate the effects of hydroxypropyl‐β‐cyclodextrin (HPCD) on the removal of phenanthrene from solid phase. Batch tests for the phenanthrene distribution between aqueous and solid phase were conducted in the presence of HPCD. Column tests and numerical simulations were conducted to evaluate the roles of HPCD cavities and interaction rates between water, HPCD, and solid phase in the enhanced removal of phenanthrene. Experimental results showed that HPCD was effective in removing sorbed phenanthrene from subsurface environment, primarily due to its negligible sorption to the solid phase and the partitioning of phenanthrene into HPCD cavities. From the numerical simulations, it was found that rate‐limited partitioning of phenanthrene into HPCD cavities was most influential factor in the enhanced elution of phenanthrene. Sorption and desorption rate of phenanthrene between aqueous and solid phase was very fast or near equilibrium state. Interaction rates of contaminant between water, HPCD, and solid phase could be affected by other factors such as soil types and organic matter contents. Results from this study implied that HPCD flushing could be effectively applied for the removal of hydrophobic organic pollutants existing in the soils as sorbed or NAPL state.     

稻壳活性炭制备及其对磷的吸附

利用农业废弃物稻壳经炭化、活化、酸洗、水洗和干燥等工艺制备出一种富含微孔和中孔结构的稻壳活性炭,其BET比表面积达886.3 m2/g。通过正交实验优化了稻壳活性炭对磷吸附条件,并在该条件下进行了吸附等温和吸附动力学实验研究。结果表明,稻壳活性炭对磷的吸附等温曲线能较好符合Langmuir模型(R2=0.9284)和Freundlich模型(R2=0.9208),由Langmuir线性拟合方程可得稻壳活性炭对磷饱和吸附量达6.93 mg/g;稻壳活性炭对磷的吸附过程可用准二级动力学方程描述(R2=0.9968),吸附速度较快,颗粒内扩散为该过程控速阶段。稻壳活性炭作为一种易得、廉价、高效的填料,在农村分散型污水生态处理技术中,具有良好的应用前景。     

二氧化钛颗粒制备及其对水中三价砷的去除

以硫酸氧钛和聚乙烯醇(PVA)为原料,通过冰水浴法制备了二氧化钛(TiO2)颗粒,并研究了其对砷的吸附性能。利用X射线衍射仪(XRD)和扫描电子显微镜(SEM)对TiO2颗粒进行了表征,结果表明,吸附剂为锐钛矿结构,比表面积246 m2/g。TiO2颗粒对模拟地下水中砷(Ⅲ)的吸附动力学研究表明,吸附过程符合准二级动力学。采用Langmuir和Freundlich方程对吸附平衡数据进行了拟合,结果表明,吸附等温线符合Langmuir模型,最大吸附量为22.3 mg/g。TiO2颗粒对三价砷的吸附在pH为9.1时吸附量最大,吸附受CO23-影响较大。将110 g TiO2颗粒装备成过滤滤壶,对山西地下水(总砷含量190μg/L)进行了除砷实验,经过3 600柱体积后,滤液中砷浓度低于10μg/L,符合国家饮用水标准。     

一株抗Cd2+菌株的筛选及其吸附性能

Cd2+为一种毒性金属元素,为了实际解决污水中低浓度重金属污染,实现污水达标排放,通过12C6+重离子束辐照诱变技术筛选到一株耐受Cd2+的菌株C2,研究其对Cd2+的抗性和低浓度Cd2+的吸附性能表明,Cd2+浓度≤100 mg/L时,C2菌株可以生长繁殖,但随Cd2+浓度升高受到抑制;SEM分析表明,受到Cd2+胁迫时,C2产生大量胞外产物与Cd2+形成络合物;吸附过程中菌粉表面空隙得到填充,形成凸起;红外光谱分析表明,吸附过程中的主要作用基团为醇羟基O—H键、氨基和酰胺基团;C2菌粉和固定化菌球都对Cd2+有较好的吸附能力,菌粉吸附效果比固定化菌球稍好;菌粉和固定化吸附剂的最佳吸附初始pH值为5~6.0,最佳投加量分别为1.0 g/L和10 g/L(实际含菌量为1.0 g/L);Cd2+浓度在2~20mg/L时,在最佳吸附条件下,菌粉和固定化吸附剂对Cd2+的吸附率均在90%左右;2种吸附剂吸附过程与Langmuir等温模型和拟二级动力学模型拟合最佳;热力学研究表明吸附反应均能自发进行。以上研究结果表明,C2菌粉和固定化吸附剂均可用于污水中低浓度Cd2+的去除。     

载钴活性焦对As(V)的吸附性能与去除效果

使用沉淀负载法制备了载钴活性焦,并研究了溶液pH值、反应时间、As(V)初始浓度以及共存阴离子等对载钴活性焦吸附去除水环境中As(V)的影响。结果表明,(1)载钴后活性焦的比表面积和孔容积分别提高了20.87%和43.47%;(2)载钴活性焦对As(V)最佳吸附pH值为4.0,当As(V)的初始浓度为10 mg/L时,As(V)去除率可达97%;(3)吸附过程符合准二级动力学模型(k2=0.66,R2=0.96),吸附等温线为Freundlich型(kF=8.227,1/n=0.396,R2=0.97);(4)稳定性实验验证了载钴活性焦的稳定性,钴不易脱附,最大脱附率仅为0.145%。     

复合纳米材料对土壤重金属离子吸持固化的模拟研究

土壤中过量重金属离子可通过食物链和地表水系统危害人群健康。通过土柱淋溶模拟实验,研究了SiO2-Al2O3-Fe2O3等复合纳米材料对土壤溶液中Cu2+、Cd2+、Pb2+、Zn2+和Ni2+的吸持与固化特征。分别向重金属含量4倍于土壤二级标准(GB15618-1995)的土壤中添加0%、4%、6%和10%的复合纳米材料,分析不同深度土壤渗滤液以及土柱上栽培植物不同部位中重金属的含量。结果表明,碱性壤质土壤中重金属向下的迁移量很少;在含4%复合纳米材料土柱中,其吸持固化土壤溶液中63%的Cu、79%的Cd、68%的Pb、89%的Zn和76%的Ni;在含6%复合纳米材料土柱中,其吸持固化土壤溶液中82%的Cu、92%的Cd、76%的Pb、91%的Zn和88%的Ni;再增加土柱中复合纳米材料的含量,其吸持固化效果并不再显著增加。