Watershed Regressions for Pesticides (warp) Models for Predicting Atrazine Concentrations in Corn Belt Streams1

Stone, Wesley W. and Robert J. Gilliom, 2012. Watershed Regressions for Pesticides (WARP) Models for Predicting Atrazine Concentrations in Corn Belt Streams. Journal of the American Water Resources Association (JAWRA) 48(5): 970‐986. DOI: 10.1111/j.1752‐1688.2012.00661.x Abstract: Watershed Regressions for Pesticides (WARP) models, previously developed for atrazine at the national scale, are improved for application to the United States (U.S.) Corn Belt region by developing region‐specific models that include watershed characteristics that are influential in predicting atrazine concentration statistics within the Corn Belt. WARP models for the Corn Belt (WARP‐CB) were developed for annual maximum moving‐average (14‐, 21‐, 30‐, 60‐, and 90‐day durations) and annual 95th‐percentile atrazine concentrations in streams of the Corn Belt region. The WARP‐CB models accounted for 53 to 62% of the variability in the various concentration statistics among the model‐development sites. Model predictions were within a factor of 5 of the observed concentration statistic for over 90% of the model‐development sites. The WARP‐CB residuals and uncertainty are lower than those of the National WARP model for the same sites. Although atrazine‐use intensity is the most important explanatory variable in the National WARP models, it is not a significant variable in the WARP‐CB models. The WARP‐CB models provide improved predictions for Corn Belt streams draining watersheds with atrazine‐use intensities of 17 kg/km² of watershed area or greater.     

Modeling urban films using a dynamic multimedia fugacity model

A thin film coats impervious urban surfaces that can act as a source or sink of organic pollutants to the greater environment. We review recent developments in the understanding of film and film-associated pollutant behavior and incorporate them into an unsteady-state version of the fugacity based Multimedia Urban Model (MUM), focusing on detailed considerations of surface film dynamics. The model is used to explore the conditions under which these atmospherically-derived films act as a temporary source of chemicals to the air and/or storm water. Assuming film growth of 2.1 nm d⁻¹ (Wu et al., 2008a), PCB congeners 28 and 180 reach air-film equilibrium within hours and days, respectively. The model results suggest that the film acts as a temporary sink of chemicals from air during dry and cool weather, as a source to air in warmer weather, and as a source to storm water and soil during rain events. Using the downtown area of the City of Toronto Canada, as a case study, the model estimates that nearly 1 g d⁻¹ of ∑₅PCBs are transferred from air to film to storm water.     

Adsorption of glyphosate on Brazilian subtropical soils rich in iron and aluminum oxides

Abstract

We investigated the adsorption of glyphosate onto five subtropical soils of Paraná and São Paulo states, Brazil, a region of intense agricultural activities, aiming at the determination of kinetic and isotherm adsorption parameters which enable the evaluation of the potential leaching of the herbicide. The adsorption was fast, being described by the pseudo-second order and intraparticle diffusion models, thus suggesting that mixed mechanisms are involved. The Oxisol containing the highest concentrations of metal oxides (209.5?g kg^?1 Fe₂O₃ and 160.2?g kg^?1 Al₂O₃) was the sample with the highest rate constant, indicating the adsorption sites are readily available. All the soils are rich in aluminum and iron oxides, explaining the Freundlich coefficients (K_F) between 642 and 1360?mg^1-1/n kg^?1 L^1/n, which are higher than most of the coefficients described for other soils around the world. The maximum desorption (15% of the adsorbed amount) was observed for the Oxisol. For the other soils, desorption ranged from 2 to 7%. These results suggest that the leaching of free glyphosate to nearby surface and groundwaters is unlikely unless excessive doses are used. The adsorption parameters are useful for managing the right doses applied to the crops, thus avoiding contamination of adjacent areas.     

改性粉煤灰对糖蜜废水的吸附效果及机理

采用改性粉煤灰(MCFA)吸附糖蜜废水中的有机污染物,对吸附行为和机理进行了考察和分析。结果表明,MCFA投加量为30 g/L及pH为5.0的优化条件下,COD去除率为88.6%,饱和吸附量为89.7 mg COD/g MCFA。准二级方程能更好地描述糖蜜废水在MCFA上的吸附动力学。颗粒内扩散方程结果表明孔扩散并非唯一的速度控制步骤。吸附平衡表明,Freundlich等温线最符合吸附模式,为优惠吸附。D-R模式中的吸附自由能Ea值推断更可能是物理吸附而不是化学吸附。吸附热力学参数ΔG0(<0)、ΔH0(5.130 kJ/mol)和ΔS0(19.936 J/(mol.K))表明MCFA对糖蜜废水的吸附过程为可行的,自发性的吸热反应。     

磁性海泡石吸附Cr(VI)特性及动力学

采用化学共沉淀法合成磁性海泡石,通过静态吸附实验研究磁性海泡石对Cr(Ⅵ)的吸附特性及其动力学。结果表明,磁性海泡石对Cr(Ⅵ)的吸附在90 min内即可达到平衡;体系的初始pH是影响磁性海泡石吸附Cr(Ⅵ)性能的重要因素;当废水中Cr(Ⅵ)的初始浓度为50 mg/L时,磁性海泡石的适宜投加量为10 g/L;随反应温度的升高,磁性海泡石对Cr(Ⅵ)的吸附量增加;温度为25、35和45℃时,磁性海泡石对Cr(Ⅵ)的饱和吸附量分别为3.32、3.72、4.08 mg/g;吸附动力学曲线可以用拟二级反应动力学模型拟合;内扩散和液膜扩散联合控制Cr(Ⅵ)在磁性海泡石上的吸附过程,其中内扩散的控速作用大于液膜扩散。     

Fe-MCM-41催化氧化2,4-二氯苯氧乙酸

采用水热法合成了Fe-MCM-41中孔分子筛,紫外、红外及XRD表征显示铁离子已进入中孔分子筛骨架。以H2O2为氧化剂形成类Fenton试剂,实验结果表明,在催化剂加入量为1 g/L、H2O2体积分数为6%、pH为4、反应时间为10h、反应温度为35℃的条件下,处理质量浓度为50 mg/L的2,4-D废水的降解率达94.95%。宏观动力学研究显示,该反应近似为一级反应,反应速率常数、表观活化能分别为0.21667 min-1和26.65 kJ/mol。     

羧甲基壳聚糖-膨润土复合吸附剂对Cu^2＋、Ni^2＋、Cr^3＋的吸附

用羧甲基壳聚糖和膨润土制备复合吸附剂,研究了复合吸附剂在不同参数下对Cu^2＋、Ni^2＋和Cr^3＋吸附的影响。结果表明,复合吸附剂对Ni^2＋的吸附可以很快达到吸附平衡,而对Cu^2＋和Cr^3＋的吸附分别在30min和180min时达到平衡;且pH值对吸附容量的影响很显著。通过计算不同温度下的热力学参数△G、△H和△S,3种金属的△G〈0,证实这3种金属吸附都是自发过程。Cu^2＋、Ni^2＋和Cr^3＋的吸附等温线较符合Langmuir型;反应动力学都更符合准二级吸附速率方程。     

一株抗Cd~（2＋）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。     

铁碳微电解-Fenton法预处理苯胺基乙腈生产废水的动力学研究

通过采用铁碳微电解-Fenton法预处理苯胺基乙腈生产废水的实验研究,分析了处理过程的COD降解动力学;同时研究了单纯活性炭吸附和微电解过程中COD去除率的变化。结果表明,铁碳微电解的初期COD降解过程近似符合一级反应动力学,并且得到微电解与活性炭吸附对铁碳微电解降解COD的关系式;Fenton反应中通过研究有机物浓度和过氧化氢初始浓度与反应进程的关系,建立了反应动力学模型;单纯吸附实验COD去除率在24h内快速下降,而微电解在相应时间内COD去除率波动较小,为实际应用提供了数据经验和理论依据。     

铁炭微电解法降解TAIC废水

TAIC（三烯丙基异氰脲酸酯）作为过氧化物交联或自由基反应交联的助交联剂被广泛应用。由于TAIC性质稳定难于生物降解,采用铁炭微电解法处理TAIC生产废水,并考察了铁炭比、进水pH值、反应时间对处理效果的影响,以及TAIC降解机理和反应动力学过程。结果表明,影响微电解工艺的因素主次关系为：pH>Fe/C质量比>反应时间;在最佳条件进水pH值为5,铁炭质量比为2：1,反应时间为135 min时,COD的去除率达到46%以上,TAIC的去除率达到48%以上。TAIC去除机理研究表明,微电解对TAIC废水的作用主要通过·H的还原和铁离子的絮凝作用,其中·H的还原作用是TAIC降解的主要原因。反应动力学分析表明,铁炭微电解法处理TAIC的降解过程基本符合二级反应动力学规律,通过建立模型并拟合出了TAIC降解的二级反应动力学方程。