Fate of anilide and aniline herbicides in plant-materials-amended soils

The fate of herbicides trifluralin, pendimethalin, alachlor and metolachlor in paddy field soils amended with plant materials was investigated. The plant materials were purple sesbania, vegetable soybean and rice straw. The investigation was performed at two temperatures (25 and 40 degrees C) and two soil water moistures (60 and 90% water-holding capacity). The results showed linear and Freudlich equations described the adsorption of amide compound to soil. Adsorption coefficient (K(d)) fit to linear equation were in general greater in plant material-amended soils than in non-amended soil, especially in soil amending with rice straw. Increasing temperature and soil water moisture content shortened the half-lives of compounds in various treated soils. The movement of compounds in the soil columns showed the maximum distribution of aniline type compound, trifluralin and pendimethalin, appeared at the upper top of 0 to 5 and 0 to 10 cm of soil column, respectively, and of anilide type, alachlor and metolachlor, were distributed at 0 to 25 cm of the soil column. The mobility of chemicals in the different treated soils was simulated by the behavior assessment model (BAM). There was no significant difference among different plant material incubated soils on dissipation and mobility of compounds in soils.     

除草剂在土壤中的吸附行为研究

除草剂在土壤上的吸附和解吸行为是支配该除草剂在环境中的生物有效性和持久性的重要因素之一 ,同时对于预测除草剂在土壤和潜层水中的运动也是有重要作用。本文从吸附机理、实验技术、动力学、影响因素、常数的计算方法等方面阐述了除草剂在土壤中的吸附行为及其环境学意义。     

Laboratory study on leachability of five herbicides in South Australian soils

Abstract

Norflurazon, oxadiazon, oxyfluorfen, trifluralin and simazine are herbicides widely used in the vineyards of the Barossa Valley, South Australia. The leaching behaviour of norflurazon, oxadiazon, oxyfluorfen and trifluralin was investigated on four key soils in the Barossa Valley. Leaching potential on packed soil columns and actual mobility using intact soil columns were investigated. On the packed soil columns, norflurazon was the most leachable herbicide. More of the herbicides were detected in the leachates from the sandy soils (Mountadam and Nuriootpa) than from the clayey soils (Lyndoch and Tanunda). Organic matter is generally low in soils in the Barossa region. Porosity and saturated conductivity significantly affect herbicide movement and in the sandy Mountadam and Nuriootpa soils, the water flux is greater than for the higher clay content Lyndoch and Tanunda soils. Increasing the time interval between herbicide application and the incidence of “rainfall”; reduced the amounts of herbicides found in the leachates. The use of intact soil columns and including simazine for comparison showed that both norflurazon and simazine were present in the leachates. Simazine was the first herbicide to appear in leachates. Sectioning of the intact soil columns after leaching clearly demonstrated that norflurazon and simazine reached the bottom of the soil columns for all soils studied. Greater amounts of norflurazon were retained in the soil columns compared with simazine. The other herbicides were mostly retained in the initial sections of the soil columns.     

阿特拉津在土壤中的环境行为研究进展

概述了阿特拉津在土壤中的迁移、降解及其对植物的影响等环境行为,阐述了土壤组成、土壤pH值以及温度、湿度等因素对各种环境行为过程的影响,并结合目前国内外的研究现状,提出了阿特拉津环境行为新的研究方向。     

改性木屑对水中苯胺的动态吸附

采用β-环糊精对木屑改性用于吸附苯胺,通过固定床实验考察了吸附床高度（10~30 mm）、进水流速（2.7~8.1 mL·min-1）和苯胺初始浓度（50~200 mg·L-1）对穿透曲线的影响,同时使用BDST模型对吸附穿透曲线进行拟合。结果表明,改性木屑可以有效吸附苯胺,随着高度的增加,穿透时间延长,固定床对苯胺的去除率增大;随着苯胺进水流速和初始浓度的增加,穿透时间缩短,固定床对苯胺的去除率降低;BDST模型对穿透曲线的拟合效果较好（Ct/C0=0.7,R2=0.999 0）,随着运行时间的增加,固定床的吸附速率常数（Ka）变小,对苯胺的吸附量（N0）增大;当改变流速时,运用该模型能较准确的预测吸附固定床的操作时间。     

苯胺污染事故应急处置技术评估体系及其应用

苯胺所造成的环境污染问题日益严重,如何正确地选择处理处置技术,对降低化学品所造成的影响有着极其重要的意义。为了在事故发生后能够最短时间内有效地消除污染物对环境的影响,选取最适合的处理处置技术,提出了苯胺污染事故处理处置技术评估指标体系,从技术性能、经济成本、环境影响和社会影响4个方面进行了评估指标选取;另外,采用基于群决策的层次分析法(AHP)进行了数据处理,以降低评估过程中专家的主观性对评估结果的影响,结合评分标准最终获得最佳的应急处理处置技术方案,可为苯胺环境污染事故应急预案的制定与事故应急处理处置技术的选取提供参考。     

以不同底物和苯胺为燃料的微生物燃料电池的产电特性

通过构建空气阴极型双室微生物燃料电池,研究了以500 mg/L苯胺作为唯一燃料以及苯胺和不同底物共基质时MFC对苯胺的降解特性及MFC的产电性能。结果表明,在外电阻1000Ω,以500 mg/L苯胺为唯一燃料以及500 mg/L苯胺分别和500 mg/L乙酸钠,葡萄糖和可溶性淀粉作为共同基时的MFC运行周期分别为3、3.4、4.6和5 d;最大输出电压分别为273、450、428和380 mV;输出功率分别为142、225、201和160 mW/m2。苯胺去除率分别为68%、85.8%、71%和65%。内阻分别为931、524、564和751Ω,COD去除率分别为68%、85%、72%和65%。库伦效率分别为1.8%、7.9%、6.6%和4.5%。MFC可以使用苯胺作为唯一燃料,且当添加的基质不同时,MFC产电性能以及苯胺降解状况有所不同。利用MFC可以使苯胺高效快速降解的同时实现稳定的电压输出。     

Speciation of zinc in contaminated soils

The chemical speciation of zinc in soil solutions is critical to the understanding of its bioavailability and potential toxic effects. We studied the speciation of Zn in soil solution extracts from 66 contaminated soils representative of a wide range of field conditions in both North America and Europe. Within this dataset, we evaluated the links among the dissolved concentrations of zinc and the speciation of Zn(2+), soil solution pH, total soil Zn, dissolved organic matter (DOM), soil organic matter (SOM) and the concentrations of different inorganic anions. The solid-liquid partitioning coefficient (K(d)) for Zn ranged from 17 to 13,100Lkg(-1) soil. The fraction of dissolved Zn bound to DOM varied from 60% to 98% and the soil solution free Zn(2+) varied from 40% to 60% of the labile Zn. Multiple regression equations to predict free Zn(2+), dissolved Zn and the solid-liquid partitioning of Zn are given for potential use in environmental fate modeling and risk assessment. The multiple regressions also highlight some of the most important soil properties controlling the solubility and chemical speciation of zinc in contaminated soils.     

钛基修饰氧化物电极制备及降解苯胺的研究

采用高温热氧化法制备了钛基锡锑铅氧化物电极,得到的电极具有较高的电催化活性和良好的稳定性,并以苯胺为目标有机物考察了电压、电解质的浓度、pH值和电解时间等因素对苯胺去除率和化学需氧量COD等的影响.在外加电压为8 V,电解质硫酸钠的浓度为0.15 mol/L,电解200 mg/L的苯胺模拟废水,40 min苯胺去除率可达100%,180 min时COD去除率达81.76%.     

生物强化技术应急处理苯胺泄漏事故

为考察生物强化技术用于苯胺水污染事故应急处理的可行性,以化工园区苯胺泄漏事故为场景,采用高效苯胺降解菌AN-P1强化序批式活性污泥法(SBR),应急处理100～500 mg/L苯胺废水。结果表明,生物强化系统应急处理500 mg/L以下苯胺废水,启动时间约3～4周期(2 d),稳定运行后对苯胺的去除率在96.3%以上,化学需氧量(COD)的去除率在81.3%以上;曝气量(溶解氧)是影响降解的制约因素,其最适曝气量为0.5 m3/h。对处理系统中微生物超氧化物歧化酶(SOD)检测表明,强化系统SOD被诱导产生,对照系统中SOD被抑制,强化系统SOD酶活是对照系统的468倍,表明强化系统可有效消除苯胺降解产生的超氧阴离子自由基的氧化压力。     

球磨硫铁矿-过硫酸盐联合降解水中硝基苯和苯胺

采用湿式球磨法制备微纳级硫铁矿粉末,研究了球磨硫铁矿(BMP)和过硫酸盐(PS)联合处理对水环境中硝基苯(NB)及其还原产物苯胺(AN)的降解效果,分别考察了BMP投加量、溶液初始pH和PS投加量对NB和AN降解的影响,采用TEM、XRD、FT-IR和XPS对反应前后的BMP进行了表征,分析了反应溶液中TOC和主要离子的变化,采用响应面法设计多因素实验,对反应条件进行了拟合和优化。结果表明,NB浓度与BMP投加量呈负相关关系,AN浓度与PS投加量呈负相关关系,pH在酸性和中性条件下NB和AN降解效果好。当BMP投加量为5 g·L⁻¹时,NB去除率达99%;当PS投加量为2.5 g·L⁻¹时,AN浓度低于1 mg·L⁻¹。BMP/PS联合处理可以高效降解NB并消减还原产物AN。采用二次多项式和逐步回归法拟合NB去除率、AN浓度和反应条件之间的关系,模拟值与验证实验结果相近,模型精度较好。表征结果表明,BMP单独处理时Fe(Ⅱ)和S²⁻作为活性物质与NB反应,生成${\rm{SO}}_3^{2 - }$和Fe(Ⅲ)以及中间产物AN;联合处理中BMP中的Fe(Ⅱ)活化PS生成具有强氧化性的${\rm{SO}}_4^{ - \cdot }$和HO·,其可与AN反应生成${\rm{SO}}_4^{2 - }$和单质S,Fe(Ⅱ)和Fe(Ⅲ)与水中的OH⁻或O₂反应,生成铁氧化物。BMP/PS联合处理可以快速高效彻底降解NB,在含NB废水处理或NB污染地下水修复中具有应用潜力。     

Fast determination of phenoxy acid herbicides in carrots and apples using liquid chromatography coupled triple quadrupole mass spectrometry

A fast, simple and inexpensive method has been developed for the analysis of phenoxy acid herbicides: 2,4-dichlorophenoxyacetic acid (2,4-D), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2-(4-chloro-o-tolyloxy)propionic acid (MCPP), 2-(4-aryloxyphenoxy)propionic acid (Fluazifop) and 2-(4-aryloxyphenoxy)propionic acid (Haloxyfop) in carrots and apples by liquid chromatography coupled to triple quadrupole mass spectrometry (LC/MS/MS). The compounds were analyzed by QuEChERS (quick, easy, cheap, effective, rugged, safe) methodology without cleanup.

The recoveries were performed at two spiked levels (0.05 and 0.5 mg/kg) for both matrices with six replicates for each level. The mean recoveries ranged from 70–92% for both apples and carrots. The precision of the method expressed as relative standard deviation (RSD%) was found to be in the range 3–15%. For all compounds, good linearity (r² > 0.99) was obtained over the range of concentration from 0.05 μ g/mL to 0.5 μ g/mL, corresponding to the pesticide concentrations of 0.05 mg/kg and 0.5 mg/kg, respectively. The determination limits (LOQs) ranged from 0.01 ng/mL to 1.3 ng/mL in solvent, whereas, the LOQs calculated in matrix ranged from 0.05 ng/g to 21.0 ng/g for apples and from 0.06 ng/g to 10.2 ng/g for carrots. The developed methodology combines the advantages of both QuEChERS and LC/MS/MS producing a very rapid, sensitive and cheap method useful for the routine analytical laboratories.     

零价铁对土壤中2-氯硝基苯的还原作用

在常温常压下利用零价铁(Fe0)还原土壤中的2-氯硝基苯(o-CNB),研究反应条件对还原率的影响以及反应产物在不同反应阶段的变化.GC-MS检测结果显示,o-CNB在还原过程中先生成2-氯亚硝基苯,最终生成2-氯苯胺.反应时间、Fe0用量、温度和土壤初始pH值等均会对o-CNB的还原率产生影响,其中土壤初始pH值控制在偏酸性、土壤温度较高时能显著提高其还原率.当o-CNB的初始浓度约为2.5×10-6 mol/g,Fe0加入量是25 mg/g时,经过4 h反应,o-CNB的还原率可达99%以上.此外,还初步探讨了Fe0还原o-CNB的反应机理.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine～ amitrole～ simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K_ow) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.     

微波辅助酸酐改性黄麻对水中苯胺的吸附性能

为开发天然纤维材料用于有机污染应急处置,以黄麻为原料采用微波快速改性制备了新型吸附剂,通过单因素实验对反应时间、反应温度和酸酐用量进行了优化,探究了改性材料对苯胺的吸附性能,并对其在应急处置中的应用可行性进行了分析。结果表明,反应时间20 min、温度130℃、酸酐用量3 g为最佳制备条件;改性材料对苯胺的吸附在30 min内基本完成,动力学拟合符合准二级动力学方程;在15℃下,改性材料对苯胺的饱和吸附量为113.64 mg/g,最佳pH为7左右,材料流阻小,可适用于突发污染的应急处置。     

窄前沿高压脉冲放电等离子体降解水中苯胺

采用高压电极在气相、接地极在液相的针-板式放电装置,考察了窄前沿高压脉冲放电等离子体降解水中苯胺的效果。比较了窄前沿高压脉冲放电(上升沿为25 μs)和常规高压脉冲放电(上升沿为5 μs)的脉冲波形、单脉冲能量、脉冲功率、对苯胺的降解效果、能量利用率以及发射光谱的差异。实验结果表明,窄前沿高压脉冲和常规高压脉冲放电的单脉冲能量分别为0.0078 J和0.016 J,脉冲功率分别为1.02 W和1.285 W,放电60 min后对苯胺的降解率分别为90%和55%,前者的能量利用率是后者的 2.06倍。利用多通道光纤光谱仪在气相放电中检测到5种活性物质,分别是O、O+、N2、N和·OH,且窄前沿脉冲产生活性物质的信号强度高于常规脉冲。     

有机配体对铁电絮凝体系中羟基自由基氧化降解苯胺的影响

铁电絮凝(Fe-EC)是一种高效的水处理方法,但其中有机污染物的去除机制尚不明晰。为研究有机废水中常见的有机配体对铁电絮凝过程中羟基自由基(·OH)产生以及有机污染物降解的影响,采用了对照实验、淬灭实验和电子自旋共振（ESR）等测试方法。结果表明：草酸(H₂C₂O₄)和乙二胺四乙酸(EDTA)能有效促进铁电絮凝对苯胺(AN)的氧化降解,而·OH是起主要作用的活性氧化物;草酸和EDTA体系中主要存在的Fe(Ⅱ)络合物浓度与羟基自由基产率成正相关关系,1 mol的Fe(Ⅱ)-EDTA²⁻会产生235 mmol的·OH,是草酸的9倍;EDTA会与污染物竞争羟基自由基。进一步分析可知,在铁电絮凝体系中,EDTA的浓度为0.05 mmol·L⁻¹时,对苯胺氧化降解的促进效果最佳。以上研究结果可为认识铁电絮凝中污染物的去除机制提供参考。     

Fate and transport of carbamazepine in soil aquifer treatment (SAT) infiltration basin soils

The transport and fate of the pharmaceutical carbamazepine (CBZ) were investigated in the Dan Region Reclamation Project (SHAFDAN), Tel-Aviv, Israel. Soil samples were taken from seven subsections of soil profiles (150 cm) in infiltration basins of a soil aquifer treatment (SAT) system. The transport characteristics were studied from the release dynamics of soil-resident CBZ and, subsequently, from applying a pulse input of wastewater containing CBZ. In addition, a monitoring study was performed to evaluate the fate of CBZ after the SAT. Results of this study indicate adsorption, and consequently retardation, in CBZ transport through the top soil layer (0-5 cm) and to a lesser extent in the second layer (5-25 cm), but not in deeper soil layers (25-150 cm). The soluble and adsorbed fractions of CBZ obtained from the two upper soil layers comprised 45% of the total CBZ content in the entire soil profile. This behavior correlated to the higher organic matter content observed in the upper soil layers (0-25 cm). It is therefore deduced that when accounting for the full flow path of CBZ through the vadose zone to the groundwater region, the overall transport of CBZ in the SAT system is essentially conservative. The monitoring study revealed that the average concentration of CBZ decreased from 1094 ± 166 ng L⁻¹ in the recharged wastewater to 560 ± 175 ng L⁻¹ after the SAT. This reduction is explained by dilution of the recharged wastewater with resident groundwater, which may occur as it flows to active reclamation wells.     

Adsorption behavior of RH‐5992 insecticide onto sandy and clay loam forest soils

Abstract

Adsorption‐desorption behavior of RH‐5992 [Mimic®, N'‐t‐butyl‐N'‐(3,5‐dimethylbenzoyl)‐N‐(4‐ethylbenzoyl) hydrazine] in sandy and clay loam forest soils was studied using the batch equilibrium method. Adsorption was higher in the clay loam soil than in the sandy loam, and increased linearly with RH‐5992 concentration, but decreased with increasing pH and temperature. The adsorption data fit better to the Freundlich, than to the Langmuir equation. The K_D (linear adsorption constant) and K_F (Freundlich constant) were similar for each soil at 5, 15 and 25°C and decreased with increase of temperature, indicating that the enthalpy of adsorption was negative. The exponent of the Freundlich equation was close to unity for both soils at all three temperatures. The low E_a (energy of activation) indicated a diffusion‐controlled process during the initial stages of adsorption. The desorption isotherm differed from that of adsorption, and the linear desorption constant, K_D(d), was ca 25 times higher than the K_D, indicating that adsorption of RH‐5992 was not readily reversible. Evaluation of thermo‐dynamic parameters confirmed the presence of strong bonds between the solute and soil. These findings suggest that RH‐5992 has a limited potential for downward mobility leading to groundwater contamination.     

新疆某矿冶区周边土壤重金属生物有效性与生态风险评价

矿业活动对土壤系统良性运转带来较大的环境负荷,矿区周边土壤重金属污染风险评估是土壤污染防治和资源可持续开发的关键。在应用单因子污染指数法、潜在生态风险指数法、风险评价编码法(RAC),并结合空间分析和冗余分析手段的基础上,对新疆某矿冶区周边土壤重金属生物有效性和生态风险进行了系统研究。结果表明：研究区土壤As、Cu、Mn和Cd超标率分别为88%、38%、49%和24%;土壤Mn、Zn、As和Cd弱酸可溶态高值区主要集中在尾砂库和收砷房的附近区域。单因子污染指数评价揭示As和Cu污染累积较为严重。潜在生态风险评价显示,As、Cd和Cu生态风险较高,Mn为低生态风险。风险编码法(RAC)评价结果进一步揭示Mn和Cd具有显著的土壤迁移风险。冗余分析结果显示,空间异质性是影响土壤重金属弱酸可溶态含量变异的主要因素。土壤pH和重金属弱酸可溶态是影响潜在生态风险指数(RI)的2个重要因素。综合风险评价手段与多尺度分析方法的联合应用有助于提高区域风险评价的准确性。