磺酰脲类除草剂研究进展

本文较全面地概述了近几年国内外有关的磺酰脲类除草剂的分析测试和降解方式等方面的研究现状，着重讨论卫磺酰脲类化合物的结构活性相关和风险评价等方面的研究进展。     

多重环境因子对氟胺磺隆在土壤中降解的影响

氟胺磺隆作为普遍使用的一种磺酰脲类除草剂,已经对土壤和作物造成了危害,其环境行为受很多物理化学或生物因素的影响.为探明不同环境因素对氟胺磺隆在土壤中降解程度的影响,通过实验室内模拟培养的方法,研究了土壤微生物、不同土壤类型、水溶性有机物（dissolved organic matter,DOM）、温度、土壤含水量等因素对氟胺磺隆在土壤中降解的影响.结果表明,各种环境因子：温度、湿度、土壤微生物和土壤类型等均在不同程度上影响了氟胺磺隆的土壤降解速率.土壤微生物量、土壤有机质和DOM的增加均有利于氟胺磺隆在土壤中的降解,并且土壤pH的降低,也会促进氟胺磺隆在土壤中的降解.其中,土壤微生物是影响氟胺磺隆土壤降解的主要因素.该研究结果将为一些生物和物理化学因子调节氟胺磺隆在土壤中消散提供初步数据.     

三唑磷在土壤中的降解与吸附特性

三唑磷农药在江西红壤，河南二合土和东北黑土中均具易降解性，其土壤降解半衰期分别为28．3，3．75、3．28d，降解速率次序为东北黑土〉河南二合土〉江西红壤。土壤对三唑磷的吸附性能强弱次序为：河南二合土〈江西红壤〈东北黑土。其Freundich吸附常数分别为2，17．6，70．100。尽管河南二合土对三唑磷农药的吸附性弱（koc〈300）．且三唑磷的水溶解度〉30mg／kg，但由于三唑磷农药的易土壤降解性，正常施用，其对地下水的实际污染风险较小。     

磺酰脲类除草剂的残留分析

磺酰脲类除草剂是一类新型超高效除草剂，大约包括２Ｖ化合物，已被广泛用于禾谷作物防除阔叶杂草以及某些禾本科杂草，该类除草剂在环境中的残留浓度〈１μｇ．ｋｇ＾－１水平。常规的分析方法包括生物鉴定，酶免疫分析，气相色谱法和高效液相色谱法（ＨＰＬＣ）、ＨＰＬＣ／ＭＳ联用后，可以准确测定复杂环境样中磺酰脲类除草剂的痕量残留。     

氯嘧磺隆降解菌的筛选及对污染土壤的生物修复

采用富集培养方法从江苏某激素研究所污水处理池排污口污泥中分离得到1株氯嘧磺隆降解菌,经菌株形态学特征和26S rDNA序列分析,鉴定为胶红酵母菌（Rhodotorula mucilaginosa ）.经降解条件优化,菌株对含100mg/L氯嘧磺隆的无机盐培养基中氯嘧磺隆的最佳降解条件为：接种量2.5%,培养温度28℃,pH 6.0,培养5d后降解率为87.33%;在氯嘧磺隆初始浓度为10mg/kg（干土）的模拟污染土壤中,菌株最佳降解条件为：接种量2.5%,温度25℃,pH 6.0,土壤含水量30%,静息培养30d后降解率为90.74%.土壤修复实验结果表明,施加胶红酵母菌后减轻了氯嘧磺隆对小麦幼苗的药害,在氯嘧磺隆浓度为10mg/kg的土壤中投加降解菌后,小麦的出苗率、株高、根长及鲜重均明显高于未投加降解菌的对照组（P < 0.05）.     

磺酰脲类除草剂在硅胶G表面的光解

应用高效薄层析方法研究了苄嘧磺隆，甲磺隆，氯磺隆，氯嘧磺隆4种磺酰脲类除草剂在氙灯与太阳光下的光解动力学，以及8种有机色素对苄嘧磺隆光降解的影响。结果表明4种除草剂在硅胶G表面的降解呈一级动力学反应；有机色素对除草剂的降解均表现显著的猝灭效应。其中以姜黄素的猝灭作用最强，色素剂量与光解中的猝灭效应存在着显著的相关性。色素剂量加大，猝灭效应加强。     

磺酰脲类除草剂在环境中的光降解研究——水溶液中的光解动力学

以汞灯为光源,研究了甲黄隆,苯黄隆,氯黄隆,氯嘧黄隆,苄嘧黄和胺苯黄隆６种磺酰脲类除草剂在水液中的光解动力淡。结果表明,５种磺酰的降解呈一级动力学反应;体系的ＰＨ值对降解速率影响不明显,光强的影响较明显著;Ｈ２Ｏ２丙酮和溶解有机质均可促进磺酰光解;党妥氧对该类除草剂光解的影响表现为光氧化与淬灭２种作用的竞争。     

太湖区域13种磺酰脲类除草剂污染特征

为了解太湖区域磺酰脲类除草剂污染水平、空间分布,作者于2019年10月对太湖及主要入湖河道开展了13种磺酰脲类除草剂监测分析,采用在线固相萃取-高效液相色谱联用三重四级杆质谱法,对采集的55个地表水样进行了分析测定.结果 显示,磺酰脲类除草剂在太湖和22条入湖河道中站点检出率分别为100％、90.9％,检出种类为7种、8种,浓度总值为1.69～38.1 ng/L、ND～70.7 ng/L;若以农产品中最大残留量的1％作为地表水中磺酰脲类除草剂限值(500ng/L～1 μg/L)参考,污染水平总体不高;甲磺隆(浓度范围ND～50.64 ng/L,检出率94.5％)和苄嘧磺隆(浓度范围ND～12.8 ng/L,检出率92.7％)残留最高、分布最广,氯嘧磺隆和烟嘧磺隆其次,浓度合计占总值85％以上.受区域农业种植面积及种类、河道流向和水量影响,宜兴市入湖河道污染水平高于其他地区,并社渎港最高;太湖西北部竺山湖、西部沿岸区污染相对较重,并呈向东南递减趋势.     

磺酰脲类除草剂DPX-E9636的水解机理

对室温下ＤＰＸ－Ｅ９６３６的水解产物分离纯化后,运用元素分析,紫外光谱及＾１Ｈ核磁共振鉴定了主要产物的结构。产物为：１－（４,６－二甲氧基嘧啶基－２）－３（乙磺酰基－２－吡啶基）脲、Ｎ－（４,６－二甲氧基嘧啶基－２）－３－乙磺酰基－２－胺基吡啶、３－乙磺酰基－２－胺基吡啶及２－胺基－４,６－二甲氧基嘧啶,由此推测了ＤＰＸ－Ｅ９６３６的水解机理。     

磺酰脲类除草剂对土壤质量生物学指标的影响

微生物生物量碳、微生物生物量氮和土壤矿化氮是3个重要的表征土壤质量的生物学指标,本文通过实验室培养研究了3种磺酰脲类除草剂（氯磺隆、甲磺隆、苄嘧磺隆）对上述生物学指标的动态影响．研究结果表明,用量为1mg/kg的3种磺酰脲类除草剂均明显降低了微生物生物量和氮的矿化量,尤其是施用后最初10d降低幅度比较显著．此后随着时间的增加,除草剂的抑制效应逐步减小．氯磺隆对这些土壤生物学指标的影响明显大于甲磺隆和苄嘧磺隆．     

Effects of phosphate on the adsorption of glyphosate on three different types of Chinese soils

Glyphosate （GPS） is a non-selective, post-mergence herbicide that is widely used throughout the world. Due to the similar molecular structures of glyphosate and phosphate, adsorption of glyphosate on soil is easily affected by coexisting phosphate, especially when phosphate is applied at a significant rate in farmland. This paper studied the effects of phosphate on the adsorption of glyphosate on three different types of Chinese soils including two variable charge soils and one permanent charge soil. The results indicated that Freundlich equations used to simulate glyphosate adsorption isotherms gave high correlation coefficients（0.990-0.998） with K values of 2751, 2451 and 166 for the zhuanhong soil（ZH soil, Laterite）, red soil（ RS, Udic Ferrisol） and Wushan paddy soil（WS soil, Anthrosol）, respectively. The more the soil iron and aluminum oxides and clay contained, the more glyphosate adsorbed. The presence of phosphate significantly decreased the adsorption of glyphosate to the soils by competing with glyphosate for adsorption sites of soils. Meanwhile, the effects of phosphate on adsorption of glyphosate on the two variable charge soils were more significant than that on the permanent charge soil. When phosphate and glyphosate were added in the soils in different orders, the adsorption quantities of glyphosate on the soils were different, which followed GPS-soil 〉 GPS-P-soil = GPS-Soil-P 〉 P-soil-GPS, meaning a complex interaction occurred among glyphosate, phosphate and the soils.     

Degradation of 14C-glyphosate and aminomethylphosphonic acid (AMPA) in three agricultural soils

Glyphosate (N-phosphonomethyl glycine) is the most used herbicide worldwide. The degradation of 14C-labeled glyphosate was studied under controlled laboratory conditions in three di erent agricultural soils: a silt clay loam, a clay loam and a sandy loam soil. The kinetic and intensity of glyphosate degradation varied considerably over time within the same soil and among di erent types of soil. Our results demonstrated that the mineralization rate of glyphosate was high at the beginning of incubation and then decreased with time until the end of the experiment. The same kinetic was observed for the water extractable residues. The degradation of glyphosate was rapid in the soil with low adsorption capacity (clay loam soil) with a short half-life of 4 days. However, the persistence of glyphosate in high adsorption capacity soils increased, with half-live of 19 days for silt clay loam soil and 14.5 days for sandy loam soil. HPLC analyses showed that the main metabolite of glyphosate, aminomethylphosphonic acid (AMPA) was detected after three days of incubation in the extracts of all three soils. Our results suggested that the possibility of contamination of groundwater by glyphosate was high on a long-term period in soils with high adsorption capacity and low degrading activities and/or acid similar to sandy loam soil. This risk might be faster but less sustainable in soil with low adsorption capacity and high degrading activity like the clay loam soil. However, the release of non-extractable residues may increase the risk of contamination of groundwater regardless of the type of soil.     

硫丹及硫丹硫酸酯的土壤降解特性

在实验室条件下研究了α-硫丹、β-硫丹及硫丹硫酸酯在东北黑壤土、江苏水稻土、江西红壤土和河南二合土4种土壤中的降解特性.结果表明,硫丹及硫丹硫酸酯降解过程可用一级动力学方程描述.4种土壤中,β-硫丹的降解半衰期(DT50)分别为39、10、14和13d;α-硫丹的DT50分别为72、56、105和42d;硫丹硫酸酯的DT50分别为39、41、53和34d,因此,硫丹硫酸酯在土壤中的持久性值得关注.α-硫丹在有机质含量丰富的土壤中降解较慢,β-硫丹在碱性土壤中降解较快.用一级动力学模型模拟的硫丹(α-硫丹+β-硫丹)和总硫丹(α-硫丹+β-硫丹+硫丹硫酸酯)降解过程的计算结果表明,硫丹的DT50为18～47d,总硫丹的DT50为48～77d.试验观察到的硫丹降解产物依次为硫丹硫酸酯、硫丹二醇、硫丹醚和硫丹羟基醚.     

除草剂草萘胺在土壤中的降解与吸附行为

采用色谱学(HPLC和GC-MS)和光谱学(UV和Ft-IR)方法研究了除草剂草萘胺在3种土壤(黑土、砖红壤和黄棕壤)中的降解和吸附行为,并对草萘胺土壤中降解的影响因素、降解产物和吸附机理进行了分析.结果表明,在本实验条件下,草萘胺降解速率随土壤温度(15～35℃)和有机质含量(r=0.9794)增加而加快;灭菌条件下的半衰期约是未灭菌时的3倍,土壤微生物是影响草萘胺在土壤中降解的主要因素;草萘胺在黄棕壤中的降解途径可能是脱烷基,降解产物可能为/v-甲基-2-(1-萘氧基)丙酰胺和/V-乙基-2-(1-萘氧基)丙酰胺.草萘胺在黄棕壤、砖红壤和黑土上的吸附系数(Kf)值分别为1.29、3.43和13.36,3种土壤上的吸附自由能(AG)均小于40U·mol-1,即以物理吸附为主,其吸附行为可用Freundlich模型描述.红外光谱学研究进一步证实了3种土壤对草萘胺吸附容量差异是黑土,砖红壤,黄棕壤.     

Adsorption of chloroacetanilide herbicides on soil (I). Structural influence of chloroacetanilide herbicide for their adsorption on soils and its components

Adsorption of chloroacetanilide herbicide acetochlor,alachlor, metolachlor and propachlor on soils and soil components was determined, and the structural differences of these herbicides were used to explain the order of sorptivity. Adsorption isotherms for all herbicide-soil combinations conformed to the Freundlich equation, and Kf increased with increasing soil organic carbon content. Kd on soil humic acid was greater than that on clay, but association of humic acid with clay reduced the overall adsorption. On all soils and soil humic acids, herbicide adsorption decreased in the order: metolachlor > acetochlor > propachlor > alachlor. On Ca²⁺-montmorrilonite, the order changed to metolachlor > acetochlor > alachlor > propachlor. FT-IR spectra of herbicide-clay or herbicide-humic acid-clay mixtures showed that H-bonding and charge transfer were the primary interaction pathways between these compounds and the surface of clay or humic acids. The different moieties attached to 2-chloro-acetanilide and their unique arrangement may have influenced the binding mechanisms and thus the sorptivity of these herbicides. This study indicates that the structural difference of pesticides in the same classes may be used as a molecular probe to obtain a better understanding of sorption mechanisms of pesticides on soil.     

除草剂绿草定-2-丁氧基乙酯的降解特性及降解机制研究

按照《化学农药环境安全评价试验准则》的规定并参考美国EPA导则,采用室内模拟试验方法,研究了绿草定-2-丁氧基乙酯在环境中的降解特性.结果表明,25℃时绿草定-2-丁氧基乙酯在pH =4、7、9缓冲溶液中的水解半衰期分别为533 d、21.8 d、＜1 d;高温、碱性条件下绿草定-2-丁氧基乙酯极易水解,其水解反应速率随反应介质pH值的增大、反应温度的升高而增大;初步确定绿草定-2-丁氧基乙酯分子在水溶液中生成的水解产物主要是绿草定.绿草定-2-丁氧基乙酯在土壤中迅速降解,酸性土壤中其降解趋势遵循一级动力学模型,中性和碱性土壤中其降解动态不能用一级动力学模型进行简单的拟合;绿草定-2-丁氧基乙酯在土壤中的降解形式主要为化学水解作用,降解生成绿草定和丁氧基乙醇;土壤pH和有机质含量是影响其土壤降解速率的主要因素,pH和有机质含量越高,其土壤降解速率越快.在人工光源氙灯条件下,绿草定-2-丁氧基乙酯在水溶液和土壤表面的光化学降解均符合一级动力学反应,不同介质对绿草定-2-丁氧基乙酯光解的影响差异显著.     

毫米级根际微域磺胺嘧啶的降解动态研究

采用特制根际箱,研究了玉米根际效应作用下磺胺嘧啶在土壤中的降解动态.在空间上将根-土界面(0~5 mm)细化到1 mm,箱内磺胺嘧啶剂量分别设为1 mg·kg-1和5 mg·kg-1,分别在出苗后第20、40和60 d取样,并将磺胺嘧啶降解率与根-土界面4种有机酸含量进行回归分析,从而得出影响磺胺嘧啶在根际土壤降解的关键因素.结果表明,种植作物可有效促进磺胺嘧啶的降解,且磺胺嘧啶的最大消减水平发生在距离根室3 mm的近根区,降解顺序依次为:近根际根室远根际.通过对不同剂量磺胺嘧啶胁迫下有机酸响应的相关分析发现,苹果酸和乙酸是影响磺胺嘧啶在根际土壤中降解的关键因素之一.     

Adsorption and correlation with their thermodynamic properties of triazine herbicides on soils

IntroductionAdsorptionofherbicidesonsoilfromwaterisanimportantfactoraffectingtheirfate,biologicalactivity,andpersistenceinsoil watersystem .Itisoftenaffectedbyseveralpropertiesofsoil.Betterunderstandingofadsorptionanditsaffectingfactorswillmakeitpossibletoadjusttheherbicidedosageaccordingtosoilproperties,thusreducingtheenvironmentalpollutionofherbicidesintheenvironment.Fig .1　StructuresofthreetriazineherbicidesAmongthepost emergentherbicides,triazineherbicidesaremostcommonlyusedworldwideonco…     

土壤有机质对土霉素在土壤中吸附-解吸的影响

采用批量平衡方法,研究了土霉素在原土及去除有机质土壤中的吸附和解吸.结果表明,土霉素在原土和去除有机质土壤中的吸附和解吸等温线均不同程度地偏离线性模型,其中Freundlich模型可以对吸附和解吸数据进行良好的非线性拟合,在不同土壤以及不同土壤处理中的拟合相关系数(r)均达到极显著水平.去除有机质能够降低土霉素在土壤中的吸附容量(lgKf),但增加了吸附强度(1/n).土霉素在土壤上的解吸过程存在明显的滞后现象,在所设土霉素浓度范围内,土霉素在褐土和红壤中的平均滞后系数(HIa)分别为0.039和0.015;去除有机质后的褐土和红壤对土霉素的解吸滞后现象显著增强(P<0.01),其HIa分别增加到0.068和0.028.     

吸附材料对钒矿污染土壤重金属的稳定化效果

选用壳聚糖和活性炭两种吸附材料,分别以不同的质量比添加到供试土壤中,固化后进行毒性浸出实验,研究吸附材料对土壤中钒(V)、铬(Cr)的稳定化效果,并通过表征吸附材料的红外光谱(FTIR)和X射线光电子能谱(XPS)探究吸附材料对V、Cr的稳定化机理.结果表明,壳聚糖对V、Cr均有较好的稳定化效果,活性炭对V的稳定化效果不稳定,对Cr的稳定化效果很好.吸附材料添加量的改变对稳定化效果影响不大.稳定化30d时,0.5%壳聚糖对V、Cr的稳定化率分别为74.04%、46.77%;0.5%活性炭对V、Cr的稳定化率分别为1.86%、87.75%.FTIR和XPS表征结果表明,壳聚糖中含活性强的氨基和羟基较多,活性炭中含氨基、羟基较少.因此壳聚糖和活性炭可作为土壤重金属的稳定剂,使钒矿污染土壤得到修复.