除草剂草甘膦在几种土壤和矿物上的吸附研究

通过批平衡实验考察了草甘膦在几种性质不同土壤和矿物上的吸附行为。研究发现土壤对草甘膦有较强的吸附能力，草甘膦在土壤上吸附量的大小与土壤理化性质密切相关。草甘膦在土壤和矿物上的吸附符合Freundlich吸附方程，其在土壤上的吸附常数K与土壤粘粒含量呈正相关，并随土壤氧化铁和氧化铝含量增加而增加，而与土壤的pH呈显著负相关。草甘膦在高岭石上的吸附量要比在蒙脱石上大，而草甘膦在金属离子饱和的蒙脱石和高岭石上的吸附研究结果表明，草甘膦在钠、钙、铁离子饱和的矿物上的吸附能力依次为Fe-蒙脱石〉Ca-蒙脱石〉Na-蒙脱石和Fe-高岭石〉Ca-高岭石〉Na-高岭石。     

施用草甘膦除草剂对土壤质量影响的研究进展

草甘膦除草剂是农业生产中不可或缺的物资,过量使用会导致大量草甘膦及其衍生物在土壤中残留,对生态环境安全构成威胁。通过系统阐述草甘膦在环境中的迁移转化过程,以及草甘膦对土壤生物及环境质量的影响,着重分析了草甘膦对土壤蚯蚓、微生物群落的毒理效应,草甘膦与土壤其他污染物的协同效应和草甘膦驱动土壤碳氮磷生物地球循环变化。同时指出当前研究的不足,并提出下一步研究的重点:(1)加强草甘膦的降解机制和影响因素的研究,并筛选更高效降解能力的微生物菌株,提高草甘膦降解效率和修复草甘膦污染环境的能力;(2)定期开展农业环境中草甘膦的检测和风险评估,摸清草甘膦在喀斯特区的迁移路径,探索草甘膦在岩溶地质中的吸附和去除能力,以更好地评估岩溶地质的碳汇稳定性和水生生态系统的安全性;(3)借助酶化学计量学等研究方法,探明草甘膦在土壤中的转化速率、通量以及与微生物代谢和营养需求、环境效应之间的耦合关系。     

草甘膦的土壤酶效应研究

为了探讨当今世界使用量最大的除草剂——草甘膦的土壤环境效应,本文采用室内模拟方法,较为系统地研究了我国4类土壤：褐土、黄绵土、风沙土和红壤,共11个土样中4种主要酶类（脲酶、转化酶、磷酸酶以及脱氢酶）活性与草甘膦间的关系,计算并得到了能够表征土壤轻度污染的生态剂量值ED10。结果表明：非缓冲液法较好地反映了土壤酶的实际情况;草甘膦总体上激活土壤脲酶、转化酶和脱氢酶活性,最大增幅分别为190％、1372％和42％;抑制磷酸酶活性,最大幅度为35％;磷酸酶与草甘膦间为完．全抑制作用机理;激活脱氢酶活性揭示出草甘膦导致了土壤中微生物活性增强,从侧面反映出草甘膦是一种毒性较低的农药。计算获得4类供试土壤褐土、黄绵土、风沙土和红壤ED10值分别为168．3、438．5、35．1和141．4mg·kg^-1;在一定程度上用土壤酶活性比生物来表征土壤污染程度更敏感。土壤性质对草甘膦的毒性有重要影响。     

红壤不同粒径团聚体对草甘膦农药降解动力学的影响

草甘膦农药的大量喷施,使其在环境特别是土壤中的残留-累积风险日益突出,从团聚体粒径角度研究红壤不同粒径团聚体中草甘膦的降解动力学及其相互作用特征仍鲜有报道。基于此,本研究通过干筛筛分、室内控制培养、液质联用定量分析相结合等探究草甘膦降解残留,并进一步分析团聚体理化性质与草甘膦降解的关系。结果表明:1)不同粒径团聚体中,草甘膦残留量随降解时间不断减小,且粒径之间降解动力学差异不显著。降解半衰期为15.8～20.6 d,粒径最小的团聚体(0.25 mm)中草甘膦的降解半衰期最长,为20.6 d。草甘膦在土壤中的主要降解产物氨甲基磷酸(AMPA)的含量随着降解时间的增加而增加,且在第5d达到峰值,而后不断减小;不同粒径团聚体间AMPA含量差异显著(P0.05)。2)相关分析及主成分分析发现,草甘膦残留量与红壤团聚体中速效磷含量呈显著正相关(P0.05),而其降解产物AMPA含量与团聚体中酸性磷酸酶活性及N-乙酰氨基-β-葡萄糖苷酶活性呈显著正相关(P0.05)。团聚体粒径与草甘膦残留量间没有显著相关性,但与AMPA含量显著正相关(P0.05)。此外,草甘膦降解过程中,团聚体中有机质含量及β-葡萄糖苷酶、N-乙酰氨基-β-葡萄糖苷酶、酸性磷酸酶活性与团聚体粒径为显著负相关关系(P0.05)。由此表明:红壤不同粒径团聚体影响草甘膦降解速率,粒径最小的团聚体(0.25 mm)中草甘膦农药的降解速率最慢,但试验结束时,各粒径红壤团聚体中的草甘膦和AMPA含量均较高,可能会影响土壤健康及生态环境安全;此外,草甘膦降解与土壤磷素密切相关,后续研究需探讨磷亏缺或丰盈条件下,草甘膦农药的土壤环境特征,为后续农田草甘膦环境风险评估提供依据。     

土壤环境草甘膦残余现状及其检测技术评述

草甘膦在土壤中极易被吸附,代谢速度相对缓慢,在高剂量多年连续施用的情况下,其残余水平可能会逐年升高。我国是除草剂草甘膦的生产和使用大国,当前草甘膦环境残余水平及其生态效应的研究尚处于起步阶段,土壤环境草甘膦痕量残余检测的标准方法还未建立。跟进草甘膦环境行为及其生态风险评估研究,优化除草剂使用管理策略,对我国环境生态安全建设具有重要意义。本文从环境化学的角度,对土壤草甘膦的环境残余水平进行综述,对土壤环境样品中草甘膦痕量残余检测方法及技术研究进展做了评述。     

冀东野生大豆对草甘膦的耐性鉴定及耐性机制初步研究

为筛选耐草甘膦野生大豆种质并了解其耐性机制,本试验对采集于冀东地区的862份野生大豆进行了草甘膦的耐性鉴定。在草甘膦处理后,测定了高耐和敏感材料的莽草酸、丙二醛和叶绿素含量,过氧化物酶(POD)、过氧化氢酶(CAT)和超氧化物歧化酶(SOD)活性,以及草甘膦相关基因EPSPS表达量。结果显示,喷施草甘膦后,862份野生大豆材料中,药害等级在4级以上的材料占82.84%,3级占9.51%,2级占4.87%,1级占2.78%。筛选到高耐草甘膦的野生大豆材料Yong-33,其在1.125 kg a.i·hm^-2 草甘膦处理后植株存活率达到96.67%。经草甘膦处理后,与对照相比,高耐材料的叶绿素、丙二醛和莽草酸含量在检测的各时间点均无显著差异,敏感材料叶绿素含量显著降低,丙二醛和莽草酸含量显著升高;高耐材料POD、CAT和SOD活性以及EPSPS基因表达量均显著升高,而敏感材料酶活性及EPSPS基因表达量无显著差异。以上结果表明,野生大豆中存在高耐草甘膦的种质资源,在草甘膦处理后其植株内活性氧清除酶系活性升高,EPSPE基因上调表达,推测这是野生大豆对草甘膦耐性较好的原因。本研究筛选到的耐草甘膦野生大豆材料可为培育耐草甘膦栽培大豆新品种提供种质资源。     

水稻草甘膦耐性浓度的筛选及其生理指标测定

为培育耐草甘膦水稻新品种,本研究以5份辐射和化学诱变育成的耐草甘膦水稻种质为试验材料,进行草甘膦耐性浓度筛选和抗性生理指标测定。结果表明,通过对5份耐草甘膦水稻种质喷施不同浓度(1、2、3和4 g·L-1)的草甘膦,发现喷施4 g·L-1草甘膦可使敏感材料P1003全部死亡,能较好地区分草甘膦耐性和敏感材料;CA21是其中草甘膦耐性最强的水稻种质;随着草甘膦浓度的增加,CA21的莽草酸含量呈下降趋势,丙二醛(MDA)和叶绿素含量则无显著变化,但谷胱甘肽-S-转移酶(GSTs)活性显著增加;随着3 g·L-1草甘膦处理时间的延长,CA21的莽草酸含量无明显变化,MDA和叶绿素含量均呈下降趋势,GSTs活性显著增加。而敏感材料P1003,无论是随着草甘膦浓度的增加,或是随着3g·L-1草甘膦处理时间的延长,其莽草酸和MDA含量均明显增加,叶绿素含量明显下降,GSTs活性则无明显变化。综上,CA21具有耐草甘膦的生理特性,可用于草甘膦耐性分子机制或育种方面的研究。本研究为进一步解析水稻耐草甘膦的分子机理及耐草甘膦水稻育种提供了理论依据。     

干旱及复水条件下草甘膦对抗草甘膦大豆幼苗渗透调节物质和莽草酸含量的影响

为探明干旱胁迫及复水条件下不同剂量草甘膦对抗草甘膦大豆(RR1)幼苗叶片渗透调节物质、莽草酸(shikimic acid, SA)含量及根系活力的影响,采用盆栽试验,在大豆的第3复叶期进行水分胁迫5d和除草剂草甘膦处理,研究RR1幼苗叶片可溶性蛋白(soluble protein, SP)、可溶性糖(soluble sugar, SS)、游离脯氨酸(free praline, FP)、莽草酸(shikimic acid, SA)含量和根系活力(RA)的变化。结果表明,干旱胁迫前期RR1叶片的SP含量随草甘膦剂量的增加呈先升高后降低趋势,0.46kg/hm2叶片SP的含量最高,胁迫后期SP含量随草甘膦剂量的增加而降低;SS、FP和SA含量随草甘膦剂量的增加和胁迫时间的延长而增加,RA随草甘膦剂量的增加和胁迫时间的延长而降低。复水12d后,不同剂量草甘膦处理的各指标均有所恢复。干旱条件下,经草甘膦处理的RR1叶片的SP含量和RA低于草甘膦在正常水分条件下的处理,而SS、FP和SA含量相反。相关性分析表明,FP和SA含量与草甘膦剂量的相关关系最明显;而SS和SA含量与干旱胁迫时间的相关关系最明显。说明正常水分条件下,草甘膦对RR1幼苗造成的伤害经过一段时间后有所缓解;干旱胁迫加剧了草甘膦对RR1幼苗叶片渗透调节物质、莽草酸含量和根系活力的影响。抗草甘膦大豆主要通过积累FP、SS和SA对草甘膦和干旱胁迫做出响应。     

草甘膦对重金属污染土壤中铜、锌淋溶的研究

草甘膦分子结构中含有膦酸基、羧基和胺基等,具有强的络合重金属离子的能力,从而影响重金属在土壤中的环境化学行为.本文采用土柱淋溶方法,研究了不同浓度草甘膦溶液( 0、5 、20 和 50 mg/L)对污染土壤中重金属溶出的影响.草甘膦的存在降低了淋滤液的pH,增加了淋滤液中Cu和Zn的含量.逐层采样并分析了土壤中重金属的生物有效性含量,发现草甘膦的存在增加了土柱下层土壤重金属的生物有效性浓度.大量使用草甘膦会导致污染土壤中重金属的溶出,进而污染地下水.     

土壤及生物炭对草甘膦的吸附作用

为了确定生物炭修复草甘膦污染土壤的可行性,通过添加不同比例和种类的生物炭到土壤中,研究土壤对草甘膦的吸附效果。采用吸附动力学拟合、等温吸附分析、红外光谱测定分析方法。结果表明:草甘膦能强烈地吸附在红壤及稻壳炭、竹炭、竹柳炭中,相比于红壤,3种生物炭达到吸附平衡时间短。吸附动力学符合准二级动力学方程,等温吸附符合Freundlich吸附等温方程。Freundlich吸附等温方程中1/n数值均<1,表明红壤和3种生物炭对草甘膦的吸附方式是非线性吸附,且非线性程度大小为竹柳炭>竹炭>红壤>稻壳炭。生物炭添加到红壤中,可以提高红壤吸附草甘膦的量,生物炭添加比例越高,土壤吸附草甘膦的量也越高。土壤中添加生物炭比例相同时,竹炭使土壤吸附草甘膦的量最高,竹柳炭次之、稻壳炭最低。3种生物炭吸附草甘膦前后的红外光谱分析阐明了酚、胺、芳香烃、羧酸、羧酸盐、脂肪醚等在吸附过程中起重要作用。     

Changes in Soluble Manganese and Iron Concentrations of Tropical Wetland Soils as Influenced by Glyphosate Dosage

Glyphosate is largely used to control weeds in wetland soils of Brazil. We investigated changes in the chemistry of soluble manganese (Mn) and iron (Fe) in these soils as affected by glyphosate dosage. Triplicate samples of the A horizon of wetland soils with different organic-matter contents were incubated with deionized water (1:2) for 1, 3, and 30 days under flooding. Three different glyphosate doses (0, 0.048, and 0.096 g L^?1 m^?2) were spiked on the flooded water at the beginning of the incubation periods. After incubation, pH was measured and samples of the supernatant were collected for determination of Mn/Fe concentrations by atomic absorption. Glyphosate application impacted Mn but had no effect on pH and Fe. Soluble Mn concentrations decreased as glyphosate dosage increased for the high organic-matter soil after 3 days of incubation. It indicated that glyphosate application can change the chemistry of soil metals. The intensity of these changes depends on the glyphosate dosage, evolved metal, incubation time, and soil properties.     

Effects of incorporated corn residues on glyphosate mineralization and sorption in soil

In modern agricultural systems employing conservation tillage practices, glyphosate is widely used as a preplant burndown herbicide in a wide range of crops. Conservation tillage systems are characterized by a significant presence of crop residues at the soil surface so that glyphosate is applied to a soil matrix rich in poorly decomposed crop residues. Incorporation of corn residues in the range from 0.5 to 4% caused different effects on mineralization and sorption of [14C]glyphosate in sandy and sandy loam soils. More specifically, low levels of incorporated corn residues did not affect or slightly stimulated herbicide mineralization in the sandy and sandy loam soils, respectively. In the sandy soil, incorporation of the highest level of corn residues (4%) caused a decrease in [14C]glyphosate mineralization. [14C]Glyphosate sorption on both soil types was reduced in samples receiving high amounts of incorporated corn residues.     

The effect of glyphosate on soil microbial activity,microbial community structure,and soil potassium

The herbicide, glyphosate [N-(phosphonomethyl) glycine] is extensively used worldwide. Long-term use of glyphosate can cause micronutrient deficiency but little is known about potassium (K) interactions with glyphosate. The repeated use of glyphosate may create a selection pressure in soil microbial communities that could affect the nutrient dynamics such as K. The objective of this study was to determine the effect of single or repeated glyphosate applications on microbial and K properties of soils. A 54 day incubation study (Exp I) had a 3 × 5 factorial design with 3 soils (silt loam: fine, illitic, mesic Aeric Epiaqualf) of similar physical and chemical characteristics, that varied in long-term glyphosate applications (no, low, and high glyphosate field treatments) and five glyphosate rates (0, 0.5×, 1×, 2×, and 3× recommended field rates applied once at time zero). A second 6 month incubation study (Exp II) had a 3 × 3 factorial design with three soils (as described above) and three rates of glyphosate (0, 1×, and 2× recommended field application rates applied monthly). For each study microbial properties [respiration; community structure measured by ester linked fatty acid methyl ester (EL-FAME) analysis and microbial biomass K] and K fractions (exchangeable and non-exchangeable) were measured periodically. For Exp I, glyphosate significantly increased microbial respiration that was closely related to glyphosate application rate, most notably in soils with a history of receiving glyphosate. For Exp II, there was no significant effect of repeated glyphosate application on soil microbial structure (EL-FAME) or biomass K. We conclude that glyphosate: (1) stimulates microbial respiration particularly on soils with a history of glyphosate application; (2) has no significant effect on functional diversity (EL-FAME) or microbial biomass K; and (3) does not reduce the exchangeable K (putatively available to plants) or affect non-exchangeable K. The respiration response in soils with a long-term glyphosate response would suggest there was a shift in the microbial community that could readily degrade glyphosate but this shift was not detected by EL-FAME.     

Glyphosate Dissipation in Different Soils Under No-Till and Conventional Tillage

Glyphosate is the most used herbicide in Argentina, accounting for 62% of the commercialized pesticides on the market. It is used as a weed controller in no-till systems, and it is also applied to various genetically modified crops (e.g., soybean, corn, and cotton). Although it has a high solubility in water, it tends to adsorb and accumulate in agricultural soils. The main objectives of this work were to compare the dissipation of glyphosate and the accumulation of its metabolite aminomethylphosphonic acid (AMPA) over time in three soils from agricultural areas of Argentina under long-term management with no-till (NT) and conventional tillage (CT) practices. There were no differences in dissipation between NT and CT, indicating that the glyphosate-degrading microflora was not modified by the different tillage managements. Moreover, tillage practices did not alter the general soil properties; therefore, glyphosate bioavailability was not affected by NT or CT practice. Forty percent of the applied glyphosate was degraded within the first three days in all soils, indicating a fast initial dissipation rate. However, the dissipation rate considerably decreased over time, and the degradation kinetics followed a bi-exponential (or two-compartment) kinetic model. No differences were found between tillage practices. Dissipation was not related to the microbial activity measured as soil respiration. The fast decrease in the concentration of glyphosate at the beginning of the dissipation study was not reflected in an increase in the concentration of AMPA. The estimated half-lives for glyphosate ranged between 9 and 38 d. However, glyphosate bioavailability decreases over time, as it is strongly adsorbed to the soil matrix. This increases its residence time, which may lead to its accumulation in agricultural soils.     

Structural and Functional Characteristics of the Prokaryotic Community of Soddy-Podzolic Soil Influenced by the Herbicide Glyphosate

The amount of chemicals used for plant protection is growing due to the intensification of agriculture. Glyphosate is one of the most widely used herbicides; consequently, its influence on the microbial communities of agricultural soils is of interest. Structural and functional changes in the prokaryotic community in soddy-podzolic soil related to glyphosate treatment have been studied. No influence of the herbicide on the total number of prokaryotes or on the indices of substrate utilization intensity by the soil microbial community was observed. An increase in CO₂ emissions was a short-term effect of glyphosate application. The numbers of metabolically active Archaea and Acidobacteria decreased, while the number of metabolically active Actinobacteria increased after long-term exposure of the soil to glyphosate.     

Microbial degradation of fluometuron is influenced by roundup weatherMAX

Laboratory experiments were conducted to describe the influence of glyphosate and fluometuron on soil microbial activity and to determine the effect of glyphosate on fluometuron degradation in soil and by Rhizoctonia solani. Soil and liquid medium were amended with formulated fluometuron alone or with two rates of formulated glyphosate. The soil carbon mineralization was measured hourly for 33 days. The fluometuron remaining in the soil was quantified following 3, 6, 10, 15, 20, 30, and 40 days of incubation. The fluometuron remaining in medium and fungal biomass was measured after 1, 3, 6, 10, 15, and 20 days of incubation. The addition of glyphosate with fluometuron increased C-mineralization and increased the rate of fluometuron degradation relative to fluometuron applied alone. However, more fluometuron remained in the media and less fungal biomass was produced when glyphosate was included.     

田间尺度下污染物在土壤中的迁移: 目前的认识和存在的问题

Agro-chemical transport processes at different scales are discussed and relevant opening question are identified by literature review to make some suggestions concerning the improvement of research methods for filed scale solute transport by aid of evaluation of existing models,and examining transport behaviors of solute in vadose zones on different scales.The results indicate that present research progess and understanding on field scale solute transport have not yet been enough to guarantee the use of our models for the management of field soulte movement.Much more research work needs to be done,particularly,in aspects of high resolution of spatial structures relevant to the hydraulic and transport properties,explicit numerical simulation of actual structure on field scale and field measurement corroborated with model development.