精异丙甲草胺在土壤中的吸附行为及 环境影响因素研究

采用平衡振荡法研究了精异丙甲草胺在粘壤土、粘土及砂壤土中的吸附和解吸附行为。结果表明,3种土壤的吸附等温线均属L型并符合Freundlich模型,吸附常数(Kf)分别为4.01、6.15及8.62,且Kf 和1/n(n为经验常数)的乘积与土壤有机质含量呈正相关性。解吸附实验结果表明,精异丙甲草胺在土壤中的解吸附与吸附并不一致,显示出明显的滞后性。温度及pH值等环境因素对吸附影响的结果显示,随温度升高精异丙甲草胺在土壤中的吸附量有所减少,中性环境下土壤吸附量较低。     

氯胺嘧草醚在土壤中的吸附行为研究

为评价氯胺嘧草醚的环境安全性,采用批量平衡法测定了氯胺嘧草醚在5种土壤中的吸附-解吸行为,并运用数学模型对其吸附-解吸特性及移动性能进行了分析。结果表明:氯胺嘧草醚在5种土壤中的等温吸附-解吸曲线符合Freundlich模型,吸附常数（Kf值）范围在6.991~18.49之间;不同土壤对其的吸附作用强弱依次为:黑土 > 水稻土 > 褐土 > 潮土 > 红土。氯胺嘧草醚在5种土壤中的有机碳吸附常数（KOC）范围在704.4~1 579之间,推测其在土壤中具有低移动性;薄层层析试验也表明,氯胺嘧草醚在土壤中的移动性较弱。氯胺嘧草醚在5种土壤中的吸附自由能绝对值均小于40 kJ/mol,表明其吸附机理主要是物理吸附。其Kf值与土壤有机质含量、黏粒含量呈正相关,而与土壤pH值呈负相关。解吸试验表明,氯胺醚在其中3种土壤中的解吸过程存在滞后现象。研究表明,在正常使用情况下,氯胺嘧草醚不易对地表水或地下水造成污染风险。     

咪鲜胺及其制剂在六种水稻土中的吸附

研究了咪鲜胺(prochloraz)及其制剂施保克(Sportak,25%咪鲜胺乳油)在6种水稻土中的吸附行为和吸附机理。结果表明:咪鲜胺和施保克在水稻土中的吸附平衡时间为5~10 h,其吸附过程符合Freundlich吸附等温式;咪鲜胺和施保克在6种水稻土中有机质吸附常数(KOM)的平均值分别为 2 439和2 111,表明它们易被水稻土吸附,属难移动的物质,且吸附反应自由能的变化量均小于40 kJ/mol, 表现为物理吸附过程;吸附常数(Kf值)与土壤理化性质的相关性分析结果表明,咪鲜胺和施保克在土壤中的吸附主要受土壤有机质含量、阳离子交换量和粘粒含量的影响,并呈正相关;咪鲜胺在加工成制剂后,不但在土壤中的吸附量减少了,而且Kf值也下降了近1/3。     

环丙酰草胺在土壤中的迁移特性

为研究环丙酰草胺在土壤中的吸附迁移规律，分别采用批平衡法和柱淋溶法测定了环丙酰草胺在江西红壤、太湖水稻土、常熟乌杉土、陕西潮土和东北黑土5种土壤中的吸附和淋溶特性，并运用数学模型对其在土壤中的吸附及迁移特性进行了分析。结果表明:环丙酰草胺在5种土壤中的等温吸附曲线符合线性吸附方程，吸附常数K_d在1.41~7.08之间；环丙酰草胺在5种土壤中的淋溶性大小依次为:东北黑土>陕西潮土>常熟乌杉土>太湖水稻土>江西红壤。通过对吸附常数K_d与土壤有机质含量和pH值的关系进行分析，发现土壤pH值在吸附过程中属主要因素，K_d与土壤pH值呈负相关。上述结果表明，环丙酰草胺在供试的5种土壤中比较容易迁移，影响其迁移的主要因素是土壤pH值。环丙酰草胺在使用过程中应关注其对地表水和地下水造成的风险。     

毒死蜱和氰戊菊酯在土壤中的吸附与迁移

为评估被用作白蚁预防药剂的毒死蜱和氰戊菊酯在土壤中的移动性,采用平衡吸附法和薄层层析法分别测定了两种农药在浙江宁波地区的东钱湖土(粉砂质壤土)、青岭土(粉砂质壤土)和象山土(粉砂质黏壤土)3种土壤中的吸附常数(Kd)和迁移率(Rf)。结果表明,两种供试药剂在东钱湖土中的吸附等温线线性化程度均较高,而在青岭土和象山土中的吸附等温线均近似于 "L"型。从Kd和有机质吸附常数Koc的数值看,氰戊菊酯在土壤中的吸附作用主要受土壤有机质因素影响,而毒死蜱的吸附并非只受土壤有机质因素的影响。毒死蜱在3种供试土壤中的Kd和Rf值均高于氰戊菊酯。这表明由Kd值推测不同农药在土壤中的相对移动性可能会存在一定偏差。毒死蜱和氰戊菊酯在3种土壤中的Rf值由大到小的顺序为:东钱湖土>青岭土>象山土;而Kd值由大到小顺序为象山土>青岭土>东钱湖土。对Kd和Rf值与土壤理化性质的多元线性回归分析表明:1)土壤有机质含量和阳离子代换量在决定Kd和Rf值中所起的作用相互重叠;2)土壤有机质含量(或土壤阳离子代换量)和土壤黏粒含量是影响Kd和Rf值的关键因素,而土壤pH值对于Kd和Rf值无决定性影响。     

双氟磺草胺在不同类型土壤中的吸附与淋溶特性研究

农药在土壤中的吸附和淋溶特性是评价其环境行为的重要指标。采用批量平衡法和土柱淋溶法,研究了双氟磺草胺在小麦种植区3种代表性土壤中的吸附和淋溶特性。结果表明:双氟磺草胺在安徽黏土、山东砂质壤土和河南砂质黏壤土中的吸附规律均可以较好地用Freundlich方程描述,其吸附系数(Kf)在0.39~0.62之间;土壤有机碳归一化吸附系数(Koc)在66.91~81.35之间,表明双氟磺草胺在3种土壤中均属于难吸附型;吸附自由能(ΔG)在-10.90~-10.42kJ/mol之间,均属于物理吸附。双氟磺草胺在3种土壤中的淋出率在71.7%~74.1%之间,说明其在3种土壤中的淋溶性均较强。双氟磺草胺初始添加量和腐殖酸对淋出率具有一定影响。综合试验结果,认为双氟磺草胺在3种土壤中的吸附和淋溶可能受土壤有机质含量、黏粒含量、阳离子交换量和土壤pH值等多个因素的综合影响,其对地下水的污染风险较大,因此应引起高度重视。     

七种农药在3种不同类型土壤中的吸附及淋溶特性

采用振荡平衡法和土柱淋溶法研究了2,4-滴酸、丁噻隆、毒草胺、炔草酸、氟环唑、甲基磺草酮和烯啶虫胺7种农药在江西红壤、太湖水稻土及东北黑土3种不同理化性质土壤中的吸附及淋溶特性,探讨了农药性质及土壤理化性质对供试农药在土壤中吸附、淋溶行为的影响。结果表明:农药的水溶性越大,其在土壤中的吸附性越弱,淋溶性越强;农药在土壤中的吸附性与土壤pH值、有机质含量以及阳离子交换量之间有较好的相关性。土壤pH值、有机质含量以及农药性质是影响农药在土壤中淋溶及迁移的主要因素。     

敌草胺在土壤中的吸附及其与持久性和生物有效性之间的关系

土壤吸附是农药在环境中归趋的关键支配因素,也是支配农药在环境中的持久性和生物有效性的重要因素之一。该文采用高效液相色谱法研究了除草剂敌草胺在不同性质土壤中的吸附、持久性和生物有效性以及吸附与土壤持久性、蚯蚓生物有效性之间的关系。结果表明,在供试浓度范围内,采用批量平衡技术测定的敌草胺土壤吸附等温线可用Freundlich模型表征（r>0.99）,土壤有机质含量（PPt50）在61.3-97.6 d之间;微生物对敌草胺在土壤中的持久性影响显著,微生物降解是敌草胺在土壤环境中降解的主要途径,灭菌处理后其在土壤中的半衰期延长了2.09~3.65倍。蚯蚓Eisenia foetida对敌草胺的吸收和生物积累也主要取决于土壤性质,特别是土壤的有机质含量水平（Pr=-0.885,Pr=-0.796,Pt50=94.210-3.535 Kf和BAF=0.264-0.014 Kf,表明吸附系数可用作模型参数来评价敌草胺在土壤中的持久性和生物有效性。     

Cu(Ⅱ)和温度对丁吡吗啉在土壤中吸附的影响

采用振荡平衡法研究了Cu(Ⅱ)和温度对丁吡吗啉在内蒙砂土,北京壤土,广西粘土中吸附等温线的影响。结果表明,丁吡吗啉添加Cu(Ⅱ)前后在3种土壤中的吸附均可以采用Langmuir方程和Freundlich方程较好的描述,Cu(Ⅱ)降低了3种土壤对丁吡吗啉的吸附,3种土壤对丁吡吗啉的吸附量及Cu(Ⅱ)对土壤吸附丁吡吗啉影响的大小顺序为:粘土壤土砂土。根据综合试验结果,Cu(Ⅱ)与丁吡吗啉在占用土壤的吸附位点上可能存在竞争,土壤有机质含量高有利于Cu(Ⅱ)的吸附,丁吡吗啉与Cu(Ⅱ)之间的相互作用减少了土壤对丁吡吗啉的固定量,增加了其在土壤中的活动性;在10、25、35℃,丁吡吗啉在3种土壤中的吸附规律亦可以较好的用Langmuir方程和Freundlich方程描述,丁吡吗啉在3种土壤中的吸附会受到温度的影响,丁吡吗啉的吸附常数Kd和吸附自由能△G的绝对值随着温度的升高而减小,说明温度的升高不利于土壤对丁吡吗啉的吸附。     

嗪吡嘧磺隆在土壤中的吸附特性及其吸附过程模型的建立

磺酰脲类除草剂是应用较为广泛的农药之一,其在土壤中迁移、降解、转化和滞留等多个过程受其吸附、解吸行为的影响。本文以嗪吡嘧磺隆为研究对象,采用批量平衡法研究了其在8种不同类型土壤中的吸附、解吸附行为。结果表明:嗪吡嘧磺隆与土壤溶液接触4 h内为快速吸附阶段。Freundlich模型可较好地拟合嗪吡嘧磺隆在土壤中的等温吸附解吸过程,相关系数 (r) 值在0.9584~0.9973之间。8种土壤对嗪吡嘧磺隆的吸附能力均为弱,吸附常数 (K_f-ads) 在0.281~3.515之间。其中,以黑龙江白浆土对嗪吡嘧磺隆的吸附能力最强,且远高于其他土壤。除广西赤红壤外,嗪吡嘧磺隆在其他7种类型土壤中的滞后系数 (H) 均小于1,解吸过程存在滞后现象,存在潜在环境风险。单因素试验结果表明,嗪吡嘧磺隆在土壤中的吸附行为受腐殖酸的影响极显著 (P＜0.01),受pH值和Mn2 + 的影响显著 (P＜0.05),受高岭土和稻壳生物炭的影响不显著 (P＞0.05)。采用中心复合试验设计,建立了具有一定预测功能的嗪吡嘧磺隆在土壤中的吸附过程BP神经网络模型,并进行了验证,拟合结果较好。     

Adsorption-desorption behaviour of flufenacet in five different soils of India

Adsorption-desorption of the herbicide flufenacet (FOE 5043) has been studied in five soils from different locations in India (Delhi, Ranchi, Nagpur, Kerala and Assam) varying in their physicochemical properties. The organic matter (OM) content varied from 0.072 to 0.864%, clay content from 2.5 to 43.7% and pH from 4.45 to 8.35. The adsorption studies were carried out using a batch equilibration technique. Ten grams of soil were equilibrated with 20 ml of aqueous 0.01 M CaCl2 solution containing different concentrations (0-30 mg litre-1) of flufenacet. After equilibration, an aliquot of supernatant was taken out for analysis. During desorption, the amount withdrawn for analysis was replenished with fresh 0.01 M CaCl2 solution and further equilibrated. Desorption studies were carried out with the 30 mg litre-1 concentration of flufenacet only. The adsorption studies revealed that there was moderate to high adsorption of flufenacet considering the comparatively low organic carbon content in the five test soils. Average Kd values ranged from 0.77 to 4.52 and Freundlich KF values from 0.76 to 4.39. The highest adsorption was observed in Kerala soil (OM 0.786%; clay 25%; pH 4.45) followed by Ranchi, Nagpur and Delhi soils, and the lowest in Assam soil (OM 0.553%; clay 2.5%; pH 6.87). The trend in adsorption could be attributed to the chemical nature of flufenacet and the physicochemical properties of the soil such as pH, OM and clay contents. OM and clay contents were positively correlated whereas pH was negatively correlated. Soils having low pH, high OM and high clay contents showed higher adsorption. Desorption studies revealed that there was a hysteresis effect in all the soils. Hysteresis coefficient values (ratio of n(ad) and n(des)) varied from 0.09 to 0.45. The study implies that, because of its moderate to high adsorption, flufenacet is likely to persist in soil for some time. However, the possibility of its movement by leaching or surface run off is less.     

Adsorption and degradation of four acidic herbicides in soils from southern Spain

BACKGROUND: Pesticide degradation and adsorption in soils are key processes determining whether pesticide use will have any impact on environmental quality. Pesticide degradation in soil generally results in a reduction in toxicity, but some pesticides have breakdown products that are more toxic than the parent compound. Adsorption to soil particles ensures that herbicide is retained in the place where its biological activity is expressed and also determines potential for transportation away from the site of action. Degradation and adsorption are complex processes, and shortcomings in understanding them still restrict the ability to predict the fate and behaviour of ionisable pesticides. This paper reports the sorption and degradation behaviour of four acidic pesticides in five soils from southern Spain. Results are used to investigate the influence of soil and pesticide properties on adsorption and degradation as well as the potential link between the two processes. RESULTS: Adsorption and degradation of four acidic pesticides were measured in four soils from Spain characterised by small organic matter (OM) contents (0.3-1.0%) and varying clay contents (3-66%). In general, sorption increased in the order dicamba < metsulfuron-methyl < 2,4-D < flupyrsulfuron-methyl-sodium. Both OM and clay content were found to be important in determining adsorption, but relative differences in clay content between soils were much larger than those in OM content, and therefore clay content was the main property determining the extent of herbicide adsorption for these soils. pH was negatively correlated with adsorption for all compounds apart from metsulfuron-methyl. A clear positive correlation was observed for degradation rate with clay and OM content (P < 0.01), and a negative correlation was observed with pH (P < 0.01). The exception was metsulfuron-methyl, for which degradation was found to be significantly correlated only with soil bioactivity (P < 0.05). CONCLUSIONS: Both OM and clay content were found to be important in determining adsorption, but relative differences in clay content between soils were much larger than those in OM content, and therefore clay content was the main property determining the extent of herbicide adsorption for soils of this type. pH was negatively correlated with adsorption for all compounds apart from metsulfuron-methyl. The contrasting behaviour shown for these four acidic pesticides indicates that chemical degradation in soil is more difficult to predict than adsorption. Most of the variables measured were interrelated, and different behaviours were observed even for compounds from the same chemical class and with similar structures.     

三氟苯嘧啶在5种土壤中的吸附与解吸附行为

为研究三氟苯嘧啶的吸附-解吸附特性,采用振荡平衡法研究了三氟苯嘧啶在采集于吉林通化、江苏扬州、江西萍乡、广西南宁和海南海口等地的5种土壤中的吸附-解吸附行为及其环境影响因素。结果表明:三氟苯嘧啶在土壤中的吸附动力学符合Elovich模型,吸附和解吸附等温线符合Freundlich模型,吸附常数在1.886~7.626。温度的升高更有利于吸附,土壤对三氟苯嘧啶的吸附主要是物理吸附;随着溶液中pH值的升高,土壤对三氟苯嘧啶的吸附能力逐渐下降。除广西南宁黏壤土外,三氟苯嘧啶在5种土壤中的解吸附过程中存在滞后现象,不易在土壤中长期积累,具有一定的迁移特性。     

Influence of the physical and chemical properties of soil on the retention process of isoxaflutole and its two main derivatives

Isoxaflutole is a new pre‐emergence herbicide for use in maize and sugarcane. Its two main derivatives are a diketonitrile derivative, the 2‐cyano‐3‐cyclopropyl‐1‐(2‐methanesulfonyl‐4‐trifluoromethylphenyl)propan‐1,3‐dione, named DKN, and a benzoic acid derivative, the 2‐methanesulfonyl‐4‐trifluoromethylbenzoic acid, named BA. The adsorption/desorption processes have never been studied for isoxaflutole (IFT) at high concentrations nor for BA, and the present work aimed at completing the knowledge of the behaviour of these three molecules in conditions close to those encountered in the context of agricultural use. The adsorption/desorption study was conducted on seven soils of different physical and chemical properties, using the batch equilibrium technique. During the experiments, IFT was chemically converted into DKN in a continuous manner. This reaction appeared to be dependent on the pH of the soil and was taken into account in the calculations of the adsorbed and desorbed amounts. The adsorption isotherms obtained were predominantly C‐shaped for IFT and DKN and S‐shaped for BA, but some differences appeared on a few soils. They fitted well the Freundlich equation, and the values of the Freundlich coefficient K_fa showed that, whatever the soil, IFT was more adsorbed than its two derivatives. The main parameter influencing the adsorption of IFT appeared to be the organic matter content, whereas this effect was not evident for DKN and BA. No correlation was found between the extent of adsorption and either clay content or pH of the soil, for the three molecules.     

施磷对不同生育期棉田土壤磷素吸持特性的影响

以两种质地棉田土壤为材料,研究不同施磷处理对不同生育期棉田土壤磷吸附与解吸的影响.结果表明:各生育期磷素等温吸附曲线与Langmuir,Temkin和Freundlich方程拟合度均达极显著水平,尤以Freundlich方程拟合度最高,相关系数均在0.96以上;磷的吸附饱和度(DPS)、零净吸附浓度磷(EPC_0)、吸附量、解吸量和解吸率随施磷量的增加均呈增长趋势,而标准需磷量(SPR)呈下降趋势;以Freundlich方程估算原状棉田土壤各个生育期的需磷量,壤质棉田苗期、花铃期和吐絮期的需磷量(按含P_2O_5 46%的磷肥折算)分别为143.7,137.4 kg/hm~2和160.2 kg/hm~2,砂壤质棉田苗期、花铃期和吐絮期的需磷量分别为106.6,251.1 kg/hm~2和173.0 kg/hm~2.