Adsorption of acetanilide herbicides on soils and its correlation with soil properties

The adsorption of metolachlor, acetochlor, pretilachlor and butachlor, as a group of acetanilide herbicides, on eight soils with various physical and chemical properties was studied. The adsorption isotherms fit the Freundlich equation well. The extent of adsorption increased in the order: metolachlor < acetochlor < pretilachlor < butachlor. The product of the Freundlich adsorption constants, K_f(1/n), showed good correlation with organic matter content (OM) of soils for each of these herbicides, suggesting that the latter is the main factor controlling the adsorption process of these acetanilide herbicides. Multivariant correlation regression between K_f(1/n) and two factors, water solubility (S_w) of herbicides and OM, was also performed. K_f(1/n) correlated well with 1/S_w and OM/S_w, showing that high S_w corresponds to a weak tendency to adsorb on soils. IR spectra and ESR parameters confirmed that multifunctional H bonds and charge-transfer bonds between humic acids (HA) and the herbicides were the main adsorption mechanisms of the latter. The ability of herbicides to form these adsorption bonds with HA increased in the same order as the extent of adsorption. © 1999 Society of Chemical Industry     

啶虫脒和阿维菌素在4种不同类型土壤中的吸附及迁移

采用薄层层析和平衡振荡法,分别测定了啶虫脒和阿维菌素在紫色土、砖红土、黄壤土和黑土4种不同类型土壤中的迁移率(Rf )和吸附常数(Kd),比较了2种农药在单用及混用下迁移和吸附行为的差异。结果表明:2种农药在单用及混用下的迁移行为几乎不存在差异,在4种土壤中的Rf 值大小顺序均为:黄壤土>紫色土>黑土>砖红土;2种农药的吸附过程均符合经典的Freundlich模型,混用时阿维菌素对啶虫脒的吸附无影响,但啶虫脒的存在会减少土壤对阿维菌素的吸附,表现为竞争吸附作用。     

Adsorption, transport and degradation of fipronil termiticide in three Hawaii soils

BACKGROUND: The behavior of the termiticide fipronil in soils was studied to assess its potential to contaminate ground and surface water. This study characterizes (1) adsorption of fipronil in three different soils, (2) transport of fipronil through leaching and runoff under simulated rainfall in these soils and (3) degradation of fipronil to fipronil sulfide and fipronil sulfone in these soils. RESULTS: The adsorption experiments showed a Freundlich isotherm for fipronil with K_oc equal to 1184 L kg^?1. In the leaching experiments, the concentration of fipronil and its metabolites in leachate and runoff decreased asymptotically with time. The concentration of fipronil in the leachate from the three soils correlated inversely with soil organic carbon content. The degradation experiment showed that the half‐life of fipronil in the soils ranged from 28 to 34 days when soil moisture content was 75% of field capacities, and that 10.7–23.5% of the degraded fipronil was transformed into the two metabolites (fipronil sulfide and fipronil sulfone). CONCLUSION: Fipronil showed large losses through leaching but small losses via runoff owing to low volumes of runoff water generated and/or negligible particle‐facilitated transport of fipronil. The half‐life values of fipronil in all three soils were similar. Copyright © 2011 Society of Chemical Industry     

Catalytic effect of dissolved humic acids on the chemical degradation of phenylurea herbicides

BACKGROUND: Although biodegradation seems to be the main cause of herbicide degradation, abiotic degradation can also be important for chemicals such as phenylureas, which are subject to catalysed soil reactions. The aim of this work is to investigate the effect of dissolved humic acids (HAs), normally present in natural waters, on the hydrolysis of phenylurea herbicides, and it presents a kinetic model that takes into account the role of adsorption. RESULTS: The linearity of the adsorption isotherms indicates that phenylurea-humic acid interaction can be considered in terms of a repartition-like equilibrium of phenylurea between water and HAs. Kinetic experiments show that the degradation rates of phenylureas increase with HA concentration. CONCLUSION: The kinetic equation adopted adequately describes the experimental data trend, allowing the evaluation of the catalytic effect of HAs on the chemical degradation of phenylureas. Carboxyl groups of HAs seem to play a leading role in the catalysis. The kinetic equation derived in this work could be helpful in predicting the persistence of phenylureas and of related compounds in natural water.     

Behaviour of thiocarbamate herbicides in soils: Adsorption and volatilization

Adsorption and volatilization of cycloate, EPTC and vernolate applied to six types of soils were studied in the laboratory. Cycloate proved to be the most and EPTC the least adsorptive molecule in all systems examined, while the volatilization order of the compounds was the reverse EPTC>vernolate>cycloate. Neither the adsorption nor the volatilization of thiocarbamates was markedly affected by formulating agents. The adsorption isotherm of several systems did not obey the classical Freundlich equation. A reciprocal relationship which was found between the adsorption coefficients and the volatilization rates of thiocarbamates permits calculation of one of these properties if data on the other are available.     

Adsorption and degradation of thiazopyr in compost‐amended and non‐amended soils

Adsorption and degradation of thiazopyr on two unamended soils and a soil amended annually during 8 years with compost were studied under laboratory conditions and compared with the results obtained on soils amended with fresh sewage sludge compost. The adsorption isotherms fitted the Freundlich equation well and a marked sorption increase was found in amended soils. Degradation data followed first‐order kinetics and thiazopyr had a half‐life of about 75 days at 25 °C and 60% water‐holding capacity of soil. The addition of fresh compost markedly decreased the rate of thiazopyr degradation, whereas the compost mineralised in the field after annual additions had only a small influence. Incubation studies with sterile soils showed a very significant decrease of the degradation rate, indicating that degradation by micro‐organisms was the main pathway of thiazopyr degradation in the soils studied. © 2001 Society of Chemical Industry     

Adsorption and degradation of chlorsulfuron and metsulfuron-methyl in soils from different depths

Adsorption and degradation rates of chlorsulfuron and metsulfuron-methyl were measured in soil taken from depths of 0–20, 20–40 and 40–60 cm at eight sites. Adsorption of both herbicides was negatively correlated with soil pH, and positively correlated with soil organic matter content. When two soils with very high organic matter were excluded from the calculations, the correlations with organic matter content were no longer statistically significant but those with soil pH were affected only slightly. Degradation rates of both herbicides generally decreased with increasing depth in the soil and were positively correlated with microbial biomass and negatively correlated with soil pH. The possible significance of the results to persistence of the herbicides in the field is discussed.     

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。     

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。     

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。     

鱼藤酮在3种土壤中的吸附-解吸附特性

为了综合评价鱼藤酮在土壤环境中的吸附-解吸附特性,采用批量平衡法,系统研究了鱼藤酮在砂壤土、黏壤土及壤土3种农业土壤中的吸附-解吸附行为。结果表明,鱼藤酮在3种土壤中的吸附-解吸附行为符合Freundlich模型 (R2≥0.946 8),吸附常数 (K_f-ads) 在1.52~11.39之间,吸附能力为:黏壤土 > 砂壤土 > 壤土;而解吸附常数 (K_f-des) 在1.02~4.55之间,解吸附强弱次序为壤土 > 黏壤土 > 砂壤土。鱼藤酮在砂壤土、黏壤土和壤土3种土壤中有机碳吸附常数 (K_OC) 分别为982、101 7和219,而滞后系数 (H) 分别为0.687 3、0.556 9和0.892 3,表明鱼藤酮在黏壤土及砂壤土中移动性较弱,有正迟滞作用,而在壤土中移动性较强,无迟滞作用。该研究将对鱼藤酮的环境风险评估具有一定的理论指导意义。     

Adsorption,desorption and dissipation of metolachlor in surface and subsurface soils

BACKGROUND: Variations in soil properties with depth influence retention and degradation of pesticides. Understanding how soil properties within a profile affect pesticide retention and degradation will result in more accurate prediction by simulation models of pesticide fate and potential groundwater contamination. Metolachlor is more persistent than other acetanilide herbicides in the soil environment and has the potential to leach into groundwater. Reasonably, information is needed about the dissipation and eventual fate of metolachlor in subsoils. The objectives were to evaluate the adsorption and desorption characteristics and to determine the dissipation rates of metolachlor in both surface and subsurface soil samples. RESULTS: Adsorption of metolachlor was greater in the high‐organic‐matter surface soil than in subsoils. Lower adsorption distribution coefficient (K_ads) values with increasing depth indicated less adsorption at lower depths and greater leaching potential of metolachlor after passage through the surface horizon. Desorption of metolachlor showed hysteresis, indicated by the higher adsorption slope (1/n_ads) compared with the desorption slope (1/n_des). Soils that adsorbed more metolachlor also desorbed less metolachlor. Metolachlor dissipation rates generally decreased with increasing soil depth. The first‐order dissipation rate was highest at the 0–50 cm depth (0.140 week^?1) and lowest at the 350–425 cm depth (0.005 week^?1). Degradation of the herbicide was significantly correlated with microbial activity in soils. CONCLUSION: Metolachlor that has escaped degradation or binding to organic matter at the soil surface might leach into the subsurface soil where it will dissipate slowly and be subject to transport to groundwater. Copyright © 2009 Society of Chemical Industry     

氰在禾谷类粮食中的吸附与降解

利用静态法研究了氰(C_2N_2)在禾谷类粮食中的吸附与降解过程,采用气相色谱法分析了C_2N_2在粮食中的吸附、残留和挥发行为,采用流动注射分析仪(FIA)测定了C_2N_2在粮食中可能的降解产物。结果表明:粮食对C_2N_2有较强的吸附能力,熏蒸1h,90%以上的C_2N_2被粮食吸附,其吸附能力为稻谷高梁玉米大麦小麦,同时C_2N_2在粮食中可降解为氰化氢(HCN)。通风后,C_2N_2及其降解产物HCN从粮食中缓慢挥发,其中C_2N_2从小麦和大麦中挥发的速率高于玉米、高梁和稻谷,HCN从小麦、大麦、玉米和高梁中挥发的速率高于稻谷。C_2N_2及其降解产物HCN在粮食中的消解动态符合一级动力学指数模型,通风后在小麦、大麦、玉米、高梁和稻谷中的半衰期(t_(1/2)),C_2N_2分别为1.82、2.57、2.81、1.97和2.98 d,HCN分别为4.46、4.30、4.01、3.94和5.26d。C_2N_2在粮食中可降解为NH_4~+和HCN,同时产生少量的NO_3~-和NO_2~-。C_2N_2在不同粮食中的降解产物存在差异,在小麦和玉米中检测到HCN、NH_4~+、NO_3~-和NO_2~-4种降解产物,在稻谷中检测到HCN、NH_4~+和NO_3~-3种降解产物,而在大麦和高梁中仅检测到HCN和NH_4~+两种降解产物。     

Irrigation erosion of irrigated soils in the foothills of southern Kazakhstan

This paper presented the results from the study of irrigation erosion of irrigated lands in southern Kazakhstan. The main purpose of the work is the conservation of the fertility of irrigated soils, and then the soils of the upper, middle and lower sections of the slopes at the experimental site were studied. Based on field investigations, authors studied the water resistance of aggregates of gray-brown soils and light gray soils before and after irrigation and qualitative indicators of changes in physical and chemical properties of structured soils in irrigation were determined by conventional methods of soil research. The results indicated that the changes in the physical properties of soils by using polymeric compounds created a fundamentally new opportunity to control water erosion of soils.     

Addition of a monovalent cationic pesticide to improve efficacy of bipyridyl herbicides in Hulah Valley soils

Bipyridyl herbicides are widely used in agriculture and gardening for non-selective weed control. Since they are toxic and relatively expensive, it is ecologically and economically desirable to reduce the amounts applied. A decrease in efficacy of these herbicides is caused by dust accumulated on leaves of weeds. This inactivation arises from the adsorption of the herbicides on dust particles, mainly made of clay minerals, lime and soil organic matter. In order to improve the efficacy and so lower the amounts applied, formulations were developed which include cationic pesticides approved for agricultural use, such as mepiquat or difenzoquat. Such addition restored the efficacy of the bipyridyl herbicides by reducing their binding to dust particles. The proposed formulations, which were tested on a number of different dust-covered plants, allowed the amounts of herbicide applied to be reduced to 50% of the minimum recommended rate. Neither mepiquat or difenzoquat had any herbicidal activity when sprayed alone at the added rates. The results suggest a procedure that may lower the required rates of contact herbicides, reducing costs and toxicity. This procedure, which can be applied immediately, may have broad implications in farming and gardening.     

Degradation of chlorsulfuron and triasulfuron in alkaline soils under laboratory conditions

The degradation of chlorsulfuron and triasulfuron was investigated in alkaline soils (pH 7.1–9.4) spiked at 40 μg a.i. kg^–1 under laboratory conditions at 25 °C and a moisture content corresponding to 70% field capacity (–33 kPa), using high-performance liquid chromatography. Degradation data for the two herbicides did not follow first-order kinetics, and observed DT₅₀ values in surface soils ranged from 19 to 42 days and from 3 to 24 days for chlorsulfuron and triasulfuron respectively. Disappearance of both chlorsulfuron and triasulfuron was faster in non-sterile than in sterile soil, demonstrating the importance of microbes in the breakdown process. The persistence of chlorsulfuron increased with increasing depth, which can be attributed to the decline in the microbial populations down the profile. The DT₅₀ value for chlorsulfuron at 30–40 cm depth was nearly four times higher than that in the top-soil. The results obtained show that persistence of these herbicides in alkaline surface soils at 25 °C and at a moisture content of 70% field capacity is similar to those reported in other European and North American soils. The study shows that if these herbicides are contained in surface soil layers, the risk of residue carry-over under southern Australian conditions is small. However, the rate of their degradation in alkaline subsoils is very slow, and under conditions conducive to leaching their prolonged persistence in the soil profile is possible.     

新疆农田土壤有机质含量及组成特征

目前新疆农田土壤有机质含量在5．30～24．21g／kg之间，平均14．65g／kg，与第二次土壤普查相比，新疆农田土壤有机质含量呈上升趋势；胡敏素碳含量占到有机质碳量的53％～70％，平均61％，腐殖酸碳量只占39％。     

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.