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.     

Potential enhancement of degradation of the nematicides aldicarb,oxamyl and fosthiazate in UK agricultural soils through repeated applications

BACKGROUND: The potential for enhanced degradation of the carbamoyloxime nematicides aldicarb and oxamyl and the organophosphate fosthiazate was investigated in 35 UK agricultural soils. Under laboratory conditions, soil samples received three successive applications of nematicide at 25 day intervals. RESULTS: The second and third applications of aldicarb were degraded at a faster rate than the first application in six of the 15 aldicarb‐treated soils, and a further three soils demonstrated rapid degradation of all three applications. High organic matter content and low pH had an inhibitory effect on the rate of aldicarb degradation. Rapid degradation was observed in nine out of the ten soils treated with oxamyl. In contrast, none of the fosthiazate‐treated soils demonstrated enhanced degradation. CONCLUSION: The potential for enhanced degradation of aldicarb and oxamyl was demonstrated in nine out of 15 and nine out of ten soils respectively that had previously been treated with these active substances. Degradation of fosthiazate occurred at a much slower rate, with no evidence of enhanced degradation. Fosthiazate may provide a useful alternative in cases where the efficacy of aldicarb and oxamyl has been reduced as a result of enhanced degradation. Copyright © 2009 Society of Chemical Industry     

The degradation of simazine, linuron and propyzamide in different soils

Simazine, linuron and propyzamide were incubated in 18 different soils at 25°C and field capacity soil moisture content. The degradation of each herbicide followed first-order kinetics. The half-life of simazine varied from 20 to 44 days, that of linuron from 22 to 86 days and that of propyzamide from 10 to 32 days. The rate of linuron degradation was highly significantly correlated with soil organic matter content, clay content, soil respiration and the extent of herbicide adsorption by the soil. The rate of simazine degradation was significantly and negatively correlated with soil pH, but the rate of propyzamide degradation was not related with any of the soil factors examined.     

Effect of soil physical and chemical properties on the sorption-desorption hysteresis of the diketonitrile metabolite of isoxaflutole

Isoxaflutole, [4-(2-methanesulfonyl-4-trifluoromethylbenzoyl)-5-cyclopropyl isoxazole] is a relatively new pre-emergence herbicide which undergoes rapid conversion to a diketonitrile metabolite in soil. The half-life of isoxaflutole is very short but the half-life of diketonitrile is much longer and hence, diketonitrile remains for a extended period of time in soil. Sorption-desorption studies were conducted with five soils varying in physical and chemical properties. The batch equilibration technique was used for the sorption experiments, while completely mixed batch reactor systems with the decant and refill method was used for the desorption experiments. Four subsequent desorptions were examined after the sorption process in each soil with an equilibration period of seven days. An apparent sorption-desorption hysteresis was observed in all five soils. Organic matter content and the clay content of the soils were the two determining factors for hysteresis. In soils with high organic matter content, the sorption-desorption hysteresis was mainly governed by organic matter content, but in soils with low organic matter clay content played an important role. With the exception of the Chelsea soil, which had a very high organic matter content (57.4%), all other soils exhibited a high correlation between the clay content and hysteresis index (HI) values calculated at 0.75 ( r ² = 0.960), 25 ( r ² = 0.934) and 150 mg L⁻¹ ( r ² = 0.928). In conclusion, the potential for leaching through soil and crop injury due to isoxaflutole and its metabolite would decrease as soil organic matter and clay content increases.     

Measured and simulated behaviour of oxamyl in fallow soils

The movement and breakdown of the insecticide and nematicide oxamyl was monitored in fallow sandy loam soils under field conditions. Using measurements of rainfall and evaporation from a water surface, the water flow in soil was simulated by a computer model, and the results were compared with the measured soil-moisture profiles. The model was extended to simulate the behaviour of oxamyl, using laboratory data for adsorption and rates of degradation in soil. The model generally underestimated oxamyl movement in the first month, whereas it tended to overestimate later movement. The rate of breakdown of oxamyl, as affected by soil type, temperature and soil-moisture content, was fairly well described. After about 2 months only small amounts of oxamyl remained. Accumulation of oxamyl near the soil surface in dry periods was overestimated, indicating deficiencies in the modelling procedure under these conditions.     

Interactions between organophosphorus compounds and soil materials I. Adsorption of ethyl methylphosphonofluoridate by clay and organic matter preparations and by soils

Data for the adsorption of ethyl methylphosphonofluoridate from aqueous and the vapour phases onto montmorillonite and kaolinite clays, onto soil organic matter preparations, and onto a limited number of soils are reported. These show that the phosphonofluoridate was absorbed from the vapour phase onto the dry clay preparations by physical-chemical forces but was not adsorbed by the organic soil materials. In a general way adsorption onto dry soils could be related to their clay contents when the organic matter contents were low. Water was found to compete effectively with the phosphonofluoridate for adsorption sites, and it is concluded that this molecule will be most effectively retained by dry soils low in organic matter and rich in clay. Mechanisms for its adsorption onto clays are discussed.     

Comportement de substances herbicides dans le sol en fonction de leur structure chimique

Behaviour of herbicides in the soil as a function of their chemical structure Studies of the adsorption and degradation of propyzamide (3,5-dichloro-N-(1,1-dimethylpropynyl)benzamide) analogues were done in different soils. A good correlation was found between adsorption and organic matter content of the soils. There is a linear connection between this adsorption and the hydrophobic parameter (coefficient of water-octanol partition). By contrast. the degradation of these compounds in different soils shows no simple relationship with nature of the soils nor with the chemical structure of the compounds. The importance of these phenomena for the results of bioassays is also analysed.     

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.     

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。     

烟嘧磺隆在土壤中的吸附及与土壤性质的相关性研究

采用平衡振荡法研究了烟嘧磺隆在8种不同类型土壤中的吸附,结果表明,其吸附过程均符合经典的Freundlich模型,最大吸附常数为6.891,最小吸附常数为0.798。根据土壤有机吸附常数和吸附自由能的大小对该除草剂的移动性能进行了评价,认为其在8种土壤中均以物理吸附为主,且具有中等或较高的移动性能。通过对吸附常数Kf与土壤有机质含量、粘土含量和pH值的关系进行分析,发现土壤有机质含量、粘土含量和pH值在吸附过程中均属支配因素,Kf与土壤有机质含量、粘土含量呈正相关,而与土壤pH值呈负相关。     

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。     

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。     

INFLUENCE OF SOIL PROPERTIES ON PHYTOTOXICITY OF 4–AMlNO-3,5,6–TRICHLOROPICOLINIC ACID (PICLORAM)

Summary. Effective dosages of picloram (4–amino-3,5,6–trichloropicolinic acid) required to reduce fresh weight of sunflowers ( Helianthus annuus L. var. Menonite) were determined for seven Saskatchewan soils under controlled environmental conditions. The relationships between ED₅₀ value and clay content, organic matter content and cation exchange capacity were evaluated by correlation and regression analysis for possible usefulness in predicting dose requirements. ED₅₀ values were also determined for Weyburn loam and in culture solutions adjusted to various pH levels.
There Was no significant correlation between ED₅₀ values of picloram and soil clay content or cation exchange capacity. ED₅₀ values were highly correlated with soil organic matter content, and they increased as the soil pH was lowered or raised from pH 6.5. The increase in ED₅₀ values in the acidic range was attributed to adsorption of the unionized molecules of picloram on the organic matter in the soil. The increase in ED₅₀ values in the alkaline range may be mainly due to reduced uptake of the ionized acid by plant roots.     

Sorption and desorption of flumioxazin to soil, clay minerals and ion-exchange resin

Flumioxazin adsorption kinetics were described using a Greenville sandy clay loam soil. Adsorption kinetics experiments showed that 72% of total herbicide was absorbed after 1 h of continuous shaking and continued to increase to 78% after 72 h. Flumioxazin adsorption was then tested on seven agriculturally important soils throughout the southern USA. Adsorption isotherms for all soils had K(f) (Freundlich distribution coefficient) values that ranged from 8.8 to 0.4, with many near 1.5. Soil organic matter content was the parameter most highly correlated with flumioxazin adsorption (r(2) = 0.95, P < 0.001). Sorption to clay minerals had K(f) values ranging from 50 for bentonite to 4.7 for kaolinite. However, normalizing K(f) for sorbent surface area revealed that aluminum hydroxide (gibbsite) possessed the greatest flumioxazin sorption per unit area. Sorption to anionic exchange resin (K(f) 676) was greater than cationic exchange resin (K(f) 42). Molecular model calculations were performed to elucidate why sorption was greater to anionic exchangers. These calculations indicated that a region of dense electronegativity exists on the 3-dione moiety of the molecule. This would lead to greater flumioxazin sorption by positively charged surface sites. Desorption isotherms from soil exhibited no effect of hysteresis. Desorption from clay minerals was very rapid and flumioxazin in solution was undetectable after three desorption steps. From these data it was concluded that flumioxazin can become readily available in soil solution with increase in soil water content.     

双唑草腈在3种典型土壤中的降解

为明确双唑草腈在环境中的降解行为特性,采用室内模拟试验方法,分别研究了积水厌气、好氧和灭菌条件下,双唑草腈在紫色土、水稻土及红壤3种典型土壤中的降解特性。结果表明:双唑草腈在3种土壤中的降解均符合一级反应动力学方程,好氧条件下,其在紫色土、水稻土及红壤中的降解半衰期分别为13.4、10.1和31.1 d,且降解速率与土壤中有机质和黏粒含量呈正相关;不同条件下的降解速率依次为积水厌气 > 好氧 > 灭菌,说明双唑草腈在土壤中的降解一定程度上受水解和微生物活性的影响;在一定的土壤持水量范围内,双唑草腈在土壤中的降解速率随土壤含水量增加而加快。研究表明,双唑草腈在稻田淹水条件下施用降解较快,残留期较短。所得结果可为双唑草腈的合理使用及其环境安全性评价提供科学依据。     

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。     

Atrazine dissipation in irrigated sorghum cropping in southern New South Wales

Dissipation of atrazine after pre-emergence application to irrigated grain sorghum was investigated in an experiment on a Birganbigil clay loam at Yanco Agricultural Research Centre in the Murrumbidgee Irrigation Areas of New South Wales. Dissipation followed first-order kinetics with a half-life of 70 days. This rate of disappearance did not differ significantly between application rates of 2.5 and 10 kg/ha. Removal of volunteer plant growth with non-residual chemicals or by cultivation during the winter fallow periods had no significant effect on the levels of atrazine residues in the soil and dissipation rate did not differ significantly between the 2 years of the experiment. A laboratory incubation experiment demonstrated that dissipation of atrazine in Birganbigil soil was more rapid than in three other soils from the Murrumbidgee and Murray Valleys. Dissipation rate and atrazine adsorption were both correlated with the organic carbon content of the soils, which ranged from 1.43% to 0.72%. There was no correlation between either dissipation rate or adsorption and clay content, even though clay contents ranged from 37 to 78%.     

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。     

THE ADSORPTIVE BEHAVIOUR OF ACID AND ESTER FORMS OF 2,4-D ON SOILS

Summary. The adsorption of acid, n-butyl, and iso-octyl ester forms of 2,4-D (2,4- dichloiophenoxyacetic acid) was studied for several Canadian prairie soils. The k values for the acid ranged from 0·09 to 1·30 and were correlated to the soil organic matter and not to the clay content. The Q , values (μg adsorbed/g of organic matter) for the acid were 7–2±l. The n-butyl and the iso-octyl esters hydrolysed to the acid form in the aqueous medium and this process was accelerated in the presence of the moist soil. Consequently, the k values for the esters, using slurry type adsorption experiments, or their distribution coefficients, using leaching columns, could not be determined. It was concluded that the adsorptive behavior of the two esters in moist soil was similar to that of the acid form.
Comportement des formes actde, et ester du 2,4-D quant à leur adsorption dans tes sols     

Trifluralin effects on the development of cotton in arid zone soils

The effect of trifluralin on the growth and development of cotton plants in low-organic-matter soils from the northern Negev of Israel was studied. Trifluralin exhibited linear sorp tion isotherms on these soils, Trifluralin and dinitramine losses from soils under varying moisture regimes and application practices were determined in open systems. The data were fitted to both first-order and biexponential kinetic equations. In about 50% of cases the biexponential kinetic model provided a better fit to the data, but no relationship could be found between the model parameters and environmental or soil properties. Losses were generally greater at field capacity than at 50% field capacity, and at 27°C than at 15°C, and in soils with a lower organic matter content. The trifluralin application rate was negatively correlated with vegetative growth parameters of cotton, but the correlation became weaker with increasing soil organic carbon content. Trifluralin delayed boll production in coarse textured soils, the longest delay occurring at higher application rates. It is concluded that in light soils that contain very little organic matter, trifluralin rates must be maintained at the minimum level required for adequate weed control to prevent damage to crops.