Spatial variability in the degradation rates of isoproturon and chlorotoluron in a clay soil

Thirty separate soil samples were taken from different locations at the Brimstone farm experimental site, Oxfordshire, UK. Incubations of isoproturon under standard conditions (15 °C; ?33 kPa soil water potential) indicated considerable variation in degradation rate in the soil, with the time to 50% loss (DT₅₀) varying from 6 to 30 days. These differences were confirmed in a second comparative experiment in which degradation rates were assessed in 11 samples of the same soil in two separate laboratories using an identical protocol. There was a significant negative linear relationship (r²= 0.746) between the DT₅₀ values and soil pH in this group of soils. In a third experiment, degradation rates of the related compound chlorotoluron were compared with those of isoproturon in 12 separate soil samples, six of which had been stored for several months, and six of which were freshly collected from the field. Degradation of both herbicides occurred more slowly in the stored samples than in the fresh samples but, in all of them, chlorotoluron degraded more slowly than isoproturon, and there was a highly significant linear relationship (r²=0.916) between the respective DT₅₀ values.     

莠去津在土壤及作物中残留量测定

本文建立了一种土壤和作物中痕量莠去津的高效液相色谱分析方法,比较了超声波提取与振荡提取的回收率,研究了弗罗里硅土净化效果。以甲醇：水（８０／２０,Ｖ／Ｖ）为流动相,检测波长２３５ｎｍ,在ＯＤＳ柱上实现了莠去津与杂质的良好分离。方法简单,分析速度快,测定费用低,检测限为２４ｎｇ／ｇ,回收率为９５％～９７％。     

Atrazine behaviour in the different pedological horizons of two Argentinean non-till soil profiles

Atrazine behaviour was investigated in the different pedological horizons from profiles of two non-tilled soils, a Typic Argiustoll and an Entic Haplustoll from the Argentinean pampas. As atrazine use in field conditions was associated with maize cropping, only one type of soil received atrazine every other year. Atrazine behaviour was characterized through the balance of ¹⁴C-U-ring atrazine radioactivity among the mineralized fraction, the extractable fraction and the non-extractable bound residues. The composition of the extractable fraction was characterized. Atrazine mineralization was the main dissipation mechanism in the superficial horizon of the Argiustoll because of microbial adaptation after repeated atrazine applications. In contrast, little atrazine mineralization was found in the Haplustoll profile, and it decreased with depth. The capacity of the soil organic matter to form bound residues was characterized using soil-size fractionation. Atrazine-bound residues depended on the soil organic matter content and the size of the fraction. Organic matter in the largest size fractions had a higher capacity to form atrazine-bound residues. In the Argiustoll profile, the atrazine degradation capacity decreased in the subsurface horizons (Bt₁ and Bt₂), where a large part of bound residues were formed. The deepest horizon (BC) of this profile had a high capacity to degrade atrazine reaching this horizon after a lag period. In the Haplustoll profile, atrazine mineralization and bound residue formation followed the organic carbon mineralization pattern.     

三种新烟碱类杀虫剂在土壤中的残留降解及影响因子

建立了吡虫啉、啶虫脒和噻虫嗪在土壤中的高效液相色谱-串联质谱（HPLC-MS/MS）检测方法。样品经乙腈提取和QuEChERS法净化后,采用HPLC-MS/MS检测,外标法定量,在0.01~1.0 mg/kg添加水平下,3种新烟碱类杀虫剂在土壤中的回收率在89%~103%之间,相对标准偏差（RSD）在1.3%~10.3%之间,定量限均为0.01 mg/kg。采用建立的方法,在室内模拟条件下,研究了土壤微生物、温度、土壤含水量及农药初始浓度对土壤中吡虫啉、啶虫脒和噻虫嗪降解的影响。结果表明:土壤微生物是影响农药残留降解的首要因素,灭菌处理土壤中农药残留降解速率明显低于非灭菌土壤。此外,环境温度、土壤含水量、初始浓度等因素也会对农药残留降解产生不同影响,土壤含水量为最大持水量的60%左右时降解最快,半衰期分别为15.6、7.2和25.8 d;农药初始浓度越高,降解速度越慢;在5~35℃范围内,随着温度的升高,降解速度加快。     

Accelerated Degradation and Mineralization of Atrazine in Surface and Subsurface Soil Materials

In surface soils, atrazine is considered to be a moderately persistent herbicide, with half-lives ranging generally from one to two months. In subsoils, however, its degradation is generally slower. This paper reports the degradation of atrazine in soil and subsoil samples taken from six Belgian maize fields. Rapid degradation can take place in some samples taken from surface and in some from subsurface soils. Subsoil samples were found to degrade atrazine either very strongly or not at all. Experiments with [ring-U-¹⁴C] atrazine showed that the micro-organisms responsible for the rapid degradation cleave the triazine ring and extensively mineralize the molecule. © 1997 SCI.     

Use of mathematical modeling and its inverse analysis for precise assessment of pesticide dissipation in a paddy environment

The extrapolability of the lysimeter test as a dissipation simulator in an actual paddy field was evaluated using mathematical models and their inverse analyses for predicting pesticide fate and transport processes in paddy test systems. As a source of experimental data, a four-year comparative experiment in lysimeters and paddy fields was conducted using various paddy pesticides. First, the dissipations for various active ingredients in granule pesticides under submerged applications were statistically compared using simple kinetic modeling. Second, the dissipation pathways, unobserved experimental components, and effect of the experimental setting were evaluated using a higher tier mathematical model with a novel inverse analysis protocol. Finally, owing to experimental constraints, the unobtainable parameters were extracted from the laboratory container test before being transferred to compare the outdoor experimental data under different formulation types.     

莠去津在土壤中的残留动态和淋溶动态

利用HPLC法对土壤中莠去津的残留动态、淋溶动态进行了研究。结果显示,莠去津以有效成分2.25 kg/hm2和4.50 kg/hm2的剂量施用时,在土壤中的半衰期分别为19.1 d和18.1 d,即其半衰期与莠去津的施用浓度无关,属于典型的一级动力学反应。在120 d的玉米生长期中,土壤中莠去津在不断降解代谢的同时,逐渐向深层土壤中淋溶,多数莠去津持留在表层土壤中。施用莠去津27 d后,高浓度处理小区莠去津的淋溶深度超过30 cm,深度为10~15 cm处的土壤在施用后27 d莠去津的浓度最大。同一土壤深度,莠去津在高浓度处理小区的残留量要远高于低浓度处理小区。这些结果显示,减小莠去津的用量可以减少莠去津在土壤中的移动,表明低剂量施用莠去津是保护地下水免受污染的一种有效措施。影响莠去津的淋溶作用的主要因素包括使用量和土壤的理化特性。     

Spatial variability in herbicide degradation in the subsurface environment of a groundwater protection zone

The aim of this study was to investigate the spatial variability in degradation and mineralization of atrazine and isoproturon in subsurface samples taken from sandy loam soils overlying gravel terraces which form part of a groundwater protection zone. Percussion drilling was used to obtain samples from 11 boreholes (maximum depth 3 m). Unlabelled atrazine or isoproturon, and ring-14C-labelled atrazine or isoproturon were added to samples, incubated at 25 degrees C for up to 16 weeks, and analyzed for the residual herbicide or [14C]carbon dioxide. All samples showed the potential to degrade these herbicides, although the percentage degradation decreased by a factor of 2-3 from the surface soil to a depth of 3 m. This was associated with a decrease in organic matter content, but there was no change in the potential to mineralize acetate, indicating that specific changes in the catabolic ability of the microbial population occurred with depth. The capacity of samples to mineralize atrazine and isoproturon to carbon dioxide decreased markedly with depth, with no mineralization potential observed at a depth of 80 cm.     

Degradation of [14C]Terbuthylazine and [14C]Atrazine in Laboratory Soil Microcosms

The degradation and formation of major chlorinated metabolites of terbuthylazine and atrazine in three soils (loamy clay, calcareous clay and high clay) were studied in laboratory experiments using molecules labelled with ¹⁴C on the s-triazine ring. Soil microcosms were treated with the equivalent of 1 kg ha^-1 of herbicide and incubated in the dark for 45 days at 20(±1)°C. The quantity of [¹⁴C]carbon dioxide evolved in the soils treated with atrazine was negligible and could not be attributed to mineralization of the parent molecule. The mineralization of terbuthylazine accounted for 0·9–1·2% of the initial radioactivity. In the soils studied, the extrapolated half-lives varied from 88 to 116 days for terbuthylazine and 66 to 105 days for atrazine, with no significant differences for the three soils and the two molecules. The deethyl metabolites of the two s-triazines and the deisopropyl-atrazine metabolite appeared during the incubation in the three soils. The completely dealkylated metabolite was not detected in any of the soils. After 45 days of incubation, the non-extractable soil residues for the high clay, loamy clay and calcareous clay soils represented for terbuthylazine, 33·5, 38·3 and 43·1% and for atrazine, 19·8, 20·8 and 22·3% of the initial radioactivity. © 1997 SCI.     

Degradation of the sulfonylurea herbicides chlorsulfuron and triasulfuron in a high-organic-matter volcanic soil

The degradation rates of two sulfonylurea herbicides, chlorsulfuron and triasulfuron, were determined at two application rates, 15 and 30 g a.i. ha^–1, in a sandy loam soil of volcanic origin under controlled environment and field conditions. Residues were measured using a modified gas chromatographic (gc) determination method. Both herbicides degraded rapidly in the acidic soil (pH 5.7) with high organic matter levels (7.3% o.m.), generally according to first-order rate kinetics. The respective half-lives ranged from 22 to 38 d for chlorsulfuron and from 31 to 44 d for triasulfuron under five controlled temperature/soil moisture regimens, ranging from 10 to 30 °C and between 40% and 80% maximum water-holding capacity. Half-lives in the field were considerably shorter (13 d for chlorsulfuron and 12–13 d for triasulfuron). The degradation rates of the herbicides were influenced more by soil temperature than by soil moisture content. Bioassays using white mustard ( Sinapis alba L.) and forage sorghum [ Sorghum bicolor (L.) Moench] were also used to determine the persistence of phytotoxic residues of both herbicides in the field, and the results showed that the effects of chlorsulfuron disappeared within 8 weeks. Triasulfuron residues disappeared within 9 and 14 weeks for the 15 and 30 g a.i. ha^–1 rates respectively.     

Degradation of atrazine and isoproturon in surface and sub-surface soil materials undergoing different moisture and aeration conditions

The influence of different moisture and aeration conditions on the degradation of atrazine and isoproturon was investigated in environmental samples aseptically collected from surface and sub-surface zones of agricultural land. The materials were maintained at two moisture contents corresponding to just above field capacity or 90% of field capacity. Another two groups of samples were adjusted with water to above field capacity, and, at zero time, exposed to drying-rewetting cycles. Atrazine was more persistent (t(1/2) = 22-35 days) than isoproturon (t(1/2) = 5-17 days) in samples maintained at constant moisture conditions. The rate of degradation for both herbicides was higher in samples maintained at a moisture content of 90% of field capacity than in samples with higher moisture contents. The reduction in moisture content in samples undergoing desiccation from above field capacity to much lower than field capacity enhanced the degradation of isoproturon (t(1/2) = 9-12 days) but reduced the rate of atrazine degradation (t(1/2) = 23-35 days). This demonstrates the variability between different micro-organisms in their susceptibility to desiccation. Under anaerobic conditions generated in anaerobic jars, atrazine degraded much more rapidly than isoproturon in materials taken from three soil profiles (0-250 cm depth). It is suggested that some specific micro-organisms are able to survive and degrade herbicide under severe conditions of desiccation.     

氰津·莠30%悬浮剂的气相色谱分析

本文采用气相色谱法,使用CP7906X;英毛细管柱和FID检测器,对混剂中的氰草津和莠去津进行分离与定量。邻苯二甲酸二正丁酯为内标物。分析结果表明氰草津和莠去津的线性相关系数分别为0．99995、0．99999;标准偏差分别为0．23、0．16：变异系数分别为1．49％、1．06％;回收率分别在98．94～100．11％和98．38～101．51％之间。     

Factors affecting degradation rates of five triazole fungicides in two soil types: 1. Laboratory incubations

Triazole fungicides are now widely used commercially and several are known to be persistent in soil. The degradation rates of five such fungicides were measured in laboratory tests with two soils over 720 days, with analysis of soil extracts by high-pressure liquid chromatography. Behaviour in a sandy loam and a clay loam were similar, and incubation of the compounds either singly or in admixture did not influence loss rates except for those of flutriafol which were lower in the latter. Triadimefon was quite rapidly reduced to triadimenol, though traces of the former were always found, indicating a possible redox equilibrium. Flutriafol, epoxiconazole and triadimenol (derived from triadimefon) were very persistent, breakdown following first-order kinetics with half-lives greater than two years at 10 °C and 80% field capacity. Propiconazole was moderately persistent, with a half-life of about 200 days under these conditions. Degradation rates increased about 3-fold as the temperature was increased from 5 to 18 °C, though decreasing soil moisture to 60% field capacity only slightly slowed degradation. The rate constants obtained are used in a companion paper describing field studies on these two soils to compare laboratory-measured degradation rates with losses in the field following commercial sprays. © 1999 Society of Chemical Industry     

The soil degradation of the herbicide florasulam

The route and rate of degradation of florasulam, a low‐rate triazolopyrimidine sulfonanilide herbicide, was investigated in six soil types under aerobic conditions at 20 or 25 °C. Degradation products were isolated and identified by mass spectroscopy. Florasulam was rapidly degraded by microbial action with an average half‐life of 2.4 days (range 0.7 to 4.5 days). The first step in the degradation pathway involved conversion of the methoxy group on the triazolopyrimidine ring to a hydroxy group to form N‐(2,6‐difluorophenyl)‐8‐fluoro‐5‐hydroxy[1,2,4]triazolo[1,5‐c]pyrimidine‐2‐sulfonamide. This metabolite degraded, with a half‐life of 10 to 61 days, via partial breakdown of the triazolopyrimidine ring to form N‐(2,6‐difluorophenyl)‐5‐aminosulfonyl‐1H‐1,2,4‐triazole‐3‐carboxylic acid. This was followed by cleavage of the sulfonamide bridge to form 5‐(aminosulfonyl)‐1H‐1,2,4‐triazole‐3‐carboxylic acid. Other degradation processes involved decarboxylation of the carboxylic acid metabolites and mineralisation to form carbon dioxide and non‐extractable residues. © 2000 Society of Chemical Industry     

三唑醇及其对映异构体在3种不同类型土壤中的降解动态

实验室条件下,初步研究了手性农药三唑醇及其非对映异构体三唑醇A(对映异构体1R,2S体和1S,2R体的混合物)与三唑醇B(对映异构体1R,2R体和1S,2S体的混合物)在浙江杭州潮土(有机质含量1.90%,pH 6.85)、金华水稻土(有机质含量1.63%,pH 4.94)和兰溪红土(有机质含量0.38%,pH 4.03)中的降解动态及对映体之间相互转化的情况。结果表明:三唑醇在潮土、水稻土和红土中的降解半衰期分别为56.4、105.0和154.0 d,180 d时降解率分别为91.9%、79.2%和57.7%;三唑醇在潮土中发生两次三唑醇A体向B体转化和1次三唑醇B体向A体的转化,而在水稻土和红土中,三唑醇A体与B体之间相互各转化1次。表明三唑醇对映异构体的降解动态因土壤性质不同而存在差异。研究结果为三唑醇的科学合理使用及其环境风险评估提供参考。     

Effect of long‐term field application of pendimethalin: enhanced degradation in soil

The effect of long‐term application of pendimethalin in a maize–wheat rotation on herbicide persistence was investigated. Pendimethalin was applied at 1.5 kg AI ha⁻¹ separately as one or two annual applications for five consecutive years in the same plots. Residues of pendimethalin were determined by gas chromatography. Harvest‐time residues of the herbicide decreased gradually over the years and at the end of five years less than 3% of applied pendimethalin was recovered from soil as against 18% in the first year. Residues were found distributed in the soil profile up to 90 cm depth at the end of the experiment with peak distribution of 0.03 µg g⁻¹ in the surface layer of soil treated with 10 herbicide applications. The minimum distribution was, however, in the deepest soil (75–90 cm) profile. Some of the metabolites of pendimethalin ie dealkylated pendimethalin derivative, partially reduced derivative and cyclized product were also traced in surface and sub‐surface soils up to 90 cm. A study of the rate of degradation of pendimethalin in field‐treated soils under laboratory conditions revealed faster degradation compared to control soils. Only the surface soil (0–15 cm) showed this enhanced degradation of the herbicide, which could be due to the adaptability of the aerobic micro‐organisms to degrade pendimethalin. Microbes capable of degrading herbicide were isolated, identified and pendimethalin degradation was confirmed in nutrient broth. © 2000 Society of Chemical Industry     

异丙·莠悬浮剂的气相色谱分析方法

本文介绍了用５％ＯＶ－１０１,长度为１ｍ的玻璃填充柱,以正二十碳烷为内标物,在１８０℃的柱温下用ＦＩＤ检测器对异丙·莠悬浮剂中有效成分异丙甲草胺及莠去津同时进行定量分析。分析测得异丙甲草胺变异系数为０．３０７％,平均回收率１００．１１％,线性相关系数０．９９９９;莠去津的变异系数为０．４１６％,平均回收率９９．９７％,线性相关系数０．９９９９。     

Potential Dissipation of Atrazine in the Soil Unsaturated Zone: a Comparative Study in Four European Countries

A European-wide project has been undertaken to establish the potential for dissipation of atrazine in the soil subsurface environment. Samples were obtained, avoiding contamination, in four countries (Belgium, Greece, Hungary and UK) and laboratory studies carried out. In order to make comparisons between results from each laboratory, a ring experiment was carried out using common methodology for sampling, extraction and analytical techniques. Subsurface materials from each country were distributed to the other countries. Atrazine dissipation was determined in each country for all materials under the same laboratory conditions. The results of this comparative study showed generally good agreement between all laboratories. Significant potential microbiological dissipation was detected in certain samples. Where differences occurred between laboratories this was attributed to small, spatially heterogeneous microbial populations in the subsurface materials. © 1997 SCI.     

Removal of Atrazine Contamination in Soil and Liquid Systems Using Bioaugmentation

Reported levels of atrazine in soils at pesticide mix-load sites can vary between 7·9×10^-5 mM and 1·9 mM . We report on a mixed microbial culture, capable of degrading concentrations of atrazine in excess of 1·9 mM . At initial concentrations of 0·046 M and 0·23 M , the mixed population degraded 78% and 21% of atrazine in soil (100 days), respectively. At the same initial concentrations in liquid cultures, 90% and 56% of the atrazine was degraded (80 days), respectively. Decreased degradation in soil samples may have resulted from atrazine sorption to soil surfaces or decreased contact between the population and the herbicide. In the 0·23 M system, we attribute incomplete degradation to phosphorous depletion. Data for carbon dioxide evolution was fitted to a three-half-order regression model, but we feel that there are limitations of the application of this model to atrazine degradation. The population uses the herbicide as a nitrogen source and little carbon is incorporated into biomass, as the energy status of carbons in the ring leads to their direct evolution as [¹⁴C]carbon dioxide. This situation contributes to an evolution pattern that, when fitted to the three-half-order model, results in underestimation of the biomass produced. Data from our study suggest that our mixed culture could be used for bioremediation of atrazine at concentrations up to and exceeding those currently reported for agrochemical mixing-loading facilities. © 1997 SCI.