Simulation of the persistence of atrazine, linuron and metolachlor in soil at different sites in the USA

The effects of soil temperature and soil moisture content on the rates of degradation of atrazine, linuron and metolachlor were measured in the laboratory in soil from different sites in the USA. Persistence of the herbicides was measured in the same soils in the field during the summers of 1978 and 1979. Weather records from the different sites for the periods of the field experiments were used in conjunction with appropriate constants derived from the laboratory data in a computer program to simulate persistence in the field. There was a general tendency for the model to overestimate the observed soil residues. For example, with atrazine, 40 of the 48 measured residues were lower than those predicted by the model; seven were more than 30% below and two were more than 50% below. With metolachlor, 16 of the 48 measured residues were more than 30% below those predicted and six were more than 50% below; almost identical results were obtained with linuron. When the model overestimated late-season residues by a large amount, the discrepancies between predicted and observed data were usually apparent from early in the experiment. Possible reasons for the discrepancies are discussed.     

Simulation of atrazine persistence in Spanish soils

The persistence of atrazine was monitored in three fields at different sites in Spain during two consecutive years (1990 and 1991). Laboratory assays for determining the influence of temperature and soil moisture content on the rate of herbicide degradation were carried out on soil samples from the same fields. The degradation constants derived from these assays, together with weather records for the period of the field experiments, were used in a computer program which simulated herbicide persistence in the field. Some adjustments were made to adapt the model to Spanish conditions. The model predicted with reasonable accuracy the persistence of the herbicide in two soils, although there was a tendency to overestimate the residues at early dates. Discrepancies between predicted and measured residues were greater in the third soil, due to rapid initial losses that were not predicted by the program. In this case, the agreement was improved if the program was run taking time zero to be one month after herbicide application. Possible reasons for these discrepancies are discussed.     

Simulation of herbicide persistence in soil .III. Propyzamide in different soil types

The effects of soil temperature and soil moisture content on the rate of degradation of propyzamide in five soils were examined under controlled laboratory conditions. Half-lives in soils incubated at field capacity varied from 23 to 42 days at 25°C and from 63 to 112 days at 15°C. The variation in half-life at 25°C and 50% of field capacity was from 56 to 94 days. When the laboratory data were used in conjunction with the relevant meteorological records and soil properties in a computer simulation program, predicted degradation curves for propyzamide in four of the soils in micro-plots were in close agreement with those observed. Use of the program to predict residues of propyzamide in the fifth soil at crop maturity in a series of field experiments concerned with continuity of lettuce production gave values fairly close to those observed when appropriate corrections were made for initial recoveries.     

Prediction of field atrazine persistence in an allophanic soil with Opus2

A modified version of the model Opus was applied to measurements of soil water dynamics and atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) persistence in a Bruntwood silt loam soil (Haplic Andosol, FAO system) in Hamilton, New Zealand. The modified model, Opus2, is briefly described and parameter estimation for the simulations is discussed. Soil water dynamics were more accurately described by applying measured soil hydraulic properties than by estimating them using pedotransfer functions. A parameter sensitivity analysis revealed that degradation was the most relevant process in simulating pesticide behaviour by Opus2. The Arrhenius equation incorporated in Opus2 did not correctly describe the effect of temperature on degradation rates obtained at 10, 20 and 30 degrees C. However, as the Arrhenius coefficient is a very sensitive parameter and soil temperature variation was relatively narrow in the field, the Arrhenius coefficient was approximated from the laboratory study. The simulation results obtained were superior to modelling at constant temperature. Field measured persistence of atrazine in the topsoil was underpredicted using the half-life determined in the laboratory at 10 degrees C. Modelling with a lag phase followed by accelerated degradation by use of a sigmoidal degradation equation in Opus2 significantly improved the modelling results. Nevertheless, degradation processes in the laboratory under controlled conditions did not accurately represent field dissipation, however well the laboratory degradation data could be described by simple kinetic equations. The study indicates the importance of improving field techniques for measuring degradation, and developing laboratory protocols that yield degradation data that are more representative of pesticide dynamics in field soils.     

Abiotic persistence of atrazine and simazine in water

Hydrolysis and photolysis experiments have been undertaken to investigate the abiotic persistence of atrazine and simazine in a variety of waters. Hydrolysis only occurs to a significant extent at pH values at the lower limit of those found in the natural aquatic environment (pH 4.0 or less). Photolysis was initiated by a wide range of wavelengths in waters at pH 4.0, but only by more energetic wavelengths of less than 300 nm at higher pH values (pH 6 to 8). Based on these data, the aquatic half-life of atrazine and simazine in well-lit acidic upland waters will be typically six days. In lowland rivers with higher pH (7 to 8.5), these triazines are likely to exhibit half-lives of months rather than days. In groundwaters, atrazine and simazine will have half-lives in the order of years, due to the exceedingly slow rate of hydrolysis. © 1999 Society of Chemical Industry     

Simulation of herbicide persistence in soil; a revised computer model

Empirical equations were used to calculate the moisture content of surface soil from measurements of rainfall and daily maximum and minimum air temperatures. Air temperatures were also used to calculate soil temperatures. There was good agreement between calculated and measured moisture contents and temperatures from Wellesbourne and from some sites in North America. The equations were incorporated into a simulation model for the prediction of herbicide persistence. Results from the model were essentially the same, whether calculated or measured soil moistures and temperatures were used in the calculations.     

Trifluralin persistence under two different soil and climatic conditions

An investigation of the persistence of trifluralin was conducted as field experiments over a two year period at latitudes 60°N and 70°N respectively, paying special attention to the soil and climatic conditions. These experiments included glasshouse bioassays with Lolium multiflorum. gas-chromatographic residue analyses and qualitative and quantitative studies on soil bacteria. Special attention was devoted to clay minerals as well as to the soil organic matter. 100 g or 500 g of trifluralin a.i. ha^?1 were applied in the spring 1978 with a reapplication on half of the area the following spring (1979). The phytotoxicity of trifluralin appeared more severe on re-treated plots compared with single applications even at approximately equal residue levels. Trifluralin did not seem to have any real influence on the total number of soil bacteria. A qualitative change of the bacterial flora was however observed as a relative increase of non-sporeformers, Gram negatives and Actinomy-cetes and a relative depression of the Coryneform bacteria/Arthrobacter group. Even at a recommended dosage, a carry-over phytotoxicity the following year may occur, especially when the content of organic matter in the soil is low. Care should therefore be taken when using this herbicide on the same field in two successive years. The properties of the soil seemed to exert a greater influence than the climatic factors on the persistence of trifluralin.     

Simulation of herbicide persistence in soil .I. Simazine and prometryne

The effects of soil temperature and soil moisture content on the rates of degradation of simazine and prometryne were measured under controlled conditions. The time for 50% disappearance of simazine in a sandy loam soil varied from 37 days at 25°C and 13 % soil moisture to 234 days at 15°C and 7% soil moisture. With prometryne, changes in soil moisture content had a greater effect on the rate of loss than similar changes with simazine. The time for 50% disappearance at 25°C was increased from 30 to 590 days with a reduction in soil moisture content from 14 to 5%. With both herbicides, the rate of degradation increased as the initial herbicide concentration decreased and the data suggest that a hyperbolic rate law may be more appropriate than simple first-order kinetics. Degradation curves for three separate field applications of the two herbicides were simulated using the laboratory data and the relevant meteorological records in a computer program. A close fit to the observed pattern of loss of incorporated prometryne was obtained, but prometryne surface-applied was lost rapidly during the first 30–40 days after application. This initial rapid loss could not be predicted by the program. With simazine, the patterns of loss of surface and incorporated treatments were similar, but the simulation model tended to overestimate residue levels. Possible reasons for the discrepancies are discussed.     

莠去津在土壤中的残留试验研究

本文介绍了莠去津在土壤中的残留消解动态试验及其检测方法和检测结果。     

不同湿润比下滴灌土壤入渗特性模拟试验研究

为了研究滴头流量和设计湿润比对土壤水分运移规律及湿润体特性的影响,前期利用粘壤土进行试验研究,然后依据非饱和土壤水动力学理论和滴灌条件下土壤水分运移特征,建立了土壤水分运动模型,利用HYDRUS-3D对不同湿润比下滴灌土壤入渗模型进行求解。通过所建模型,对11个观测点的模拟结果与实测结果进行了对比,得出灌水结束时各观测点模拟与实测含水率的相对误差均小于10%,实测与模拟湿润比的相对误差为4.75%~11.78%。利用所建模型对不同情景下湿润体运移规律进行了模拟,获得了湿润体特征变化规律:滴头流量主要影响水平湿润锋的运移距离,而设计湿润比对垂直湿润锋运移距离的影响较大;滴头流量相同时,设计湿润比越大,湿润体内平均含水率越大,高含水区(含水率0.410 cm~3·cm~(-3))半径也越大;设计湿润比相同时,湿润体内含水率高于0.410 cm~3·cm~(-3)的湿润半径随流量增大而增大。     

Simulation of herbicide persistence in soil .II. Simazine and linuron in long-term experiments

The rates of degradation of simazine and linuron were measured in soil from plots not treated previously with these herbicides. Degradation of both compounds followed first-order kinetics and soil temperature and soil moisture content had a marked effect on the rate of loss. With linuron, half-lives increased from 36 to 106 days with a reduction in temperature from 30° to 5°C at 4% soil moisture, and from 29 to 83 days at 12% soil moisture. Similar temperature changes increased the half-life of simazine from 29 to 209 days and from 16 to 125 days at soil moisture contents of 4 and 12% respectively. A computer program which has been developed for simulation of herbicide persistence was used in conjunction with the laboratory data and the relevant meteorological records for the years 1964 to 1968 in order to test the model against previously published field persistence data for the two herbicides. The results with simazine showed a close correspondence between observed and predicted residue levels but those for linuron, particularly in uncropped plots, were satisfactory for limited periods only.     

Availability of atrazine to plants in different soils

The concentrations of atrazine in the shoots of wheat plants growing in 12 different soils were directly proportional to the soil solution concentrations of herbicide estimated from slurry adsorption measurements. There was a marked discrepancy between the total uptake of herbicide and the amount theoretically supplied by mass-flow in response to transpiration. This discrepancy was less when plants were grown in nutrient solutions. In an experiment with one soil only, the half-life of atrazine was 22 days and when the solution concentration in this soil was corrected for this change, a much closer prediction of atrazine uptake could be obtained. The ways in which interactions between adsorption, breakdown and transpiration rates may affect herbicide toxicity under field conditions are discussed.     

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.     

Factors that influence the persistence of TCA in soil

The persistence of TCA in soil was examined using the pyridine-alkali colorimetric procedure. Loss of TCA was essenlially similar when determined by colorimetry, chloride release or bioassay. Persistence of TCA when incubated with soil at 25°C or sprayed on the soil surface in the field was slightly influenced by soil type. Degradation of TCA occurs largely by microbial action after a lag phase. Soils treated with TCA acquire the ability to degrade further additions of ihe compound without a lag phase. The three soils examined still possessed this ability to differing extents 32 months after they had been sprayed once with TCA at the rate of 22.4 kg/ha. In one experiment the persistence of TCA was shortened appreciably in a plot that had twice previously been sprayed with TCA.     

Behaviour and persistence of trifluralin in soil

The growth response of sorghum to trifluralin, on various soils and soil mixtures, was significantly correlated with organic matter (ranging from <0–1% to 20–4%) but not with clay content (ranging from 3% to 63%). However, in soils with a similar, low organic matter content, the activity of trifluralin increased with increasing clay content. No correlation was found between phytotoxicity of trifluralin and lime content of soils. The persistence of trifluralin incorporated in soil was examined by repeated reseedings of sorghum. Phytotoxicity lasted longer in soil dried and mixed at each interval between seedings than in soil left undisturbed; after 2 months about 50% of the original 4 ppm trifluralin remained in undisturbed soil vs 60 % in repeatedly mixed soil. The rate of degradation, after 2 months of incubation at 50% field capacity, increased with temperatures from 10°to40° the concentration of trifluralin required for a given growth reduction was approximately eight times greater after incubation at 40° than at 10°C. Comportement et persistattce de la trifluraline dans le sol Les effets de Ia trifluraline sur la croissance du sorgho cultivé dans divers sols ou mélanges de sol se sont révlés être en corrélation significative avec la matiere organique (entre < 0,1 % et 20,4 %) mais pas avec la teneur en argile (de 3 % A 63 %). Toutefois dans les sols contenant un taux analogue et faible de matiére organique, l'activité de la trifluraline s'est accrue en même temps que Ia leneur en argile. Aucune corrélation n'a été constatée entre la phytotoxicité de la trifluraline et la teneur en calcaire des sols. La persistance de la trifluraline incorporée dans le sol a été examinée au moyen de ressemis répétés de sorgho. La phytotoxicité dura plus longtemps dans le sol séché et remuéà chaque intervalle entre les semis que dans le sol non travaillé; au bout de 2 mois, 50% environ des 4 ppm de trifluraline apportés à. I'origine restaient dans le sol non remué contre 60% dans le sol plusieurs fois remué. Le taux de degradation, aprés deux mois d'inciibation à 50% de la capacityé au champ, augmenta avec la température de 10°à 40°C; la concentration de trifturaline nécessaire pour obtenir une réduction de croissance donnée fut approximativement huit fois plus grande aprés incubation. à 40° qu'aprés incubation à 10°C. Verhalten und Perststenz von Trifluralin im Boden Die Wachstumsreaktion von Hirse gegenubcr Trifluralin in verschiedenen Böden und Bodenmischungen war signifikant mit dem Gehalt an organischer Substanz (<0–1 %–20–4%) korreliert, nicht aber mit dem Tongehalt (von 3%-63%). Jedoch nahm in Böden mit annähernd gleich niedrigen Gehalten an organischer Substanz die Wirksamkeit von Trifluralin mit steigendeni Tongehalt zu. Zwischen der Phytotoxizität von Trifluralin und dem Kalkgehalt der Böden wurde keine Korrelation gefunden. Die Persistenz von in den Boden eingearbeitetem Trifluralin wurde durch wiederholte Einsaat von Hirse untersucht. Die Phytotoxizität dauerte im Boden, der jeweils zwischen den Einsaaten getrocknet und gemischt worden war, langer an als im nicht derartig behandelten Boden. Nach 2 Monaten waren im letzteren Boden ungefähr 50% der ursprüinglichen 4 ppm Trifluralin verblicben gegenüber 60% im wiederholt durchmischten Boden. Nach 2 Monatlen Inkubation bei 50% Feldkapazität stieg die Abbaurate, wenn die Temperatur von 10° auf 40°C stieg; die für eine gegebene Wachstumsreduktion benötigte Trifluralinkonzentration war bei 40° annShernd achtfach grösser als bei 10°C.     

Behavior and persistence in soil of benefin

The phytotoxicity of benefin, as assessed by sorghum on various soils and soil mixtures, was significantly correlated with the organic matter content but not with the clay or lime content of the soils. After 1 month of incubation no significant activity remained from 2 ppm benefin, and after 2 months only slight activity remained from 4 ppm. Benefin was less persistent than trifluralin and more persistent than nitralin.     

Adsorption of transformation products of atrazine by soil

The adsorption of atrazine and its transformation products, desisopropylatrazine (2-chloro-4-ethylamino-6-amino-l,3,5-triazine), desethyl-atrazine (2-chloro-4-amino-6-isopropylamino-l,3,5-triazine) and hydroxyatrazine (2-hydroxy-4-ethylamino-6-isopropylamino-l,3,5-triazine) to four top-soils was measured. Adsorption coefficients decreased in the order hydroxy atrazine, atrazine, desisopropylatrazine, and desethyl-atrazine: the distribution coefficient between organic matter and water (K_OM) ranged from 40 to 100 dm³ kg^?1 for atrazine, from 30 to 60 dm³ kg^?1 for desisopropylatrazine, from 20 to 50 dm³ kg^?1 for desethylatrazine and from 100 to 590 dm³ kg^?1 for hydroxy atrazine. Data are discussed in the context of earlier literature.     

Sulcotrione versus atrazine transport and degradation in soil columns

A soil column experiment under outdoor conditions was performed to monitor the fate of 14C-ring-labelled sulcotrione, 2-(2-chloro-4-mesylbenzoyl)cyclohexane-1,3-dione and atrazine, 6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine, in water leachates and in the ploughed horizon of a sandy loam soil. Two months after treatment, the cumulative amounts of herbicide residues leached from the soil were 14.5% and 7% of the applied radioactivity for sulcotrione and atrazine, respectively. Maximum leachate concentrations for each herbicide were observed during the first month following application: 120 and 95 microg litre(-1) for sulcotrione and atrazine respectively. After 2 weeks, 78% of the sulcotrione and atrazine was extractable from the soil, whereas after two months only 10 and 4%, respectively, could be extracted. The maximum sulcotrione content in the first 10 cm of soil was identical with that of atrazine. For both molecules, the content of non-extractable residues was low, being around 15%. Sulcotrione seems to be more mobile than atrazine but the consequences for water contamination are similar since lower doses are used.     

Enzyme immunoassay for atrazine analysis in water and soil

Enzyme immunoassay (EIA) has been tested for the detection of atrazine in soil and water. EIA kits and atrazine-fortified samples were received from the International Atomic Energy Agency. Atrazine concentrations of about 0·01 μg litre^-1 could be detected and the central detection point was found at about 0·15 μg litre^-1 which is a reasonably sensitive region for atrazine. A validation study with spiked local water samples yielded acceptable results. No treatment was required for water samples. Extraction of atrazine from soil was done by simple shaking with methanol without any clean-up steps. Detection limits of 1×10^-2 μg litre^-1 for water and 5×10^-3 μg kg^-1 for soil were achieved. © 1998 SCI.