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.     

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.     

Residualwirkung von Chlortriazin-Herbiziden im Boden an drei rumänischen Standorten. I. Prognose der Persistenz von Simazin und Atrazin im Boden

Residual effects of chlorotriazine herbicides in soil at three Rumanian sites. I. Prediction of the persistence of simazine and atrazine Persistence of simazine and atrazine in the top 10 cm soil was measured at three sites in Rumania with variations in climate and soil conditions. Both herbicides were applied at 1 and 3 kg ai ha^?1 to uncropped plots and to plots cropped with maize (Zea mays L.). Rates of residue decline were independent of application rate and crop cover but varied between sites. The time for 50% loss of atrazine varied from 36 to 68 days and that of simazine from 48 to 70 days. Laboratory studies were made with atrazine to characterize degradation rates under standard conditions and to measure adsorption and leaching behaviour in the different soils. Weather records for the periods of the field experiments were used in conjunction with appropriate constants derived from the laboratory results, or from data in the literature, in a computer program to simulate persistence in the field. Results from the model were in reasonable agreement with the observed soil residues although there was a tendency to overestimate rates of loss on some occasions. The results suggest that the model of persistence was sufficiently accurate for practical purposes, and that its use could preclude the need for extensive analytical measurements of residues.     

Residues of atrazine, simazine, linuron and diuron after repeated annual applications in a peach orchard

Annual applications of the herbicides atrazine, simazine, linuron and diuron at 45 kg/ha were made to the same plots for 9 consecutive years from 1963 to 1971 in a peach (Prunus persica (L.) Batsch.) orchard located on sandy loam soil near Harrow, Ontario. Soil samples from these plots were collected in late October for the last 3 years (1969–1971) and trees were cut down in December, 1969. Herbicide residues were determined by bioassays based on the fresh and dry weight of oats (Avena sativa L.) and in one year results were confirmed by chemical analysis. Significant accumulation of herbicides was not observed. The maximum residue levels measured in October over the 3 years of sampling were 7′3 kg/ha for diuron, 3–8 kg/ha for linuron, 1–6 kg/ha for simazine and 04 kg/ha for atrazine in the top 15 cm of the soil profile. Simazine and atrazine showed a rapid decrease in amount after treatment but diuron and linuron were degraded more slowly. Measurable residues of all herbicides were confined to the upper 15 cm of the soil profile and the majority of herbicide remained in the 0–5-cm soil layer. Oats were planted in the orchard plots from 1972 to 1974 to follow the disappearance of the herbicides. All herbicides caused highly significant yield decreases in 1972, atrazine causing the least (38%) and diuron the greatest (86%) reductions. Diuron reduced the yield of oats in 1973 and caused a highly significant decrease in the weight of young oat plants in 1974.     

THE EFFECT OF REPEATED FIELD APPLICATIONS OF FOUR HERBICIDES ON THE EVOLUTION OF CARBON DIOXIDE AND MINERALIZATION OF NITROGEN IN SOIL

The effect of repeated annual applications over 7-8 years of MCPA, triallate, simazine and linuron to field plots on the evolution of CO₂ and mineralization of nitrogen in soil samples incubated in the laboratory is described. The plots were either cropped and treated with standard doses, or uncropped and sprayed with doses 3-4 times above the level used in agricultural practice. While the applications of MCPA and tri-allate did not exert any inhibitory effects in soils from the uncropped plots those of simazine and linuron led to a lowering in CO₂ output in several instances and in mineral N on infrequent occasions. These effects are assumed to be the result of a difference in the content of easily-degradable organic matter between the treated plots and the controls. A direct anti-microbial action of the two herbicides is not very probable because in laboratory experiments with simazine up to 512 ppm the output of CO₂ and the mineralization of N was not affected while linuron at 500 ppm gave only a minor depression in CO₂ evolution. Effects on soil fertility are unknown but seem unlikely in view of the small extent and infrequency of the reductions observed. On the cropped plots the MCPA and tri-allate treatment showed no effects. With linuron and simazine a significant lowering in respiration and mineralization of N occurred on single occasions only, during a 5-year period.     

Enhanced degradation of some soil-applied herbicides

In a field experiment involving repeated herbicide application, persistence of simazine was not affected by up to three previous doses of the herbicide. With propyzamide, there was a trend to more rapid rates of degradation with increasing number of previous treatments. Persistence of linuron and alachlor was affected only slightly by prior applications. In a laboratory incubation with soil from the field that had received four doses of the appropriate herbicide over a 12–month period, there was again no effect from simazine pretreatments on rates of loss. However, propyzamide, linuron and alachlor all degraded more rapidly in the previously treated than in similar untreated soil samples. Propyzamide, linuron, alachlor and napropamide degradation rates were all enhanced by a single pretreatment of soil in laboratory incubations, whereas degradation rates of isoproturon, metazachlor, atrazine and simazine were the same in pretreated and control soil samples.     

Evaluation of a simulation model for prediction of herbicide movement and persistence in soil

The movement and persistence of residues of propyzamide, linuron, isoxaben and R-40244 were measured in a sandy loam soil in field experiments prepared in spring and autumn. None of the herbicides moved to depths greater than 12 cm in the soil during the winter period, following application in autumn, and none moved more than 6 cm in the soil, following application in spring. The general order of persistence of total soil residues was isoxaben > linuron = R-40244 > propyzamide. Appropriate constants to describe the moisture and temperature dependence of degradation were derived from laboratory incubation experiments and used with measurements of the strengths of adsorption of the different herbicides by the soil, in a computer model of herbicide movement. The model, in general, gave good predictions of total soil residues, but overestimated herbicide movement, particularly in winter. Measurements of herbicide desorption from the soil at intervals, during a laboratory incubation experiment, demonstrated an apparent increase in the strength of adsorption with time. When appropriate allowance was made for these changes in adsorption in the computer model, improved predictions of the vertical distribution of the herbicide residues were obtained.     

The effect of age on the availability of linuron and simazine residues in soil

Residues of linuron and simazine were measured by both bioassay and gas-chromatographic methods in soil from field plots that had been treated either 20 weeks (both compounds). 41/2 years (linuron) or 51/2 years (simazine) previously. There were no significant differences between the results obtained with the two methods; therefore the relationship between extractable herbicide and that available to plants was independent of the age of the residue. Hence‘bound’residues, if they existed in these plots, had no phytocidal significance.     

Tests of soil fertility following repeated applications of MCPA, tri-allate, simazine and linuron

The following herbicides were applied annually from 1963 to experimental plots of appropriate crops grown in monoculture: MCPA 1.7 kg ha^?1, triallate 1.7 kg ha^?1, simazine 1.7 kg ha^?1 and linuron 0.84 kg ha^?1 (applied twice per year). Before the eighth treatment in 1970, nutrient status, pH and growth in greenhouse tests of a range of plants were similar in soils from treated and control plots. There were no significant differences in yield when several test crops were grown in the field plots in 1977. In a similar experiment which ran for 6 years, the same herbicides were applied twice per year at twice the above rates on each occasion (three times a year at 1.7 kg ha^?1 in the case of linuron) to uncropped plots. Three years after the last treatment, there were no differences in extractable nutrients, pH, soil structure and crop yield on treated or control plots. These results support the conclusion from the main monitoring of the experiments reported elsewhere that annual treatments with these herbicides have had no adverse affect on the soil.     

Effect of soil water content at the time of application on herbicide content in soil solution extracted in a pressure membrane apparatus

Wettable powder formulations of simazine, metribuzin and linuron and a suspension concentrate of simazine were sprayed on to soil particles which were either at a water content equivalent to pF 2·5 or air dry. Air dry samples were then wetted to pF 2·5 immediately or after 24 h. Soil solutions were removed using a pressure membrane apparatus at intervals up to 96 h after wetting. In each case the concentration in soil solutions expressed after 96 h following application to wet soil, or dry soil wetted immediately, were close to those predicted on the basis of Freundlich adsorption isotherm data obtained in slurry equilibrium conditions. There were, however, some differences after shorter periods. Concentrations were always lower in solutions obtained from air dry soil that was not wetted for 24 h. After 96 h simazine and metribuzin concentrations were about 50% of those obtained following application to wet soil, while that of linuron was about 25%. Differences of this size may be large enough to affect mass transfer phenomena and phytotoxicity. It seems likely that suspension of these herbicides sprayed in formulations on to wet soil dissolved in soil water at least as fast as would be predicted theoretically.     

Simulation of the persistence of eight soil-applied herhicides

The effects of soil temperature and soil moisture content on the rates of degradation of simazine, atrazine, propyzamide, linuron, metamitron, trifluralin, metribuzin und chlorthaldimethyl were measured in a sandy loam soil under controlled laboratory conditions, Atrazine degradation was the least dependent on soil moisture and metamitron degradation the most. Linuron degradation was the least affected by temperature and degradation of chlorthal-dimethyl was the most temperature-dependent. In the field, trifluralin, linuron and chlorthal-dimethyl were the most persistent herbicides with over 40% of the amounts applied remaining 5 months after application in spring, Simazine and propyzamide were intermediate with residues between 20 and 30% of the initial dose. Atrazine, metamitron and metribuzin were the least persistent with residues generally less than 20% of the amounts present initially. Weather records for the periods of the field experiments were used in conjunction with the appropriate constants derived from the laboratory data in a computer program to simulate persistence in the field. The model predicted with reasonable accuracy the relative order of persistence of the different herbicides, with the exception of metribuzin. With simazine, atrazine, propyzamide and in particular, metribuzin, there was a tendency to underestimate rates of loss. It is suggested that herbicide mobility in the soil was responsible for the poor agreement in some experiments. ASimulation de la persis tanee de huit herbicides appliqués sur le sol Les effets de la lempérature du sol et de sa teneur en eau sur les laux de dégradation ont étéétudiés pour les herbicides suivants:simazine, atrazinc, propyzamide, linuron, métamitrone, trifluraline, métribuzine et chlorthal-diméthyle. Ces taux de dégradation ont été mesurés dans un sol limono-sableux, dans des conditions contrôlés au laboratoire. La dépendance de la dégradation vis-á-vis de l'humidité du sol a été minimale pour I'atrazine et maximale pour la métamitrone. La dégradation du linuron a été Ia moins affectée par la température et celle du chlorthal-diméthyle la plus affectée. Au champ, la trifluraline, le linuron et le chlorthal-diméthyle ont été les herbicides les plus persistants, plus de 40% des quantités appliquées au printemps persistant encore 5 mois après. La simazine et le propyzamide se sont comportés de f açon intermédiaire, avec des résidus situés entre 20 et 30% de la dose initiale. L'atrazine, la métamitrone et la métribuzine ont été les moins persistants avec des résidus généralement inférieurs à 20% de la quantité initialement présente. L'enregistrement des conditions climatiques pendant la période des expériences au champ a été utilisé, avec les constantes appropriées provenant des résultats au laboratoire, dans le programme d'un ordinateur pour simuler la persistance au champ, Le modéle obtenu a permis de prévoir avec une précision raisonnable I'ordre relatif des pcrsistances des différents herbicides, à I'exception de la métribuzine. II s'est manifesté une tendance à la sous-estimation des taux de pertes pour la simazine, Tatrazine, le propyzamide et en particulier pour la métribuzine, II est suggéré que la mobilité des herbicides dans le sol a été responsable de la médiocre concordance observée dans quelques expériences. Simulation der Persistenz von acht Bodenherbiziden Es wurde die Wirkung der Bodentemperatur und der Bodenfeuchtigkeit aut die Abbaurate folgender Herbizide unter kontrollierten Laborbedingungen festgestellt: Simazin, Atrazin, Propyzamid, Linuron, Metamitron, Trifluralin, Metribuzin und Chlorthal-dimethyl. Der Abbau von Atrazin war am wenigsten, der Abbau von Metamitron am stärksten von der Bodenfeuchtigkeit abhängig. Der Abbau von Linuron wurde am geringsten durch die Temperatur beeinflusst, während der Abbau von Chlorthal-dimethyl am stärksten temperaturabhängig war. Unter Feldbedingungen wurden Trifluralin. Linuron und Chlorthal-dimethyl am langsamsten abgebaut - von der im Frühjahr ausgehrachten Menge waren nach fünf Monaten noch 40% vorhanden. Simazin und Propyzamid nahmen mit 20 und 40% eine miltlere Stellung ein. Alrazin, Metamitron und Metribuzin waren am wenigsten persistent: bei ihnen waren nur noch weniger als 20% des Anfangsgehalts festzustellen. Mit Hilfe der Klimadaten für die entsprechenden Perioden der Feldversuche und den entsprechenden Konstanten aus den Laborversuchen wurde mit einem Computerprogramm die Herbizidpersistent für Feldbedingungen simuliert. Mit dem Modell konnte die relative Rangfolge der Herbizidpersistenz mit hinreichender Genauigkeit vorhergesagt werden; Metribuzin machte jedoch eine Ausnahme. Für Simazin, Atrazin, Propyzamid und besonders für Metribuzin wurden die Abbsuraten etwas unterschätzt. Es wird angenommen, dass die mangelnde Übereinstimmung bei einigcn Versuchen auf den Transport der Herbizide im Boden zurückzuführen ist.     

Detection of triazine and urea herbicide residues by various characteristics of oat seedlings in bioassays

Atrazine, simazine, diuron, and linuron applied to soil increased the percentage moisture of oat (Avena sativa L.) shoots in bioassays at the lowest dose tested of 0·25 ppm. Further increases occurred up to 2 ppm but at higher concentrations the percentage moisture decreased. At all doses of each herbicide, shoot dry weight was decreased. In oats grown on soil collected from a peach orchard which had received repeated annual applications of these herbicides, the percentage moisture of the oat shoots was higher than the control value whenever the oat dry weight was decreased and provided a method of residue detection as sensitive as dry weight measurements. Treatment of oats by soil application of the above herbicides in bioassays also caused increases in the electrical conductivity of an aqueous extract of the oat shoots per mg of dry weight and this characteristic was slightly more sensitive than dry weight in detecting herbicides in orchard soil. The conductivity of the extract per mg of water in the shoots, however, only increased as percentage moisture decreased. The weight of neutral water-soluble material in oat shoots decreased much more rapidly than dry weight in bioassays with standard herbicide concentrations. Determination of the weight of neutral water-soluble material in oat plants grown on orchard soil samples indicated the presence of herbicide residues in 50% of the cases in which residues were not detectable by dry weight. The weight of neutral material as a percentage of dry weight was almost as sensitive. Chemical analysis of soil in which oat plants had a decreased level of neutral water-soluble compounds indicated that this characteristic had a lower limit of detection for herbicide residues of approximately 0.10 ppm.     

Transport to ground‐water of six commonly used herbicides: a prediction for two Italian scenarios

In Italy suitable standard scenarios for pesticide risk assessment based on computer models are lacking. In this paper we examine the use of the VARLEACH model to assess the potential danger of ground‐water pollution by six herbicides (alachlor, atrazine, cyanazine, linuron, simazine and terbuthylazine) which are used to protect irrigated (maize) and non‐irrigated (sorghum) crops in the Po Plain, one of the most important agricultural lands in Italy. Two extreme scenarios are taken: real worst case (sandy soil) and real best case (clay loam soil). The simulation suggests that cyanazine, linuron and terbuthylazine can be safely used in clay loam soil in both non‐irrigated and irrigated crops, while alachlor, atrazine and simazine can be safely used only in non‐irrigated crops. On the other hand, the application of all the herbicides tested should be avoided in sandy soil, with the exception of linuron in non‐irrigated crops. © 2000 Society of Chemical Industry     

PERSISTENCE OF PHYTOTOXIC RESIDUES OF TRIAZINE HERBICIDES IN SOIL

Summary. A bioassay technique for the determination of phytotoxic residues of triazine herbicides and monuron in soil from field plots is described. The effect of a dilution series with untreated soil on shoot growth of Italian ryegrass ( Lolium multiflorum Lam.) is compared with that in a corresponding assay at the lime of application of the herbicide. This method was used to compare the persistence of residues of simazine, propazine, prometon and monuron, and to compare persistence in 3 years and in three soil types. The time required for disappearance of 80% of the activity following application of 2 lb/ac of simazine varied from 7 to 27 weeks, according to the year. Prometon was the most persistent of the triazines tested.
Persistance de résidus phyloloxiques d'herbicides à base de triazines dans le sol     

Persistence of 2,4,5-T in a heavy clay soil

The persistence of the herbicide 2,4,5-T was studied at different controlled temperatures and moisture levels in Regina heavy clay. Degradation approximated to first-order kinetics and the half-life varied from about 4 days at 35°C and 34% soil moisture to about 60 days at 10°C and 20% soil moisture. The laboratory data were used in conjunction with the appropriate measurements of surface soil temperature and moisture content in the field to simulate the degradation pattern for the herbicide in five separate micro-plot experiments. Satisfactory agreement with the observed patterns of loss was obtained in two of the experiments but in the other three, the model over-estimated rates of loss. It is suggested that the reason for this was the difficulty of obtaining a correct measure of soil moisture content to use in the simulation program.     

Specific microbial responses to herbicides*

Examples from the literature and from the authors’own laboratory demonstrate that herbicides can exert adverse effects on the soil micro-flora, depending on concentration, though often at higher rates than the herbicidal dose. Examples refer to changes in microbial growth (asulam, linuron, paraquat) and equilibrium (metoxuron), respiration and nitrification in samples from field experiments (linuron, simazine) and laboratory experiments (bentazone, glyphosate, barban, etc.), enzyme activities (urease, phosphatase; barban, chlorpropham, linuron) and the decay of sprayed vegetation (glyphosate, paraquat).     

Persistence of pronamide in soil

Under field conditions, there was little loss of herbicidal activity following spring application of pronamide when the soil temperature remained below about 13°c, but under normal summer conditions loss was rapid (half-life 2–4 weeks). The rate of loss was retarded when the surface soil became very dry. After autumn application, there was no change in activity during the winter months and assays on samples taken in the following spring showed that little leaching had taken place from the surface 5 cm. In laboratory studies, breakdown was shown to follow first-order kinetics. Half-lives at 10% soil moisture were 29 days at 23°c, 63 days at 15°c and 140 days at 8°c. At 23°c the half-life was extended to 52 days when the soil moisture content was reduced by half.     

Field experiments to investigate long-term effects of repeated applications of MCPA, tri-allate, simazine and linuron: II. Crop performance and residues 1969–78

In four field experiments begun in 1963, each of four herbicides was applied to plots planted wilh the same crop each year. The annual treatments were: MCPA at 17 kg/ha to barley (Hordeum sativa Jess) and wheat (Triticum aestivum L.) at growth stage 15. tri-allate at 17 kg/ha pre-emergcnce to barley and wheat, simazine at l7kg/ha pre-emergence to maize (Zea mays L.) and linuron in two applications of 084 kg/ha pre- and post-emergence to carrots (Daucus carota L.). MCPA did not affect growth or yield of either barley or wheat. In general tri-allate also did not aftect the crops although wheat yield was depressed in 1978, wheat 1000 grain weight was reduced in 1972 and barley germination percentage was increased in 1973. Simazine did not influence the height, yield or appearance of maize. Linuron normally produced no effect on carrot yield, density and size. However, in 2 years when the post-emergence application was late, density but not yield was lower than in control plots. There was no accumulation of residues of any of these compounds in the soil. Rates of loss were similar to those predicted on ihe basis of laboratory experiments. In a fifth experiment these herbicides were applied twice per year (3 times in the case of linuron) at double the rales above on each occasion to bare plots. These applications ceased in 1968 (1969 for MCPA) but residues were monitored until 1972 except in the case of MCPA. Disappearance rates were similar to those in the cropped plots and residues were largely confined to the top 10 cm. The plots treated with MCPA had developed an enhanced ability lo degrade il prior to 1968. This persisted for 5 years after the final application.     

Spatial variability in the mineralisation of the phenylurea herbicide linuron within a Danish agricultural field: multivariate correlation to simple soil parameters

The spatial variability in the mineralisation rate of linuron [N-(3,4-dichlorophenyl)-N'-methoxy-N'-methylurea] was studied within a previously treated Danish agricultural field by sampling soils from eleven different plots randomly distributed across an area of 20 x 20 m. The soils were characterised with respect to different abiotic and biotic properties including moisture content, organic matter content, pH, nutrient content, bacterial biomass, potential for mineralisation of MCPA [(4-chloro-2-methylphenoxy)acetic acid] and linuron. Five soils had a potential for mineralisation of linuron, with 5-15% of the added [ring-U-14C]linuron metabolised to 14CO2 within 60 days at 10 degrees C, while no extensive mineralisation of linuron was observed in the six remaining soils within this period. A TLC analysis of the methanol-extractable residues showed no development of 14C-labelled metabolites from linuron in any of the samples. Multivariate analysis was conducted to elucidate relationships between the intrinsic properties of single soil samples and initial rate of linuron mineralisation. The analysis indicated that important soil parameters in determining the spatial heterogeneity included the C(total)/N(total) ratio, pH and the water-extractable potassium contents, with the first of these highly negatively correlated and the last two highly positively correlated to the initial linuron mineralisation rate. This study shows that enhanced biodegradation of linuron may develop with successive field treatments, but that considerable in-field spatial heterogeneity in the degradation rate still exists. Combined with a parallel enrichment study focused on the underlying microbial processes, the present results suggest that intrinsic soil properties affect the linuron-metabolising bacterial population and thereby determine the spatial variability in the linuron mineralisation activity.     

Evidence for cross-adaptation between s-triazine herbicides resulting in reduced efficacy under field conditions

BACKGROUND: Enhanced atrazine degradation has been observed in agricultural soils from around the globe. Soils exhibiting enhanced atrazine degradation may be cross-adapted with other s-triazine herbicides, thereby reducing their control of sensitive weed species. The aims of this study were (1) to determine the field persistence of simazine in atrazine-adapted and non-adapted soils, (2) to compare mineralization of ring-labeled (14)C-simazine and (14)C-atrazine between atrazine-adapted and non-adapted soils and (3) to evaluate prickly sida control with simazine in atrazine-adapted and non-adapted soils.RESULTS: Pooled over two pre-emergent (PRE) application dates, simazine field persistence was 1.4-fold lower in atrazine-adapted than in non-adapted soils. For both simazine and atrazine, the mineralization lag phase was 4.3-fold shorter and the mineralization rate constant was 3.5-fold higher in atrazine-adapted than in non-adapted soils. Collectively, the persistence and mineralization data confirm cross-adaptation between these s-triazine herbicides. In non-adapted soils, simazine PRE at the 15 March and 17 April planting dates reduced prickly sida density at least 5.4-fold compared with the no simazine PRE treatment. Conversely, in atrazine-adapted soils, prickly sida densities were not statistically different between simazine PRE and no simazine PRE at either planting date, thereby indicating reduced simazine efficacy in atrazine-adapted soils.CONCLUSIONS: Results demonstrate the potential for cross-adaptation among s-triazine herbicides and the subsequent reduction in the control of otherwise sensitive weed species. Copyright (c) 2008 Society of Chemical Industry.