THE PHYTOTOXICITY OF SOME HERBICIDES IN FIELD AND POT EXPERIMENTS IN RELATION TO SOIL PROPERTIES

Summary. The phytotoxicities in a number of soils of lenacil, linuron, prometryne and simazine to two indicator plants were determined in field and glasshouse experiments. The results were compared with estimates of the adsorption capacity of the soils obtained by two methods using dimethylaminobenzaldehyde as a model adsorbate. The possible influence of other soil properties was also considered.
One of the adsorption measurements had some predictive value for glasshouse behaviour but was not markedly superior to soil organic carbon content for this purpose. None of the factors studied was usefully correlated with field performance. Results from field experiments in spring were poorly correlated with those from similar experiments in autumn. Neither set of field results related closely to those obtained in the glasshouse. It is concluded that the influence of climate was more important than that of soil type.
La phytotoxiciti de quelquts herbicides dans des experiences en pots et en plein champ, en relation avec les propriétés du sol     

Effects of repeated applications of ten soil-active herbicides on weed population,residue accumulation and nitrification*

Ten herbicides, bromacil, chlorthal-dimethyl, diphenamid, diuron, fluometuron, neburon, prometryne, pyrazon, simazine and trifluralin at two doses were repeatedly sprayed, in autumn and in spring, for 4 consecutive years on non-cultivated, sprinkler-irrigated field plots. Herbicidal effect was assessed at 1–2 month intervals on the natural weed population and after each observation a paraquat + diquat spray destroyed emerged weeds. The response of various weed species to herbicides varied markedly but a herbicide-induced shift in the composition of weed population did not occur, presumably because of the paraquat treatment. The overall phytotoxicity to weeds present was, in decreasing order: diuron, bromacil, simazine, trifluralin, prometryne, neburon, fluometuron, pyrazon, diphenamid, chlorthal-dimethyl. Persistence of herbicides was in decreasing order: diuron = bromacil, simazine, neburon (at higher rate), fluometuron, trifluralin, prometryne. Control produced by pyrazon improved with the number of applications, but that of diphenamid and chlorthal-dimethyl remained weak and short. After repeated applications, the activity of these herbicides increased or remained at similar level, but in no case decreased. Soil samples were taken 5 months after each application and bioassayed. Phytotoxic residues were detected beneath the disturbed top-soil from bromacil, diuron, fluometuron and simazine after the first application, and from neburon after the second application; residues from trifluralin were found in the top soil only after the fifth application. After the seventh spraying, residues of bromacil were found in the 45–60-cm soil layer. Ammonia content in soil samples taken from treated plots after the fourth, sixth and seventh application was generally similar to the untreated control. In these samples, nitrate content appeared to be correlated negatively with remaining weed number; the control thus contained less nitrate than efficient herbicidal treatments. Soil samples taken after the seventh application of bromacil, diuron, fluometuron, neburon and simazine, which contained appreciable residual concentrations, did not show significant differences from control, in an in vitro nitrification test.     

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.     

COMPLEX FORMATION AS AN ADSORPTION MECHANISM FOR LINURON AND ATRAZINE

Summary. Measurements were made of the effect of exchangeable cations on the adsorption of linuron and atrazine by an ion-exchange resin, cellulose phosphate powder, bentonite and a peat soil. The cations studied were Ca²⁺, Ni²⁺, Cu²⁺, Fe³⁺ and Ce⁴⁺. The results with linuron were consistent with the hypothesis that complex formation with exchangeable cations is a possible mechanism of adsorption. This was not so with atrazine due to complications arising from pH effects, and it seems unlikely that adsorption of atrazine by this process is significant.     

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 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.     

EVALUATION OF HERBICIDE PERSISTENCE IN SOIL*

Summary. The persistence of ten herbicides in soil was tested in the glasshouse over a 5–month period, using an oat bioassay. Simazine and diuron were highly persistent, atrazine persistent, fluometuron, trifluralin, bromacil and noruron moderately persistent, and pyrazon, prometryne and ametryne of short persistence. Six of these herbicides were also included in a field experiment consisting of logarithmically sprayed strips on which oats were sown at ten intervals of 1 month; changes of herbicidal activity with time were evaluated by measuring the length of the strip showing herbicidal injury. Results corroborate those of the glasshouse experiments except for trifluralin which was more persistent in the field. Disappearance curves were generally sigmoidal. The more persistent compounds showed a long period of slow disappearance followed by rapid disappearance.     

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.     

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.     

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.     

Phytotoxicity of four herbicides in different synthetic soils

The relative phytotoxicity of four soil-applied herbicides, benzthiazuron, cycloate, delachlor, and pyrazon, used for sugar beet (Beta vulgaris L.), was tested on a dilution series of peat, Newe Ya’ar clay soil and Hamadia calcareous clay soil mixed with sand, and of Newe Ya’ar clay soil mixed with lime. The phytotoxicity was assessed with oats (Avena sativa L. cv. Mulga). Cycloate was the most potent herbicide of the four, except in soils with high organic matter ( ?11%), where delachlor was more active. Benzthiazuron was the least phytotoxic herbicide in the peat + sand mixtures, but it was more active than pyrazon in lighter soils of the Newe Ya’ar series. The addition of sand to the peat and the soils increased the phytotoxicity of all herbicides. The addition of lime to Newe Ya’ar clay soil decreased the phytotoxicity of benzthiazuron and pyrazon but not of delachlor.     

THE ADSORPTION OF LINURON, ATRAZINE AND EPTC BY MODEL ALIPHATIC ADSORBENTS AND SOIL ORGANIC PREPARATIONS

Summary. Model adsorbents were prepared by treating cellulose phosphate powder with a series of alkyltrimethylammonium compounds in which the size of the alkyl group was varied from C₈to C₁₈. The adsorption of linuron, atrazine and EPTC by these materials was found to increase logarithmically with increasing chain length. The extent of the adsorption was large compared with the adsorption of these herbicides by a humic acid and by a preparation made by removing the bulk of the inorganic constituents of a peat soil with a mixture of HCl and HF. Since soil organic matter is thought to contain alkyl groups, it is concluded that the possible influence of such groups should be considered in any discussion of the mechanisms involved in the adsorption of organic molecules by soils.
Adsorption du linuron, de I'atrazine de l'EPTC par des adsorbants de la série aliphatique et des préparations organiques de sol     

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.     

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 ADSORPTION OF UREA AND SOME OF ITS DERIVATIVES BY A VARIETY OF SOILS

Summary. The absorption of urea and a number of its derivatives by different soils was investigated using a slurry-type procedure. The materials could be listed in the following order of increasing tendancy to be adsorbed: urea, fenuron, methylurea, phenylurea, monuron, monolinuron, diuron. linuron, neburon and chloroxuron. Both N -aryl and N -alkyl substituents appeared to play a part in adsorption. Increasing chain length in the alkyl substituents and chloro- and chlorophenoxy substitution in the aryl substituent increased adsorption. There was no relationship between adsorption and water solubility.
Organic matter content was the only soil property that could be related to adsorptive capacity. The evidence of Langmuir isothermal equilibrium plots suggests that only a fraction of the total soil surface is available for the adsorption of substituted ureas.
L'adsorption Je l'uré de ses dérivés sur dfférents sols     

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     

ADSORPTION AND DESORPTION OF SIMAZINE BY SOME ROTHAMSTED SOILS

Summary. The adsorption of simazine from, and subsequent desorption into, 0–01 M calcium chloride solution was investigated using twenty-three Rothamsted soil samples from sites differing greatly in cropping history and manurial treatment. Organic carbon content was the only factor related to the ability of the soils to sorb simazine; this accounted for 90% or more of the variation between soils Equilibrium was attained during adsorption in from fewer than 2 to more than 24 hr. Equilibrium during desorption was only occasionally attained within 24 hr. Differences between theoretically predicted and measured concentrations of simazine in solution following desorption were least for soils that attained equilibrium fastest during adsorption. Differences in adsorption and desorption kinetics between soils could not be related to soil pH, organic carbon content or cropping and manuring history. Comparisons of unlimed and limed soils suggested that no simnazine was lost by acid hydrolysis during the experiments.
Adsorption et désorption de la simazine par quelques sols de Rothamsted     

Interactions between soil-applied herbicides in the roots of some legume species

The effects on plant growth of applying trifluralin or nitralin combination with simazine, atrazine, prometryne and linuron to the upper 5-cm root region of vetch (Vicia sativa L.), pea (Pisum sativum L.) and soybean (Glycine max) were investigated. Foliar injury due to herbicides of the second group was markedly reduced in each species by simultaneous treatment with trifluralin or nitralin both of which inhibited lateral root growth without affecting aerial plant growth or tap root extension growth. This inhibition of lateral root growth in roots treated with trifluralin or nitralin was associated with reduced uptake and subsequent transport to the foliage of ¹⁴C-labelled simazine in vetch and pea and ¹⁴C-labelled atrazine in soybean. This probably accounted for the reduction in simazine and atrazine phytotoxicity. In the presence of trifluralin or nitralin comparatively higher amounts of radioactivity were retained in the roots of pea and soybean and this reduced the amount of ¹⁴C available for transport to the foliage. This was not evident in vetch.     

Shoot zone uptake of soil-applied herbicides in some legume species

Localized placement of prometryne, linuron and diuron in the soil at the first or second shoot internodes of dwarf broad bean (Vicia faba L.) equally reduced aerial plant growth, whereas simazine and atrazine had no effect. Growth reduction also occurred when the first shoot internode of scarlet runner bean (Phaseolus multiflorus L.) in the soil was treated with all five herbicides, especially with diuron. Localized placement of these herbicides at the first or second shoot internodes of vetch (Vicia sativa L.) in the soil equally reduced aerial plant growth. Foliar injury to vetch due to placement of these herbicides in the shoot zone of the soil was markedly reduced by simultaneous treatment with trifluraiin or nitralin which prevented adventitious root development on the shoot without otherwise affecting plant growth. This lack of root development on the shoots treated with trifluraiin was associated with a marked decrease in ¹⁴C-labelled atrazine uptake, which probably accounted for the reduction in atrazine phytotoxicity. A similar explanation may account for the reduced phytotoxicity of the other herbicides in the presence of trifluraiin or nitralin.     

Effect of herbicides on cell membrane permeabUity in Lemna minor

Leakage of electrolytes was the criterion used to study the effects of several herbicides on cell membrane permeability in Lemna minor L. Dinoseb. sodium azide, linuron, prometryne and simazine were the most active in increasing cell membrane permeability, followed by oxyfluorfen, amitrole, and 2,4—D. Glyphosate and dalapon were the least active. In all cases, the longer the period elapsed after treatment (i.e. 96 h) the lower was the concentration needed to alter cell membrane permeability. Light was necessary for oxyfluorfen activity. With glyphosate, dalapon and oxyfluorfen, visible injury symptoms were noted after 48–96 h, but no further significant increase in cell membrane permeability occurred as a result.