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.     

Relations entre la vitesse de dégradation du propyzamide et les propriétés physicochimiques des sols

Relationship between rate of propyzamide degradation and physico-chemical properties Propyzamide was incubated in 29 different soils at a soil moisture content of 25%. The degradation of the herbicide followed first-order kinetics. The rate of propyzamide degradation was correlated with soil resistivity. Addition of mineral fertilizers inhibited propyzamide degradation.     

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.     

Effect of pH on the degradation of atrazine,dichlorprop, linuron and propyzamide in soil

The rates of disappearance of atrazine, dichlorprop, linuron and propyzamide were measured in two soils incubated at 22°C and 80% water holding capacity. Observations were made at four pH levels in each soil. Atrazine degradation was relatively insensitive to pH; it increased slightly with increasing pH in one soil and decreased in the other. The other compounds all degraded more slowly at low pH in both soils although dichlorprop had essentially disappeared in 14 days under all conditions, so that the effect of pH is not unlikely to be of practical interest. The ratios of the degradation rates of atrazine, linuron, and propyzamide varied with the soil and the pH.     

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.     

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.     

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.     

Effects of soil moisture content on the availability of soil-applied herbicides to plants

The phytotoxicities of atrazine, simazine, linuron, lenacil and aziprotryne were increased as the moisture content of the soil increased. Results from studies with ¹⁴C-labelled atrazine suggested that these differences could be related to differences in concentrations of herbicide accumulated by the plants. Total uptake of atrazine was directly proportional to water uptake, but a comparison of the amounts taken up with those supplied by mass-flow in the transpiration stream suggested that some exclusion factor was operative. It was concluded that herbicide transport within the soil-plant system was the main factor affecting phytotoxicity under the different soil moisture regimes. The significance of the results to herbicide behaviour under field conditions is discussed.     

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.     

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.     

THE ADSORPTION OF FOUR HERBICIDES BY DIFFERENT TYPES OF ORGANIC MATTER AND A BENTONITE CLAY*

Summary. A bioassay was used to study, adsorption of prometryne, simazine, linuron and pyrazon by fibrous peat, sphagnum moss, muck soil and bentonite as 1 % mixtures with quartz sand. Of these bentonite caused least reduction in bioactivity, and sphagnum moss reduced it only slightly more. Fibrous peat and muck soil were the most adsorptive. Prometryne, simazine and pyrazon were more highly adsorbed by fibrous peat than by muck soil, while for linuron the opposite occurred. Fibrous peat was approximately three, seven, thirteen and three times more adsorptive than bentonite for pyrazon, linuron, prometryne and simazine, respectively, while for muck soil the corresponding values were two, fourteen, seven and two. Studies with prometryne and five different soils indicated that percentage organic matter, cation-exchange capacity and specific surface area were all highly correlated with adsorption.     

Persistence and management of enhanced carbetamide biodegradation in soil

The extent of enhanced degradation of the herbicide carbetamide declined over time after herbicide application was discontinued. The kinetics of carbetamide degradation were determined in the same soil for three consecutive years (1994–96) after single annual applications from 1989 to 1992. The DT₅₀ of carbetamide increased from 5.4 d in 1994 to 10.2 d in 1996. However, this was still less than the DT₅₀ in previously untreated soil (23–44 d). A most probable number (MPN) assay demonstrated a link between carbetamide degradation rate and the numbers of micro-organisms capable of carbetamide mineralization. Degradation of six other herbicides was assayed in the carbetamide-pretreated and the previously untreated soils. Propham was the only herbicide which degraded more rapidly in the soil with a history of carbetamide application. Rapid degradation of chlorpropham, a herbicide structurally similar to carbetamide and propham, and propyzamide, a herbicide with similar mode of action and weed control spectrum, was not observed. The results suggest that enhanced biodegradation of carbetamide can be managed by less frequent carbetamide application as a part of a herbicide rotation involving compounds which are structurally dissimilar.     

Studies on a mixed bacterial culture from soil which degrades the herbicide linuron

A stable mixed bacterial culture which degrades the herbicide linuron was isolated from soil by enrichment with linuron in a liquid mineral medium. Radio-respirometry studies showed that the culture mineralised linuron completely. No intermediate degradation products were detected in the medium. The culture was able to utilise linuron as a source of both nitrogen and carbon and was also able to degrade the related herbicides monolinuron and chlorbromuron and the possible intermediate degradation products of linuron: 3,4-dichlorophenyl-l-methylurea, 3,4-dichlorophenylurea and 3,4-dichloroaniline. The culture was unable to degrade the 1,1-dimethyl substituted ureas monuron, diuron or metoxuron. The culture contained Gram-negative aerobic rods, and Gram-positive aerobic non-spore-forming rods and cocco-bacilli. Of 124 isolates from the mixed culture, none degraded linuron in pure culture, indicating that a consortium of organisms is involved. Further investigation suggested that Pseudomonas spp. were important components of the population responsible for degradation.     

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.     

EWRS Herbicide-Soil Working Group: Collaborative experiment on simazine persistence in soil

The effects of soil temperature and soil moisture content on the rate of simazine degradation were measured in the laboratory in soils from sixteen sites located in several different countries. First-order half-lives under standard incubation conditions were significantly correlated with clay content, organic carbon content and soil pH in a multiple linear regression. The temperature dependence of degradation was similar in the different soils whereas the moisture dependence showed considerable variation between soils. Persistence of simazine was also measured in the same soils in the field and at live additional sites. Weather records from the different sites for the periods of the Held experiments were used in conjunction with constants derived from the laboratory data in a computer program to simulate persistence in the field. In general, the model overestimated residues in the field. About half of the calculated residues were within 25% of those observed, an accuracy sufficient for practical purposes, but on several occasions the discrepancies between calculated and observed residues were greater than 50%. Possible reasons for the discrepancies and requirements for further experiments are discussed.     

SHOOT ZONE UPTAKE OF SOIL-APPLIED HERBICIDES IN PISUM SATIVUM L.

Summary. The effects of localized herbicide placement at different internodes of pea ( Pisum sativum L. cv. Alaska) shoots below the soil surface after plant emergence were studied by removing the soil from around the shoots and replacing with herbicide-treated soil. The first internode proved insensitive to linuron, diuron, atrazine and simazine at 4·5 kg/ha, while treatment of the second and third internodes markedly reduced plant growth 4–6 days after treatment. Separate exposure of the first internode alone, and the second and part of the third together to ¹⁴C-labelled atrazine indicated no difference in herbicide metabolism. However, a two- to threefold increase in ¹⁴C uptake and movement to the foliar parts occurred when the second and part of the third internode was treated, as compared to first internode treatment. Thus the differential sensitivity of the internodes to atrazine, and possibly to the other herbicides, may be because the more mature first internode allows less uptake and subsequent movement to the foliar parts.
Absorption dans la zone des tiges des herbicides appliqués dans le sol chez Pisum sativum L.     

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.     

Reduced efficacy and enhanced degradation of carbetamide after repeated application in Australia

Following reports of poor weed control, the effectiveness of repeated applications of carbetamide atid propyzamide in controlling Lolium rigidum Gaud, (annual ryegrass) was examined under field conditions. Repeated applications of carbetamide or propyzamide were less effective in controlling L. rigidum than an initial application. A single application of carbetamide or propyzamide was sufficient approximately to halve the efficacy of a subsequent treatment with the satne herbicide. Laboratory incubations of soil linked the poor performance of carbetamide upon repeated application to an enhanced deg-radation rate. We conclude that the repeated application of carbetamide or propyzamide results in less effective weed control under field conditions and that this can be partially avoided by rotation between carhetamide and propyzamide.     

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.