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 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.     

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.     

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.     

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.     

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     

Evidence for the Accelerated Degradation of Isoproturon in Soils

The herbicide isoproturon was degraded rapidly in a sandy loam soil under laboratory conditions (incubation temperature, 15°C; soil moisture potential, -33 kPa). Degradation was inhibited following treatment of the soil with the antibiotic chloramphenicol, but unaffected by treatment with cycloheximide, thus indicating an involvement of soil bacteria. Rapid degradation was not observed with other phenylurea herbicides, such as diuron, linuron, monuron or metoxuron incubated in the same soil under the same experimental conditions. Three successive applications of isoproturon to ten soils differing in their physicochemical properties and previous cropping history induced rapid degradation of the herbicide in most of them under laboratory conditions. There were, however, no apparent differences in ease of induction of rapid degradation between soils which had been treated with isoproturon for the last five years in the field and those with no pre-treatment history. A mixed bacterial culture able to degrade isoproturon in liquid culture was isolated from a soil in which the herbicide degraded rapidly.     

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

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

Rapid dissipation of atrazine in soils taken from various maize fields

A laboratory study was carried out in order to measure the degradation rate of atrazine in 36 different soils taken from maize ( Zea mays L.) fields in Belgium. These soils differed in their alrazme treatment histories. pH. organic matter content and type of organic and mineral fertili-zation, Half-lives of less than 10 days were found in more than 60% of the soils sampled. This rapid dissipation could be linked in a significant way to repeated pretreaiments with atrazine (intensive maize cropping) as well as to higher pH values (from neutral to alkaline), A low organic matter content might also be a factor explaining the rapid degradation of atrazine. but to a lesser extent than the first two factors. On the other hand mineral fertilization was shown to slow down atrazine dissipation. It is hypothesized that repeated treatments of atrazine cause a mi-crobial adaptation to atrazine degradation and that acidic soil conditions impede this adaptation. To date, this is the first time that evidence for widespread accelerated degradation of atrazine has been reported.     

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.     

Chemical versus microbial degradation of cyanazine and atrazine in soils

A laboratory study was performed to investigate the relationship between chemical (non-biological) and microbial degradation of cyanazine and atrazine in soils ranging in pH from 5.3 to 8.1. Atrazine degradation was dominated by chemical processes in both a moderately acidic and a neutral pH soil, but showed a significant microbial involvement in the neutral pH soil. The primary cyanazine degradative mechanism was dependent on soil properties. Cyanazine was short-lived in neutral to slightly basic soils, due to rapid microbial degradation. Cyanazine amide and cyanazine acid were the major metabolites formed. In a moderately acidic soil, microbial degradation was slowed and chemical processes were the primary means of cyanazine degradation.     

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     

Effect of concentration on the decomposition rates in soil of atrazine,linuron and picloram

The decomposition of atrazine, linuron and picloram when incubated with two soils at four levels of application was measured for periods of 3 or 4 months. The applicability of zero-order, half-order, first-order and Michaelis-Menten kinetics was considered. None of the equations described the breakdown rates adequately in spite of the apparent theoretical advantage for using an expression of the Michaelis-Menten type. In each case the rate of decomposition increased as the initial herbicide concentration decreased.     

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.     

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.     

Simulation of the persistence of atrazine in soil at different sites in Portugal

The effects of soil temperature and soil moisture content on the rates of degradation of atrazine, were measured in the laboratory in soils from different sites in Portugal. Persistence of atrazine was measured in the same soils in the field during the spring and summer of 1984, 1985, 1986 and 1987. Weather records from the different sites, measured during the periods of the field experi ments, were used in conjunction with appropriate constants derived from the laboratory data in a computer program to simulate persistence in the field. The model generally overestimated the ob served soil residues, particularly during the first 7–14 days after application. The fit from the model was good from day 14 to the end of the experiments.     

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.     

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.     

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

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

Spatial variability in 14C-herbicide degradation in surface and subsurface soils

The spatial variability in mineralization of atrazine, isoproturon and metamitron in soil and subsoil samples taken from a 135-ha catchment in north France was studied. Fifty-one samples from the top layer were taken to represent exhaustively the 31 agricultural fields and 21 soil types of the catchment. Sixteen additional samples were collected between depths of 0.7 and 10 m to represent the major geological materials encountered in the vadose zone of the catchment. All these samples were incubated with 14C-labelled atrazine under laboratory conditions at 28 degrees C. Fourteen selected surface samples which exhibited distinctly different behaviour for atrazine dissipation (including sorption and mineralization) were incubated with 14C-isoproturon and 14C-metamitron. Overall soil microbial activity and specific herbicide degradation activities were monitored during the incubations through measurements of total carbon dioxide and 14C-carbon dioxide respectively. At the end of the incubations, extractable and non-extractable (bound) residues remaining in soils were measured. Variability of herbicide dissipation half-life in soil surface samples was lower for atrazine and metamitron (CV < 12%) than for isoproturon (CV = 46%). The main contributor to the isoproturon dissipation variability was the variability of the extractable residues. For the other herbicides, spatial variability was mainly related to the variability of their mineralization. In all cases, herbicide mineralization half-lives showed higher variability than those of dissipation. Sorption or physicochemical soil properties could not explain atrazine and isoproturon degradation, whose main factors were probably directly related to the dynamics of the specific microbial degradation activity. In contrast, variability of metamitron degradation was significantly correlated to sorption coefficient (K(d)) through correlation with the sorptive soil components, organic matter and clay. Herbicide degradation decreased with depth as did the overall microbial activity. Atrazine mineralization activity was found down to a depth of 2.5 m; beyond that, it was negligible.