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.     

Residues of carbofuran and 2,3-dihydro-3-hydroxy- 2,2-dimethylbenzofuran-7-yl methylcarbamate in the mushroom,agaricus bisporus,cultivated in casing soils treated with the insecticide

Residues of carbofuran ( 1 ) and 2,3-dihydro-3-hydroxy-2,2-dimethylbenzofuran-7-yl methylcarbamate ( 2 ) in and on mushrooms, cultivated on casing soils containing added carbofuran granular insecticide, were determined. The quantitative estimations in cleaned mushroom extracts were done on thin-layer plates using a cholinesterase inhibition method. Samples were analysed, which had been harvested at different times from cultures, to which different amounts of carbofuran were added. Residues in washed and unwashed mushroom samples were compared. Residues did not exceed 0.5 mg (carbofuran) kg^?1 and 0.25 mg (compound 2 ) kg^?1 for fresh unwashed mushrooms grown on casing soil treated with carbofuran granules 1 g (a.i.) m^?2.     

Effect of the herbicides EPTC and linuron on cotton diseases caused by Rhizoctonia solani and Fusarium oxysporum f. sp. vasinfectum

The herbicides EPTC and linuron applied to soil in the field at three different concentrations X₂X, 1X, and 2X of recommended dose) decreased post-emergence, but not pre-emergence daraping-off in cotton incited by Rhizoctonia solani. Both herbicides at the two high concentrations significantly reduced wilt incited by Fusarium oxysporum f. sp. vasinfectum. Both herbicides reduced germination of chlamydospores of Fusarium in natural soil, but not in steamed soil. The 2X concentration of EPTC and linuron reduced the saprophytic activity of R. solani in soil. The effects of EPTC and linuron on post-emergence damping-off and wilt were attributed Ic their ability to suppress the saprophytic ability of R. solani and chlamydospore germinability of Fusarium in soil, respectively.     

Potency of some nematicides for controlling nematodes and improving banana production in the southern region of Oman (Dhofar)

Abstract

An established banana field was treated by applying three compounds, fenamiphos, isazofos and carbofuran, to the soil around each mat. The tested compounds were found to reduce significantly soil and root nematode populations. The production cycle of the nematocide treatments was 24 days faster than that of the untreated control. Application of the above chemicals enhanced to the total production of banana. Carbofuran may be ranked top of these nematocides, followed by isazofos. Application of 2 g a.i. of carbofuran three times at intervals of 4 months, yielded 2.66 tonnes per acre more than that of the control.     

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.     

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.     

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.     

Modeling environmental effects on enhanced carbofuran degradation

Prediction of the fate of pesticides in soil is of interest from an environmental (pollution) as well as an agricultural (efficacy, carryover) viewpoint. Two environmental parameters that control microbial degradation of pesticides in soil are moisture and temperature. This study was designed to quantify the impact of soil water content and temperature on microbial degradation rates of the insecticide carbofuran (2, 3-dihydro-2, 2-dimethylbenzofuran-7-yl methyl-carbamate). Carbofuran degradation was determined by monitoring the [ 14 C] carbondioxide production from soils amended with [carbonyl- 14 C]carbofuran. Soils were incubated at seven soil-water tensions over the range of 0–03 to 1–5 MPa, and at five temperatures (10°C to 30°C). The sigmoidal degradation kinetics observed from these incubations were modeled using a general saturation model. For the moisture experiments, maximum rate of hydrolysis and half-life (DT₅₀) were accurately modeled by an exponential relationship. The response of carbofuran degradation to temperature was also well described by an exponential relationship, from which it was estimated that the Q₁₀ associated with the maximum rate was 1.68, and the Q₁₀ for DT₅₀ was 1–89.     

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.     

Persistence of hexachlorocyclohexane isomers and carbofuran applied to surface and sub-surface layers of a flooded soil

The persistence of carbofuran (2, 3-dihydro-2, 2-dimethylbenzofuran-7-yl methylcarbamate) and the β- and γ-isomers of HCH (hexachlorocyclohexane) applied to surface (oxidised) and sub-surface (reduced) layers of a flooded soil was studied using radiolabelled insecticides. In one experiment, these compounds were placed in the surface (2–5 mm) and sub-surface (10–15 cm) layers of 10-day flooded soil columns. HCH isomers were unstable under flooded soil conditions irrespective of their placement, but disappeared slightly faster when applied to the sub-surface layer, possibly due to the more reduced conditions prevailing. In contrast, sub-surface-applied carbofuran was more stable than surface-applied carbofuran. The decreased stability of surface-applied carbofuran may be due to a relatively higher pH in the surface layer and in the flood water which was in immediate contact with the surface layer. In another experiment, surface and sub-surface soil samples were collected from a rice field which had been flooded for 30 days. These soils were then again flooded under laboratory conditions prior to addition of carbofuran and β-HCH. Upon submergence, both surface and sub-surface soil samples attained almost equally reduced conditions. In flooded surface soil samples, more rapid degradation not only of carbofuran but also of β-HCH occurred, compared with similarly incubated sub-surface soil samples.     

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.     

Influence of nitrogen fertilisers on the persistence of carbaryl and carbofuran in flooded soils

Ammonium sulphate and urea, but not potassium sulphate, increased the persistence of carbaryl in a flooded laterite soil with a low native nitrogen content (0.04%), but not in an alluvial soil with a higher nitrogen content (0.11%). Thus, NH₄⁺ but not SO₄^2-, contributed to the increased persistence of carbaryl. Likewise, ammonium sulphate increased the persistence of carbofuran in the laterite soil, but not in the alluvial soil. Significant accumulations of 1-naphthol and 2,3-dihydro-2, 2-dimethylbenzofuran-7-ol (‘carbofuran phenol’), in soils treated with carbaryl or carbofuran, suggested hydrolysis as the major pathway of degradation. Treatment of the two soils with ammonium sulphate, urea or potassium sulphate led to a decrease in soil-bound residues and an increase in the respective hydrolysis products, compared with untreated soils. Sorption studies indicated that NH₄⁺ and SO₄^2- compete with carbaryl, 1-naphthol and carbofuran for sorption and exchange sites in the complex soil system. Evolution of [¹⁴C]carbon dioxide from ring-¹⁴C in carbaryl and carbofuran was negligible. Consequently, after 40 days, more than 50% of the ¹⁴C in [¹⁴C]carbaryl and [¹⁴C]carbofuran remained in the soils as hydrolysis products (1-naphthol or 2,3-dihydro-2,2-dimethylbenzofuran-7-ol) plus soil-bound residues.     

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.     

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.     

丙硫克百威及其主要代谢物在棉田中的残留降解研究

将20% 丙硫克百威乳油施于棉田, 采用气相色谱分析技术研究了丙硫克百威及其主要代谢产物在棉田中的残留降解情况。结果表明: 1) 丙硫克百威在棉田土壤和棉叶中可很快降解转化为克百威, 克百威在棉叶中的最大残留值出现在施药后当天, 在棉田土壤中出现在施药后3d, 说明丙硫克百威在棉叶中的降解速率快于在棉田土壤中; 2) 克百威可进一步转化为3-羟基克百威, 后者在棉叶和棉田土壤中的残留量表现为先升后降, 到第10 天才达最大值,明显滞后于克百威最大值出现的时间; 3) 丙硫克百威和克百威在棉叶和棉田土壤中的降解过程符合Ct= C0·e-kt方程, 它们在棉叶中的降解半衰期为3.6～4.4d, 在棉田土壤中则为10.4～11.9d; 4) 当丙硫克百威的用量按有效成份计为200～400g/hm2, 每季棉花施药3～4 次(每次间隔7d) , 最后一次施药距采收时间分别为20、30d时, 丙硫克百威(含克百威和3-羟基克百威) 在棉籽和棉田耕层土壤中的残留量均小于0. 5 mg/kg。     

The effect of seven substituted urea herbicides on the soil microflora

Chloroxuron, diuron, fluometuron, metobromuron and monuron added to soil at 500 parts/million a.i. on a dry weight basis caused an initial stimulation of CO₂ production, followed by indications of inhibition. Nitrification was clearly inhibited, particularly by monuron and metobromuron. Metoxuron at 5 and 50 parts/million a.i. had no effect on CO₂ output and nitrification, but at 500 parts/million a.i. both were greatly reduced. Numbers of fungal propagules were temporarily lower at 50 parts/million a.i., and severely curtailed at 500 parts/million a.i. but total counts of bacterial propagules were greatly increased. Linuron had an inhibitory effect on CO₂ evolution at 500 parts/million a.i. but this varied in extent and duration; some reduction was also found at 50 parts/ million a.i. At 500 parts/million a.i. there was no effect on mineralisation of N but in soil supplemented with ammonium sulphate nitrification was reduced. Changes in microbial equilibrium occurred, but were less marked than with metoxuron. Cellulose decomposition was also reduced. Small amounts of 3,4dichloroaniline were found in linuron-treated soils, but microbial activities were not affected when 5 parts/million 3,4-dichloroaniline was added to the soil. However, at 140 parts/million microbial activities were affected adversely, but in a different pattern to that for linuron; nitrification was severely reduced, but numbers of fungal propagules were hardly affected, suggesting that the effects observed in linuron-treated soil were not due to this metabolite.     

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.     

A comparative study of carbofuran metabolism in treated and untreated soils

Soils which have been pretreated with carbofuran can degrade the insecticide more rapidly than untreated soils, with a consequent loss of efficacy. In laboratory studies, soils pretreated with carbofuran were found to degrade the chemical more rapidly than soils which were not so pretreated. When pretreated soils were sterilised, the rate of carbofuran degradation was much reduced, indicating that most of it was due to microbial action. Incubation of pretreated soil with [phenyl-U-¹⁴C]carbofuran led to the rapid disappearance of the parent compound (3 % left after seven days). Most of the ¹⁴C was accounted for as bound residue after seven days, whilst smaller amounts were recovered as carbon dioxide, 3-hydroxycarbofuran, 3-ketocarbofuran, and an unknown metabolite. Incubation of pretreated soil with [carbonyl-¹⁴C]carbofuran led to rapid loss of the parent compound and the recovery of 73% of ¹⁴C as carbon dioxide by five days. Most of the bound ¹⁴C (>90%) arising from [phenyl-U-¹⁴C]carbofuran treatment of pretreated soil was extracted by 1 M sodium hydroxide and about half of the extracted ¹⁴C was precipitated with ‘humic acids’ after acidification. These and other results suggest that the major metabolic route for carbofuran in pretreated soils involves hydrolysis of the ester bond leading to (1) release of carbofuran phenol which rapidly binds to soil organic matter and, (2) release of the carbonyl moiety which quickly degrades to generate carbon dioxide.     

The effect of nutrients on the decomposition of the herbicides atrazine and linuron incubated with soil

The rates of disappearance of atrazine and linuron when incubated at 22°C with soil or soil containing added nutrient materials were determined with 2 contrasting soils. Inorganic salts, straw or a combination of both increased atrazine degradation in both soils. None of the treatments influenced linuron breakdown greatly. It is concluded that in these soils the rate limiting step in atrazine degradation could be microbiological, not chemical.     

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.