Degradation of mecoprop at different concentrations in surface and sub-surface soil

Biodegradation of [ring-¹⁴C] mecoprop (2-(4-chloro-2-methylphenoxy)propionic acid) was determined in surface and sub-surface soil at concentrations of 0·0005, 0·05, 0·5, 5, 50, 500, 5000 and 25000 mg kg^-1. The kinetics of mineralisation were evaluated from the mineralisation rates as a function of time and by non-linear regression analysis. In the sub-surface soil, degradation was 6–8 times slower than in surface soil, but the shape of the curves was the same in both layers. At concentrations between 0·0005 and 0·5 mg kg^-1, in both surface and sub-surface soil, degradation was initially zero-order followed by first-order kinetics. At 5 to 500 mg kg^-1 in surface soil and 5 to 50 mg kg^-1 in sub-surface soil the degradation rate was initially either constant or decreasing followed by exponential degradation indicating increasing populations of mecoprop decomposers in the soil. At 5000 and 25000 mg kg^-1 in the surface soil and at 500, 5000 and 25000 mg kg^-1 in the sub-surface soil, the degradation was negligible, as determined by the percentage [¹⁴C] carbon dioxide evolved. By non-linear regression, the three-half order model was found to describe the mineralisation. © 1998 SCI     

Dissipation of acetochlor and its distribution in surface and sub-surface soil fractions during laboratory incubations

Pesticides in soil are subject to a number of processes that result in transformation and biodegradation, sorption to and desorption from soil components, and diffusion and leaching. Pesticides leaching through a soil profile will be exposed to changing environmental conditions as different horizons with distinct physical, chemical and biological properties are encountered. The many ways in which soil properties influence pesticide retention and degradation need to be addressed to allow accurate predictions of environmental fate and the potential for groundwater pollution. Degradation and sorption processes were investigated in a long-term (100 days) study of the chloroacetanilide herbicide, acetochlor. Soil cores were collected from a clay soil profile and samples taken from 0-30 cm (surface), 1.0-1.3 m (mid) and 2.7-3.0 m (deep) and treated with acetochlor (2.5, 1.25, 0.67 microg acetochlor g(-1) dry wt soil, respectively). In sterile and non-sterile conditions, acetochlor concentration in the aqueous phase declined rapidly from the surface and subsoil layers, predominantly through nonextractable residue (NER) formation on soil surfaces, but also through biodegradation and biotic transformation. Abiotic transformation was also evident in the sterile soils. Several metabolites were produced, including acetochlor-ethane sulphonic acid and acetochlor-oxanilic acid. Transformation was principally microbial in origin, as shown by the differences between non-sterile and sterile soils. NER formation increased rapidly over the first 21 days in all soils and was mainly associated with the macroaggregate (>2000 microm diameter) size fractions. It is likely that acetochlor is incorporated into the macroaggregates through oxidative coupling, as humification of particulate organic matter progresses. The dissipation (ie total loss of acetochlor) half-life values were 9.3 (surface), 12.3 (mid) and 12.6 days (deep) in the non-sterile soils, compared with 20.9 [surface], 23.5 [mid], and 24 days [deep] in the sterile soils, demonstrating the importance of microbially driven processes in the rapid dissipation of acetochlor in soil.     

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.     

Pharmacokinetics of dicamba isomers applied dermally to rats

The pharmacokinetic profile of the herbicide dicamba (3,6-dichloro-2-methoxybenzoic acid) and its isomer (3,5-dichloro-2-methoxybenzoic acid) present in dicamba formulation was examined in rats given single dermal applications of 100 mg/kg of dicamba, 20 mg/kg of the isomer, or their combination at those rates. The concentration of the isomer in blood increased up to 9 hr following application and then declined slowly. The rate of clearance of dicamba from the blood greatly exceeded that of the isomer and was apparently of first order for both. The rate constants for first-order elimination (k_e) were 1.7 and 0.19 hr⁻¹ for dicamba and the isomer, respectively. The rates of absorption of the two chemicals through the skin as determined by urinary excretion was 0.0029 hr⁻¹ for dicamba and 0.0012 hr⁻¹ for the isomer. Urinary excretion of the original dose was 16.5% for dicamba and 7.5% for the isomer. Following the combined application, the kinetics of uptake and clearance was similar to that determined for each chemical administered alone.     

Degradation of atrazine and isoproturon in surface and sub-surface soil materials undergoing different moisture and aeration conditions

The influence of different moisture and aeration conditions on the degradation of atrazine and isoproturon was investigated in environmental samples aseptically collected from surface and sub-surface zones of agricultural land. The materials were maintained at two moisture contents corresponding to just above field capacity or 90% of field capacity. Another two groups of samples were adjusted with water to above field capacity, and, at zero time, exposed to drying-rewetting cycles. Atrazine was more persistent (t(1/2) = 22-35 days) than isoproturon (t(1/2) = 5-17 days) in samples maintained at constant moisture conditions. The rate of degradation for both herbicides was higher in samples maintained at a moisture content of 90% of field capacity than in samples with higher moisture contents. The reduction in moisture content in samples undergoing desiccation from above field capacity to much lower than field capacity enhanced the degradation of isoproturon (t(1/2) = 9-12 days) but reduced the rate of atrazine degradation (t(1/2) = 23-35 days). This demonstrates the variability between different micro-organisms in their susceptibility to desiccation. Under anaerobic conditions generated in anaerobic jars, atrazine degraded much more rapidly than isoproturon in materials taken from three soil profiles (0-250 cm depth). It is suggested that some specific micro-organisms are able to survive and degrade herbicide under severe conditions of desiccation.     

Morphological observation on development of juvenile seedlings of Monochoria vaginalis establishing on a flooded paddy soil surface

The development of juvenile seedlings of Monochoria vaginalis (Burm.f.) Kunth var. vaginalis concerning its hypocotyl hairs was investigated morphologically at establishing on 1 mm flooded paddy soil surface and in distilled water. Prime germination of M. vaginalis seeds sown after breaking dormancy was found on a flooded paddy soil surface and in distilled water at 6 h after seeding (HAS). Elongation of cotyledons and hypocotyl hairs of juvenile seedlings appeared at 12 HAS on a paddy soil surface, while lengths of hypocotyl hairs were almost the same as longitudinal length of seeds and cotyledons formed arch on the soil surface at 18 HAS. Seminal roots began to emerge and seedlings adhered completely to the soil surface by hypocotyl hairs, which were longer in length than seminal roots at 24 HAS. At 36 HAS, seed chaffs completely separated from the soil surface, as cotyledons had elongated from standing up, and lengths of seminal roots became longer than those of hypocotyl hairs. Emergence of first leaves and crown roots was simultaneously observed at 48 HAS. Elongations of cotyledons, seminal roots and hypocotyl hairs were completely terminated at 96, 120 HAS and 120 HAS respectively, and the elongation of 2 to 4 crown roots was observed at 120 HAS. Almost half the number of hypocotyl hairs putrefied at 240 HAS. In distilled water, hypocotyl hairs elongated to their longest at 36 HAS earlier than those on a paddy soil surface. It was concluded that hypocotyl hairs supported a strongly physical mechanism in establishing M. vaginalis seedlings on a paddy soil surface.     

The combined effects of dichloropropane-dichloropropene mixture injected into the soil and of dazomet applied to the soil surface

The effect of injection of different dosages of dichloropropane-dichloropropene (DD) mixture at 15-cm depth combined with different dosages of dazomet distributed on the surface of the soil on densities ofRotylenchus uniformis was investigated in a field experiment on sandy soil. The treatments were given at the end of October 1970. The water content of the soil was at field capacity and the temperature about 10°C. Distributing 5 g or 10 g dazomet per m² on the surface of plots treated with 10 ml DD mixture per m² (mortality 82%) had the same effects as repeating the DD treatment once or twice, respectively. A better horizontal distribution of the DD mixture would probably have made distributing 5 g dazomet per m² on the surface of soil in which a DD treatment killed 80% of the nematodes in the top 20 cm, equivalent to adding two similar DD treatments.To kill a certain percentage of the eggs ofR. uniformis in the soil, twice as high a dosage of DD mixture was necessary as to kill the same percentage of juveniles and adults. Eggs and active nematodes were equally sensitive to dazomet.Samenvatting De uitwerking op dichtheden vanRotylenchus uniformis van verschillende doses dichloorpropaan-dichloorpropeen(DD)mengsel, op 15 cm diepte in de grond gebracht, gecombineerd met verschillende doses dazomet, die op de oppervlakte van de grond werden gestrooid, werd onderzocht op een proefveld op zandgrond. De behandelingen werden eind oktober 1970 uitgevoerd bij een bodemtemperatuur van ongeveer 10°C (Tabel 1). Het watergehalte van de grond was ongeveer op veldcapaciteit door regenval voor de behandelingen. De werking van de verschillende behandelingen op de aaltjes in de bovenste 20 cm van de grond is weergegeven in de Tabel 2 en 3 en Fig. 2 en 3, die van enkele behandelingen op verschillende diepten in de grond in Tabel 4 en 5 en Fig. 6. Strooien van 5 g en 10 g dazomet per m² op de oppervlakte van veldjes, die tevens behandeld waren met 10 ml DD mengsel per m² (sterfte van de aaltjes 82%) had hetzelfde effect als wanneer deze behandeling met DD éénmaal resp. tweemaal herhaald zou zijn. Bij een betere horizontale verdeling van het DD-mengsel in de grond zou een behandeling met dit nematicide, die 80% van de aaltjes in de bovenste 20 cm van de grond doodde, gecombineerd met strooien van 5 g dazomet per m² op de oppervlakte waarschijnlijk gelijkwaardig zijn geweest aan drie behandelingen met DD-mengsel, die telkens 80% van de bij de behandeling nog aanwezige aaltjes doodden.Volgens berekeningen naar aanleiding van Fig. 7 is voor het doden van een bepaald percentage van de eieren vanR. uniformis tweemaal zoveel DD-mengsel nodig als voor het doden van hetzelfde percentage jonge en volwassen dieren. Alle stadia van het aaltje waren even gevoelig voor dazomet.     

Persistence of gamma-BHC and beta-BHC in Indian rice soils under flooded conditions

The relative persistence of [¹⁴C]-gamma-BHC and [¹⁴C]-beta-BHC in Indian rice soils under flooded conditions was studied. In alluvial, laterite and pokkali (acid sulphate, saline) soils, rapid degradation of both isomers occurred; in sandy and kari (acid sulphate, saline) soils, both isomers persisted even after 41 days of flooding. The rapid degradation of BHC isomers in the former three soils was related to highly negative redox potentials within 20 days of flooding in contrast to oxidised conditions in sandy and kari soils even after 41 days. During the degradation in the soils, beta-BHC showed longer lag than gamma-BHC. Results suggest that the degradation of beta-BHC commences at a potential lower than that required for gamma-BHC degradation. Greater decomposition of gamma-BHC occurred in rice straw-amended soils than in unamended soils when the insecticide was incorporated to the soils in an aqueous solution. Addition of BHC isomers to the soils in ethanol resulted in comparable rates of rapid decomposition in both rice straw-amended and unamended soils, since ethanol was as effective as rice straw in lowering the redox potentials of the soils favouring BHC decomposition in unamended soil as well.     

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

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

Photolytic versus microbial degradation of clomazone in a flooded California rice field soil

BACKGROUND: Clomazone is a popular herbicide used on California rice fields and exhibits rapid anaerobic microbial degradation (t_1/2 = 7.9 days). To test the potential of direct and indirect photolytic degradation as a cofactor in the overall degradation rate, sacrificial time‐series microcosms were amended with water, non‐sterilized soil + water and sterilized soil + water. Clomazone was added to each microcosm, which was then exposed to natural and artificial sunlight over 35 days. Water and acetonitrile extracts were analyzed for clomazone and metabolites via LC/MS/MS. RESULTS: The calculated pseudo‐first‐order degradation rate constants (k) were k_water = 0–0.005 ± 0.003 day^?1, k_sterile = 0–0.005 ± 0.003 day^?1 and k_non?sterile = 0.010 ± 0.002–0.044 ± 0.007 day^?1, depending on light type. The formation of ring‐open clomazone, a microbial metabolite, correlated with clomazone degradation. Trace amounts of 5‐hydroxyclomazone (m/z = 256 → 125), aromatic hydroxyclomazone (m/z = 256 → 141) and an unknown product (m/z = 268 → 125) were observed. CONCLUSIONS: The photolytic degradation rate depends on both light type and the quality of the chromophores that induce indirect photolysis. Microbial degradation was found to be sensitive to temperature fluctuations. Overall, microbes are shown to be more detrimental to the environmental fate of clomazone than photolysis. Copyright © 2012 Society of Chemical Industry     

Persistence and movement of ethofumesate in soil*

Persistence of ethofumesate [(±)2-ethoxy-2.3-dihydro-3,3-dimethylbenzofuran-5-yl-methansulphonate] in soil was associated with soil temperature. Ethofumesate applied at 4.5 kg/ha in November persisted about twice as long in soil as that applied the following March. In another field study, 88–91% of the herbicide had dissipated after 24 weeks in sandy loam soil, compared to 72–77% in loam soil when it was applied at rates of 2.2, 3.4, 4.5, and 9.0 kg/ha. The rate of degradation was independent of the initial rate of chemical applied. The time required for 50% of the herbicide to dissipate in sandy loam and loam soils was 7.7 and 12.6 weeks, respectively. The movement of ethofumesate in these two soils over a 24-weeks sampling period was confined mainly to the upper 7.5 cm of the soil profile.     

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.     

Persistence of benomyl and thiophanate compounds in soil and various plants following soil application

Control ofSclerotinia sclerotiorum in muskmelons was obtained by a single soil drench with benomyl. The material was found in the apical parts of the plant and in the soil until the end of the growing season. Benomyl [methyl l-(butylcarbamoyl)-2-benzi-midazolecarbamate] and thiophanate methyl-NF 44 [1.2- bis (3 methoxycarbonyl-2-thioureido) benzene], applied to seedbeds, were taken up by and then persisted in tomato, pepper and eggplant for approximately 8 weeks after application. Thiophanate-NF 35 [1.2-bis (ethoxycarbonyl-2-thioureido) benzene] could be detected only in the bottom leaves of pepper and eggplant, for up to 4 weeks after application.     

Persistence of dichlobenil in a sandy soil and effects of residues on plant growth

The persistence of dichlobenil following the application of dichlobenil granules was studied in a replicated plot experiment including both surface and incorporated treatments of 8·3 and 16·6 kg/ha ai. Soil analyses showed an initial half-life of about 4 weeks but the persistence increased with time and a year after application the half-life was about 1 year. Incorporation of the granules into the soil markedly increased the persistence of dichlobenil and its metabolite dichlorobenzamide. The most sensitive crop was carrot which was damaged by residues of only 1–2% of the recommended dose. Residues phytotoxic to carrots persisted for 2 years from the 8·3 kg/ha surface application and 5 years from the 18·6 kg/ha incorporated application. Lettuce was also highly sensitive to residues.     

Movement of pesticides to surface waters from a heavy clay soil

A field experiment at Cockle Park, Northumberland on a clay loam soil (Dunkeswick series) cropped with winter wheat investigated the effects of drainage and season of application on pesticide movement. Isoproturon, mecoprop, fonofos and trifluralin were applied in two consecutive seasons at normal agricultural rates to three hydrologically isolated plots each of 0.25 ha. Two of the plots were mole-drained and the third was an undrained control. Surfacelayer flow and drainflow from each plot were monitored at 10-min intervals. Samples of flow were analysed for pesticides to evaluate transport of applied chemicals from the site. Despite widely differing properties (K_oc 20–8000 ml g^?1, t_1/2 10–60 days), all four pesticides were found in surface-layer flow and mole drainflow from the site. Maximum concentrations of pesticides in flow ranged from 0.1 to 121 μg litre^?1 (aqueous phase) and < 0.2 to 48 μg litre^?1 (particulate phase). Over two contrasting seasons, total losses of pesticides in flow followed total amounts of flow and were approximately four and five times larger, respectively, in 1990/91 than in 1989/90. The maximum loss occurred from the undrained plot and was 2.8 g isoproturon (0.45% of that applied). Total losses of autumn-applied pesticides from an undrained plot were up to four times greater than losses from a mole-drained plot. Mole drainage decreased movement of pesticides from this slowly permeable soil by reducing the amount of surfacelayer flow. Maximum concentrations of mecoprop and isoproturon in drainflow were 10–20 times larger following spring application than after application in autumn. Bypass flow down soil cracks was an important process by which pesticide was lost from the site, with transport to the drainage system via mole channels (55 cm depth) after less than 0.5 and 6.7 mm net drainage in the two winters.     

Persistence and leaching of beta-cyfluthrin in alluvial soil of India

Persistence as affected by rate of application and moisture regimes and leaching of beta-cyfluthrin was studied in alluvial soil under laboratory conditions. The effects of rate of application and moisture regimes on persistence were studied by incubating fortified soil at 0.1, 1.0 and 10.0 mg kg(-1) under air-dry, field capacity and submerged moisture regimes. The initial deposits of 0.09, 1.11 and 10.1 mg kg(-1) dissipated with time and 78.4-100% loss was recorded at 90 days. The half-life values varied from 7.8 to 41.8 days. The rate of dissipation decreased as the rate of application increased under field capacity and submerged conditions. However, under air-dry conditions, the effect was less pronounced, and half-life values showed a reverse trend. Persistence of beta-cyfluthrin under different moisture regimes followed the trend: air-dry > field capacity > submerged. The trend could be attributed to the effect of moisture on number and type of microbes. Leaching was studied in a packed soil column under saturated flow conditions. beta-Cyfluthrin was found to be highly immobile in alluvial soil. No residues were detected in any leachate fraction under the experimental conditions. In column soil, residues were detected at 0-10 cm depth and the major amount (>99%) was recovered from 0-5 cm depth. Although beta-cyfluthrin showed moderate persistence in alluvial soil, the possibility of its leaching to ground water is negligible as a result of its immobility.     

塿土不同发生层铬（Ⅵ）吸附特性及还原容量研究

研究了土娄土对Cr( )的吸附特性、影响因素及还原容量。结果表明:1土娄土不同土层对Cr( )的吸附量大小顺序为粘化层>犁底层 老耕层>耕层>钙积层;土壤对Cr( )的吸附量与土壤中Fe2O3、粘粒含量和pH有关;2土娄土中Cr( )被吸附的主要形态是HCrO4-;3土壤对Cr( )的等温吸附可以用Langmuir模型和Freundlich模型较好描述。根据Langmuir模型求得土娄土粘化层对Cr( )的最大吸附量最高,为228.3μg/g;4土娄土各土层的测定还原容量在9323～17318mg/kg之间,与土壤有机质有关;土娄土各土层对Cr( )的有效(条件)还原容量只有其测定还原容量的1/1844-1/3586。     

Persistence of benfluralin in soil and its uptake by carrots

Analytical methods are described for the determination of residues of benfluralin in soil and carrots. All plots treated with 1.3 or 1.9 kg benfluralin/ha produced average carrot yields significantly higher than untreated plots. Degradation of benfluralin in soil was very slow during the winter. As the temperature rose, the rate of benfluralin decline was accelerated; 324 days after incorporation, benfluralin residues were reduced to about 11 and 14% of the applied dose. The average total residues of benfluralin found in whole carrots were 210 ± 18 and 240 ± 47 ng/g following doses of 1.3 and 1.9 kg a.i./ha respectively. The peel of carrots contained 92% of the total residue, and there seemed to be little translocation of the compound through the plant tissues.     

Persistence of terbacil and trifluralin under different soil and climatic conditions

Soil samples were collected from forty-three field trials conducted on ten soil types to investigate the residual activity of terbacil and trifluralin at the end of the cropping season, approximately 6 months after application. The soil was bioassayed in a glasshouse using soya beans and German millet for terbacil and trifluralin respectively. At 1 kg/ha terbacil phytotoxic residues occurred in a majority of the trials, while at 2 kg/ha such a carry-over could be found in every case. Trifluralin doses of up to 1 kg/ha did not persist in toxic amounts in most soils, while application of 2 kg/ha showed residual activity in 74% of the trials and application of 4 kg/ha killed German millet in all instances. Results are also presented from the time-rate dissipation studies conducted on both herbicides by assaying soil samples collected at monthly intervals. Both organic matter and clay content of the trial sites affected the persistence of terbacil, while trifluralin residues were influenced only by the soil organic matter content. Trial sites receiving high rainfall showed considerably less residues of terbacil, but the persistence of trifluralin was not affected by rainfall to any appreciable extent.