Dissipation of alachlor in cotton plant, soil and water and its bioaccumulation in fish

Dissipation of alachlor in soil and plant in field condition (cotton cropping system), and in soil, water and fish in simulated model ecosystem was investigated. The acetanilide herbicide, alachlor (50% w/w EC) was applied as pre-emergence at 2.5 and 5.0 kg a.i.ha(-1) three days after sowing the cotton seeds in the field. Soil and plant samples were collected at intervals and analyzed for alachlor residues. To study the fate of alachlor in water and fish, a simulated model ecosystem was constructed and fish was introduced one day after herbicide application. The dissipation of alachlor in water and soil and bioaccumulation in fish was observed in model ecosystem. At harvest, cotton lint and seed samples were found to contain alachlor well below the detectable level. However, trace amounts of residues were found in cotton oil. After harvest of cotton, coriander (Coriandrum sativum) and edible amaranth (Amaranthus mangostanus L.) were raised for herbicide bioassay. The green leafy vegetable samples did not show any toxic symptoms of alachlor residues.     

Fate of anilide and aniline herbicides in plant-materials-amended soils

The fate of herbicides trifluralin, pendimethalin, alachlor and metolachlor in paddy field soils amended with plant materials was investigated. The plant materials were purple sesbania, vegetable soybean and rice straw. The investigation was performed at two temperatures (25 and 40 degrees C) and two soil water moistures (60 and 90% water-holding capacity). The results showed linear and Freudlich equations described the adsorption of amide compound to soil. Adsorption coefficient (K(d)) fit to linear equation were in general greater in plant material-amended soils than in non-amended soil, especially in soil amending with rice straw. Increasing temperature and soil water moisture content shortened the half-lives of compounds in various treated soils. The movement of compounds in the soil columns showed the maximum distribution of aniline type compound, trifluralin and pendimethalin, appeared at the upper top of 0 to 5 and 0 to 10 cm of soil column, respectively, and of anilide type, alachlor and metolachlor, were distributed at 0 to 25 cm of the soil column. The mobility of chemicals in the different treated soils was simulated by the behavior assessment model (BAM). There was no significant difference among different plant material incubated soils on dissipation and mobility of compounds in soils.     

Soil dehydrogenase, phosphomonoesterase and arginine deaminase activities in an insecticide treated groundnut (Arachis hypogaea L.) field

Chlorpyrifos (O,O-diethyl O-3,5,6-trichloro-2 pyridyl phosphorothioate) 20 EC and Quinalphos (O,O-diethyl O-quinoxalin-2-yl phosphorothioate) 25 EC, were applied in groundnut (Arachis hypogaea L.) field as seed treatment at 25 ml/kg and soil treatment at 4 l/ha in 1998 and 1999. The residues of these insecticides were monitored during the entire crop season and their effect on the soil enzymes dehydrogenase, phosphomonoesterase and arginine deaminase were studied. Ninety nine percent of chlorpyrifos residues were dissipated within 60 days from seed treated soil and 98% dissipation was observed in soil treated field for the same days. Its half lives in seed treated soil were 8 days and 7 days and in soil treated field were 9.2 days in and 7.5 days in 1998 and 1999 respectively. Dissipation of quinalphos in comparison to chlorpyrifos was slow both in seed treated and soil treated field. Eighty seven percentage to 92% dissipation of quinalphos residues were observed from seed treated soil and 98% residues were dissipated from soil treated field within 75 days. Its half lives in seed treated soil were 20 days and 18 days and in soil treated field, its half lives were 13 days and 17 days 1998 and 1999 respectively. Inhibition in dehydrogenase activity followed by recovery was observed both in seed and soil treatments with chlorpyrifos. An inhibition of 17.2% was estimated after 60 days of seed treatment in comparison to control. Dehydrogenase activity was significantly reduced to 63% after 15 days of quinalphos seed treatment in comparison to control in 1998. Similar trends were observed in 1999. A significant inhibition in dehydrogenase activity was observed after soil treatment both in 1998 and 1999. Phosphomonoesterase activities were significantly inhibited upto 25.2% as compared to the control, on the 15th day of chlorpyrifos seed treatment in 1998 and similarly, after one day of treatment in 1999. Quinalphos inhibited the phosphomonoesterase activity till the end of the experimental period in the soil treated fields, whereas recovered within 30-60 days of treatment in the seed treated fields. Arginine deaminase activity was significantly stimulated within one day after chlorpyrifos seed and soil treatments in both years. The activity was almost threefold higher on the 30th and the 15th day of soil treatment in 1998 and 1999, respectively. A temporary inhibition of arginine deaminase activity was observed after quinalphos treatment. It was observed that in most of cases insecticides have temporary inhibitory effect on soil enzymes. However, inhibition was smaller in seed treated soil than in direct soil treatment.     

A comparison of the persistence in a clay loam of single and repeated annual applications of seven granular insecticides used for corn rootworm control

In May 1983, granular formulations of carbofuran, chlorpyrifos, disulfoton, fonofos, isofenphos, phorate, and terbufos were applied in incorporated bands to duplicate 2 m2 field plots of clay loam. Insecticide concentrations were determined in the bands at 0,1,2,3,4,6,8,10,12,16, and 20 wk. Following spring cultivation, the insecticides were applied to the same plots in 1984 and 1985. In addition, carbofuran was applied to previously untreated plots in 1984 and all 7 materials were applied to previously untreated plots in 1985. Sampling and analysis were carried out as in 1983. Persistence was assessed on the basis of the disappearance rates measured for the 1st 8 wk and of a calculated Effectiveness Potential (the ratio of the average residue in the upper 5 cm of the band at 8, 10 and 12 wk and the published LC95 for western corn rootworm in clay loam soil). Soils treated with carbofuran and isofenphos in 1984 and all soils treated in 1985 were tested for anti-insecticide activity. Soil cores from some carbofuran, chlorpyrifos and terbufos treated plots were sectioned vertically to establish the distribution of the insecticides during 1985. In addition, granular and pure chemical forms of isofenphos and carbofuran were applied at 10 ppm to anti-isofenphos and anti-carbofuran active and control soils (from field plots) maintained at 10 and 20% moisture in the laboratory to assess the effect of formulation and moisture on persistence in active soils. Insecticide concentrations were determined at 0,1,3,7, 10,14,21,28, and 35 days. The persistence of chlorpyrifos, terbufos and phorate was relatively constant over the 3 years and between plots receiving single and multiple treatments. Disulfoton and fonofos behavior was more variable and that of carbofuran and isofenphos was extremely variable. Anti-insecticide activity against carbofuran and isofenphos was detectable 2 wk after an initial application and was still present the following spring. Anti-insecticide activity against fonofos, terbufos sulfoxide, phorate sulfone and disulfoton sulfone was also generated in this soil. Anti-insecticide activity against chlorpyrifos, disulfoton, terbufos and phorate was not present. Carbofuran, chlorpyrifos and terbufos (+ metabolites) present in the upper 5 cm of soil averaged 93, 94 and 94%, respectively, of the total core contents over 12 wk. Significant moisture dependent differences were observed between the behavior of granular carbofuran and granular isofenphos in anti-insecticide active soils.(ABSTRACT TRUNCATED AT 400 WORDS)     

Fate of anilide and aniline herbicides in plant-materials-amended soils

The fate of herbicides trifluralin, pendimethalin, alachlor and metolachlor in paddy field soils amended with plant materials was investigated. The plant materials were purple sesbania, vegetable soybean and rice straw. The investigation was performed at two temperatures (25 and 40°C) and two soil water moistures (60 and 90% water-holding capacity). The results showed linear and Freudlich equations described the adsorption of amide compound to soil. Adsorption coefficient (K _d ) fit to linear equation were in general greater in plant material-amended soils than in non-amended soil, especially in soil amending with rice straw. Increasing temperature and soil water moisture content shortened the half-lives of compounds in various treated soils. The movement of compounds in the soil columns showed the maximum distribution of aniline type compound, trifluralin and pendimethalin, appeared at the upper top of 0 to 5 and 0 to 10 cm of soil column, respectively, and of anilide type, alachlor and metolachlor, were distributed at 0 to 25 cm of the soil column. The mobility of chemicals in the different treated soils was simulated by the behavior assessment model (BAM). There was no significant difference among different plant material incubated soils on dissipation and mobility of compounds in soils.     

Tillage management to mitigate herbicide loss in runoff under simulated rainfall conditions

Conservation tillage mitigates soil loss in cropland because plant residues help protect the soil, but effects on pesticide movement in surface runoff are not as straightforward. Effects of soil disturbance on surface runoff loss of chlorimuron and alachlor were evaluated utilizing runoff trays. Soil in the trays was either disturbed (tilled) and kept bare or was not tilled, and existing decomposed plant residue was left on the surface. Rainfall (25mm, 20min) was simulated 1d after alachlor (2.8kg ha(-1)) or chlorimuron (54g ha(-1)) application, and runoff was collected. Runoff fractions were analyzed for herbicide and sediment. Total alachlor loss from bare plots was greater than that in no-tillage plots (4.5% vs. 2.3%, respectively). More than one-third of total alachlor lost from bare plots occurred in the first l of runoff, while no-tillage plots had less runoff volume with a more even distribution of alachlor concentration in the runoff during the rainfall simulation and subsequent runoff period. In contrast, more chlorimuron was lost from no-tillage plots than bare plots (12% vs. 1.5%) even though total runoff volume was lower in the no-tillage plots (10.6mm vs. 13.6mm). This was attributed to dense coverage with partially decomposed plant residue in no-tillage plots (1652kg ha(-1)) that intercepted chlorimuron. It was likely that chlorimuron, a polar compound, was more easily washed off surface plant residues and transported in runoff.     

Phytotoxicity of atrazine and alachlor in soil amended with sludge,manure and activated carbon

Abstract

Greenhouse studies were conducted to determine the influence of waste‐activated carbon (WAC), digested municipal sewage sludge (DMS), and animal manure on herbicidal activity of atrazine [2‐chloro‐4‐(ethylamino)‐6‐(isopropylamino)‐s‐trazine] and alachlor [2‐chloro‐2’,6'‐diethyl‐N‐(methoxymethyl)acetanilide] in a Plainfield sandy soil. Amendments generally reduced bioactivity against oat (Avena sativa L.) and Japanese millet (E. crus‐galli frumentacea). The extent to which herbicide phytotoxicity was inhibited depended upon the application rate and the kind of soil amendment. WAC, applied at the loading rate of 2.1 mt C/ha, showed a significant inhibitory effect on both herbicides. In DMS‐ and manure‐amended soil, the reduction of atrazine activity was not significant at the rate of 8.4 mt C/ha, but reduction of alachlor activity was significant at the rate of 4.2 mt C/ha. Despite inhibition of herbicidal activity, the ED₅₀ of atrazine and alachlor was below 2 ppm in most of the amendment treatments. Before adopting carbon‐rich waste amendments as management practices for controlling pesticide leaching in coarse‐textured soils, further studies are needed to characterize how alterations in sorption, leaching and degradation may affect herbicidal activity.     

Fate and transport of monoterpenes through soils. Part II: calculation of the effect of soil temperature, water saturation and organic carbon content

This theoretical study was performed to investigate the influence of soil temperature, soil water content and soil organic carbon fraction on the mobility of monoterpenes (C10HnOn') applied as pesticides to a top soil layer. This mobility was expressed as the amount volatilized and leached from the contaminated soil layer after a certain amount of time. For this, (slightly modified) published analytical solutions to a one dimensional, homogeneous medium, diffusion/advection/biodegradation mass balance equation were used. The required input-parameters were determined in a preceding study. Because the monoterpenes studied differ widely in the values for their physico-chemical properties, the relative importance of the various determinants also differed widely. Increasing soil water saturation reduced monoterpene vaporization and leaching losses although a modest increase was usually observed at high soil water contents. Organic matter served as the major retention domain, reducing volatilization and leaching losses. Increasing temperature resulted in higher volatilization and leaching losses. Monoterpene mobility was influenced by vertical water flow. Volatilization losses could be reduced by adding a clean soil layer on top of the contaminated soil. Detailed insight into the specific behaviour of different monoterpenes was obtained by discussing intermediate calculation results; the transport retardation factors and effective soil diffusion coefficients. One insight was that the air-water interface compartment is probably not an important partitioning domain for monoterpenes in most circumstances. The results further indicated that biodegradation is an important process for monoterpenes in soil.     

Analytical methods for the determination of alachlor, metolachlor, simazine and atrazine mobility in soils

A method for the determination of the mobility of the herbicides, alachlor, metolachlor, simazine and atrazine in soil is described. The method is based on the use of soil thin-layer chromatography (TLC) and does not require the use of radiolabelled compounds. Soil on the TLC plate after development was separated into various bands, the material in each band was extracted with solvents and analyzed by gas chromatography.     

Persistence of granular and EC formulations of chlorpyrifos in a mineral and an organic soil incubated in open and closed containers

Abstract

Samples of a mineral soil (Plainfield sand) and an organic soil (muck) were treated with granular and EC formulations of chlorpyrifos and incubated at 27±1°C and 65±5% RH in open and closed containers. Duplicate samples of each soil‐formulation‐container combination were analyzed for residual chlorpyrifos during a 23 wk period. The disappearance rates observed demonstrate that the relative importance of formulation and containment on overall persistence depends on soil type. For the mineral soil, disappearance was slower from closed containers and formulation had only a slight effect while, in the organic soil the granular formulation disappeared slower than the EC and there was little difference between open and closed containers. The relative importance of degradation and volatilization in the disappearance of chlorpyrifos from soil is discussed.     

Risk assessment of heavy metal toxicity of soil irrigated with treated wastewater using heat shock proteins stress responses: case of El Hajeb,Sfax, Tunisia

Heavy metal contamination of soil resulting from treated wastewater irrigation can cause serious concerns resulting from consuming contaminated crops. Therefore, it is crucial to assess hazard related to wastewater reuse. In the present investigation, we suggest the use of biomarker approach as a new tool for risk assessment of wastewater reuse in irrigation as an improvement to the conventional detection of physicochemical accumulation in irrigated sites. A field study was conducted at two major sites irrigated with treated wastewater and comparisons were made with a control site. Different soil depths were considered to investigate the extent of heavy metal leaching, the estrogenic activity, and the biomarker response. Results have shown that a longer irrigation period (20 years) caused a slight decrease in soil metal levels when compared to the soil irrigated for 12 years. The highest levels of Cr, Co, Ni, Pb, and Zn were detected at 20 and 40 cm horizons in plots irrigated with wastewater for 12 years. The latter finding could be attributed to chemical leaching to deeper plots for longer irrigation period. Furthermore, the treated wastewater sample showed a high estrogenic activity while none of the soil samples could induce any estrogenic activity. Regarding the stress response, it was observed that the highest stress shown by the HSP47 promoter transfected cells was induced by a longer irrigation period. Finally, the treated wastewater and the irrigated soils exhibited an overexpression of HSP60 in comparison with reference soil following 1 h exposure. In conclusion, in vitro techniques can be efficiently used to assess potential hazard related to wastewater reuse.     

Reduced downward mobility of metolachlor and metribuzin from surfactant-modified clays

The study aims to prepare the organoclay complexes of metolachlor and metribuzin so as to reduce their downward mobility in soil profile. The organoclays were preadsorbed with phenyltrimethylammonium (PTMA) (50% of cation exchange capacity [CEC]) and hexadecyltrimethylammonium (HDTMA) (100% of CEC). Four metolachlor formulations, two for each organoclay, were prepared having 1% and 2% load of herbicide and were called PTMA-Metol-1%, PTMA-Metol-2%, HDTMA-Metol-1% and HDTMA-Metol-2%. Two metribuzin formulations were prepared and were called PTMA-Metri-1% and HDTMA-Metri-1%. Soil column leaching experiment showed that compared to their commercially available formulations, organoclay complexes were effective in reducing the downward mobility of both herbicides. Organoclay complexes of metolachlor and metribuzin prepared using PTMA-Montmorillonite performed better than the HDTMA-Montmorillonite complexes.     

Analytical methods for the determination of alachlor,metolachlor, simazine and atrazine mobility in soils

Abstract

A method for the determination of the mobility of the herbicides, alachlor, metolachlor, simazine and atrazine in soil is described . The method is based on the use of soil thin‐layer chromatography (TLC) and does not require the use of radiolabelled compounds. Soil on the TLC plate after development was separated into various bands, the material in each band was extracted with solvents and analyzed by gas chromatography.     

Reduced Downward Mobility of Metolachlor and Metribuzin from Surfactant-Modified Clays

The study aims to prepare the organoclay complexes of metolachlor and metribuzin so as to reduce their downward mobility in soil profile. The organoclays were preadsorbed with phenyltrimethylammonium (PTMA) (50% of cation exchange capacity [CEC]) and hexadecyltrimethylammonium (HDTMA) (100% of CEC). Four metolachlor formulations, two for each organoclay, were prepared having 1% and 2% load of herbicide and were called PTMA-Metol-1%, PTMA-Metol-2%, HDTMA-Metol-1% and HDTMA-Metol-2%. Two metribuzin formulations were prepared and were called PTMA-Metri-1% and HDTMA-Metri-1%. Soil column leaching experiment showed that compared to their commercially available formulations, organoclay complexes were effective in reducing the downward mobility of both herbicides. Organoclay complexes of metolachlor and metribuzin prepared using PTMA-Montmorillonite performed better than the HDTMA-Montmorillonite complexes.     

Effects of the organic matter from swine wastewater on the adsorption and desorption of alachlor in soil

The application of swine wastewater to the soil for agricultural purposes results in the addition of total and dissolved organic matter to the soil, which may interfere with the dynamics of pesticides in the soil. The objective of this study was to evaluate the effects of the application of total and dissolved organic matter from a biodigester and a treatment lagoon of swine wastewater in the adsorption and desorption of alachlor [2-chloro-2,6-diethyl-N(methoxymethyl acetamide)]. The assay was performed by the batch equilibrium method, and the results were fitted to the Freundlich model. The curve comparison test revealed a greater adsorption of alachlor in the soil treated with swine wastewater from the biodigester. The adsorption and desorption of alachlor increased in the soils where swine wastewater was added, and hysteresis was observed in all of the treatments.     

Effects of the organic matter from swine wastewater on the adsorption and desorption of alachlor in soil

The application of swine wastewater to the soil for agricultural purposes results in the addition of total and dissolved organic matter to the soil, which may interfere with the dynamics of pesticides in the soil. The objective of this study was to evaluate the effects of the application of total and dissolved organic matter from a biodigester and a treatment lagoon of swine wastewater in the adsorption and desorption of alachlor [2-chloro-2,6-diethyl-N(methoxymethyl acetamide)]. The assay was performed by the batch equilibrium method, and the results were fitted to the Freundlich model. The curve comparison test revealed a greater adsorption of alachlor in the soil treated with swine wastewater from the biodigester. The adsorption and desorption of alachlor increased in the soils where swine wastewater was added, and hysteresis was observed in all of the treatments.     

Dissipation of chlorpyrifos in two soil environments of semi-arid India

The dissipation of chlorpyrifos (20 EC) at environment-friendly doses in the sandy loam and loamy sand soils of two semi-arid fields and the presence of pesticide residues in the harvested groundnut seeds, were monitored. The movement of chlorpyrifos through soil and its binding in the loamy sand soil was studied using 14C chlorpyrifos. Chlorpyrifos was moderately stable in both loamy sand and sandy loam soils, with half-life of 12.3 and 16.4 days, respectively. With 20 EC treatments the dissipation was slower for standing crop than seed treatment, indicative of the high degradation rates in the bioactive rhizosphere. In soil, 3,5,6-trichloro-2-pyridinol (TCP) was the principal breakdown product. Presence of 3,5,6-trichloro-2-methoxypyridine (TMP), the secondary metabolite, detected in the rhizospheric samples during this study, has not been reported earlier in field soils. The rapid dissipation of the insecticide from the soil post-application might have resulted from low sorption due to the alkalinity of the soil and its low organic matter content, fast topsoil dissipation possibly by volatilization and photochemical degradation, aided by the low water solubility, limited vertical mobility due to confinement of residues to the upper 15 cm soil layers and microbial mineralization and nucleophilic hydrolysis. Contrary to the reports of relatively greater mobility of its metabolites in temperate soils, TMP and TCP remained confined to the top 15 cm soil. The formation of bound residues (half-life 13.4 days) in the loamy sand soil was little and not "irreversible." A decline in bound residues could be correlated to decreasing TCP concentration. Higher pod yields were obtained from pesticide treated soils in comparison to controls. Post-harvest no pesticide residues were detected in the soils and groundnut seeds.     

Dissipation and mobility of permethrin in the field with repeated applications under tropical conditions

Studies on persistence, mobility and the effect of repeated application of permethrin on its half-life were carried out under field conditions. The half-life of permethrin in the top 20 cm of the soil increased from 11.5 to 23.6 days as the application rates increased from 35 to 140 g ha(-1). Induced by heavier rainfall, more residues moved downward in trial 2 than in trial 1. Repeated applications enhanced degradation rates and mobility of permethrin in the soil. The residue level in the 0-5-cm layer was reduced at day 28 after 17 consecutive applications to a level lower than after 5 applications. The half-life of permethrin was reduced from 15.9 days to 11.2 days after 5 and 17 applications, respectively. The residue reached the 15-20 cm layer much earlier (approximately 3 days after treatment) in soil that received 17 applications as compared to those with two applications.     

Downward movement of cadmium and phosphorus from phosphatic fertilisers in a pasture soil in New Zealand

Total cadmium (Cd) and phosphorus (P) concentrations in a pastoral soil, amended annually for 10 years with four forms of P fertilisers, decreased with soil depth. Single superphosphate (SSP) and North Carolina phosphate rock (NCPR) which had higher Cd contents (32 and 41 mg kg(-1), respectively) produced higher total soil Cd than diammonium phosphate (DAP-10 mg kg(-1)), Jordan phosphate rock (JPR-5 mg kg(-1)) and control treatments to a depth of 120 mm. Total soil P in SSP treated plots to a depth of 120 mm and NCPR treated plots to a depth of 75 mm was also higher than the control plots. No significant fertiliser P and Cd moved below 120 mm depth. Approximately 90% of the applied Cd was recovered in the soil of which 93% remained within the top 120 mm. Plant recovery of applied Cd was 1.5-4.5%. Plant available P (Olsen P) also decreased with depth. Plant available Cd (0.01 M CaCl2 extractable Cd) was higher in the 30-75 and 75-120 mm soil depths compared to 0-30 mm soil depth. This may be due to strong adsorption of Cd by the surface soils which have a higher organic matter content and higher pH; factors which are known to increase Cd adsorption in soils     

Mobility of atrazine from alginate-bentonite controlled release formulations in layered soil

The mobility of atrazine [6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine] from alginate-bentonite-based controlled release (CR) formulations was investigated by using soil columns. Two CR formulations based on sodium alginate (14.0 g kg(-1), atrazine (6.0 g kg(-1), natural or acid-treated bentonite (50 g kg(-1), and water (924 g kg(-1) were compared to technical grade product and commercial liquid (CL) formulation (Gesaprim 500FW). All herbicide treatments were applied to duplicate layered bed systems simulating the typical arrangement under a plastic greenhouse, which is composed of sand (10 cm), peat (2 cm), amended soil (20 cm) and native soil (20 cm). The columns were leached with 39 cm (1500 ml) and 156 cm (6000 ml) of 0.02 M CaCl2 solution to evaluate the effect of water volume applied on herbicide movement. When 39 cm of 0.02 M CaCl2 solution was applied, there was no presence of herbicide in the leachate for the alginate-bentonite CR treatments. However, 0.11% and 0.14% of atrazine appeared in the leachate when the treatment was carried out with technical grade and CL formulations, respectively. When 156 cm of 0.02 M CaCl2 solution was applied, the use of the alginate-acid treated bentonite CR formulation retards and reduces the presence of atrazine in the leachate as compared to technical product. Analysis of the soil columns showed the highest atrazine concentration in the peat layer. Alginate-bentonite CR formulations might be an efficient system for reducing atrazine leaching in layered soil and thus, it could reduce the risks of pollution of groundwater.