Persistence of hexaconazole, a triazole fungicide in soils

Persistence of hexaconazole (2-(2,4-dichlorophenyl)- 1-(1H-1,2,5-triazol-1-yl) hexan-2-ol) was studied in alluvial, red and black soils under flooded and nonflooded conditions. This fungicide was more persistent in all soils under flooded conditions than under nonflooded conditions and at 27 degrees C than at 35 degrees C. Degradation of hexaconazole in sterilized and nonsterilized soils proceeded at identical rates indicating a minor role of micro-organisms in its degradation. The soil persistence of hexaconazole was not affected by the addition of wheat straw both under flooded and nonflooded conditions.     

Persistence and biodegradation of carbaryl in soils

Abstract

The persistence of the methylcarbamate pesticide carbaryl was studied in four soils under flooded conditions. A substantial portion of the pesticide was recovered from all soils even after 15 days of its application, with the recovery ranging from 37% in an alluvial soil to 73% in an acid sulfate soil. The degradation of carbaryl was more rapid under flooded conditions than under nonflooded conditions. A bacterium, Pseudomonas cepacia, isolated from a flooded soil amended with a related methylcarbamate pesticide carbofuran, degraded carbaryl in a mineral medium supplemented with yeast extract.     

Volatilization of lindane from water in soil‐free and flooded soil systems

Abstract

Volatilization of ¹⁴C‐lindane from water in planchets and under flooded soil ecosystem was investigated. Lindane disappeared faster than parathion from planchets. More rapid loss of both insecticides occurred from water than from chloroform. Loss of lindane and parathion was related to measured losses of water by evaporation. During 5‐day incubation under flooded soil conditions, disappearance of lindane was faster from open vials than from sealed vials, whereas in nonflooded soil, no volatile loss of the insecticide was evident despite water evaporation. Over 5 day incubation under flooded conditions, greater volatile loss of lindane occurred in sandy soil than in alluvial soil apparently due to greater adsorption to the soil colloids decreasing the insecticide concentration in the standing water of the laterite soil. Under identical conditions of water evaporation, lindane loss was directly proportional to its initial concentration in the water. These results suggest that considerable loss of soil applied pesticides can occur by volatilization from the standing water in flooded rice fields, particularly under tropical conditions.     

Effect of moisture and compost on fate of azoxystrobin in soils

The effect of compost-amendment and moisture status on the persistence of azoxystrobin [methyl (E)-2-{2-(6-(2-cyanophenoxy) pyrimidin-4-yloxy) phenyl}-3-methoxyacrylate], a strobilurin fungicide, in two rice-growing soils was studied. Azoxystrobin is more sorbed in the silt loam (K _f – 4.66) soil than the sandy loam (K _f – 2.98) soil. Compost-amendment at 5 % levels further enhanced the azoxystrobin sorption and the respective K _f values in silt loam and sandy loam soils were 8.48 and 7.6. Azoxystrobin was more persistent in the sandy loam soil than the silt loam soil. The half–life values of azoxystrobin in nonflooded and flooded silt loam soil were 54.7 and 46.3 days, respectively. The corresponding half–life values in the sandy loam soils were 64 and 62.7 days, respectively. Compost application enhanced persistence of azoxystrobin in the silt loam soil under both moisture regimes and half-life values in non–flooded and flooded soils were 115.7 and 52.8 days, respectively. However, compost enhanced azoxystrobin degradation in the sandy loam soil and half-life values were 59 (nonflooded) and 54.7 days (flooded). The study indicates that compost amendment enhanced azoxystrobin sorption in the soils. Azoxystrobin is more persistent in non-flooded soils than the flooded soils. Compost applications to soils had mixed effect on the azoxystrobin degradation.     

Metabolism of 14C‐carbaryl and 14C‐1‐naphthol in moist and flooded soils

Abstract

The metabolism of ¹⁴C‐carbaryl and ¹⁴C‐1‐naphthol in moist and flooded soils was studied in a continuous flow‐through system over a period of 28 days permitting ¹⁴C‐mass balance. The percent distribution of radiocarbon in organic volatiles, carbon dioxide, extractable and non‐extractable (bound) fractions of soils were determined. Organic volatiles could not be detected in both carbaryl and 1‐naphthol treated soils. More of ¹⁴CO₂ (25.6%) was evolved from moist than flooded soil (15.1%) treated with carbaryl. However, the mineralization of ¹⁴C‐1‐naphthol was negligible. The extractable radiocarbon was more in flooded soil (28.9%) than moist soil (5.5%) from carbaryl treatment. Less than one percent was present as parent compound, whereas carbaryl was mainly metabolized to 5‐hydroxy carbaryl in moist soil and to 4‐ and 5‐hydroxy carbaryl in flooded soil. The extractable radiocarbon amounted to 18.2 and 24.3% in moist and flooded soils respectively and the parent compound was less than one percent with 1‐naphthol treatment. Most of the radiocarbon was found as soil bound residues; the formation being more with 1‐naphthol than carbaryl. Humin fraction of the soil organic matter contributed most to soil bound residues of both carbaryl and 1‐naphthol.     

Studies of the effects of temperatures and solar radiation on volatilization,mineralization and binding of 14c‐DDT in soil under laboratory conditions

Abstract

The effects of temperatures and solar radiation on the dissipation of ¹⁴C‐p,p'‐DDT from a loam soil was studied by quantifying volatilization, mineralization and binding. The major DDT loss occurred by volatilization, which was 1.8 times more at 45^oC than at ambient temperature (30°C). Mineralization of DDT slowly increased with time but it decreased slightly with increase in temperature. Binding of DDT to soil was found to be less at higher temperatures (35 and 45°C) as compared to ambient temperature. Degradation of DDT to DDE was faster at higher temperatures.

Exposure of non‐sterilized and sterilized soils treated with ¹⁴C‐DDT to sunlight in quartz and dark tubes for 6 weeks resulted in significant losses. Volatilization and mineralization in quartz tubes were more as compared to dark tubes. The volatilized organics from the quartz tubes contained larger amounts of p,p'‐DDE than the dark tubes. Further, higher rates of volatilization were found in non‐sterilized soils than in sterilized soils. The results suggest that faster dissipation of DDT from soil under local conditions relates predominantly to increased volatilization as influenced by high temperature and intense solar radiation.     

Persistence of phorate in soils: role of moisture, temperature, preexposure, and microorganisms

In laboratory incubation studies with three soils of varying physicochemical characteristics, phorate was more persistent in nonflooded (60% water holding capacity) soils than in flooded soils. Phorate sulphoxide was recovered as the only metabolite of phorate in nonflooded soils while three metabolites (diethyl dithiophosphate, triethyl dithiophosphate and an unidentified metabolite) were formed in flooded soils. Study indicates that in nonflooded soils phorate is degraded via oxidation while in flooded soils hydrolysis is the major degradation process. Degradation of phorate was accelerated by an increase in incubation temperature. Preexposure or repeated application of soils to phorate slightly decreased the persistence of phorate or its metabolites. Decreased persistence of phorate and its metabolites formed in nonsterile soils compared to sterile soils suggested the role of microorganisms in their transformation.     

Bioavailability and dissipation of fluridone under controlled conditions

Abstract

Bioavailability of fluridone, l‐methyl‐3‐phenyl‐5‐[3‐(trifluoromethyl) phenyl]‐4(1H)‐pyridinone, as affected by soil temperature, soil moisture regime, and duration of incubation was investigated in three soil types by grain sorghum (Sorghum bicolor [L.] Moench cv. Abu Sabien) chlorophyll bioassay. Initial loss of fluridone was rapid and dissipation followed first‐order kinetics under most of the incubation treatments investigated. Soil moisture, in general, had a greater impact than soil temperature on dissipation of fluridone. The herbicide dissipated faster at the fluctuating room temperature (18–24°C) than at the constant 10°C in Sonning sandy clay loam (O.M. = 1.2%) and Erl Wood sandy loam (O.M. = 2.5%) but not in Shropshire loamy peat (O.M. = 33%). In the two mineral soils, bioassay‐detectable residues from an initial rate of 1.00 μg/g were least (0.00 ‐ 0.10 μg/g) at 1/2 field capacity (FC) and greatest (0.16 ‐ 0.37 μg/g) at 1/4 FC, 400 days after treatment. At 10°C, the DT₅₀ values (days) at 1/4 FC and 1/2 FC were, respectively, 147 ± 16 and 69 ± 6 for Erl Wood soil, and 257 ± 28 and 51 ± 12 for Sonning soil. In Shropshire soil, concentrations of bioavailable fluridone were least at each bioassay date when soil moisture was maintained at FC, at both temperatures of incubation. At 10°C, herbicide concentrations in the organic soil from an initial rate of 10.00 μg/g were 0.95 and 4.69 μg/g, respectively, at FC and 1/4 FC.     

Persistence of azadirachtin A and B in soil: Effects of temperature and microbial activity

Abstract

The persistence of two insecticidally active compounds from the neem tree, azadirachtin A and B, was determined at two different temperatures (15 and 25°C) in the laboratory after application of the commercial neem insecticide, Margosan‐O, to a sandy loam soil. The influence of microbial activity on degradation was also examined by comparing autoclaved and non‐autoclaved soils also at 15 and 25°C. Temperature influenced degradation rates. The DT ₅₀ (time required for 50% disappearance of the initial concentration) for azadirachtin A was 43.9 and 19.8 d for non‐autoclaved soil kept at 15 and 25°C, respectively. The DT ₅₀ for azadirachtin B was 59.2 and 20.8 d for non‐autoclaved soil kept at 15 and 25°C, respectively. Microbial activity was also responsible for faster degradation because DT ₅₀ ’s for autoclaved soil were much longer than for non‐autoclaved soils. DT ₅₀ ‘_s for azadirachtin A in autoclaved soil were 91.2 (15°C) and 31.5 d (25°C). DT50’s for azadirachtin B in autoclaved soil were 115.5 (15°C) and 42.3 d (25°C). Two degradation products of azadirachtin were detected, but were not identified. Higher levels of the two degradation products were detected in non‐autoclaved soil.     

Degradation of fenamiphos in soils collected from different geographical regions: The influence of soil properties and climatic conditions

The persistence of fenamiphos (nematicide) in five soils collected from different geographical regions such as Australia, Ecuador and India under three temperature regimes (18, 25 and 37°C) simulating typical environmental conditions was studied. The effect of soil properties (soil pH, temperature and microbial biomass) on the degradation of fenamiphos was determined. The rate of degradation increased with increase in temperature. Fenamiphos degradation was higher at 37°C than at 25 and 18°C (except under alkaline pH). The degradation pathway differed in different soils. Fenamiphos sulfoxide (FSO) was identified as the major degradation product in all the soils. Fenamiphos sulfone (FSO₂), and the corresponding phenols: fenamiphos phenol (FP), fenamiphos sulfoxide phenol (FSOP) and fenamiphos sulfone phenol (FSO₂P) were also detected. The degradation of fenamiphos was faster in the alkaline soils, followed by neutral and acidic soils. Under sterile conditions, the dissipation of the pesticide was slower than in the non-sterile soils suggesting microbial role in the pesticide degradation. The generation of new knowledge on fenamiphos degradation patterns under different environmental conditions is important to achieve better pesticide risk management.     

Metolachlor persistence in laboratory and field soils under Indian tropical conditions

Abstract

Metolachlor [2‐chloro‐N‐(2‐methoxy‐1‐methylethyl)‐2'‐ethyl‐6'‐methyl acetanilide] dissipation under both field and laboratory conditions were studied during summer season in an Indian soil. Metolachlor was found to have moderate persistence with a half‐life of 27 days in field. The herbicide got leached down to 15–30 cm soil layer and residues were found up to harvest day of the sunflower crop in both 0–15 cm and 15–30 cm soil layers. Metolachlor was found to be more persistent in laboratory studies conducted for 190 days. The rate of degradation was faster in soil under flooded partial anaerobic conditions as compared to aerobic soil with a half‐life of 44.3 days. In aerobic soil, metolachlor was very stable with only 49% dissipation in 130 days. Residues remained in both the soils up to the end of the experimental period of 190 days.     

The aerobic soil degradation of spinosad ‐ a novel natural insect control agent

Abstract

Spinosad is a natural product with biological activity against a range of insects including lepidoptera. It is comprised of two major components namely spinosyns A and D. The degradation of spinosad in soil under aerobic conditions was investigated using two U.S. soils (a silt loam and a sandy loam) which were treated with either ¹⁴C‐spinosyn A or ‐spinosyn D at a 2X use rate of 0.4mg/kg soil for spinosyn A and 0.1mg/kg for spinosyn D. Further samples of soil were pre‐sterilised prior to treatment in order to establish whether spinosyns A and D degrade abiotically. Flasks of treated soil were incubated in the dark at 25°C for up to one year after treatment.

HPLC and LC‐MS of soil extracts confirmed that the major degradation product of spinosyn A was spinosyn B, resulting from demethylation on the forosamine sugar. Other dégradâtes were hydroxylation products of spinosyns A and B, with hydroxylation probably taking place on the aglycone portion of the molecule. Half lives were similar for both spinosyns and were in the range 9–17 days, with longer half lives in the pre‐sterilised soils (128–240 days) suggesting that degradation was largely microbial.     

Persistence of metsulfuron‐methyl in two soils

Abstract

The persistence of metsulfuron‐methyl in sandy loam and clay soil incubated at different temperatures and moistures contents was investigated under laboratory conditions using longbean (Vigna sesquipedalis L.) as bioassay species. A significant degradation of metsulfuron‐methyl was observed in non‐autoclaved soil rather than the autoclaved soil sample. At higher temperature, the degradation rate in non‐autoclaved soil improved with increasing soil moisture content. In non‐autoclaved sandy loam and clay soil, the half‐life was reduced from 9.0 to 5.7 and from 11.2 to 4.6 days, respectively when moisture level of sandy loam increased from 20 to 80% field capacity at 35°C. In the autoclaved soil, herbicide residue seems to have been broken down by non‐biological process. The rate of dissipation was slightly increased after the second application of the herbicide to non‐autoclaved soils but not in autoclaved soil, indicating the importance of microorganisms in the breakdown process.     

17β-Estradiol mineralization under field and laboratory incubations

Mineralization studies of natural steroid hormones (e.g., 17β-estradiol, E2) are performed in environmental incubators, usually under a constant temperature such as 20°C. In this paper, we present a microcosm protocol that quantified the mineralization of E2 in soils under field temperatures. The nine agricultural soils tested had a wide range of soil organic carbon (1.1 to 5.2%) and clay (9 to 57%) contents. The calculated time over which half of the applied E2 was mineralized (E2-½) ranged from 299 to 910 d, and total E2 mineralization at 48 d (E2-TOT48) ranged from 4 to 13%. In subsequent laboratory incubations, the same soils were incubated under a constant temperature of 20°C, as well as under cyclic temperatures of 14.5°C (14 h) and 11.5°C (10h), which was within the temperature extremes observed in the field microcosms. E2-½ ranged from 157 to 686 d at 20°C and from 103 to 608 d at the cyclic temperatures, with the E2-TOT48 ranging from 6 to 21% at 20°C and from 7 to 30% under cyclic temperatures. Despite the overall 6.75°C lower mean temperatures under the cyclic versus constant temperatures, E2 mineralization was stimulated by the temperature cycles in three soils. Regardless of the incubation, the same loamy sand soil always showed larger E2 mineralization than the other eight soils and this loamy sand soil also had the smallest E2 sorption. Current modeling approaches do not take into consideration the effects of temperature fluctuations in the field because the input parameters used to describe degradation are derived from laboratory incubations at a constant temperature. Across the eight soils, E2-½ was on average 1.7 times larger and E2-TOT48 was on average 0.8 times smaller under field temperatures than under a constant 20°C. Hence, we conclude that incubations at 20°C give a reasonable representation of E2 mineralization occurring under field conditions to be expected in a typical Prairie summer season.     

Biodegradation of Trifluralin in Harran Soil

Abstract

Degradation of trifluralin (α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine) was investigated in soils taken from three different locations at Harran region of Turkey under laboratory conditions. Surface (0–10 cm) soils, which were taken from a pesticide untreated field Gürgelen, Harran-1 and Ikizce regions in the Harran Plain, were incubated in biometer flasks for 350 days at 25°C. Ring-UL-¹⁴C-trifluralin was applied at the rate of 2 µg g^?1 with 78.7 kBq radioactivity per 100 g soil flask. Evolved ¹⁴CO₂ was monitored in KOH traps throughout the experiment. Periodically, soil sub-samples were removed and extracted by supercritical fluid extraction (SFE). Unextractable soil-bound ¹⁴C residues were determined by combustion. During the 350 days incubation period 6.6, 5.4, and 3.3% of the applied radiocarbon was evolved as ¹⁴CO₂ from the Harran-1, Gürgelen, and Ikizce soil, respectively. At the end of 350 days the SFE-extractable and bound ¹⁴C-trifluralin residues were 39.0 and 29.2% of the initially applied herbicide in Gürgelen soil. The corresponding values for Harran-1 and Ikizce soils were 36.2, 28.4% and 41.6, 18.5% respectively.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

Degradation of terbutryn in sediments and water under various redox conditions

Abstract

A laboratory study was conducted to examine the degradation of terbutryn [2‐(t‐butylamino)‐4‐(ethylamino)‐6‐(methylthio)‐s‐triazine] in sediment and water under different redox conditions. Terbutryn degraded slowly in static aerobic systems (loosely capped flask, 25°C) with half‐lives of 240 and 180 days in pond and river sediment, respectively. Degradation products, identified by co‐chromatography on TLC and HPLC systems, included hydroxy‐terbutryn, terbutryn‐sulfoxide and N‐deethyl terbutryn. Hydroxyterbutryn was the major degradation product in sediments and water representing 60–70% of the extractable radioactivity after 515 days incubation. Under nitrogen aeration in respirometer flasks (redox potential ‐46 to +210 mv) degradation of terbutryn was very slow with half lives greater than 650 days.     

Degradation kinetics of tebufenozide in model aquatic systems under controlled laboratory conditions

Abstract

The hydrolysis of the insecticide tebufenozide was studied in the dark at 20 to 40°C in buffered (pH 4 to 10) distilled water, and at 20°C in unbuffered, sterilized and unsterilized stream water. Tebufenozide was very stable in acidic and neutral buffers at 20°C and the corresponding pseudo‐first‐order rate constants (k_obsd) and half‐lives (T_1/2) were 5.946 × 10^‐4 and 13.10 × 10^‐4 d^‐1, and 1166 and 529 d, respectively. The hydrolytic degradation was dependent on pH and temperature. At pH 10 and at 20,30 and 40°C, the k_obsd (10^‐4 d^‐1) and T_1/2 (d) values were 34.22, 66.72 and 130.0; and 203, 104 and 53.3, respectively. The energy of activation (E_a) values for the hydrolysis of tebufenozide at pH 4, 7 and 10, calculated from the Arrhenius plots, were 83.50, 66.71 and 50.87 kJ/mol, respectively. Tebufenozide was stable in sterilized stream water in the dark (T_1/2 = 734 d) but it degraded fairly rapidly in unsterilized stream water (T_1/2 = 181 d). Sunlight photodegradation of the chemical was slower (T_1/2 = 83.0 h) than the photolysis by ultraviolet radiations (T_1/2 values at 254 and 365 nm were 9.92 and 27.6 h, respectively); nevertheless, it was still appreciable during the summer months at 46°31’ N latitude. The differences in degradation rates between the unsterilized and sterilized stream water and the degradation of the chemical in the sterile, distilled water in sunlight, suggests that microbial processes and photolysis are the two main degradative routes for tebufenozide in natural aquatic systems.     

Microbial degradation characteristics and kinetics of novel pyrimidynyloxybenzoic herbicide ZJ0273 by a newly isolated Bacillus sp. CY

ZJ0273 (propyl 4-(2-(4,6-demethoxy pyrimidin-2-yloxy)benzylamino)benzoate) is a novel herbicide developed in China for oilseed crop. Sixteen bacteria capable of utilizing ZJ0273 as the sole carbon source were isolated from soils. One of the isolates was designated as Bacillus sp. CY based on its physiological and biochemical characteristics and phylogenetic analysis of 16S rDNA sequences. The present study aimed to investigate the ZJ0273 degradation characteristics and kinetics by Bacillus sp. CY which has the ability to utilize ZJ0273 as the sole source of carbon and energy under aerobic conditions. The optimum biodegradation temperature, pH, and ZJ0273 initial concentration were 20–40 °C, 5.0–9.0, and 50–400 mg/l, respectively. Strain CY degraded 65 % of ZJ0273 (initial concentration of 50 mg/l) during 30 days of incubation in basal mineral medium at pH 8.0 and 35 °C. DT50 (half-life value), k (degradation rate constant of ZJ0273), and R ² are 19.20 days, 0.0361 day^?1, and 0.9464, respectively.     

Comparison of calculated evaporation rates of water droplets with those of pesticide droplets measured in a wind tunnel by Dennison and Wedding (1984)

Abstract

Calculations, based on Fuchs’ (1959) formula, of evaporation rates of water droplets freely falling through air are compared with those of water‐based pesticide droplets measured by Dennison and Wedding (1984) in a wind tunnel. Results indicate that calculations of evaporation rates of water droplets, are not significantly different from measurements of that of water‐based pesticide droplets under conditions of 20 °C and 20% relative humidity, but different under other measurement conditions.