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 degrees 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 degrees C than at 25 and 18 degrees 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.     

Toxicity of fenamiphos and its metabolites to the cladoceran Daphnia carinata: the influence of microbial degradation in natural waters

The acute toxicity of an organophosphorous pesticide, fenamiphos and its metabolites, fenamiphos sulfoxide, fenamiphos sulfone, fenamiphos phenol, fenamiphos sulfoxide phenol and fenamiphos sulfone phenol, to a cladoceran, Daphnia carinata was studied in both cladoceran culture medium and natural water collected from a local river. The toxicity followed the order: fenamiphos>fenamiphos sulfone>fenamiphos sulfoxide. The hydrolysis products of fenamiphos, F. sulfoxide (FSO) and F. sulfone (FSO(2)) (F. phenol, FSO phenol and FSO(2) phenol) were not toxic to D. carinata up to 500microgl(-1) water, suggesting hydrolysis reaction leads to detoxification. Also the toxicity was reduced in natural water compared to the cladoceran culture medium due to microbial mediated degradation of toxicants in the natural water. Fenamiphos and its metabolites were stable in both cladoceran water and filter-sterilised natural water while these compounds showed degradation in unfiltered natural water implicating the microbial role in degradation of these compounds. To our knowledge this is the first study on acute toxicity of fenamiphos metabolites to cladoceran and this study suggests that the organophosphate pesticides are highly toxic to fresh water invertebrates and therefore pollution with these compounds may adversely affect the natural ecosystems.     

Sorption of fenamiphos to different soils: the influence of soil properties

Fenamiphos (0-ethyl-0(3-methyl-4-methylthiophenyl)-isopropylamido-phosphate) is a widely used nematicide and insecticide in bowling greens and agriculture, but information on its sorption including its metabolites is limited. Hence, the sorption of fenamiphos (nematicide) and its major degradation products fenamiphos sulfoxide (FSO) and fenamiphos sulfone (FSO2) were determined in thirteen contrasting soils collected from Australia and Ecuador. The sorption coefficients (Kd) exhibited a wide range of variation from 2.48 to 14.94 L/Kg for fenamiphos; from 0 to 7.42 L/Kg for FSO and from 0 to 9.49 L/Kg for FSO2. The sorption affinity of the three compounds for all soils tested was as follows: fenamiphos > fenamiphos sulfone > fenamiphos sulfoxide. The results showed that the sorption of fenamiphos and its metabolites in some soils is very low, and in one case is nonexistant for the metabolites. This is of particular concern as due to its low sorption coefficient, the compound could easily migrate and contaminate water bodies. Fenamiphos and its oxidation products have been reported to be highly toxic to aquatic invertebrates and therefore, the information generated in this study assumes great importance in the risk assessment of fenamiphos and its metabolites in the environment.     

Leaching of fenamiphos,fenamiphos sulfoxide and fenamiphos sulfone in soil columns

Abstract

Leaching of fenamiphos and its thiooxidation products, sulfoxide and sulfone, has been studied in two different soils in laboratory conditions. Fenamiphos was much less mobile than its derivatives. A large volume of water was necessary to leach completely the three chemicals. Fenamiphos required an amount of water twice as large as that required by either sulfoxide or sulfone. Mobility and leaching efficiency of the chemicals examined were highly dependent on the properties of the two soils considered.     

Transformation and adsorption of Fenamiphos, f. sulfoxide and f. sulfone in molokai soil and simulated movement with irrigation

The ban of commonly used soil fumigants, DBCP and EDB, for control of nematodes in pineapple fields has prompted investigations into a non-fumigant nematicide, fenamiphos (Nemacur^®). The transformation and adsorption in soil of fenamiphos and its transformation products, f. sulfoxide and f. sulfone were studied in the laboratory. Fenamiphos adsorption on soil exceeded that of f. sulfoxide and f. sulfone. F. sulfoxide, however, was the most persistent. A one-dimensional simulation model was used to assess the impact of transformation and adsorption on the mobility and distribution of fenamiphos and f. sulfoxide in soil. Simulated results showed that fenamiphos stayed in the topsoil and transformed rapidly to f. sulfoxide. Because of the persistence and mobility of f. sulfoxide, this metabolite leached rapidly and significant amounts remained in the soil. This suggests that for times exceeding three weeks, f. sulfoxide may be the dominant compound providing nematode control in drip-irrigated pineapple.     

Use of coal to retard pesticide movement in soil

Abstract

Three different coals and an activated carbon were mixed with prescribed amounts of a sandy loam soil and added to soil columns to test their ability to retard pesticide movement. The pesticides chosen were prometon, prometryn, 2,4‐D, carbofuran, dinoseb, fenamiphos, and two oxidation products of fenamiphos, fenamiphos sulfoxide, and fenamiphos sulfone. These compounds were chosen to represent different chemical classes of pesticides and because they were considered to have a high potential for transport in soils. All the coals were more effective in retaining the pesticides than the soil, however, some were more effective than others. One of the coals was the most effective in retaining the majority of the pesticides with an overall retention of 94.7% in a 4:1 soil/coal ratio compared to the soil only with a retention of 48.5%. The moisture content of the coal appears to have a positive correlation with the ability of the coal to retain the pesticides under the conditions used for this experiment.     

Adsorption,desorption, soil mobility,aqueous persistence and octanol‐water partitioning coefficients of terbufos,terbufos sulfoxide and terbufos sulfone

Abstract

Terbufos, t. sulfoxide and t. sulfone (5 μg ml^‐1) were incubated in natural, sterilized natural and distilled water, with initial pH values of 8.8, 8.8 and 6.0, respectively, at 20°C. First‐order disappearance was observed for the three compounds. Rates in natural and sterilized water were similar indicating chemical degradation predominated. Terbufos disappeared rapidly (t½>=3 days) in all systems. T. sulfoxide and t. sulfone were more persistent in the natural (t½>=18–40 days) and distilled water (t½>=280–350 days). Adsorption data for the three compounds in four soil‐water systems showed the decreasing order of adsorption to be terbufos>>t. sulfoxide=t. sulfone. Desorption from soils fortified at 5 μg g^‐1 with water was examined for 4 successive 18‐hr cycles. T. sulfoxide and t. sulfone were totally desorbed; terbufos was too unstable to study. The mobility of the compound in soil eluted with water was in the order, t. sulfoxide=t. sulfone>> terbufos, in agreement with adsorption‐desorption results. The octanol‐water partitioning coefficients for terbufos, t. sulfoxide and t. sulfone, at 23°C, were 3:30 x 10 , 164, and 302, respectively.     

Biotic and abiotic degradation of pesticide Dufulin in soils

Dufulin is a newly developed antiviral agent (or pesticide) that activates systemic acquired resistance of plants. This pesticide is widely used in China to prevent abroad viral diseases in rice, tobacco and vegetables. In this study, the potential impacts such as soil type, moisture, temperature, and other factors on Dufulin degradation in soil were investigated. Degradation of Dufulin followed the first-order kinetics. The half-life values varied from 2.27 to 150.68 days. The dissipation of Dufulin was greatly affected by soil types, with DT₅₀ (Degradation half time) varying between 17.59, 31.36, and 43.32 days for Eutric Gleysols, Cumulic Anthrosols, and Dystric Regosols, respectively. The elevated moisture accelerated the decay of Dufulin in soil. Degradation of Dufulin increased with temperature and its half-life values ranged from 16.66 to 42.79 days. Sterilization of soils and treatment with H₂O₂ resulted in a 6- and 8-fold decrease in degradation rates compared to the control, suggesting that Dufulin degradation was largely governed by microbial processes. Under different light spectra, the most effective degradation occurred with 100-W UV light (DT₅₀?=?2.27 days), followed by 15-W UV light (DT₅₀?=?8.32 days) and xenon light (DT₅₀?=?14.26 days). Analysis by liquid chromatography-mass spectroscopy (LC-MS) revealed that 2-amino-4-methylbenzothiazole was one of the major decayed products of Dufulin in soils, suggesting that elimination of diethyl phosphate and 2-fluorobenzaldehyde was most like the degradation pathway of Dufulin in Eutric Gleysols.     

Phenol degradation and microbial characteristics in upflow anaerobic sludge blanket reactors at ambient and mesophilic temperatures

A synthetic wastewater containing phenol as sole substrate was respectively treated at temperatures of 26±1°C and 37±1°C in 2.8 litre upflow anaerobic sludge blanket (UASB) reactors. At the two temperatures, pH 7.0–7.5, with a 1:1 effluent recycle ratio, phenol in wastewater was efficiently degraded in a UASB reactor. Microbial community analysis using denaturing gradient gel electrophoresis (DGGE) showed that less shift in the microbial community occurred with the temperature changing. Phenol degradation in wastewater was recommended to select ambient temperature in UASB reactors. The optimal HRT was 12 to 16 hours corresponding to 6.0–4.5 g COD/(l.d) loading rate at ambient temperature in UASB reactors. The distribution of archaeal and bacterial populations in the UASB granular consortium was revealed using fluorescence in situ hybridisation (FISH) technique.     

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.     

Effect of UV radiation and temperature on mineralization and volatilization of coumaphos in water

This study was undertaken to determine the dissipation and degradation of coumaphos [O-(3-chloro-4-methyl-2-oxo-2H-1-benzopyran-7-yl) O,O-diethyl phosphorothioate] under different sunlight conditions and at different temperatures. The effect of the ultra violet (UV) component of solar radiation was also studied using quartz tubes in addition to other radiation in the visible range using glass tubes and the results were compared with those obtained under the dark light conditions. Water suspensions of coumaphos were incubated at three temperatures viz. 22°C, 37°C and 53°C in closed systems to study the effect of temperature. Volatilization, mineralization and degradation of coumaphos increased with an increase in temperature and exposure to solar radiation, particularly under the UV component of the solar radiation. Major loss of the pesticide occurred through volatilization. The optimum temperature for the degradation of coumaphos was found to be at 37°C. The data obtained from the mineralization and degradation studies indicated that 53°C crosses the biological range for suitable growth of microorganism. UV radiation exposure along with maintaining temperature at 37°C may prove useful in the dissipation and/or degradation of coumaphos prior to its disposal as waste from cattle dipping vats.     

The persistence of insecticidal chemicals in soils treated with granular formulations of disulfoton and their uptake by potato plants

Abstract

Potatoes were grown from cut seed in Plainfield sand treated in‐furrow with disulfoton (Di‐Syston 15G, 3.36 kg Al/ha) in 1983 and from whole seed in similarly treated loam in 1991. Soils were contained in 2 m² field plots. Soil, seed potato and foliage were analyzed for the insecticide and its sulfoxide and sulfone metabolites during the 8–12 wk following planting. Disulfoton disappeared at different rates from the two soils (k_sand=0.024 day^‐1, k_loam=0.056 day^‐1) with partial conversion to the sulfoxide and sulfone in both. Larger quantities of the three insecticidal components were absorbed by the seed potato in the cut‐seed/sand combination. The relative amounts of these components in the seed potato also differed between treatments with disulfoton being the largest component of the cut‐seed/sand and smallest in the whole‐seed/loam. Disulfoton sulfoxide and sulfone were the major insecticidal components of the foliage and concentrations in the initial foliage (each ca. 10 ppm) were similar for both treatments. Sulfoxide concentrations in the foliage decreased more rapidly than the sulfone and the decrease in concentration of each of the components was similar for the two treatments.     

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.     

Simultaneous Cr(VI) reduction and phenol degradation using Stenotrophomonas sp. isolated from tannery effluent contaminated soil

This study presents simultaneous hexavalent chromium (Cr(VI)) reduction and phenol degradation using Stenotrophomonas sp., isolated from tannery effluent contaminated soil. Phenol was used as the sole carbon and energy source for Cr(VI) reduction. The optimization of different operating parameters was done using Placket–Burman design (PBD) and Box–Behnken design (BBD). The significant operating variables identified by PBD were initial Cr(VI) and phenol concentration, pH, temperature, and reaction time. These variables were optimized by a three-level BBD and the optimum initial Cr(VI) concentration, initial phenol concentration, pH, temperature, and reaction time obtained were 16.59 mg/l, 200.05 mg/l, 7.38, 31.96 °C and 4.07 days, respectively. Under the optimum conditions, 81.27 % Cr(VI) reduction and 100 % phenol degradation were observed experimentally. The results concluded that the Stenotrophomonas sp. could be used to decontaminate the effluents containing Cr(VI) and phenol effectively.     

Effects of copper fungicide residues on the microbial function of vineyard soils

The use of copper-based fungicides leads to an accumulation of copper (Cu) in vineyard soils, potentially causing adverse effects to the microbial function and fertility of the soil. This study used a soil microcosm approach to assess the effects of Cu accumulation on microbial function in vineyard soils. Surface soil samples were collected from 10 vineyards and a number of un-impacted reference sites in each of three different viticultural regions of Australia. The field-collected soils were transferred to microcosms and maintained for up to 93 days in the laboratory at 20–22 °C and 60 % of their maximum water-holding capacity. The microbial function of the soils was indicated by measuring phosphomonoesterase, arylsulfatase, urease, and phenol oxidase activities. In general, the vineyard soils had greater concentrations of Cu and lower enzyme activities than in the reference soils, although a weak negative relationship between Cu and enzyme activity could only be found for phosphomonoesterase activity. The results show that soil physical–chemical properties (i.e., organic carbon, pH) are greater determinants of soil enzyme activity than increased soil Cu concentration at the Cu concentrations present in vineyard soils.     

The environmental dynamics of the carbamate insecticide aldicarb in soil and water

Aldicarb is a soil-applied systemic pesticide the USEPA is now considering banning in the USA. Aldicarb is fairly rapidly oxidized to the sulfoxide, with a half-life of approximately 7 days in some soils, and much more slowly to the sulfone (pH-dependent with half-lives varying from a few minutes at a pH of > 12 to approximately 560 days at a pH of 6.0). Persistence, carry-over and translocation vary with soil and environmental conditions. Drainage aquifers and drinking water wells are known to be susceptible to contamination, levels of approximately 550 ppb have been recorded. Foods are also known to take up the pesticide; levels of 600 ppb have been found in potatoes.     

Environmental fate of pesticides used in Australian viticulture: Behaviour of dithianon and vinclozolin in the soils of the South Australian Riverland

The red calcareous earth soils of the South Australian Riverland produce more than one-third of the grapes used in Australian winemaking. As part of on-going investigations into pesticide transport in Australian vineyard soils, the movement of the fungicides dithianon and vinclozolin through such strongly alkaline soils was investigated. Small, undisturbed soil cores were extracted from the inter-row topsoil of a vineyard adjacent to the River Murray, approximately 10 km S.W. of Overland Corner, South Australia. The vines were grown in a deep (1 – 4 m) reddish brown, strongly alkaline, sandy loam with a low organic carbon content (1 – 2 %). Surface fluxes of pesticide were applied at the maximum recommended application rates to the surface of the cores, which were then irrigated, and pesticide residues in the leachate determined by HPLC. No leaching of either dithianon or vinclozolin occurred. Dithianon was immobilised in the top 2 cm of the soil. Dithianon concentrations were low ( 0 – 37 % applied dose) suggesting that rapid degradation of this compound occurs in these soils (63 – 100 % degradation in 10 days). Extremely low concentrations of vinclozolin were found throughout the soil core profiles (0.05 – 1.4 % applied dose) suggesting that this fungicide was somewhat mobile, but also that it too was unstable in such alkaline soils (> 98 % degradation in 10 days). These results suggest that the irrigated vineyard soils of this region are unlikely to be prone to leaching of dithianon or vinclozolin, and therefore that groundwater supplies in this area are unlikely to be at any significant risk of contamination through viticultural use of these compounds.     

Effects of temperature on sorption-desorption processes of imidacloprid in soils of Croatian coastal regions

Sorption-desorption behavior of imidacloprid in six soils collected from five coastal regions in Croatia at 20, 30 and 40°C was investigated using batch equilibrium technique. Isothermal data were applied to Freundlich, Langmuir and Temkin equations, and the thermodynamic parameters ΔH°, ΔG°, ΔS° were calculated. The sorption isotherm curves were non-linear and may be classified as L-type, suggesting a relatively high sorption capacity for imidacloprid. Our results showed that the K ^sor _F values decreased for all the tested soils as the temperature increased, indicating that the temperature strongly influences the sorption. Values of ΔG° were negative (?4.65 to ?2.00 kJ/mol) indicating that at all experimental temperatures the interactions of imidacloprid with soils were spontaneous processes. The negative and small ΔH° values (?19.79 to ?8.89 kJ/mol) were in the range of weak forces, such as H-bonds, consistent with interactions and partitioning of the imidacloprid molecules into soil organic matter. The ΔS° values followed the range of ?57.12 to ?14.51 J/molK, suggesting that imidacloprid molecules lose entropy during transition from the solution phase to soil surface. It was found that imidacloprid desorption from soil was concentration and temperature-dependent, i.e. at lower imidacloprid concentrations and temperature, lower desorption percentage occurred. Desorption studies revealed that hysteretic behavior under different temperature treatments existed, and it was more pronounced at 20°C in the soils with higher OC content. The study results emphasize the importance of thermodynamic parameters in controlling soil pesticide mobility in different geographical locations, seasons and greenhouse conditions.     

Dissipation and sorption of six commonly used pesticides in two contrasting soils of New Zealand

We investigated dissipation and sorption of atrazine, terbuthylazine, bromacil, diazinon, hexazinone and procymidone in two contrasting New Zealand soils (0–10 cm and 40–50 cm) under controlled laboratory conditions. The six pesticides showed marked differences in their degradation rates in both top- and subsoils, and the estimated DT₅₀ values for the compounds were: 19–120 (atrazine), 10–36 (terbuthylazine), 12–46 (bromacil), 7–25 (diazinon), 8–92 (hexazinone) and 13–60 days for procymidone. Diazinon had the lowest range for DT₅₀ values, while bromacil and hexazinone gave the highest DT₅₀ values under any given condition on any soil type. Batch derived effective distribution coefficient (K _d ^eff) values for the pesticides varied markedly with bromacil and hexazinone exhibiting low sorption affinity for the soils at either depth, while diazinon gave high sorption values. Comparison of pesticide degradation in sterile and non-sterile soils suggests that microbial degradation was the major dissipation pathway for all six compounds, although little influence of abiotic degradation was noticeable for diazinon and procymidone.     

Mathematical prediction of imidacloprid persistence in two Croatian soils with different texture,organic matter content and acidity under laboratory conditions

In the present laboratory study, persistence of imidacloprid (IMI) as a function of initial insecticide concentration and soil properties in two Croatian soils (Krk sandy clay and Istria clay soils) was studied and described mathematically. Upon fitting the obtained experimental data for the higher concentration level (5 mg/kg) to mathematical models, statistical parameters (R ², scaled root mean squared error and χ ² error) indicated that the single first-order kinetics model provided the best prediction of IMI degradation in the Krk sandy clay soil, while in the Istria clay soil biphasic degradation was observed. At the lower concentration level (0.5 mg/kg), the biphasic models Gustafson and Holden models as well as the first-order double exponential model fitted the best experimental data in both soils. The disappearance time (DT₅₀) values estimated by the single first-order double exponential model (from 50 to 132 days) proved that IMI can be categorized as a moderately persistent pesticide. In the Krk sandy clay soil, resulting DT₅₀ values tended to increase with an increase of initial IMI concentration, while in the Istria clay soil, IMI persistence did not depend on the concentration. Organic matter of both experimental soils provided an accelerating effect on the degradation rate. The logistic model demonstrated that the effect of microbial activity was not the most important parameter for the biodegradation of IMI in the Istria clay soil, where IMI degradation could be dominated by chemical processes, such as chemical hydrolysis. The results pointed that mathematical modeling could be considered as the most convenient tool for predicting IMI persistence and contributes to the establishment of adequate monitoring of IMI residues in contaminated soil. Furthermore, IMI usage should be strictly controlled, especially in soils with low organic matter content where the risk of soil and groundwater contamination is much higher due to its longer persistence and consequent leaching and/or moving from soil surface prior to its degradation.