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.     

Photosynthesis inhibition of soybean leaves by insecticides

Field grown soybean cv. Williams-82 plants were sprayed with malathion or carbaryl formulations at 30, 60 and 90 days after planting. Net photosynthesis (PN) was measured in the control (water-sprayed) and pesticide-treated plants, 1, 3 and 7 days after treatment, with a LICOR 6200 Portable Photosynthesis System. The pesticide-treated plants showed a significant reduction (24% with malathion and 20% with carbaryl) in PN after the first application. After the 60-day spray treatment PN suppression on day 1 and day 3 after treatment was the same as after the first application; but PN reached the same level as that of the water-sprayed control 7 days after treatment. After the 90-day treatment no change in PN was observed with the pesticide-treated plants compared to the control. These data indicate that malathion and carbaryl formulations may exert a detrimental influence on soybean physiology.     

Effect of some organophosphate insecticides on acetylcholinesterase of adult coccinella septempunctata (coccinellidae)

Abstract

The in vitro enzyme activity of head homogenates of Coccinella septempunctata from different habitats (wheat, barley, rye and set‐aside fields in Belgium and Hungary) and the effect of in vivo surface contact treatments with organophosphorous active ingredients on the same species were investigated. The in vitro studies indicated that the acetylcholinesterase (AChE) of C. septempunctata was less sensitive to inhibition by paraoxon than by malaoxon in the case of each population. The differences found between parathion and malathion treatments in in vivo testing were not significant. The inhibition process of paraoxon suggests that the seven‐spot ladybird may have at least two AChEs responding differently for the paraoxon inhibition.     

Membrane bioreactor treatment of commonly used organophosphate pesticides

Five pesticide formulations registered for use in Canada containing organophosphate-insecticide active ingredients azinphos-methyl, chlorpyrifos, diazinon, malathion and phorate were subjected to treatment by membrane bioreactor (MBR) technology. The target active ingredients were introduced to the MBR at ppm level concentrations. The biodegradation of these compounds was analyzed daily using selected ion monitoring gas chromatography-mass spectrometry (GC/MS-SIM) following extraction of the analytes using solid-phase extraction (SPE). Amounts measuring 83 % to 98 % of the target analytes were removed with steady-state concentrations being reached within 5 days of their introduction. The dissolved oxygen, temperature, pH, and total heterotrophic bacterial population were monitored daily to ensure optimal conditions for biodegradation. The quality of the effluent from the MBR was assessed daily through spectrophotometric methods. Measurements were conducted for the concentration of ammonia, nitrate, nitrite, total and reactive phosphorus, as well as the chemical oxygen demand (COD) of the effluent. This study demonstrated that the MBR technology is feasible and efficient for treatment of organophosphate pesticides without introducing additional chemical additives.     

The Fate of Endosulfan in Water

Although the use of endosulfan to control cotton pests has declined, this insecticide still has widespread application in agriculture and can contaminate riverine systems as runoff from soil or by aerial deposition. The degradation of endosulfan in pure water at different pH values of 5, 7 and 9 and in river water from the Namoi and the Hawkesbury rivers of New South Wales (NSW), Australia, was studied in the laboratory. Endosulfan transformation into endosulfan sulfate in river water using artificial mesocosms was also investigated. The results show endosulfan is stable at pH 5, with increasing rates of disappearance at pH 7 and pH 9 by chemical hydrolysis. Incubation of endosulfan with river water at pH 8.3 resulted in the disappearance of endosulfan and the formation of endosulfan diol due to the alkaline pH as well as formation of endosulfan sulfate. Although the degradation of endosulfan by Anabaena, a blue-green alga, did not result in the transformation of endosulfan to endosulfan sulfate, we conclude that other microorganisms catalyzed the formation of the sulfate. Significant conversions of endosulfan into endosulfan sulfate were also reported from associated field studies using artificial mesocoms containing irrigation water from rivers inhabitated by micro-macro fauna. From these results, we conclude that the presence of endosulfan sulfate in river water cannot be used to distinguish contamination by runoff from soil from contamination by aerial drift or redeposition.     

Treatment of two insecticides in an electrochemical Fenton system

Abstract

The ability of an electrochemical Fenton system to degrade the organophosphorous insecticides malathion and methyl parathion was studied. A combination of hydrogen peroxide and electrochemically‐generated iron was found to be successful in degrading the two insecticides, and optimization of the system was pursued. Augmentation with near UV light at an intensity of 1.67xl0¹⁷ quanta/sec and centered at a wavelength of 370 nm improved the degradation of malathion at low iron concentrations but did not affect other treatments. Adding the hydrogen peroxide slowly over the course of treatment rather than all at once at the beginning of each treatment did, however, greatly improve the system. Removal efficiencies of 98.0% or greater were achieved for both pesticides.     

Growth,photosynthesis and removal responses of the cyanobacteria Chroococcus sp. to malathion and malaoxon

Abstract

Malathion is an organophosphorus pesticide widely used in agricultural crops, despite its toxicity. In addition, malaoxon occurs by oxidation of malathion being more toxic. The toxic effects of malathion and malaoxon in humans include hepatoxicity, breast cancer, genetic damage and endocrine disruption. The aim of this study involved assessing the effect of malathion commercial grade on Chroococcus sp., and its potential as an alternative to the removal of this pesticide and its transformation product such as malaoxon. We evaluated the effect of malathion at different concentrations (1, 25, 50, 75 and 100?ppm) on the biomass of the cyanobacteria Chroococcus sp. grown in medium BG-11; also, we analyse its ability to degrade both malathion and malaoxon into a temperature of 28?±?2?°C and at pH 6. The results showed that 50?ppm of malathion the cyanobacteria Chroococcus sp. reached the highest removal efficiency of malathion and malaoxon (69 and 65%, respectively); also, the growth rate of Chroococcus sp. increased without inhibiting the production of chlorophyll “a”, this can be explained by the hormesis phenomenon. Therefore, we consider that the cyanobacteria Chroococcus sp. may be a good candidate for bioremediation of aquatic systems contaminated with organophosphorus pesticides such as malathion and its transformation product such as malaoxon.     

Chemoreception of botanical nematicides by Meloidogyne incognita and Caenorhabditis elegans

Plant-parasitic nematodes, such as Meloidogyne incognita, cause serious damage to various agricultural crops worldwide, and their control necessitates environmentally safe measures. We have studied the effects of plant secondary metabolites on M. incognita locomotion, as it is an important factor affecting host inoculation inside the soil. We compared the effects to the respective behavioral responses of the model saprophytic nematode Caenorhabditis elegans. The tested botanical nematicides, all reported to be active against Meloidogyne sp. in our previous works, are small molecular weight molecules (acids, alcohols, aldehydes, and ketones). Here, we specifically report on the attractant or repellent properties of trans-anethole, (E,E)-2,4-decadienal, (E)-2-decenal, fosthiazate, and 2-undecanone. The treatments for both nematode species were made at sublethal concentration levels, namely, 1 mM (<EC₅₀), and the chemical controls used for the experiments were the commercial nematicides fosthiazate and oxamyl. According to our results, trans-anethole, decenal, and oxamyl attract C. elegans, while 2-undecanone strongly attracts M. incognita. These findings can be of use in the development of nematicidal formulations, contributing to the disruption of nematode chemotaxis to root systems.     

Tropical surface water quality studies: Implications for the aquatic fate of N-methyl carbamate pesticides

Water quality assessment was conducted on the Ruiru River, a tributary of an important tropical river system in Kenya, to determine baseline river conditions for studies on the aquatic fate of N-methyl carbamate (NMC) pesticides. Measurements were taken at the end of the long rainy season in early June 2013. Concentrations of copper (0.21–1.51 ppm), nitrates (2.28–4.89 ppm) and phosphates (0.01–0.50 ppm) were detected at higher values than in uncontaminated waters, and attributed to surface runoff from agricultural activity in the surrounding area. Concentrations of dissolved oxygen (8–10 ppm), ammonia (0.02–0.22 ppm) and phenols (0.19–0.83 ppm) were found to lie within normal ranges. The Ruiru River was found to be slightly basic (pH 7.08–7.70) with a temperature of 17.8–21.2°C. The half-life values for hydrolysis of three NMC pesticides (carbofuran, carbaryl and propoxur) used in the area were measured under laboratory conditions, revealing that rates of decay were influenced by the electronic nature of the NMCs. The hydrolysis half-lives at pH 9 and 18°C decreased in the order carbofuran (57.8 h) > propoxur (38.5 h) > carbaryl (19.3 h). In general, a decrease in the electron density of the NMC aromatic ring increases the acidity of the N-bound proton removed in the rate-limiting step of the hydrolysis mechanism. Our results are consistent with this prediction, and the most electron-poor NMC (carbaryl) hydrolyzed fastest, while the most electron-rich NMC (carbofuran) hydrolyzed slowest. Results from this study should provide baseline data for future studies on NMC pesticide chemical fate in the Ruiru River and similar tropical water systems.     

The fate of acephate and carbaryl in water.

Acephate was resistent to hydrolysis in distilled, buffered water at pH 4.0 to 6.9, but not at pH 8.2, held for 20 days at 20 or 30 degrees C. The maximum conversion to methamidophos was 4.5% of the added acephate at pH 8.2 and 20 degrees C. The persistence of acephate in two natural waters, held at 9 degrees C for up to 42 and 50 days varied: 80% were recovered from pond water after 42 days, and 45% from creek water after 50 days. Rates of acephate degradation increased greatly when treated water samples were incubated in the presence of sediments, but not if water and sediment were autoclaved prior to treatment and incubation. The greatest conversion to methamidophos, 1.3% of the added acephate, had occurred after 42 days in pond water without sediment. Under the same conditions, carbaryl was less persistent than acephate in the natural waters: 18 to 20% were recovered from pond water after 42 days, and 37 to 40% from creek water after 50 days. The presence of sediment did not affect its degradation significantly. But more than 55% were recovered after 50 days if water and sediment were autoclaved prior to treatment and incubation. Neither acephate, methamidophos, nor carbaryl could be shown to escape from water into the atmosphere.     

Does malaoxon play a role in the geno- and cytotoxic effects of malathion on human choriocarcinoma cells?

This investigation was undertaken to elucidate whether the active metabolite of malathion, malaoxon, has any role in exerting cyto- and genotoxic effects for human choriocarcinoma (JAR) cell line which is an acceptable model for human placental cells. Gas chromatography-mass spectrometry (GC-MS) analysis were separately performed on the cell compartment and supernatant cell culture medium after subjecting the cell line to different malathion concentrations (10–400 μg/mL) and for various incubation periods (0.5 to 24 hours). GC-MS analysis showed that the sonication performed for the disruption of the cells did not cause the chemical change of malathion. The uptake of malathion by the cells was relatively fast. However, the presence of malaoxon, even in trace amounts, could not be confirmed either in samples originating from disrupted cells or in the cell culture medium. Although the hydrolysis of malaoxon occurred in the culture medium, this degradation process could not be counted as a reason for the absence of malaoxon. Since both malathion and malaoxon standard compounds could be accurately detected and distinguished by the applied liquid-liquid extraction and GC-MS methods, one can conclude that, in the case of JAR cells, the parent compound, (i.e. malathion itself) is responsible for the observed in vitro cyto- and genotoxic effects. Our results indicate that the direct toxicity of malathion contributes to the complications of pregnancy observed for environmental malathion exposure.     

Toxicity and biochemical impact of certain oxime carbamate pesticides against terrestrial snail,Theba pisana (Müller)

Abstract

The bran toxic baits (0.5 % w/w) of five oxime carbamate pesticides; aldicarb, aldoxycarb, methomyl, oxamyl and thiofanox were tested for their molluscicidal activity against Theba pisana snails under Laboratory conditions. In addition, the in vivo effects of these compounds on seven vital enzymes namely Acetylcholin‐esterase (AchE), glutathion‐S‐transferase (GST), glutamic oxlaoacetic transaminase (GOT), glutamic pyruvic transaminase (GPT), acid phosphatase (AcP), alkaline phosphatase (AIP), and adenosine triphosphatase (ATPase) activities of the snail tissue were also investigated after 1,3, and 5 days of exposure. The results showed that methomyl was the most potent candidate, whereas thiofanox was the least effective one against the snails. LT₅₀’s values of aldicarb, aldoxycarb, methomyl, oxamyl and thiofanox were 5.77, 4.69, 2.31, 3.97 and 6.67 days, respectively. Results of the potency of the tested pesticides against AchE activity were in harmony with the toxicity of these compounds to snails. AchE, AcP, and AIP activities were inhibited by the tested pesticides. GST activity was inhibited by aldicarb but stimulated by oxamyl and thiofanox. Methomyl and oxamyl lead to significant elevation of GOT and GPT, whereas thiofanox treated snail induced a reduction of both enzymes activities. Aldicarb and aldoxycarb caused significant induction of ATPase activity.     

Loss of carbofuran from rice paddy water: Chemical and physical factors

Abstract

The loss of carbofuran was studied from rice paddy water treated with a granular formulation of the insecticide, and from ponds filled with drainage from the paddy. The average half‐life (t_1/2) for carbofuran loss was 57 hr. Controlled experiments indicated that pH was the predominating factor governing carbofuran loss from water in the environment studied. The loss due to hydrolysis was over 700 times more rapid at pH 10 (t_1/2 = 1.2 hr.) than at pH 7 (t_1/2 = 864 hr.) in buffered deionized water. The average pH of the rice paddy was 8, but diurnal fluctuations of 7 to 9.5 are common in similar environments. Impurities in the water, sunlight, and temperature influence the rate of carbofuran loss but not nearly so much as pH. There was no evidence for significant loss due to evaporation or oxidation. The results have important implications for the duration of the insecticide's activity and the effect on fish within or downstream from treated paddies.     

Soluble esterases as biomarkers of neurotoxic compounds in the widespread serpulid Ficopomatus enigmaticus (Fauvel, 1923)

Abstract

The characterization of soluble cholinesterases (ChEs) together with carboxylesterases (CEs) in Ficopomatus enigmaticus as suitable biomarkers of neurotoxicity was the main aim of this study. ChEs of F. enigmaticus were characterized considering enzymatic activity, substrate affinity (acetyl-, butyryl-, propionylthiocholine), kinetic parameters (K_m and V_max) and in vitro response to model inhibitors (eserine hemisulfate, iso-OMPA, BW284C51), and carbamates (carbofuran, methomyl, aldicarb, and carbaryl). CEs were characterized based on enzymatic activity, kinetic parameters and in vitro response to carbamates (carbofuran, methomyl, aldicarb, and carbaryl). Results showed that cholinesterases from F. enigmaticus showed a substrate preference for acetylthiocholine followed by propionylthiocholine; butyrylthioline was not hydrolyzed differently from other Annelida species. CE activity was in the same range of cholinesterase activity with acetylthiocholine as substrate; the enzyme activity showed high affinity for the substrate p-nytrophenyl butyrate. Carbamates inhibited ChE activity with propionylthiocholine as substrate to a higher extent than with acetylthiocoline. Also CE activity was inhibited by all tested carbamates except carbaryl. In vitro data highlighted the presence of active forms of ChEs and CEs in F. enigmaticus that could potentially be inhibited by pesticides at environmentally relevant concentration.     

Influence of pesticides on acetylene reduction and growth of microorganisms in an organic soil 1

Abstract

The effects of 32 pesticides at two concentrations on acetylene reduction (non‐symbiotic nitrogen fixation), nitrogen fixers, bacteria and fungi in an organic soil were assessed. None of the pesticide treatments suppressed C H reduction as compared to controls. No significant inhibition of the population of non‐symbiotic nitrogen fixers occurred. However, stimulatory effects were observed with treatments of fensulfothion, fonofos, oxamyl, DD^R , Telone^R and Telone C^R . Bacterial and fungal populations showed temporary declines but all recovered within 7 days to levels similar to or higher than those in the controls.     

A rapid,colorimetric, procedure for determination of fenitrothion

Abstract

Fenitrothion in formulations and on grains is determined colorimetrically as 4‐nitro‐3‐methylphenoxide, after hydrolysis at room temperature catalysed by alkaline peroxide. Interferences in determination of residue levels are removed by filtration of commodity extract through basic alumina or by barium chloride plus excess oxidant.     

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.     

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.     

Kinetics and mechanism of the hydrolysis of thiamethoxam

The degradation of thiamethoxam [(EZ)-3-(2-chloro-1,3-thiazol-5-yl-methyl)-5-methyl-1,3,5-oxadiazinan-4-ylidene (nitro) amine] insecticide in buffers at different pH and temperature levels was investigated in laboratory studies. Acidic hydrolysis under conventional heating conditions and alkaline hydrolysis under both conventional heating and microwave conditions were carried out. Different hydrolysis products were found to form under alkaline and acidic conditions. Hydrolysis of thiamethoxam in acidic, neutral and alkaline buffers followed first-order reaction rate kinetics at pH 4, 7 and 9.2, respectively. Thiamethoxam readily hydrolyzed in alkaline buffer but was comparatively stable in neutral buffer solution. The main products formed under different conditions were characterized on the basis of infrared (IR), ¹H-NMR and Mass spectroscopy. The possible mechanisms for the formation of these hydrolysis products have also been proposed.     

A field study on residues of four insecticides used in strawberry protection

Abstract

In 1986 strawberry plots were treated with dimethoate, malathion, permethrin and cypermethrin at 80% bloom of primary flowers. In 1987 the plots were sprayed with dimethoate, malathion and permethrin at 30% bloom. Residue analysis of these insecticides on the flowers were analyzed using solvent extraction and gas liquid chromatography. Residue analysis at 0 to 18 days on flowers and fruit showed an exponential decrease. Organophosphates tended to degrade more quickly than synthetic pyrethroids. The results are discussed in the context of an integrated pest management program.