The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

Organophosphorus insecticide residues in farm ditches of the Lower Fraser Valley of British Columbia

Abstract

Farm ditches flowing into three important rivers in the Lower Fraser Valley of British Columbia, Canada, were sampled periodically at seven locations from July to December in 1991, to determine the occurrence and levels of seven organophosphorus (OP) insecticides. Based oh sales records for the year, the uses of OP insecticides in this area were as follows: malathion > diazinon > parathion > dimethoate > azinphos‐methyl > fensulfothion, but no sales of chlorfenvinphos. Residues of parathion, diazinon, fensulfothion, dimethoate and chlorfenvinphos were detected at levels ranging from 1 ‐ 7,785 >μg/kg in cropped soils collected from areas adjacent to the sites for sampling ditch water and sediments. Malathion and azinphos‐methyl were not detected in any of the substrates studied, demonstrating their rapid degradation in the environment. Diazinon and dimethoate were consistently found in ditch water at seven locations, with an average concentration of 0.07 μg/L and 0.27 μg/L, respectively. Fensulfothion and parathion, with an average concentration of 0.08 μg/L and 0.17 μg/L, respectively, were sporadically found in ditch water at two locations. In ditch sediments, diazinon was detected at three locations and fensulfothion at two. The average concentrations of these two insecticides were 16 μg/kg and 9 jug/kg, respectively. The potential impact on aquatic organisms of these OP insecticides in ditches is discussed.     

Persistence of fensulfothion in a sandy‐loam soil and uptake by rutabagas,carrots and radishes using microplots

Abstract

Field microplots were treated with 141 and 282 ppm fensulfothion and 37.1 and 74.2 ppm fensulfothion sulfone. These concentrations are equivalent to field treatment rates of 8.48 and 16.96 kg Al/ha, fensulfothion, and 2.23 and 4.47 kg Al/ha, fensulfothion sulfone, respectively, for banded application (10 cm wide, rows 80 cm apart). The half‐lives in a sandy loam soil were 30–39 and 14–23 days, respectively. Fensulfothion sulfone and sulfide were the main derivatives found in fensulfothion treated soil.

The maximum levels of these derivatives were 21.22 and 22.95 ppm, respectively for the 8.48 kg/ha treatment and 33.90 and 42.45 ppm, respectively, for the higher treatment, which occurred between 30–60 days.

Carrots appeared to take up more fensulfothion from soil than rutabagas or radishes. The residue levels at harvest decreased in the order carrot peel > pulp > rutabagas root > peel > pulp. Residue levels of fensulfothion and sulfone in radishes were similar to those found in rutabagas. The ratio sulfoxide/sulfone in rutabagas ranged from 0.4–1.5 and in carrots from 1.7–7.6. This phenomenon is thought to be due to oxidative enzyme systems present in rutabagas. Dimethyl phosphorothioic acid, but not dimethyl phosphoric acid was detected (max. 1.33 ppm) in some rutabagas samples but not in carrots.     

Degradation of the insecticide fensulfothion by a mixed culture of soil microorganisms

Abstract

Fensulfothion was incubated in nutrient media with a mixed culture of soil microorganisms obtained from sandy loam. The half life of fensulfothion in both inoculated samples and sterile controls was about 16 wk. There was some conversion to fensulfothion sulfone (16% at 6 wk) in inoculated samples, but not in the controls. Traces of fensulfothion sulfide were found in both inoculated samples (<3%) and controls (<2%) . When 1% ethanol was added to the inoculated nutrient mixture the fensulfothion disappeared rapidly (t_½>～1_½> wk) with 32% conversion at 20 wk to fensulfothion sulfide.     

The aqueous solubility of twenty‐seven insecticides and related compounds.

Abstract

The aqueous solubilities of 27 insecticides and related compounds were determined. Diazinon, fensulfothion and paraoxon had solubilities greater than reported in the literature. The presence of impurities and/or additional components in the mixture altered the measured solubility values. Addition of acetone in amounts up to 1% (volume) produced increases in parathion solubility up to 11%. The pH values of the equilibrated solubility systems were, in most instances, acidic and, in several instances, were in the pH 3–4 range.     

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.     

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.     

Adsorption, desorption, soil mobility and aqueous persistence of fensulfothion and its sulfide and sulfone metabolites

Soil/water interactions with the insecticide fensulfothion and its sulfide and sulfone metabolites and described. Adsorption to, and desorption from four soils were studied. There was a general inverse relationship between water solubilities of the three chemicals and their adsorption K values. Order of adsorption was f. sulfide greater than f. sulfone greater than fensulfothion. Adsorption K values correlated significantly with soil organic content. Desorption of fensulfothion and the sulfone were similar whereas the less soluble sulfide desorbed to a lesser extent. To facilitate comparison of desorption tendencies of the three compounds of desorption index was developed. Mobilities through the soils were directly related to the water solubilities of the three chemicals. Mobilities in decreasing order were - fensulfothion greater than f. sulfone greater than f. sulfide. Persistence of fensulfothion was similar in both sterile and non-sterile natural water - about 50% remaining at the end of the 16 wk experiment. Under reducing conditions fensulfothion disappeared from water in 8-12 wk with almost complete conversion to the sulfide.     

The aqueous solubility of twenty-seven insecticides and related compounds

The aqueous solubilities of 27 insecticides and related compounds were determined. Diazinon, fensulfothion and paraoxon had solubilities greater than reported in the literature. The presence of impurities and/or additional components in the mixture altered the measured solubility values. Addition of acetone in amounts up to 1% (volume) produced increases in parathion solubility up to 11%. The pH values of the equilibrated solubility systems were, in most instances, acidic and, in several instances, were in the pH 3-4 range.     

Sorption of imidacloprid and its metabolites on tropical soils

Abstract

The sorption of imidacloprid (l‐[(6‐chloro‐3‐pyridinyl)‐methyl]‐N‐nitro‐2‐imidazolid‐inimine) (IMI) and its metabolites imidacloprid‐urea (l‐[(6‐chloro‐3‐pyridinyl)‐methyl]‐2‐imidazol‐idinone) (IU), imidacloprid‐guanidine (l‐[(6‐chloro‐3‐pyridinyl)‐methyl]‐4,5‐dihydro‐lH‐imidazol‐2‐amine) (IG), and imida‐cloprid‐guanidine‐olefin ( 1 ‐[(6‐chloro‐3‐pyridinyl)methyl]‐lH‐imidazol‐2‐amine) (IGO) was determined on six typical Brazilian soils. Sorption of the chemicals on the soil was characterized using the batch equilibration method. The range and order of sorption (Kd) on the six soils was IG (4.75–134) > IGO (2.87–72.3) > IMI (0.55 ‐16.9) > IU (0.31–9.50). For IMI and IU, Kd was correlated with soil organic carbon (OC) content and CEC, the latter due to the high correlation between OC and cation exchange capacity (CEC) (R²=0.98). For IG and IGO, there was no correlation of sorption to clay, pH, OC or CEC due to the high sorption on all soils. Average Koc values were IU = 170, IMI = 362, IGO = 2433, and IG = 3500. Although Kd and Koc values found were consistently lower than those found in soils developed in non‐tropical climates, imidacloprid and its metabolites were still considered to be slightly mobile to immobile in Brazilian soils.     

Enhanced degradation of carbofuran in pacific northwest soils

Abstract

Persistence of ¹⁴C‐carbonyl carbofuran was measured in Pacific Northwest soils that had received 1–14 applications of the insecticide for root weevil control on perennial crops. Insecticide decay curves were obtained in nonautoclaved soil and several autoclaved soil samples from previously‐treated fields and in nonautoclaved soils from paired control sites not previously treated with carbofuran. The insecticide usually degraded faster in soil from previously‐treated fields than in soil from corresponding control fields. Among 26 previously‐treated fields, the pseudo half‐life (time for 50% loss) of carbofuran was < one wk in 11 soils, 1–3 wks in 8 soils and > 4 wks in the remaining soils. Among the nontreated control fields the pseudo half‐life was > than 2 wks in all cases and > than 15 wks in 5 of the soils. The carbofuran decay curve always possessed an initial lag phase where soil mixing enhanced insecticide decline. Carbofuran degraded very slowly in autoclaved soil samples. The half‐life of carbofuran exceeded 16 wk in all autoclaved soils tested and in most instances 85–90% of the original dosage remained when the tests were terminated 112 days after treatment. These results provided evidence that many of the soils which received applications of carbofuran over the past several years have developed a capacity to degrade carbofuran very rapidly.     

Laboratory studies on volatilization and mineralization of 14c‐p,p'‐DDT in soil,release of bound residues and dissipation from solid surfaces

Abstract

In support of field data, laboratory studies were conducted on volatilization, mineralization and binding of ¹⁴C‐p,p'‐DDT in soils at Sao Paulo. Incubation of soil for 6 weeks did not result in volatilized organics or mineralization; with >95% extractable radiocarbon in the form of p,p'‐DDT. Small amounts of bound residues (1.8%) were detected in soil. These data confirm the very slow dissipation of DDT in the field which presumably relates to the acidic pH of soil (4.5–4.8).

Bound ¹⁴C‐residues in soils treated with ¹⁴C‐p,p'‐DDT at Praia Grande and Sao Paulo could be released (5–21%) by sulphuric acid treatment. The released residue had the composition: 69–90% DDT, 7–32% DDD and 0–3% DDE. Incubation of soil bound ¹⁴C‐residues with fresh inoculum for 3 months did not result in release of ¹⁴C.

Dissipation from wooden surfaces was fairly slow. After 20 weeks, 74% of the applied radioactivity could be recovered; 44% hexane‐non‐extractable.     

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

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 C2H2 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, DDR, TeloneR and Telone CR. Bacterial and fungal populations showed temporary declines but all recovered within 7 days to levels similar to or higher than those in the controls.     

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.     

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.     

Sorption and degradation of neonicotinoid insecticides in tropical soils

ABSTRACT

Neonicotinoids are the most widely applied class of insecticides in cocoa farming in Ghana. Despite the intensive application of these insecticides, knowledge of their fate in the Ghanaian and sub-Saharan African environment remains low. This study examined the behavior of neonicotinoids in soils from cocoa plantations in Ghana by estimating their sorption and degradation using established kinetic models and isotherms. Studies of sorption were conducted using the batch equilibrium method on imidacloprid, thiamethoxam, clothianidin, acetamiprid and thiacloprid, while degradation of imidacloprid, thiamethoxam and their respective deuterated counterparts was studied using models proposed by the European forum for coordination of pesticide fate and their use (FOCUS). Analytes were extracted using the quick, easy, cheap, effective, rugged and safe (QuEChERS) procedure and quantified by liquid chromatography-tandem mass spectrometry (LC–MS/MS). Average recoveries were high (≥ 85%) for all analytes. The findings from the study suggest that neonicotinoid insecticides may be persistent in the soils studied based on estimated half-lives > 150 days. The study also revealed generally low-sorption coefficients for neonicotinoids in soils, largely influenced by soil organic carbon.     

Fate of 14C‐allylalcohol herbicide in soils and crop residues

Abstract

Residue disappearance and leaching of ¹⁴C‐allyl‐alcohol from different soils were studied in laboratory experiments. Additionally, the uptake of residues by lettuce and carrots was investigated in the greenhouse. In laboratory experiments, residue disappearance and leaching from soils was correlated negatively to the organic matter content. In greenhouse experiments with a sandy loam soil at an application rate normally used in practice, an average of 12.5 % of the applied radioactivity was recovered after an eight day interval between application and sowing. Furthermore, an average of 8 % (sum in soil and plants) of the applied radioactivity was recovered after lettuce or carrot growing. Uptake of residues was higher by carrots than by lettuce, and higher by lettuce roots than by lettuce tops. No bioaccumulation was observed. The residues in soils and plants were, to a high percentage, unextractable and, to a smaller extent, fully water‐soluble products. Unchanged allylalcohol could not be detected by the analytical methods used.     

Solubility products of six metal‐glyphosate complexes in water and forestry soils,and their influence on glyphosate toxicity to plants

Abstract

The solubility products (K_sp) of 1:1 complexes of glyphosate, [N‐(phosphonomethyl)glycine], with Mg²⁺, Ca²⁺, Mn²⁺, Zn²⁺, Cu²⁺ and Fe³⁺, were determined in buffered (pH 7.0) distilled water, moist Ottawa sand, sandy loam and clay loam soils, each adjusted to 0.02 M with respect to KNO₃. The K_sp values decreased in the order of Mg ? Ca > Mn > Zn > Cu > Fe, regardless of the medium in which they were determined. The constants measured in Ottawa sand were similar to those in water, but those in the forestry soils depended upon the type of metal ion involved. The values for the Mg, Ca, Mn and Zn complexes were about 2 to 3 times lower in sandy loam soil than those in water, but those in clay loam were about 3 to 10 times lower. The K_sp of the Cu and Fe complexes were similar to those in water regardless of the soil type used.

In a bioassay experiment using tomato plants, immersed in the saturated solutions of the complexes or planted in the sand and soils containing saturated solutions of the complexes, no mortality occurred although slight inhibition in growth was observed in all cases. The most soluble complexes of Mg and Ca caused the most reduction in plant height, while the least soluble complex of Fe caused little growth inhibition. The Zn, Cu and Mn complexes caused some growth inhibition depending on their K_sp values. The larger the solubility product, the greater the concentration of glyphosate ion in solution, and the greater the growth inhibition. In a similar experiment using white spruce seedlings, growth inhibition was insignificant over the 12‐d bioassay period.     

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.     

Occurrence of pesticides and polychlorinated biphenyls in water of the Nile river at the estuaries of Rosetta and Damiatta branches,north of delta,Egypt

Abstract

A study was conducted from summer 1995 to summer 1997 to assess the seasonal occurrence of pesticide residues and other organic contaminants, polychlorinated biphenyls (PCBs), in water at the estuaries of Rosetta and Damiatta branches of the Nile river. The results indicated that organochlorine compounds (OCs) including HCB, lindane, p,p‘‐DDE, p,p‘DDD, p,p‘‐DDT, aroclor 1254 and aroclor 1260 were present in all the water samples at concentration levels ranging between 0.195–0.240, 0.286–0.352, 0.035–0.067, 0.019–0.033, 0.024–0.031, 0.390–0.70 and 0.166–0.330 μg/l, respectively. The levels of these compounds were higher in water of Damiatta branch than those found in water of Rosetta branch. Aldrin, dieldrin and endrin were not detected in all water samples. Only 4 compounds from 36 organophosphorus insecticides, fungicides and s‐triazine herbicides tested were detected in water samples collected during summer and autumn seasons from Rosetta branch. The concentration levels of these detected compounds, dimethoate, malathion, captan, and ametryne, ranged from 0.011 to 0.340 μg/l, respectively. Similar compounds during the same seasons as found in water of Rosetta branch were also detected in water of Damiatta branch except ametryne. The levels of the detected compounds (dimethoate, malathion and captan) ranged between 0.030 and 0.330 μg/l. The levels of detected organophosphorus insecticides, fungicides and s‐triazine herbicides were in the order: dimethoate > malathion > captan > ametryne.