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.     

Environmentally friendly system for the degradation of multipesticide residues in aqueous media by the Fenton’s reaction

A Fenton oxidation system employing zero-valent iron (whose source was swarf, a residue of metallurgical industries, in powder form) and hydrogen peroxide for the treatment of an aqueous solution with six pesticides was developed, and the effect of the iron metal content, pH, and hydrogen peroxide concentration was evaluated. The characterization of the aqueous solution resulted in: pH 5.6, 105 mg L^?1 of dissolved organic carbon, and 44.6 NTU turbidity. In addition, the characterization of the swarf by FAAS and ICP-MS showed 98.43?±?7.40 % of zero-valent iron. The removal was strongly affected by the content of iron metal, pH, and hydrogen peroxide concentration. The best degradation conditions were 2.0 g swarf, pH 2.0, and 5 mmol L^?1 H₂O₂. At the end of the treatment, the pesticide degradation ranged from 60 to 100 %, leading to 55 % mineralization. Besides, all hydrogen peroxide was consumed and the determination of total dissolved iron resulted in 2 mg L^?1. Thus, the advantages of this system are rapid degradation (up to 20 min), high-degradation rates, simple handling, and low cost.

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.     

Microwave enhanced advanced oxidation treatment of dairy manure

Abstract

The microwave enhanced advanced oxidation process (MW-AOP) was used to treat dairy manure in a continuous-flow 915?MHz microwave wastewater treatment system. The treatment efficiency increased with an increase in temperature, as well as hydrogen peroxide dosage. The settling property was also improved in all treated sets, regardless of temperature applied. The system operated at temperatures >100?°C had a much higher soluble chemical oxygen demand than at temperatures <100?°C. The highest soluble carbonaceous compounds, orthophosphate and ammonia were obtained at 110?°C and 0.6%H₂O₂ per % of total solids content. The process should be operated at higher temperatures and higher hydrogen peroxide dosages for maximizing solids disintegration, nutrient release and energy efficiency. An energy fingerprint correlating the cumulative energy consumption and temperature rise was developed. The results demonstrated that the custom designed MW-AOP system is suitable for the effective treatment of dairy manure. The system can readily be scaled up and integrated into a dairy farm manure treatment and resource recovery system.     

Kinetics of simazine advanced oxidation in water

Abstract

Comparison of the effects and kinetics of UV photolysis and four advanced oxidation systems (ozone, ozone/hydrogen peroxide, ozone/UV radiation and UV radiation/hydrogen peroxide) for the removal of simazine from water has been investigated. At the conditions applied, the order of reactivity was ozone < ozone/hydrogen peroxide < UV radiation < ozone/UV radiation and UV radiation/hydrogen peroxide. Rate constants of the reactions between ozone and simazine and hydroxyl radical and simazine were found to be 8.7 M^‐1s^‐1 and 2.1x10⁹ M^‐1s^‐1, respectively. Also, a quantum yield of 0.06 mol.photon^‐1 was found for simazine at 254 nm UV radiation. The high value of the quantum yield corroborated the importance of the direct photolysis process. Percentage contributions of direct reaction with ozone, reaction with hydroxyl radicals and direct photolysis were also quantified.     

Effects of atrazine on acetylcholinesterase activity in midges (Chironomus tentans) exposed to organophosphorus insecticides

Acetylcholinesterase activity was determined for midge larvae (Chironomus tentans) exposed to either organophosphorus insecticides (OPs) alone or OP insecticides in binary combination with atrazine (200 μg/l). Although atrazine by itself did not reduce the level of acetylcholinesterase activity, atrazine in combination with chlorpyrifos significantly decreased acetylcholinesterase activity as compared to chlorpyrifos only treatments. Although similar trends existed for malathion and methyl parathion, differences were not statistically significant. These results match previously published toxicity data where atrazine, although not acutely toxic even at much higher levels, decreased EC₅₀ values for chlorpyrifos by a magnitude of 4, decreased methyl parathion values by a magnitude of 2, and did not decrease values for malathion.     

菱铁矿催化过氧化氢-过硫酸钠修复地下水中1,2-二氯乙烷污染

采用菱铁矿催化过氧化氢-过硫酸钠双氧化剂体系去除地下水中的1,2-二氯乙烷,通过研究菱铁矿催化机理以及氧化剂浓度两方面探讨双氧体系较单氧体系有较高去除率的原因,探讨了双氧体系1,2-DCA降解动力学和氯离子平衡。研究结果表明,菱铁矿催化双氧体系可以有效去除溶液中的1,2-DCA,本体系条件下去除率可达到95%以上。其较低的pH,较高Fe2+浓度,较高自由基生成量和氧化剂浓度,使得双氧体系较Fenton-Like体系有较高1,2-DCA去除率。菱铁矿催化双氧体系去除1,2-DCA反应过程中有中间产物生成,但最终完全脱氯,没有中间产物残留。     

Nutrient release from fish silage using microwave-enhanced advanced oxidation process

The microwave-enhanced advanced oxidation process was used to treat fish silage for nutrient release and solids reduction prior to its use as a fertilizer for greenhouse operations. Fifteen sets of experiments with varying hydrogen peroxide dosages and treatment temperatures were conducted to evaluate the effectiveness of the process on the solubilization of fertilizer constituents. It was found that up to 26% of total Kjeldahl nitrogen could be released as ammonia with 6% hydrogen peroxide dosage at 170°C. An increase of nitrate/nitrite concentration was observed with higher hydrogen peroxide dosage and higher microwave temperature; the highest concentration of 10.2 mg L^{? 1} nitrates/nitrites was achieved at at 170°C and 6% H₂O₂ dosage. Up to 20 ± 9.5% of total chemical oxygen demand was reduced at temperatures between 120 and 170°C. Large quantities of volatile fatty acids were generated at lower temperatures, corresponding to an increase in soluble chemical oxygen demand, but not at higher temperatures. The treatment of fish silage using the microwave-enhanced advanced oxidation process appears to be promising.     

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.     

Continuous flow photo-Fenton treatment of ciprofloxacin in aqueous solutions using homogeneous and magnetically recoverable catalysts

The degradation of ciprofloxacin was studied in aqueous solutions by using a continuous flow homogeneous photo-Fenton process under simulated solar light. The effect of different operating conditions on the degradation of ciprofloxacin was investigated by changing the hydrogen peroxide (0–2.50 mM) and iron(II) sulphate (0–10 mg Fe L^?1) concentrations, as well as the pH (2.8–10), irradiance (0–750 W m^?2) and residence time (0.13–3.4 min) of the process. As expected, the highest catalytic activity in steady state conditions was achieved at acidic pH (2.8), namely 85 % of ciprofloxacin conversion, when maintaining the other variables constant (i.e. 2.0 mg L^?1 of iron(II), 2.50 mM of hydrogen peroxide, 1.8 min of residence time and 500 W m^?2 of irradiance). Additionally, magnetite magnetic nanoparticles (ca. 20 nm of average particle size) were synthesized, characterized and tested as a possible catalyst for this reaction. In this case, the highest catalytic activity was achieved at natural pH, namely a 55 % average conversion of ciprofloxacin in 1.8 min of residence time and under 500 W m^?2. Some of the photocatalytic activity was attributed to Fe²⁺ leaching from the magnetic nanoparticles to the solution.     

Effect and mechanism of action of methomyl and cypermethrin insecticides on kynurenine metabolizing enzymes of mouse liver

Abstract

The effect of methomyl and cypermethrin insecticides on the B₆‐dependent kynurenine hydrolase(KH) and kynurenine aminotransferase (KATE) was studied. These insecticides induced pronounced inhibition on the (KH) and (KATE) enzymes after single dose treatment. Repeated doses of methomyl induced inhibition on the (KH) and (KATE) activities, whereas repeated treatment with cypermethrin had no effect on the activities of these enzymes. In vitro methomyl inhibited (KH) and (KATE) enzymes at 10 M up to 10^‐3 M, through a competitive mechanism. Methomyl and cypermethrin are capable of causing alterations in the kynurenine metabolizing enzymes of mouse liver.     

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.     

Hydrogen peroxide stabilization in one-dimensional flow columns

Rapid hydrogen peroxide decomposition is the primary limitation of catalyzed H(2)O(2) propagations in situ chemical oxidation (CHP ISCO) remediation of the subsurface. Two stabilizers of hydrogen peroxide, citrate and phytate, were investigated for their effectiveness in one-dimensional columns of iron oxide-coated and manganese oxide-coated sand. Hydrogen peroxide (5%) with and without 25 mM citrate or phytate was applied to the columns and samples were collected at 8 ports spaced 13 cm apart. Citrate was not an effective stabilizer for hydrogen peroxide in iron-coated sand; however, phytate was highly effective, increasing hydrogen peroxide residuals two orders of magnitude over unstabilized hydrogen peroxide. Both citrate and phytate were effective stabilizers for manganese-coated sand, increasing hydrogen peroxide residuals by four-fold over unstabilized hydrogen peroxide. Phytate and citrate did not degrade and were not retarded in the sand columns; furthermore, the addition of the stabilizers increased column flow rates relative to unstabilized columns. These results demonstrate that citrate and phytate are effective stabilizers of hydrogen peroxide under the dynamic conditions of one-dimensional columns, and suggest that citrate and phytate can be added to hydrogen peroxide before injection to the subsurface as an effective means for increasing the radius of influence of CHP ISCO.     

Effects of atrazine on acetylcholinesterase activity in midges (Chironomus tentans) exposed to organophosphorus insecticides

Acetylcholinesterase activity was determined for midge larvae (Chironomus tentans) exposed to either organophosphorus insecticides (OPs) alone or OP insecticides in binary combination with atrazine (200 μg/l). Although atrazine by itself did not reduce the level of acetylcholinesterase activity, atrazine in combination with chlorpyrifos significantly decreased acetylcholinesterase activity as compared to chlorpyrifos only treatments. Although similar trends existed for malathion and methyl parathion, differences were not statistically significant. These results match previously published toxicity data where atrazine, although not acutely toxic even at much higher levels, decreased EC₅₀ values for chlorpyrifos by a magnitude of 4, decreased methyl parathion values by a magnitude of 2, and did not decrease values for malathion.     

Highly sensitive and selective determination of malathion in vegetable extracts by an electrochemical sensor based on Cu-metal organic framework

Abstract

This article demonstrates the first application of a copper-based porous coordination polymer (BTCA-P-Cu-CP) as a carbon paste electrode (CPE) modifier for the detection of malathion. The electrochemical behavior of BTCA-P-Cu-CP/CPE was explored using cyclic voltammetry (CV) while chrono-amperometry methods were applied for the analytical evaluation of the sensor performance. Under optimized conditions, the developed sensor exhibited high reproducibility, stability, and wide dynamic range (0.6–24?nM) with the limits of detection and sensitivity equal to 0.17?nM and 5.7 µAnMcm^?1, respectively, based on inhibition signal measurement. Furthermore, the presence of common coexisting interfering species showed a minor change in signals (<4.4%). The developed sensor has been applied in the determination of malathion in spiked vegetable extracts. It exhibited promising results in term of fast and sensitive determination of malathion in real samples at trace level with recoveries of 91.0 to 104.4%. (RSDs < 5%, n?=?3). A comparison of the two studied techniques showed that the HPLC technique is unable to detect malathion when the concentration is lower than 1.8?µM while 0.006 µM is detected with appropriate RSDs 0.2–5.2% (n?=?3) by amperometric method. Due to the high sensitivity and selectivity, this new electrochemical sensor will be useful for monitoring trace malathion in real samples.     

Atrazine removal by ozonation processes in surface waters

Abstract

Atrazine (6‐chloro‐N‐ethyl‐N'‐isopropyl‐1,3,5‐triazinedyl‐2,4‐diamine) was treated with ozone alone and in combination with hydrogen peroxide or UV radiation in three surface waters. Experiments were carried out in two bubble reactors operated continously. Variables investigated were the ozone partial pressure, temperature, pH, mass flow ratio of oxidants fed: hydrogen peroxide and ozone and the type of oxidation including UV radiation alone. Residence time for the aqueous phase was kept at 10 min. Concentrations of some intermediates, including deethylatrazine, deisopropylatrazine and deethyldeisopropylatrazine, were also followed. The nature of water, specifically the alkalinity and pH were found to be important variables that affected atrazine (ATZ) removal. Surface waters with low alkalinity and high pH allowed the highest removal of ATZ to be reached. There was an optimum hydrogen peroxide to ozone mass flow ratio that resulted in the highest ATZ removal in each surface water treated. This optimum was above the theoretical stoichiometry of the process. Therefore, to reach the maximum removal of ATZ in a O₃/H₂O₂ process, more hydrogen peroxide was needed in the surface waters treated than in ultrapure water under similar experimental conditions. In some cases, UV radiation alone resulted in the removal of ATZ higher than ozonation alone. This was likely due to the alkalinity of the surface water. Ozonation and UV radiation processes yield different amounts of hydrogen peroxide. Combined ozonations (O₃/H₂O₂ and O₃/UV) lead to ATZ removals higher than single ozonation or UV radiation but the formation of intermediates was higher.     

Biological activity and bioavailability of grain bound 14C‐malathion residues in rats

Abstract

Paddy (unmilled rice), milled rice and maize‐bound ¹⁴C residues were prepared using ¹⁴C‐succinate‐labelled malathion at 10 and 152 ppm. After 3 months, the bound residues accounted for 12%, 6.5% and 17.7% of the applied dose in paddy, milled rice and maize respectively in the grains treated at 10 ppm. The corresponding values for the 152 ppm were 16.6%, 8.5% and 18.8%. Rats fed milled rice ‐ bound ¹⁴C‐residues eliminated 61% of the ¹⁴C in the faeces and 28% in the urine. The corresponding percentages for paddy and maize were 72%, 9% and 53%, 41% respectively; indicating that bound residues from milled rice and maize were moderately bioavailable. When rice‐bound malathion residues (0.65 ppm in feed) were administered to rats in a 5 week feeding study, no signs of toxicity were observed. Plasma and RBC cholinesterase activities were slightly inhibited: blood urea nitrogen was significantly elevated in the test animals. Other parameters examined showed no or marginal changes.     

Cytoprotective and anti-apoptotic action of HSP70 stress protein in Oreochromis niloticus exposed to residual dilutions of insecticides with fipronil and ethiprole

Abstract

The objective of this research was to investigate the potential damage caused by the residual concentrations of the insecticides Regent^® WS 800 and Curbix^® SC 200, containing fipronil and ethiprole, respectively as active ingredients, on the liver of Oreochromis niloticus. The analyses of HSP70 shock protein labelling and cell death process by TUNEL method were performed in order to measure the effects of the exposure of cell repair system of fish to both insecticides. Statistical analyses showed no significant molecular damage to the hepatic tissue of animals. Nevertheless, variations in HSP70 and DNA fragmentation levels, endpoint of cell repair system response and cellular death, respectively, were observed in several groups. These results indicate that the cell repair machinery was efficient when in contact with residual concentrations of insecticides. However, the DNA fragmentation detected by the TUNEL method suggests that even in face of the cytoprotective action of the HSP70 protein, there are damages that become irreparable. To finish, it is worth mentioning that given the results obtained from residual concentrations, use in the field should be with caution.     

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.     

Dissipation and Leaching of 14C-Monocrotophos in Soil Columns under Subtropical Climate

Dissipation and leaching behavior of ¹⁴C-monocrotophos was studied for 365 days under field conditions using PVC cylinders. The first set (24 cylinders) was spiked with 1.0 μCi ¹⁴C-labeled monocrotophos along with 1.06 mg unlabeled monocrotophos to give a concentration of 2 mg kg ^?1 in the soil up to 15 cm depth. The second set (24 cylinders) received ¹⁴C-labeled monocrotophos along with other non-labeled insecticides viz., dimethoate @ 300 g a.i ha^?1, deltamethrin @ 12.5 g a.i ha^?1, endosulfan @ 750 g a.i ha^?1, cypermethrin @ 60 g a.i ha^?1, and triazophos @ 600 g a.i ha^?1 at an interval of 15 days each as recommended for the cotton crop. ¹⁴C-monocrotophos dissipated faster, up to 45% in first 90 days in columns treated with only monocrotophos compared to 25% in columns that received monocrotophos along with other insecticides. However, both the columns showed similar residues 180 days onward. After 180 days of treatment, 46% radiolabeled residues were observed, which reduced up to 39.6% after 365 days. Leaching of ¹⁴C-monocrotophos to 15–30 cm soil layer was observed in both the experimental setups. In the 15–30 cm soil layer of both soil columns, up to 0.19 mg ¹⁴C-monocrotophos kg^?1d. wt. soil was detected after 270 days.