Photolysis-Induced Neurotoxicity Enhancement of Chlorpyrifos in Aquatic System: A Case Investigation on Caenorhabditis elegans.

Contamination of the environment by toxic pesticides has become of great concern in agricultural countries. Chlorpyrifos (CP) is among the pesticides most commonly detected in the environment owing to its wide agricultural applications. The aim of this study was to compare potential changes in the toxicity of CP after irradiation. To this end, photolysis of CP was conducted under simulated sunlight, and neurotoxicity assessment was carried out at CP of 20 and 50 µg L-1 and its corresponding irradiated mixture solutions which contain a mixture of identified intermediates using the nematode, Caenorhabditis elegans as a model organism. Photodegradation of 20 µg L-1 CP for 1 h produced no obvious reduction of physiological damage, and more serious effects on animal movement were detected after exposure of the animals to a solution of 50 µg L-1 for 1 h irradiation compared with unirradiated solution. GABAergic and cholinergic neurons were selectively vulnerable to CP exposure, and maximal neuropathological alterations were observed after 1 h irradiation of the CP solutions in coherence with the behavioral impairment. The generation of photoproducts was considered to be responsible for the enhanced disturbance on those biological processes. This work provided useful information on the toxicological assessments of chemicals that were produced during the environmental transformation of pesticides.

UV-C light irradiation enhances toxic effects of chlorpyrifos and its formulations.

UV-C irradiation is widely used in the food industry. However, the health effects from dietary exposure to the irradiated pesticide residues retained in foodstuffs are underestimated. In this study, technical chlorpyrifos (TCPF) and its oil in water (EW) and emulsifiable concentrate (EC) formulations were irradiated by UV-C, and their photodegradation products were subjected to toxicity assessment, including determination of acetylcholinesterase (AChE) activity, genotoxicity and oxidative stress using human blood cells as a model system. Toxicity studies were performed using the chlorpyrifos concentrations in the range of those proposed as the maximum residue levels in plant commodities. TCPF, EW and EC photodegradation products induced DNA damage and oxidative stress, and their genotoxicity did not decrease as a function of irradiation time. Irradiated TCPF and EC are more potent AChE inhibitors than irradiated EW. Accordingly, the application of UV-C irradiation must be considered when processing the plants previously treated with chlorpyrifos formulations.

Ecotoxicity response of chlorpyrifos in Aedes aegypti larvae and Lactuca sativa seeds after UV/H2O2 and UVC oxidation.

Chlorpyrifos (CP) is an organophosphate pesticide widely used in agriculture known to cause neurological and immunological effects in addition to interfering in the reproduction and development of organisms. In this study, CP degradation by UV/H2O2 process and UVC radiation was investigated, and the ecotoxicity and phytotoxicity was evaluated using bioassays of Aedes aegypti larvae and Lactuca sativa seeds. CP degradation was monitored by HPLC-DAD, and kinetic parameters were calculated for all processes evaluated. Results demonstrated that both processes are efficient, showing a reduction of over 97% of initial CP after 20 and 60 min of UV/H2O2 and UVC radiation, respectively. However, samples treated by UV/H2O2 process demonstrated increase of toxicity, leading to larvae mortality (>90% of organisms) and inhibition effects in seed root growth. The relationship between increased toxicity and the CP byproducts formed was not confirmed due to its low concentration. However, the direct influence of acetonitrile solvent, specifically their toxic byproducts, was observed. This study provides insights into parent compound abatement using oxidative treatment and the changes in toxicity due to the transformation of CP byproducts and complex mixtures (acetonitrile as solvent and hydrogen peroxide).

Response surface methodology modeling to improve degradation of Chlorpyrifos in agriculture runoff using TiO2 solar photocatalytic in a raceway pond reactor.

This paper deals with the use of a raceway pond reactor (RPR) as an alternative photoreactor for solar photocatalytic applications. Raceway pond reactors are common low-cost reactors which can treat large volumes of water. The experiments were carried out with TiO2 in the agriculture effluent spiked with Chlorpyrifos (CPF) at circumneutral pH. The Response Surface Methodology (RSM) was used to find the optimum process parameters to maximize CPF oxidation from the mathematical model equations developed in this study using R software. By ANOVA, p-value of lack of fit > 0.05 indicated that, the equation was well-fitted. The theoretical efficiency of CPF removal, under the optimum oxidation conditions with UV solar energy of around 697 ± 5.33 lux, was 84.01%, which is in close agreement with the mean experimental value (80 ± 1.42%) confirming that the response model was suitable for the optimization. As far as the authors know, this is the first study of CPF removal using RPR in agriculture runoff at circumneutral pH.

Cu(2+) and Fe(2+) mediated photodegradation studies of soil-incorporated chlorpyrifos.

The influences of Cu(2+) and Fe(2+) on the photodegradation of soil-incorporated chlorpyrifos were investigated in the present study. The soil samples spiked with chlorpyrifos and selected metal ions were irradiated with UV light for different intervals of time and analyzed by HPLC. The unsterile and sterile control soil samples amended with pesticides and selected metals were incubated in the dark at 25 °C for the same time intervals. The results of the study evidenced that photodegradation of chlorpyrifos followed the first-order kinetics. The dissipation t0.5 of chlorpyrifos was found to decrease from 41 to 20 days under UV irradiation. The rate of chlorpyrifos photodegradation was increased in the presence of both metals, i.e., Cu(2+) and Fe(2+). Thus, initially observed t0.5 of 19.8 days was decreased to 4.39 days in the case of Cu(+2) and 19.25 days for Fe(+2). Copper was found to increase the rate of photodegradation by 4.5 orders of magnitude while the microbial degradation of chlorpyrifos was increased only twofold. The microbial degradation of chlorpyrifos was only negligibly affected by Fe(2+) amendment. The studied trace metals also affected the abiotic degradation of the pesticide in the order Cu(2+) > Fe(2+).

Photochemical fate and photocatalysis of 3,5,6-trichloro-2-pyridinol, degradation product of chlorpyrifos.

In this study we have focused on 3,5,6-trichloro-2-pyridinol (TCP), degradation product of chlorpyrifos. Photolysis experiments were conducted in order to elucidate its degradation mechanism. Identification of products was performed using the LC-MS technique. To evaluate the mineralization efficiency, TiO2 photocatalytic study was performed. Under photolytic experimental conditions, the concentration of TCP after 120 min of irradiation reached 5.9 ± 1.5% of the initial concentration, while chloride concentration reached approximately 73% of total chloride concentration. The TOC measurements after 120 min of photocatalytic degradation experiment revealed high mineralization rate, i.e. 53.6 ± 1.9%, while chloride concentration reached 26.6 mg L(-1) what means almost quantitative transformation of organic chlorine into chloride. TIC chromatogram (ESI, negative ion mode) of the reaction mixture after 30 min of irradiation revealed the presence of several peaks. One of them has already been reported previously. Two other products have been identified in this study for the first time. They have been formed by radical attack of the reactive OH(•) species on the carbonyl group followed by the corresponding N-C or C-C bond cleavages and recyclization with formation of the pyrrol structures substituted with carboxylic groups. Both deprotonated molecules easily lose CO2 in ESI conditions.

Photodegradation of chlorpyrifos in water by UV/H2O2 treatment: toxicity evaluation.

Chlorpyrifos (CP) is an organophosphorus pesticide widely used in agriculture. Due to its toxicity, it has been necessary to develop a treatment to eliminate the environmental wastes generated by this substance. The combination of UV radiation and hydrogen peroxide seemed an interesting option to reduce the concentration of CP in water, as it has proved to be a simple and effective method to degrade other similar pesticides. The purpose of this work is to study the effect of different initial concentrations of H2O2 on the degradation of commercial CP in water using UV/H2O2. Conversions of 93% were achieved in 20 min with 450 mg L(-1) of H2O2 initial concentration (0.16 mg of CP degraded per mg of H2O2 consumed). The total organic carbon analysis showed interesting mineralization values, reaching a 70% conversion after 4 h of reaction. In addition, this degradation procedure leads to a clear reduction of the toxicity of the reaction mixture over Vibrio fischeri.

Phototransformation of selected organophosphorus pesticides: roles of hydroxyl and carbonate radicals.

The phototransformation of two organophosphorus pesticides, parathion and chlorpyrifos, by hydroxyl radicals and carbonate radicals in aqueous solution were studied. Addition of hydrogen peroxide increased the UV degradation rates of both pesticides and data were simulated through kinetic modeling. The second-order rate constants of parathion and chlorpyrifos with hydroxyl radical were determined to be 9.7 +/- 0.5 x 10(9) and 4.9 +/- 0.1 x 10(9) M(-1) s(-1), respectively. The presence of bi/carbonate ions reduced the pesticide degradation rates via scavenging of hydroxyl radical but the formation of carbonate radical also contributed to the degradation of the pesticides with second-order reaction rate constants of 2.8 +/- 0.2 x 10(6) and 8.8 +/- 0.4 x 10(6) M(-1) s(-1) for parathion and chlorpyrifos, respectively. The dual roles of bicarbonate ion in UV/H2O2 treatment systems, i.e., scavenging of hydroxyl radicals and formation of carbonate radicals, were examined and discussed using a simulative kinetic model. The transformation of pesticides by carbonate radicals at environmentally relevant bi/carbonate concentrations was shown to be a significant contributor to the environmental fate of the pesticides and it reshaped the general phototransformation kinetics of both pesticides in UV/H2O2 systems.

Degradation behavior and products of malathion and chlorpyrifos spiked in apple juice by ultrasonic treatment.

Apple juice (13 degrees Brix) spiked with malathion and chlorpyrifos (2-3 mg l(-1) of each compound) was treated under different ultrasonic irradiations. Results showed that ultrasonic treatment was effective for the degradation of malathion and chlorpyrifos in apple juice, and the output power and treatment time significantly influenced the degradation of both pesticides (p<0.05). The maximum degradations were achieved for malathion (41.7%) and chlorpyrifos (82.0%) after the ultrasonic treatment at 500 W for 120 min. The degradation kinetics of both pesticides were fitted to the first-order kinetics model well (R(2)>or=0.90). The kinetics parameters indicated that chlorpyrifos was much more labile to ultrasonic treatment than malathion. Furthermore, malaoxon and chlorpyrifos oxon were identified as the degradation products of malathion and chlorpyrifos by gas chromatography-mass spectrometry (GC-MS), respectively. The oxidation pathway through the hydroxyl radical attack on the P=S bond of pesticide molecules was proposed.

Microbial toxicity of pesticide derivatives produced with UV-photodegradation.

Our study aimed at acquiring information about the biological effect of pesticides and their degradates produced by UV-treatment on microbiological activity. Five photosensitive pesticides (carbendazim, acetochlor, simazine, chlorpyrifos, EPTC) and six representative soil microbes (Bacillus subtilis, Pseudomonas fluorescens, Mycobacterium phlei, Fusarium oxysporum, Penicillium expansum, Trichoderma harzianum) were applied throughout our model experiments. The antimicrobial effects of the pesticides and their degradates were assessed with filter paper disk method. The antimicrobial effect of the degradation products exhibited marked differences in terms of pesticide types, irradiation time, and the test organisms. Acetochlor and its photolytic degradation products were found to be more toxic to bacteria than fungi. All the three bacteria proved to be sensitive to the basic compound and its degradation products as well. The end product of carbendazim was weakly antibacterial against P. fluorescens and B. subtilis but strongly antifungal against T. harzianum. Chlorpyrifos and its end product inhibited neither test organisms, but the degradates hindered the growth of four of them. The basic compound of EPTC and the degradates of simazine exhibited significant toxicity to the test bacteria. It might be claimed that the pesticide photodegradation may result in significant changes in soil microbiota, as well as formation of biologically harmful degradates.

[The effect of microwaves (UHF) and magnetic fields on the insecticidal properties of biological and chemical preparations]. / Vliianie mikrovoln (SVCh) i magnitnykh polei na insektitsidnye svoistva biologicheskikh i khimicheskikh preparatov.

The larvicidal activity of preparations from different groups of compounds was assayed after their exposure to microwaves and magnetic field. The radiation was found to have a varying impact on the insecticidal properties of the preparations. Thus, the efficiency of spheric larvicides decreased, which is likely to be associated with the structural changes of toxin crystals, whereas the larvicidal activity of the organophosphorus compound dursban and the pyrethroid aikon increased 2-5-fold. The higher activity of dursban irradiated with a magnetic field was demonstrated to retain for over 2 months.

[Changes in the acaricidal properties of organophosphorus compounds under the influence of magnetic resonance treatment]. / Izmenenie akaritsidnykh svoistv fosfororganicheskikh soedinenii pod vliianiem magnitorezonansnoi obrabotki.

The authors demonstrate the possibility of enhancing pesticidal properties of some organophosphorus compounds by their single treatment for 40 min by pulsed magnetic field, 100 kHz, 10-15 microT with 16 Hz sinusoidal modulation. The treatment efficacy is up to 30 days.