Antioxidative cellular response of lepidopteran ovarian cells to photoactivated alpha-terthienyl.

Photodynamic sensitizers as useful alternative agents have been used for population control against insect pests, and the response of insect ovarian cells towards the photosensitizers is gaining attention because of the next reproduction. In this paper, antioxidative responses of lepidopteran ovarian Tn5B1-4 and Sf-21 cells to photoactivated alpha-terthienyl (PAT) are investigated. PAT shows positive inhibitory cytotoxicity on the two ovarian cells, and its inhibition on cell viability is enhanced as the concentrations are increased and the irradiation time is extended. Median inhibitory concentrations (IC50) are 3.36µg/ml to Tn5B1-4 cells, and 3.15µg/ml to Sf-21 cells at 15min-UV-A irradiation 2h-dark incubation. Under 10.0µg/ml PAT exposure, 15min-UV-A irradiation excites higher ROS production than 5min-UV-A irradiation does in the ovarian cells, the maximum ROS content is about 7.1 times in Tn5B1-4 cells and 4.3 times in Sf-21 cells, and the maximum malondialdehyde levels in Tn5B1-4 and Sf-21 cells are about 1.47- and 1.36-fold higher than the control groups, respectively. Oxidative stress generated by PAT strongly decreases the activities of POD, SOD and CAT, and induces an accumulation of Tn5B1-4 cells in S phase and Sf-21 cells in G2/M phase in a concentration-dependent fashion. Apoptosis accumulation of Tn5B1-4 cells and the persistent post-irradiation cytotoxicity are further observed, indicating different antioxidative tolerance and arrest pattern of the two ovarian cells towards the cytotoxicity of PAT.

Effect and interaction study of acetamiprid photodegradation using experimental design.

The methodology of experimental research was carried out using the MODDE 6.0 software to study the acetamiprid photodegradation depending on the operating parameters, such as the initial concentration of acetamiprid, concentration and type of the used catalyst and the initial pH of the medium. The results showed the importance of the pollutant concentration effect on the acetamiprid degradation rate. On the other hand, the amount and type of the used catalyst have a considerable influence on the elimination kinetics of this pollutant. The degradation of acetamiprid as an environmental pesticide pollutant via UV irradiation in the presence of titanium dioxide was assessed and optimized using response surface methodology with a D-optimal design. The acetamiprid degradation ratio was found to be sensitive to the different studied factors. The maximum value of discoloration under the optimum operating conditions was determined to be 99% after 300 min of UV irradiation.

Investigating Role of Abiotic Factors on Spinosad Dissipation.

The effect of abiotic factors on dissipation of spinosad (soil moisture regimes, pH, and light) was studied. Spinosad residues were estimated using high performance liquid chromatography fitted with a UV detector. Under laboratory conditions, half-lives of spinosad were 9.0 and 7.7 days for air dried and field capacity soils, respectively. Percent dissipation of spinosad after 30 days was 47.02, 22.35, 62.5, 68.23 and 76.47 in solution with an aqueous pH of 10.85, 9.15, 6.97, 3.90 and 2.04, respectively. The half-life of spinosad in UV and sunlight was only 1.6 and 5.2 h, respectively. Light, especially the UV component, is an important factor for degradation of spinosad compared to other abiotic conditions.

Enhanced Ga2O3-photocatalyzed and photochemical degradation of the Fipronil insecticide by UVC irradiation in mixed aqueous/organic media under an inert atmosphere.

Agrochemicals such as the insecticide Fipronil that bear fluoro groups are generally fat-soluble and nearly insoluble in water, so that their photodegradation in a heterogeneous aqueous gallium oxide dispersion presents some challenges. This article examined the photodegradation of this insecticide by solubilizing it through the addition of organic solvents (EtOH, MeOH, THF, 1,4-dioxane and ethylene glycol) to an aqueous medium and then subjecting the insecticide to 254 nm UVC radiation under photocatalytically inert (Ga2O3/N2) and air-equilibrated (Ga2O3/O2) conditions, as well as photochemically in the absence of Ga2O3 but also under inert and air-equilibrated conditions. Defluorination, dechlorination, desulfonation and denitridation of Fipronil were examined in mixed aqueous/organic media (10, 25 and 50 vol% in organic solvent). After 3 h of UVC irradiation (50 vol% mixed media) defluorination with Ga2O3/N2 was ∼65% greater than in aqueous media, and ca. 80% greater than the direct photolysis of Fipronil under inert (N2) conditions; under air-equilibrated conditions both Ga2O3-photocatalyzed and photochemical defluorination were significantly lower than in aqueous media. Dechlorination of Fipronil was ∼160% (Ga2O3/N2) and 140% (photochemically, N2) greater than in aqueous media; under air-equilibrated conditions, both photocatalyzed and photochemical formation of Cl(-) ions in mixed media fell rather short relative to aqueous media. The photocatalyzed (Ga2O3/N2) and photochemical (N2) conversion of the sulfur group in Fipronil to SO4(2(-)) ions was ca. 20% and 30% greater, respectively, in mixed media, while under air-equilibrated conditions photocatalyzed desulfonation was nearly twofold less than in the aqueous phase; direct photolysis showed little variations in mixed media. Denitridation of the nitrogens in Fipronil occurred mostly through the formation of ammonia (as NH4(+)) under all conditions with negligible quantities of NO3(-); again mixed media offered enhanced denitridation, particularly under inert N2 conditions. Time-of-flight electrospray (TOF-MS/ESI(-)) mass spectrometry revealed a fairly large number of intermediates formed in the degradation of Fipronil, particularly under photocatalytic conditions. Only a couple of intermediates were identified in the photodegradation and the presence of Ga2O3 enhanced the complexity of an already cumbersome problem owing to the involvement of organic solvents.

Photoelectrocatalytic degradation of high COD dipterex pesticide by using TiO2/Ni photo electrode.

A TiO2 thin film electrode deposited on porous nickel net (TiO2/Ni) was prepared by the sol-gel method, and the surface morphology, crystal structure features and the grain size were characterized by Field emission scan electron microscopy (FESEM) and X-ray diffraction (XRD). The photoelectrocatalytic system was set up using a UV high-pressure mercury lamp as the light source, TiO2 coated on foamed nickel as photo anode, Pt sheet as counter electrode and the pesticide dipterex in synthetic wastewater. Various factors that influence the photoelectrocatalytic decomposition of dipterex pesticide have been studied, such as degradation time, the type of electrolyte, current density, original pH value and different degradation methods. The prepared catalysts were employed to photoelectrocatalytically degrade the pesticide dipterex under UV irradiation, comparing the results with photocatalytic degradation and electrochemical oxidation. The results indicated that under the optimal conditions of 0.02 mol/L NaCl as the supporting electrolyte, current density = 2.5 mA/cm2, pH 6.0 and dipterex pesticide 40 mg/L, and reaction time 2 hr, dipterex chemical oxygen demand (COD) removal rate and organophosphorous conversion of up to 82.6% and 83.5% were achieved, respectively. The method of photoelectrocatalytic degradation is more efficient than photocatalysis and electrochemical oxidation. The possible roles of the electrolytes on the reactions and probable mechanisms were also discussed.

Effect of light and pH on persistence of flubendiamide.

Persistence of flubendiamide in soil as affected by UV and sunlight exposure and in water as affected by pH was studied. At field capacity moisture regime, soil was treated with flubendiamide and exposed to UV and sunlight. Dissipation for the pesticide followed mono-phasic first order kinetics. Residues of flubendiamide, as thin film on petri-plates and soil thin film, dissipated with half-lives of 7.0 and 9.1 days under UV light and 12.0 and 19.1 days under sunlight, respectively. Residues of flubendiamide dissipated faster under UV light as compared to sunlight. Persistence study in aqueous medium under different pH condition indicated that flubendiamide residues persisted in water beyond 250 days with half-lives ranging from 250.8 to 301.0 days. Dissipation in water was faster at pH 4.0 (T(1/2) 250.8 days), followed by pH 9.2 (T(1/2) 273.6 days) and 7.0 (T(1/2) 301.0 days).

A facile strategy for photocatalytic degradation of seven neonicotinoids over sulfur and oxygen co-doped carbon nitride.

Mounting evidence highlights the negative impacts of neonicotinoids on non-target organisms and ecosystem, yet there are a few of methods to address the residual neonicotinoids in environment. Herein, series of sulfur and oxygen co-doped carbon nitride (SOCNx) were successfully synthesized via one-step thermal polymerization and applied in photodegradation of multi-neonicotinoids (dinotefuran, acetamiprid, clothianidin, thiacloprid, imidacloprid, nitenpyram and thiamethoxam) simultaneously for the first time. Unique tubular structure was observed at the specific doping ratio, which enhanced both mass transfer and specific surface area of graphitic carbon nitride (g-C3N4). The doping process changed the morphology of g-C3N4 materials and also affected its photocatalytic performance. The degradation rate of optimized material (SOCN8) for nitenpyram could surpass 90% just in 30 min under visible light in aqueous matrix. The degradation for target insecticide increased maximum efficiency of 57.6% compared to bulk g-C3N4. Moreover, the possible mechanism of the degradation process was proposed. The results revealed that photon-induced hole (h+) was the primary active species during the degradation of seven investigated neonicotinoids. Moreover, the SOCN8 showed excellent recyclability after four consecutive cycles, which implied promising applications for pesticide-contaminated water remedy.

Fabrication of smart stimuli-responsive mesoporous organosilica nano-vehicles for targeted pesticide delivery.

It is highly desirable to construct stimuli-responsive nanocarriers for improving pesticides targeting and preventing the pesticides premature release. In this work, a novel redox and α-amylase dual stimuli-responsive pesticide delivery system was established by bonding functionalized starch with biodegradable disulfide-bond-bridged mesoporous silica nanoparticles which loaded with avermectin (avermectin@MSNs-ss-starch nanoparticles). The results demonstrated that the loading capacity of avermectin@MSNs-ss-starch nanoparticles for avermectin was approximately 9.3 %. The starch attached covalently on the mesoporous silica nanoparticles could protect avermectin from photodegradation and prevent premature release of active ingredient. Meanwhile, the coated starch and disulfide-bridged structure of nanoparticles could be decomposed and consequently release of the avermectin on demand when nanoparticles were metabolized by glutathione and α-amylase in insects. The bioactivity survey confirmed that avermectin@MSNs-ss-starch nanoparticles had a longer duration in controlling Plutella xylostella larvae compared to avermectin emulsifiable concentrate. In consideration of the superior insecticidal activity and free of toxic organic solvent, this target-specific pesticide release system has promising potential in pest management.

Insect metabolism of photoaldrin and photodieldrin.

Photoaldrin and photodieldrin, sunlight products of adrin and dieldrin, are rapidly metabolized to a more toxic material by flies and mosquito larvae. It is suggested that this conversion is the cause for the enhanced toxicities of the photoproducts.

Fate of azadirachtin A and related azadirachtoids on tomatoes after greenhouse treatment.

The degradation of the main azadirachtoids on tomatoes was studied after greenhouse treatment. These experiments were carried out at 1 and 5x the concentration recommended by the manufacturer. In all experiments the deposition of azadirachtin A (AZA-A) was below the maximum residue level (MRL). Even if at the highest dose, AZA-A half-life time calculated as pseudo first order kinetic was 1.2 days in agreement with the recommended preharvest interval (PHI) of 3 days. Experiments with a model system showed that sunlight photodegradation is the main factor influencing the rate of disappearance of AZA-A after greenhouse treatment while tomato epicuticular waxes doubled the photodegradation rate of AZA-A in a commercial formulation.

Degradation of fipronil (Termidor) in aqueous solution stored in polyethylene tanks exposed to sunlight or shade.

Pest Management Professionals commonly use polyethylene or fiberglass tanks for mixing and applying termiticides. We investigated the stability of fipronil (Termidor SC) (0.06%, 0.09% and 0.125% active ingredient) in aqueous solutions stored in polyethylene tanks under sun and shade for 2 week. Chemical analysis of tank-mixed solutions sampled at 0, 24, 48, 72, 168 and 336 h indicated that fipronil remained stable. Our data indicated that polyethylene tanks prevent fipronil from photodegradation and these tanks can be safely used for short term storage (up to 2 week) of liquid termiticides.

Stability of imidacloprid (Premise 75) in a tank-mixed aqueous solution when stored in shade or sunlight.

Polyethylene tanks are commonly used by pest management professionals to mix and apply termiticides. These termiticides are susceptible to rapid photolysis and the ability of application tanks to filter sunlight has been questioned. We investigated the stability of imidacloprid (Premise 75) in aqueous solutions stored in polyethylene tanks under shade or sunlight. Chemical analysis of aqueous solutions sampled at 0, 24, 48, 72, 168 and 336 h revealed that imidacloprid was relatively stable. Our results indicate that polyethylene tanks are adequate to protect imidacloprid from photo degradation.

Hydrolysis and photolysis of diacylhydrazines-type insect growth regulator JS-118 in aqueous solutions under abiotic conditions.

JS-118 is a diacylhydrazines-type insect growth regulator which is now used extensively in China. The hydrolysis and photolysis of the pesticide JS-118 in aqueous solutions have been assessed under natural and controlled conditions in this project. Hydrolysis experimental results show that JS-118 is quite stable in aqueous solutions in dark, with no significant variations be observed in degradation under various conditions. Abiotic hydrolysis is relatively unimportant compared to photolysis. The rate of photodecomposition of JS-118 in aqueous solutions follows first-order kinetics both in UV radiation and natural sunlight. The degradation rates are faster under UV light than sunlight, with the half-lives (t (1/2) = ln2/k) of 6.00-10.85 min and 6.63-10.16 day, respectively. Under UV light, two major photoproducts are detected, and tentatively identified according to HPLC-MS spectral information as N-t-butyl-N-(3,5-dimethylbenzoyl) and 3,7-dimethyl-benzoatedihydrofuran. The corresponding photolysis pathways of JS-118 are also proposed. The results obtained indicate that direct photoreaction is an important dissipation pathway of JS-118 in natural water systems.

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.

Evaluation of tumour promoting potency of fish borne toxaphene residues, as compared to technical toxaphene and UV-irradiated toxaphene.

In this study the potential impact of food chain-based biotransformation and physico-chemical weathering of toxaphene on its tumour promoting potential was investigated in vitro and in vivo. Human exposure to toxaphene is mainly through consumption of contaminated fish, therefore fish-borne residues of toxaphene (cod liver extract, CLE) were prepared by exposing cod to technical toxaphene (TT) for 63 days. UV-irradiated toxaphene (uvT) was included to represent a physico-chemical weathered toxaphene mixture. In vitro, TT, uvT and CLE all showed a dose- and time-dependent inhibition of gap junctional intercellular communication (GJIC) with a relative potency of CLE>TT=uvT. Tumour promoting potency was further studied in vivo in a medium term two-stage initiation/promotion bioassay in female Sprague-Dawley rats, using an increase in altered hepatic foci positive for glutathione-S-transferase-P (AHF-GST-P) as read out. No increase in AHF-GST-P occurred following exposure to either TT, uvT, or CLE, except for the positive control group (2,3,7,8-TCDD). Based on this study the no observed adverse effect level (NOAEL) for tumour promoting potency is at least 12.5mg/kg/week, or higher for CLE. Considering current human exposure levels in Europe it is doubtful that consumption of fish at current levels of toxaphene contamination give rise to human health risk.

Imidacloprid oxidation by photo-Fenton reaction.

This paper presents experimental results on the imidacloprid removal from wastewater using homogeneous photo-Fenton reactions illuminated with black light lamps. Multivariate experimental design was used to identify the effect of initial Fe(II) and H(2)O(2) concentrations on process performance. The initial iron concentration played a key role in the process kinetics, whereas hydrogen peroxide concentration directly affected the extent of the oxidation process. Imidacloprid degradation proceeded via two distinctive kinetics regimes, an initial stage of rapid imidacloprid reduction, followed by a slower oxidation process until complete removal. Under optimal conditions, more than 50% imidacloprid degradation was observed after less than 1 min treatment, and TOC and COD removal up to 65% and 80%, respectively, were measured after all hydrogen peroxide was consumed. Raw imidacloprid samples presented significant acute toxicity to Daphnia magna and genotoxic effects on Bacillus subtilis sp. Such toxic effects remained detectable even after significant pesticide removal had been achieved, due to the presence of toxic by-products. Both acute toxicity and genotoxicity disappeared after considerable mineralization resulting in final low molecular weight by-products. Results obtained here confirm that design and operation of photo-Fenton processes should focus on toxicity removal rather than on specific target pollutants.

Effect of temperature on Imidacloprid oxidation by homogeneous photo-Fenton processes.

This paper presents experimental results on the effect of temperature on the rate of Imidacloprid removal from waste water using homogeneous photo-Fenton processes. Experiments were conducted in a 2 L photo reactor set at 15-42 degrees C, initial concentrations in the range of 10 to 40 mg L(-1) Fe(II) and 100-450 mg L(-1) H(2)O(2); 30 150 min processing times. Initial H(2)O(2) concentration determined the extent of the oxidation process, whereas iron concentration played a key role in the process kinetics. Homogeneous photo-Fenton showed a fast initial reaction leading to 50% Imidacloprid degradation after less than 1 min of treatment, followed by a slower process until full removal was achieved. Rapid Fe(II) oxidation to Fe(III) seems responsible for the initial Imidacloprid removal. Imidacloprid removal fitted well a pseudo-first order kinetic scheme, with apparent activation energy of approximately 31.6 kJ/mole. Untreated Imidacloprid samples showed significant acute toxicity to Daphnia magna and genotoxic effects on Bacillus subtilis. Acute toxicity and genotoxicity remained detectable even after complete pesticide removal, showing that toxic by-products were present. The design and operation of photo Fenton processes should focus on toxicity removal rather than on specific target pollutants.

Improvement of Vip3Aa16 Toxin Production and Efficiency Through Nitrous Acid and UV Mutagenesis of Bacillus thuringiensis (Bacillales: Bacillaceae).

Bacillus thuringiensis Berliner (Bacillales: Bacillaceae) strain BUPM95 was known by the efficiency of its vegetative insecticidal protein (Vip3Aa16) against different Lepidoptera such as Spodoptera littoralis (Lepidoptera: Noctuidae). To overcome the problem of the low quantities of Vip3 proteins secreted by B. thuringiensis strains in the culture supernatant, classical mutagenesis of vegetative cells of BUPM95 strain was operated using nitrous acid and UV rays. The survivors were screened on the basis of their hemolytic activity and classified in three groups: unaffected, overproducing, and hypo-producing mutants. Using different mutants improved in their hemolytic activity, the supernatants showed an improved toxicity toward S. littoralis larvae (83.33-100% of mortality) compared with the wild-type supernatant (76%). After Vip3 protein quantification in the different supernatants, bioassays against S. littoralis larvae demonstrated that mutants M62, M43, and M76 were improved in the efficiency of their toxin as demonstrated by the lower values of LC50 and LC90 compared with the wild-type Vip3Aa16 protein. However, M26 and M73 mutants were improved in the toxin quantities produced in the supernatant. The improvement of the production and the efficiency of B. thuringiensis Vip3 toxins should contribute to a significant reduction of the production costs of these very interesting B. thuringineis proteins and facilitate the use of these toxins in the pest control management.

Photolytic degradation of the insecticide thiamethoxam in aqueous medium monitored by direct infusion electrospray ionization mass spectrometry.

Photodegradation of the insecticide thiamethoxam (1), 3-[(2-chloro-5-thiazolyl)methyl]tetrahydro-5-methyl-N-nitro-4H-1,3,5-oxadiazin-4-imine, in an aqueous medium was monitored by electrospray ionization mass spectrometry in the positive ion mode, ESI(+)-MS. An aqueous solution of (1) was incessantly exposed to a UV radiation source and aliquots were taken after reaction times of 1, 2, 3, and 4 h. Analysis by GC/NCI-MS revealed that (1) was continuously degraded under these experimental conditions. However, the total organic carbon (TOC) content remained practically constant during the exposition period, thereby indicating that 1 was not mineralized but continuously converted into other compounds. ESI(+)-MS monitoring revealed that whereas the intensity of the ions of m/z 292/294 ([1 + H](+)) constantly decreased, there was the emergence of other ions of m/z 247/249, 197, 168, and 116 whose intensities simultaneously increased. Their structures were proposed on the basis of: (1) the data of their ESI(+)-MS/MS; (2) their high resolution m/z values; and (3) a plausible reactivity of the thiamethoxam molecule exposed to UV radiation in aqueous solution. Finally, these data allowed us to suggest a reaction route for the photodegradation of 1 in an aqueous medium.

Photocatalytic degradation of triazophos in aqueous titanium dioxide suspension: identification of intermediates and degradation pathways.

The photocatalytic degradation of triazophos in aqueous TiO2 suspension has been studied in a photoreactor operating with simulated solar radiation. The decrease in triazophos concentration followed first-order kinetics with a half-life of 4.76+/-0.42 h at a TiO2 suspension concentration of 10 mg/L. Seventeen degradation products were identified using HPLC-UV, HPLC/MS/MS, GC/MS/MS and IC, and by comparing retention times and spectra with commercially available authentic standards. On the basis of the observed transformation products, two routes were proposed, one based on the initial oxidative cleavage of PS bond to PO bond, and the other on initial cleavage of the ester P-O bonds. Photocatalysis holds promise for the solar treatment of pesticide-contaminated waters.