Impact of Micronutrient Supplementation on Pesticide Residual, Acetylcholinesterase Activity, and Oxidative Stress Among Farm Children Exposed to Pesticides.

The present interventional study aimed to assess the impact of micronutrient supplementation on pesticide-residues concentrations, vitamins, minerals, acetylcholinesterase activity and oxidative stress among 129 farm children (9-12 years, n = 66 and 13-15 years, n = 63) involved in farming activities in Ranga Reddy district, Telangana, India. Our data showed the presence of five organophosphorus pesticide residues (chlorpyrifos, diazinon, malathion, monocrotophos, and phosalone) among children before-supplementation (both age-groups); while post-supplementation, only two pesticide residues (chlorpyrifos and diazinon) were detected indicating improved metabolic rate. Vitamin E, copper, magnesium and zinc levels were also improved in both the age-groups and manganese levels were significantly increased only among children of 13-15 years age group. Further, post-supplementation also showed an improvement in acetylcholinesterase activity and a decrease in lipid peroxidation among both the age groups of children. However, further research for ascertaining the ameliorating effect of micronutrients in preventing adverse effects of organophosphorus pesticides must be conducted.

Characterization of organophosphate pesticide sorption of potato peel biochar as low cost adsorbent for chlorpyrifos removal.

There has been a growing interest in the scientific world in the production of biochar from natural organic wastes as potential sustainable precursors for bioremediation. Potato peel biochar was produced by slow pyrolysis method under oxygen-limited conditions and used as bio adsorbent in bioremediation of commercial pesticide having Chlorpyrifos as an active component. Chlorpyrifos is an organophosphate pesticide, highly neurotoxic, and primarily targets the central nervous system of pests and insects. The excess residues of chlorpyrifos are hazardous to environmental flora and fauna. Chlorpyrifos was treated against biochar at varying physical parameters and further optimized by using response surface methodology through Box-Behnken design (BBD). 72.06% of pesticide removal was observed post 24 h of treatment against a pesticide concentration of 1346.85 µg/ml with a biochar concentration of 1.04 mg/ml under room temperature at pH 5.04. Biochar was characterized by proximate and ultimate analysis, FTIR, and SEM-EDX. Characterization by SEM-EDX showed the surface morphology and minerals on the peel and biochar. Microgram of potato peel shows pores of larger size than biochar having many cavities with different dimensions. In the plant system, growth morphology, nutritional status, polyphenols, total antioxidant content, and free radical scavenging activity were assessed. Enhancement in presence of biochar was recorded in growth morphology and plant biomolecules including photosynthetic pigments. Better translocation of the nutrient is recorded in biochar treated plants, as evidenced by the low amount of carbohydrate and protein in treated leaves. Biocompatibility assessment of chlorpyriphos in fish erythrocytes showed 43.26% hemolysis by pesticide-treated biochar. The practical use of this approach can also be best utilized if applied to those geographical regions where the soil pH is acidic. Biochar is a marketable bio-product, which can have a positive impact in agriculture, industries, and the energy sector creating a bio-based economy with reduced environmental pollution.

Magnetically controlled colorimetric aptasensor for chlorpyrifos based on copper-based metal-organic framework nanoparticles with peroxidase mimetic property.

The fabrication of a magnetically controlled colorimetric aptasensor for chlorpyrifos is reported. The aptasensor was fabricated by the attachment of the colorimetric labels onto the magnetic carrier due to the hybridization reaction between the complementary DNA and aptamer. Chlorpyrifos detection was realized by monitoring the color changes of the TMB/H2O2 solution before and after incubation of the aptasensor with chlorpyrifos via exposure to external magnetic force. The color change was monitored at 650 nm by UV-Vis spectrophotometer. Under the optimal conditions, this magnetically controlled Cu-MOF-based aptasensor showed a detection limit of 4.4 ng/mL with a linear range of 0-1250 ng/mL. The colorimetric aptasensor displayed high selectivity for chlorpyrifos toward other interfering pesticides. The aptasensor was successfully applied for the spiked test of chlorpyrifos in fruits and vegetable samples with good recovery, which were in agreement with data obtained by GC-MS analysis. This magnetically controlled Cu-MOF-based sensing strategy not only leads to development of efficient and facile phase separation, but also expands the MOF's target scope from H2O2 or glucose to pesticides. Graphical abstract.

Magnetic amino-functionalized hollow silica-titania microsphere as an efficient sorbent for extraction of pesticides in green and roasted coffee beans.

This study describes the synthesis and application of a magnetic amino-functionalized hollow silica-titania microsphere as a new sorbent for magnetic dispersive micro-solid phase extraction of selected pesticides in coffee bean samples. The sorbent was fully characterized by Fourier-transform infrared spectroscopy, field emission scanning electron microscopy, transition electron microscopy, energy-dispersive X-ray spectroscopy, and vibrating sample magnetometry techniques. Significant extraction parameters affecting the proposed method, such as extraction time, sorbent amount, sample solution pH, salt amount, and desorption conditions (desorption solvent and time) were investigated and optimized. All the figures of merits were validated in coffee bean samples under the matrix-matched calibration method. Linear dynamic ranges were 5-250 µg/kg with the determination coefficients (R2 ) > 0.9980. The limits of detection for the pesticides of chlorpyrifos, malathion, hexaconazole, and atrazine were 1.42, 1.43, 1.35, and 1.33 µg/kg, respectively. Finally, the method was successfully applied for the determination of the pesticides in green and roasted coffee bean samples, and the obtained recoveries were in the range of 74-113% for spiked samples. The prepared sorbent could be used for the magnetic dispersive micro-solid phase extraction of pesticides in the plant-derived food matrix.

Ameliorative Effect of Beta vulgaris Root Extract on Chlorpyrifos-Induced Oxidative Stress, Inflammation and Liver Injury in Rats.

Exposure to organophosphorus insecticides causes several health problems to animals and humans. Red beetroot (RBR) is rich in antioxidant ingredients and possesses a promising hepatoprotective activity. This study evaluated the potential of RBR extract to prevent chlorpyrifos (CPF)-induced liver injury, with an emphasis on oxidative stress, inflammation and apoptosis. Rats received 10 mg/kg CPF and were treated with 300 mg/kg RBR extract for 28 days. CPF caused liver injury evidenced by elevated serum levels of serum alanine aminotransferase (ALT), aspartate aminotransferase (AST), alkaline phosphatase (ALP) and bilirubin, along with several histological alterations. Hepatic lipid peroxidation (LPO) and nitric oxide (NO) levels, as well as inducible nitric oxide synthase (iNOS) and pro-inflammatory cytokines were increased in CPF-intoxicated rats. RBR prevented CPF-induced histological alterations, and ameliorated liver function, LPO, NO, iNOS and pro-inflammatory cytokines. RBR boosted glutathione and antioxidant enzymes, and increased Nrf2 expression. In addition, RBR diminished Bax and caspase-3, and increased Bcl-2 expression. In conclusion, RBR prevented CPF-induced liver injury via attenuation of oxidative stress, inflammation and apoptosis. RBR enhanced antioxidant defenses, suggesting that it could be used as a potential therapeutic intervention to minimize CPF hepatotoxicity.

Establishing the impact of food matrix effects on the bioaccessibility of nutraceuticals and pesticides using a standardized food model.

It is important to establish the impact of food matrix effects on the bioaccessibility of co-ingested substances, such as nutraceuticals, engineered nanomaterials, pharmaceuticals, and pesticides. Recently, a standardized food model (SFM) representing a typical US diet has been developed to facilitate these investigations. This model consists of caseinate-stabilized fat droplets, free casein, pectin, starch, sucrose, and sodium chloride. The SFM was stable to creaming for 2 days, contained small particles (d ≈ 180 nm), and had a narrow particle size distribution. The SFM was mixed with pureed tomato that had been deliberately contaminated with chlorpyrifos (a hydrophobic pesticide). The resulting mixture was then exposed to an in vitro digestion model. The structural and physicochemical characteristics of the samples (microstructure, particle diameter, and surface potential) were determined after each GIT stage. Also, the bioaccessibility of both chlorpyrifos and lycopene (a hydrophobic nutraceutical) from the pesticide-contaminated tomatoes was determined after the final digestion process. For lycopene, the bioaccessibility was much lower for tomato alone (0.75%) than for tomato plus SFM (19.0%) (p < 0.05). For chlorpyrifos, the bioaccessibility was also appreciably lower for tomato alone (40.4%) than for tomato plus SFM (58.7%), but the effect was less dramatic (p < 0.05). Our results indicate that a standardized food matrix impacts the bioaccessibility of hydrophobic bioactives in fresh produce by an amount that depends on the nature of the bioactive agent. The SFM developed here may therefore be useful for screening the potential impact of food matrix effects on the bioaccessibility of ingested bioactives and other substances.

An integrated approach for assessing the migration behavior of chlorpyrifos and carbaryl in the unsaturated soil zone.

Chlorpyrifos (O, O-diethyl O-3,5,6-trichloropyridin-2-yl phosphorothioate) and carbaryl (1-naphthyl methylcarbamate) are often applied concurrently as insecticides in food production. The aim of this study was to research their migration behavior in a real environment. We researched the leaching of both pesticides by setting up field lysimeters on a farm with the typical soil used in fruit production today. In order to analyze the variables involved in this process, we performed complementary adsorption studies, we performed complementary adsorption studies using batches and undisturbed soil laboratory columns for both compounds. The results for pesticide transport through the lysimeters showed that less than 1% of chlorpyrifos was recovered in the leachates, while almost 17% was recovered for carbaryl. Having completed the experiment in undisturbed laboratory columns, soil analysis showed that chlorpyrifos mainly remained in the first 5 cm, while carbaryl moved down to the lower sections. These results can be explained in view of the sorption coefficient values (KD) obtained in horizons A and B for chlorpyrifos (393 and 184 L kg-1) and carbaryl (3.1 and 4.2 L kg-1), respectively. By integrating the results obtained in the different approaches, we were able to characterize the percolation modes of these pesticides in the soil matrix, thus contributing to the sustainable use of resources.

Facile synthesis of amine-functional reduced graphene oxides as modified quick, easy, cheap, effective, rugged and safe adsorbent for multi-pesticide residues analysis of tea.

Amine-functional reduced graphene oxide (amine-rGO) with different carbon chain length amino groups were successfully synthesized. The graphene oxides (GO) reduction as well as amino grafting were achieved simultaneously in one step via a facile solvothermal synthetic strategy. The obtained materials were characterized by X-ray diffraction, Raman spectroscopy, Fourier-transform infrared spectrometry and X-ray photoelectron spectroscopy to confirm the modification of GO with different amino groups. The adsorption performance of catechins and caffeine from tea acetonitrile extracts on different amine functional rGO samples were evaluated. It was found that tributylamine-functional rGO (tri-BuA-rGO) exhibited the highest adsorption ability for catechins and caffeine compared to GO and other amino group functional rGO samples. It was worth to note that the adsorption capacity of catechins on tri-BuA-rGO was 11 times higher than that of GO (203.7mgg-1 vs 18.7mgg-1). Electrostatic interaction, π-π interaction and surface hydrophilic-hydrophobic properties of tri-BuA-rGO played important roles in the adsorption of catechins as well as caffeine. The gravimetric analysis confirmed that the tri-BuA-rGO achieved the highest efficient cleanup preformance compared with traditional dispersive solid phase extraction (dSPE) adsorbents like primary-secondary amine (PSA), graphitized carbon black (GCB) or C18. A multi-pesticides analysis method based on tri-BuA-rGO is validated on 33 representative pesticides in tea using gas chromatography coupled to tandem mass spectrometry or high-performance liquid chromatography coupled with tandem mass spectrometry. The analysis method gave a high coefficient of determination (r2>0.99) for each pesticide and satisfactory recoveries in a range of 72.1-120.5%. Our study demonstrated that amine functional rGO as a new type of QuEChERS adsorbent is expected to be widely applied for analysis of pesticides at trace levels.

Evaluation of the efficacy of insecticidal coatings based on teflutrin and chlorpyrifos against Rhynchophorus ferrugineus.

BACKGROUND: The date palm (Phoenix dactylifera L.), an important economic resource for many nations worldwide, has recently been threatened by the presence of different insect pests, like the red palm weevil (RPW) Rhynchophorus ferrugineus. RESULTS: Two products, a glue (polyvinyl acetate) and an oil (raw linseed oil) were used as coatings and applied together with a repellent and two insecticides (teflutrin and chlorpyrifos) at different dosages on two species of palm (P. dactylifera and P. canariensis). Phytotoxic effects of the treatments were evaluated in a greenhouse on 260 potted palms (130 P. dactylifera and 130 P. canariensis) and no negative effects were observed. Afterwards, a trial lasting 400 days was carried out in a nursery located in Sicily (south Italy), treating 572 potted palm trees (286 P. dactylifera and 286 P. canariensis) with an average diameter at the base of 18-20 cm. After 400 days, 48% of the untreated palms were infested, while only 3% of date palms and 7% of Canary palms treated with insecticide at lower dosages were infested. CONCLUSIONS: The application of an insecticide-based coating is a good strategy to control and prevent the red palm weevil infestation, in particular on date palms. © 2017 Society of Chemical Industry.

Application of acclimated sewage sludge as a bio-augmentation/bio-stimulation strategy for remediating chlorpyrifos contamination in soil with/without cadmium.

This experiment was performed to investigate the effects of acclimated sewage sludge (ASS) and sterilized ASS on the fates of chlorpyrifos (CP) in soil with or without cadmium (Cd), as well as the improvement of soil biochemical properties. Results showed that both ASS and sterilized ASS could significantly promote CP dissipation, and the groups with ASS had the highest efficiency on CP removal, whose degradation rates reached 71.3%-85.9% at the 30th day (40.4%-50.2% higher than non-sludge groups). Besides, the degradation rate of CP was not severely influenced by the existence of Cd, and the population of soil microorganism dramatically increased after adding sludge. The soil enzyme activities (dehydrogenase, acid phosphatase and FDA hydrolase activities) ranked from high to low were as follows: groups with sterilized ASS>groups with ASS>groups without sludge. Simultaneously, 16S rRNA gene sequencing revealed that ASS changed bacterial community structure and diversity in soil. In addition, alkali-hydrolyzable nitrogen and Olsen- phosphorus increased after application of sludge, indicating that the addition of ASS (or sterilized ASS) could effectively improve soil fertility.

Understanding the degradation pathway of the pesticide, chlorpyrifos by noble metal nanoparticles.

Application of nanoparticles (NPs) in environmental remediation such as water purification requires a detailed understanding of the mechanistic aspects of the interaction between the species involved. Here, an attempt was made to understand the chemistry of noble metal nanoparticle-pesticide interaction, as these nanosystems are being used extensively for water purification. Our model pesticide, chlorpyrifos (CP), belonging to the organophosphorothioate group, is shown to decompose to 3,5,6-trichloro-2-pyridinol (TCP) and diethyl thiophosphate at room temperature over Ag and Au NPs, in supported and unsupported forms. The degradation products were characterized by absorption spectroscopy and electrospray ionization mass spectrometry (ESI MS). These were further confirmed by ESI tandem mass spectrometry. The interaction of CP with NP surfaces was investigated using transmission electron microscopy, energy dispersive analysis of X-rays, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). XPS reveals no change in the oxidation state of silver after the degradation of CP. It is proposed that the degradation of CP proceeds through the formation of AgNP-S surface complex, which is confirmed by Raman spectroscopy. In this complex, the P-O bond cleaves to yield a stable aromatic species, TCP. The rate of degradation of CP increases with increase of temperature and pH. Complete degradation of 10 mL of 2 ppm CP solution is achieved in 3 h using 100 mg of supported Ag@citrate NPs on neutral alumina at room temperature at a loading of ∼0.5 wt %. The effect of alumina and monolayer protection of NPs on the degradation of CP is also investigated. The rate of degradation of CP by Ag NPs is greater than that of Au NPs. The results have implications to the application of noble metal NPs for drinking water purification, as pesticide contamination is prevalent in many parts of the world. Study shows that supported Ag and Au NPs may be employed in sustainable environmental remediation, as they can be used at room temperature in aqueous solutions without the use of additional stimulus such as UV light.

Differential acetylcholinesterase inhibition of chlorpyrifos, diazinon and parathion in larval zebrafish.

Zebrafish are increasingly used for developmental neurotoxicity testing because early embryonic events are easy to visualize, exposures are done without affecting the mother and the rapid development of zebrafish allows for high throughput testing. We used zebrafish to examine how exposures to three different organophosphorus pesticides (chlorpyrifos, diazinon and parathion) over the first five days of embryonic and larval development of zebrafish affected their survival, acetylcholinesterase (AChE) activity and behavior. We show that at non-lethal, equimolar concentrations, chlorpyrifos (CPF) is more effective at equimolar concentrations than diazinon (DZN) and parathion (PA) in producing AChE inhibition. As concentrations of DZN and PA are raised, lethality occurs before they can produce the degree of AChE inhibition observed with CPF at 300 nM. Because of its availability outside the mother at the time of fertilization, zebrafish provides a complementary model for studying the neurotoxicity of very early developmental exposures.

Use of ultra-high-pressure liquid chromatography-quadrupole time-of-flight MS to discover the presence of pesticide metabolites in food samples.

In this paper we illustrate the use of two different methodologies to investigate the presence of pesticide metabolites in parent pesticide-positive food samples, using ultra-high-pressure liquid chromatography coupled to hybrid quadrupole time-of-flight (UHPLC-QTOF) mass spectrometry. First, a common fragmentation pathway between the parent pesticide and its metabolites has been considered to search for metabolites in two positive market samples (imazalil in lemon, chlorpyrifos in grape). Secondly, olive oil samples from field residue trials were used for automated application of comparative software (MetaboLynx), which was used with treated and untreated samples to search for expected and unexpected metabolites of phosmet. One of the main objectives when using these approaches was to avoid the tedious manual searching for potential metabolites within the huge amount of information contained in the total ion chromatogram acquired by TOF MS. The common fragmentation approach applied to TOF MS full-acquisition data, considering an enhanced fragmentation in the collision cell, has allowed the discovery of two metabolites of imazalil (1-[2-(2,4-dichlorophenyl)-2-hydroxyethyl]-1H-imidazole and 1-[2-(2,4-dichlorophenyl)-2-oxoethyl]-1H-imidazole) in a lemon positive sample, as well as another two metabolites of chlorpyrifos (chlorpyrifos-oxon and 3,5,6-trichloro-2-pyridinol) in a grape positive sample. Moreover, MetaboLynx application to TOF MS data, without promoting fragmentation, from treated and untreated olive oil samples has been helpful in detecting the metabolite phosmet-oxon. In both strategies, every metabolite detected by TOF MS was confirmed using QTOF and/or triple quadrupole instruments. Accurate masses given by TOF MS together with the valuable information on product ions given by QTOF MS/MS experiments were crucial for the unambiguous identification of metabolites.

Reduced plant uptake of pesticides with biochar additions to soil.

We investigated the effectiveness of two types of biochars in reducing the bioavailability of two soil-applied insecticides (chlorpyrifos and carbofuran) to Spring onion (Allium cepa). The biochars prepared from the pyrolysis of Eucalyptus spp. wood chips at 450 and 850 degrees C (BC850) were thoroughly mixed into the soil to achieve 0%, 0.1%, 0.5% and 1% by soil weight. A spring onion crop was grown for 5 wk in the biochar-amended soils spiked with 50 mgkg(-1) of each pesticide. The loss of both pesticides due to degradation and or sequestration in soils decreased significantly with increasing amounts of biochars in soil. Over 35 d, 86-88% of the pesticides were lost from the control soil, whereas it was only 51% of carbofuran and 44% of chlorpyrifos from the soil amended with 1.0% BC850. Despite greater persistence of the pesticide residues in biochar-amended soils, the plant uptake of pesticides decreased markedly with increasing biochar content of the soil. With 1% of BC850 soil amendment, the total plant residues for chlorpyrifos and carbofuran decreased to 10% and 25% of that in the control treatment, respectively. The BC850 was particularly effective in reducing phytoavailability of both pesticides from soil, due to its high affinity for and ability to sequester pesticide residues.

The effect of plasma lipids on the pharmacokinetics of chlorpyrifos and the impact on interpretation of blood biomonitoring data.

Lipophilic molecules, like chlorpyrifos (CPF), present a special problem for interpretation of biomonitoring data because both the environmental dose of CPF and the physiological (pregnancy, diet, etc.) or pathological levels of blood lipids will affect the concentrations of CPF measured in blood. The objective of this study was to investigate the distribution of CPF between plasma and tissues when lipid levels are altered in late pregnancy. CPF was sequestered more in the low-density lipid fraction of the blood during the late stages of gestation in the rat and returned to nonpregnant patterns in the dam after birth. Plasma partitioning of CPF increased with increases in plasma lipid levels and the increased partitioning of CPF into plasma lipids resulted in less CPF in other tissue compartments. Gavage dosing with corn oil also increased plasma lipids that led to a moderate increase of CPF partitioning into the plasma. To mechanistically investigate the potential pharmacokinetic effects of blood lipid changes, an existing CPF physiologically based pharmacokinetic/pharmacodynamic model for rats and humans was modified to account for altered lipid-tissue partition coefficients and for major physiological and biochemical changes of pregnancy. The model indicated that plasma CPF levels are expected to be proportional to the well-known changes in plasma lipids during gestation. There is a rapidly growing literature on the relationship of lipid profiles with different disease conditions and on birth outcomes. Increased blood concentrations of lipophilic chemicals like CPF may point to altered lipid status, as well as possibly higher levels of exposure. Thus, proper interpretation of blood biomonitoring data of lipophilic chemicals requires a careful consideration of blood lipids.

Extraction of chlorpyrifos and malathion from water by metal nanoparticles.

The nanoparticles of gold and silver in solution state and supported over activated alumina are effective systems for the quantitative removal of chlorpyrifos and malathion, two common pesticides found in surface waters of developing nations, from water. In the solution phase, these pesticides adsorb onto the nanoparticles' surfaces and upon interaction for a long time, the nanoparticles with adsorbed pesticides precipitate. In contrast, complete removal of these pesticides occurs when contaminated water is passed over nanoparticles supported on alumina. A prototype of an on-line filter was made using a column of activated alumina powder loaded with silver nanoparticles and the device was used for pesticide removal for extended periods. We believe that the method has great technological potential in drinking water purification, especially using silver nanoparticles.

Volatilization of the pesticides chlorpyrifos and fenpropimorph from a potato crop.

Volatilization of pesticides from crops in the field can be an important emission pathway. In a field experiment with characterization of meteorological conditions, the pesticides chlorpyrifos and fenpropimorph were sprayed onto a potato crop, after which concentrations in the air and on/in the plants were measured. Rates of volatilization were estimated with the aerodynamic profile (ADP), energy balance (EB), relaxed eddy accumulation (REA), and plume dispersion (PD) methods. The volatilization rates obtained with the ADP and EB methods were similar, while some rates obtained with the REA and PD methods in the initial period were lower. Cumulative volatilization of chlorpyrifos during daylight hours (ADP and EB methods) was estimated to be about 65% of the dosage. By far the majority of this volatilization occurred in the first few days. Competing processes at the plant surface had a considerable effect on the dissipation of fenpropimorph, so cumulative volatilization during daylight hours was estimated to be only 7% of the dosage. Plant surface residues were higher than would correspond with the volatilization rate, indicating that penetration into the leaves had occurred.

Physicochemical and biological data for the development of predictive organophosphorus pesticide QSARs and PBPK/PD models for human risk assessment.

A search of the scientific literature was carried out for physiochemical and biological data [i.e., IC50, LD50, Kp (cm/h) for percutaneous absorption, skin/water and tissue/blood partition coefficients, inhibition ki values, and metabolic parameters such as Vmax and Km] on 31 organophosphorus pesticides (OPs) to support the development of predictive quantitative structure-activity relationship (QSAR) and physiologically based pharmacokinetic and pharmacodynamic (PBPK/PD) models for human risk assessment. Except for work on parathion, chlorpyrifos, and isofenphos, very few modeling data were found on the 31 OPs of interest. The available percutaneous absorption, partition coefficients and metabolic parameters were insufficient in number to develop predictive QSAR models. Metabolic kinetic parameters (Vmax, Km) varied according to enzyme source and the manner in which the enzymes were characterized. The metabolic activity of microsomes should be based on the kinetic activity of purified or cDNA-expressed cytochrome P450s (CYPs) and the specific content of each active CYP in tissue microsomes. Similar requirements are needed to assess the activity of tissue A- and B-esterases metabolizing OPs. A limited amount of acetylcholinesterase (AChE), butyrylcholinesterase (BChE), and carboxylesterase (CaE) inhibition and recovery data were found in the literature on the 31 OPs. A program is needed to require the development of physicochemical and biological data to support risk assessment methodologies involving QSAR and PBPK/PD models.

Degradation of atrazine and several organophosphorus pesticides in oranges.

The degradation of atrazine and four organophosphorus pesticides (chlorpyriphos, fenamiphos, methidathion and methyl-parathion) in oranges was studied. Oranges were immersed in a Milli-Q water solution spiked with 10 mg litre-1 of each pesticide for one day, allowing their adsorption on the orange peel. Then, the oranges were rinsed with Milli-Q water and left outdoors to expose them to natural ambient conditions for two weeks. In parallel, an aqueous solution containing 1 mg litre-1 of each pesticide was placed in a Pyrex flask, which was tightly closed, and exposed to the same ambient conditions. Both samples (orange peel and Milli-Q water) were analyzed periodically by gas chromatography coupled to a nitrogen-phosphorus detector. The pesticide degradation in both samples could be described using a first-order degradation curve. Half-lives varied from 14.5 to more than 30 days in aqueous solution and from 2.3 to 4.1 days in oranges for organophosphorus pesticides, while those for atrazine were 3.1 days and 14.2 days, respectively. The presence of some organophosphorus degradation products in water samples after storage under the above conditions was confirmed by gas chromatography-mass spectrometry.