Bioactive Paper Sensor Based on the Acetylcholinesterase for the Rapid Detection of Organophosphate and Carbamate Pesticides

In many countries, people are becoming more concerned about pesticide residues which are present in or on food and feed products. For this reason, several methods have been developed to monitor the pesticide residue levels in food samples. In this study, a bioactive paper-based sensor was developed for detection of acetylcholinesterase (AChE) inhibitors including organophosphate and carbamate pesticides. Based on the Ellman colorimetric assay, the assay strip is composed of a paper support (1×10 cm), onto which a biopolymer chitosan gel immobilized in crosslinking by glutaraldehyde with AChE and 5,5′-dithiobis(2-nitrobenzoic) acid (DTNB) and uses acetylthiocholine iodide (ATChI) as an outside reagent. The assay protocol involves introducing the sample to sensing zone via dipping of a pesticide-containing solution. Following an incubation period, the paper is placed into ATChI solution to initiate enzyme catalyzed hydrolysis of the substrate, causing a yellow color change. The absence or decrease of the yellow color indicates the levels of the AChE inhibitors. The biosensor is able to detect organophosphate and carbamate pesticides with good detection limits (methomyl=6.16×10-4 mM and profenofos=0.27 mM) and rapid response times (~5 min). The results show that the paper-based biosensor is rapid, sensitive, inexpensive, portable, disposable, and easy-to-use

Toxicity Assessment of Buprofezin, Lufenuron, and Triflumuron to the Earthworm Aporrectodea caliginosa

Earthworms are particularly important soil macroinvertebrates and are often used in assessing the general impact of pesticide pollution in soil. The present study was conducted in order to investigate the toxicity of three insect growth regulators (IGRs) buprofezin, lufenuron, and triflumuron, at different application rates and exposure times toward mature earthworms Aporrectodea caliginosa. The effects of these pesticides on the growth rate in relation to the activities of acetylcholinesterase (AChE) and glutathione S-transferase (GST) as biochemical indicators were evaluated to elucidate the mechanisms of action. Toxicity studies indicated that lufenuron was the most harmful pesticide to mature earthworms, followed in descending order by buprofezin and triflumuron. A reduction in growth rate in all pesticide-treated worms was dose-dependent over the 28-day exposure period, which was accompanied by a decrease in AChE and GST activities. Relationships between growth rate, AChE, and GST provided strong evidence for the involvement of pesticidal contamination in the biochemical changes in earthworms, which can be used as a bioindicator of soil contamination by pesticides

Impact of organic amendments addition to sandy clay loam soil and sandy loam soil on leaching process of chlorantraniliprole insecticide and bispyribac-sodium herbicide

The leaching of two pesticides, cholantraniliprole (CAP) and bispyribac-sodium (BPS) in sandy clay loam soil (soil A) and sandy loam soil (soil B) were examined, by soil columns under laboratory conditions. In addition, the effect of adding 5% biochar and wheat straw to the soils on the leaching of CAP and BPS was studied. It is clear from the results that BPS is more leachable than CAP in all soil columns, and more leached to soil B. It was found that the addition of biochar and wheat straw has a significant effect on the movements of these pesticides and can be used to reduce the environmental impact. For CAP, 71 to 97% and 84 to 97% were recovered from the soil A columns and soil B columns, respectively, while for BPS, 94 to 99% were recovered from columns of soil A and soil B

Effect of soil organic amendments on sorption behavior of two insecticides and two herbicides

The effect of biochar, compost, peat and wheat straw at 1 and 5% on adsorption isotherm of chlorantraniliprole, dinotefuran, bispyribac-sodium, and metribuzin was studied in clay loam soil and sandy loam soil. Biochar, compost, peat and wheat straw (at a rate of 1 % in soil) improved the adsorption capacity of chlorantraniliprole and metribuzin in sandy loam soil. The sorption coefficients are higher for chlorantraniliprole and metribuzin whereas lower for dinotefuran and bispyribac-sodium in amended soil compared to unamended sandy loam soil. There is not a clear direct correlation between Freundlich parameters as well as Kd or Koc and type of organic amendment. The sorption of all tested pesticides on biochar was increased, whereas on compost was decreased. The order of pesticides sorption in soils and different organic amendments is generally inversely proportional to their aqueous solubilites. Adsorption of chlorantraniliprole increases on the sandy loam soil amendment at the rate of 1% in the following order: peat > compost > biochar > original soil. Also, the magnitude of adsorption on soil A amendment at the rate of 5% can be arranged for dinotefuran in the order; peat > biochar > compost > original soil and for bispyribac-sodium and metribuzin peat = wheat straw > biochar > original soil

Experimental modeling design to study the effect of different soil treatments on the dissipation of metribuzin herbicide with effect on dehydrogenase activity

The dissipation and side-effect of metribuzin (MBZ) were studied with various factors; two soil types (clay loam and sandy loam), soil amendment (wheat straw and without amendment), two temperature levels (25 and 50°C), sterilization (sterilized and unsterilized soil) and time of incubation (15 and 30 days) and designed by Windows version of MINITAB software package to reduce the time and the cost as well as increased the precision. Determination of MBZ by HPLC with recoveries ranged from 50.85 to 108.09%. The MBZ residues were detected in all samples up to 60 days of storage, respectively with decline in their concentrations with the time of incubation. The clay loam soil showed higher dissipation than the sandy loam soil. The different factors in the present study confirmed that the wheat straw amendment, non-sterilization and incubation at 50°C caused higher dissipation of MBZ than without wheat straw, sterilization and incubation at 25°C. The dissipation was described mathematically by a first order equation with t0.5 was ranged from 9.62 to 16.82 days in clay loam soil and from 10.01 to 16.04 days in sandy loam soil. The side-effect of MBZ was tested on soil dehydrogenase activity that can be considered as an indicator of the biological activity and microbial degradation. The result proved that the enzyme activity was significantly decreased in all treatments compared with the controls at 1 and 3 days of incubation then it was gradually increased at 7, 10, 15 and 30 days of incubation. Treatments of wheat straw, non-sterilized and incubated at 25°C or 50°C showed the lowest enzyme inhibition among all treatments

Investigation of dissipation kinetics and half-lives of fipronil and thiamethoxam in soil under various conditions using experimental modeling design by Minitab software

Abstract To determine the extent of pesticide buildup and their environmental contamination, the environmental half-lives of pesticides are examined. The influence of the factors affecting the half-lives of fipronil and thiamethoxam including soil type, sterilization, temperature, and time and their interactions was studied using experimental modeling design by Minitab software. Based on the dissipation kinetics data, fipronil concentrations reduced gradually over 60 days while thiamethoxam concentrations decreased strongly. Also, fipronil and thiamethoxam dissipated more rapidly in calcareous soil than in alluvial soil. Thiamethoxam, however, disappeared more rapidly than fipronil in all treatments. Incubation at 50 °C leads to rapid the pesticide degradation. For prediction of the dissipation rate, model 5 was found to be the best fit, Residue of insecticide (%) = 15.466 − 11.793 Pesticide − 1.579 Soil type + 0.566 Sterilization − 3.120 Temperature, R2 = 0.94 and s = 3.80. Also, the predicted DT50 values were calculated by a model, DT50 (day) = 20.20 − 0.30 Pesticide − 7.97 Soil Type + 0.07 Sterilization − 2.04 Temperature. The shortest experimental and predicted DT50 values were obtained from treatment of thiamethoxam at 50 °C in calcareous soil either sterilized (7.36 and 9.96 days) or non-sterilized (5.92 and 9.82 days), respectively. The experimental DT50 values of fipronil and thiamethoxam ranged from 5.92 to 59.95 days while, the modeled values ranged from 9.82 to 30.58 days. According to the contour plot and response surface plot, temperature and sterilization were the main factors affecting the half-lives of fipronil and thiamethoxam. The DT50 values of fipronil and thiamethoxam increased in alluvial soil and soil with low temperature. In general, there is a high agreement between the experimental results and the modeled results

Toxicity Assessment of Buprofezin, Lufenuron, and Triflumuron to the Earthworm Aporrectodea caliginosa

Earthworms are particularly important soil macroinvertebrates and are often used in assessing the general impact of pesticide pollution in soil. The present study was conducted in order to investigate the toxicity of three insect growth regulators (IGRs) buprofezin, lufenuron, and triflumuron, at different application rates and exposure times toward mature earthworms Aporrectodea caliginosa. The effects of these pesticides on the growth rate in relation to the activities of acetylcholinesterase (AChE) and glutathione S-transferase (GST) as biochemical indicators were evaluated to elucidate the mechanisms of action. Toxicity studies indicated that lufenuron was the most harmful pesticide to mature earthworms, followed in descending order by buprofezin and triflumuron. A reduction in growth rate in all pesticide-treated worms was dose-dependent over the 28-day exposure period, which was accompanied by a decrease in AChE and GST activities. Relationships between growth rate, AChE, and GST provided strong evidence for the involvement of pesticidal contamination in the biochemical changes in earthworms, which can be used as a bioindicator of soil contamination by pesticides

Chemical composition of the essential oils isolated from peel of three citrus species and their mosquitocidal activity against <i>Culex pipiens</i>

<p>Three essential oils (EOs) were isolated from the peel of citrus fruits <i>Citrus reticulata</i> L.<i>, Citrus reticulata chinase</i> Blanco and <i>Citrus sinensis</i> (L.) Osbeck (Family: Rutaceae) and evaluated against <i>Culex pipiens</i> L.1758 (Family: Culicidae)<i>.</i> Chemical composition indicated that the EOs were rich in essential phytochemicals including hydrocarbons, monoterpenes and sesquiterpenes. These constituents revealed some variability among the oils displaying interesting chemotypes limonene (35–51%), 1<i>R</i>-α-pinene (1.04–2.5%), γ-terpinene (0.46–5.65%) and sabinene (0.51–5.42%). The toxicity proved that <i>C. sinensis</i> oil had more effect than <i>C. reticulata chinase</i> and <i>C. reticulata</i> oils against larvae (LC₅₀ = 15.35, 16.11 and 32.84 mg/L, respectively). However, <i>C. reticulate</i> was the most active as fumigant against adults (LC₅₀ 2.74 μL/L air). The <i>in vivo</i> effect on acetylcholine esterase (AChE), carboxyl esterase (CbE), acid phosphatase (ACP), alkaline phosphatase (ALP), adenosine triphosphatase (ATPase) and glutathione-S-transferase (GST) were also demonstrated. To the best of our knowledge, this is the first report about the chemical composition and mosquitocidal activity of <i>C. reticulata chinase</i> essential oils. Conclusively, the tested essential oils could be used as eco-friendly alternatives in mosquitoes control programme.</p

Volatiles profiling and bioactivities of <i>Cupressus</i> spp. leaf and cone essential oils as analyzed via chemometrics tools

<p><i>Cupressus</i> is a genus of considerable medicinal value worldwide. The present work aims at assessing essential oil compositional differences within <i>Cupressus</i> in the context of its different genotypes and organs. Volatiles profiling was determined via gas chromatography-mass spectrometry coupled to chemometrics. A total of 75 volatile components were identified. Monoterpene hydrocarbons amounted for the major volatile class, with α-pinene and 3-carene most abundant in <i>Cupressus sempervirens</i> versus sabinene and terpinen-4-ol in <i>Cupressus macrocarpa</i>. Multivariate data analyses revealed that α-pinene, sabinene, terpinen-4-ol and 3-carene are the most significant for species classification. The five examined essential oils exhibited potential insecticidal and anticholinesterase effects, with C. <i>sempervirens</i> var. pyramidalis cone oil being the most potent for acetylcholinesterase inhibitory effect. The oil also exhibited potential fumigant toxicity toward <i>Sitophilus oryzae</i> and <i>Tribolium castaneum</i>.  The results of the orthogonal partial least-square discriminant analysis revealed that α-pinene is the key bioactive component in <i>Cupressus oil</i>.</p