QuEChERS and solid phase extraction methods for the determination of energy crop pesticides in soil,plant and runoff water matrices

QuEChERS and solid phase extraction (SPE) methods were applied for determining four herbicides (metazachlor, oxyfluorfen, quizalofop-p-ethyl, quinmerac) and one insecticide (α(±)-cypermethrin) in runoff water, soil, sunflower and oilseed rape plant matrices. Determination was performed using gas chromatography mass spectrometry (GC-MS), whereas high-pressure liquid chromatography mass spectrometry (HPLC-MS) was used for quinmerac. In all substrates linearity was evaluated using matrix-matched calibration samples at five concentration levels (50–1000 ng L^?1 for water, 5–500 μg kg^?1 for soil and 2.5–500 μg kg^?1 for sunflower or oilseed rape plant). Correlation coefficient was higher than 0.992 for all pesticides in all substrates. Acceptable mean recovery values were obtained for all pesticides in water (65.4–108.8%), soil (70.0–110.0%) and plant (66.1–118.6%), with intra- and inter-day RSD% below 20%. LODs were in the range of 0.250–26.6 ng L^?1 for water, 0.10–1.8 μg kg^?1 for soil and 0.15–2.0 μg kg^?1 for plants. The methods can be efficiently applied for field dissipation studies of the pesticides in energy crop cultivations.     

Chemical characterisation of a new estuarine pollutant (2,4-Dichloro-6-Nitrophenol) and assessment of the acute toxicity of its quinoid form for Artemia salina

It is known that the compound 2,4-dichloro-6-nitrophenol (2,4DC6NP) is formed upon nitration of 2,4-dichlorophenol, which in turn is a transformation intermediate of the herbicide dichlorprop. However, the chemical and spectroscopic characteristics of 2,4DC6NP, as well as its toxicity, are poorly known. This work shows that 2,4DC6NP behaves as a diprotic acid in aqueous solutions, with pK_a values of 3.0?±?0.9 and 4.9?±?0.5. At pH?<?3, 2,4DC6NP would undergo protonation. The absorption spectra suggest that anionic 2,4DC6NP, which prevails at pH?>?5 would have an ortho-quinoid structure that is responsible for the absorption peak centred at 428?nm. Considering that 2,4DC6NP has been detected in the brackish lagoons of the Rhône delta (southern France), where its levels are comparable to those of the parent herbicide, it is necessary to examine the possible effects of 2,4DC6NP on the species living in that environment. For this reason, the acute toxicity of the anionic form of 2,4DC6NP was assessed for the brine shrimp Artemia salina, a zooplankton species that lives both in brackish and in saline aquatic environments. The toxicity test yielded a LC₂₀ value of 8?±?2?mg?L^?1 and a LC₅₀ value of 18.7?±?0.8?mg?L^?1. Such values are safely higher than the maximum detected concentration of 2,4DC6NP in the Rhône delta lagoons. Further studies should be concentrated on the long-term effects of 2,4DC6NP, and in particular on its potential genotoxicity.     

Determination of 61 organic pollutants in drinking water by solid phase extraction followed by liquid and gas chromatography coupled to tandem mass spectrometry: an analytical strategy for a routine laboratory

A method for determination of 61 organic pollutants (polycyclic aromatic hydrocarbons and organochlorine, organophosphorous and organonitrogen pesticides) is proposed. It is based on solid phase extraction (SPE) and subsequent analysis of the extract by liquid and gas chromatography coupled to tandem mass spectrometry. Method validation yielded to the following values: limits of quantification, from 0.005 to 0.020?µg?L^?1; trueness, 95% to 113% and reproducibility (as percent relative standard deviation), 2% to 15%. Additionally, the method performed well in various proficiency tests.     

Graphene oxide reinforced polyamide nanocomposite coated on paper as a novel layered sorbent for microextraction by packed sorbent

ABSTRACT

In this work, a novel layered sorbent for microextraction by packed sorbent (MEPS) was introduced, which has been prepared by coating graphene oxide/polyamide (GO/PA) nanocomposite (NC) onto cellulose paper through solvent exchange method. Scanning electron microscopy (SEM) was applied to investigate the surface characteristic and morphology of PA and GO/PA NC coated on cellulose paper. The prepared MEPS device was used for extraction of organophosphorous pesticides (OPPs) including chlorpyrifos, fenthion, fenithrothion, ethion, edifenphos and phosalone in environmental aqueous samples followed by detection using gas chromatography-flame ionisation detector (GC-FID). Important parameters affecting the MEPS method including pH of sample solution, extraction draw-discard cycles, sorbent layers, desorption solvent volume and desorption draw-eject number were studied and optimised using central composite design (CCD). Based on the method validation, limits of detection (LODs) were in the range of 0.2–1 µg L^?1. The calibration graphs for chlorpyrifos, fenthion and edifenphos are linear in the concentration range of 1 to 500 µg L^?1; for ethion and phosalone are linear in the range of 1–1000 µg L^?1 and for fenithrothion is linear in the range of 3–1000 µg L^?1. The method precision (RSD %) with six replicates determinations was in the range of 3 to 9.4 % and 3.9 to 11.9% for distilled water and spiked river water sample, respectively, at the concentration level of 300 µg L^?1 . The developed method was applied successfully to determine OPP compounds in river, dam and tap water samples; accordingly, the relative recoveries (RR%) were obtained in the range of 77.8 to 113.3%.     

One-pot synthesis of tryptanthrin by the Dakin oxidation of indole-3-carbaldehyde

A one-pot approach to indolo[2,1-b]quinazolines from indole-3-carbaldehydes through the Dakin oxidation was developed. It was shown that the reaction proceeded through the condensation of indole-3-carbaldehydes with isatoic anhydrides, derived in situ from indole-3-carbaldehydes by the Dakin oxidation, and further oxidation/cyclization steps.     

Computer‐assisted design and synthesis of molecularly imprinted polymers for the simultaneous determination of six carbamate pesticides from environmental water

The computer‐assisted design and synthesis of molecularly imprinted polymers for the simultaneous capture of six carbamate pesticides from environmental water are reported in this work. The quantum mechanical computational approach was employed to design the molecularly imprinted polymers with carbofuran as template. The interaction energies between the template molecule and different functional monomers in various solvents were calculated to assist in the selection of the functional monomer and porogen. The optimised molecularly imprinted polymer was subsequently used as a class‐selective sorbent in solid‐phase extraction for pre‐concentration and determination of carbamates from environmental water. The parameters influencing the extraction efficiency of the molecularly imprinted solid‐phase extraction procedure were systematically investigated to facilitate the class‐selective extraction. For the proposed method, linearity was observed over the range of 2–500 ng/mL with the correlation coefficient ranging from 0.9760 to 1.000. The limits of detection ranged from 0.2 to 1.2 ng/mL, and the limit of quantification was 4 ng/mL. These results confirm that computer‐assisted design is an effective evaluation tool for molecularly imprinted polymers synthesis, and that molecularly imprinted solid‐phase extraction can be applied to the simultaneous analysis of carbamates in environmental water.     

Two organophosphorus pesticides: methyl parathion and dicapthon

Structural studies performed in this laboratory of organophosphorus pesticides continue with these related compounds. The –NO₂ groups of methyl parathion (systematic name: dimethyl 4‐nitrophenyl phosphorothioate, C₈H₁₀NO₅PS) and dicapthon (systematic name: 2‐chloro‐4‐nitrophenyl dimethyl phosphorothioate, C₈H₉ClNO₅PS) make dihedral angles of 10.67 (8) and 5.8 (1)°, respectively, with the planes of their attached rings, which accompanies angular distortion at the ring C atoms to which the –NO₂ groups are attached. Similar distortions are observed at the C atom to which the thiophosphate groups are attached. Significant differences in distances and angles around the phenolic O, versus the –OMe groups, explain why it is the site of hydrolysis for these compounds. A comparison of a torsion angle involving the thiophosphate group and phenolic O atom with similar pesticide structures is given and indicates steric influences on that angle.     

Riboflavin as a green sorbent in dispersive micro-solid-phase extraction of several pesticides from fruit juices combined with dispersive liquid–liquid microextraction

A vortex-assisted dispersive micro-solid-phase extraction procedure using a new and green sorbent was developed as a simple, fast, and efficient sample preparation method for the extracting five pesticides in several fruit juice samples. In this study, for the first time, riboflavin was used as an efficient sorbent. A few milligrams of riboflavin was directly added into the aqueous solution containing the analytes to adsorb them. After adsorption the analytes, they were desorbed and more concentrated by a dispersive liquid–liquid microextraction procedure. The influence of several effective parameters such as amount of riboflavin, pH, vortex time, eluent nature and volume, and extraction solvent type and volume on the extraction efficiency was investigated. In optimal conditions, linear ranges of the calibration curves were broad. The limits of detection and quantification were attained in the ranges of 0.56–1.5  and 1.9–0.52 ng mL⁻¹, respectively. The proposed method demonstrated to be suitable for concurrent extraction of the studied pesticides in various fruit juice samples with high enrichment factors (320–360) and precision (relative standard deviation ≤7.8% for intra- [n = 6] and interday [n = 4] precisions at a concentration of 25 ng mL⁻¹ of each pesticide).     

Cockle shell-derived nanoparticles for optical urea biosensor development based on reflectance transduction

An optical biosensor for urea based on urease enzyme immobilised on functionalised calcium carbonate nanoparticles (CaCO₃-NPs) was successfully developed in this study. CaCO₃-NPs were synthesised from discarded cockle shells via a simple and eco-friendly approach, followed by surface functionalisation with succinimide ester groups. The fabricated biosensor is comprised of two layers. The first (bottom layer) contained functionalised NPs covalently immobilised to urease, and the second (uppermost layer) was alginate hydrogel physically immobilised to the pH indicator phenolphthalein. The biosensor provided a colorimetric indication of increasing urea concentrations by changing from colourless to pink. Quantitative urea analysis was performed by measuring the reflectance intensity of the colour change at a wavelength of 633.16 nm. The determination of urea concentration using this biosensor yielded a linear response range of 30–1000 mM (R² = 0.9901) with a detection limit of 17.74 mM at pH 7.5. The relative standard deviation of reproducibility was 1.14%, with no signs of interference by major cations, such as K⁺, Na⁺, NH?⁺, and Mg²⁺. The fabricated biosensor showed no significant difference with the standard method for the determination of urea in urine samples.     

High-efficiency absorption of low NOX concentration in metallurgical flue gas using a three dimensional printed large-flow microstructured reactor

In the process of nitric acid dissolving precious metals, a large amount of NOx exhaust gas will be produced. This research aims at the development of a new method for the removal of low-concentration nitrogen oxides from metallurgical flue gas. In this process, a printed three-dimensional large-flow microstructure reactor and urea solution are used for the removal of NOx, which facilitates the greater efficiency of denitrification(≥94%). Urea plays an important role in the redox of NO₂, such as NO₂ is reduced to N₂ in solution. Both the gas and the liquid phase simultaneously react in the microchannels of the microfluidic reactor. The channels allow the proper mixing of urea and NaClO₂ during the flow which efficiently removes NO_x at low concentrations. The optimum condition for high denitration efficiency is outlined: the urea solution with 3%,temperature of the mixed solution is 293.15 K, gas–liquid flow mass ratio is 1:1, pH value (8.0–10.0), C_NaClO2 = 0.02 mol/L. This work successfully describes the use of a microfluidic reactor to enhance and maintain the denitration efficiency. This work describes how to successfully enhance and maintain the denitration efficiency while using a printed three-dimensional large-flow microstructure reactor.