Vortex-assisted dispersive micro-solid-phase extraction using silica-supported Fe2O3-modified khat (Catha edulis) biochar nanocomposite followed by GC-MS for the determination of organochlorine pesticides in juice samples.

In this paper, dispersive micro-solid phase extraction technique was developed for the purpose of extracting and preconcentrating organochlorine pesticide residues in juice samples before their separation and quantitative analysis by gas chromatography-mass spectrometry. A sorbent composed of a silica-supported Fe2O3-modified khat leftover biochar nanocomposite (SiO2-Fe2O3-KLBNC) was implemented in the process. To improve the dispersion of the sorbent in the solution, vortex mixer was employed. Experimental parameters influencing the performance of the method were optimized, and the optimal conditions were established. With these conditions, linear dynamic ranges ranged from 0.003 to 100.0 ng/mL were achieved, with a correlation coefficient (r2) ≥ 0.9981. The limits of detection and quantification, determined by signal-to-noise ratios of 3 and 10, respectively, were found to be in the ranges of 0.001-0.006 ng/mL and 0.003-0.020 ng/mL. Intra- and inter-day precision, values ranging from 0.3-4.8% and 1.7-5.2% were obtained, respectively. The matrix-matched extraction recoveries demonstrated favorable outcomes, falling within the range of 83.4-108.3%. The utilization of khat leftover as an adsorbent in contemporary sample preparation methodologies offers a cost-effective alternative to the currently available, yet expensive, adsorbents. This renders it economically viable, particularly in resource-constrained regions, and is anticipated to witness widespread adoption in the coming future.

MnOx-Coffea arabica Husk and Catha edulis Leftover Biochar Nanocomposites for Removal of Methylene Blue from Wastewater.

In this study, we investigated the use of manganese oxide-biochar nanocomposites (MnOx-BNC), synthesized from coffee husk (CH) and khat leftover (KL) for the removal of methylene blue (MB) from wastewater. Pristine biochars of each biomass (CH and KL) as well as their corresponding biochar-based nanocomposites were synthesized by pyrolyzing at 300°C for 1 h. The biochar-based nanocomposites were synthesized by pretreating 25 g of each biomass with 12.5 mmol of KMnO4. To assess the MB removal efficiency, we conducted preliminary tests using 0.2 g of each adsorbent, 20 mL of 20 mg·L-1 MB, pH 7.5, and shaking the mixture at 200 rpm and for 2 h at 25°C. The results showed that the pristine biochar of CH and KL removed 39.08% and 75.26% of MB from aqueous solutions, respectively. However, the MnOx-BNCs removed 99.27% with manganese oxide-coffee husk biochar nanocomposite (MnOx-CHBNC) and 98.20% with manganese oxide-khat leftover biochar nanocomposite (MnOx-KLBNC) of the MB, which are significantly higher than their corresponding pristine biochars. The adsorption process followed the Langmuir isotherm and a pseudo-second-order model, indicating favorable monolayer adsorption. The MnOx-CHBNC and MnOx-KLBNC demonstrated satisfactory removal efficiencies even after three and six cycles of reuse, respectively, indicating their potential effectiveness for alternative use in removing MB from wastewater.

Ternary solvent based homogeneous liquid-liquid microextraction for the preconcentration of organochlorine pesticides from water and apple juice samples.

In the present study, the optimal experimental conditions were determined by optimizing the effect of extraction solvent types and volume, salt types and concentration, centrifugation speed and time using one variable at a time. Under optimal experimental conditions, calibration curves were constructed separately using water and apple juice samples as representative matrices, and good linearities were achieved over a wide concentration range of 0.2-1600 ng L-1 with a coefficient of determination (r2) ≥ 0.998. The limits of detection (LOD) and limits of quantification (LOQ), determined to be 3 and 10 times the signal-to-noise ratios (S/N), were between 0.07-3.9 and 0.2-12.0 ng L-1 for water samples and 2.6-10.0 and 8.0-30.0 ng L-1 for the apple juice sample respectively. The precisions study showed %RSD values of ≤6% for both matrices, indicating satisfactory precisions. The enrichment factors and recoveries of the proposed method ranged from 41.4-74.5 and 86-109% respectively. The proposed method could be used as a simple and environmentally friendly alternative for the analysis of OCPs from environmental and food matrices. This method potentially offers a more sustainable and effective approach to monitoring OCPs in environmental and food products. Its use in the analysis of apple juice samples is particularly novel and can provide valuable insights into pesticide contamination in fruit juices.

Effervescent powder-assisted floating organic solvent-based dispersive liquid-liquid microextraction for determination of organochlorine pesticides in water by GC-MS.

An effervescent powder-assisted floating organic solvent-based dispersive liquid-liquid microextraction was introduced for determination of 13 organochlorine pesticides in water samples. In this method, a less toxic low-density organic solvent was used as extraction solvent. The extraction solvent was dispersed in to the aqueous sample via CO2 bubbles, in-situ generated up on addition of water to a falcon tube containing the mixture of effervescent powder precursors as well as the extraction solvent. Various experimental parameters such as effervescent and its weight fractions, extraction solvent type and its volume, the total mass of effervescent precursors, and the effect of salt were investigated and the optimal conditions were established. Under the optimum conditions, the proposed method exhibited good linearity for all target pesticides with the coefficient of determinations varying from 0.9981 to 0.9997. The limits of detection and quantification were within the range of 0.03-0.24 and 0.26-0.75 µg/L, respectively. The intra- and inter-day precisions which were expressed in terms of the relative standard deviation ranged from 0.33 to 4.47 and 0.51-5.52%, respectively. The enrichment factors and recoveries ranged from 24 to 293 and 76-116%, respectively. The proposed method could be used simple, cheap, fast, and environmentally friendly alternative for analysis of organochlorine pesticides from environmental water and other similar matrices.

Determination of total phenolic content and antioxidant activity of Commiphora mollis (Oliv.) Engl. resin.

In this study, total phenolic contents (TPC) and antioxidant activity of Commiphora mollis (Oliv.) Engl. (Burseraceae) resin were investigated. The resin was extracted using petroleum ether, chloroform, and methanol to give 27.46 ± 0.48, 46.56 ± 0.42, and 53.00 ± 1.39% extractable solids, respectively. The Folin-Ciocalteu (F-C) redox assay was optimized considering relevant parameters such as reaction time, maximum wavelength, and sample dilution effect before the determination of TPC. The concentration of antioxidants necessary to decrease by 50% the initial concentration of DPPH (EC50) was determined at 60 min. The reaction kinetics was analyzed using the pseudo-first-order kinetics model. For the F-C assay, the optimum conditions for the maximum absorbance and analysis time were 760 nm and 30 min, respectively. Under these conditions, the method exhibited good sensitivity and linear instrumental responses over wide ranges of concentrations. The highest TPC;168.27 ± 3.44, 137.43 ± 1.32, and 136.16 ± 0.42 mgGAE/g were recorded in the diluted samples (500 µg/mL) of methanol, chloroform, and petroleum ether extracts, respectively. By using different concentrations of the test sample, exhaustive reduction of phenolics and/or antioxidant substrates was achieved. Regarding the DPPH radical scavenging capacity, the EC50 values for methanol, chloroform, and petroleum ether extracts were 295.03 ± 3.55, 342.75 ± 9.72, and 353.69 ± 7.30 µg/mL, respectively. The standard (L-ascorbic acid), however, exhibited much lower EC50 value (44.72 ± 0.48 µg/mL). The methanol extracts showed kinetic behavior (k2 values,115.08 to 53.28 M-1 s-1; steady-state time, < 29 min) closer to that of L-ascorbic acid (k2 values, 190 to 109 M-1 s-1; steady-state time, < 16 min), than other two extracts (k2 values,14 to 28 M-1 s-1; steady-state time, 63 to 130 min). For all tested samples, the rate of the DPPH radical scavenging increases with concentration from 50 to 250 µg/mL. The current study demonstrated that the polar solvent (methanol) extract has a better F-C reducing capacity and DPPH radical scavenging activity than the nonpolar solvents extracts. This could be due to phenolics and other oxidation substrates extracted by methanol from the C. mollis resin. For a better understanding of the antioxidant constituents of the resin, a further study including isolation of its compounds is recommended.

Corrigendum to "Organochlorine pesticide residues in tea and their potential risks to consumers in Ethiopia" [Heliyon 7 (7) (July 2021) e07667].

[This corrects the article DOI: 10.1016/j.heliyon.2021.e07667.].

Ionic-liquid-based dispersive liquid-liquid microextraction combined with high-performance liquid chromatography for the determination of multiclass pesticide residues in water samples.

Ionic-liquid-based dispersive liquid-liquid microextraction in combination with high-performance liquid chromatography and diode array detection has been proposed for the simultaneous analysis of four multiclass pesticide residues including carbaryl, methidathion, chlorothalonil, and ametryn from water samples. The major experimental parameters including the type and volume of ionic liquid, sample pH, type, and volume of disperser solvent and cooling time were investigated and optimum conditions were established. Under the optimum experimental conditions, limits of detection and quantification of the method were in the range of 0.1-1.8 and 0.4-5.9 µg/L, respectively, with satisfactory enrichment factors ranging from 10-20. The matrix-matched calibration curves, which were constructed for lake water, as a representative matrix were linear over wide range with coefficients of determination of 0.996 or better. Intra- and interday precisions, expressed as relative standard deviations, were in the range of 1.1-9.7 and 3.1-7.8%, respectively. The relative recoveries of the spiked environmental water samples at one concentration level were in the range of 77-102%. The results of the present study revealed that the proposed method is simple, fast, and uses environmentally friendly extraction solvent for the analysis of the target pesticide residues in environmental water samples.

Vortex-assisted ionic liquid dispersive liquid-liquid microextraction for the determination of sulfonylurea herbicides in wine samples by capillary high-performance liquid chromatography.

A new sample treatment, namely vortex-assisted ionic liquid dispersive liquid-liquid microextraction (VA-IL-DLLME), followed by capillary liquid chromatography has been developed for the determination of four sulfonylurea herbicides (SUHs): flazasulfuron (FS), prosulfuron (PS), primisulfuron-methyl (PSM) and triflusulfuron-methyl (TSM) in wine samples. The ionic liquid (IL) 1-hexyl-3-methylimidazolium hexafluorophosphate ([C6MIM][PF6]) was used as extraction solvent and was dispersed using methanol into the sample solution, assisted by a vortex mixer. Various parameters influencing the extraction efficiency, such as type and amount of IL, type and volume of disperser solvent, sample pH, salting-out effect, vortex and centrifugation time were studied. Under the optimum conditions, the limits of detection and quantification of the proposed method were in the ranges of 3.2-6.6 and 10.8-22.0 µg kg(-1), respectively; lower than the maximum residue limits set by the EU for these matrices. The proposed method was successfully applied to different wine samples and satisfactory recoveries were obtained.

Salting-out assisted liquid-liquid extraction combined with capillary HPLC for the determination of sulfonylurea herbicides in environmental water and banana juice samples.

A salting-out assisted liquid-liquid extraction (SALLE) combined with capillary high performance liquid chromatography with diode array detector (capillary HPLC-DAD) was proposed for extraction and determination of residues of nine sulfonylurea herbicides (SUHs) in environmental water and banana juice samples. Various parameters affecting the extraction process such as the type and volume of the organic solvent, sample volume, type and amount of salt, pH of the sample and vortex time were optimized. Under optimum conditions, matrix matched calibration curves were established using river water and banana juice samples. Good linear relationships as well as low limits of detection, LODs (0.4-1.3 and 3-13 µg/L) and quantification, LOQs (1.3-4.3 and 10-43 µg/L) were obtained in water and banana juice samples, respectively. The precision (intra- and inter-day) of the peak areas expressed as relative standard deviations (%, RSD), at two concentration levels were below 10 % in both matrices. Recoveries obtained from spiked environmental waters (river water and groundwater) and banana juice samples, at two concentration levels, ranged from 72 to 115%. The results of the analysis revealed that the proposed SALLE-capillary HPLC method is simple, rapid, cheap and environmentally friendly, being successfully applicable for the determination of SUH residues in waters and banana juices.

Hollow-fiber liquid-phase microextraction combined with capillary HPLC for the selective determination of six sulfonylurea herbicides in environmental waters.

A three-phase hollow-fiber liquid-phase microextraction combined with a capillary LC method using diode array detection was proposed for the determination of six sulfonylurea herbicides, triasulfuron, metsulfuron-methyl, chlorsulfuron, flazasulfuron, chlorimuron-ethyl, and primisulfuron-methyl, in environmental water samples. Different factors that can affect the extraction process such as extraction solvent, acidity of the donor phase, composition and pH of the acceptor phase, salt addition, stirring speed, and extraction time were optimized. Under the optimum conditions, detection and quantitation limits between 0.1-1.7 and 0.3-5.7 µg/L, respectively, and enrichment factors ranging from 71 to 548 were obtained. The calibration curves were linear within the range of 0.3-40 µg/L. Intra- and interday RSDs were <6.3 and 8.4%, respectively. The relative recoveries of the spiked ground and river water samples were in the range of 69.4-119.2 and 77.4-111.7%, respectively. The results of the study revealed that the developed methodology involves an efficient sample pretreatment allowing the preconcentration of analytes, combined with the use of a miniaturized separation technique, suitable for the accurate determination of sulfonylurea herbicides in water.