Natural Thymol– tert ‐Butylhydroquinone–Based Deep Eutectic Solvent/Vortex‐Assisted Dispersive Liquid–Liquid Microextraction for Organophosphorus Pesticide Extraction in Water Samples

Probably not a substantial claim: may not pass S3 (load-bearing). May combine two claims.

WHO analyses indicate that annual human mortality from pesticide poisoning via water has surpassed 0.4% and 1.9%.

“The World Health Organization's (WHO) analysis and statistical observations show that the death rate of humans caused by pesticide poisoning by water has exceeded the rates of 0.4% and 1.9% annually [1,10].”

• cites [1] 1. J. da Silva Sousa, H. O. do Nascimento, H. de Oliveira Gomes, and R. F. do Nascimento, "Pesticide Residues in Groundwater and Surface Water: Recent Advances in Solid-Phase Extraction and Solid-Phase Microextraction Sample Preparation Methods for Multiclass Analysis by Gas Chromatography-Mass Spectrometry," Microchemical Journal 168 (2021): 106359, https://doi.org/10.1016/j.microc.2021.106359. sourceCould not verify

  The Introduction and Conclusions discuss pesticide contamination of water and potential harm to human health, but neither gives an annual mortality rate. Searches for the 0.4% and 1.9% figures and for WHO pesticide-poisoning mortality found no passage addressing the claimed rates. Page numbers were not available in our copy. (LLM, conf=0.75)

  Experimental — accuracy not yet measured
• cites [10] 10. M. Eddleston, "Poisoning by Pesticides," Medicine 48 (2020): 214-217, https://doi.org/10.1016/j.mpmed.2019.12.019. sourceNot checked — no full text of the source

Probably not a substantial claim: may not pass S3 (load-bearing). May combine two claims.

DLLME is among the most effective extraction techniques, widely used because it is simple, inexpensive, easy, rapid, gives high recovery, and uses only microliters of extraction solvent.

“DLLME is one of the most effective extraction techniques commonly used mainly due to its simplicity, inexpensiveness, ease of operation, rapidity, high extraction recovery, and consumption of microliter levels of extraction solvent [22].”

• cites [22] 22. J. Grau, C. Azorín, J. L. Benedé, A. Chisvert, and A. Salvador, "Use of Green Alternative Solvents in Dispersive Liquid-Liquid Microextraction: A Review," Journal of Separation Science 45 (2022): 210-222, https://doi. org/10.1002/jssc.202100609. sourcePartly supported

  The Introduction (page not provided) describes DLLME as one of the most widespread microextraction techniques, citing its simplicity, rapidity, low cost, and high enrichment factors. It also says the extraction solvent is used in microliter volumes. It does not establish that DLLME is among the most effective techniques or that it gives high extraction recovery; enrichment factor is not the same measure as recovery. (LLM, conf=0.85)

  Experimental — accuracy not yet measured

Probably not a substantial claim: may not pass S2 (checkable).

To use HDESs well, the HBA and HBD must be chosen and combined appropriately, guided by understanding their chemical structures and how they interact with pesticides.

“Suitable application of the HDESs requires the appropriate selection and combination of the HBA and HBD, which can be achieved through the interpretation and knowledge of their chemical structure and mechanism of interaction between the HDESs and pesticides [36].”

• cites [36] 36. D. O. Adeoye, Z. S. Gano, O. U. Ahmed, S. M. Shuwa, A. Y. Atta, and B. Y. Jubril, "Synthesis and Characterisation of Thymol-Based Hydrophobic Deep Eutectic Solvents," Chemistry Proceedings 14 (2023): 96. sourcePartly supported

  The Introduction (page not provided) says that suitable HDES applications depend on understanding their interactions and physicochemical properties, which vary with HBA–HBD combinations and HDES structure. It does not discuss interactions between HDESs and pesticides, so that application-specific part of the claim is unsupported. (LLM, conf=0.88)

  Experimental — accuracy not yet measured

May combine two claims.

The method's LODs (3.44-15.43 ng/L) are much lower than those reported for conventional DLLME (1-25 ng/L [55]) and LPME (7-19 ng/L [56]), and far better than QuEChERS (<3000 ng/L [57]).

“The method achieves low LODs (3.44-15.43ng L -1 ), which are substantially below those reported for conventional DLLME (1-25 ng L -1 [55]) and LPME (7-19 ng L -1 [56]), and significantly outperforms QuEChERS (<3000 ng L -1 [57]).”

• cites [55] 55. C. Cortada, L. Vidal, R. Pastor, N. Santiago, and A. Canals, "Deter- mination of Organochlorine Pesticides in Water Samples by Dispersive Liquid-Liquid Microextraction Coupled to Gas Chromatography-Mass Spectrometry," Analytica Chimica Acta 649 (2009): 218-221, https://doi. org/10.1016/j.aca.2009.07.041. sourceNot checked — no full text of the source
• cites [56] 56. H. Farahani, Y. Yamini, S. Shariati, M. R. Khalili-Zanjani, and S. Mansour-Baghahi, "Development of Liquid Phase Microextraction Method Based on Solidification of Floated Organic Drop for Extraction and Preconcentration of Organochlorine Pesticides in Water Samples," Analytica Chimica Acta 626 (2008): 166-173, https://doi.org/10.1016/j.aca. 2008.08.001. sourceNot checked — no full text of the source
• cites [57] 57. S. H. G. Brondi, A. N. De Macedo, G. H. L. Vicente, and A. R. A. Nogueira, "Evaluation of the QuEChERS Method and Gas Chromatography-Mass Spectrometry for the Analysis Pesticide Residues in Water and Sediment," Bulletin of Environmental Contamination and Toxicology 86 (2011): 18-22, https://doi.org/10.1007/s00128-010-0176-9. sourceSupported

May combine two claims.

ACN gave the highest extraction efficiencies among the five tested disperser solvents, especially for phosphamidon and chlorpyrifos, with recoveries significantly greater than other solvents (p < 0.05).

“As shown in Figure 3A, ACN produced the highest extraction efficiencies, especially for phosphamidon and chlorpyrifos, with recoveries significantly greater than those obtained with other solvents (p < 0.05).”

May combine two claims.

Spectroscopic data show Thy and TBHQ coexisting in one homogeneous phase without chemical change, held together by a dynamic hydrogen-bond network.

“The spectroscopic data confirms the coexistence of Thy and TBHQ in a single homogeneous phase without chemical modification, stabilized by a dynamic hydrogen bond network.”

May combine two claims.

In the DES FT-IR spectrum, the O-H stretch shifts to 3256 cm-1 from 3228 cm-1 in Thy and 3457 cm-1 in TBHQ, a red shift that suggests strong intermolecular hydrogen bonding.

“The broad -OH stretching band, which previously appeared at higher wavenumbers in the individual components (3228 cm -1 in Thy and 3457 cm -1 in TBHQ), shifts to a lower frequency at 3256 cm -1 in the DES, suggesting the establishment of strong intermolecular hydrogen bonds.”

May combine two claims.

A univariate optimization step selected acetonitrile as disperser and the following conditions as optimal: ACN/DES ratio 1:1 (v/v), 100 mL sample volume, 3 min extraction time, and pH 2-6.

“Univariate optimization identified acetonitrile (ACN) as a disperser and ACN/DES = 1:1 (v/v), 100 mL sample, 3 min extraction, and pH 2-6 as optimal.”

May combine two claims.

The DES 1H-NMR spectrum has a downfield signal near δ = 9.05 ppm from phenolic -OH protons in strong hydrogen bonds, plus another peak near δ = 9.01 ppm from TBHQ's para-substituted phenolic group.

“Notably, a downfield signal appears around δ = 9.05 ppm, which can be attributed to the phenolic -OH protons involved in strong hydrogen bonding.”

• Also stated in: § 3.1.2 1 H-NMR Spectroscopy · plain

  “A second peak near δ = 9.01 ppm corresponds specifically to the para-substituted phenolic group of TBHQ, further confirming its participation in the hydrogen-bonding network.”

May combine two claims.

ACN offered superior reproducibility and broader applicability across all tested analytes compared with other disperser solvents.

“For diazinon, ACN, acetone, and n-hexane yielded comparable values; however, ACN offered superior reproducibility and broader applicability across all tested analytes.”

May combine two claims.

The formation and stability of the Thy:TBHQ DES were confirmed by FTIR, which showed an O-H red shift, and by 1H-NMR, which showed deshielded phenolic signals.

“DES formation and stability were confirmed by Fourier transform infrared spectroscopy (O-H red shift) and 1 H-NMR (deshielded phenolic signals).”

May combine two claims.

In seawater, the lowest recoveries were observed: phosphamidon 54.0% ± 4.4% and 54.0% ± 8.8%; diazinon 65.8% ± 2.1% and 65.9% ± 4.2%; chlorpyrifos 63.1% ± 3.6% and 63.0% ± 7.1%.

“In seawater, the lowest recoveries were observed: phosphamidon at 54.0% ± 4.4% and 54.0% ± 8.8%, diazinon at 65.8% ± 2.1% and 65.9% ± 4.2%, and chlorpyrifos at 63.1% ± 3.6% and 63.0% ± 7.1%.”

May combine two claims.

Calibration was highly linear, with R2 values of 0.995 (chlorpyrifos), 0.997 (diazinon), and 0.991 (phosphamidon).

“Calibration was highly linear (R 2 = 0.995, 0.997, 0.991) with EFs of 27, 15, and 13 for chlorpyrifos, diazinon, and phosphamidon, respectively.”

May combine two claims.

Recoveries increased gradually up to 90 s and then rose more sharply between 120 and 180 s.

“As shown in Figure 4B, recoveries increased gradually up to 90 s, followed by a sharper rise between 120 and 180 s, indicating accelerated analyte migration into the [Thy]:[TBHQ] DES phase.”

May combine two claims.

Intra-day repeatability RSD ranged from 2.06 ± 0.1 to 3.79 ± 0.17 for phosphamidon, 1.91 ± 0.07 to 2.99 ± 0.14 for diazinon, and 1.67 ± 0.02 to 2.20 ± 0.03 for chlorpyrifos.

“Intra-day repeatability, based on three replicate analyses performed on the same day, ranged from 2.06 ± 0.1 to 3.79 ± 0.17 for phosphamidon, 1.91 ± 0.07 to 2.99 ± 0.14 for diazinon, and 1.67 ± 0.02 to 2.20 ± 0.03 for chlorpyrifos.”

May combine two claims.

The thymol-tert-butylhydroquinone deep eutectic solvent formed and remained stable, as shown by an FT-IR O-H red shift indicating hydrogen bonding and by deshielded phenolic signals in 1H-NMR.

“Spectroscopy confirmed DES formation and stability (FT-IR O-H red shift consistent with H-bonding; 1 H-NMR deshielded phenolic signals)”

May combine two claims.

In river water, recoveries were lower: phosphamidon 59.5% ± 4.9% and 59.5% ± 9.8%; diazinon 74.6% ± 4.3% and 74.6% ± 8.7%; chlorpyrifos 82.5% ± 4.9% and 82.5% ± 9.8%.

“In river water, recoveries were lower, with phosphamidon showing 59.5% ± 4.9% and 59.5% ± 9.8%, diazinon 74.6% ± 4.3% and 74.6% ± 8.7%, and chlorpyrifos 82.5% ± 4.9% and 82.5% ± 9.8%.”

May combine two claims.

In Table 2, recoveries for phosphamidon were 107.3% ± 8.5% at 50 ng/L and 93.2% ± 3.2% at 250 ng/L; diazinon 80.8% ± 5.5% at 20 ng/L and 95.0% ± 3.8% at 100 ng/L; chlorpyrifos 84.4% ± 5.1% at 10 ng/L and 99.4% ± 1.4% at 100 ng/L.

“The results from Table 2 demonstrated that recoveries for phosphamidon were 107.3% ± 8.5% at 50 ng L -1 and 93.2% ± 3.2% at 250 ng L -1 .Diazinon showed recoveries of 80.8% ± 5.5% at 20 ng L -1 and 95.0% ± 3.8% at 100 ng L -1 .Chlorpyrifos achieved recoveries of 84.4% ± 5.1% at 10 ng L -1 and 99.4% ± 1.4% at 100 ng L -1 .”

May combine two claims.

Recoveries for all three pesticides increased markedly under acidic to near-neutral conditions (pH 2-6), with highest efficiencies at pH 2-6 for phosphamidon and pH 2-4 for diazinon.

“As shown in Figure 4D, recoveries for all three pesticides increased markedly under acidic to near-neutral conditions (pH 2-6), with the highest efficiencies observed at pH 2-6 for phosphamidon and pH 2-4 for diazinon.”

May combine two claims.

In tap water, recoveries were consistently high: phosphamidon 98.2% ± 3.8% at 50 ng/L and 98.3% ± 7.7% at 100 ng/L; diazinon 90.1% ± 3.0% and 90.1% ± 6.0%; chlorpyrifos 99.9% ± 3.1% and 99.8% ± 6.2%.

“In tap water, recoveries were consistently high, with phosphamidon yielding 98.2% ± 3.8% at 50 ng L -1 and 98.3% ± 7.7% at 100 ng L -1 , diazinon achieving 90.1% ± 3.0% and 90.1% ± 6.0%, and chlorpyrifos reaching 99.9% ± 3.1% and 99.8% ± 6.2% for the same concentrations.”

May combine two claims.

The method's limits of detection were 3.44 ng/L for chlorpyrifos, 6.81 ng/L for diazinon, and 15.43 ng/L for phosphamidon.

“LODs of 3.44 (chlorpyrifos), 6.81 (diazinon), and 15.43 ng L -1 (phosphamidon)”

May combine two claims.

The enrichment factor was 166 for phosphamidon, 183 for diazinon, and 192 for chlorpyrifos.

“EF or pre-concentration (PF), calculated as the ratio of the final analyte concentration in the extract (C f ) to the initial concentration in the aqueous phase (C 0 ), was 166 for phosphamidon, 183 for diazinon, and 192 for chlorpyrifos.”

May combine two claims.

Interday reproducibility RSD was 9.66 ± 0.27 for phosphamidon, 8.18 ± 0.16 for diazinon, and 5.25 ± 0.05 for chlorpyrifos.

“Interday reproducibility, determined over 4 separate days (n = 9), was 9.66 ± 0.27 for phosphamidon, 8.18 ± 0.16 for diazinon, and 5.25 ± 0.05 for chlorpyrifos.”

May combine two claims.

The method exhibited good linearity across the studied ranges: 50-250 ng/L for phosphamidon (R2 = 0.991), 30-150 ng/L for diazinon (R2 = 0.997), and 10-200 ng/L for chlorpyrifos (R2 = 0.995).

“The method exhibited good linearity across the studied ranges: 50-250 ng L -1 for phosphamidon (R 2 = 0.991), 30-150 ng L -1 for diazinon (R 2 = 0.997), and 10-200 ng L -1 for chlorpyrifos (R 2 = 0.995).”

May combine two claims.

Univariate optimization identified an acetonitrile-to-DES volume ratio of 1:1, a 100 mL sample volume, a 3 min extraction time, and a pH of about 2-6 as the operating conditions.

“univariate optimization established ACN/DES = 1:1 (v/v), 100 mL sample volume, and 3 min extraction at acidic-near-neutral pH (≈2-6) as operating conditions that maximize mass transfer.”

May combine two claims.

Recoveries increased sharply when DES dosage rose from 10 to 60 mg, with statistically significant improvement (p < 0.05) across all pesticides tested.

“As illustrated in Figure 4A, recoveries increased sharply when the DES dosage rose from 10 to 60 mg, with a statistically significant improvement (p < 0.05) across all pesticides tested.”

May combine two claims.

The enrichment factors were 27 (chlorpyrifos), 15 (diazinon), and 13 (phosphamidon).

“Calibration was highly linear (R 2 = 0.995, 0.997, 0.991) with EFs of 27, 15, and 13 for chlorpyrifos, diazinon, and phosphamidon, respectively.”

May combine two claims.

Intra-day precision RSDs were 1.67%-3.79%, and inter-day RSDs were 5.25%-9.66%.

“Precision supported routine implementation (intra-day RSD 1.67%-3.79%;inter-day RSD 5.25%-9.66%).”

May combine two claims.

The method's limits of quantification were 10.32 ng/L for chlorpyrifos, 20.43 ng/L for diazinon, and 51.38 ng/L for phosphamidon.

“LOQs of 10.32, 20.43, and 51.38 ng L -1”

May combine two claims.

Matrix spike recoveries were approximately 90-100% for tap water, 60-82% for river water, and 54-66% for seawater, with all RSDs under 10%.

“Matrix spikes demonstrated accuracy and robustness across diverse aqueous media, with recoveries of ∼90%-100% in tap water, ∼60%-82% in river water, and ∼54%-66% in seawater (all RSD < 10%), consistent with EC acceptance criteria when precision is adequate.”

Probably not a substantial claim: may not pass S3 (load-bearing).

OPPs are used extensively in agriculture and pest control because they are affordable, effective, and have low environmental impact.

“Among several classes of insecticides, organophosphorus pesticides (OPPs) are widely utilized for agricultural purposes and pest control owing to their affordability, effectiveness, and low environmental impact [8].”

• cites [8] 8. V. Elencovan, J. Joseph, N. Yahaya, et al., "Exploring a Novel Deep Eutectic Solvents Combined With Vortex Assisted Dispersive Liquid- Liquid Microextraction and Its Toxicity for Organophosphorus Pesticides Analysis From Honey and Fruit Samples," Food Chemistry 368 (2022): 130835, https://doi.org/10.1016/j.foodchem.2021.130835. sourceNot checked — no full text of the source

May combine two claims.

Compared with ionic liquids, DESs are cheaper and more environmentally benign because of their water-miscible and water-immiscible properties.

“Despite the water decontamination and purification capabilities of both DESs and ILs, due to their watermiscible and water-immiscible characteristics, DESs are more cost-effective and more eco/environmentally friendly solvents [33,34].”

• cites [33] 33. A. Sarkar and S. Pandey, "Ionic Liquids and Deep Eutectic Solvents in Wastewater Treatment: Recent Endeavours," International Journal of Environmental Science and Technology 21 (2024): 977-996, https://doi.org/ 10.1007/s13762-023-04865-1. sourceNot checked — no full text of the source
• cites [34] 34. R. Castro-Muñoz, R. Cabezas, and M. Plata-Gryl, "Mangiferin: A Comprehensive Review on Its Extraction, Purification and Uses in Food Systems," Advances in Colloid and Interface Science 329 (2024): 103188, https://doi.org/10.1016/j.cis.2024.103188. sourceNot checked — no full text of the source

Probably not a substantial claim: may not pass S3 (load-bearing).

Hydrophobic DESs were introduced in 2015 as water-immiscible solvents for extracting lipophilic compounds.

“In 2015, hydrophobic DESs (HDESs) were presented as a new water-immiscible solvent for extracting lipophilic moieties [35].”

• cites [35] 35. L. Sportiello, F. Favati, N. Condelli, et al., "Hydrophobic Deep Eutectic Solvents in the Food Sector: Focus on Their Use for the Extraction of Bioactive Compounds," Food Chemistry 405 (2023): 134703, https://doi. org/10.1016/j.foodchem.2022.134703. sourceNot checked — no full text of the source

May combine two claims.

A larger amount of [Thy]:[TBHQ] DES enhances dispersion and extraction, but too much can dilute the analyte, raising detection limits and lowering precision.

“Increasing the [Thy]:[TBHQ] DES volume improves dispersion and extraction efficiency; however, excessively large volumes can dilute the analyte, increasing detection limits and precision [45].”

• cites [45] 45. B. Tesfaye, A. Gure, T. G. Asere, and G. J. Molole, "Deep Eutectic Solvent-Based Dispersive Liquid-Liquid Microextraction for Determi- nation of Organochlorine Pesticides in Water and Apple Juice Sam- ples," Microchemical Journal 195 (2023): 109428, https://doi.org/10.1016/ j.microc.2023.109428. sourceNot checked — no full text of the source

May combine two claims.

The [Thy:TBHQ]-based VA-DLLME/GC-μECD platform enables trace analysis that is sensitive, precise, and reusable while using less solvent.

“Overall, the [Thy:TBHQ]-based vortex-assisted DLLME/GC with µECD platform delivers sensitive, precise, and reusable trace analysis with reduced solvent use,”

Probably not a substantial claim: may not pass S3 (load-bearing).

The European Commission's standard for total pesticide residue in drinking water is 500 ng/L.

“The European Commission (EC) has set a standard of 500 ng L -1 for total pesticide residue in drinking water [13].”

• cites [13] 13. M. Dettori, A. Arghittu, G. Deiana, P. Castiglia, and A. Azara, "The Revised European Directive 2020/2184 on the Quality of Water Intended for Human Consumption. A Step Forward in Risk Assessment, Consumer Safety and Informative Communication," Environmental Research 209 (2022): 112773, https://doi.org/10.1016/j.envres.2022.112773. sourceNot checked — no full text of the source

Probably not a substantial claim: may not pass S3 (load-bearing).

Water quality is being degraded by pollutants, especially pesticides, released into the environment through intensive agriculture and industrial growth.

“However, its quality is increasingly compromised by the widespread release of pollutants, particularly pesticides, into the environment because of intensive agricultural activities and industrial expansion [1][2][3].”

• cites [1][2][3]Not matched

  Couldn’t be matched to a paper in Crossref, so it can’t be checked.

May combine two claims.

The decline beyond 100 mL may be attributed to dilution effects, reduced analyte-extractant interaction, and a decreased concentration gradient.

“Beyond 100 mL, a noticeable decline in recovery was observed, which may be attributed to dilution effects, reduced analyte-extractant interaction, and an overall decrease in the concentration gradient driving the extraction.”

Probably not a substantial claim: may not pass S3 (load-bearing).

Rather than being taken up by crops, most pesticides spread into the environment and water bodies.

“Most of these chemicals are dispersed throughout the environment and water sources instead of being absorbed by crops [6,7].”

• cites [6] 6. D. Pietrzak, K. Wątor, D. Pękała, et al., "LC-MS/MS Method Validation for Determination of Selected Neonicotinoids in Groundwater for the Purpose of a Column Experiment," Journal of Environmental Science and Health, Part B 54 (2019): 424-431, https://doi.org/10.1080/03601234.2019. 1574173. sourceNot checked — no full text of the source
• cites [7] 7. P. Joolaei Ahranjani, K. Dehghan, S. Farhoudi, M. Esmaeili Bidhendi, Z. Sotoudehnia Korrani, and S. Rezania, "Effective Removal of Nitrate and Phosphate Ions From Water Using Nickel-Doped Calcium Alginate Beads," Process Safety and Environmental Protection 194 (2025): 486-496, https://doi.org/10.1016/j.psep.2024.12.034. sourceNot checked — no full text of the source

Probably not a substantial claim: may not pass S3 (load-bearing).

The FAO/WHO Codex Alimentarius Commission sets the drinking-water maximum residue limit at 100 ng/L.

“According to the FAQ (Food and Agriculture Organization)/WHO Codex Alimentarius Commission, the maximum residue limit (MRL) accepted from drinking water is reported as 100 ng L -1 [11,12].”

• cites [11] 11. H. Sereshti, M. Seraj, S. Soltani, H. R. Nodeh, M. H. S. AliAbadi, and M. Taghizadeh, "Development of a Sustainable Dispersive Liquid- Liquid Microextraction Based on Novel Hydrophobic and Hydrophilic Natural Deep Eutectic Solvents for the Analysis of Multiclass Pesticides in Water," Microchemical Journal 175 (2022): 107226, https://doi.org/10.1016/ j.microc.2022.107226. sourceNot checked — no full text of the source
• cites [12] 12. S. V. Mousavi, P. J. Ahranjani, S. F. Saei, et al., "Ammonia Removal From Industrial Effluent Using Zirconium Oxide and Graphene-Oxide Nanocomposites," Chemosphere 297 (2022): 134008, https://doi.org/10. 1016/j.chemosphere.2022.134008. sourceNot checked — no full text of the source

Classified as probably not a substantial claim.

Measuring pesticide residues in water needs analytical, pre-concentration, and clean-up steps combined.

“Consequently, determining the concentration of pesticide residue in water requires a combination of analytical, pre-concentration, and clean-up techniques.”

• AssumptionRests on an assumption: OPPs have deleterious impacts on ecosystems and human health and can cause DNA damage and mutations.

May combine two claims.

The 1H-NMR chemical shifts and peak multiplicities match the proposed [Thy]:[TBHQ] structure and support hydrogen bonding as the main driver of eutectic formation.

“The chemical shifts and peak multiplicities observed in the 1 H-NMR spectrum are consistent with the proposed structure of the [Thy]:[TBHQ] DES and support the hypothesis that hydrogen bonding is the primary driving force for eutectic formation.”

Probably not a substantial claim: may not pass S3 (load-bearing). May combine two claims.

OPPs are derivatives of phosphoric acid whose toxicity is linked to sulfur content and phosphorus valence.

“OPPs are phosphoric acid derivatives known for their toxicity, which is related to their sulfur content and phosphorus valence [9].”

• cites [9] 9. T. O. Ajiboye, P. O. Oladoye, C. A. Olanrewaju, and G. O. Akinsola, "Organophosphorus Pesticides: Impacts, Detection and Removal Strate- gies," Environmental Nanotechnology, Monitoring & Management 17 (2022): 100655, https://doi.org/10.1016/j.enmm.2022.100655. sourceNot checked — no full text of the source

May combine two claims.

An adequate DES/ACN amount is necessary to provide sufficient extraction sites and interfacial areas, while excessive volume compromises sensitivity by lowering analyte enrichment.

“The trend indicates that while an adequate DES/ACN amount is necessary to provide sufficient extraction sites and interfacial areas, excessive volume compromises sensitivity by lowering analyte enrichment.”

May combine two claims.

Rabs (54.01-99.90%) and RR (54.01-107.33%) fall within or above the EC acceptance range, even in difficult matrices like seawater.

“Additionally, the Rabs (54.01%-99.90%)and RR (54.01%-107.33%)values are within or above the EC acceptance range, even for challenging matrices such as seawater, where ionic strength can hinder extraction efficiency.”

May combine two claims.

The validated method demonstrates high sensitivity, excellent linearity, strong enrichment capability, and consistent precision, making it suitable for routine monitoring of phosphamidon, diazinon, and chlorpyrifos in various water matrices.

“Overall, the validated method demonstrates high sensitivity, excellent linearity, strong enrichment capability, and consistent precision, making it a suitable analytical approach for routine monitoring of phosphamidon, diazinon, and chlorpyrifos in various water matrices.”

May combine two claims.

Despite reductions, all RSD values remained below 10%, meeting EC acceptance criteria, and recoveries below 60% for phosphamidon in river and seawater are still permissible under guideline provisions when RSD ≤ 20%.

“Despite these reductions, all RSD values remained below 10%, meeting EC acceptance criteria, and recoveries below 60% for phosphamidon in river and seawater are still permissible under the guideline provisions when RSD ≤ 20%.”

May combine two claims.

The sharp drop at alkaline pH can be attributed to full ionization or decomposition, diminished hydrophobicity, and electrostatic repulsion between negatively charged pesticide molecules and DES components.

“At alkaline pH, recoveries dropped sharply for all analytes, which can be attributed to full ionization or decomposition, diminished hydrophobicity, and potential electrostatic repulsion between the negatively charged pesticide molecules and the DES components.”

May combine two claims.

The platform compares favorably with, and in many cases outperforms, other reported microextraction methods.

“competitive with, and often superior to, many reported microextraction approaches”

May combine two claims.

All determination coefficients exceeded 0.99, indicating excellent calibration performance and suitability for quantitative analysis.

“All determination coefficients exceeded 0.99, indicating excellent calibration performance and suitability for quantitative analysis.”

May combine two claims.

Overall, pesticide adsorption on [Thy]:[TBHQ] DES involves multiple mechanisms-π-π stacking, van der Waals forces, hydrogen bonding, electrostatic interactions, and hydrophobic effects-that act together to enhance removal from water.

“Overall, adsorption onto [Thy]:[TBHQ] DES is a multi-mechanistic process involving π-π stacking, van der Waals forces, hydrogen bonding, electrostatic interactions, and hydrophobic effects, all of which act synergistically to enhance pesticide removal from aqueous media.”

Probably not a substantial claim: may not pass S3 (load-bearing).

The DES's aromatic, hydroxyl-rich, low-volatility, and hydrogen-bonding character points to wider uses outside pesticide extraction.

“Furthermore, the chemical features of the [Thy:TBHQ] DES, its aromatic and hydroxyl-rich structure, low volatility, and hydrogen-bonding capacity, suggest strong potential beyond pesticide extraction.”

May combine two claims.

Too little extractant provides too few active sites for partitioning and lowers recovery, while too much can dilute the analyte in the DES phase and reduce detector sensitivity.

“Insufficient extractant limits the available active sites for analyte partitioning, thereby reducing recovery, whereas excessive dosage may dilute the analyte within the DES phase and negatively impact detector sensitivity [32].”

• cites [32] 32. T. Li, L. Duan, M. Du, et al., "Hydrophobic Deep Eutectic Solvent- Based Vortex Assisted Liquid-Liquid Microextraction for the Determina- tion of Famciclovir in Water Samples Coupled With High Performance Liquid Chromatography," Microchemical Journal 197 (2024): 109697, https://doi.org/10.1016/j.microc.2023.109697. sourceNot checked — no full text of the source

May combine two claims.

All RSD values were below 10%, ranging from 1.4% to 8.5%, which is within the EC's acceptance limits, confirming precision and robustness of the method.

“All RSD values were below 10%, ranging from 1.4% to 8.5%, which is well within the EC's acceptance limits, confirming both the precision and robustness of the method.”

Classified as probably not a substantial claim. May combine two claims.

EC guidance sets acceptable initial-validation relative recovery at 60-140% with RSD no more than 20%, allowing exceptions when RSD stays ≤20%, recovery is at least 30%, and no residues are found.

“According to the EC guidelines [50], acceptable RR values for initial validation range from 60% to 140% with RSD ≤ 20%.Exceptions are allowed if RSD remains ≤20%, recovery is not below 30%, and no residues are detected.”

• cites [50] 50. T. Pihlström, A. R. Fernández-Alba, C. F. Amate, et al., "Analytical Quality Control and Method Validation Procedures for Pesticide Residues Analysis in Food and Feed," SANTE 11312/2021 (European Commission, 2021).Not matched

  Couldn’t be matched to a paper in Crossref, so it can’t be checked.

May combine two claims.

These LOD and LOQ values are significantly below the MRLs for pesticides in drinking water set by the EC, demonstrating high sensitivity of the proposed method.

“These values are significantly below the MRLs for pesticides in drinking water set by the EC, demonstrating the high sensitivity of the proposed method [48].”

• cites [48] 48. А. Hristozova, L. Vidal, M. Á. Aguirre, K. Simitchiev, and A. Canals, "Natural Deep Eutectic Solvent-Based Dispersive Liquid-Liquid Microex- traction of Pesticides in Drinking Waters Combined With GC-MS/MS Detection," Talanta 282 (2025): 126967, https://doi.org/10.1016/j.talanta. 2024.126967. sourceNot checked — no full text of the source

May combine two claims.

The recoveries met the European Commission's acceptance criteria provided precision was sufficient.

“consistent with EC acceptance criteria when precision is adequate.”

• AssumptionRests on an assumption: The European Commission's acceptance criteria for pesticide residue analysis apply to these matrix-spike recoveries when precision is adequate.

May combine two claims.

At pH 2-6, the analytes are predominantly in their neutral form, favoring hydrophobic interactions and π-π stacking with aromatic DES components and enhancing HBD-HBA interactions.

“At these pH values, the analytes are predominantly in their neutral form, favoring hydrophobic interactions and π-π stacking with the aromatic components of the DES, while also enhancing HBD-HBA interactions.”

• AssumptionRests on an assumption: At pH 2-6, the target pesticides are predominantly in their neutral form.

May combine two claims.

HDESs are only partly miscible with water; slight solubilization helps partition moderately polar analytes, but too much water uptake can disrupt the hydrogen-bond network and lower reusability over cycles.

“Another consideration is the limited, though non-negligible, miscibility of HDESs with water; although a small degree of solubilization assists the partitioning of moderately polar analytes, excessive water uptake may gradually disrupt the hydrogen bond network and reduce reusability over repeated cycles.”

May combine two claims.

Precision is much improved, with intra-day RSDs of 1.67-3.79% and inter-day RSDs of 5.25-9.66%, better than many methods with RSDs >10%, such as HF-LPME [58] and CPME [59].

“Precision is also markedly improved, with intra-day RSDs of 1.67%-3.79%and inter-day RSDs of 5.25%-9.66%,outperforming many other approaches that typically exhibit RSDs >10%, such as HF-LPME [58] and CPME [59].”

• cites [58] 58. C. Basheer, R. Balasubramanian, and H. K. Lee, "Determination of Organic Micropollutants in Rainwater Using Hollow Fiber Membrane/Liquid-Phase Microextraction Combined With Gas Chromatography-Mass Spectrometry," Journal of Chromatography A 1016 (2003): 11-20, https://doi.org/10.1016/S0021-9673(03)01295-0. sourceNot checked — no full text of the source
• cites [59] 59. A. Ferracane, N. Manousi, A. Kabir, et al., "Monolithic Capsule Phase Microextraction Prior to Gas Chromatography-Mass Spectrometry for the Determination of Organochlorine Pesticides in Environmental Water Samples," Microchemical Journal 186 (2023): 108355, https://doi.org/10. 1016/j.microc.2022.108355. sourceNot checked — no full text of the source

May combine two claims.

In VA-DLLME, vortex agitation helps overcome this kinetic limit by briefly lowering interfacial tension and promoting microdroplets, but some viscosity-related sluggishness remains for very short extraction times.

“In the VA-DLLME configuration, vortex agitation helps overcome this kinetic limitation by transiently decreasing interfacial tension and promoting microdroplet formation, but partial viscosity-induced sluggishness remains a constraint for very short extraction times.”

May combine two claims.

The [Thy]:[TBHQ] DES provides high extraction efficiency and cost-effective reusability, can be reused multiple times without significant loss of efficiency, making it viable for large-scale or routine water sample analysis.

“These results demonstrate that the [Thy]:[TBHQ] DES provides high extraction efficiency and cost-effective reusability, as it can be reused multiple times without significant loss of efficiency, making it a viable option for large-scale or routine water sample analysis.”

May combine two claims.

The observed stability confirms the robustness of the hydrogen bond network between Thy and TBHQ, which supports efficient pesticide binding and release.

“Nevertheless, the observed stability confirms the robustness of the hydrogen bond network between Thy and TBHQ, which supports efficient pesticide binding and release [47].”

• cites [47] 47. A. Imran and S. Ahmed, "Innovative Approaches to Adsorptive Detoxification of Pesticides in Aquatic Environments: A Comprehensive Review," International Journal of Environmental Science and Technology 22 (2025): 8377-8404, https://doi.org/10.1007/s13762-025-06350-3. sourceNot checked — no full text of the source

May combine two claims.

The DES maintained strong extraction capability and structural stability under repeated use.

“Even after the ninth cycle, recoveries exceeded 85% for all pesticides, demonstrating that the DES maintained strong extraction capability and structural stability under repeated use.”

May combine two claims.

Water has two roles here: it is the continuous phase for analyte transfer and it modulates DES polarity, affecting selectivity.

“Water in this system therefore plays a dual role, as the continuous phase enabling analyte transfer and as a modulator of DES polarity that influences selectivity.”

Probably not a substantial claim: may not pass S3 (load-bearing).

The slight reduction in performance over extended cycling is likely due to gradual physical losses of the DES phase or minor degradation of active hydrogen-bonding sites during repeated mixing and separation.

“The slight reduction in performance over extended cycling is likely due to gradual physical losses of the DES phase or minor degradation of active hydrogen-bonding sites during repeated mixing and separation.”

May combine two claims.

All precision values were below the generally accepted threshold for intra-day analysis and within acceptable ranges for inter-day testing, confirming the method's robustness and reliability.

“All precision values were well below the generally accepted threshold for intra-day analysis and within acceptable ranges for inter-day testing, confirming the method's robustness and reliability.”

May combine two claims.

DES-DLLME [45] and NADES-DLLME [48] give good recoveries but use much smaller sample volumes (≤10 mL), while this method keeps high recovery with 100 mL, improving ultra-trace detection.

“Furthermore, although DES-DLLME methods [45] and NADES-DLLME [48] achieve good recoveries, their sample volumes are significantly smaller (≤10 mL), whereas our method maintains high recovery rates using larger sample volumes (100 mL), improving detection capability for ultra-trace residues.”

• cites [45] 45. B. Tesfaye, A. Gure, T. G. Asere, and G. J. Molole, "Deep Eutectic Solvent-Based Dispersive Liquid-Liquid Microextraction for Determi- nation of Organochlorine Pesticides in Water and Apple Juice Sam- ples," Microchemical Journal 195 (2023): 109428, https://doi.org/10.1016/ j.microc.2023.109428. sourceNot checked — no full text of the source
• cites [48] 48. А. Hristozova, L. Vidal, M. Á. Aguirre, K. Simitchiev, and A. Canals, "Natural Deep Eutectic Solvent-Based Dispersive Liquid-Liquid Microex- traction of Pesticides in Drinking Waters Combined With GC-MS/MS Detection," Talanta 282 (2025): 126967, https://doi.org/10.1016/j.talanta. 2024.126967. sourceNot checked — no full text of the source

May combine two claims.

The combined properties of [Thy]:[TBHQ] DES and VA-DLLME enable efficient analyte-solvent interaction, better dispersion, and robust recovery in diverse waters, providing a reliable and sensitive alternative to established methods.

“These results highlight that the synergistic properties of the [Thy]:[TBHQ] DES, combined with VA-DLLME, enable efficient analyte-solvent interaction, enhanced dispersion, and robust recovery across diverse water samples, offering a reliable and highly sensitive alternative to established methods.”