Development and application of an advanced algorithm for environmental risk assessment and safety management of pesticide residues in agricultural soils: Monitoring of currently used pesticide in upland soils.

This study conducted the development of an advanced risk assessment algorithm system and safety management strategies using pesticide residue monitoring data from soils. To understand the status of pesticide residues in agricultural soils, monitoring was performed on 116 types of pesticides currently in use across 300 soil sites. The analysis of the monitoring results, alongside the physicochemical properties of the pesticides, led to the selection of soil half-life as a critical component in residue analysis. The use of Toxicity Exposure Ratio (TER) and Risk Quotient (RQ) for environmental risk assessment, based on monitoring data, presents limitations due to its single-component, conservative approach, which does not align with actual field conditions. Therefore, there is a necessity for a risk assessment process applicable in real-world scenarios. In this research, an efficient and accurate risk assessment algorithm system, along with a safety management model, was developed. Using the physicochemical properties of pesticides (such as soil half-life), monitoring results, and toxicity data, cluster analysis and Principal Component Analysis (PCA) validation identified four pesticides: boscalid, difenoconazole, fluquinconazole, and tebuconazole. The k-mean cluster analysis selected three priority management sites where the contribution of these four pesticides to the RQ was between 94-99 %, showing similar results to the RQ calculated for all pesticides. Predictions made with the developed model for the time required for soil half-life based RQ to drop below 1 at these priority sites showed only a 1-9 day difference between the four pesticides of concern and all pesticides, indicating comparable outcomes. The scenario of replacing high-risk pesticides with those of lower risk demonstrated that the RQ could be consistently maintained at about 50 % level. The results of this study suggest that through monitoring, evaluation, and management, effective and accurate environmental safety management of pesticides in soil can be achieved.

Evaluation of soil pesticide leaching to groundwater using undisturbed lysimeter: development of the pesticide groundwater leaching scoring system (PLS).

Groundwater pesticide safety management is essential for providing consistently safe water for humans, but such management is limited globally. In this study, we developed an accurate and convenient exposure assessment method for the safety management of pesticides in groundwater by conducting a lysimeter experiment to evaluate the leaching of 11 pesticides into groundwater. During the experimental period, flutoalanil and oxadiazon had the highest cumulative leaching amounts, 603.7 and 83.5 ng, respectively. Comparative analysis of existing groundwater exposure prediction indices, including the GUS, LEACH, modified LEACH, Hornsby index, and GLI showed no correlations with the measured data (p > 0.05). To enhance the accuracy of the assessment method, we used lysimeter data and principal component analysis to determine the main factors affecting groundwater leaching, and developed the "pesticide groundwater leaching scoring system" (PLS). The soil and water half-life, which had the greatest positive impact on groundwater leaching, was set as a 10-point indicator, whereas log P was set as a 1-point indicator. In contrast, solubility in water was determined as a 5-point indicator, and organic carbon partition coefficient and vapor pressure were determined as 2.5-point indicators owing to their negative relationship. The correlation coefficient was 0.670, indicating a significant correlation with the lysimeter data (p < 0.05). Using our scoring system, we ranked 376 pesticides. As an exposure assessment method developed using actual data, the PLS is expected to be applicable to groundwater safety management.

A comparison of the effectiveness of QuEChERS, FaPEx and a modified QuEChERS method on the determination of organochlorine pesticides in ginseng.

This study provides a review of methods used in the determination of organochlorine pesticides (OCPs) in ginseng and compares the effectiveness of three extraction methods (Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS), a modified QuEChERS and a Fast Pesticide Extraction (FaPEx)) in the analyses of 20 OCPs in ginseng root samples. For each method, sample mass, solvent volume and sorbent mass were varied to identify the optimum combination to effectively isolate analytes of interest from the complex sample matrix. Extracts were analyzed using the gas chromatography-µ-electron capture detector (GC-µ-ECD), and confirmatory analyses performed by gas chromatography-tandem-mass spectrometry (GC-MS/MS). Eighteen out of 20 OCPs spiked onto in-house prepared ginseng samples produced acceptable recoveries (51-156%) when extracted using QuEChERS and FaPEx. All 20 analytes, including dichlorodiphenyldichloroethane (p, p'- DDD) and dichlorodiphenyltrichloroethane (o, p'-DDT), produced acceptable recoveries (51-129%) with the use of a modified QuEChERS method. The applicability of the modified QuEChERS method was demonstrated through the analysis of ginseng samples grown in endosulfan-treated soil. The samples were analyzed by both GC-µ-ECD and GC-MS/MS with no significant difference identified in the results of each analytical method. This study highlights the applicability of the modified QuEChERS method, in combination with GC- µ-ECD, to determine organochlorine pesticides in ginseng. This may be especially useful for laboratories in developing countries and less advanced institutions without access to MS/MS instrumentation.

Environmental and dietary exposure of perfluorooctanoic acid and perfluorooctanesulfonic acid in the Nakdong River, Korea.

This study performed the first environmental and dietary exposure assessment to explore plant uptake of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) from agricultural soil and irrigation water in the Nakdong River delta, South Korea. Annual average concentrations of total PFOA and PFOS ranged from 0.026 to 0.112 µg L-1 (irrigation water), and from 0.818 to 1.364 µg kg-1 (soil), respectively. PFOA and PFOS hotspots were identified downstream of the Nakdong River and were influenced by seasonal climatic variations. The observed average biennial concentration of the sum of PFOA and PFOS decreased in irrigation water, from 0.112 µg L-1 in 2013 to 0.026 µg L-1 in 2015, suggests that the 2013 Persistent Organic Pollutants Control Act may have helped to reduce levels of PFAS at this location. This study calculated some of the highest plant uptake factors reported to date, with values ranging from 0.962 in green onions to < 0.004 in plums. Leafy vegetables and rice are important components of the Korean diet; these groups had the largest contribution to the estimated dietary intake of PFOA and PFOS, which was calculated at 0.449 and 0.140 ng kg bw -1 day-1, respectively. This corresponded to 66.4% for PFOA and 7.9% for PFOS of the EFSA reference dose (RfD). The dietary intake of PFOA and PFOS from crops alone did not exceed the RfD. However, when the estimated daily intake (EDI) from other sources such as tap water, meat, fish, dairy, and beverages was included in the exposure risk assessment, both of the EDIs to PFOA and PFOS exceeded the RfDs, indicating that there may be a risk to human health. This study concludes that consumption of crops might, therefore, be a significant and underappreciated pathway for human exposure to PFAS.

Application of high-surface-area graphitized carbon black with primary secondary amine as an alternative quick, easy, cheap, effective, rugged, and safe cleanup material for pesticide multi-residue analysis in spinach.

A multi-residue method has been developed and validated to determine 46 pesticides in spinach using liquid chromatography tandem mass spectrometry. The method is based on modified quick, easy, cheap, effective, rugged, and safe sample preparation, where high-surface-area graphitized carbon black was used first as sorbent material in the dispersive solid-phase extraction. The method was compared with the quick, easy, cheap, effective, rugged, and safe method. The morphology, surface area, pore size, and pore volume of the sorbent was determined. The results obtained show that the sorbent consists of high surface area (233 m2 /g) and large pore volume (1.5 cm3 /g). The calibration curve correlation coefficient (R2 ) of the method was at least 0.99. The average recoveries ranged from 74 to 116%, and limits of detection and quantification from 0.0001 to 0.002 mg/kg and from 0.0002 to 0.005 mg/kg, respectively. Using the method, the pesticides exhibited low matrix effect (< 20%), except for nicosulfuron (29.86%), methomyl (26.77%), and flufenoxuron (24.65%). The method showed better potential to remove pigments than the quick, easy, cheap, effective, rugged, and safe method. It is demonstrated that the proposed method could be useful alternative for sample preparation of spinach and other matrices in future.

Identification and characterization of matrix components in spinach during QuEChERS sample preparation for pesticide residue analysis by LC-ESI-MS/MS, GC-MS and UPLC-DAD.

In this article matrix components in spinach were investigated in detail. The samples were prepared using two QuEChERS (quick, easy, cheap, effective, rugged and safe) methods, AOAC and CEN. Liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS), gas chromatography-mass spectrometry (GC-MS) and ultra performance liquid chromatography-diode array detector (UPLC-DAD), were applied for component identification. The strategies of identification by LC-ESI-MS/MS include accurate mass spectra of the parent ion, comparison with previous literature data and investigation of the mass spectral decomposition pattern. Overall, fourteen components were identified by LC-ESI-MS/MS in each methods of AOAC and CEN, which were phytosteroids, flavonoids, fatty acids and fatty acid amides. Fifty components using AOAC method and fifty-seven components using CEN method were identified in GC-MS by comparing mass data with the National Institute of Standards and Technology (NIST, U.S.) database. The results indicate that the major components of the matrix are terpenoids, fatty acids and fatty acid esters. Moreover, three pigments (neoxanthin, violaxanthin and lutein) in the AOAC method and eight pigments (neoxanthin, violaxanthin, zeaxanthin, lutein, chlorophyll a, chlorophyll b, pheophytin a and beta-carotene) in the CEN method that gave a characteristics peak at 440 nm were identified by the UPLC-DAD. According to the sample preparation condition using different amounts of graphitized carbon black (GCB) in this study, the AOAC method had higher matrix component removal efficiency than the CEN method. A better understanding of matrix components would increase the current knowledge for improvement of existing QuEChERS methodology, as well as contribute to new method developments.