Method Development and Validation of Seven Pyrethroid Insecticides in Tea and Vegetable by Modified QuEChERS and HPLC-MS/MS.

This study developed a quick, easy, cheap, effective, rugged, and safe (QuEChERS) procedure for determining seven pyrethroid pesticide residues in tea, cucumber, and tomato via high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The overall average recoveries of the seven pyrethroids were 72%-104% (relative standard deviation (RSD); 2.0%-16.1%, 89%-109% (RSD; 0.7%-17.3%), 82%-110% (RSD; 1.6%-17.1%) for tea, cucumber and tomato, respectively. The determination coefficient (R2), the limit of detection (LOD), and the limit of quantification (LOQ) were ≥ 0.99, 0.007-1.875 µg kg-1, and 0.025-6.250 µg kg-1, respectively. The method was successfully used to monitor the pyrethroid pesticide residues in market samples. HPLC-MS/MS rapidly, sensitively, and accurately determined the pyrethroid pesticide residues.

Effects of Pymetrozine and Tebuconazole with Foliar Fertilizer Through Mixed Application on Plant Growth and Pesticide Residues in Cucumber.

The mixed application of pesticides and foliar fertilizer has been widely used in the production of cucumber, however, their effects on plant growth and pesticide dissipation are still unclear. In this study, the effects of mixed application of pymetrozine, tebuconazole and foliar fertilizer on the cucumber plant growth and pesticide dissipation were investigated simultaneously. The results show that the mixed use of pymetrozine, tebuconazole, especially adding foliar fertilizer, improved the physiological indexes (i.e., area, nitrogen content and chlorophyll content of the leaves, and root growth) of cucumber plants compared to those with the application of single pesticide. Meanwhile, it can significantly affect the dissipation of pymetrozine even in the slower growth matrices (lower leaves, stems, and plants). The residue of tebuconazole in cucumber plants was affected by the combination of formulation type and foliar fertilizer. This study can provide data for scientifically guiding the mixed application of pesticide and fertilizer.

Development, optimization, and validation of a method for detection of cartap, thiocyclam, thiosultap-monosodium, and thiosultap-disodium residues in plant foods by GC-ECD.

A method was developed for the simultaneous determination of four nereistoxin-related pesticides, viz. cartap, thiocyclam, thiosultap-monosodium, and thiosultap-disodium, in 20 plant foods. The samples were extracted using a hydrochloric acid solution containing cysteine hydrochloride, derivatized to nereistoxin under alkaline conditions, and analyzed by gas chromatography with electron capture detector. The average recoveries of the method were 72-108%, with relative standard deviations (RSDs) of 0.3-14.7% (n = 1200, p < 0.05). The intermediate precision and reproducibility experiments using established methods were also carried out. All the results passed the Cochrane and Grubbs tests (n = 2400, p < 0.05). The RSDs of intermediate precision and RSDs of reproducibility among laboratories were in the ranges 1.7-10.9% and 2.4-15.3% (n = 2400, p < 0.05), respectively, indicating that the accuracy and precision of the method are satisfactory. This method can be used to detect nereistoxin-related pesticides in plant foods.

Metabolomics analysis of cucumber fruit in response to foliar fertilizer and pesticides using UHPLC-Q-Orbitrap-HRMS.

Pesticides and fertilizers are often used to improve the yield and quality of cucumber fruit. In this study, the effect of pesticide applied with or without foliar fertilizer on the cucumber fruit metabolism was investigated. The results showed that the mixed use of pesticides and foliar fertilizer could significantly increase the contents of organic acids and the antioxidant level. When pesticide was used without foliar fertilizer, cucumber fruit up-regulated (1.3 times) shikimate-phenylpropanoid pathway and improved the antioxidant capacity to deal with the pesticide stress. However, the tricarboxylic acid cycle was up-regulated 1.1 times and the antioxidant capacity was improved to promote the pesticide dissipation when pesticide was applied with foliar fertilizer. These observations indicate that the mixed application of foliar fertilizer and pesticides can regulate related metabolites and metabolic pathways, improve the quality and antioxidant capacity of cucumber fruit, and promote the dissipation of pesticides.

Dynamics and risk assessment of pesticides in cucumber through field experiments and model simulation.

Pesticides are often applied multiple times during cucumber cultivation in China. In order to obtain the residue concentrations and subsequently human health risk assessment after pesticide multiple applications, plenty of field trials have been conducted, consuming a lot of labor force and funds. The application of kinetic models can address this problem to some extent by predicting the residue values of pesticides in cucumber. In this study, a dynamic model (dynamiCROP) was applied in combination with field experiments to investigate the distribution, translocation, and dissipation after the one-time application of seven pesticides in a cucumber-soil environment. Moreover, the residue concentrations after the second and third applications of the seven pesticides were estimated through a "simple superposition method", i.e., superimposing the output results of dynamiCROP after each single pesticide application. The estimated residue concentrations show good agreement with that measured through field experiments with R2 = 0.865 and relative root mean squared error (RRMSE) = 13.2%. Meanwhile, the short- and long-term risks of each pesticide were assessed according to the concentrations estimated by the "simple superposition method" with the dynamiCROP model. It shows that the seven pesticides, applied multiple times during cucumber cultivation, pose a very low dietary risk to human health through cucumber intake. Our study presents a cost- and time-efficient way to investigate the dissipation of pesticides in the cucumber-soil environment, predicate the residue concentrations of pesticides after multiple applications and assess the dietary risk of pesticides to human health through cucumber intake.

Dynamic modeling of famoxadone and oxathiapiprolin residue on cucumber and Chinese cabbage based on tomato and lettuce archetypes.

We analyzed the uptake and distribution of two pesticides (famoxadone and oxathiapiprolin) in herbaceous vegetables (cucumber and tomato) and leafy vegetables (Chinese cabbage and lettuce) to test the viability of applying existing archetypes in the dynamic plant uptake model dynamiCROP to modeling pesticide residue in other crops. Using field data and modeling, we showed that tomato was an unsuitable match for cucumber (R2 of 0.5325-0.6862) though lettuce was a good fit for Chinese cabbage (R2 of 0.8649-0.8862). We then used our cucumber data to add this as a new crop species archetype in dynamiCROP; further tests proved the accuracy of this approach (R2 of 0.8097-0.9152). In addition, we analyzed the distribution, uptake, and translocation of the two pesticides in cucumber and Chinese cabbage, using the model to better understand the mechanisms of pesticide residues over time and evaluate potential human exposure to pesticide residues from consumption of these crops. The fractions of famoxadone and oxathiapiprolin eventually ingested by humans based on our field trials ranged from 10-4 to 10-3 kg intake kg applied-1; that is, per kilogram of pesticide applied, humans would eventually consume less than one gram.

Determination and distribution of pesticides and antibiotics in agricultural soils from northern China.

Different types of soil samples from a typical farmland in northern China were collected and evaluated for the presence of the pesticides and antibiotics. 47 pesticides were extracted with a quick, easy, cheap, effective, rugged, and safe (QuEChERS) preparation method and cleanup with 50 mg C18, while 10 antibiotics were extracted with methanol/EDTA-McIlvaine buffer solution (v/v = 1/1), then both of them were analyzed with high performance liquid chromatography-tandem mass spectrometer (HPLC-MS/MS). Total concentrations of the 47 pesticides in the soil samples ranged from not detectable (ND) to 3.8 mg kg-1. The soil exhibited relatively high ecological risk for atrazine, chlorpyrifos, tebuconazole, difenoconazole, pymetrozine, and thiamethoxam, as over 1.0% of the sample concentrations exceeded 0.1 mg kg-1. The residual levels of the 10 antibiotics were relatively low (ND-951.0 µg kg-1). Tetracyclines exhibited a high detection rate (20.9%), with 2.8% of the soil samples exhibiting tetracyclines concentrations exceeding 100 µg kg-1, implying high ecological risk. The 4 sulfonamides and 2 macrolides analyzed showed detection rates below 0.8%. Spatial changes in the distribution of pesticides and antibiotics appear to be related to land use patterns, particularly orchards and vegetable plots. The over-standard rate of pesticides and antibiotics in orchards was greater than that of vegetable plots, and grain fields had the lowest over-standard rate. These data were helpful to figure out the pollution of these pesticides and antibiotics, and provided valuable information for soil quality assessment and risk assessment.

Measured and Modeled Residue Dynamics of Famoxadone and Oxathiapiprolin in Tomato Fields.

A reliable analytical method for the simultaneous determination of famoxadone and oxathiapiprolin dissipation kinetics as well as the metabolites of oxathiapiprolin (IN-E8S72 and IN-WR791) in tomato and soil was developed. We studied the dissipation of famoxadone and oxathiapiprolin in tomatoes grown using different kinetic curves in the area of Beijing in 2015 and 2016. Our results show that the most suitable model for two fungicides in 2015 and 2016 was first-order kinetic and second-order kinetic with the half-lives of 3.4 to 5.2 and 2.4 to 3.0 days, respectively. In addition, we applied the dynamic plant uptake model dynamiCROP and combined it with results from the field experiments to investigate the uptake and translocation of famoxadone and oxathiapiprolin in the soil-tomato environment. Modeled and measured results of two years fitted well with R2 values ranging from 0.8072 to 0.9221. The fractions of famoxadone and oxathiapiprolin applied during tomato cultivation that are eventually ingested by humans via residues in crop harvest were finally evaluated and found to be in the range of one part per thousand, that is one gram intake per kilogram applied.

Residue analysis and risk assessment of pyrethrins in open field and greenhouse turnips.

A sensitive and selective method was developed and validated for the determination of pyrethrin residues in turnips (turnip leaves, turnip tubers, and the whole of plant) and cultivated soil using gas chromatography coupled with mass spectrometry (GC-MS). Six major components of pyrethrins (pyrethrin I and II, cinerin I and II, and jasmolin I and II) were separated and identified. The method involving solid-phase extraction (SPE) cleanup led to satisfactory average recoveries (88.1-104%) with limits of quantification (LOQs) of 0.05 mg/kg. The dissipation and final residue of pyrethrins in six provinces (among these places, two experiments were conducted in greenhouse and other four experiments in open filed) in China were studied. The trial results suggested that the half-lives of pyrethrins in the whole of turnips and soil were 0.5-1.6 and 1.0-1.3 days, respectively, and the degradation of pyrethrins in the greenhouse was quicker than that in open fields. The final residues of pyrethrins in turnip leaves and tubers were all below the maximum residue limit (MRL) established by the EU (1.0 mg/kg). A pre-harvest interval of 2 days and MRL of 1.0 mg/kg are recommended to ensure food safety standards for pyrethrins in turnips. Long-term risk assessment and short-term risk assessment of turnip tubers were evaluated. Hazard quotient (HQ) and acute hazard index (aHI) were significantly less than 100%, indicating negligible risk for consumption of turnip tubers.

Residue and risk assessment of fluopicolide and cyazofamid in grapes and soil using LC-MS/MS and modified QuEChERS.

The residue behavior of fluopicolide, cyazofamid and their metabolites (M-01, M-02 and CCIM) was evaluated in open field conditions. The dissipation and terminal residue of these five compounds were determined via a modified QuEChERS method, by adjusting the liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) conditions and optimizing the purification process. This led to a satisfactory average recovery of between 71.6% and 107.7%, as well as limit of quantitation (LOQ) values of 0.05 mg kg-1. The dissipation results recorded in two places in China illustrated that the half-life values of fluopicolide are 11.4 (Anhui, grape), 19.7 (Anhui, soil) and 21.8 (Hebei, grape), 21.2 (Hebei, soil) days, respectively. As for the dissipation of cyazofamid, it was found to have half-life values of 8.7 (Anhui, grape) and 20.1 (Hebei, grape) days. The final residues in grapes were found to be below the maximum residue limit (MRL) of 2 mg kg-1 for fluopicolide and 1 mg kg-1 for cyazofamid. Thus, a preharvest interval of 10 days and recommended MRLs from the Joint FAO/WHO Meeting on Pesticide Residues (JMPR) are appropriate to ensure the food safety of fluopicolide and cyazofamid in grapes. The hazard quotient (HQ) and acute hazard index (aHI) values were found to be below 100%, demonstrating negligible risk in consuming grapes, regardless of long or short-term exposure.

Dissipation and Residues of Pyrethrins in Leaf Lettuce under Greenhouse and Open Field Conditions.

Pyrethrins are nowadays widely used for prevention and control of insects in leaf lettuce. However, there is a concern about the pesticide residue in leaf lettuce. A reliable analytical method for determination of pyrethrins (pyrethrin-and П, cinerin І and П, and jasmolin І and П) in leaf lettuce was developed by using gas chromatography-mass spectrometry (GC-MS). Recoveries of pyrethrins in leaf lettuce at three spiking levels were 99.4-104.0% with relative standard deviations of 0.9-3.1% (n = 5). Evaluation of dissipation and final residues of pyrethrins in leaf lettuce were determined at six different locations, including the open field, as well as under greenhouse conditions. The initial concentration of pyrethrins in greenhouse (0.57 mg/kg) was higher than in open field (0.25 mg/kg) and the half-life for pyrethrins disappearance in field lettuce (0.7 days) was less than that greenhouse lettuce (1.1 days). Factors such as rainfall, solar radiation, wind speed, and crop growth rate are likely to have caused these results. The final residue in leaf lettuce was far below the maximum residue limits (MRLs) (1 mg/kg established by the European Union (EU), Australia, Korea, Japan).

Dissipation and Residues of Dichlorprop-P and Bentazone in Wheat-Field Ecosystem.

Dichlorprop-P and bentazone have been widely used in the prevention and control of weeds in wheat field ecosystems. There is a concern that pesticide residues and metabolites remain on or in the wheat. Thus, the study of the determination and monitoring of their residues in wheat has important significance. A rapid, simple and reliable QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method was modified, developed and validated for the determination of dichlorprop-P, bentazone and its metabolites (6-hydroxy-bentazone and 8-hydroxy-bentazone) in wheat (wheat plants, wheat straw and grains of wheat) using high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). The average recoveries of this method ranged from 72.9% to 108.7%, and the limits of quantification (LOQs) were 2.5-12 µg/kg. The dissipation and final residue of four compounds in three provinces (Shandong, Jiangsu and Heilongjiang) in China were studied. The trial results showed that the half-lives of dichlorprop-P and bentazone were 1.9-2.5 days and 0.5-2.4 days in wheat plants, respectively. The terminal residues in grains of wheat and wheat straw at harvest were all much below the maximum residue limit (MRL) of 0.2 mg/kg for dichlorprop-P and 0.1 mg/kg for bentazone established by the European Union (EU, Regulation No. 396/2005).

[Study on composite stabilization of arsenic (As) contaminated soil].

Since the contaminated soil may contain various kinds of heavy metals, use of single chemical reagent leads to poor remediation and high cost. In this study, soil containing As, Zn, Cd was sampled, and different reagents were selected to carry out the rapid stabilization of contaminated soil. The TCLP (toxicity characteristic leaching procedure) was used to evaluate the leachate toxicity of heavy metals and the results indicated that calcium-containing, sulphur-containing and iron-containing reagents had good performance in reducing the metal mobility. The stabilization efficiency of the six reagents tested ranked in the order of CaO > Na2S > organic sulfur > Chitosan > FeSO4 > (C2H5)2NCS2Na. Two types of reagents (six reagents) were combined based on the target properties of different reagents and the stabilization efficiency was evaluated and analyzed. The results indicated that the composite reagents had higher stabilization efficiency: the efficiency of 3% FeSO4 + 5% CaO was 81.7%, 97.2% and 68.2% for As, Cd and Zn, respectively, and the efficiency of 3% CaO + 5% organic sulfur was 76.6%, 95.7% and 93.8% for these three metals, respectively. Speciation analysis was carried out in this study and the results suggested that it was the change of metals from the exchangeable state to the reduction (for inorganic reagent) or oxidation state (for organic reagent) that caused the soil stabilization and the degree of change determined the stabilization efficiency.