In this study, 10 frequently used pesticides in apple orchards from the major apple production area of China were identified through 150 questionnaires. Based on Orbitrap high-resolution mass spectrometry, a method for detecting these pesticides in soils was developed. Typically, these compounds can be extracted from dry soil samples using dichloromethane: acetone (2:1, v:v) and purified by dispersive solid-phase extraction (PSA and C18). The qualitative and quantitative analyses can be undertaken by monitoring the MS1 precursor ions under full scan mode within a mass error of <5 ppm (resolution 120000). The recoveries ranged from 68.4% to 102.4% (SD<10.5%), the matrix effects induced signal fluctuation was less than 10%, and the intra- and inter-day precisions were all below 5%. For 14 surface soil samples randomly collected from an apple orchard in China, most pesticides presented the highest detection frequencies (100%), with imidacloprid and tebuconazole showing the highest residue levels (4.1-39.1 and 9.8-350.2 ng/g dry weight, respectively). Compared with previous methods for analyzing individual or several pesticides, the proposed method represents a promising means of investigating these frequently used pesticide residues in apple orchards in China.

Environmental context: Low availability of calcium (Ca2+) in soils is one of the major factors in Ca2+ deficiency of plants and physiological plant disorders. A device based on functionalised silica was developed for in-situ measurement of the available Ca2+ in soils. Application of the proposed device to measure available Ca2+ may help to develop and improve agricultural practices. Calcium is an ion of particular interest due to its importance in plant nutrition and soil structure. A novel device of diffusion gradients in thin-films (DGT) based on the benzo-crown ether-functionalised silica (BCES) as the binding agent and the polyethersulfone (PES) membrane as diffusive layer (BCES-DGT) was developed for in-situ sampling of available calcium (Ca2+) in freshwater and soil samples. The performance characteristics of the BCES-DGT device were assessed. The BCES was prepared using the sol-gel process and characterised by Fourier transform infrared spectroscopy, scanning electron microscopy, thermal gravimetric analysis and N2 adsorption–desorption. Results evinced that BCES was obtained successfully with a rough wrinkled surface and good specific surface area of 111.3 m2 g-1. The diffusion coefficient of Ca2+ ions in PES membrane was found to be 1.23 × 10-6 cm2 s-1 at 25 °C and was independent of pH in the range of 3–10 and ionic strength (as pNaCl) from 1 to 3. The high binding capacity of BCES binding gel for Ca2+ ions was determined to be 9822.4 ± 452.9 µg Ca2+/disk and was conducive to the deployment of long-term or high concentration. The BCES-DGT device can accurately measure the concentrations of Ca2+ over wide ranges of ionic strengths (1–3 as pNaCl) and pH (5–10). There was no significant interference on the uptake of Ca2+ by the BCES-DGT device at the tolerance limits up to 500 for Mg2+, Li+, HCO3-, H2PO4-, NO3- and SO42-, 250 for Sr2+, 2000 for K+ and 50 for fulvic acid. The results from BCES-DGT device were in excellent agreement with those measured directly using ion selective electrode in several water and soil samples. Field application in river water indicated that a good agreement was obtained between BCES-DGT value and mean grab sample measurements of Ca2+ and that the relative standard deviation of BCES-DGT measurement (4.7 %) was superior to that of grab sample measurements (13.5 %), suggesting that BCES-DGT was reliable for in-situ sampling and measurement of available Ca2+ with good accuracy and precision.