Pesticide-Leaf Interactions and Their Implications for Pesticide Fate Modeling

The work described here provides measured data to improve the understanding of the interaction between a pesticide and leaf surface after application. Two methods were developed, one using a newly introduced instrument, for the extraction of pesticides from leaves. This is required to measure the concentration of pesticide in the leaves. Using one of the developed extraction methods, measurements were made to determine how a pesticide equilibrates between a leaf and the air above it. These measurements were incorporated into a pesticide fate model that predicts how a pesticide moves through the environment after application to an agricultural field. The updated fate model was used to predict the danger the pesticide posed to honeybees

Comparison of Accelerated Solvent Extraction (ASE) and Energized Dispersive Guided Extraction (EDGE) for the Analysis of Pesticides in Leaves

Various techniques have been evaluated for the extraction and cleanup of pesticides from environmental samples. In this work, a Selective Pressurized Liquid Extraction (SPLE) method for pesticides was developed using a Thermo Fisher Scientific Accelerated Solvent Extraction (ASE) system. This instrument was compared to the newly introduced (2017) extraction instrument, the Energized Dispersive Guided Extraction (EDGE) system, which combines Pressurized Liquid Extraction (PLE) and dispersive Solid Phase Extraction (dSPE). We first optimized the SPLE method using the ASE instrument for pesticide extraction from alfalfa leaves using layers of Florisil and graphitized carbon black (GCB) downstream of the leaf homogenate in the extraction cell (Layered ASE method). We then compared results obtained for alfalfa and citrus leaves with the Layered ASE method to those from a method in which the leaf homogenate and sorbents were mixed (Mixed ASE method) and to similar methods modified for use with EDGE (Layered EDGE and Mixed EDGE methods). The ASE and EDGE methods led to clear, colorless extracts with low residual lipid weight. No significant differences in residual lipid masses were observed between the methods. The UV-Vis spectra showed that Florisil removed a significant quantity of the light-absorbing chemicals, but that GCB was required to produce colorless extracts. Recoveries of spiked analytes into leaf homogenates were generally similar among methods, but in several cases, significantly higher recoveries were observed in ASE extracts. Nonetheless, no significant differences were observed among pesticide concentrations in field samples when calculated with the isotope dilution method in which labelled surrogates were added to samples before extraction. The extraction time with the ASE methods was ~45 minutes, which was ~4.5 times longer than with the EDGE methods. The EDGE methods used ~10 mL more solvent than the ASE methods. Based on these results, the EDGE is an acceptable extraction instrument and, for most compounds, the EDGE had a similar extraction efficiency to the ASE methods

Molecular Rotation in 3 Dimensions at an Air/Water Interface Using Femtosecond Time Resolved Sum Frequency Generation

This paper presents the first study of the rotations of rigid molecules in 3 dimensions at the air/water interface, using the femtosecond time resolved sum frequency generation (SFG) technique. For the purpose of this research, the aromatic dye molecule C153 was chosen as an example of a molecule having two functional groups that are SFG active, one being the hydrophilic −−C==O group and the other the hydrophobic −−CF3 group. From polarized SFG measurements, the orientations of the two chromophores with respect to the surface normal were obtained. On combining these results with the known relative orientation of the two chromophores in the molecule yields the absolute orientation of C153 at the air/water interface. It was found that the −−CF3 axis projected towards the bulk air at an angle of 59○ with respect to the interface normal and the −−C==O group projected towards the bulk water at an angle of 144○ . In order to observe the rotational motions of C153 at the air/water interface, the approach was used to perturb the ground electronic state equilibrium orientational distribution using a polarized resonant pump pulse, which preferentially excites ground state molecules that have their electronic S0 → S1 transition moment aligned closely to the electric field of the incident pump pulse. As a consequence of the photoselection perturbation, the orientational distribution of the remaining ground state molecules was not the equilibrium distribution. Similarly, the orientational distribution of the excited state molecules that were created by the polarized pump pulse was not in their final equilibrium orientational distribution. The rotational motions of the interfacial molecules towards equilibrium were obtained from time dependent measurements of the intensities of the SFG signal generated by the simultaneous incidence at the air/water interface of a visible probe pulse plus an IR probe pulse. In this way, the recovery times to achieve the orientational equilibrium of the two chromophores including the orientation of the normal of the C153 plane with respect to the interface were obtained. The photo-selection process shifts the average orientation angle of the hydrophilic −−C==O group by an increase of 4○ ± 0.6○ with a rotational recovery time constant of 130 ± 20 ps, which is the time to return to an orientational equilibrium distribution. The hydrophobic –CF3 group undergoes a shift that increases its angle by 8○ ± 1.5○ with a rotational recovery time constant of 210 ± 38 ps. We find that the orientational change of the molecular normal is 4○ ± 0.5○ and has a rotational recovery time constant of 125 ± 26 ps. The interface-specific time-dependent polarized measurements allowed us to monitor the orientational motions of molecules at interfaces, both in 3 dimensions and in real time