Importance of adjuvant formulation properties in predicting wetting on leaf surfaces.

BACKGROUND: Leaf wettability can be a barrier to retention of agrichemical sprays. Adjuvants are used to modify leaf wetting by sprays to enhance retention. A previous study developed a model that accurately predicted nonadjuvant formulation wetting (contact angle) on both synthetic and leaf surfaces. Model inputs were the surface properties, roughness and polarity, as measured by the wetting tension dielectric method, coupled with the formulation properties, surface tension and dielectric constant. Preliminary work has indicated that the wetting ability of adjuvant formulations on different surfaces could be modelled in a similar way if the effect of adjuvants on solution polarity could be accurately quantified. RESULTS: The wetting of nine agrichemical adjuvants, at a range of concentrations, were measured on seven synthetic and 14 leaf surfaces. A novel method was developed to quantify the interfacial dielectric polarity (IDP) of adjuvant formulations. Adjuvant concentration did not change the IDP indicating the surface-active surfactant molecules migrate to the interface, loading until saturation. Formulation properties of surface tension and IDP were found to be strong predictors of wetting in conjunction with surface properties of the substrate. The previously developed unaltered comprehensive wetting model could predict the wetting of adjuvant formulations on synthetic and leaf surfaces (R2  = 0.9) using these inputs. CONCLUSIONS: Wetting of adjuvant formulations can be modelled for a wide range of surfaces and this model is expected to advance the selection, and development, of adjuvants to target specific surfaces generating the desired wetting outcome. © 2022 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Importance of leaf surface and formulation properties in predicting wetting outcomes.

BACKGROUND: Leaf wettability is a major hurdle for the retention of agrichemical sprays that is combated, in part, by using adjuvant modified formulations. Scientists must understand the properties of the leaf surface and the formulation that govern wetting to intelligently select or formulate products to target specific pests. RESULTS: A comprehensive database comprising 11 synthetic surfaces and 54 leaf surfaces (species, adaxial and abaxial sides, cultivars, and plant age) using 35 formulations (neat solutions and adjuvants solutions at different concentrations) was compiled. Surface properties of the physical roughness and chemical polarity, as quantified by the wetting tension dielectric method, and formulation properties of surface tension and polarity, as quantified by dielectric constant, were found to govern wetting. A comprehensive wetting model was developed that employed these variables and was capable of accurately predicting the wetting outcome (R2  = 0.86) on all the leaf and synthetic surfaces investigated. This model adequately predicts adjuvant formulation wetting despite exact formulation polarity being unknown. CONCLUSIONS: Wetting can be modelled for a wide range of surfaces and solutions. The comprehensive wetting model developed shows potential to better predict the wetting outcome of adjuvant formulations should a method to quantify the formulation dielectric constant be developed. This research provides a significant advancement in the understanding of the properties governing wetting, which may aid the selection and development of adjuvants to target specific surfaces. © 2022 Society of Chemical Industry.

Evaporating droplets on inclined plant leaves and synthetic surfaces: Experiments and mathematical models.

HYPOTHESIS: Evaporation of surfactant droplets on leaves is complicated due to the complex physical and chemical properties of the leaf surfaces. However, for certain leaf surfaces for which the evaporation process appears to follow the standard constant-contact-radius or constant-contact-angle modes, it should be possible to mimic the droplet evaporation with both a well-chosen synthetic surface and a relatively simple mathematical model. EXPERIMENTS: Surfactant droplet evaporation experiments were performed on two commercial crop species, wheat and capsicum, along with two synthetic surfaces, up to a 90° incline. The time-dependence of the droplets' contact angles, height, volume and contact radius was measured throughout the evaporation experiments. Mathematical models were developed to simulate the experiments. FINDINGS: With one clear exception, for all combinations of surfaces, surfactant concentrations and angles, the experiments appear to follow the standard evaporation modes and are well described by the mathematical models (modified Popov and Young-Laplace-Popov). The exception is wheat with a high surfactant concentration, for which droplet evaporation appears nonstandard and deviates from the diffusion limited models, perhaps due to additional mechanisms such as the adsorption of surfactant, stomatal density or an elongated shape in the direction of the grooves in the wheat surface.

Image analysis of shatter and pinning events on hard-to-wet leaf surfaces by drops containing surfactant.

BACKGROUND: A key challenge for developing computer models of spray retention by plants is to accurately predict how spray drops behave when impacting leaf surfaces. One poorly understood outcome occurs when drops bounce or shatter on impact but leave behind a proportion of the liquid on the surface (designated as pinning). This process is studied via impaction experiments with two hard-to-wet leaf surfaces (fat-hen: Chenopodium album and barnyard grass: Echinochloa crus-galli L. P. Beauv) and one hydrophobic artificial surface (Teflon) using three liquid formulations. RESULTS: Drops that impact upon Teflon underwent pinning shatter events via a well-known mechanism referred to as receding breakup. Drops impacting on leaf surfaces did not undergo receding breakup because the liquid rim was not in direct contact with the leaf surface when it broke into secondary droplets. However, pinning did occur on plant surfaces via a different mechanism, especially when using formulations containing a surfactant. CONCLUSION: Newly developed image analysis and methodology has allowed quantification of the volume fraction pinned to surfaces when drops shatter. The addition of surfactant can increase both the probability of pinning and the pinned volume when drops shatter on fat-hen or Teflon. However, the surfactants studied did not substantially improve the probability of pinning on barnyard grass. The difference in behaviour between the two leaf surfaces and the underlying mechanism is worth further study. © 2020 Society of Chemical Industry.

Simulating spray droplet impaction outcomes: comparison with experimental data.

BACKGROUND: A suite of plant retention spray models has been developed to simulate spray retention using virtual surfaces (either single leaves or whole plants) and their outputs compared with experimental data for the equivalent spray scenarios. RESULTS: The results for a single formulation (0.1% v/v lecithin mixture in water) and difficult to wet plant species Chenopodium album L (common lambsquarters) are presented. They include experimental observations with single leaves, as well as simulations of virtual impaction events, conducted to provide for the first time estimates of f (the proportion of theoretical impact drop diameter at shatter). With this factor prescribed, multi-plant simulations using a range of nozzle types and droplet sizes (volume mean diameter (VMD) range 241 to 530 µm) are compared with equivalent experimentally determined spray retention by real plants. The simulations demonstrated that impaction resulted predominantly in shatter with the production of daughter droplets, and that retention is mainly due to re-capture of these droplets. Overall the simulations show the same trends as experimental retention results from different nozzle applications, but at best predicted retention results were 68% to 79% of experimental percentage retention, depending on plant spacing. CONCLUSIONS: Retention is the result of some primary drop capture but predominantly by recapture of shatter droplets as the modelling illustrates. The value of f affects the droplet shatter outcome and can result in fewer, more energetic daughter droplets, or more droplets but with lower energies. However, this effect alone cannot explain the discrepancy between actual and simulated results. Possible operational influences are discussed. © 2020 Society of Chemical Industry.

Mathematical Modelling of Hydrophilic Ionic Fertiliser Diffusion in Plant Cuticles: Lipophilic Surfactant Effects.

The global agricultural industry requires improved efficacy of sprays being applied to weeds and crops to increase financial returns and reduce environmental impact. Enhancing foliar penetration is one way to improve efficacy. Within the plant leaf, the cuticle is the most significant barrier to agrochemical diffusion. It has been noted that a comprehensive set of mechanisms for ionic active ingredient (AI) penetration through plant leaves with surfactants is not well defined, and oils that enhance penetration have been given little attention. The importance of a mechanistic mathematical model has been noted previously in the literature. Two mechanistic mathematical models have been previously developed by the authors, focusing on plant cuticle penetration of calcium chloride through tomato fruit cuticles. The models included ion binding and evaporation with hygroscopic water absorption, along with the ability to vary the AI concentration and type, relative humidity, and plant species. Here, we further develop these models to include lipophilic adjuvant effects, as well as the adsorption and desorption, of compounds on the cuticle surface with a novel Adaptive Competitive Langmuir model. These modifications to a penetration model provide a novel addition to the literature. We validate our theoretical model results against appropriate experimental data, discuss key sensitivities, and relate theoretical predictions to physical mechanisms. The results indicate the addition of the desorption mechanism may be one way to predict increased penetration at late times, and the sensitivity of model parameters compares well to those present in the literature.

Nonlinear Porous Diffusion Modeling of Hydrophilic Ionic Agrochemicals in Astomatous Plant Cuticle Aqueous Pores: A Mechanistic Approach.

The agricultural industry requires improved efficacy of sprays being applied to crops and weeds in order to reduce their environmental impact and deliver improved financial returns. Enhanced foliar uptake is one means of improving efficacy. The plant leaf cuticle is known to be the main barrier to diffusion of agrochemicals within the leaf. The usefulness of a mathematical model to simulate uptake of agrochemicals in plant cuticles has been noted previously in the literature, as the results of each uptake experiment are specific to each formulation of active ingredient, plant species and environmental conditions. In this work we develop a mathematical model and numerical simulation for the uptake of hydrophilic ionic agrochemicals through aqueous pores in plant cuticles. We propose a novel, nonlinear, porous diffusion model for ionic agrochemicals in isolated cuticles, which extends simple diffusion through the incorporation of parameters capable of simulating: plant species variations, evaporation of surface droplet solutions, ion binding effects on the cuticle surface and swelling of the aqueous pores with water. We validate our theoretical results against appropriate experimental data, discuss the key sensitivities in the model and relate theoretical predictions to appropriate physical mechanisms. Major influencing factors have been found to be cuticle structure, including tortuosity and density of the aqueous pores, and to a lesser extent humidity and cuticle surface ion binding effects.

Methods for evaluating leaf surface free energy and polarity having accounted for surface roughness.

BACKGROUND: Leaf surfaces can have similar wettability, while their roughness and polarity may be very different. This may affect agrochemical bioefficacy, hence there is a need to characterise leaf surface polarity and roughness separately. This paper reviews established surface evaluation techniques and then uses a comprehensive dataset of static contact angles (12 chemical solutions on 15 different species) to compare and contrast them for their ability to characterise leaf surface polarity in isolation from roughness. RESULTS: Many techniques were severely limited when applied to leaf surfaces. A failing of the surface free energy (SFE) concept is that both physical and chemical properties affect the SFE. Additionally, whilst the leaf surface chemistry does not change, the SFE values generated are dependent on the chemical properties of the probe solution employed. CONCLUSIONS: The wetting tension-dielectric (WTD) method stands out due to its ability to isolate and quantify leaf surface roughness and polarity. A novel (WTD) roughness correction factor is proposed to improve SFE determination. The strong correlation between leaf polarity and leaf wettability for polar solutions (such as water) makes the WTD method a valuable tool for the evaluation of leaf surface-droplet behaviour and the advancement of agrochemical spray formulation technologies. © 2017 Society of Chemical Industry.

Effect of solution and leaf surface polarity on droplet spread area and contact angle.

BACKGROUND: How much an agrochemical spray droplet spreads on a leaf surface can significantly influence efficacy. This study investigates the effect solution polarity has on droplet spreading on leaf surfaces and whether the relative leaf surface polarity, as quantified using the wetting tension dielectric (WTD) technique, influences the final spread area. Contact angles and spread areas were measured using four probe solutions on 17 species. RESULTS: Probe solution polarity was found to affect the measured spread area and the contact angle of the droplets on non-hairy leaves. Leaf hairs skewed the spread area measurement, preventing investigation of the influence of surface polarity on hairy leaves. WTD-measured leaf surface polarity of non-hairy leaves was found to correlate strongly with the effect of solution polarity on spread area. CONCLUSIONS: For non-polar leaf surfaces the spread area decreases with increasing solution polarity, for neutral surfaces polarity has no effect on spread area and for polar leaf surfaces the spread area increases with increasing solution polarity. These results attest to the use of the WTD technique as a means to quantify leaf surface polarity. © 2015 Society of Chemical Industry.

Simulating droplet motion on virtual leaf surfaces.

A curvilinear thin film model is used to simulate the motion of droplets on a virtual leaf surface, with a view to better understand the retention of agricultural sprays on plants. The governing model, adapted from Roy et al. (2002 J. Fluid Mech. 454, 235-261 (doi:10.1017/S0022112001007133)) with the addition of a disjoining pressure term, describes the gravity- and curvature-driven flow of a small droplet on a complex substrate: a cotton leaf reconstructed from digitized scan data. Coalescence is the key mechanism behind spray coating of foliage, and our simulations demonstrate that various experimentally observed coalescence behaviours can be reproduced qualitatively. By varying the contact angle over the domain, we also demonstrate that the presence of a chemical defect can act as an obstacle to the droplet's path, causing break-up. In simulations on the virtual leaf, it is found that the movement of a typical spray size droplet is driven almost exclusively by substrate curvature gradients. It is not until droplet mass is sufficiently increased via coalescence that gravity becomes the dominating force.

The contribution of spray formulation component variables to foliar uptake of agrichemicals.

BACKGROUND: The objective of the present study was to determine the contribution of the active ingredient (AI) and surfactant, and their concentrations, to the foliar uptake of agrichemicals, and to examine the physical properties that would need to be included in a model for foliar uptake. RESULTS: All spray formulation component variables significantly affected uptake, explaining 73% of the deviance. The deviance explained by each factor ranged from 43% (AI concentration nested within AI) to 5.6% (surfactant). The only significant interaction was between AI and surfactant, explaining 15.8% of the deviance. Overall, 90% of the deviance could be explained by the variables and their first-order interactions. CONCLUSIONS: Uptake increased with increasing lipophilicity of the AI at concentrations below those causing precipitation on the leaf surface. AI concentration had a far greater (negative) effect on the uptake of the lipophilic molecule epoxiconazole. The uptake of 2-deoxy-D-glucose (DOG) and 2,4-dichlorophenoxyacetic acid (2,4-D) increased with increasing hydrophile-lipophile balance (HLB) of the surfactant, the effect of HLB being far greater on the hydrophilic molecule DOG. However, the differences observed in epoxiconazole uptake owing to the surfactant were strongly positively related to the spread area of the formulation on the leaf surface. For all AIs, uptake increased in a similar manner with increasing molar surfactant concentration.

Quantification of physical (roughness) and chemical (dielectric constant) leaf surface properties relevant to wettability and adhesion.

BACKGROUND: Spray droplet adhesion is dependent not only on formulation and droplet parameters but also on the surface properties (physical and chemical) of the leaf. Quantifying these leaf surface properties would aid understanding and modelling of adhesion, helping to optimise spray formulations. Fractal dimensions (FDs) were used to quantify the relative leaf surface roughness of ten plant species. Static droplet contact angles were measured on each leaf surface, and wetting tension was calculated. Chemical profiles of the leaf surfaces were developed by evaluating contact angle behaviour relative to solution dielectric constants. RESULTS: The FDs of Cryo-SEM micrographs taken at 300× magnification gave the best correlation with adhesion. The wetting tension intercept had a strong relationship with mean adhesion, and successfully accounted for the wettability of the outlier species. CONCLUSIONS: The microroughness of the leaf surface, as revealed by Cryo-SEM, can be quantified by fractal dimension analysis. However, the wetting tension intercept is a more useful universal measure of the surface properties of the leaf (including roughness) as they pertain to adhesion. The slope of the wetting tension versus dielectric constant plot allowed preliminary quantification of the chemical contribution of leaf surface dielectric behaviour to adhesion.

Cuticular uptake of xenobiotics into living plants. Part 2: influence of the xenobiotic dose on the uptake of bentazone, epoxiconazole and pyraclostrobin, applied in the presence of various surfactants, into Chenopodium album, Sinapis alba and Triticum aestivum leaves.

This study has determined the uptake of three pesticides, applied as commercial or model formulations in the presence of a wide range of surfactants, into the leaves of three plant species (bentazone into Chenopodium album L. and Sinapis alba L., epoxiconazole and pyraclostrobin into Triticum aestivum L.). The results have confirmed previous findings that the initial dose (nmol mm(-2)) of xenobiotic applied to plant foliage is a strong, positive determinant of uptake. This held true for all the pesticide formulations studied, although surfactant concentration was found to have an effect. The lower surfactant concentrations studied showed an inferior relationship between the amount of xenobiotic applied and uptake. High molecular mass surfactants also produced much lower uptake than expected from the dose uptake equations in specific situations.

Mechanisms of cuticular uptake of xenobiotics into living plants: evaluation of a logistic-kinetic penetration model.

The objective of this study was to determine whether a logistic-kinetic penetration model could be applied to whole plant uptake. Uptake over 24 h was determined for three model compounds, applied in the presence and absence of surfactants, into the leaves of two plant species. Data for two time intervals were used in the model to predict uptake at intermediate intervals and compared with experimental results. Overall, the model fit the whole plant uptake data well. The study confirmed that an increase (or decrease) in active ingredient (ai) concentration or an increase in contact area will have no effect on the penetration rate factor, q, within the normal working concentration range. This enabled uptake to be predicted at different times for concentrations of ai not already studied, having first derived q for one concentration of the formulation of interest and having 24 h (maximum) uptake results for all formulations and concentrations of interest. The advantages of the models and equations described are that few variables are required, and they are simple to measure.

Mechanisms of cuticular uptake of xenobiotics into living plants: 1. Influence of xenobiotic dose on the uptake of three model compounds applied in the absence and presence of surfactants into Chenopodium album, Hedera helix and Stephanotis floribunda leaves.

This study determined the uptake of three model compounds, applied in the presence and absence of surfactants, into the leaves of three plant species (Chenopodium album L, Hedera helix L and Stephanotis floribunda Brongn). The results with 2-deoxy-D-glucose, 2,4-dichlorophenoxyacetic acid and epoxiconazole in the presence ofsurfactants (the polyethylene glycol monododecyl ethers C12EO3, C12EO6, C12EO10 and a trisiloxane ethoxylate with mean EO of 7.5, all used at one equimolar concentration and therefore different percentage concentrations) illustrate that the initial dose (nmol mm(-2)) of xenobiotic applied to plant foliage is a strong positive determinant of uptake. This held true for all the xenobiotics studied over a wide concentration range in the presence of these surfactants. Uptake on a unit area basis (nmol mm(-2)) could be related to the initial dose of xenobiotic applied per unit area (ID) by an equation of the form: Uptake = a [ID]b at time t = 24h. ID is given by the mass of xenobiotic applied, M divided by the droplet spread area, A. Total mass uptake is then calculated from an equation of the form: Total Uptake = a [ID]b x A.