Influence of surfactant concentration on foliar retention of pesticides used in forestry

Abstract

Aqueous tank mixes of permethrin, fenitrothion, Bacillus thuringiensis (B.t.), diflubenzuron (DFB), and glyphosate containing different amounts of Triton® X‐114, a nonionic surfactant, were prepared. Glyphosate formed clear solutions, permethrin and fenitrothion formed emulsions, DFB and B.t provided suspensions. Emulsion stability of permethrin and fenitrothion increased with increasing surfactant level, while the emulsion drop size decreased.

Foliage of white oak, trembling aspen, white spruce and balsam fir were dipped in tank mixes of pesticides (except B.t.) labelled with ¹⁴carbon. The amount of pesticide retained on foliage was determined by liquid scintillation counting. Foliage was also dipped in non‐radioactive B.t. tank mixes, and the protein retained was determined colorimetrically. With all tank mixes, a direct relationship was observed between the mass of liquids retained on foliage and liquid viscosity. In contrast, the amount of pesticide retained was unaffected by viscosity, but was influenced by emulsion drop size. Initially, the amount of pesticide retained on foliage increased with increasing surfactant concentration. Beyond an optimum surfactant level, the emulsion drop sizes were too small and the emulsions became too stable to allow maximum retention of pesticides on foliage. With the glyphosate solutions, however, no optimum surfactant level was indicated because foliar concentrations continued to increase with increasing surfactant levels.     

Effects of droplet density and concentration on the efficacy of bacillus thuringiensis and carbaryl against gypsy moth larvae (Lymantria dispar L.)

Abstract

The feeding behavior of gypsy moth larvae exposed to two pesticide deposits (Bt and carbaryl) on oak leaf disks was monitored to determine the relationships between its efficacy and application parameters (droplet density and pesticide concentration). A range of pesticide concentrations and droplet densities (from 9 to 149 droplets/cm²) was used to simulate high and low application rates produced by different methods of application in the field.

The LD₅₀ and the LC₅₀, appeared to be affected by the spatial distribution of the deposit on the leaf surface. Both Bt and carbaryl showed a decreasing LD₅₀ at increasing time after spray. The LD₅₀ of Bt decreased from 14.1 BIU/liter to 3.1 BIU/Iiter between 48 and 144 hours after spray. The results show that feeding inhibition by Bt is more closely related to concentration than to droplet density and dose per unit area with the highest feeding inhibition occurring at 10 BIU/liter at 9 droplets/cm². With carbaryl, an increase in both concentration and droplet density was necessary to cause a decrease in leaf area eaten by larvae.     

Dose transfer of Bacillus thuringiensis from cabbage to the diamondback moth: A graphical simulator

Abstract

The application of agrichemicals is a highly inefficient process and one of the main causes of the environmental and health risks currently associated with pesticide usage. Efforts to mitigate this inefficiency have largely been unsuccessful, due principally to the poor understanding of the processes involved in the spray application of pesticides, from atomization to biological effect. A generalized model of the application system for pesticides from atomization to biological result is described in this overview. The model allows the investigation of the biological consequences of altering the application parameters for the bacterial insecticide Bacillus thuringiensis when used against the diamondback moth (Plutella xylostella L.) with cabbage as the substrate. Parameters input into the model include the in‐flight droplet size frequency distribution of the spray cloud, spatial distribution of the deposit, spread and subsequent environmental degradation of the deposit, and behavioral and toxicological effects.

It is hoped that such a modelling approach can afford insights into the application process, and, through a better understanding of the inefficient but still highly effective hydraulic application systems used worldwide, reduce that inefficiency to tolerable levels.     

Influence of additives in the end‐use mixes of tebufenozide on deposition,adhesion and persistence in spruce foliage

Abstract

A commercial flowable formulation of tebufenozide, RH‐5992 2F [N'‐t‐butyl‐N'‐(3,5‐dimethylbenzoyl)‐N‐(4‐ethylbenzoyl) hydrazine], was diluted with water, water and canola oil, and water and the methyl ester of canola oil, to provide six end‐use mixes with concentrations of 35 and 70 g of active ingredient (Al) litre^‐1. The mixes were applied at 70 and 140 g Al ha^‐1 over white spruce [Picea glauca (Moench) Voss] seedlings in a laboratory spray chamber and foliar concentrations of tebufenozide were determined over a 60‐d period. At intervals of time post‐spray, seedlings were sprayed with monosized droplets of Sunspray®11N as rainfall, and the amount of tebufenozide knocked off from foliage was determined. The potential energy of adhesion (PEA) of the Al particles on the foliage increased with time and varied according to the type of end‐use mix, its viscosity and the dosage sprayed.

The end‐use mixes were applied over white spruce trees under field conditions and persistence of tebufenozide was investigated. DT₅₀ values were influenced by the type of mix and dosage sprayed. Oil‐containing mixes and higher dosages increased the PEA of tebufenozide particles.     

The effects of drop size and formulation upon the spread of pesticide droplets impacting on water‐sensitive papers

Abstract

The effects of drop size and formulation upon the spread of pesticide droplets impacting on water‐sensitive papers (WSPs) was investigated. Droplets of diameter 70–350 μm, of four permethrin formulations, were produced using a monosize droplet generator. The droplets were collected on WSPs and in Dow Corning fluid and their diameters measured using a binocular microscope. Spread factors, upon the WSPs, for each dropsize/formulation combination were then calculated. Spread factors varied with both formulation and droplet size and for droplets of 200 and 300 μm diameter spread was significantly correlated with the dynamic surface tension of the formulation. The results suggest that proper calibration of WSPs is necessary for effective droplet sizing.     

Effect of additives in the Neem formulations on deposition,volatilization and persistence of Azadirachtin in spruce foliage

Abstract

Foliar deposits, volatilization and persistence of azadirachtin‐A (AZ‐A) were investigated after application of four spray mixes prepared from a wettable powder (WP) and three emulsifiable concentrate (EC) formulations of neem. They were applied at the dosage rate of 50 g AI in 4 L/ha onto potted spruce seedlings in a laboratory spray chamber. Droplet‐size spectra and deposits were assessed using Kromekote^® card/glass plate collection units. Foliar residues [dislodgeable residues (DR), penetrated residues (PR) and total residues (TR)] of AZ‐A and their volatilization were measured by HPLC at different intervals of time up to 60 h after treatment. Differences in the droplet‐size spectra and deposit levels were observed among the four spray mixes due to the influence of additives present in them. Dissipation half‐lives (DT₅₀) of the DR, PR and TR in the foliage were low (range, 19.5 to 38.9 h) and varied according to the residue type and the spray mix used. The DT₅₀ values of the DR were consistently lower (range, 19.5 to 31.9 h) than those of the PR (range, 30.5 to 38.9 h) due to preferential loss of the surface residues. The low DT₅₀ values observed for the DR and TR in the foliage sprayed with the WP spray mix were attributed to the particulate nature of the deposit. AZ‐A volatilized appreciably from the DR rather than from the PR. The variations found in the amounts of AZ‐A volatilized (42 to 58%) and unaccountable (38 to 46%) from the initial TR values in spruce foliage, after 60 h, were attributed to the physical form of the deposits on the target surface and the influences of additives present in the different spray mixes.     

Rain‐washing of mimic®, RH‐5992, from balsam fir foliage following application of two formulations

Abstract

Two formulation concentrates of the insecticide, RH‐5992 [N'‐t‐butyl‐N'‐(3,5‐dimethylbenzoyl)‐N‐(4‐ethylbenzoyI) hydrazine], an aqueous flowable (2F) and an emulsion‐suspension (ES), were diluted with water to provide spray mixes containing dosage rates ranging from 35 to 150 g of the active ingredient (AI)/ha. The mixes were sprayed in a laboratory chamber, onto balsam fir branch tips collected from field trees and greenhouse‐grown seedlings. Droplet spectra and spray mass recovery were determined on artificial samplers. Simulated rainfall of two different intensities was applied at different rain‐free periods, and rain droplet sizes were determined. Foliar washoff of RH‐5992 was assessed after application of different amounts of rain, and the increase in soil residues was evaluated.

A direct relationship was indicated between the amount of rainfall and RH‐5992 washoff. The larger the rain droplet size, the greater the amount washed off. Longer rain‐free periods made the deposits more resistant to rain. Regardless of the amount of rainfall, rain droplet size and rain‐free period, foliar deposits of the 2F formulation were washed off to a greater extent than the ES formulation. The increase in soil residues due to foliar washoff was greater for the 2F than for the ES formulation. The deposits of the emulsion‐suspension were consistently more resistant to rain‐washing than those of the aqueous flowable formulation.     

Effect of sunlight radiation,rainfall and droplet spectra of sprays on persistence of bacillus thuringiensis deposits after application of dipel® 76af formulation onto conifers

Abstract

The effect of sunlight radiation, rainfall and droplet spectra of sprays on per ‐sistence of a Bacillus thuringiensis subspp. kurstaki (Btk) formulation, DiPel^® 76AF, was examined after application onto spruce [Picea glauca (Moench) Voss] foliage. The investigation consisted of three studies: (i) Study I: a laboratory microcosm study to examine the photostability of DiPel 76AF deposits on foliage after different periods of exposure to two radiation intensities, (ii) Study II: a laboratory microcosm study to examine the rainfastness of foliar deposits after exposure to different amounts of rainfall consisting of two separate droplet spectra, and (iii) Study III: a field microcosm study to investigate the influence of two different droplet spectra of DiPel 76AF sprays on foliar persistence of Btk under natural weathering conditions. In all studies, persistence of Btk was investigated both by bioassay [using spruce budworm (Choristoneura fumiferana Clemens)] and total protein assay.

The findings of Study I indicated that bioactivity of foliar deposits decreased with increasing duration of exposure to radiation, and with increasing radiation intensity. The half‐life (DT₅₀, the exposure period required for 50% of the initial bioactivity to disappear) was 5.1 d for the low intensity, and 3.9 d for the higher intensity. In contrast with the bioassay results, the total protein levels [determined by the bicinchoninic acid (BCA) method] showed no decrease with increasing duration of exposure, or with increasing radiation intensity.

The findings of Study II indicated that bioactivity of foliar deposits decreased with increasing cumulative rainfall. A new term, RF₅₀ [the amount of rain (in mm) required to washoff 50% of the initial deposit], was introduced to understand the relationship between rainfall intensity and reduction in bioactivity. When the same amount of rain was applied in different droplet sizes, the RF₅₀ value was high (5.2 mm) for the small rain droplets, and was low (2.9 mm) for the large rain droplets. Similar to the bioassay results, the total protein concentrations (determined by the BCA method) decreased with increasing amount of rain and with increasing rainfall intensity. The RF₅₀ value (obtained using ng protein /cm²) was 5.4 mm for the small rain droplets, and was 3.4 mm for the large rain droplets.

The field microcosm study indicated that when DiPel 76AF was applied in small droplets (D_v.5 of 65 μm), the persistence of bioactivity was ca 8.0 d, whereas when it was applied in large droplets (D_v.5 of 130 nm) it was ca 11 d. Bioactivity decreased with time after spray, and the DT₅₀ was 1.98 d for the spray of small droplets, and 2.87 d for that of large droplets. Similar to the bioactivity, the total protein concentrations also decreased with time after spray, and the DT₅₀ values for the small and large droplet spectra were 3.45 and 6.07 d respectively.     

The effect of fluorescent tracers on droplet spectrum,viscosity, and density of pesticide formulations

The most important factor affecting efficacy and drift of pesticide applications is the droplet spectrum. To measure pesticide drift, researchers utilize fluorescent tracers to rapidly quantify spray deposition. Although fluorescent tracers have been used for more than 50 years, no experiments have been performed on the effect they have on the properties of pesticide formulations (density and viscosity) or droplet spectrum, which affect the drift of pesticides. Therefore, we examined the effect of an oil- and water-based tracer on the volume median diameter (VMD), viscosity, and density of oil- and water-based pesticide formulations. In addition, we experimentally fit and demonstrate the utility of using distributions to characterize pesticide droplet spectra. The addition of tracers to both water- and oil-based formulations did not significantly alter the VMD, viscosity, and density. Lognormal distributions provided the best fit for the water- and oil-based formulations with and without tracer. Our results demonstrated that the addition of oil- and water-based tracers do not significantly alter pesticide formulations properties and droplet spectrum, and most likely do not alter the movement of pesticide droplets in the environment.     

Spray atomization characteristics as a function of pesticide formulations and atomizer design

Abstract

The use of formulation adjuvants to increase the drop size of pesticide sprays has followed a practice which has evolved through many years of experimentation and development. The earliest materials used were simply designed to make the spray mix viscous on the premise that a mayonnaise‐like fluid would produce larger drops and hence increase the deposit efficiency. These viscomer materials, emulsions and water soluble thickeners such as starch and agars, as well as more complex cellulose materials, produced thick non‐Newtonian fluids which were difficult to mix, pump and spray, and provided questionable results. First, the larger drops reduced target coverage from a given volume of spray; and second, field tests with these definitely showed that a large volume of small drops were still being produced even with the thickest of formulations.

The next step in adjuvant evolution was the introduction of polyvinyl, polyacrylamide and polyamide elastomer materials. These polymers are also non‐Newtonian, but due to their peculiar molecular bonding, they have the capability of forming long string‐like streams which when atomized can retract into a spray of large drops. Pure forms of these polymers are blended by commercial producers to enable compatibility with pesticide chemicals. We have conducted a series of laboratory and wind tunnel tests; first, to try and establish some physical parameters identifying their characteristics and second, to determine how these adjuvants affect atomization and the production of small drift‐prone drops (i.e., those smaller than 120 μm in diameter).

Our results with the laboratory studies of physical properties and of the wind tunnel drop size tests have been inconclusive. The elastomer materials have relatively low viscosity (1.5 to 6 mPa.s) and reduced surface tension (50 to 60 mN/m) but our stream‐flow extension tests were non‐productive. The drop size studies comparing water sprays with polymer‐water mixtures gave us a mixed picture. Generally drop size was increased for all of the fan (deflector and milled orifice) and cone type atomizers. But an increase was also indicated of the volume of spray in drops less than 120 μm showing that the polymer did not fully control the production of these small drops under all of the testing procedures we studied.

It is difficult to evaluate the capability of these additives for controlling or reducing production of the drift‐prone small drops. While the pure solutions of the water soluble polymers would appear to be capable of this desirable effect, it is also evident that in order to make these formulations compatible with pesticide spray solutions, several other solvents, emulsifiers and surface active chemicals are added to the formulation, thus affecting the atomization characteristics and hence their drift‐control capability.     

Polymer and invert emulsifying oil effects upon droplet size spectra of sprays

Abstract

A series of wind tunnel atomization studies were carried out to investigate the effects of polymer and invert suspension oil “drift control adjuvants” upon the droplet size distribution spectra produced by nozzles typically used in aerial and ground based spraying of pesticides. A D8–46 disc and core was used as a typical aerial application nozzle, and an 8003 fan nozzle was used for the ground based sprayers simulation. The droplet size spectra were evaluated in a wind tunnel using a Malvern 2600 laser particle size analyzer immediately upon mixing and at 15 minutes after re‐circulation through a pumping system. The addition of the polymer‐based adjuvants significantly increased the droplet size spectra parameters of the spray cloud, but all the polymer products showed signs of breakdown of their molecular arrangements in the liquid medium, as a result of agitation. The invert suspension oil adjuvant did not change the droplet size spectra markedly, nor did it show signs of breakdown of the internal liquid structure after re‐circulation.     

Influence of nozzle type upon the control of the stalkborer using chlorpyrifos and cyfluthrin 1

Abstract

Field experiments were conducted in corn plots during 1988 that were artificially Infested with stalkborers, Papianema nebris (Guenee'). Two atomizers, a flatfan and a flood nozzle chosen for different droplet size distributions were used to apply two insecticides, chlorpyrifos and cyfluthrin at two application rates. Nozzles, insecticides, rates, and associated interactions were evaluated for control of stalkborer in the field. Laboratory studies involved application of insecticides to soil and glass via a spray track for bioassay at field application rates. Image analysis of percent area travelled on water sensitive paper by stalkborers was compared to droplet percent area covered to obtain percent area contacted per insect. Droplet size distributions for each nozzle were obtained using an Aerometrics particle sizing instrument. Significant differences in stalkborer control were attributed to percent area covered by smaller droplets measured by image analysis.     

Atmospheric loss of pesticides above an artificial vineyard during air-assisted spraying

A procedure to assess pesticide emission to the air and characterise possible air pollution sources was carried out using a tracer dye and 2 mm PVC lines during air-assisted spraying of an artificial vineyard. Three experiments were performed to evaluate the method feasibility, quantify upward movements of sprayed droplets and investigate the influence of microclimatic variables on pesticide emission. During each experiment two test series were carried out with two droplet size distributions (very fine and fine spray, according to the BCPC classification). The amount of sprayed liquid collected at 2.5 m above ground varied between 9.0% and 10.7% of the total dose applied for very fine spray and between 5.6% and 7.3% for fine spray. In stable atmospheric conditions the spray drifted along the mean wind direction over the crop whereas in unstable conditions the sprayed liquid plume was larger, with a greater amount of material sent to higher levels. A statistical model based on a simple multiple regression featuring droplet characteristics and microclimatic variables (wind speed, temperature, stability parameter and relative humidity) provided a robust estimate of spray loss just above the crop, with an acceptable determination coefficient (R²=0.84). This method is therefore suitable for quantifying spray drift and provides a way to study the influence of several variables on the amount of pesticide released into the atmosphere by air-assisted spraying, with suitable accuracy.     

Comparison of calculated evaporation rates of water droplets with those of pesticide droplets measured in a wind tunnel by Dennison and Wedding (1984)

Abstract

Calculations, based on Fuchs’ (1959) formula, of evaporation rates of water droplets freely falling through air are compared with those of water‐based pesticide droplets measured by Dennison and Wedding (1984) in a wind tunnel. Results indicate that calculations of evaporation rates of water droplets, are not significantly different from measurements of that of water‐based pesticide droplets under conditions of 20 °C and 20% relative humidity, but different under other measurement conditions.     

Measurements of surface contamination of spray equipment with pesticides after various methods of application

Abstract

A traditional method to determine operator dermal exposure is to quantify the amount of pesticide coming into contact with specific body regions and then to integrate the deposition density values with the total body surface. It is known that extremely high deposition values may occur in the hand region; however, the source of contamination is generally assumed to be direct splash or contact with the pesticide container. One of the parameters affecting operator/pilot exposure could be the transfer of pesticide residue, particularly in the case of pesticides with a longer half‐life, from contaminated surfaces of spray equipment by direct contact over extended periods. If the rate of skin absorption of pesticide is readily known, the expected values of daily dose for an operator or pilot may significantly rise due to the extended contact period. This study produced field data on the surface contamination of spray equipment used for ground and aerial applications. If field data on precise work practice (time‐motion) observations are incorporated, it may be possible to estimate the potential exposure of operator/pilot due to hand contact with contaminated surfaces.     

Control of bacterial speck of tomato by copper and ethylenebisuithiocarbamate fungicides: Their efficacy and residues on leaves

Abstract

Field studies were conducted to determine the synergism, persistence, and efficacy of a tank‐mix spray of cupric hydroxide and mancozeb for control of bacterial speck of tomato. The increased efficacy of the cupric hydroxide‐mancozeb mixture could not be attributed to the formation of a bacteriostatic compound in the tank mixture nor to a greater persistence of the mixture on the tomato foliage.     

Determination of organochlorine and organophosphate pesticide residues in fruits,vegetables and sediments

Abstract

A method is described for the determination of organochlorine and organophosphate pesticide residues in fruits, vegetables and sediments. The concentrated solvent extract was sealed in a polymeric membrane tube, dialysed in cyclohexane and the solvent replaced with hexane. The organophosphates were analysed on a specific thermionic detector without further clean‐up. For the organochlorine pesticides the extract was eluted through 3 g of alumina and analysed on GC/ECD. The clean‐up for sediment extract was carried out on a10 g alumina column with 100 mL hexane containing 5% acetone and the eluate was concentrated to 5 mL.

The detection limit for organophosphates on a 40 g sample and a final volume of 10 mL was on the average 0.01 mg/kg. The detection limit for organochlorine pesticides, with the final volume of 25 mL, was 0.005 mg/kg for all pesticides except for p,p'‐DDT and endosulfan sulphate, which was 0.01 mg/kg.

The detection limit for oganochlorine pesticides in sediment, with the final volume of 2 mL, was less than 1 μg/kg and for organophosphate pesticides less than 10 μg/kg when the final volume was made to 0.5 mL. At the detection limits the method produced a very high coefficient of variation for both organochlorine and organophosphate pesticides.     

Pesticide concentrations in agricultural storm drainage inlets of a small Swiss catchment

Agricultural pesticides transported to surface waters pose a major risk for aquatic ecosystems. Modelling studies indicate that the inlets of agricultural storm drainage systems can considerably increase the connectivity of surface runoff and pesticides to surface waters. These model results have however not yet been validated with field measurements. In this study, we measured discharge and concentrations of 51 pesticides in four out of 158 storm drainage inlets of a small Swiss agricultural catchment (2.8 km²) and in the receiving stream. For this, we performed an event-triggered sampling during 19 rain events and collected plot-specific pesticide application data. Our results show that agricultural storm drainage inlets strongly influence surface runoff and pesticide transport in the study catchment. The concentrations of single pesticides in inlets amounted up to 62 µg/L. During some rain events, transport through single inlets caused more than 10% of the stream load of certain pesticides. An extrapolation to the entire catchment suggests that during selected events on average 30 to 70% of the load in the stream was transported through inlets. Pesticide applications on fields with surface runoff or spray drift potential to inlets led to increased concentrations in the corresponding inlets. Overall, this study corroborates the relevance of such inlets for pesticide transport by establishing a connectivity between fields and surface waters, and by their potential to deliver substantial pesticide loads to surface waters.

     

Use pattern of pesticides and their predicted mobility into shallow groundwater and surface water bodies of paddy lands in Mahaweli river basin in Sri Lanka

Pesticides applied on agricultural lands reach groundwater by leaching, and move to offsite water bodies by direct runoff, erosion and spray drift. Therefore, an assessment of the mobility of pesticides in water resources is important to safeguard such resources. Mobility of pesticides on agricultural lands of Mahaweli river basin in Sri Lanka has not been reported to date. In this context, the mobility potential of 32 pesticides on surface water and groundwater was assessed by widely used pesticide risk indicators, such as Attenuation Factor (AF) index and the Pesticide Impact Rating Index (PIRI) with some modifications. Four surface water bodies having greater than 20% land use of the catchment under agriculture, and shallow groundwater table at 3.0 m depth were selected for the risk assessment. According to AF, carbofuran, quinclorac and thiamethoxam are three most leachable pesticides having AF values 1.44 × 10^?2, 1.87 × 10^?3 and 5.70 × 10^?4, respectively. Using PIRI, offsite movement of pesticides by direct runoff was found to be greater than with the erosion of soil particles for the study area. Carbofuran and quinclorac are most mobile pesticides by direct runoff with runoff fractions of 0.01 and 0.08, respectively, at the studied area. Thiamethoxam and novaluron are the most mobile pesticides by erosion with erosion factions of 1.02 × 10^?4 and 1.05 × 10^?4, respectively. Expected pesticide residue levels in both surface and groundwater were predicted to remain below the USEPA health advisory levels, except for carbofuran, indicating that pesticide pollution is unlikely to exceed the available health guidelines in the Mahaweli river basin in Sri Lanka.     

Removal of pesticides from rinsate by adsorption using agricultural residuals as medium

Abstract

The feasibility of using agricultural residual with highly organic matter content ‐ spent mushroom compost (SMC) as adsorption medium for removal of pesticides including carbaryl, carbofuran, and aldicarb with a concentration range of 0–30 mg/L from rinsate was investigated. Bottle‐point method was used to determine adsorption isotherms for single‐pesticide and multi‐pesticides. It was found that SMC might potentially be used for on‐farm treatment of pesticide rinsate. The adsorption capacity of SMC was increased compared to most soils, possibly related to the increased organic matter content. The rapid equilibrium of pesticide solution and SMC was consistent with a physical type of adsorption mechanism. The adsorption of carbamate pesticides on SMC was found to exhibit nonlinear “favorable”; adsorption behavior that could be characterized well by the Freundlich isotherm model. In addition, the multi‐pesticide adsorption tests displayed the characteristics of competitive behavior. The competitive ability of these three pesticides in multi‐components adsorption was in the order carbaryl > carbofuran > aldicarb, which was consistent with the adsorbability of pesticides.