Influence of formulation properties on droplet spectra and soil residues of aminocarb aerial sprays in conifer forests

The influence of formulation properties on spray droplet spectra and soil residues was studied in conifer forests in New Brunswick following aerial application of two oil-based aminocarb formulations of variable viscosities and volatilities. For a given volume rate of application, the formulation of low viscosity and high volatility provided a spectrum of small droplets and a low volume deposit on ground cards. For the same volume rate, the nonvolatile formulation of high viscosity provided a spectrum of larger droplets and consequently a higher volume deposit. Both formulations provided low soil residues, although those obtained with the nonvolatile formulation were much higher and persisted for much longer periods than those obtained with the volatile formulation. However, with both formulations the soil residues decayed to undetectable levels (less than 3 ng/g) within 5 days after spraying, indicating that none of the formulations caused any undue persistence of aminocarb in forest soils.     

Droplet size spectra and deposits of Bacillus thuringiensis aerial sprays,following application at two volume rates over an oak forest

Abstract

Dipel® 8AF, a commercial formulation of Bacillus thuringiensis (B.t.) was sprayed undiluted at 30 BIU in 1.8L/ha over a block B1, and sprayed after dilution with water at 30 BIU in 6.2 L/ha over another block B2 in an oak forest infested with the gypsy moth (Lymantria dispar L.) in southeastern Ontario, Canada. Spray was applied in May 1987 using a Cessna 188 Agtruck aircraft equipped with four Hicronair^® AU4000 atomizers. Droplet sizes were measured at mid‐canopy level of oak trees and at ground level using cylindrical Kromekote® cards. Deposit per unit area was assessed on aluminum oak leaves.

At the lower volume rate of 1.8 L/ha, spray droplets were smaller and droplets/cm² were lower on the cylindrical Kromekote cards in B1 than those obtained in B2 which received the higher volume rate of 6.2 L/ha. The average deposit per unit area of the aluminum oak leaves, expressed in nL of the spray volume per cm² surface area, was also correspondingly lower in B1 than in B2. This was attributed to the higher volume rate of spray application used in B2 than in B1, which resulted in larger droplets and a greater volume deposit/cm² in B2.     

Spray atomization and deposition patterns of one newtonian and two pseudoplastic formulations after aerial application over a mature conifer forest in Newfoundland

Abstract

Spray atomization and deposition patterns of three formulations were investigated in five aerial spray trials in Newfoundland, to understand the inter‐relationships between physical properties, drop size spectra and recovery of the spray volume at ground level. Diflubenzuron (DFB) was sprayed at 30 g active ingredient in 2.0 L/ha. Futura XLV (Fu‐XLV) and Thuricide® 48LV (Thu‐48LV), spray formulations of Bacillus thuringiensis (B.t.), were both applied undiluted at 30 BIU/ha, but in volume rates of 2.1 L/ha and 2.36 L/ha respectively. Each of the three formulations was applied over a 15 ha plot using a Piper Pawnee aircraft fitted with six Micronair® AU5000 atomizers. Spray drops were sampled with Kromekote® cards and deposits were collected on glass plates. Physical properties measured were: viscosity at variable shear rates, volatility and surface tension. The viscosities increased progressively from low (for DFB), moderate (for Thu‐48LV) to high (for Fu‐XLV) values, showing a gradual increase in pseudoplastic behaviour of the three formulations. The volatility data indicated an inverse relationship to the viscosities, but the surface tensions were similar for all the formulations.

The highly pseudoplastic Fu‐XLV atomized into the least wide drop size spectrum. The Newtonian formulation of DFB, on the other hand, atomized into the widest drop spectrum; and the moderately pseudoplastic Thu‐48LV, into an intermediate drop spectrum. Thus viscosity and volatility were more important factors in liquid atomization and drop deposition, than surface tension. Among the three meteorological factors measured, relative humidity appeared more important in drop deposition than did wind speed and temperature, within the range measured.     

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.     

Rain‐washing of foliar deposits of Dimilin®WP‐25 formulated in four different carrier liquids

Abstract

Dimilin^® WP‐25, a wettable powder formulation of diflubenzuron (DFB) [1‐(4‐chlorophenyl)‐3‐(2,6‐difluorobenzoyl) urea], was formulated in four different carrier liquids, viz., water; a light petroleum paraffinic oil, ID 585; a heavy paraffinic oil, Sunspray^® 7N; and a 1:2 mixture of a light petroleum aromatic solvent (Cyclosol^® 63) and canola oil; to provide four end‐use mixtures, Dim‐W, Dim‐585, Dim‐7N and Dim‐Cy‐C respectively, each containing 28 g of DFB per litre. Balsam fir branch tips clipped from greenhouse‐grown seedlings, and sugar maple branch tips clipped from field‐grown young trees, were exposed to uniform‐sized droplets (ranging in diameters from 135 to 190 μm) of the four end‐use mixtures which were atomized using a monodispersed droplet generator. Droplets were collected on the fir and maple branch tips and the initial residue per g fresh weight of foliage was determined by high‐performance liquid chromatography (HPLC). The branch tips were exposed to cumulative rainfall of 3, 6 and 10 mm at an intensity of 5 mm/h and at time intervals of 1, 12, 36 and 72 h after DFB treatment, to test the influence of ‘ageing’ of foliar residues on rainfastness. Foliar samples were collected for residue determination just before the onset of rainfall, and at 0.5 h post‐rain. DFB was quantified by the HPLC method. In the case of fir foliage, the Dim‐W formulation was the most susceptible to rain‐washing and the rainfastness did not increase with the ageing period of foliar deposits. In contrast, the three oil‐based mixtures showed greater rainfastness depending upon the carrier liquid and the ageing period. Rainfastness decreased in the order of Dim‐Cy‐C > Dim‐7N > Dim‐585 > Dim‐W. In contrast, the data on maple foliage indicated that the ageing of deposits increased the rainfastness of all the 4 end‐use mixtures. Dim‐585 was the most susceptible to rain washing, and rainfastness decreased in the order of Dim‐W > Dim‐Cy‐C > Dim‐7N > Dim‐585.     

Influence of surfactants and polymeric adjuvants on physicochemical properties, droplet size spectra and deposition of fenitrothion and Bacillus thuringiensis formulations under laboratory conditions

The effect of two surfactants and two polymeric adjuvants on droplet size spectra and deposition patterns of nine spray formulations was investigated following atomization in a laboratory chamber using a spinning disc atomizer that can produce a narrow droplet size spectrum. Spray droplets were sampled using Kromekote cards and deposit recoveries were examined on glass plates. Physicochemical properties studied were: viscosity-shear rate relationship, surface tension, volatility, pH, conductance, electrophoretic mobility and zeta potential. Formulations containing low surfactant concentrations provided Newtonian liquids with low viscosities. These liquids atomized into small droplets and provided low recoveries of spray deposits on sampling units. However, formulations containing polymeric adjuvants, and a high concentration of a non-ionic surfactant provided pseudoplastic liquids with high viscosities. These formulations resulted in large droplets with high recoveries of spray deposits on sampling units. Among the physicochemical properties studied, viscosity, surface tension, volatility and electrophoretic mobility, played important roles on liquid atomization and droplet deposition.     

Deposition of aerially sprayed mexacarbate on balsam fir canopy and the forest floor: Relevance to ULV applications

Abstract

Spray deposit patterns were measured on aluminum coils and live balsam fir needles at different canopy heights, following aerial application of mexacarbate (4‐dimethylamino‐3,5‐xylyl N‐methylcarbamate) over a conifer forest in New Brunswick. Droplet size spectra of the spray cloud were determined on cylindrical Kromekote® cards placed at the corresponding crown heights. Ground deposits were collected on cylindrical Kromekote cards, aluminum coils and natural balsam fir foliage placed In forest clearings and under different types of vegetation.

Canopy deposits decreased progressively from the top to the bottom level of the tree crown. This trend was observed on aluminum coils, live fir foliage, and Kromekote cards. Droplet size spectra were similar at all sampling heights of the tree crown, and were comparable to those obtained on the ground cards placed in the forest clearings. Deposits of mexacarbate obtained on ground samplers on the open forest floor were markedly lower than those found at the top canopy but were similar to those at the mid or bottom canopy level. Droplet size spectra and mexacarbate deposits obtained on samplers placed under different types of forest vegetation indicated a selective filtration of the large droplets present in the spray cloud by plant canopies.     

An improved method to study the impact of pesticide sprays on small song birds

Abstract

Four test groups of small songbirds (Zebra Finch, Poephila guttata) were sprayed in a chamber with varying concentrations of fenitrothion. Exposure levels were assessed by monitoring air concentrations, deposits of the active ingredient (AI) on glass plates and droplets/cm² on Kromekote® cards. All indices of exposure were linearly correlated and the mean AI deposit on glass plates for the four groups tested were equivalent to 38, 51, 139 and 255 g/ha or 14%, 18%, 50% and 91% of the highest permissible emitted rate for broadscale forest spraying in Canada. Significant depression in body weights and brain acetylcholinesterase levels were noted only for the highest exposure group. Fenitrothion residues in blood were detectable only at the highest exposure level, and in liver at the two higher levels. Carcass and feather residues were much higher than those in blood and liver, and were detectable at all exposure levels but the residues did not increase linearly with exposure. For one of the spray groups, we were able to compute an equivalent acute oral dose based on matching acetylcholinesterase inhibition.     

Droplet size spectra and deposits of two aerially sprayed Bacillus thuringiensis formulations on artificial samplers and live foliage

Abstract

Two commercial formulations of Bacillus thuringiensis var. kurstaki (BTK), Foray^® 48B and Thuricide^® 48LV, were applied aerially over nine spray blocks in a hardwood forest in West Virginia in 1991. Droplet spectra and spray mass deposits were determined using water‐sensitive paper strips (WSPS), glass micro‐fiber filters (GMFFs), glass plates and castor oil. Mass deposits of BTK were also assessed on natural foliage by two bioassay methods, i.e., feeding of homogenized foliage containing a starch‐sucrose solution and force‐feeding bioassay of foliar extracts containing re‐dissolved protein precipitate. Deposits on canopy foliage and ground samplers were also assessed by total protein assay and enzyme‐linked immunosorbent assay (ELISA). Droplet spectra on the WSPS were different from those on castor oil. Droplets on horizontal ground WSPS were larger than those on vertical ground WSPS. WSPS placed at canopy level collected more droplets than those at ground level. The total protein deposits (ng/cm²) were consistently higher on all blocks than the delta‐endotoxin protein deposits. Spray mass recovery on the ground samplers were low, and ranged from 2.9 to 8.0% of the applied rates.     

Assessment of aerial spray deposits in a spruce forest using in‐flight microencapsulation technique

Abstract

Spray drops were counted and sized on Kromekote® cards at ground level, and on spruce foliage at canopy level, after aerial application of a formulation containing a microencapsulation medium, over a spruce forest in Ontario. The majority of drops (70%) on foliage was 20 ‐ 75 µm range. A coarse drop size spectrum was observed on cards with a maximum diameter (Dmax) of 380 µm, and with 85% of the drops = 130 µm in diameter. Foliar drop analysis, on the other hand, indicated a finer spectrum with a Dmax of 150 µm, and with 85% of the drops = 75 µm. These results were explained on the basis of formulation ingredients, atomizer setting, weather factors, and drop retention on target surfaces. The assessment of spray deposits on glass plates at ground level indicated that about 16% of the applied spray volume reached the forest floor, a value which is comparable to those obtained in previous forestry applications using the ultra‐low‐volume (ULV) technique.     

Efficiency of deposition of pesticide droplets on flat cards and spheres

Abstract

The mass flux of a cloud of droplets heading towards a collector can be decomposed into its horizontal and vertical components. While only the vertical mass flux contributes to droplet deposition on a flat card by the mechanism of sedimentation, both flux components contribute to deposition on a sphere by both mechanisms of inertial impaction and sedimentation. Calculated collection efficiencies decrease as wind speed increases for cards but as wind speed increases for spheres, a minimum collection efficiency is reached at a certain wind speed. The average collection efficiencies, as measured in the field trial portion of this study, are highly linearly correlated with wind speed for cards. For spheres, however, no correlation was found between the average collection efficiency and wind speed.     

Metabolism of gamma‐hexachlorocyclohexah (HCH) in vivo. Metabolism of orally administered gamma‐2,3,4,5,6‐pentachlorocyclohexen (PCCH)

Abstract

Mexacarbate (4‐dimethylamino‐3,5‐xylyl N‐methylcarbamate) insecticide has potential for use in spruce budworm (Choristoneura fumiferana Clem.) control operations in Canada. Its persistence and fate in balsam fir (Abies balsamea (L.) Mill.), litter and soil samples were studied by spraying aerially oil‐based and water‐based formulations, each at 70 g A.I./ha over a coniferous forest near Bathurst, New Brunswick. The oil‐based formulation gave the maximum concentration of the chemical in the substrates studied. In fir needles, the highest concentrations observed were 0.51 ppm and 0.19 ppm (fresh weight) for the oil‐based and emulsion formulations respectively, 1 h after application. The residue levels decreased very rapidly with a half‐life of approximately 5 h. Three and eight days after the spray application of the emulsion and oil formulations respectively, the concentrations of mexacarbate in foliage decreased to trace levels ( 0.008 ppm). Only very low levels of residue were detected in litter and soil. The peak concentrations for the two formulations ranged from 0.02 to 0.11 ppm (fresh weight) in litter and from 0.01 to 0.06 ppm (fresh weight) in soil. The residue levels in both litter and soil decreased to below the detection limit (0.005 ppm) within 1 d. The ground deposit levels found on glass plates and the droplet density and size spectra measured on Kromekote® cards reflected the variations in concentrations found in fir needles, litter and soil samples and correlated with the observed maximum concentrations in them. Under the stipulated use pattern, mexacarbate concentrations found in the terrestrial components studied were low and are not likely to have any undue adverse effects on non‐target species.     

Effect of fatty acids and oils on photodegradation of azadirachtin‐A

Abstract

Azadirachtin‐A on exposure to UV‐light (254 nm) as a thin film on glass surface gave a isomerised (Z)‐2‐ methylbut‐2‐enoate product. Half‐life of azadirachtin‐A as thin film under UV light was found to be 48 min. Azadirachtin ‐A was irradiated along with saturated and unsaturated fatty acids, and fatty oils under ultra‐violet light as thin film. Saturated fatty acid increased the rate of photodegradation of azadirachtin‐A, whereas unsaturated fatty acids such as oleic, linoleic and elaidic acid reduced the rate of degradation. Castor, linseed and olive oil accelerated the rate of degradation, whereas neem oil showed no or little change in the rate of degradation of azadirachtin‐A. None of these fatty acids and fatty oils were effective in controlling the rate of degradation of azadirachtin‐A under UV‐light as thin film.     

Effect of in vitro administered 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) on DNA-binding activities of nuclear transcription factors in NIH-3T3 mouse fibroblasts

Abstract

Most modern pesticides are expensive. Application of excessive dosage rates is likely to cause undesirable biological side‐effects and is economically wasteful. Non‐uniform distribution of the spray cloud, or application at the wrong time, may result in failure to control the pest. It is the responsibility of the field operator to acquire sufficient knowledge and skill to ensure proper use of the control agents, to increase efficiency of their usage and to reduce unwanted side‐effects. To achieve this goal, he must take into consideration the various physical factors that govern field performance of pesticides.

A simple relationship exists between the spray volume and emission rate used, and droplet size produced. The use of extremely low spray volumes (i.e., those less than 2.0 litre per ha) for forest insect control in Canada, as opposed to higher volumes used in agriculture, necessitates the release of fine droplets (ranging from 20 to 70 μm in diameter) to obtain adequate coverage of the target area. These droplets take a long time to sediment downwards, evaporate in‐flight, become smaller in size and/or form powdery residues, thus contributing to off‐target drift and impaired droplet adhesion to target surfaces. Physical factors such as rain washing, degradation by sunlight and erosion by wind also influence the longevity of pesticide deposits on foliage which is crucial during the critical period of pest control.

Factors affecting the mode of entry into insects are related to the type of ingredients used in formulation. If a pesticide acts via crawling contact, formulations which would provide surface deposits would be more beneficial than emulsions or oil‐based mixes which tend to undergo penetration into foliar cuticle. Physical factors that affect field performance of a pesticide tank mix are related to phase separation and ‘breakdown of emulsions’ in the application equipment; ‘agglomeration and caking’ of wettable powder dispersions at the bottom of the tank; impaired flow behaviour of highly viscous formulations; and coarse atomization of high‐viscosity tank mixes leading to poor target cover.     

Determination of pendimethalin (PROWL®480 EC) spray drift from ground applications

Abstract

Pendimethalin herbicide (PROWL^®480 EC) spray drift was determined from ground applications representing the highest rate applied to corn in eastern Canada. A novel drift collector pattern was laid out on the ground immediately before herbicide application. Most of the drift collectors were located downwind of the application target area. The maximum labelled rate of 1.68 kg ai/Ha was applied on 2 occasions on separate sites. In both applications, drift collector cards indicated that concentrations of pendimethalin were not detectable outside the target zone (<0.01 μg/cm²) at or beyond the 10 metre drift collector stations. Risk assessment calculations indicated that non‐target organisms would not be at significant risk from off‐site movement of pendimethalin.     

Persistence of Bacillus thuringiensis deposits in a hardwood forest,after aerial application of a commercial formulation at two dosage rates

Abstract

A commercial formulation of Bacillus thuringiensis Berliner var. kurstaki (BTK), Foray® 48B, was sprayed aerially over four blocks B13, B14, B15A and B15B in an oak forest in Wayne County, Pennsylvania during May 1990. B13 and B14 were sprayed at 75 billion international units (BIU) in 5.91 litres/ha and the other two at 50 BIU in 3.94 litres/ha. Oak foliage was collected at different intervals of time after treatment. Three types of bioassays were conducted against fourth instar gypsy moth larvae, viz., direct feeding of sprayed foliage, feeding on diet containing homogenized foliage, and force‐feeding of foliar extracts. Larval mortalities were converted into international units of BTK activity per unit area (IU/cm²) of foliage. Foliar extracts were also subjected to enzyme‐linked immunosorbent assay (ELISA) to determine the concentration of delta‐endotoxin protein. Regardless of the type of bioassay used, bioactivity of BTK persisted in foliage for about a week in all the blocks. The half‐life of inactivation, DT₅₀, ranged from ca 12 to 22 h. The immunoassay data indicated a shorter duration of persistence (i.e., about 2 d) of the delta‐endotoxin protein, with DT₅₀ values ranging from 10 to 15 h. Formulation ingredients present in Foray 48B played a role in the toxicity of BTK to gypsy moth larvae.     

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.     

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.     

Effect of tracer dyes on initial deposits and persistence of bacillus thuringiensis subsp. kurstaki toxin after application of two commercial formulations onto spruce trees

Abstract

The effect of two tracer dyes [Erio Acid Red (EAR) and Acid Black 48 (AB‐48)] on initial deposits and persistence of Bacillus thuringiensis subsp. kurstaki (Btk) toxin (delta‐endotoxin) was studied after spraying two commercial formulations, Foray® 48B and Foray® 76B, over potted white spruce [Picea glauca (Moench) Voss] seedlings, at a dosage rate of 30 billion international units (BIU) per ha. Spray was applied using a spinning disc atomizer calibrated to deliver droplet sizes similar to those utilized in ultra‐low‐volume (ULV) treatments in operational insect control programs. The sprayed seedlings were left outdoors at the Sault Ste. Marie laboratory for 18 days under natural conditions of sunlight, wind and rainfall. Initial deposits and persistence of delta‐endotoxin protein in spruce foliage were determined by immunoassay [enzyme linked immunosorbent assay (ELISA)] quantification of the delta‐endotoxin. The total protein (inactive plus active) and delta‐endotoxin (active protein) concentrations in the two formulations were determined by a gravimetric procedure and by ELISA respectively.

The initial deposit levels of the toxin on foliage were not markedly affected by the addition of either of the two tracer dyes, and showed only a narrow range of 1521 to 1625 ng/g foliage (fresh weight) for Foray 48B, and 1789 to 2056 ng/g for Foray 76B. However, the persistence of the toxin was significantly influenced by the presence of the dyes. The toxin persisted in foliage only for 7 d post‐spray When the EAR dye was added to Foray 48B, compared to 10 d when no dye was added. The average half‐life (DT₅₀) of disappearance was 17.4 h for Foray 48B with EAR, and 20.9 h when no dye was present. In contrast, the situation was reversed in Foray 76B, since the duration of persistence was 10 d when EAR was added to Foray 76B, compared to 7 d when no dye was added. The average DT₅₀ was 27.9 h for Foray 76B with EAR, and 22.2 h without the dye. Persistence was the longest (14 d) when the AB‐48 dye was added to Foray 76B, and the DT₅₀ was 44.9 h.     

A Simple Model for SO2 Removal in the Duct Injection Process

Abstract

In the In-Duct Injection Process, a lime slurry is sprayed into the flue gas between the air preheater and solids collection equipment, and about 30-60 percent removal of SO₂ is achieved. A simple model of this process has been developed based on heat and mass transfer theories, and this model was fitted to the data obtained at proof-of-concept test units. Data taken with separate injection of dry lime and water were also modeled, but the SO₂ removal was less than for slurry injection, probably because of incomplete capture of lime particles by the water droplets.