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.     

Physical properties,droplet spectra and deposits of oils used in pesticide sprays

Abstract

The influence of liquid properties on spray atomization and deposition characteristics was studied using two oils of different viscosities and volatilities. For a given volume of oil sprayed, insecticide diluent 585 (ID 585), a petroleum distillate of low viscosity and high volatility, provided numerous small droplets on Kromekote^® cards. However, volume of oil deposited was low. For the same volume of oil sprayed, Sun‐spray® 6N, a non‐volatile paraffinic oil of high viscosity provided fewer but larger droplets, and consequently, the volume of oil deposited was much higher on the cards. These observations are explained on the basis of viscosities and volatilities of the two oils.     

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.     

Influence of adjuvants on physicochemical properties, droplet size spectra and deposit patterns: relevance in pesticide applications

The influence of adjuvants on physicochemical properties, droplet size spectra and deposit patterns of five aqueous spray mixtures was studied under laboratory conditions, using two surfactants, Atlox 3409F and Triton X-114; two humectants, propylene glycol and glycerol; and one polymeric adjuvant, Agrisol FL-100F. For the sake of comparison, two fenitrothion formulations containing polymeric adjuvants, and water were also included in the study. Spray was applied at 25 degrees C and 75 +/- 5% relative humidity, in an enclosure using a twin fluid atomizer. Deposits were collected on Kromekote card/glass plate units. Physicochemical properties studied were: relative viscosity, surface tension, apparent viscosity-shear rate relationship, volatility, pH and conductance. The first four of these properties played significant roles on the droplet and deposit patterns on sampling units. However, the chemical nature of the adjuvants also played some role. Between the two surfactants tested, Triton X-114 provided a pseudoplastic medium, but both surfactant solutions provided similar droplet size spectra and deposit patterns. Between the two humectants, glycerol proved to be more advantageous than propylene glycol. The polymeric adjuvant provided droplet sizes similar to those of the two surfactants, although the recovery of the applied spray volume was higher. Among the two fenitrothion formulations, the one containing lower amounts of polymeric adjuvants showed some advantages, although deposits on the actual biological target should be examined before any definite conclusions can be drawn on the optimum adjuvant concentrations in end-use formulations.     

Residue levels of fenitrothion and aminocarb in the air samples collected from experimental spray blocks in New Brunswick in 1982

Abstract

Fenitrothion and aminocarb formulations were aerially sprayed over mixed coniferous forests near Fredericton and Bathurst, New Brunswick, Canada. Insecticide concentrations inside the spray blocks were measured at intervals of time by trapping the airborne toxicants in a fritted‐glass bubbler containing dimethylformamide (DMF). The residues in DMF were analysed by gas chromatography. Concentrations of the insecticides in the air sampled decreased rapidly with time from peak levels of 1997 ng/m³ (fenitrothion) and 1201 ng/m³ (aminocarb). Concentrations of the two insecticides in the air samplers were dependent upon the nature of the chemicals, type of formulation used, spray timings and other environmental factors.     

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.     

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.     

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.     

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

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 with 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.     

Simultaneous determination of fenitrothion and aminocarb in blueberry foliage and fruits: Application to the analysis of residues in field samples

Abstract

Samples of blueberry foliage and fruits were collected from spray blocks in Ontario after aerial application of fenitrothion and aminocarb at dosage rates of 210 g active ingredient (AI)/ha and 70 g AI/ha respectively. Residues were extracted from the samples by homogenizing with ethyl acetate, cleaned up by microcolumn chromatography using alumina as adsorbent, and analyzed by GLC‐AFID with a glass column packed with 1.5% OV‐17 and 1.95% OV‐210 on 80–100 mesh Chromosorb W‐HP. Average recoveries for fenitrothion and aminocarb from foliage at three fortification levels (1.0, 0.10 and 0.01 ppm) were respectively 99 and 96%. The corresponding values for the fruits were 99 and 95%. Foliage samples collected 1 h post‐spray contained on average 1.13 ppm of fe‐nitrothion and 1.14 ppm of aminocarb. However, residue levels reached below the detection limit (<0.01 ppm) in foliage collected 15 d after treatment. In addition, the fruit samples collected after 15 d post‐spray contained extremely low levels (0.03 ppm for fenitrothion and 0.02 ppm for aminocarb) of residues, and were barely above the detection limit.     

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.     

Foliar and ground deposits of fenitrothion following aerial application over a plantation forest

Abstract

Spray deposits were measured on spruce foliage at tree canopy level and on glass plates at ground level, after aerial application of an emulsion formulation of fenitrothion at the rate of 0.21 kg AI in 1.46 L per ha over a 16 ha plot in a plantation forest. Fenitrothion deposits were quantified by gas‐liquid chromatography. A wide variation was observed in deposits on foliage and at the forest floor. Deposits were relatively higher on foliar samples collected from the upwind side of a tree canopy than those on the downwind side. Similarly, the glass plate placed under a tree on the upwind side received relatively higher deposit than the one on the downwind side. However, the glass plates placed in the adjacent forest openings collected markedly higher deposits. Results clearly indicate filtration of the spray droplets by canopy foliage. Assessment of the average deposit of fenitrothion at ground level (mean deposit from all sampling locations) indicated that ca. 19.4% of the applied material reached the forest floor. Within a sampling station, correlation was poor between foliar depsits and those on glass plates under the same trees or in nearby clearings. Analysis of fenitrothion deposits on foliage collected at 1 and 2 h after application indicated that the droplets took, more than 1 h for deposition on the tree canopy. On the other hand, deposition on the glass plates at ground level appeared to be practically complete within 1 h post‐treatment. This was attributed to the higher sedimentation velocities of the larger droplets which tend to travel faster to the floor level than the smaller droplets which float for a longer period near the tree canopy.     

Distribution and persistence of aminocarb in stream water, sediment and fish after application of three Matacil formulations

Three aminocarb formulations, water-based Matacil 180F, oil-based Matacil 180F and oil-based Matacil 180D, were applied separately to the surface of a stream at 2.40 g a.i./min for 5 minutes. The highest aminocarb concentration in the top 1 cm of water was found 5 min after application of oil-based 180F (5000 ppb). The next highest concentration was 1862 ppb found in the top 1 cm layer of water 3 min after application of oil-based 180D, followed by 1306 ppb found 5 min after application of water-based 180F. Residue accumulations were first observed in sediment at 3 min and in fish tissues 0.5 h after application. The levels of accumulation were in the order of water-based 180F greater than oil-based 180F greater than oil-based 180-D. After the application of water-based 180F, the highest concentrations were 20.2 ppb in sediment after 5 min and 127 ppb in fish tissues after 3 h. Residues disappeared rapidly from all three matrices and could not be detected after a period of 3-25 h.     

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.     

Residue and bio-efficacy evaluation of controlled release formulations of imidacloprid against pests in soybean (Glycine max)

Controlled release (CR) formulations of imidacloprid (1-(6 chloro-3-pyridinyl methyl)-N- nitro imidazolidin-2- ylideneamine) were prepared using novel amphiphilic polymers synthesized from polyethylene glycol and aliphatic diacids employing encapsulation technique. The bioefficacy of the prepared CR formulations was evaluated against major pests of soybean, namely stem fly, Melanagromyza sojae Zehntmer and white fly, Bemisia tabaci Gennadius along with a commercial formulation at the experimental farm of Indian Agricultural Research Institute (IARI), New Delhi during kharif 2009 and 2010. Most of the CR formulations of imidacloprid gave significantly better control of the pests compare to its commercial formulations, however the CR formulations, Poly [poly (oxyethylene-1000)-oxy suberoyl] amphiphilic polymer based formulation performed better over others for controlling of both stem fly incidence and Yellow Mosaic Virus (YMV) infestation transmitted by white fly. Some of the developed CR formulations recorded higher yield over commercial formulation and control. Nodulation pattern of soybean was not affected due to treatment of CR and commercial formulations of imidacloprid. Also the residues of imidacloprid in seed and soil at harvest were not detectable for both CR and commercial formulations.     

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.     

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.     

Chitosan/glyphosate formulation as a potential,environmental friendly herbicide with prolonged activity

Although there are many reports on the dangers posed by glyphosate, this herbicide is still one of the most popular and widely used total weed killers. Therefore, great effort should be made to minimize exposure to this herbicide and limit its losses into the environment. The aim of this study was to prepare a new formulation consisted of various molecular weight chitosans with glyphosate and their evaluation toward active substance release, phytotoxicity, and preliminary herbicidal efficiency. The phytotoxicity study of the obtained chitosan/glyphosate formulations was determined based on the Organisation for Economic Co-operation and Development 208 guideline. Among all tested formulations evaluated for phytotoxicity, that containing the highest molecular weight of chitosan was found to be the least toxic, showing simultaneously the most effective herbicidal activity against selected weeds. The release rate of glyphosate from the obtained formulations was dependent on the molecular weight and viscosity of chitosan.     

Persistence of granular and EC formulations of chlorpyrifos in a mineral and an organic soil incubated in open and closed containers

Abstract

Samples of a mineral soil (Plainfield sand) and an organic soil (muck) were treated with granular and EC formulations of chlorpyrifos and incubated at 27±1°C and 65±5% RH in open and closed containers. Duplicate samples of each soil‐formulation‐container combination were analyzed for residual chlorpyrifos during a 23 wk period. The disappearance rates observed demonstrate that the relative importance of formulation and containment on overall persistence depends on soil type. For the mineral soil, disappearance was slower from closed containers and formulation had only a slight effect while, in the organic soil the granular formulation disappeared slower than the EC and there was little difference between open and closed containers. The relative importance of degradation and volatilization in the disappearance of chlorpyrifos from soil is discussed.     

Controlled release formulations of metribuzin: Release kinetics in water and soil

Controlled release (CR) formulations of metribuzin in Polyvinyl chloride [(PVC) (emulsion)], carboxy methyl cellulose (CMC), and carboxy methyl cellulose-kaolinite composite (CMC-KAO), are reported. Kinetics of its release in water and soil was studied in comparison with the commercial formulation (75 DF). Metribuzin from the commercial formulation became non-detectable after 35 days whereas it attained maxima between 35–49 days and became non-detectable after 63 days in the developed products. Amongst the CR formulations, the release in both water and soil was the fastest in CMC and slowest in PVC. The CMC-KAO composite reduced the rate of release as compared to CMC alone. The diffusion exponent (n value) of metribuzin in water and soil ranged from 0.515 to 0.745 and 0.662 to 1.296, respectively in the various formulations. The release was diffusion controlled with half release time (t_1/2) from different controlled release matrices of 12.98 to 47.63 days in water and 16.90 to 51.79 days in soil. It was 3.25 and 4.66 days, respectively in the commercial formulation. The period of optimum availability of metribuzin in water and soil from controlled released formulations ranged from 15.09 to 31.68 and 17.99 to 34.72 days as against 5.03 and 8.80 days in the commercial formulation.