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.     

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.     

Heavy metals and couple fecundity, the LIFE Study

The effect of heavy metals at environmentally relevant concentrations on couple fecundity has received limited study despite ubiquitous exposure. In 2005-2009, couples (n = 501) desiring pregnancy and discontinuing contraception were recruited and asked to complete interviews and to provide blood specimens for the quantification of cadmium (μg L⁻¹), lead (μg dL⁻¹) and mercury (μg L⁻¹) using inductively coupled plasma-mass spectrometry. Couples completed daily journals on lifestyle and intercourse along with menstruation and pregnancy testing for women. Couples were followed for 12 months or until pregnant. Fecundability odds ratios (FORs) and 95% confidence intervals (CIs) were estimated adjusting for age, body mass index, cotinine, and serum lipids in relation to female then male exposures. FORs <1 denote a longer time to pregnancy. In adjusted models, reduced FORs were observed for both female cadmium (0.78; 95% CI 0.63-0.97) and male lead (0.85; 95% CI 0.73-0.98) concentrations. When jointly modeling couples’ exposures, only male lead concentration significantly reduced the FOR (0.82; 95% CI 0.68, 0.97), though the FOR remained <1 for female cadmium (0.80; 95% CI 0.64, 1.00). This prospective couple based cohort with longitudinal capture of time to pregnancy is suggestive of cadmium and lead’s reproductive toxicity at environmentally relevant concentrations.     

Mathematical model for abrasive content estimation in a pulse-electroplated abrasive microtool

A mathematical model was developed to estimate the weight percent of diamond abrasive particles incorporated in nickel binder matrix during abrasive microtool fabrication by pulse-plating process. The proposed model is based on the hypothesis that, embedment of an inert micro abrasive diamond particle on the substrate will only occur when a few nickel ions from the adsorbed ionic cloud are chemically reduced at the cathode by hydrogen ions present in the diffusion layer. Experimental verification of the model developed was performed by pulse electroplating of diamond abrasive particles on tungsten micro tool shank using an in-house built experimental setup. The predictive model developed was found to estimate diamond abrasive content in nickel binder matrix within 1–7 wt% of experimental results for different pulse-plating conditions.     

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.     

Droplet trajectories and deposition with an airblast forestry sprayer

Abstract

The characteristics of the air pattern and spray droplet trajectories from the Algonquin airblast forestry sprayer were investigated. An experiment with water and Rhodamine tracer dye was conducted in a shelterwood location to evaluate droplet deposition on Kromekote^® card targets above and within a canopy of poplar saplings. Computer simulation of a free jet was used to model the airblast in order to investigate droplet trajectories. Measured deposits indicated that the effective swath width is 14 m from the blower outlet. Mean simulated droplet trajectory data were in good agreement with the droplet density data observed in the field. Both sets of results predicted a very low level of spray deposition beyond 14 m.     

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.     

Inhibition of brain AChE in brook trout by aminocarb and its toxic metabolites

In-vitro inhibitions of brain AChE in brook trout, Salvelinus fontinalis (Mitchill), by aminocarb (4-dimethylamino-m-tolyl N-methylcarbamate) and its toxic metabolites, MAA (4-methylamino-m-tolyl N-methylcarbamate), AA(4-amino-m-tolyl N-methylcarbamate), MFA (4-methylformamido-m-tolyl N-methylcarbamate) and FA (4-formamido-m-tolyl N-methylcarbamate) were investigated. The molar concentrations of inhibitors causing 50% inhibition (I50s) were AA (3.62 X 10(-6] less than MAA (7.92 X 10(-6] less than aminocarb (1.01 X 10(-5] less than MFA (4.29 X 10(-5] less than FA (7.11 X 10(-5]. After exposure of fish to various concentrations of aminocarb (25, 250 and 2500 ppb) and MAA (25, 250, 500 and 2500 ppb) at 9 degrees C in dechlorinated tap water for 96 h, inhibitions of brain AChE ranged from 13 to 77%. Mortality occurred only in fish exposed to 500 ppb (22%) and 2500 ppb (100%) of MAA. Enzyme activities recovered to the control levels 12 to 96 h after the fish had been transferred to clean water for clearing; in survivors of the 500-ppb MAA exposure, however, AChE activities decreased again thereafter.     

Adsorption behavior of RH‐5992 insecticide onto sandy and clay loam forest soils

Abstract

Adsorption‐desorption behavior of RH‐5992 [Mimic®, N'‐t‐butyl‐N'‐(3,5‐dimethylbenzoyl)‐N‐(4‐ethylbenzoyl) hydrazine] in sandy and clay loam forest soils was studied using the batch equilibrium method. Adsorption was higher in the clay loam soil than in the sandy loam, and increased linearly with RH‐5992 concentration, but decreased with increasing pH and temperature. The adsorption data fit better to the Freundlich, than to the Langmuir equation. The K_D (linear adsorption constant) and K_F (Freundlich constant) were similar for each soil at 5, 15 and 25°C and decreased with increase of temperature, indicating that the enthalpy of adsorption was negative. The exponent of the Freundlich equation was close to unity for both soils at all three temperatures. The low E_a (energy of activation) indicated a diffusion‐controlled process during the initial stages of adsorption. The desorption isotherm differed from that of adsorption, and the linear desorption constant, K_D(d), was ca 25 times higher than the K_D, indicating that adsorption of RH‐5992 was not readily reversible. Evaluation of thermo‐dynamic parameters confirmed the presence of strong bonds between the solute and soil. These findings suggest that RH‐5992 has a limited potential for downward mobility leading to groundwater contamination.