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.     

Pesticide distribution in an agricultural environment in Argentina

An assessment of the off-site migration of pesticides from agricultural activity into the environment in the Neuquen River Valley was performed. The aim of this study was to evaluate the distribution of pesticides in several compartments of a small agricultural sub-catchment. Soil, surface water, shallow groundwater and drift deposition were analyzed for pesticide residues. Results showed the presence of some pesticide residues in soil, surface water and shallow groundwater compartments. The highest detection frequencies in water (surface and subsurface) were found for azinphos-methyl and chlorpyrifos (>70%). In terms of concentration, the highest levels were observed in shallow groundwater for azinphos methyl (22.5 μg/L) and carbaryl (45.7 μg/L). In the soil, even before the application period had started, accumulation of residues was present. These residues increased during the period studied. Spray drift during pesticide application was found to be a significant pathway for the migration of pesticide residues in surface water, while leaching and preferential flows were the main transport routes contributing to subsurface contamination.     

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.     

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.     

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.     

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.     

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.     

A simple empirical model to predict forest insecticide ground-level deposition from a compendium of field data

Deposit data from 205 aerial forest insecticide applications conducted in field trials by the Canadian Forest Service, Great Lakes Forestry Centre over a 15-year period are summarized. Deposit measurements were taken under “worst case” scenarios in the sense that direct applications were made over water bodies, and ground samplers were intentionally placed in open or cleared areas of forest. The median % deposit on shoreline collectors (32 separate applications) was 5.7%, on mid-stream collectors (44 separate applications) was 6.2%, and on forest floor collectors (129 separate applications) was 4.9%. Forest floor deposit was most closely associated with application rate and droplet size (r = 0.624, p < 0.001 and r = 0.662, p = 0.011, respectively) but these variables combined only explained 44% of the variation in deposit. Data from all three collector types were grouped by 10% deposit increments and combined to provide a data set from all deposition scenarios. A negative exponential model was fitted to the proportion of these combined sites regressed on % deposit in 10% increments and plotted as a deposit probability distribution curve (p < 0.001, r² = 0.992). The probability distribution curve indicated that 5–10% deposit would be expected about 57–91% of the time, whereas 50% deposit or greater would be expected about 2% of the time or less. In a probabilistic risk assessment for aerially applied insecticides in a conifer-dominated forest environment, the probability distribution curve based on empirical data presented here can be used to refine the characterization of exposure scenarios from which effects estimates can be derived.     

A chemical residue survey in relation to the 1930 spruce budworm spray program in New Brunswick (Canada)

Abstract

This paper describes the results from a pesticide residue survey conducted in relation to the 1980 spraying of insecticides in New Brunswick (Canada) to preserve the coniferous forest from an on‐going spruce buciworm infestation. A total of 465 water and air samples were collected from 12 sites throughout the Province.

In water, fenitrothion was usually detected at about the same time that spraying occurred in the immediate area of the sites. The maximum that was ever detected was 2 0.0 ppb and persistence was usually United to a few days except in a small pond where fenitrothion was detected for a total of 18 consecutive days. Aminofenitrothion was also detected at a maximum of 8.0 ppb.

Fenitrothion was only detected occasionally in air samples the maximum being 1.2 ng/dm³. However, aminofenitrothion was present in several air samples at c. maximum of 12.0 ng/dm ³.     

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.     

Environmental scanning electron microscopy as a new technique to determine the hygroscopic behaviour of individual aerosol particles

The hygroscopic behaviour of NaCl, (NH₄)₂SO₄, Na₂SO₄ and NH₄NO₃ particles in the size range of 0.1–20 μm was studied by environmental scanning electron microscopy (ESEM). This technique allows the in-situ observation of individual aerosol particles while changing the temperature and/or relative humidity (RH) in the sample chamber. The hygroscopic behaviour of these particles (e.g., deliquescence, adsorption of water on the particle surface) becomes directly observable with a lateral resolution of the order of 8–15 nm. The deliquescence relative humidities (DRH) of the different salts, the temperature dependence of the DRH for NH₄NO₃, and the growth factors (at increasing relative humidities) for NaCl were determined. Generally, a good agreement between the values obtained by ESEM and those found in literature was achieved. However, the DRH of NaCl determined by ESEM is systematically higher (approximately 2%, absolute) than the values obtained by other techniques, which can be explained by the observed strong absorption of water onto the crystal surface prior to droplet formation. The efflorescence behaviour of individual particles can be studied only qualitatively due to influences of the sample substrate. Furthermore, it is demonstrated that the activation of soot can be studied at high resolution by ESEM.     

The chemistry and behaviour of antimony in the soil environment with comparisons to arsenic: A critical review

This article provides a critical review of the environmental chemistry of inorganic antimony (Sb) in soils, comparing and contrasting findings with those of arsenic (As). Characteristics of the Sb soil system are reviewed, with an emphasis on speciation, sorption and phase associations, identifying differences between Sb and As behaviour. Knowledge gaps in environmentally relevant Sb data for soils are identified and discussed in terms of the limitations this imposes on understanding the fate, behaviour and risks associated with Sb in environmental soil systems, with particular reference to mobility and bioavailability.     

Influence of thermally activated paper sludge on the behaviour of blended cements subjected to saline and non-saline environments

Background, aim and scope  One of the problems to affect Portland cement matrices is low resistance to aggressive agents, due principally to the presence of a high content of portlandite in the hydrated cements. Pozzolanic materials have played an important role in the improving the durability of cement-based materials for decades. This work studies the behaviour of cement mortar matrices blended with 10% calcined paper sludge (source for metakaolinite) and exposed to different environmental conditions (saline and non-saline environments) after 6 and 12 months of exposure. Materials and methods  Two cements were studied: an ordinary Portland cement (CEM 1, 42.5R), acting as reference cement, and a blended cement formulated by mixing 90% (by mass) of CEM 1, 42.5R with 10% (by mass) of paper sludge calcined at 700°C for 2 h. The specimens were exposed 1 year to saline and non-saline environments. All the mineralogy samples were studied through X-ray diffraction and scanning electron microscopy (SEM) equipped with an energy dispersive X-ray analyser. The in-depth study on ionic mobility was performed on samples subjected to natural exposure (coast and tableland) for 6 and 12 months. Results  Portland cement was composed of quartz, calcite, calcium hydroxide and tobermorite gels. The pozzolanic cement (10% calcined paper sludge) is of the same composition but a high calcite concentration and barium carbonate. SEM analysis from coastline show deposits of variable composition. The deposits are identified on the surface of different mineral components. The minerals from tableland are much fractured, i.e. calcite and feldspars. Inside the fractures, the deposits and the ions are located and trapped superficially. Discussion  SEM analysis of control cement Portland and 10% calcined paper sludge shows deposits on quartz and calcite with a very high concentration of Pb, Zn, Cl and barium sulphate. A very porous aspect is due to the presence of the different aggregate types. This porous configuration permits retention of the ion environment. The pozzolanic cement in environments subject to the saline mist favours the retention and transport of ions observed. Something similar also happens with the increase in exposure to outdoor weather. Non-saline samples show temperature changes (ice or thaw cycles). Barium retention is kept on the surface in fracture lines by the gelification processes. In general, it may be inferred that an increase in exposure time increases the diffusion of ions towards test piece interiors. The chemical composition profiles show that the ions present different penetration speeds. Conclusions  The results indicate the better vulnerability of pozzolanic cements from calcined paper sludge in saline and non-saline environments. The cements with a 10% addition of calcined paper sludge favour retention and transport of ion has been observed. Recommendations and perspectives  Today, projects are centred on a new recycling line for industrial waste of this kind, with special attention on its incorporation in cement manufacture as a pozzolanic material, setting the most appropriate activation conditions of the mineralogical compound in this waste (kaolinite and metakaolinite) and taking them as a starting point for this project. The use of pozzolanic cement with 10% addition of calcined paper sludge is a system which favours ionic retention.     

Acute effects of copper and mercury on the estuarine fish Pomatoschistus microps: Linking biomarkers to behaviour

The main objective of the present study was to investigate possible links between biomarkers and swimming performance in the estuarine fish Pomatoschistus microps acutely exposed to metals (copper and mercury). In independent bioassays, P. microps juveniles were individually exposed for 96 h to sub-lethal concentrations of copper or mercury. At the end of the assays, swimming performance of fish was measured using a device specially developed for epibenthic fish (SPEDE). Furthermore, the following biomarkers were measured: lipid peroxidation (LPO) and the activity of the enzymes acetylcholinesterase (AChE), lactate dehydrogenase (LDH), glutathione S-transferases (GST), 7-ethoxyresorufin-O-deethylase (EROD), superoxide dismutase (SOD), catalase (CAT), glutathione reductase (GR) and glutathione peroxidase (GPx). LC₅₀s of copper and mercury (dissolved throughout metal concentrations) at 96 h were 568 μg L⁻¹ and 62 μg L⁻¹, respectively. Significant and concentration-dependent effects of both metals on swimming resistance and covered distance against water flow were found at concentrations equal or higher than 50 μg L⁻¹ for copper and 3 μg L⁻¹ for mercury (dissolved throughout metal concentrations). These results indicate that SPEDE was efficacious to quantify behavioural alterations in the epibenthic fish P. microps at ecologically relevant concentrations. Significant alterations by both metals on biomarkers were found including: inhibition of AChE and EROD activities, induction of LDH, GST and anti-oxidant enzymes, and increased LPO levels, with LOEC values ranging from 25 to 200 μg L⁻¹ for copper and from 3 to 25 μg L⁻¹ for mercury (dissolved throughout metal concentrations). Furthermore, significant and positive correlations were found between some biomarkers (AChE and EROD) and behavioural parameters, while negative correlations were found for others (LPO, anti-oxidant enzymes and LDH) suggesting that disruption of cholinergic function through AChE inhibition, decreased detoxification capability due to EROD inhibition, additional energetic demands to face chemical stress, and oxidative stress and damage may contribute to decrease the swimming performance of fish. Since a reduced swimming capability of fish may reduce their ability to capture preys, avoid predators, and interfere with social and reproductive behaviour, the exposure of P. microps to copper and/or mercury concentrations similar to those tested here may decrease the fitness of wild populations of this species.     

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.     

Bioaccumulation behaviour of transplants of the lichen Flavoparmelia caperata in relation to total deposition at a polluted location in Portugal

This experiment compares the short and long time element accumulation behaviour of transplants of Flavoparmelia caperata lichen thalli and total deposition in an atmospheric polluted area. It was found that lichens exposed for a short time behaved differently from lichens in cumulative exposition suggesting the presence of acclimatization behaviour. The lichen transplant elemental content does not unequivocally represent the average or cumulative environmental availability of the exposure period. Reflection characteristics depend on the element and the lichen physiological conditions. Good correlations between lichen elemental contents and total deposition were obtained when a physiological lichen parameter was introduced in a mathematical model, suggesting that metabolically mediated accumulation is important.     

Avoidance behaviour of Eisenia fetida to carbofuran, chlorpyrifos, mancozeb and metamidophos in natural soils from the highlands of Colombia

Earthworm avoidance behaviour test is an important screening tool in soil eco-toxicology. This test has been developed and validated under North American and European conditions. However, little research has been performed on the avoidance test in the tropics. This work demonstrates the potential suitability of the avoidance behaviour test as screening method in the highlands of Colombia using Eisenia fetida as the bio-indicator species on contaminated soils with carbofuran and chlorpyrifos. Though for the two active ingredients 100% avoidance was not reached, a curve with six meaningful concentrations is provided. No significant avoidance behaviour trend was found for mancozeb and methamidophos. Tests were conducted in the field yielded similar results to the tests carried out in the laboratory for chlorpyrifos and mancozeb. However, for the case of carbofuran and methamidophos, differences of more than double in avoidance were obtained. Divergence might be explained by soil and temperature conditions.