An impingement plate method to detect deposits of pyrethroid insecticides

A silica gel impingement plate for monitoring pyrethroid deposits in environmentally sensitive areas is described. The plate is simple, commercially available, and inexpensive. A residue analysis method is given for deltamethrin deposits with 83.3% mean recovery and a minimum quantifiable limit of 0.005 microgram/plate. Pyrethroid deposits are strongly adsorbed to the silica gel, which prevents wash-off by rainfall and slows photodegradation. In two field experiments, deltamethrin was readily detected 3 weeks after direct spray applications at 6 and 10 g ai/ha. Deltamethrin dissipation on the plates was first-order with a half-life of 2.9-3.7 d. Photoisomers of deltamethrin were also detected on the plates and the ratio of photoisomers to deltamethrin increased over time. This ratio will indicate the age of deposits in monitoring situations.     

Persistence of deltamethrin and cypermethrin on wheat and sweetclover

Abstract

Residues of cypermethrin and deltamethrin in wheat herbage and grain and deltamethrin in sweetclover herbage were determined. Cypermethrin was applied at 28 g/ha to wheat and the residues on the herbage declined exponentially from 3.74 ppm immediately after spraying to 0.20 ppm 27 days after spraying. No cypermethrin residues were detected in the grain. Deltamethrin was applied at 6 g/ha to wheat and the residues on the herbage declined exponentially from 0.70 ppm immediatly after spraying to 0.05 ppm 27 days after spraying. No deltamethrin residues were detected in the grain. Deltamethrin was applied to sweetclover at 3, 4, 5, 10, and 16 g/ha. Residues on the herbage declined exponentially from 0.10, 0.16, 0.22, 0.40 and 0.70 ppm immediatly after spraying to 0.02, 0.03, 0.04, 0.15 and 0.18 ppm 5 days after spraying, respectively.     

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.     

Decomposition of 14C-fenitrothion under the influence of UV and sunlight under tropical and subtropical conditions

The decomposition of (14)C-fenitrothion on silica gel chromatoplates as well as in polar and non polar solvents under sunlight and ultraviolet light was investigated, Its stability to sunlight on leaf surfaces of bean plants and on different surfaces (such as glass, quartz and plastic) was also determined. The main photoproducts were identified as carboxyfenitrothion, fenitrooxon, carboxyfenitrooxon and 3-methyl-4-nitrophenol and a small amount 3-caboxy-4-nitrophenol and methyl parathion. The addition of carbaryl and deltamethrin insecticides slightly accelerated the photodecomposition of fenitrothion on silica gel plates and in solution.     

Effects of deltamethrin on hepatic microsomal cytochrome p450‐dependent monooxygenases in carp

Abstract The in vivo effects of sublethal concentrations of deltamethrin (DM), a pyrethroid insecticide, on the hepatic microsomal cytochrome P450 (Cyt P450) content and the Cyt P450‐dependent monooxygenase activities (para‐nitrophenetole‐O‐deethylase, pNPOD; aminopyrene‐N‐demethylase, APND; ethylmorphine‐N‐demethylase, EMND; 7‐ethoxycoumarin‐O‐deethylase, ECOD; and ethoxyresorufin‐O‐deethylase, EROD) were examined in adult carp (Cyprinus carpió L.).

0.2 μg/1 DM treatment resulted in significant increases in APND, EMND and ECOD activities, whereas 2 μg/1 DM resulted in significant inhibitions of all studied isoenzyme activities with the exceptions of pNPOD and APND after 72 h. EROD was the only enzyme for which a slight increase in activity was observed. On repeated treatment, Cyt P450 could not be detected after 48 h, but the Cyt P420 level increased. All tested isoenzyme activities were inhibited, with the exception ofthat of EROD, which was enhanced.

All these changes in enzyme activities and Cyt P450 content demonstrate the effects of DM on fish. DM treatment at low concentration is presumed to cause induction of the Cyt P450‐dependent monooxygenases which may lead to faster metabolization of the insecticide. In contrast, DM at higher concentration strongly inhibited the activities of the studied enzymes. This finding may be due to the damaging effect of DM on the xenobiotic metabolizing enzyme systems offish.     

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.     

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.     

High affinity binding of 3H‐verapamil to rat brain synaptic membrane is antagonized by pyrethroid insecticides

Abstract

Deltamethrin is a powerful neuroactive agent causing increased neurotransmitter release at the synapse. To understand the cause for such an action of this pyrethroid insecticide, we have studied its binding characteristics to the calcium channel by utilizing ³H‐verapamil as a specific ligand. It was found that deltamethrin is capable of competing at the same binding site as ³H‐verapamil. Also, it was found that nonlabeled verapamil could reduce the binding of ³H‐deltamethrin (tested at 1 nM) to its binding site. The EC₅₀ value of verapamil to displace 50% of ³H‐deltamethrin was in the order of 0.3 μM, which coincides with the approximate K_D value for this ligand to bind with calcium channels in the rat brain synaptosomal plasma membranes.     

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.     

Toxic effects of deltamethrin and λ-cyhalothrin on Xenopus laevis tadpoles

This study evaluates the toxic effects of deltamethrin and λ-cyhalothrin on Xenopus laevis tadpoles after 168 h of exposure. The LC₅₀ of deltamethrin and λ-cyhalothrin at 168 h was calculated as the μg of active ingredient per liter (μg AI/L). According to these values, the LC₅₀ was 6.26 and 3.94 μg AI/L for deltamethrin and λ-cyhalothrin, respectively. Several enzymes were studied for early signs of intoxication following exposure to the pesticides for 24 h. Glutathione-S-transferase,carboxylesterase, and lactate dehydrogenase were inhibited by λ-cyhalothrin, and both pesticides inhibited acid phosphatase and aspartate aminotransferase. In contrast, acetylcholinesterase was activated by deltamethrin. The results suggest that X. laevis is sensitive to the pyrethroids that were tested, and the enzyme responses suggest that they are potential biomarkers for evaluating the toxic effect of pyrethroids on amphibians in environmental conditions.     

Behavior of atrazine in soils of tropical zone

Abstract

Movement and degradation of ¹⁴C‐atrazine (2‐chloro 4‐(ethylamino)‐6‐(isopropylamino)‐s‐triazine, was studied in undisturbed soil columns (0.50m length × 0.10m diameter) of Gley Humic and Deep Red Latosol from a maize crop region of Sao Paulo state, Brazil. Atrazine residues were largely confined to the 0–20cm layers over a 12 month period Atrazine degraded to the dealkylated metabolites deisopropylatrazine and deethylatrazine, but the major metabolite was hydroxyatrazine, mainly in the Gley Humic soil. Activity detected in the leachate was equivalent to an atrazine concentration of 0.08 to 0.11μg/1.

The persistence of ¹⁴C‐atrazine in a maize‐bean crop rotation was evaluated in lysimeters, using Gley Humic and Deep Red Latosol soils. Uptake of the radiocarbon by maize plants after 14‐days growth was equivalent to a herbicide concentration of 3.9μg/g fresh tissue and was similar in both soils. High atrazine degradation to hydroxyatrazine was detected by tic of maize extracts. After maize harvest, when beans were sown the Gley Humic soil contained an atrazine concentration of 0.29 μg/g soil and the Deep Red Latosol, 0.13 μg/g soil in the 0–30 cm layer. Activity detected in bean plants corresponded to a herbicide concentration of 0.26 (Gley Humic soil) and 0.32μg/g fresh tissue (Deep Red Latossol) after 14 days growth and 0.43 (Gley Humic soil) and 0.50 μg/g fresh tissue (Deep Red Latossol) after 97 days growth. Traces of activity equivalent to 0.06 and 0.02μg/g fresh tissue were detected in bean seeds at harvest. Non‐extractable (bound) residues in the soils at 235 days accounted for 66.6 to 75% (Gley Humic soil and Deep Red Latossol) of the total residual activity.     

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.     

Study of PCDD/Fs distribution in fly ash,ash deposits,and bottom ash from a medical waste incinerator in China

Over the past decades in China, the number of medical waste incinerators (MWIs) has been rising rapidly, causing emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). In this study, samples of fly ash, ash deposits, and bottom ash from typical MWIs were analyzed for PCDD/Fs and their distribution characteristics. Results showed international toxic equivalent (I-TEQ) values in the range of 6.9–67 ng I-TEQ/g in fly ash and ash deposits, whereas the concentration in bottom ash was extremely low (only 1.33 pg I-TEQ/g), yet the generation of PCDD/Fs was mostly de novo synthesis in fly ash and ash deposits according to the ratio of PCDFs to PCDDs; the major distribution differences of PCDD/Fs in fly ash was manifested by the content of toxic furan 2,3,7,8-TCDF, but other toxic PCDD/Fs showed similar distribution. Other findings are that 2,3,4,7,8-PeCDF had the most contribution to TEQ concentration, and that the most abundant toxic furan congener is 1,2,3,4,6,7,8-HpCDF. Correlation analysis showed that there was no significant correlation between PCDD/Fs concentration and several other physical and chemical parameters.

Implications: This paper is of interest because it presents the emission performances of PCDD/Fs in ash from medical waste incineration in China. PCDD/F contents in fly ash and ash deposits vary between 6.9 and 67.3 ng I-TEQ/g. However, the concentration in bottom ash was extremely low (only 1.33?×?10^?3 ng I-TEQ/g). The fingerprints of PCDD/Fs in fly ash are almost similar, except for 2,3,7,8-TCDF. There is no marked correlation between PCDD/Fs and other physicochemical properties.

Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association.     

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.     

Photostabilization of the botanical insecticide azadirachtin in the presence of lecithin as UV protectant

Abstract

The phytochemical insecticide, azadirachtin (AZ), undergoes UV‐induced photodegradation. Using the isomer AZ‐A as a standard, its photochemical stability was studied with and without adding lecithin surfactant as a UV protectant. Standard solutions of pure AZ‐A and Margosan‐O^® were prepared in methanol‐hexane with (AZ‐A:lecithin, 1:2 by weight) and without lecithin, applied separately onto glass plates and maple (Acer L.) foliage and exposed to radiant energy under controlled conditions. Noticeable photostabilization of AZ‐A was achieved in the samples containing lecithin compared to AZ‐A samples without the lecithin additive. First‐order kinetic evaluation of the data showed that the DTy₅₀ (half‐life) and C (rate constant) values for AZ‐A with and without lecithin on glass plates were 5.68 d and 0.122, and 5.42 d and 0.128, respectively. The corresponding values for the Margosan‐0 formulation were 7.37 d and 0.094, and 6.24 d and 0.111. The DT₅₀ and C values for the pure AZ‐A on maple foliage with and without lecithin were 8.77 d and 0.079, and 6.54 d and 0.106, respectively. The corresponding values for the Margosan‐0 formulation on foliage were 8.35 d and 0.083, and 7.45 d and 0.093. The kinetic data gave quantitative information regarding the photostabilization of AZ‐A in the presence of lecithin. Good UV protection can only be achieved if the additive has the matching X_max of AZ‐A. The mechanism of photostabilization of AZ‐A in the presence of lecithin was due to either energy transfer from the excited AZ‐A to lecithin and/or competitive absorption of UV photons by the latter.     

Microwave extraction of incurred salinomycin from chicken tissues

Abstract

A rapid, accurate, environmentally friendly and cost‐effective microwave extraction technique was developed for the extraction of spiked and incurred salmomycin from chicken tissues (kidney, liver, muscle, ovarian yolk and fat). Extraction of salinomycin from various tissues was achieved by irradiating the sample in absolute ethanol and 2‐propanol (15+2) for 9 sec. in a common household microwave oven. The extract was analysed without further cleanup by HPLC on a C₁₈ column (5 μm) and detected at 592 nm via post‐column reaction with 4‐dimethylaminobenzaldehyde (DMABA) in a heated reactor coil at 86° C. Recoveries of salinomycin from spiked tissues at 30 ng/g level ranged between 87 and 100%. The limit of quantitation was found to be 10 ng/g. The developed method was applied for the analysis of incurred tissues and ovarian yolk of laying chickens given sodium salinomycin in feed at different levels for 14 consecutive days followed by withdrawal periods. Residues were detected in all tissues and ovarian yolk at 0 withdrawal time but declined during the withdrawal period. Highest residue were found in fat and ovarian yolk.     

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.     

Influence of foliar morphology and crown geometry on insecticide deposition and dissipation following an aerial spray over a mixed forest

Abstract

Deposition and dissipation of aerially sprayed phosphamidon insecticide over a mixed forest consisting of different species of coniferous and deciduous trees were studied. The data showed that the chemical deposited more and dissipated slower from deciduous foliage than from conifer needles. Differences in deposits and persistence were also found within each of the two foliar types. Leaf shape and orientation, crown geometry and foliar morphology appear to have played a role. No correlation was found between initial deposit levels and cuticular wax content of different foliar species. A controlled laboratory study showed that surface area/mass ratio played a more important role on initial deposits than pubescence/serrations present on foliar surfaces.     

Zeolite Formation from Coal Fly Ash and Its Adsorption Potential

Abstract

The possibility in converting coal ?y ash (CFA) to zeolite was evaluated. CFA samples from the local power plant in Prachinburi province, Thailand, were collected during a 3-month time span to account for the inconsistency of the CFA quality, and it was evident that the deviation of the quality of the raw material did not have significant effects on the synthesis. The zeolite product was found to be type X. The most suitable weight ratio of sodium hydroxide (NaOH) to CFA was approximately 2.25, because this gave reasonably high zeolite yield with good cation exchange capacity (CEC). The silica (Si)-to-aluminum (Al) molar ratio of 4.06 yielded the highest crystallinity level for zeolite X at 79% with a CEC of 240 meq/100 g and a surface area of 325 m²/g. Optimal crystallization temperature and time were 90 °C and 4 hr, respectively, which gave the highest CEC of approximately 305 meq/100 g. Yields obtained from all experiments were in the range of 50–72%.     

Use of Membrane Collectors in Electrostatic Precipitators

ABSTRACT

Membrane collection surfaces, developed and patented by researchers at Ohio University, were used to replace steel plates in a dry electrostatic precipitator (ESP). Such replacement facilitates tension-based rapping, which shears the adhered particle layer from the collector surface more effectively than hammer-based rapping. Tests were performed to measure the collection efficiency of the membranes and to quantify the potential improvements of this novel cleaning technique with respect to re-entrainment. Results indicate that even semiconductor materials (e.g., carbon fibers) collect ash nearly as efficiently as steel plates, potentially indicating that collection surface resistivity is primarily dictated by the accumulated ash layer and not by the underlying plate conductivity. In addition, virtually all sheared particles separated from the collecting membranes fell within the boundary layer of the membrane, indicating extremely low potential for re-entrainment.