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.     

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.     

Effects of amendments on the uptake and distribution of DDT in Cucurbita pepo ssp pepo plants

The effects of soil amendments on the phytoextraction of ∑DDT (DDT + DDD + DDE) from soil ([∑DDT] ∼ 1500 ng/g) by a pumpkin variety of Cucurbita pepo ssp pepo were tested and the patterns of ∑DDT storage throughout the plant shoot were examined. The soil amendments did not increase the total amount of ∑DDT extracted into plant shoots, but new information about ∑DDT distribution in the plants was obtained. As observed previously, the ∑DDT concentration in plant leaves (mean 290 ng/g) was significantly lower than in plant stems (mean 2600 ng/g). Further analysis revealed that ∑DDT composition was consistent throughout the plant shoot and that ∑DDT concentration in leaves and stems decreased exponentially as distance from the root increased, which was previously unknown. This new information about the patterns of ∑DDT uptake and translocation within pumpkin plants highlights the need for appropriate plant sampling strategies in future POPs phytoextraction research.     

Estimation of plant protection product application dates for environmental fate modeling based on phenological stages of crops

According to the EU directive 91/414/EEC potential environmental concentrations of pesticides have to be assessed with environmental fate models. For the calculation of pesticide concentrations it is necessary to provide an application date which has to match the specific Biologische Bundesanstalt, Bundesamt, Chemische Industrie (BBCH) stage at which the pesticide shall be applied. If these application dates are not available for a specific stage, crop and country they must be estimated, which adds an additional uncertainty to the predicted concentrations. In the present study, we therefore evaluate to which extent application dates can be derived from phenological data. For this analysis phenological data, converted to BBCH stages, of two field crops provided by the German Weather Service (DWD) were analyzed. We found a linear correlation between BBCH stages and the respective appearance dates, which can be used for interpolation of appearance dates of specific BBCH stages. Remarkably, when comparing BBCH stages from Germany and the Czech Republic almost identical correlations of appearance dates and BBCH stages were found. In the next step, soil and climate data from Joint Research Centre (JRC) were analyzed together with phenological data in order to evaluate if BBCH stages can be estimated for countries with other climate or soil conditions. This analysis revealed that temperature, global radiation and evaporation were the parameters with the strongest impact. These parameters were used for estimating appearance dates of BBCH stages for other countries. Exemplarily, appearance dates for maize BBCH were calculated for Italy. Estimated and observed appearance dates showed a high concordance (on average six days difference). Finally, the political of impact a variation of a few days on calculated pesticide concentration was analyzed. Exemplarily, the pesticide fate model FOCUS PEARL was used to estimate pesticide groundwater concentrations. When calculating concentrations for application dates varying by ± two weeks, concentrations in groundwater usually varied very little. The highest variation was found for application at BBCH 30 in maize (6.6 % variation over all scenarios). These results showed that the uncertainty included in the estimation of appearance dates of BBCH stages for other countries has a relatively small effect on the results of PEARL and consequentially on the decision of the pesticide risk assessment by changing only the application date.     

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.     

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

Abstract

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

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

Comparing growth development of <Emphasis Type="Italic">Myriophyllum</Emphasis> spp. in laboratory and field experiments for ecotoxicological testing

BACKGROUND, GOALS AND SCOPE: Risk assessment of herbicides and the evaluation of contaminated sediments based on algae and the macrophyte Lemna sp. alone may underestimate the potential hazard of certain compounds. Therefore, various test systems with Myriophyllum spp. have been developed recently to assess the phytotoxicity in surface waters and natural sediments. In the present study, experiments investigating the growth development of Myriophyllum spp. were performed in the laboratory under defined conditions and in mesocosms under environmentally realistic exposure conditions to evaluate the suitability of these species as potential standard test organisms in ecotoxicological testing. This study provides data on the endpoints biomass, plant length and root development. MATERIALS AND METHODS: Six independent experiments were performed to investigate the plant development of Myriophyllum spp. under control conditions. The main difference in the experiments was the complexity of the test systems ranging from simple laboratory experiments to complex outdoor mesocosm studies. At the start of each experiment, uniform cuttings of Myriophyllum spp. were placed in vessels with or without sediments to reduce variability between replicates. The endpoints considered in this investigation were biomass (fresh weight of the whole plant), length of the main shoot, length of the side shoots, total length of the plant (calculated from the length of the main and side shoots) and root formation. Root to shoot ratios were calculated as a further measure for plant development. Relative growth rates (RGR) based on plant length (RG(L)R) and on biomass (RG(B)R) were calculated. RESULTS: Despite the various experimental conditions, comparable growth was obtained in all test systems and the variability of endpoints, such as total length and biomass of plants, was low. It was observed that the RGR of M. spicatum in the simple laboratory test system with sediment were comparable to growth data obtained for M. verticillatum and M. spicatum grown in indoor and outdoor mesocosms, thus indicating that Myriophyllum growth tends to increase by the addition of sediment. High variability was determined for the endpoints length of the side shoots, total root length and biomass of roots. DISCUSSION: One challenge for a test design to investigate phytotoxicity on aquatic plants is to obtain good growth of the plants. From the results, it can be concluded that the experimental conditions in the various test systems were suitable to study the plant development of Myriophyllum spp. because obtained growth rates were comparable between laboratory and field investigations. Another challenge for developing a plant biotest system is the definition of sensitive endpoints. Low variability is preferred to detect minor effects of chemicals or polluted sediments on plant development. In our studies, the variability of the endpoints biomass and total length of plant was low and, therefore, they have much potential as endpoints for assessing toxicity. CONCLUSIONS: The methodologies presented in this study have applications within the risk assessment for aquatic plants and have the advantage of assessing effects taking into account the relevant exposure pathways via water and/or sediment for compounds under investigation. RECOMMENDATIONS AND PERSPECTIVES: Setting safe quality criteria for surface water and sediments is one of the challenges authorities are facing today. Myriophyllum spp. is recommended as suitable test species to investigate phytotoxicity in surface water and sediments. These results, thus, might serve as a basis for the compilation of a new harmonised guideline for ecotoxicological testing with aquatic macrophytes.     

Feasibility of Applying a Stable Isotopic Tracer for Direct Determination of Dry Particulate Deposition to Soybean Plants

ABSTRACT

A stable rare-earth isotopic tracer was used to measure the deposition of KNO₃ particles on soybean leaves by direct measurement of the tracer on the plant surfaces by thermal-ionization mass spectrometry. Submicrometer particles, made from a solution containing 3 |mg mL^-1 neodymium isotope (¹⁴⁸Nd, 87.9%) and 1,000 mg mL^-1 KNO₃, were dispersed with a two-fluid nozzle and released upwind of a soybean field. Total suspended- and size-fractionated-aerosol particles were collected on an open-face filter and in a micro-orifice impactor, respectively, at a distance of 40 m from the release point. Soybean leaves exposed to the plume were collected at distances ranging from 25 to 100 m. As little as 5.5 pg of the tracer (i.e., excess ¹⁴⁸Nd) was detected in soybean leaves at signal-to-noise ratios ranging from 7,500 to 240,000, in the presence of 200 to 2,700 pg of naturally occurring Nd. The dry-particle deposition velocity, determined from the ratio of the aerial concentration and directly deposited aerosol (geometric mass mean diameter, 0.20 mm) flux, and its corresponding analytical uncertainty were 0.30 cm sec^-1 and 2.5%, 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.     

Diflubenzuron residue and persistence on an oak forest after aerial application

Abstract

A twenty hectare forest block in central Pennsylvania was aerially sprayed with diflubenzuron (Dimilin 25W®) at the dose of 33.23g A.I./ha in 9.4 litres/ha. Leaf samples were collected from the upper and lower canopies of 27 oaks and understory within this block on the day of spray, May 29, 1991. Canopy leaves were also collected on May 31, June 10, July 29 and September 26, 1991.

Recovery of diflubenzuron residues on fortified canopy‐leaf and litter‐leaf samples using analytical techniques employed in this study averaged 87.4% (SE = 7.5%) and 66.2% (SE = 8.2%), respectively.

On the day of spray, diflubenzuron residues on the upper canopy, lower canopy and understory averaged 81.18, 39.65 and 8.35 ng/cm², respectively. Diflubenzuron residues on canopy‐leaf samples collected 2, 12, 61 and 120 days post‐spray averaged 14.83 (SE = 10.19), 16.75 (SE = 9.95), 12.84 (SE = 8.25) and 11.20 (SE = 7.52) ng/cm², respectively. Diflubenzuron residues on litter‐leaf samples collected after leaf senescence ‐ 169 and 323 days post spray contained measurable amounts of diflubenzuron in 51 and 59% of the samples, respectively. Of the samples with measurable amounts of diflubenzuron, residues averaged 1.36 (SE = 2.44) and 0.65 ng/cm² (SE = 0.73) respectively.     

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

Abstract

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

Droplet size spectra and deposits of 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.     

Residues and mutagenicity of captan applied to apple trees and potential human exposure

The fungicide captan (cis-N-((trichloromethyl)thio) 4-cyclo-hexene-1,2-dicarboximide) was applied at the rate of 2.4 g/l to apple trees (c.v. Golden Delicious) individually or as part of a standard treatment program where it was applied eight times during the growing season together with several pesticides. Leaf samples (100 discs of 2.2 cm diameter) were collected from treated and control trees before treatment and at 0, 1, 3, 7, 14, 28, 56, 90 and 112 days after treatment. Fruit samples were taken at mid-season (56 days) and at harvest (112 days). The objective of this study was to determine the captan residue and mutagenicity of leaf and fruit extracts to ascertain the potential health hazard to agricultural workers in these orchards. Surface residues were extracted from leaves and fruits with methylene chloride. These extracts were subsequently analyzed for captan by gas-liquid chromatography (GLC) utilizing an electron-capture detector, and for mutagenicity with two strains (TA98 and TA100) of Salmonella typhimurium, with and without microsomal enzyme activation. Positive mutagenic effects were observed with strain TA100 at 0-14 days post spray, even with extracts from one leaf disc's surface (3.8 cm2) of the single treatment. Captan residues in these samples indicated a decline from 9.3 micrograms/cm2 at 0 days to 0.80 micrograms/cm2 at 14 days and a trace after 112 days. With the standard treatment, in which captan was incorporated eight times in the program starting at the 7-day interval, leaf extracts showed mutagenic activity at 7, 14, 28 and 90 days. Captan residues at these intervals were 11.4, 5.0, 4.1 and 3.4 micrograms/cm2, respectively. Fruit sample extracts of the standard spray were mutagenic to the tester strains TA100 and TA98 both at mid-season and at harvest. Residues of captan on fruits declined from 10.4 micrograms/cm2 at mid-season to 1.1 micrograms/cm2 at harvest. No mutagenic activity was detected with extracts from fruit samples from the single captan application.     

Effects of droplet density and concentration on the efficacy of bacillus thuringiensis and carbaryl against gypsy moth larvae (Lymantria dispar L.)

Abstract

The feeding behavior of gypsy moth larvae exposed to two pesticide deposits (Bt and carbaryl) on oak leaf disks was monitored to determine the relationships between its efficacy and application parameters (droplet density and pesticide concentration). A range of pesticide concentrations and droplet densities (from 9 to 149 droplets/cm²) was used to simulate high and low application rates produced by different methods of application in the field.

The LD₅₀ and the LC₅₀, appeared to be affected by the spatial distribution of the deposit on the leaf surface. Both Bt and carbaryl showed a decreasing LD₅₀ at increasing time after spray. The LD₅₀ of Bt decreased from 14.1 BIU/liter to 3.1 BIU/Iiter between 48 and 144 hours after spray. The results show that feeding inhibition by Bt is more closely related to concentration than to droplet density and dose per unit area with the highest feeding inhibition occurring at 10 BIU/liter at 9 droplets/cm². With carbaryl, an increase in both concentration and droplet density was necessary to cause a decrease in leaf area eaten by larvae.     

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

Abstract

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

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

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.     

Temporal processes that contribute to nonlinearity in vegetation responses to ozone exposure and dose

Ozone interacts with plant tissue through distinct temporal processes. Sequentially, plants are exposed to ambient O₃ that (1) moves through the leaf boundary layer, (2) is taken up into plant tissue primarily through stomata, and (3) undergoes chemical interaction within plant tissue, first by initiating alterations and then as part of plant detoxification and repair. In this paper, we discuss the linkage of the temporal variability of apoplastic ascorbate with the diurnal variability of defense mechanisms in plants and compare this variability with daily maximum O₃ concentration and diurnal uptake and entry of O₃ into the plant through stomata. We describe the quantitative evidence on temporal variability in concentration and uptake and find that the time incidence for maximum defense does not necessarily match diurnal patterns for maximum O₃ concentration or maximum uptake. We suggest that the observed out-of-phase association of the diurnal patterns for the above three processes produces a nonlinear relationship that results in a greater response from the higher hourly average O₃ concentrations than from the lower or mid-level values. The fact that these out-of-phase processes affect the relationship between O₃ exposure/dose and vegetation effects ultimately impact the ability of flux-based indices to predict vegetation effects accurately for purposes of standard setting and critical levels. Based on the quantitative aspect of temporal variability identified in this paper, we suggest that the inclusion of a diurnal pattern for detoxification in effective flux-based models would improve the predictive characteristics of the models. While much of the current information has been obtained using high O₃ exposures, future research results derived from laboratory biochemical experiments that use short but elevated O₃ exposures should be combined with experimental results that use ambient-type exposures over longer periods of time. It is anticipated that improved understanding will come from future research focused on diurnal variability in plant defense mechanisms and their relationship to the diurnal variability in ambient O₃ concentration and stomatal conductance. This should result in more reliable O₃ exposure standards and critical levels.     

Airborne foliar transfer of particular metals in Lactuca sativa L.: translocation,phytotoxicity, and bioaccessibility

The uptake, translocation, and human bioaccessibility of metals originating from atmospheric fine particulate matters (PM) after foliar exposure is not well understood. Lettuce (Lactuca sativa L.) plants were exposed to micronic PbO, CuO, and CdO particulate matters (PMs) by the foliar pathway and mature plants (6 weeks old) were analyzed in terms of: (1) metal accumulation and localization on plant leaf surface, and metal translocation factor (TF) and global enrichment factor (GEF) in the plants; (2) shoot growth, plant dry weight (DW), net photosynthesis (Pn), stomatal conductance (Gs), and fatty acid ratio; (3) metal bioaccessibility in the plants and soil; and (4) the hazard quotient (HQ) associated with consumption of contaminated plants. Substantial levels of metals were observed in the directly exposed edible leaves and newly formed leaves of lettuce, highlighting both the possible metal transfers throughout the plant and the potential for human exposure after plant ingestion. No significant changes were observed in plant biomass after exposure to PbO, CuO, and CdO-PMs. The Gs and fatty acid ratio were increased in leaves after metal exposure. A dilution effect after foliar uptake was suggested which could alleviate metal phytotoxicity to some degree. However, plant shoot growth and Pn were inhibited when the plants are exposed to PbO, and necrosis enriched with Cd was observed on the leaf surface. Gastric bioaccessibility of plant leaves is ranked: Cd?>?Cu?>?Pb. Our results highlight a serious health risk of PbO, CuO, and CdO-PMs associated with consumption of vegetables exposed to these metals, even in newly formed leaves in the case of PbO and CdO exposure. Finally, the study highlights the fate and toxicity of metal rich-PMs, especially in the highly populated urban areas which are increasingly cultivated to promote local food.

     

Impact of fungicides on active oxygen species and antioxidant enzymes in spring barley (Hordeum vulgare L.) exposed to ozone.

Two modern fungicides, a strobilurin, azoxystrobin (AZO), and a triazole, epoxiconazole (EPO), applied as foliar spray on spring barley (Hordeum vulgare L. cv. Scarlett) 3 days prior to fumigation with injurious doses of ozone (150-250 ppb; 5 days; 7 h/day) induced a 50-60% protection against ozone injury on leaves. Fungicide treatments of barley plants at growth stage (GS) 32 significantly increased the total leaf soluble protein content. Additionally, activities of the antioxidative enzymes superoxide dismutase (SOD), catalase (CAT), ascorbate-peroxidase (APX) and glutathione reductase (GR) were increased by both fungicides at maximal rates of 16, 75, 51 and 144%, respectively. Guiacol-peroxidase (POX) activity was elevated by 50-110% only in AZO treated plants, while this effect was lacking after treatments with EPO. This coincided with elevated levels of hydrogen peroxide (H2O2) only in EPO and not in AZO treated plants. The enhancement of the plant antioxidative system by the two fungicides significantly and considerably reduced the level of superoxide (O2*-) in leaves. Fumigation of barley plants for 4 days with non-injurious ozone doses (120-150 ppb, 7 h/day) markedly and immediately stimulated O2*- accumulation in leaves, while H2O2 was increased only after the third day of fumigation. Therefore, O2*- itself or as precursor of even more toxic oxyradicals appears to be more indicative for ozone-induced leaf damage than H2O2. Ozone also induced significant increases in the activity of antioxidant enzymes (SOD, POX and CAT) after 2 days of fumigation in fungicide untreated plants, while after 4 days of fumigation these enzymes declined to a level lower than in unfumigated plants, due to the oxidative degradation of leaf proteins. This is the first report demonstrating the marked enhancement of plant antioxidative enzymes and the enhanced scavenging of potentially harmful O2*- by fungicides as a mechanism of protecting plants against noxious oxidative stress from the environment. The antioxidant effect of modern fungicides widely used in intense cereal production in many countries represents an important factor when evaluating potential air pollution effects in agriculture.     

Residues of dicofol on cucumber grown under plastic covers in Jordan

Residues of dicofol were determined on cucumber leaves and fruits under plastic house (PH) and plastic tunnels (PT). Five sprays, 8 d apart, were applied at 0.15% concentration. Initial deposits on leaves were 48 and 58 ppm under PH and PT, respectively. In the last sampling date of leaves, the amounts of 191 and 135 ppm were detected under both cultures, respectively. There was a continuous increase in the initial residue after each spray. The highest amount of dicofol (401) was determined 1 d after the fifth spray under PH. The exposure to high residues may pose a risk to fieldworkers. On cucumber fruits, residues of 0.95 and 1.60 ppm were determined 1 d after the fourth spray under PH and PT, respectively. These residues decreased after 4 d to 0.40 and 1.49 ppm, respectively. Almost no detectable residues could be determined 8 d after sprays number 4 and 5 under both cultures. All dicofol residues on the fruits were below the tolerance level of 2 ppm.