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

Abstract

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

Metabolism of gamma‐hexachlorocyclohexah (HCH) in vivo. Metabolism of orally administered gamma‐2,3,4,5,6‐pentachlorocyclohexen (PCCH)

Abstract

Mexacarbate (4‐dimethylamino‐3,5‐xylyl N‐methylcarbamate) insecticide has potential for use in spruce budworm (Choristoneura fumiferana Clem.) control operations in Canada. Its persistence and fate in balsam fir (Abies balsamea (L.) Mill.), litter and soil samples were studied by spraying aerially oil‐based and water‐based formulations, each at 70 g A.I./ha over a coniferous forest near Bathurst, New Brunswick. The oil‐based formulation gave the maximum concentration of the chemical in the substrates studied. In fir needles, the highest concentrations observed were 0.51 ppm and 0.19 ppm (fresh weight) for the oil‐based and emulsion formulations respectively, 1 h after application. The residue levels decreased very rapidly with a half‐life of approximately 5 h. Three and eight days after the spray application of the emulsion and oil formulations respectively, the concentrations of mexacarbate in foliage decreased to trace levels ( 0.008 ppm). Only very low levels of residue were detected in litter and soil. The peak concentrations for the two formulations ranged from 0.02 to 0.11 ppm (fresh weight) in litter and from 0.01 to 0.06 ppm (fresh weight) in soil. The residue levels in both litter and soil decreased to below the detection limit (0.005 ppm) within 1 d. The ground deposit levels found on glass plates and the droplet density and size spectra measured on Kromekote® cards reflected the variations in concentrations found in fir needles, litter and soil samples and correlated with the observed maximum concentrations in them. Under the stipulated use pattern, mexacarbate concentrations found in the terrestrial components studied were low and are not likely to have any undue adverse effects on non‐target species.     

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.     

Distribution and persistence of carbaryl in some terrestrial and aquatic components of a forest environment

Abstract

An oil‐based formulation of carbaryl (1‐naphthyl N‐methyl‐carbamate) (Sevin‐2‐Oil) was applied twice by a fixed‐wing aircraft at a dosage rate of 280 g of A.I./ha/application to a coniferous forest near Allardville, New Brunswick. The highest concentrations of the chemical in fir foliage, litter and forest soil 1 h after application were respectively 4.20, 1.21 and 0.59 ppm (fresh weight). The residues dissipated rapidly and the DT50 values obtained from the depletion curves were 2.3 d for foliage and 1.5 d for litter and soil samples. Very low levels (<0.1 ppm) of carbaryl persisted in foliage and litter beyond the 10 d sampling period. The maximum residue level found in stream water was 0.314 ppm and more than 50% of it had dissipated within 1 h. Low but detectable levels (0.001 ppm) of the chemical persisted in water until the end of the 10 d sampling period. Sediment samples contained a maximum level of 0.04 ppm, which dissipated below the detection limit within 5 h. Brook trout and slimy sculpins captured in the stream 1 d after the spray contained on average about 0.04 ppm of carbaryl and none of it was found in 3 d postspray samples.     

Residues of chlorpyrifos-methyl in balsam fir foliage, forest litter, soil, stream water, sediment and fish tissue after double aerial applications of Reldan

Chlorpyrifos-methyl was applied twice at 70 g A.I./ha by means of a fixed-wing aircraft to a mixed coniferous forest near Allardville, New Brunswick. Residue in balsam fir foliage was highest (1 ppm wet wt) 1 hr after spraying and rapidly declined to about 30% within 1 day, but persisted at a very low level (0.03 ppm wet wt) for 125 days. Current year's foliage contained a higher level of residue than old foliage. Chlorpyrifos-methyl persisted longer in forest litter than in soil. After 125 days, trace amounts (less than 6 ppb wet wt) were still found in litter but were not detected in soil. In stream water the residue dissipated very rapidly; more than 90% disappeared 3 hours after the second application and were not detected after 4 days. Low-level residue (less than 0.1 ppm wet wt) was present in the sediment and persisted for 10 days. Although brook trout and slimy sculpin captured in the stream within 3 days of the second application contained residues (less than 0.05 ppm fresh wt) none were detected in any fish captured, 9 and 47 days later.     

Residues of chlorpyrifos‐methyl in balsam fir foliage,forest litter,soil, stream water,sediment and fish tissue after double aerial applications of Reldan®

Abstract

Chlorpyrifos‐methyl was applied twice at 70 g A.I./ha by means of a fixed‐wing aircraft to a mixed coniferous forest near Allardville, New Brunswick. Residue in balsam fir foliage was highest (1 ppm wet wt) 1 hr after spraying and rapidly declined to about 30% within 1 day, but persisted at a very low level (0.03 ppm wet wt) for 125 days. Current year's foliage contained a higher level of residue than old foliage. Chlorpyrifos‐methyl persisted longer in forest litter than in soil. After 125 days, trace amounts (< 6 ppb wet wt) were still found in litter but were not detected in soil. In stream water the residue dissipated very rapidly; more than 90% disappeared 3 hours after the second application and were not detected after 4 days. Low‐level residue (< 0.1 ppm wet wt) was present in the sediment and persisted for 10 days. Although brook trout and slimy sculpin captured in the stream within 3 days of the second application contained residues (< 0.05 ppm fresh wt) none were detected in any fish captured, 9 and 47 days later.     

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.     

Terbufos residues in wheat and barley

A granular formulation of terbufos (Counter 15G) was added in-furrow at time of planting of wheat and barley. Foliage collected at several times was analyzed for total terbufos residues as terbufoxon sulfone. Maximum residues from application of 1.5 and 3.0 kg/ha were 7.4 and 10.6 ppm, respectively, in wheat foliage samples collected 10 days postseeding. Wheat foliage collected at 53 days postseeding had residues averaging 0.32 and 0.58 ppm from the 1.5 and 3.0 kg/ha applications, respectively. In 1985 residues in barley were consistently less than in wheat in 1985 with 4.4 and 7.0 ppm detected in foliage collected 10 days post application from the 1.5 and 3.0 kg/ha applications, respectively and 0.21 and 0.34 ppm detected at 53 days. Grain samples had 0.01 ppm or less residue at harvest. Straw samples had up to 0.75 ppm total terbufos residues at harvest.     

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.     

Comparison of gas chromatography and immunoassay methods in quantifying fenitrothion residues in grape juice processed into alcoholic drinks

Abstract

Wine and Arak, the national alcoholic drink in Lebanon, were prepared from grape juice fortified with fenitrothion to a concentration of 20ppm. Samples of the 11 fractions produced by the fermentation and distillation steps were analyzed for fenitrothion residues using gas chromatography (GC) and enzyme‐linked immunosorbent assay (ELISA). Results of residue analyses showed that the two techniques were highly correlated (r = 0.978) and indicated that fenitrothion was stable during the fermentation steps but not during distillation. The clarified wine 35 days later contained about 85% (15.3 ppm) of the fenitrothion concentration found in the juice as determined by GC analysis. Arak was prepared by a two‐steps distillation of the clarified wine. The alcohol distillate and undistilled fraction from the first distillation contained 2.5 ppm and 5.8 ppm of fenitrothion, respectively. No fenitrothion residues were detected by both techniques in the four fractions collected from the second distillation step.     

Comparison of gas chromatography and immunoassay methods in quantifying fenitrothion residues in grape juice processed into alcoholic drinks.

Wine and Arak, the national alcoholic drink in Lebanon, were prepared from grape juice fortified with fenitrothion to a concentration of 20ppm. Samples of the 11 fractions produced by the fermentation and distillation steps were analyzed for fenitrothion residues using gas chromatography (GC) and enzyme-linked immunosorbent assay (ELISA). Results of residue analyses showed that the two techniques were highly correlated (r = 0.978) and indicated that fenitrothion was stable during the fermentation steps but not during distillation. The clarified wine 35 days later contained about 85% (15.3 ppm) of the fenitrothion concentration found in the juice as determined by GC analysis. Arak was prepared by a two-steps distillation of the clarified wine. The alcohol distillate and undistilled fraction from the first distillation contained 2.5 ppm and 5.8 ppm of fenitrothion, respectively. No fenitrothion residues were detected by both techniques in the four fractions collected from the second distillation step.     

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.     

Buffer zone widths for honeybees from ground and aerial spraying of insecticides

The relative field hazards of insecticides to honeybees have been estimated by considering intrinsic toxicity levels and field application rates. This approach is extended here to a consideration of buffer zones downwind of sprayed areas by estimating the distance at which bees would encounter an LD(50) dose from spray drift. 'LD(50) distances' are determined for both ground and aerial spraying of ground crops in Britain using published data on spray deposition under various weather conditions. For ground spraying at low wind speeds (< or =3 m s(-1)), this zone of risk is up to 5 m for the great majority of compounds. Aerial spraying in unstable atmospheric conditions appears to produce drift deposits of about the same order of magnitude as from ground spraying at wind speeds of about 4 m s(-1), with maximum LD(50) distances of < or =40 m for chlorpyrifos, fenitrothion and triazophos. For aerial spraying in stable atmospheric conditions these distances would be much greater. Pieris brassicae larvae are contrasted with honeybees in their relative sensitivities to insecticides and consequent LD(50) distances.     

Bioconcentration and metabolism of DDT, fenitrothion and chlorpyrifos by the blue-green algae Anabaena sp. and Aulosira fertilissima

Anabaena and Aulosira fertilissima showed a marked ability to accumulate DDT, fenitrothion and chlorpyrifos. Although the maximum accumulation of DDT was almost the same in both organisms, there were significant differences in their abilities to accumulate fenitrothion and chlorpyrifos. Patterns of uptake of DDT under different treatments were also similar in both Anabaena and Aulosira, but there were significant differences in the patterns of accumulation of fenitrothion between these two organisms. In Aulosira the maximum accumulation of fenitrothion was observed on the second day, whereas, in Anabaena, maximum accumulation was noticed on the first day. A completely different pattern of accumulation of chlorpyrifos was observed in Aulosira, which continued to accumulate chlorpyrifos throughout the experimental period. Bioconcentration of DDT in Anabaena and Aulosira ranged from 3 to 1568 ppm (microg g(-1)) and 6 to 1429 ppm, respectively. Bioconcentration of fenitrothion and chlorpyrifos in Anabaena varied from 53 to 3467 ppm and 7 to 6779 ppm, respectively. In Aulosira the bioconcentration varied from 100 to 6651 ppm and 53 to 3971 ppm for fenitrothion and chlorpyrifos, respectively. Anabaena and Aulosira metabolised DDT to DDD and DDE. Amounts of these DDT metabolites detected in the organisms were dependent on the concentration of treatment. DDD was the major, and DDE the minor, metabolite. These organisms were not able to metabolise the organophosphorus insecticides, fenitrothion and chlorpyrifos.     

A Simple Technique for Stack Design in Complex Terrain

The main objective of this study is to apply neutral electrolyzed water (NEW) spraying to inactivate bioaerosols. We evaluated the inactivation efficiency of NEW applied to inactivate two airborne bacterial Escherichia coli and Bacillus subtilis aerosols inside an environmental-controlled chamber in the study. Generated with electrolyzing 6.15 M sodium chloride brine, the NEW with free available chlorine (FAC) concentration 50, 100, and 200 ppm was pumped with an air pressure of 70 kg/cm² through nozzle into the chamber to inactive E. coli and B. subtilis aerosols precontaminated air (initial counts of 3?×?10⁴ colony-forming units [CFU]/m³). Bacterial aerosols were collected and cultured from chamber before and after NEW spray. The air exchange rate (ACH, hr^?1) of the chamber was set to simulate fresh air ventilating dilution of indoor environment. First-order concentration decaying coefficients (Ka, min^?1) of both bacterial aerosols were measured as an index of NEW inactivation efficiency. The result shows that higher FAC concentration of NEW spray caused better inactivation efficiency. The Ka values under ACH 1.0 hr^?1 were 0.537 and 0.598 for E. coli of FAC 50 and 100 ppm spraying, respectively. The Ka values of FAC 100 ppm and 200 ppm spraying for B. subtilis were 0.063 and 0.085 under ACH 1.0 hr^?1, respectively. The results indicated that NEW spray is likely to be effective in inactivation of bacterial airborne contamination. Moreover, it is observed in the study that the increase of ventilation rate and the use of a larger orifice-size nozzle may facilitate the inactivation efficiency.

Implications: Bacterial aerosols have been implicated in deterioration of air quality and occupational health. Effective, safe, and economic control technology is highly demanded, especially for agricultural and food industries. In the study, NEW mist spraying performed effectively in controlling E. coli and B. subtilis modeling bioaerosols contamination. The NEW revealed its potential as an alternative airborne disinfectant worth being discovered for improving the environmental quality in the future.     

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.     

Pyrethrins and piperonyl butoxide residues on potato leaves and in soil under field conditions.

Residues of pyrethrin-I (Py-I) and pyrethrin-II (Py-II), the major insecticidal components of the pyrethrum daisy (Tanacetum cinerariifolium) as well as residues of piperonyl butoxide (PBO, a pyrethrum synergist) were determined in soil and on potato foliage grown under field conditions. A pyrethrum formulation (Multi-Purpose Insecticide) containing the three active ingredients was sprayed twice at the rate of 6 lbs of formulated product.acre(-1) ( 5.4 and 27.2 g A.I. of pyrethrin and PBO, respectively) on potato foliage during the growing season. In soil, three management practices (yard waste compost, grass filter strips, and a no mulch treatment) were used to study the impact of surface soil characteristics on the amount of pyrethrins (Pys) and PBO retained in soil. Soil samples and potato leaves were collected at different time intervals after spraying. Samples were purified and concentrated using solid-phase extraction columns containing C18-Octadecyl bonded silica. Residues were quantified by high-performance liquid chromatograph equipped with a UV detector. The first spray resulted in mean initial deposits of 0.18, 0.40, and 0.99 microg.g(-1) potato leaves for Py-I, Py-II, and PBO, respectively. Residues in soil were higher in compost treatments compared to no mulch treatments.     

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.     

Rain‐washing of foliar deposits of Dimilin®WP‐25 formulated in four different carrier liquids

Abstract

Dimilin^® WP‐25, a wettable powder formulation of diflubenzuron (DFB) [1‐(4‐chlorophenyl)‐3‐(2,6‐difluorobenzoyl) urea], was formulated in four different carrier liquids, viz., water; a light petroleum paraffinic oil, ID 585; a heavy paraffinic oil, Sunspray^® 7N; and a 1:2 mixture of a light petroleum aromatic solvent (Cyclosol^® 63) and canola oil; to provide four end‐use mixtures, Dim‐W, Dim‐585, Dim‐7N and Dim‐Cy‐C respectively, each containing 28 g of DFB per litre. Balsam fir branch tips clipped from greenhouse‐grown seedlings, and sugar maple branch tips clipped from field‐grown young trees, were exposed to uniform‐sized droplets (ranging in diameters from 135 to 190 μm) of the four end‐use mixtures which were atomized using a monodispersed droplet generator. Droplets were collected on the fir and maple branch tips and the initial residue per g fresh weight of foliage was determined by high‐performance liquid chromatography (HPLC). The branch tips were exposed to cumulative rainfall of 3, 6 and 10 mm at an intensity of 5 mm/h and at time intervals of 1, 12, 36 and 72 h after DFB treatment, to test the influence of ‘ageing’ of foliar residues on rainfastness. Foliar samples were collected for residue determination just before the onset of rainfall, and at 0.5 h post‐rain. DFB was quantified by the HPLC method. In the case of fir foliage, the Dim‐W formulation was the most susceptible to rain‐washing and the rainfastness did not increase with the ageing period of foliar deposits. In contrast, the three oil‐based mixtures showed greater rainfastness depending upon the carrier liquid and the ageing period. Rainfastness decreased in the order of Dim‐Cy‐C > Dim‐7N > Dim‐585 > Dim‐W. In contrast, the data on maple foliage indicated that the ageing of deposits increased the rainfastness of all the 4 end‐use mixtures. Dim‐585 was the most susceptible to rain washing, and rainfastness decreased in the order of Dim‐W > Dim‐Cy‐C > Dim‐7N > Dim‐585.     

Analyses of enzyme activities and other metabolic criteria after five years of fumigation

Enzymatic activity (peroxidase, glutamate dehydrogenase, glutamine synthetase), foliage buffering capacity, soluble protein and nitrogen content were measured in current and previous year needles from young spruce (Picea abies) and fir (Abies alba). The trees were exposed to low levels of SO(2) and/or O(3) and simulated acidic precipitation (pH 4.0) in open-top chambers from 1983 through 1988. Needle samples were taken during March 1988 at the end of the five-year fumigation period. Exposure to SO(2) substantially increased sulphur content in both needle age classes of spruce and fir, and concomitantly reduced the foliage buffering capacity index (BCI), whereas the combined fumigation with SO(2) and O(3) had no effect on BCI. Peroxidase activity was markedly higher in year-old needles compared to current-year needles. However, trees from the SO(2) and SO(2) + O(3) treatments exhibited statistically significant stimulated peroxidase activities. Similarly, changes in the activities of the nitrogen-metabolizing enzymes indicated an altered cellular function of the trees after the long-term pollution stress. Levels of activity of both glutamate dehydrogenase and glutamine synthetase were increased by exposure to SO(2), especially in spruce. Although glutamate dehydrogenase in spruce was affected by all treatments, such changes in activity were found in fir only with the SO(2) treatment. The highest activity of glutamine synthetase, however, occurred in the older needles of trees exposed to SO(2) + O(3). Total nitrogen concentration was either unaffected by the pollutant treatments or decreased in spruce compared to the controls. No statistically significant changes due to the fumigation were found in soluble protein concentrations. Results indicated that chronic exposure to air pollutants lead to alterations in metabolic processes in conifer needles, detectable either by changes in typical stress indicating values or by increases in ammonium assimilation capacity.