DISLODGEABLE AZINPHOSMETHYL RESIDUES

FROM AIR BLAST SPRAYING OF

APPLE FOLIAGE IN OHIO 1,2
F. R. HALL3, D. L. REICHARD4, and H. R. KRUEGER3
Department o f Entomology
Ohio Agricultural Research anti Development Center
Wooster, Ohio 44691

The distribution and decay rates of dislodgeable residues of azinphosmethyl ap-

plied by two types of air blast sprayers on apple foliage in Ohio were investigated.
Leaf discs were taken from nine sites located on the periphery of Cortland apple
trees at five dates after spraying. The sprayer delivering the higher airflow rate, but
lower velocity, deposited the pesticide much more uniformly over the trees and
applied more in the top of the tree. The other sprayer deposited the greatest pro-
portion of pesticide on the site nearest the sprayer. The residue decreased at all
sites and ranged from 42 to near 100% decrease at 14 days after spraying.

Pest control is directly related to initial deposit and residual quantities of the pesticide
on target surfaces. Knowledge of these factors is invaluable to those who design sprayers,
make pest control recommendations and establish safety rules for workers in orchards.
Hoerger and Kenaga (1972) reported that if the spray volume is held below the point of
significant run-off, the application of a pesticide to a given plant surface results in resi-
dues in direct proportion to the dosage, if other variables are similar. However, Young and
Ditman (1963) demonstrated that increasing the spray concentration (s lower spray
volume) increased the pesticide residues, but deposition did not increase proportionately
with concentration.

Brann (1964), Himel (1969) and Brann e t al. (1967) have demonstrated that droplet
size, air velocity, and volume affect the magnitude of deposits and, subsequently, pest
control with low-volume sprayers. Brann e t al. (1967) and, more recently, Carman e t al.
(1972) and Reil e t al. (1973) reported potential problems associated with greater depo-
sition of pesticides on certain areas of apple trees by low-volume sprayers.

1Approved by the Associate Director of the Ohio Agricultural Research and Development Center,
Wooster, Ohio, as Journal Article No. 39-74. Received for publication July 24, 1974.
2Mention of a pesticide or a commercial or proprietary product does not constitute recommendation
or endorsement by the authors or their agencies.
3Associate Professor of Entomology, Department of Entomology, Ohio Agricultural Research and
Development Center, Wooster, Ohio.
4Agricultural Engineer, USDA-ARS, Insect Conlzol Equipment and Practices Research, Wooster, Ohio.

Archives of Environmental Contamination 352

and Toxicology Vol. 3,352-363 (1975)
9 1975 by Springer-Verlag New York Inc.
 Dislodgeable Azinphos Residues on Apple Foliage 353

Recent investigations on the economic impact of pending reentry periods for orchard
workers have shown the financial impact that could result if California re-entry times
were adopted for the humid area orchards (Gavett 1973). Lewis and Hickey (1969) noted
that we have not yet fulfilled our responsibility to provide new information regarding
pesticide ecology and practical pest management. Accuracy of rates, control of applica-
tion techniques, and amounts of chemical placed into the environment will be mandatory
under pending legislation. Efficient low-volume spraying requires even greater accuracy in
sprayer calibration, pesticide measurement, and application than does dilute spraying.

In view of the widespread use and dissemination of orchard insecticides in the north
ceritral section of the United States, an investigation of the efficienty of spray applica-
tion methods was warranted. We were also interested in the magnitude of external resi-
dues persisting on fruit crops in this region when insecticides are applied by low-volume
systems, especially with regard to the distribution and persistence of dislodgeable resi-
dues, as defined by Gunther e t al. (1973).

The objectives of the experiment were to measure the distribution of dislodgeable

residues of azinphosmethyI [0,0-dimethyl S-(4-oxo-l,2,3-benzotriazin-3(4H)-ylmethyl)
phosphorodithioate] (Guthion| sprayed from two different sprayers on apple foliage
and to determine the effect of time on these residues. Since Westlake et al. (1973) indi-
cated that the major potential hazard to workers in an orchard is dermal contact, the
magnitude and changes of dislodgeable foliar residues under different application systems
were evaluated.

Equipment, methods and materials

Treatment of plots. The F. E. Myers Co. 2A-36 and Kinkelder Royal sprayers used in
this experiment (Fig. 1) are considerably different in delivery characteristics. The Myers
sprayer contains its own engine and delivers a higher air flow rate (70,000 cfm) at veloci-
ties of ca. 80 mph. Its centrifugal pump delivers up to 100 gpm at 200 psi. The Kinkelder
is power takeoff driven and delivers 18,000 cfm of air at velocities up to 210 mph. It has
a low-pressure centrifugal pump. Another difference between these sprayers is the
method each uses to produce droplets. The Myers sprayer has disc-type, cone-pattern
spray nozzles, whereas the Kinkelder has vacuum spray jets that utilize the high-velocity
air to produce small droplets. Only the rear bank of nozzles on the Myers sprayer was
used. These nozzles contained Spraying Systems Company discs and cores from top to
bottom as follows: D7-25, D10-25, D10-25, D8-25, D7-25, D5-25, D4-25, D4-25, D3-25,
D3-25.

The sprayers were set up to apply different amounts of solution and pesticide per acre.
Normally, the trees used in this experiment would be sprayed from both sides. However,
for this study, they were only sprayed from one side so that spray penetration of the
foliage could be evaluated. If the trees had been sprayed from both sides, the Myers
sprayer would have applied 150 gallons of water per acre (gpa) containing 3.59 lb of
50W azinphosmethyl and the Kindelder 26.7 gpa with 0.713 lb of 50W azinphosmethyl.
The actual quantities applied were one-half of these. The spray heads on the Kindelder
 354 F. R. Hall et al.

Fig. 1. Myers 2A-36 and Kinkelder Royal sprayers.

sprayer were rotated to one side and positioned for best direction of spray. The Myers
and Kinkelder sprayers were pulled at 2.0 and 1.7 mph, respectively.

Trees, sample sites, and collection. Eight 'Cortland' apple trees, as near alike as
possible, were selected in a large orchard, and each was divided into nine sample sites. All
trees were 40 ft apart in and between rows. The height of the trees ranged from 15-16 ft
(x = 15.5), and the canopy diameters varied from 20-26 ft (x = 22.2). Sample sites were
selected on the periphery of the foliage as shown in Fig. 2. Site no. 1 was nearest to
sprayer and no. 9 was on the opposite side of tree. All sample sites were about three ft
wide, except no. 5, which was approximately five ft in diameter.

One side of each of four trees was sprayed by each sprayer between about 1:30 and
2:00 PM EDT on October 9, 1973. The temperature was about 75~ and wind velocity
was less than one mph. While spraying, the tractor operator followed guide strings posi-
tioned so that the sprayers would provide optimum coverage with the air outlets close
to the trees.

At about one-half hour after spraying, the first sampling started (0 days). Twenty-five
leaf discs (2.50 cm dia.) were taken (Fig. 3) from each sample site in each tree. Immedi-
ately after each sample (25 leaf discs) wa.s collected, the bottle was capped and placed in
a styrofoam chest with coolant. Within about one hr after sampling, all samples were
stored in a freezer at -20~ until the residue analyses were made. This same sampling
procedure was followed at 1, 3, 7, and 14 days after spraying.
A second experiment was established on October 19. Analyses were made on initial
residues after both sprayers applied the equivalent of 1.6 Ib of 50WP azinphosmethyl per
 Dislodgeable Azinphos Residues on Apple Foliage 355

1.97 (E) 0.112

( ~ 0.294 2.17

5.43 (~) 0.628 1.58 (~ 0.075i

553 | o.81o 0.780 |

4.09| 0.993 0.s47| 0.05~

-2.5

Fig. 2. Tree site locations and dislodgeable residues of azinphosmethyl in #g/cm 2 at 0

days: at each site, the 1st figure = deposits from high-airflow-rate sprayer; 2rid figure =
deposits from low-airflow-rate sprayer.

Fig. 3. Leaf punch apparatus, counter and collection jars used for sampling apple foliage.
356 F . R . Hall et al.

acre when spraying both sides of the trees. All other conditions, except trees, were as
close as possible to those used in the October 9 application. Trees were selected from the
same orchard but it was impossible to Fred trees as near alike as those used before.
Samples were taken from four sites in each of the seven trees. Site nos. 1 and 2 were on
the same side of the tree as the sprayer andwere from 5.0 to 7.5 and 10.0 to 12.0 ft above
ground, respectively. Site no. 3 was in the top center of the tree and no. 4 was the same
height as no. 1 but on the opposite side of the tree.

Sample extraction and analysis. Forty ml of acetone was added to the 25 leaf discs in
the 110-ml glass jars with polyethylene snap caps. The contents of each jar were shaken
vigorously for 20 sec. Then the acetone wash solutions from the sample were flash evapo-
rated to a final volume of five ml and analyzed within two hr.

All analyses were made with a Packard Model 871 gas chromatograph equipped with a
flame photometric detector (Tracer, Inc.). The chromatographic column was glass, 2.2 m
• 4.2 mm id, with 10% DC 200 on 60/80 mesh Gas Chrom Q. Operating parameters were:
column temperature, 190~ carrier gas (N2) , 100 ml/min; 02, 20 ml/min; air, 80
ml/min; and H2, 180 ml/min. Under these conditions, the retention time for azinphos-
methyl was two min. Quantitation was by peak height as compared with a standard curve
made from standard solutions containing 10 ng//A of azinphosmethyl.

The percentages of recovery for azinphosmethyl were 95, 97, and 98. The results pre-
sented have not been corrected to compensate for recoveries.

Results and discussion

Fig. 2 shows the mean of the four samples at each site on October 9 for both sprayers
at zero days. There was considerably less variation in initial deposits over all sites on trees
sprayed with the high-airflow-rate sprayer. Based on the 36 initial samples for each
sprayer, the coefficients of variation (CV) were 68% and 133%, respectively, for the resi-
dues from the high- and low-airflow-rate sprayers. The high- and low-airflow-rate sprayers
deposited 370 and 980% on sides nearest the sprayer (sites 1-4) than on opposite sides of
the trees (sites 6-9). Mean deposits at site no. 5 in trees sprayed with the high- and low-
airflow-rate sprayers were 48% and 11%, respectively, of those at site no. 1. If trees were
sprayed from both sides and each side received a distribution of deposits similar to those
in this experiment, then the predicted CV would be 18.3 and 40.5%, respectively, for all
sites sprayed with the high- and low-airflow-rate sprayers.

Similar data were obtained by Reil et al. (1973) who demonstrated higher residues at
the lower outside of trees. Carman et al. (1972) also recorded higher residues from low-
volume application at certain locations 6n the trees. Randall (1971) measured deposits
from three sprayers delivering air from one side with the same energy but at different
velocities (201, 151, ~1 mph), with respective flow rates of 3246, 5220, and 16260 cfm.
He also reported that the sprayer delivering the highest airflow rate produced the most
uniform deposits throughout the trees, and the one delivering the lowest airflow rate
deposited the most material on sites nearest the sprayers, Randall's data, as well as data
 Dislodgeable Azinphos Residues on Apple Foliage 357

from this experiment, suggest that a certain air velocity threshold must be obtained to
deflect foliage at the outer canopy so that the spray can pass through. In another experi-
ment (unpublished data), we found that sprayers delivering lower airflow rates tend to
lose their air velocity more rapidly as the distance from the outlet is increased. It is also
known that a certain minimum air velocity is needed to convey droplets and effect im-
pingement (Sell 1931). Hall et al. (1974) showed that air velocity produced by an air blast
sprayer decreases very rapidly when measured at increasing distances from the discharge.
Brann et al. (1967) concluded that efficient pest control must include proper distribution
and uniform deposition of pesticide throughout the tree.

Table I shows the mean values of residue at each sampling site for the five sampling
dates. Analyses of variance were calculated on the logarithums of the sample residue
values. The log transformation was used because, among other reasons, it is consistent
with the usual mathematical model of a decay curve. These analyses indicated that the
sampling site (S), day of sampling (D), and D x S interaction had significant effect, at the
1% level, on the quantity of residue for both sprayers. The tree (T) source of variation
was not significant (5% level), nor were the S x T, D x T, and D x T x S interactions.

Comparisons between residues deposited by the two sprayers were made on trees,
sites, and days. Because the high-airflow-rate sprayer applied 5.04 times more azinphos-
methyl than did the other sprayer, statistical tests were used to determine whether resi-
dues from the high-airflow-rate sprayer significantly (5% level) exceeded this factor. Dis-
lodgeable residues on trees and sites sprayed with the high-airflow-rate sprayer were sig-
nificantly greater on all trees and on all sites except no. 1. Also, the total residue in all
samples sprayed with the high-airflow-rate sprayer was significantly greater on all
sampling days except 14 days after application.

Regression computations were performed to show the relationship of time after spray-
ing to residue at each site. These computations were based on a model of the form:

Y = a lObt

where Y = residue (/lg/cm2), t = time after spraying (days), and a and b are regression co-
efficients as listed in Table I. The regression of residue on day was significant (5% level)
for both sprayers on all sites except no. 4. There was no evidence that the rate of decline
varied significantly from one tree to another within plots sprayed by each sprayer. Figures
4 and 5 show regressions of time after spraying on residue for sites No. 1 through 5 for
the high- and low-airflow-rate sprayers. Based on the regressions, the proportion of the
previous day's residue remaining are listed in Table I. These values are generally higher for
the greater initial deposits from both sprayers. Although the high-airflow-rate sprayer
deposited considerably more azinphosmethyl throughout the tree, there was little differ-
ence between the sprayers in the proportion of residue remaining per day on sites 1-5.
The table also shows the percentage of decrease in mean residues from the initial deposits
at 7 and 14 days after spraying. With the exception of site no. 4, the percentage of de-
crease at 14 days ranged from 58 to 100 and 42 to 100, respectively, for the high- and
low-airflow-rate sprayers.
 Table I. Amount o f dislodgeable azinphosmethyl residue on apple leaves - October 9 application

Decrease from Calculated

Mean residue (/~g/cm 2) initial deposit Regression
Tree proportion
site Days after spraying % coefficients remaining
no. 1 3 7 14 7 days 14 days a b per day
Sprayed with high-airflow-rate sprayer
1 4.09 3.09 3.72 4.15 1.47 0 64.1 4.16 -0.0274 0.939
2 5.53 4.05 3.95 3.95 2.72 28.6 59.0 4.67 -0.0170 0.962
3 5.43 3.90 4.81 3.09 2.27 43.1 58.2 4.90 -0.0267 0.940
4 3.96 2.33 3.19 1.42 2.01 64.1 49.2 2.90 -0.0191 0.957
5 1.97 1.44 1.46 0.263 0.152 86.6 92.3 1.78 -0.0889 0.815
6 2.17 1.57 1.08 0.106 0.071 95.1 96.7 1.74 -0.125 0.751
7 1.58 1.01 0.628 0.0557 0.0307 96.5 98.1 1.17 -0.129 0.743
8 0.780 0.389 0.284 0.0659 * 91.6 100.0 0.541 -0.126 0.748
9 0.547 0.284 0.314 0.0710 0.0305 87.0 94.4 0.410 -0.101 0.772
Mean 2.89 2.01 2.16 1.47 0.971 . . . . .
Sprayed with low-airflow-rate sprayer
1 0.993 0.729 0.729 0.668 0.314 32.7 68.4 0.913 -0.0324 0.928
2 0.810 0.547 0.506 0.527 0.314 34.9 61.2 0.568 -0.0167 0.962
3 0.628 0.486 0.466 0.385 0.364 38.7 42.0 0.510 -0.0131 0.970
4 0.294 0.243 0.247 0.284 0.1264 3.4 10.2 0.236 -0.0098 0.978
5 0.112 0.081 0.0454 0.0304 0.0101 72.8 91.0 0.0784 -0.0584 0.874
6 0.109 0.0648 0.0152 0.0101 * 90.7 100.0 0.0720 -0.0755 0.840
7 0.0751 0.0162 0.0051 * * 93.2 100.0 0.0532 -0.137 0.729
8 0.0446 * * * * 100.0 100.0 0.0383 -0.583 0.261
9 0.0506 * * * * 100.0 100.0 0.0482 -0.683 0.208
Mean 0.346 0.241 0.224 0.212 0.141 . . . . .

* < 2/.lg
 Dislodgeable Azinphos Residues on Apple Foliage 359

4 8 12
Days
Fig. 4. Regression of time after spraying on azinphosmethyl residue for sites 1 through 5
for the high-airflow-rate sprayer.

Remits of the residue and statistical analyses on samples taken from trees sprayed on
October 19 indicate the following. The mean deposits on the three trees sprayed with the
high airflow rate were 2.13, 1.69, 0.642, and 0.608/ag/cm2, respectively, at site nos. 1,
2, 3, and 4. The mean deposits on the four trees sprayed with the low-airflow-rate sprayer
were 2.52, 0.942, 0.304, and 0.152/ag/cm 2, respectively, at site nos. 1, 2, 3, and 4. The
analysis of variance for each sprayer showed that there was a significant (1% level) effect
of the amount of residue among sites. Although the tree shapes varied considerably more,
the remits were similar to those from the October 9 application. Again, results from the
high-airflow-rate sprayer showed greater mean deposits of azinphosmethyl at all sites
except the site nearest the sprayers. These deposits were significantly greater (5% level)
at sites 2 and 4, but not at 3, even though the mean deposit from the high-airflow-rate
sprayer was about twice as much. Mean deposits at the top center were 30% and 12%,
respectively, of those on sites nearest the high- and low-airflow-rate sprayers.

Undoubtedly, the residues in the trees were influenced by weather conditions. Table II
summarizes weather data that were taken about one mile from the orchard. Rainfall oc-
360 F.R. Hall et al.

.7

~.E. . 3 = ;.,

,2=~ , ~

-1. -

4 8 12
Days

Fig. 5. Regression of time after spraying on azinphosmethyl residue for sites 1 through 5
for the low-airflow-rate sprayer.

curred on only one day during the sampling period, but it was foggy on several mornings.
Also, the relative humidity was quite high during most of this experiment.

The distribution of residues observed after these applications agrees with the biological
observations of Brarm et al. (1967), Refl (1973), and, more recently, Hall et al. (1974),
who showed that more apple scab Venturia inaequalis (Cke) Wint. and European red mite,
Panonychus ulrni (Koch), appear in the top center sections of large mature apple trees
then in lower sections. On well-pmned trees, however, the distribution of azinphosmethyl
50WP at 1.6 lb per acre by either of thase two sprayers provided adequate control of
orchard insects and diseases (Hall eta/. 1972). The differences in deposits throughout the
tree (depending on site) are substantial, and the averaging of dislodgeable deposits may
be misleading. In large mature trees, greater deposits should be anticipated on the areas
nearest the sprayer. If the distribution of the pesticide were more uniform, a reduction of
the amount of azinphosmethyl applied per acre could be recommended.
 Table II. Daily weather data - Wooster, Ohio

Air Wind Relative

remit_ rature (miles) humidity
Evaporation Solar
(~ Rainfall (in. of radiation He igh t %
Date Max Min (in) water) (g eal/em 2) 10 m 0.5 m Min Max
5"
October 9 73 52 0.00 0.08 230 30 8.0 92 99 ~"
10 76 51 0.00 0.07 279 27 7,0 76 99 cr

11 75 48 0.00 0.10 344 91 32.0 84 99 >

N

12 77 53 0.00 0.11 338 - 64.0 82 99 =

13 69 58 0.74 0,12 123 210 73.0 94 99 ~
14 65 48 0.00 0.16 395 190 156.0 56 99 ~.
15 73 51 0.00 0.14 287 193 97.0 60 98 ~
16 54 41 0.00 0.23 353 240 112.0 64 99 o

17 54 40 0.00 0.05 225 203 120.0 68 90 ,~

18 56 37 0.00 0.09 220 133 56.0 74 98 ~"

0
19 62 29 0.00 0.12 359 169 111.0 64 98 ~--.
20 56 47 0.00 0.06 225 86 32.0 66 98 N

21 60 35 0,00 0.05 360 48 13.0 74 99

22 69 34 0.00 0.09 348 31 8.0 66 99

23 72 34 0.00 0.06 333 33 10.0 66 98

L~
O~
362 F.R. Hall et al.

Acknowledgment

We thank William Kwolek (ARS) for statistical analyses of these experiments. We also
thank Donald Collins (ARS), and John Gregory and James Mason (Ohio Agricultural Re-
search and Development Center) for technical assistance.

References

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 Dislodgeable Azinphos Residues on Apple Foliage 363

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Manuscript received July 24, 1974; accepted October 4, 1974.