Monitoring the Performance of Eastern Spruce Budworm Pheromone

Jun 18, 1982 - Insect Pheromone Technology: Chemistry and Applications. Chapter 11, pp ... both in the laboratory and following aerial application in ...
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11 Monitoring the Performance of Eastern Spruce Budworm Pheromone Formulations C. J. WIESNER and P. J. SILK

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New Brunswick Research and Productivity Council, Fredericton, New Brunswick, E 3 B 5H1, Canada New methods and a p p a r a t u s a r e described for evaluating t h e pheromone release characteristics of controlled release formulations o f Δ11-tetradecenal b o t h in the laboratory and following aerial application in the field. L a b o r a t o r y release r a t e s d e t e r m i n e d b y t h e s e methods correlate well with rates o b s e r v e d in t h e

field.

The f i r s t a t t e m p t s t o i n f l u e n c e m a t i n g b e h a v i o u r o f i n s e c t s i n t h e i r n a t u r a l h a b i t a t using broadcast formulations of sex pheromones were c o n d u c t e d i n t h e e a r l y s e v e n t i e s ( 1 , 2., 3 ) . B e r o z a and h i s c o - w o r k e r s were a b l e t o show e f f e c t i v e r e d u c t i o n o f m a t i n g s u c c e s s i n l o w - l e v e l i n f e s t a t i o n s o f g y p s y moth. I n t h e i n t e r v e n i n g t e n y e a r s , a l a r g e number o f " m a t i n g - d i s r u p t i o n " t e s t s have b e e n c a r r i e d o u t a g a i n s t b o t h a g r i c u l t u r a l a n d f o r e s t i n s e c t s ( 4 ) . I n v i r t u a l l y a l l i n s t a n c e s , t h e problem has proven t o b e f a r more c o m p l e x t h a n h a d b e e n a n t i c i p a t e d . The i n t e r p l a y of b i o l o g i c a l , c h e m i c a l and e n v i r o n m e n t a l f a c t o r s has o f t e n l e d to i n c o n c l u s i v e f i e l d t r i a l r e s u l t s . A l ltoooften the c r i t e r i a f o r s u c c e s s h a v e n o t b e e n met, w h i l e t h e c a u s e f o r f a i l u r e h a s b e e n o b s c u r e d due t o a l a c k o f c o n t r o l o r u n d e r s t a n d i n g o f t h e many v a r i a b l e s . One o f t h e s e v a r i a b l e s w h i c h o b v i o u s l y h a s a p o w e r f u l i n ­ f l u e n c e on t h e r e s u l t i s t h e performance o f t h e c o n t r o l l e d r e ­ l e a s e f o r m u l a t i o n . H a p p i l y , t h i s v a r i a b l e i s one w h i c h c a n , i n p r i n c i p l e , be p r e d i c t e d and c o n t r o l l e d . The e a s t e r n s p r u c e budworm, C h o r i s t o n e u r a f u m i f e r a n a , C l e m . , i s one o f t h e most e c o n o m i c a l l y i m p o r t a n t c o n i f e r o u s f o r e s t d e f o ­ l i a t o r s i n t h e w o r l d . S e v e r a l mating d i s r u p t i o n experiments and f i e l d t r i a l s have b e e n c o n d u c t e d s i n c e t h e m i d 1 9 7 0 s (_5, 6), A g r e a t d e a l h a s b e e n l e a r n e d i n t h e p r o c e s s b u t no c l e a r - c u t c o n ­ c l u s i o n s r e g a r d i n g t h e f e a s i b i l i t y o f t h i s a p p r o a c h a s a manage­ ment t o o l h a v e , a s y e t , emerged. I n an e f f o r t t o s i m p l i f y t h e i n t e r p r e t a t i o n o f f u t u r e f i e l d e x p e r i m e n t s , we u n d e r t o o k a s t u d y T

0097-6156/82/0190-0209$06.00/0 © 1982 American Chemical Society

In Insect Pheromone Technology: Chemistry and Applications; Leonhardt, B., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

INSECT

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210

PHEROMONE

TECHNOLOGY

of the performance of v a r i o u s c o n t r o l l e d r e l e a s e f o r m u l a t i o n s of ΔΙΙ-tetradecenal ( T D A L ) , t h e s e x pheromone o f t h e e a s t e r n s p r u c e budworm. The a i m was t o f i n d one o r more f o r m u l a t i o n s whose p e r ­ f o r m a n c e i s p r e d i c t a b l e and e f f i c i e n t u n d e r o u r p a r t i c u l a r N o r t h ­ e a s t e r n e n v i r o n m e n t a l c o n d i t i o n s . T h i s p a p e r d e s c r i b e s and i l l u s ­ t r a t e s t h e t e c h n i q u e s w h i c h were developed d u r i n g t h e course o f that study. E a r l y e x p e r i m e n t s i n o u r l a b o r a t o r y were concerned w i t h methods f o r s a m p l i n g and a n a l y s i s o f TDAL f r o m f o r m u l a t i o n s ( 6 ) , i n s e c t s (7_) and f r o m t h e f o r e s t a t m o s p h e r e ( 8 ) . T h i s w o r k was l a r g e l y f o u n d e d upon c o n c e p t s d e v e l o p e d p r e v i o u s l y by B e r o z a et_ a l . ( 9 , 1Ό, 1 1 ) . S i n c e t h e n , s e v e r a l o t h e r g r o u p s h a v e a p p l i e d t h e s e c o n c e p t s t o t h e measurement o f a number o f d i f f e r e n t i n s e c t pheromone r e l e a s e r a t e s ( 1 2 , 1 3 ) . On t h e b a s i s o f o u r e a r l y f i n d i n g s , we w e r e c o n v i n c e d t h a t t h e e x i s t i n g l a b o r a t o r y t e c h ­ n i q u e s f o r r e l e a s e r a t e d e t e r m i n a t i o n f r o m f o r m u l a t i o n s were inadequate. Laboratory tested formulations d i d not experience t h e e x t r e m e s o f c l i m a t i c v a r i a t i o n w h i c h a r e t h e norm i n t h e f i e l d and c o n s e q u e n t l y t h e r e l e a s e r a t e r e s u l t s w e r e n o t t r a n s f e r a b l e to f i e l d performance. I n o r d e r t o d e v i s e r e l e a s e r a t e methods w h i c h more c l o s e l y s i m u l a t e d t h e n a t u r a l a g e i n g p r o c e s s , we c o n c e n t r a t e d o u r e f f o r t s on t h r e e m a i n a s p e c t s o f f o r m u l a t i o n e v a l u a t i o n : 1. Wind T u n n e l A g e i n g , 2. E f f l u v i a l A n a l y s i s , and 3. A t m o s p h e r i c C o n c e n t r a t i o n . Wind T u n n e l A g e i n g E s t i m a t i o n o f r e l e a s e r a t e s by measurement o f r e s i d u a l p h e r ­ omone as a f u n c t i o n o f age i s s i m p l e and e c o n o m i c a l . However, s i n c e t h e method q u a n t i t a t e s t h e amount o f a c t i v e i n g r e d i e n t s r e m a i n i n g i n t h e f o r m u l a t i o n , t h e r e l e a s e r a t e i s d e t e r m i n e d by i n f e r e n c e and d o e s n o t t a k e i n t o a c c o u n t e i t h e r d e g r a d a t i o n o r p o l y m e r i z a t i o n ( 1 4 ) . G i v e n a l a b i l e a l d e h y d i c pheromone s u c h as TDAL, t h e s e p o t e n t i a l c h e m i c a l c h a n g e s must be t a k e n i n t o a c c o u n t . N e v e r t h e l e s s , a l a b o r a t o r y method f o r s i m u l a t i n g t h e n a t u r a l ageing process i s e s s e n t i a l . Our f i r s t s t e p was t o d e v e l o p a s i m p l e e f f e c t i v e w i n d t u n n e l w h i c h a l l o w e d us t o age f o r m u l a t i o n s i n t h e l a b o r a t o r y u n d e r v e r y n e a r l y n a t u r a l c o n d i t i o n s . Rather than attempt to c o n t r o l a l l c l i m a t i c parameters - temperature, pressure, humidity, l i g h t i n ­ t e n s i t y , wind speed, t u r b u l e n c e , e t c . - w h i c h would have been a f o r m i d a b l e e n g i n e e r i n g t a s k , a v e r y s i m p l e d e s i g n was c h o s e n i n w h i c h o n l y a i r s p e e d , t e m p e r a t u r e and i l l u m i n a t i o n w e r e c o n t r o l l e d The o n l y r e a l d e f i c i e n c y i n t h i s s y s t e m i s t h e l a c k o f c o n t r o l o f humidity. However, t h a t a s p e c t was a d d r e s s e d s e p a r a t e l y by meas­ u r i n g t h e pheromone r e l e a s e r a t e o f e a c h f o r m u l a t i o n u n d e r c o n ­ d i t i o n s o f v e r y h i g h and v e r y l o w h u m i d i t y . To d a t e , none o f t h e c a n d i d a t e s t e s t e d h a s shown a m a j o r h u m i d i t y d e p e n d e n c e . The w i n d t u n n e l i s shown i n F i g u r e 1. A i r f l o w w h i c h i s g e n ­ e r a t e d b y an e x h a u s t f a n ( D ) c a n be v a r i e d f r o m a b o u t 0.2 - 3.0

In Insect Pheromone Technology: Chemistry and Applications; Leonhardt, B., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

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m e t e r s p e r s e c o n d . A i r i s drawn t h r o u g h a h e a t e r ( A ) , p a s s e s i n t o a m i x i n g c h a m b e r ( B ) and i n t o t h e t e s t s e c t i o n ( C ) . A c c e s s t o t h e t e s t s e c t i o n i s through a glass port(E) which a l s o permits i l l u m i n a t i o n by a s t a n d a r d s u n l a m p ( F ) . The o p e r a t i n g c o n d i t i o n s w e r e a r r i v e d a t e m p i r i c a l l y b y a d j u s t i n g t e m p e r a t u r e , w i n d s p e e d and i l l u m i n a t i o n on a d i u r n a l c y c l e u n t i l c o n d i t i o n s were f o u n d w h i c h g e n e r a t e d t h e same r e s i d u a l pheromone c u r v e f r o m a s t a n d a r d f o r m u l a t i o n i n t h e t u n n e l as t h a t f o r m u l a t i o n e x p e r i e n c e d i n t h e f i e l d . For t h i s standardi z a t i o n , o n e - e i g h t h i n c h s q u a r e H e r e o n f l a k e s c o n t a i n i n g an a v e r age 1 3 . 3 % TDAL by w e i g h t w e r e u s e d . T h i s , as w e l l as a l l o t h e r f o r m u l a t i o n s , w e r e t e s t e d , as n e a r l y as p o s s i b l e , i n t h e same f o r m w h i c h t h e y w o u l d h a v e upon a e r i a l a p p l i c a t i o n . They w e r e e i t h e r c o a t e d o r m i x e d w i t h a recommended s t i c k e r and m e a s u r e d a l i q u o t s were a p p l i e d t o r o u n d s o f f i l t e r p a p e r . T h e s e w e r e t h e n mounted on r a c k s i n t h e t e s t s e c t i o n o f t h e t u n n e l . H a v i n g shown t h a t i d e n t i c a l a g e i n g c u r v e s c o u l d be g e n e r a t e d w i t h one f o r m u l a t i o n , t h e a s s u m p t i o n was made t h a t , u n d e r t h e same o p e r a t i n g c o n d i t i o n s , o t h e r f o r m u l a t i o n s would a l s o behave s i m i l a r l y i n t h e t u n n e l and t h e f o r e s t . The o p e r a t i n g c o n d i t i o n s o f t h e t u n n e l a r e as f o l l o w s : L i g h t / 8 h o u r s / 25 ± 1°C / 2.4 ± 0.1 m/s D a r k / 16 h o u r s / 14 ± 1°C / 0.55 ± 0.02 m/s Effluvial

Analysis

The a c t u a l a i r v e l o c i t y i n o u r o r i g i n a l e f f l u v i a l pumping chamber (6) o p e r a t i n g a t 100 c c / m i n was a b o u t 5 cm/min, w h i c h we r e g a r d as n e g l i g i b l e . T h i s , we b e l i e v e d , was l a r g e l y r e s p o n s i b l e f o r t h e l a c k o f c o r r e l a t i o n b e t w e e n l a b o r a t o r y e f f l u v i a l and f i e l d r e s i d u a l pheromone r e l e a s e r a t e s . I n o r d e r t o a c h i e v e r e a l i s t i c a i r v e l o c i t i e s , t h e d i a m e t e r o f t h e chamber was c o n s t r i c t e d c o n siderably. The m o d i f i e d chamber i s shown i n F i g u r e 2. The f o r m u l a t i o n i s s u s p e n d e d on a w i r e i n t h e c a s e o f l a r g e p a r t i c l e s w h i l e m i c r o d i s p e r s e d m a t e r i a l s a r e c o a t e d o n a wooden p o p s i c l e stick. These a r e p l a c e d i n t h e i n n e r tube(A) w i t h o u t t o u c h i n g t h e glass wall. The t u b e i s t h e n i n s e r t e d t h r o u g h a s t o p p e r i n t o t h e l a r g e r c h a m b e r ( B ) t o w i t h i n 2 cm o f t h e bed o f P o r a p a k Q® r e s i n ( C ) s u p p o r t e d on a g l a s s s i n t e r . The a p p a r a t u s i s p l a c e d i n a t e m p e r a t u r e c o n t r o l l e d chamber and c o n n e c t e d t o a n i t r o g e n s o u r c e . With t h i s a r r a n g e m e n t , i t i s p o s s i b l e t o g e n e r a t e a i r v e l o c i t i e s up t o 102 m/min i n t h e i n n e r t u b e . The s a m p l e s a r e pumped f o r two h o u r s a f t e r w h i c h t h e r e s i n and t h e w a l l s o f t h e m a i n chamber a r e washed w i t h p e n t a n e . The TDAL i s t h e n q u a n t i t a t e d by GC. Experi m e n t s r u n a t maximum f l o w r a t e s w i t h two a d s o r b e r s i n s e r i e s , showed n e g l i g i b l e b r e a k t h r o u g h ( a p p r o x . 0 . 4 % ) . The a n a l y t i c a l methods h a v e b e e n d e s c r i b e d i n d e t a i l e l s e w h e r e ( 7 ) . 1.

T h i s a p p a r a t u s i s u s e d f o r two t y p e s o f e x p e r i m e n t s : A i r v e l o c i t y d e p e n d e n c e o f t h e r e l e a s e r a t e a t 25°C and 2.7,

In Insect Pheromone Technology: Chemistry and Applications; Leonhardt, B., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

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Mixing Chamber Β

PHEROMONE

Sunlamp

TECHNOLOGY

F , Heat Sensor

7'

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[v/ννννννγι w w w w ^ Λ Λ Λ Λ Λ Λ Λ Α > Λ Λ Λ Λ Λ Λ Λ Γ

νΛΛΛΛΛΛΛ/

Heater A Figure 1.

Test Section C

Wind tunnel for formulation aging. Dimensions of test section are: length, 40; width, 20; and height, 20 cm.

N;

FLOWMETER

PORAPAK Q c

Figure 2.

Modified effluvial pumping chamber. Key: A, inner tube; B, larger chamber; and C, Porapak Q resin.

In Insect Pheromone Technology: Chemistry and Applications; Leonhardt, B., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

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wiESNER A N D S I L K

Eastern Spruce Budworm

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26.9 and 102 m/min and 2. T e m p e r a t u r e dependence o f t h a t r a t e a t f o u r t e m p e r a t u r e s (10°, 15°, 20° and 30°C) and 26.9 m/min a i r v e l ­ ocity. A l l measurements a r e made on f o r m u l a t i o n s w h i c h h a v e been aged f o r s e v e n days i n t h e w i n d t u n n e l .

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Laboratory

Release Rate

Results

To d a t e , o v e r a d o z e n d i f f e r e n t f o r m u l a t i o n s h a v e b e e n t e s t e d i n o u r l a b o r a t o r y . The f o l l o w i n g t h r e e e x a m p l e s r e p r e s e n t a c r o s s s e c t i o n o f t h e t e s t r e s u l t s and a r e p r e s e n t e d t o i l l u s t r a t e t h e a p p l i c a t i o n o f t h e s e new t e c h n i q u e s : (A) H e r e o n 1/8" f l a k e s , (B) C a p s u l a r P r o d u c t s Company m i c r o c a p s u l e s , (C) I m p e r i a l Chemical I n d u s t r i e s microcapsules. The w i n d t u n n e l r e s i d u a l pheromone c u r v e s f o r t h e t h r e e f o r ­ m u l a t i o n s a r e shown i n F i g u r e 3. Examination o f these curves suggests immediately t h a t formu­ l a t i o n s A and C have r e a s o n a b l y c o n s t a n t r a t e s o f r e l e a s e and an e f f e c t i v e l i f e - t i m e o f p o s s i b l y f o r t y days w h i l e Β has l o s t 90% o f i t s a c t i v e i n g r e d i e n t i n t h e f i r s t week. The s c a t t e r a b o u t t h e c u r v e C may b e due t o t h e d i f f i c u l t y o f r e p r o d u c i b l y s a m p l i n g microdispersed formulations. F i g u r e 4. shows t h e e f f e c t o f a i r v e l o c i t y upon t h e r e l e a s e r a t e o f f o r m u l a t i o n "A" pumped f o r a t o t a l o f s i x h o u r s . Measure­ ments w e r e made a t t h r e e f l o w r a t e s ( 2 . 7 , 26.9 and 102 m/min) and a t 25°C. E a c h p o i n t r e p r e s e n t s t h e a v e r a g e r e l e a s e r a t e o f a c t i v e i n g r e d i e n t i n t h e p r e c e d i n g two h o u r s o f pumping. A t 2.7 m/min t h e r a t e o f r e l e a s e i s c o n s t a n t w i t h t i m e o f pumping, h o w e v e r , a t t h e h i g h e r f l o w r a t e s a b o u t f o u r h o u r s o f e x p o s u r e were r e q u i r e d to achieve a steady-state r a t e of r e l e a s e . A b r i e f i n s p e c t i o n o f t h e s l o p e o f t h e r e s i d u a l pheromone c u r v e "A" i n F i g u r e 3. i n d i c a t e s a r e l e a s e r a t e o f 4.3% p e r day on day 7 and 1.1% p e r day on d a y 28. T h i s t r a n s l a t e s t o 2 y g / h r and 0.5 y g / h r , r e s p e c t i v e l y . The s e v e n day v a l u e compares v e r y w e l l w i t h 1.75 y g / h r , t h e s t e a d y s t a t e r e l e a s e r a t e m e a s u r e d a t 102 m/min. ( F i g u r e 4.) F i g u r e 5. i l l u s t r a t e s t h e s t e a d y - s t a t e r e l e a s e r a t e d e p e n d ­ ence o f f o r m u l a t i o n C. I n a l l c a s e s , e x t r a p o l a t i o n o f t h e c u r v e s s u g g e s t s t h a t t h e y p l a t e a u beyond a b o u t 100 m/min. F i n a l l y , F i g u r e 6. i l l u s t r a t e s t h e t e m p e r a t u r e d e p e n d e n c e o f f o r m u l a t i o n A. Atmospheric Concentration

Analysis

The f i n a l s t e p i n t h e t e s t i n g p r o g r a m e v a l u a t e s t h e p e r ­ f o r m a n c e o f m a t e r i a l a e r i a l l y a p p l i e d on s m a l l f i e l d p l o t s . Since t h i s p r o c e d u r e aims t o d e f i n e t h e p h y s i c o - c h e m i c a l c h a r a c t e r i s t i c s o f e a c h p r o d u c t , n o t t h e b i o l o g i c a l e f f e c t , t h e f o l l o w i n g two processes are monitored: 1. R e s i d u a l pheromone f r o m f o r m u l a t i o n c o l l e c t e d i n t h e f i e l d z e r o t o f o r t y d a y s p o s t a p p l i c a t i o n and 2. a t m o s p h e r i c c o n c e n t r a t i o n o f TDAL i n t h e f o r e s t c a n o p y .

In Insect Pheromone Technology: Chemistry and Applications; Leonhardt, B., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

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χ

0

2

4

6

8

10 12 14 16 18 20 22 24 26 28 30 A G E (days)

Figure 3. Residual pheromone curves for formulations A, B, and C aged 3-4 weeks in the wind tunnel. Key: Α, (Πλ Hereon flakes; B, (O), Capsular Products Company microcapsules; C, (X), Imperial Chemical Industries microcapsules.



Figure 4. Release rates at 3 wind velocities and 25°C of formulation A aged 7 days in the wind tunnel. Key: 2.7 m/min (^); 26.9 m/min (Αλ* and 102 m/min (·)·

In Insect Pheromone Technology: Chemistry and Applications; Leonhardt, B., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

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11.

Eastern

wiESNER A N D S I L K

5

Spruce Budworm

215

Pheromone

100

50 V E L O C I T Y (m/min)

Figure 5.

10

Wind velocity dependence of the steady-state release rate of formulation C at 25°C, aged 7 days in the wind tunnel.

15

TEMPERATURE Figure 6.

30

20 °C

Temperature dependence of the release rate of formulation A aged 7 days in the wind tunnel at a wind velocity of 26.9 m/min.

In Insect Pheromone Technology: Chemistry and Applications; Leonhardt, B., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

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216

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TECHNOLOGY

The measurement o f pheromone c o n c e n t r a t i o n s i n t h e atmos­ p h e r e was f i r s t d e s c r i b e d b y C a r o e t a l . f o r d i s p a r l u r e ( 1 1 ) . U s i n g a n a d a p t a t i o n o f h i s method we h a v e d e v e l o p e d s a m p l i n g and a n a l y t i c a l techniques s p e c i f i c a l l y f o r tetradecenal q u a n t i t a t i o n . The a l d e h y d e i s t r a p p e d w i t h h i g h v o l u m e s a m p l e r s s u s p e n d e d i n m i d - c a n o p y d r a w i n g 25 - 30 nrfyhr o f a i r t h r o u g h a b e d o f 20 g o f A m b e r l i t e XAD-2® r e s i n . O r i g i n a l l y t h e pheromone was d e r i v a t i z e d t o t h e p e n t a f l u o r o b e n z y l oxime a f t e r s o l v e n t e x t r a c t i o n f r o m t h e r e s i n ( 8 ) . T h i s was f o l l o w e d by s i l i c a g e l c o l u m n c l e a n - u p and q u a n t i t a t i o n b y c a p i l l a r y GC w i t h e l e c t r o n c a p t u r e d e t e c t i o n . T h i s gave s a t i s f a c t o r y r e s u l t s b u t was t e d i o u s and e x p e n s i v e . A l s o the d e r i v a t i z a t i o n produced e l e c t r o n c a p t u r i n g i m p u r i t i e s w h i c h o c c a s i o n a l l y i n t e r f e r e d w i t h t h e t e t r a d e c e n a l peak. Our p r e s e n t method o f a n a l y s i s i n v o l v e s q u a n t i t a t i o n o f TDAL u s i n g a c a p i l l a r y c o l u m n GC/MS t e c h n i q u e . The GC/Mass S p e c t r o m e t e r ( F i n n i g a n 4021) i s u s e d i n t h e m u l t i p l e i o n d e t e c t i o n (MID) mode u n d e r computer c o n t r o l . S p e c i f i c ions i n both the i n t e r n a l stan­ d a r d ( d e c y l b e n z e n e ) and t h e pheromone a r e r e c o r d e d . The c o m b i n ­ a t i o n o f h i g h r e s o l u t i o n c a p i l l a r y g a s c h r o m a t o g r a p h y and t h e s p e c i f i c i t y o f t h e mass s p e c t r o m e t e r i n t h e MID mode, makes t h i s t e c h n i q u e s u p e r i o r t o t h e oxime method, a l b e i t , a l i t t l e l e s s sensitive. (EC M O O p e g ; MID ^ 5 0 0 peg) F i g u r e 7. shows t h e r e s u l t s o f a f i e l d t e s t o f f o r m u l a t i o n A. The p l a s t i c l a m i n a t e d f l a k e s w e r e a p p l i e d a t a v e r y h i g h r a t e ( 5 0 0 g A . I . / h a ) on J u n e 2 9 t h , 1980 t o a m i x e d s p r u c e / f i r s t a n d n e a r M a c h i a s , M a i n e . The two c u r v e s r e p r e s e n t mid-day (12:00 - 14:00) canopy c o n c e n t r a t i o n s o f TDAL as w e l l as t h e t e m p e r a t u r e s a t t h a t time. A p e r i o d o f h e a v y r a i n s p a n n i n g J u l y 1 s t and 2nd i s r e ­ f l e c t e d b o t h i n l o w noon t e m p e r a t u r e s and l o w a l d e h y d e c o n c e n t r a ­ tions. As m e n t i o n e d a b o v e , t h e s l o p e o f r e s i d u a l pheromone c u r v e "A" ( F i g U r e 3.) g i v e s t h e r e l e a s e r a t e on day 7 a s 2 y g / h r and on day 28 a s 0.5 y g / h r , a r a t i o o f 4:1. The a t m o s p h e r i c c o n c e n t r a t i o n s on t h o s e days w e r e 5 ng/m^ and 0.5 ng/m^, a r a t i o o f 1 0 : 1 . I n v i e w o f t h e unknown d i l u t i o n e f f e c t o f v a r y i n g m e t e o r o l o g i c a l c o n d i t i o n s , t h e r e l a t i v e c o r r e s p o n d e n c e b e t w e e n r e l e a s e r a t e and a t m o s p h e r i c c o n c e n t r a t i o n i s q u i t e good. Conclusions The t e c h n i q u e s d e s c r i b e d and i l l u s t r a t e d above now e n a b l e us to p r e d i c t r e l i a b l y t h e i n f l u e n c e o f t h e major c l i m a t i c v a r i a b l e s upon t h e r a t e o f r e l e a s e o f ΔΙΙ-tetradecenal f r o m c o n t r o l l e d r e ­ l e a s e f o r m u l a t i o n s under f i e l d c o n d i t i o n s . With s u i t a b l e r e c a l i b r a t i o n , t h e s e methods s h o u l d be a p p l i c a b l e t o any c l i m a t i c c o n d i t i o n s as w e l l as any c h e m i c a l s . A complete understanding o f the r e l e a s e performance o f a given f o r m u l a t i o n w i l l , f o r t h e f i r s t t i m e , p e r m i t us t o i n t e r p r e t t h e r e s u l t s o f a f i e l d treatment w i t h t h e c o n f i d e n c e t h a t we a r e d e a l i n g w i t h a b i o l o g i c a l e f f e c t , n o t a formulation effect.

In Insect Pheromone Technology: Chemistry and Applications; Leonhardt, B., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

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11.

wiESNER A N D S I L K

JUNE Figure 7.

Eastern

JULY

Spruce Budworm

Pheromone

AUGUST

Midday pheromone concentrations and temperatures at mid-canopy following aerial application of formulation A (500 g a.i./ha).

In Insect Pheromone Technology: Chemistry and Applications; Leonhardt, B., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

217

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TECHNOLOGY

Acknowledgments Support o f t h i s p r o j e c t by t h e Canadian F o r e s t r y S e r v i c e , En­ v i r o n m e n t Canada u n d e r C o n t r a c t 1SS80-00066, i s g r a t e f u l l y acknow­ ledged.

Literature Cited 1. 2.

Downloaded by PURDUE UNIV on August 28, 2014 | http://pubs.acs.org Publication Date: June 18, 1982 | doi: 10.1021/bk-1982-0190.ch011

3. 4.

5.

6.

7. 8. 9. 10.

11. 12. 13. 14.

Stevens, L.J., and Beroza, M. J. Econ. Entomol. 1972, 65, 1090-5. Beroza, M.; Stevens, L.J.; Bierl, B.A.; Philips, F.M.; T a r d i f f , J . G . R . E n v i r o n . Entomol. 1973, 2, 1051-7. Beroza, M.; Hood, C.S.; Trefey, D . ; Leonard, D.E.; K l a s s e n , W.; Stevens, L.J. J. Econ. Entomol. 1974, 67, 659-64. R o e l o f s , Wendell L., E d . " E s t a b l i s h i n g E f f i c a c y of Sex A t t r a c t a n t s and D i s r u p t a n t s f o r Insect C o n t r o l " ; The Entom­ ological Society of America, 1979. Sanders, C.J. in "Chemical Ecology: Odour Communication i n A n i m a l s " ; F.J. Ritter, E d . ; E l s e v i e r / N o r t h - H o l l a n d Biomedical P r e s s : Amsterdam, 1979; p 281. Wiesner, C.J., and Silk, P.J. "Report of Spruce Budworm Pher­ omone Trials - Maritimes 1978"; Maritimes F o r . Res. Centre, File Rep.; 62-64. S i l k , P.J.; Tan, S . H . ; Wiesner, C.J.; Ross, R.J.; Lonergan, G.C. E n v i r o n . Entomol. 1980, 9, 640-644. Wiesner, C.J.; Silk, P.J.; Tan, S . H . ; Fullarton, S. Can. E n t . 1980, 112, 333-334. Beroza, M.; Bierl, B.A.; James, R.; Devilbiss, D. J. Econ. Entomol. 1975, 68, 369-372. Beroza, M. in "Pest Management w i t h Insect Sex A t t r a c t a n t s and other Behaviour C o n t r o l l i n g Chemicals"; M. Beroza, E d . ; ACS Symposium S e r i e s , Number 23. American Chemical S o c i e t y : Washington, D . C . , 1976; p 99. Caro, J.H.; Bierl, B.A.; Freeman, H.P.; Sonnet, P . E . J . Agric. Food Chem. 1978, 26, 461-463. Look, M. J. Chem. E c o l . 1976, 2, 482-486. C r o s s , J.H.; Tumlinson, J.H.; Heath, R.E.; B u r n e t t , D . E . J. Chem. E c o l . 1980, 6, 759-770. C r o s s , J . H . J. Chem. E c o l . 1980, 6, 789-795.

RECEIVED February 24,

1982.

In Insect Pheromone Technology: Chemistry and Applications; Leonhardt, B., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1982.