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UBC Theses and Dissertations

Radial distribution of thujaplicins and thujic acid in old growth and second growth western redcedar.. Nault, Jason Ray 1986

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RADIAL DISTRIBUTION OF T H U J A P L I C I N S AND THUJIC ACID I N OLD GROWTH AND SECOND GROWTH WESTERN REDCEDAR (THUJA P L I C A T A DONN)  by JASON RAY NAULT B.Sc,  The U n i v e r s i t y o f W i n n i p e g , 1976  A THESIS SUBMITTED I N P A R T I A L FULLFILLMENT OF THE REQUIREMENT FOR THE DEGREE OF MASTER OF SCIENCE in THE FACULTY OF GRADUATE STUDIES (DEPARTMENT OF FORESTRY)  We a c c e p t t h i s to  r e p o r t as conforming  the required standard.  The U n i v e r s i t y o f B r i t i s h  April  13,  Columbia  1986  ® J a s o n R a y N a u l t , 1986  In p r e s e n t i n g  this  thesis i n partial  f u l f i l m e n t of the  r e q u i r e m e n t s f o r an a d v a n c e d d e g r e e a t t h e  University  of B r i t i s h Columbia, I agree that the L i b r a r y s h a l l it  freely  a v a i l a b l e f o r r e f e r e n c e and s t u d y .  agree t h a t p e r m i s s i o n f o r extensive for  s c h o l a r l y p u r p o s e s may  for  financial  of  FORESTRY  The U n i v e r s i t y o f B r i t i s h 1956 Main M a l l V a n c o u v e r , Canada V6T 1Y3 Date  APRIL 14, 1986  Columbia  my  It is thesis  s h a l l n o t be a l l o w e d w i t h o u t my  permission.  Department  thesis  be g r a n t e d by t h e h e a d o f  copying or p u b l i c a t i o n of t h i s  gain  further  copying of t h i s  d e p a r t m e n t o r by h i s o r h e r r e p r e s e n t a t i v e s . understood that  I  make  written  ii  ABSTRACT Radial cross  sections  of seven o l d growth cedars  second growth cedars taken increments averaging and  at  breast  height  were  and t e n cut  into  a b o u t 60 y e a r s g r o w t h f o r o l d g r o w t h  10 y e a r s g r o w t h f o r s e c o n d g r o w t h t r e e s .  These  trees  increments  w e r e e x t r a c t e d w i t h e t h a n o l : b e n z e n e (1:2). The e x t r a c t i v e s w e r e analyzed chelates,  f o rt h u j a p l i c i n content by c o l o r i m e t r y a s w e l l a s b y a new m e t h o d  chromatography statistical 0.81  (GC)  of  their  utilizing  methylated  a n a l y s i s o f t h e two methods gave  and a s l o p e  of  0.99.  Thujic  of t h e i r  acid  ferric  capillary derivatives.  an  r^  contents  value were  gas A of also  d e t e r m i n e d b y t h e new GC method. D i s t r i b u t i o n of t h u j a p l i c i n s increased  from p i t h t o o u t s i d e  and  thujic  acid  generally  heartwood, then decreased i n t h e  sapwood. Maximum t h u j a p l i c i n c o n t e n t s w e r e a l s o r e l a t e d t o t h e t r e e age.  TABLE OF CONTENTS page ABSTRACT TABLE OF CONTENTS L I S T OF TABLES L I S T OF FIGURES L I S T OF APPENDICES  i  i  i  i  i i v v ix  ACKNOWLEDGEMENT  x  INTRODUCTION  1  LITERATURE REVIEW  2  MATERIALS AND METHODS  7  RESULTS  10  DISCUSSION  12  CONCLUSION  16  LITERATURE CITED  17  iv  L I S T OF TABLES TABLE 1.  GC SAMPLES ANALYZED WITH R E P L I C A T I O N  21  TABLE 2.  COMPARISON OF DATA WITH LITERATURE VALUES...21  L I S T OF FIGURES FIGURE  1.  SAMPLING PROCEDURE  22  FIGURE  2.  RADIAL DISTRIBUTION OF ETHANOL:BENZENE EXTRACTIVES FOR SECOND GROWTH S I T E #1  FIGURE  3.  RADIAL DISTRIBUTION OF ETHANOL BENZENE EXTRACTIVES FOR SECOND GROWTH S I T E #2  FIGURE  4.  5.  6.  7.  26  COMPARISON OF T H U J A P L I C I N RESULTS OBTAINED BY COLORIMETRY AND GLC  FIGURE  25  ETHANOL:BENZENE EXTRACTIVE CONTENT I S AVERAGE RINGS FROM P I T H FOR A L L TRES  FIGURE  24  RADIAL DISTRIBUTION OF ETHANOL:BENZENE EXTRACTIVES FOR OLD GROWTH TREES  FIGURE  23  T H U J A P L I C I N CONTENT BY TWO  27  METHODS  AVERAGE RINGS FROM P I T H FOR SECOND GROWTH TREE #1.1 FIGURE  8.  28  T H U J A P L I C I N CONTENT BY TWO METHODS VS AVERAGE RINGS FROM P I T H FOR SECOND GROWTH TREE #1.2  FIGURE  9.  28  T H U J A P L I C I N CONTENT BY TWO METHODS VS. AVERAGE RINGS FROM P I T H FOR SECOND GROWTH TREE #1.3  FIGURE 10.  29  T H U J A P L I C I N CONTENT BY TWO METHODS Y £ AVERAGE RINGS FROM P I T H FOR SECOND GROWTH TREE #1.4  29  vi  FIGURE 1 1 .  T H U J A P L I C I N CONTENT BY TWO METHODS VS. AVERAGE RINGS FROM P I T H FOR SECOND GROWTH TREE #1.5  FIGURE 12.  30  T H U J A P L I C I N CONTENT BY TWO METHODS VS. AVERAGE RINGS FROM P I T H FOR SECOND GROWTH TREE #2.1  FIGURE 13.  30  T H U J A P L I C I N CONTENT BY TWO METHODS Y £ AVERAGE RINGS FROM P I T H FOR SECOND GROWTH TREE #2.2  FIGURE 14.  31  T H U J A P L I C I N CONTENT BY TWO METHODS V_S_ AVERAGE RINGS FROM P I T H FOR SECOND GROWTH TREE #2.3  FIGURE 15.  31  T H U J A P L I C I N CONTENT BY TWO METHODS VS AVERAGE RINGS FROM P I T H FOR SECOND GROWTH TREE #2.4  FIGURE 16.  32  T H U J A P L I C I N CONTENT BY TWO METHODS V_S AVERAGE RINGS FROM P I T H FOR SECOND GROWTH TREE #2.5  FIGURE 17.  32  T H U J A P L I C I N CONTENT BY TWO METHODS VS AVERAGE RINGS FROM P I T H FOR OLD GROWTH TREE #1  FIGURE 18.  33  T H U J A P L I C I N CONTENT BY TWO METHODS Y_S AVERAGE RINGS FROM P I T H FOR OLD GROWTH TREE #2  33  vii  FIGURE 19.  T H U J A P L I C I N CONTENT BY TWO METHODS V§ AVERAGE RINGS FROM P I T H FOR OLD GROWTH TREE #3  FIGURE 20.  34  T H U J A P L I C I N CONTENT BY TWO METHODS VS. AVERAGE RINGS FROM P I T H FOR OLD GROWTH TREE #4  FIGURE 2 1 .  34  T H U J A P L I C I N CONTENT BY TWO METHODS VS AVERAGE RINGS FROM P I T H FOR OLD GROWTH TREE #5  FIGURE 22.  35  T H U J A P L I C I N CONTENT BY TWO METHODS VS AVERAGE RINGS FROM P I T H FOR OLD GROWTH TREE #6  FIGURE 23. N  T H U J A P L I C I N CONTENT BY TWO METHODS Y § AVERAGE RINGS FROM P I T H FOR OLD GROWTH TREE #7  FIGURE 24.  36  BETA+GAMMA T H U J A P L I C I N CONTENT V§ AVERAGE RINGS FROM P I T H FOR A L L TREES  FIGURE 25.  35  37  BETA+GAMMA T H U J A P L I C I N CONTENT 1 § LOG (AVERAGE RINGS FROM P I T H ) FOR A L L TREES...38  FIGURE 26.  BETA T H U J A P L I C I N CONTENT Y £ AVERAGE RINGS FROM P I T H FOR A L L TREES  FIGURE 27.  39  BETA T H U J A P L I C I N CONTENT Y£_ LOG (AVERAGE RINGS FROM P I T H ) FOR A L L TREES...40  FIGURE 28.  GAMMA T H U J A P L I C I N CONTENT Y £ AVERAGE RINGS FROM P I T H FOR A L L TREES  .41  viii  FIGURE 29.  GAMMA T H U J A P L I C I N CONTENT V£ LOG (AVERAGE RINGS FROM P I T H ) FOR A L L TREES...42  FIGURE 30.  T H U J A P L I C I N CONTENT V g ETHANOL:BENZENE EXTRACTIVE CONTENT FOR A L L TREES  FIGURE 3 1 .  THUJIC A C I D CONTENT V£ ETHANOL:BENZENE EXTRACTIVE CONTENT FOR A L L TREES  FIGURE 32.  50  MULTIPLE ANALYSES OF T H U J A P L I C I N CONTENT I N OLD GROWTH TREE #3  FIGURE 39.  49  MULTIPLE ANALYSES OF T H U J A P L I C I N CONTENT I N SECOND GROWTH TREE #1.1  FIGURE 38.  48  THUJIC ACID CONTENT I S AVERAGE RINGS FROM P I T H FOR A L L TREES  FIGURE 37.  47  RADIAL DISTRIBUTION OF THUJIC ACID CONTENT FOR OLD GROWTH TREES  FIGURE 36.  46  RADIAL DISTRIBUTION OF THUJIC A C I D CONTENT FOR SECOND GROWTH S I T E #2  FIGURE 35.  45  RADIAL DISTRIBUTION OF THUJIC ACID CONTENT FOR SECOND GROWTH S I T E #1  FIGURE 34.  44  THUJIC ACID CONTENT Y S T H U J A P L I C I N CONTENT FOR A L L TREES  FIGURE 33.  43  51  BETA+GAMMA T H U J A P L I C I N CONTENT I S LOG (AVERAGE RINGS FROM P I T H ) FOR A L L TREES...52  ix  L I S T OF APPENDICES APPENDIX 1.  PHYSICAL DATA FOR OLD GROWTH TREES  53  APPENDIX 2.  OLD GROWTH SAMPLE DATA  53  APPENDIX 3.  EXPERIMENTAL DATA FOR OLD GROWTH TREES  55  APPENDIX 4.  PHYSICAL DATA FOR SECOND GROWTH TREES  57  APPENDIX 5.  SECOND GROWTH SAMPLE DATA  58  APPENDIX 6.  EXPERIMENTAL DATA FOR SECOND GROWTH TREES.60  APPENDIX 7.  LINEAR REGRESSION S T A T I S T I C S FOR GC VS. COLORIMETRIC RESULTS  61  X  ACKNOWLEDGEMENT The  author  wishes t o express  his gratitude  p e o p l e who a s s i s t e d w i t h t h i s s t u d y . by D r . J . W. W i l s o n ,  to  In particular,  U.B.C. F a c u l t y o f F o r e s t r y ,  a l l those assistance  and  Research  S c i e n t i s t D r . E. P. Swan, F o r i n t e k C a n a d a C o r p . i s a p p r e c i a t e d . In a d d i t i o n , thanks a r e extended Ltd.  (Port McNeill) f o r supplying  to  Western  the  Forest  o l d growth  Products material.  1  INTRODUCTION Western  r e d c e d a r (Thu.ia p l i c a t a Donn) h a s b e e n l o n g  f o r the natural  resistance  This resistance  has r e s u l t e d  (WRC)  of i t s heartwood i n the  use  to  of  decay  (11,26).  western  redcedar  i n a p p l i c a t i o n s where t h i s p r o p e r t y i s u s e f u l ,  where e x p o s u r e t o t h e e l e m e n t s poles,  shakes, s h i n g l e s ,  is  expected,  s i d i n g and  noted  for  especially example  in  gutters.  T h i s u n i q u e d u r a b i l i t y has been a t t r i b u t e d t o t h e p r e s e n c e of  thujaplicins  Thujaplicins  in  have  been  b a c t e r i a l and f u n g a l WRC 1977 7.8  the  heartwood shown  growth  to  extractive be  potent  components. inhibitors  of  (24,25,26,27,28,30,33,37).  i s an i m p o r t a n t C a n a d i a n c o m m e r c i a l wood. I n t h e y e a r s  t o 1983 B r i t i s h C o l u m b i a ' s million  l o g p r o d u c t i o n o f WRC  p e r y e a r ( 9 ) , w h i l e e x p o r t s o f WRC  averaged  shingles  and  s h a k e s a c c o u n t e d f o r $68 m i l l i o n p e r y e a r ( 6 ) . An i n c r e a s i n g  share of our  from second growth f o r e s t s ,  timber  and  production  silvacultural  r e s u l t i n g i n f a s t e r growth of t h e s e  stands.  is  coming  practices  This  has  raised  concerns over the q u a l i t y of products b e i n g produced from f a s t - g r o w n wood. W i t h WRC  the concern i s  f a c t o r i s m a i n t a i n e d i n second growth The  purpose  of  this  study  that  the  are  this  durability  trees.  is  to  analyze  d i s t r i b u t i o n o f t h u j a p l i c i n s and t h u j i c a c i d  to  the  radial  determine  i f  t h e y a r e r e l a t e d t o t r e e age and how  much t h e y v a r y b e t w e e n o l d  growth  As  and  second  growth  trees.  c h r o m a t o g r a p h i c method o f a n a l y s i s colorimetric  method.  well,  a  i s compared t o t h e  new  gas  previous  2  LITERATURE REVIEW Sowder ( 3 0 ) f o u n d t h a t t h e h o t a n d  cold  water  e x t r a c t i v e s o f WRC h e a r t w o o d a n d sapwood w e r e t o x i c w h i l e e x t r a c t e d wood m e a l was more s u s c e p t i b l e unextracted. Rennerfelt thujaplicin  t o be t o x i c  ( 2 4 ) showed  He a l s o f o u n d t h e m t o b e more pinosylvin,  heartwood.  The  to  fungi,  to  decay  than  beta  and  gamma  t o decay f u n g i i n low c o n c e n t r a t i o n s ,  w i t h b e t a b e i n g t h e most t o x i c ,  than  alpha,  soluble  f o l l o w e d b y gamma, t h e n effective  t h e most  potent  thujaplicins  i n decay  fungicide  were  of  alpha.  prevention  i n hard  about  pine  the  same  e f f e c t i v e n e s s i n decay i n h i b i t i o n as p e n t a c h l o r o p h e n o l . Raa and Goksoyr (23) d i s c o v e r e d t h a t t h u j a p l i c i n s i n yeast i n t h e i r  study on y e a s t  inhibited  metabolic  respiration  reactions.  ( 2 7 ) s t u d i e d t o x i c i t i e s o f a l p h a , b e t a , a n d gamma and b e t a  thujaplicinol  inhibitors  o f f u n g a l growth,  (<.1%) t h e y w e r e fungus.  stimulants  He a l s o  compared  e x t r a c t i v e chemicals to  and  although  low  to  their  growth  thujaplicin  t o be a b r o a d  spectrum  Coombs  following  Anderson and Gripenberg  (1) e l u c i d a t e d  activity  gamma  thujaplicin  other toxic  agent. of  to  beta light,  had occurred. the structure  f o l l o w e d by Erdtman and G r i p e n b e r g  and  of  ( 3 3 ) showed  exposure  decomposition  alpha  to  antibacterial  showed t h a t p h o t o c h e m i c a l  isolated  species  relative  that antibacterial  was g r e a t l y r e d u c e d  beta t h u j a p l i c i n ,  potent  concentrations  f o r one  toxicity  be  ( 2 8 ) a n d f o u n d t h e m t o b e t h e most  Coombs a n d T r u s t ( 8 ) f o u n d  and  a l l to  a l l s p e c i e s o f f u n g i t e s t e d . T r u s t and  beta t h u j a p l i c i n  thujaplicin,  demonstrated at  Rudman  and  of  ( 1 2 ) , who  identified  their  3  structures.  The t h u j a p l i c i n s  were  discovered  s e v e n member r i n g s w h i c h a r e s t r u c t u r a l (22)  described  the isolation  "Hiba-wood". G a r d n e r e t related  substance,  thujaplicinol  al  of  isomers.  alpha  be  unusual  Nozoe  and  from  identified  isopropyltropolone  (which i s beta t h u j a p l i c i n  et a l  thujaplicin  (14) i s o l a t e d  7-hydroxy-4-  to  or  with a hydroxyl  occurred i n concentrations of  that of thujaplicins, to  fungi.  Zavarin  and t h a t i t had r e l a t i v e l y  et  a l  (38) i s o l a t e d  (7-hydroxy-6-isopropyltropolone) R o f f and W h i t t a k e r to  brown  r o t fungi  as  thujaplicin.  and  gamma  b u t much l e s s  Aulin-Erdtman  thujaplicins,  from Cupressus  (2) presented  molecular  Doering  weight  t o white  tenth  toxicity  thujaplicinol pygmaea  Lemm.  t o be as t o x i c  thujaplicin toxic  that  one  low  alpha  (25) found b e t a t h u j a p l i c i n o l  pentachlorophenate, either.  about  beta group  i n t h e 7 p o s i t i o n ) f r o m e x t r a c t i v e s o f WRC. They r e p o r t e d t h i s substance  a  and  sodium  r o tfungi  than  ultraviolet spectra f o r the determinations  f o r beta  a n d Knox ( 1 0 ) a n d Cook e t a l ( 7 ) d e s c r i b e d  methods f o r s y n t h e s i z i n g v a r i o u s t r o p o l o n e s . Gardner e t a l (14) s t u d i e d t h e c o l l e c t i o n including  thujaplicins  of  tropolones  a s c o p p e r c h e l a t e s on a c o p p e r s c r e e n i n  a k i l n d r y i n g WRC l u m b e r . They a l s o d e s c r i b e d t h e f r a c t i o n a t i o n of t h i s t r o p o l o n e m i x t u r e .  G a r d n e r and B a r t o n  occurrence  i n t h e steam v o l a t i l e  and  of thujaplicins  discussed separation of thethujaplicins  (13) s t u d i e d t h e o i l of  from t h e o i l .  Barton and Gardner (3) used acetone e x t r a c t i o n sample  (2.8 kg)  of  WRC  butt  heartwood  c o n c e n t r a t i o n s o f b e t a a n d gamma t h u j a p l i c i n  WRC,  to  of a  determine  and  thujic  large the acid  4  gravimetrically. 0.35%  They f o u n d t h a t t h e  t h u j a p l i c i n s and  G a r d n e r (17)  0.11  presented  t o 0.68%  the  first  method f o r a n a l y z i n g t h u j a p l i c i n s , f e r r i c c h e l a t e s of these described  WRC  and  0.17  to  thujic acid.  Maclean  and  instrumental  quantitative  i n v o l v i n g c o l o r i m e t r y of  compounds. J o h n s o n and  t h u j a p l i c i n isomers.  the weathering  shakes.  described  Cserjesi  paper  optimal  A n d e r s o n (35)  conditions  for  used  (5)  Zavarin et a l of  analysis,  and  has  studied  been found  and  o r g a n i s m s i n B r i t i s h C o l u m b i a , and  be  the  to  (11)  and  Scheffer  studied  the  most  durable.  They  also  showed  r e s i s t a n c e v a r i e d w i t h r a d i a l p o s i t i o n and M a c L e a n and  G a r d n e r (18)  found the  c o n c e n t r a t i o n o f t h u j a p l i c i n s i n WRC to  1.2%.  MacLean  and  Gardner  c o n c e n t r a t i o n of t h u j a p l i c i n f o u n d i t t o be s t u d i e d WRC origin.  the  that  kiln  found the  WRC  also  "included  relative drying  to did  Roff  i n the  pole. in  the  from 0  studied  the  sapwood"  and  et  seasoning not  WRC  decay  heartwoods, ranging  same a s r e g u l a r sapwood.  decay r e s i s t a n c e  They f o u n d  in  decay  same v a r i a t i o n  (19)  of stand  the  that  height  decay  from  r e s i s t a n c e o f f o u r w e s t e r n s p e c i e s u s e d as p o l e s , and t o be  widely  extent  y o u n g t r e e s and  Englerth  and  WRC  d e c a y v a r i e d g r e a t l y b e t w e e n o l d and stand.  (36,37)  discussed  to  that  in  salts.  identified  found  of (16)  tropolones,  as d i c y c l o h e x y l a m i n e  d e c a y r e s i s t a n c e o f WRC Buckland  and  chromatography  c h a r a c t e r i z a t i o n of t r o p o l o n e s  variable.  analysis  T h i s method was  the (15)  e f f e c t on t h u j a p l i c i n c o n c e n t r a t i o n s  Z a v a r i n and the  determined  The  contained  a g a s - l i q u i d c h r o m a t o g r a p h i c method f o r  tropolones t o study  wood  al  (26)  and  log  significantly  5  change decay r e s i s t a n c e , and t h a t decay r e s i s t a n c e v a r i e d radial  position.  Scheffer  (29)  d u r a b i l i t y and f o u n d l a r g e t r e e  studied  to  tree  with  variations  in  WRC  variations,  and  no  r e l a t i o n s h i p s b e t w e e n d u r a b i l i t y a n d s i t e o r e l e v a t i o n . He a l s o reported  t h a t decay r e s i s t a n c e i n c r e a s e d  from  pith  h e a r t w o o d , t h e n d e c r e a s e d i n t h e sapwood. Swan a n d a n d Swan e t  al  (32) d i s c u s s e d  e x t r a c t i v e s i n WRC,  the  formation  (including thujaplicins  to  outer  Jiang  (31)  of  and  heartwood  thujic  acid)  and r e v i e w e d t h e i r a n a l y s i s by p a p e r chromatography, t h i n l a y e r chromatography, proposed  a  gas chromatography and c o l o r i m e t r y .  sequence  hydroxylation  for  reactions  inhibitory role.  formation  in  which  Their analysis of  of  They  lignans  thujaplicins a  90  year  through play  o l d WRC  showed a maximum t h u j a p l i c i n c o n t e n t o f 0.34% o c c u r r i n g r i n g s from t h e p i t h , radius.  but they  d i d not  analyze  I n t h e i r a n a l y s i s o f a 260 y e a r o l d WRC  a maximum t h u j a p l i c i n c o n t e n t o f 0.42% a t 210 pith,  with concentrations  increasing  also  the  (31) at  60  complete  (32) t h e y found  rings  gradually  an  from  from  pith  the to  t h i s maximum, t h e n d e c r e a s i n g r a p i d l y i n t h e sapwood. B a r t o n and MacDonald  (4) p r e s e n t e d a comprehensive  review  o f WRC c h e m i s t r y t o 1971. Nault  (20) s t u d i e d t h e r a d i a l  i n s e c o n d g r o w t h WRC b y method  of  Maclean  and  a  d i s t r i b u t i o n of t h u j a p l i c i n s  modification Gardner  of  ( 1 7 ) . He  the  showed  d i s t r i b u t i o n o f t h u j a p l i c i n i n s e c o n d g r o w t h WRC same p a t t e r n  as  in  o l d growth  trees,  maximum l e v e l s w e r e r e a c h e d i n b o t h .  and  colorimetric that  the  followed  the  that  comparable  6  Recently, Nault chromatographic thujaplicin present  (21)  method  and t h u j i c  developed  for acid.  a  determining This i s the  capillary beta method  gas-liquid and  used  gamma i n the  study.  The m a j o r r e s e a r c h p e r i o d f o r t h e t h u j a p l i c i n s  and  related  compounds was 1948-63. More r e c e n t w o r k h a s b e e n b y J o h n s o n a n d Cserjesi Trust  (15,16),  Nault  (20,21),  Swan e t a l ( 3 1 , 3 2 ) Coombs  ( 8 ) a n d T r u s t a n d Coombs ( 3 3 ) .  and  7  MATERIALS AND B r e a s t h e i g h t samples WRC  from s i x f r e s h l y f e l l e d  old  were o b t a i n e d from Western F o r e s t P r o d u c t s a t P o r t  B.C. of  METHODS growth McNeill,  T h e s e t r e e s w e r e c u t f r o m a s t a n d a b o u t 11 k i l o m e t e r s  Port McNeill,  and r a n g e d  from  260  to  710  (Appendix 1 ) . Trees s e l e c t e d were f r e e from  years  west  of  age  obvious  signs  of  obtained  from  UBC  butt rot. A s e v e n t h o l d growth t r e e sample Forestry.  I t was  was  c u t f r o m a f r e s h l y f e l l e d WRC  r e s e a r c h f o r e s t i n Haney, B.C. ( A p p e n d i x 1 ) , and e x h i b i t e d  This  tree  obvious  grown a t t h e  was  signs  420  of  UBC  years  decay  old  in  the  heartwood. All  o l d growth  samples  obtained  a c r o s s t h e d i a m e t e r of t h e t r e e , deep. The  sapwood was  r e m a i n d e r was  a b o u t 10  separated  cut into sections  were  from  cut  cm  wide  these  consisting  rings to provide sufficient material f o r  into and  strips of  strips 5  and  enough  analyses  cm the  growth  (Figure  1,  Appendix 2). The  samples were a i r - d r i e d ,  screen, with  a l l material  extracted i n  a  soxhlet  ( 1 : 2 ) , and t h e e x t r a c t i v e loss.  The  then ground t o pass a  saved.  with  The  reagent  content  was  ground grade  50-mesh  samples  were  ethanol:benzene  determined  by  weight  e x t r a c t i v e s from each sample were c o n c e n t r a t e d  on  a  r o t a r y e v a p o r a t o r , t h e n made up t o 25 m l . Ethanol:benzene Nault  (1:2) e x t r a c t i v e s f r o m a p r e v i o u s s t u d y by  (20) r e p r e s e n t i n g r a d i a l b r e a s t h e i g h t samples  s e c o n d g r o w t h WRC  f r o m two  s i t e s on V a n c o u v e r  from  I s l a n d were  ten also  8  i n c l u d e d i n t h e s t u d y ( A p p e n d i x 4, A p p e n d i x  5).  These  samples  and t h e i r e x t r a c t i v e s w e r e p r e p a r e d i n a manner s i m i l a r t o t h a t described.  However, i n t h e s e  samples,  w e r e n o t s e p a r a t e d . The o u t e r m o s t c o n t a i n e d heartwood  heartwood  and  sample i n t h e s e  a n d sapwood m i x e d  sapwood  radii  i n varying ratios.  P u r e s a m p l e s o f b e t a a n d gamma t h u j a p l i c i n a n d t h u j i c were p r o v i d e d b y F o r i n t e k Canada Corp. was p r e p a r e d f r o m n i t r o s o m e t h y l u r e a  thus  Diazomethane and  acid  i n ether  potassium  hydroxide  (34). P u r e s t a n d a r d s were p r e p a r e d by amount o f r e a g e n t i n e t h a n o l / b e n z e n e methylated  by  diazomethane,  addition  of  an  dissolving  volume  evaporated  m e t h y l a t e d s t a n d a r d s were  then  dissolved  (1:2)  g/ml  naphthalene  containing  standard.  .00515  A l lextractive  required  ( 1 : 2 ) . The s t a n d a r d s  equal  t h e n t h e s o l v e n t was  the  samples,  of at  in  etheral  70 *C.  The  ethanol/benzene  as  pure  were  an  internal  standards,  d e r i v a t i z e d samples were s t o r e d i n a d a r k f r e e z e r  to  and  minimize  degradation by heat o r l i g h t . All  s a m p l e s w e r e a n a l y z e d o n a S p e c t r a - P h y s i c s SP7100  chromatograph capability. micrometer  with  A 12M  a  dedicated  QC2/SE30  data  column  system  with  and  0.02mm  t h i c k c o a t i n g was u s e d , w i t h h e l i u m a s  g a s . Oven t e m p e r a t u r e was h e l d a t  110 C a  capillary  ID  a n d 0.25  the  f o r 10  gas  carrier  min., then  r a i s e d t o 200 C a t 10*C/min. D e t e c t i o n was a c c o m p l i s h e d w i t h  a  flame i o n i z a t i o n d e t e c t o r . Peak a r e a system,  data  were  collected  on  a n d s t a n d a r d c u r v e s were p r e p a r e d  the dedicated using  2  data  microliter  9  sample i n j e c t i o n s . and  C a l i b r a t i o n c u r v e s were  gamma t h u j a p l i c i n ,  and  for  thujic  prepared acid  for  utilizing  technique.  A l l e x t r a c t i v e samples were a n a l y z e d u s i n g t h e  procedures  as f o r t h e s t a n d a r d s .  Because m e t h y l a t i o n of t h u j i c a c i d y i e l d s methyl the  reported  concentrations  c o n c e n t r a t i o n s of methyl of methyl  are  the  t h u j a t e and t h u j i c a c i d .  t h u j a t e c o u l d be p e r f o r m e d e a s i l y by  the e t h y l d e r i v a t i v e s , which would t h u j i c a c i d l e a v i n g methyl All  actually  samples  were  yield  ethyl  this same  thujate,  sum  of  the  Determination  preparation  of  thujate  from  colorimetrically  for  t h u j a t e unchanged.  also  analyzed  t h u j a p l i c i n c o n t e n t by t h e method o f MacLean and G a r d n e r as m o d i f i e d by N a u l t ( 2 0 ) .  beta  (17),  10  RESULTS Seven o l d growth and t e n analyzed i n r a d i a l  second  growth  WRC  increments from p i t h t o bark  trees  were  (Appendices  3  and 6 ) . The e t h a n o l : b e n z e n e  (1:2) e x t r a c t i v e c o n t e n t i n a l l  trees  f o l l o w e d a g e n e r a l p a t t e r n of i n c r e a s i n g from t h e p i t h  to  most r e c e n t l y formed h e a r t w o o d ,  sapwood  ( F i g u r e s 2-4).  A l l old  then decreasing i n the  growth  trees  attained  much  the  higher  e t h a n o l : b e n z e n e e x t r a c t i v e c o n t e n t s t h a n were e x h i b i t e d i n  the  s e c o n d g r o w t h t r e e s . Maxima r a n g e d f r o m 1 2 . 4 % t o 2 2 . 8 %  the  o l d growth t r e e s ,  and f r o m 6.2% t o 9.8% i n  t r e e s . E x t r a c t i v e c o n t e n t s i n heartwoods  the  in  second  seemed t o  growth  be  related  t o t r e e age ( F i g u r e 5 ) . T h u j a p l i c i n c o n t e n t s as  determined  by  the  colorimetric  method (20) a g r e e d r o u g h l y w i t h t h o s e o b t a i n e d by  GLC  (Figure  6 , A p p e n d i x 7 ) , y i e l d i n g a n r ^ v a l u e o f 0.81 a n d a s l o p e o f f o r GC yj5 c o l o r i m e t r i c r e s u l t s .  Colorimetric values  be s l i g h t l y h i g h e r f o r s e c o n d g r o w t h t r e e s and f o r o l d growth t r e e s data  in  this  ( F i g u r e s 7-23).  paper  are  0.99  tended  slightly  to  lower  To s i m p l i f y r e p o r t i n g , a l l  based  on  the  t h u j a p l i c i n c o n t e n t b e i n g t h e sum  of  beta  GLC  results,  and  gamma  with isomer  fractions. T h u j a p l i c i n c o n t e n t i n t h e second t h e p a t t e r n d e s c r i b e d by MacLean and  growth Gardner  very low content i n the i n n e r heartwood, i n t h e l a t e s t formed heartwood  trees  followed  (18), that i s ,  with a rapid  increase  ( F i g u r e s 7 - 1 6 ) . However, t h e o l d  growth t r e e s d i d not demonstrate 1 7 - 2 2 ) . The o l d g r o w t h  trees  a  showed  similar  pattern  appreciable  (Figures  thujaplicin  close t o thepith. trees i nthis  The maximum l e v e l s a t t a i n e d  study  were  higher  than  any  by  o l d growth  reported  i n the  literature. T h u j a p l i c i n c o n t e n t s a l s o seemed t o b e d i r e c t l y r e l a t e d t o t r e e a g e , w i t h o l d g r o w t h t r e e s h a v i n g a maximum second  growth t r e e s  having  a  maximum  of  t h u j a p l i c i n s vg. r i n g s f r o m p i t h shows t h i s and  of  0.7%. trend  2 5 ) . B e t a t h u j a p l i c i n a n d gamma t h u j a p l i c i n ,  separately,  also exhibited s i m i l a r trends  No r e l a t i o n s h i p s w e r e o b s e r v e d  A  1.8% a n d plot  of  (Figures  24  when  analyzed  ( F i g u r e s 26  t o 29).  f o r r e l a t i v e amounts o f b e t a a n d  gamma t h u j a p l i c i n a n d d i s t a n c e f r o m p i t h .  Thujaplicin  contents  seemed t o b e r e l a t e d a l s o t o e x t r a c t i v e c o n t e n t s p r e s e n t  i n the  samples ( F i g u r e 30). Thujic acid contents  (thujic  acid  seemed t o be r e l a t e d t o e x t r a c t i v e obvious  plus  contents  relationship to thujaplicin  content  methyl  thujate)  (Figure  3 1 ) . No  i s seen  (Figure  3 2 ) , a l t h o u g h t h u j i c a c i d f o l l o w e d t h e same g e n e r a l p a t t e r n thujaplicin,  increasing  from  the pith  through  the  h e a r t w o o d , t h e n d e c r e a s i n g i n t h e sapwood ( F i g u r e s well,  no o b v i o u s  r i n g s from p i t h  33-35).  r e l a t i o n s h i p i s seen between t h u j i c  acid  as  outer As and  (Figure 36).  The e x t r a c t i v e s f r o m one s e c o n d  g r o w t h and one o l d g r o w t h  t r e e analyzed w i t h r e p l i c a t i o n demonstrate t h e  reproducibility  o f t h e GLC method ( T a b l e 1, F i g u r e s 37 a n d 3 8 ) . F i g u r e 39 p r e s e n t s a summary o f  thujaplicin  distribution  i n a l l 17 t r e e s s t u d i e d . Table 2 presents a comparison  o f r e s u l t s from  w i t h r e s u l t s o b t a i n e d by other r e s e a r c h e r s .  this  study  DISCUSSION Ethanol:benzene e x t r a c t i v e contents were g e n e r a l l y i n t h e r a n g e s although  T r e e t o t r e e v a r i a t i o n was h i g h ,  same s t a n d  general  2,3,4).  (Figures  A  trees  previously  some o l d g r o w t h t r e e s e x c e e d e d a n y  reported. the  reported  i n the  increase i n e x t r a c t i v e content  (Table  levels  even i n  surprising with  studied 2),  previously trees  find  rings  from  i s the  from  pith  (Figure 5). This experiment i s t h e f i r s t utilizing  capillary  concentrations  of  GLC.  The  study  of t h u j a p l i c i n s i n  method  thujaplicins,  and  is  sensitive  requires  s a m p l e p r e p a r a t i o n . The method g i v e s r e p e a t a b l e two 38). and  trees analyzed  i n t r i p l i c a t e demonstrate  no  to  (Figures  as t h e 37  of  C s e r j e s i (15) i n t h a t g r e a t e r r e s o l u t i o n of t h e  t i m e consuming t h a n t h e i r method u s i n g The  and  Johnson  components  i s p o s s i b l e due t o t h e u s e o f a c a p i l l a r y c o l u m n . A s w e l l , d e r i v a t i v e p r e p a r a t i o n u s i n g diazomethane i s  low  extensive  results,  T h i s method i s an improvement o v e r t h e method  WRC  easier  and  the less  silylation.  d a t a c o l l e c t e d o n t h e GC e x h i b i t e d s e v e r a l m a j o r p e a k s  which have n o t identified,  yet  been  identified.  and c a l i b r a t i o n c u r v e s  on t h e o v e r a l l  pattern  of  When  these  prepared,  extractive  more  peaks  are  information  distribution  will  be  f o r injection  (2  available. The  s m a l l volumes o f  sample  required  m i c r o l i t e r s ) and t h e h i g h s e n s i t i v i t y o f t h a t by d e c r e a s i n g  sample s i z e  s m a l l samples c o u l d be a n a l y z e d .  and This  the  method  extraction  suggests  volumes,  very  i s a major advantage over  13  the  standard  to analyze  c o l o r i m e t r i c method, a n d c o u l d c o n c e i v a b l y be u s e d  increment cores  Concerns  have  from s t a n d i n g t r e e s .  been  expressed  by  the  forest  products  i n d u s t r y on t h e q u a l i t y o f wood f r o m o u r f u t u r e f o r e s t s , i n t e n s i v e management w i l l  result  younger ages t h a n has been t h e stands.  This study  i n harvesting case  trees  at  for existing  in  i s r e l a t e d t o t h e age o f t h e t r e e ( F i g u r e s 24 a n d 2 5 ) .  ages  may  give  wood  compounds. T h i s c o u l d durable  t o decay and  f o r w h i c h WRC  lower  yield  concentrations  the  wood  young  of  that  (traditional  these  is  less  characteristics  high  variability  in  i n o l d growth and second g r o w t h  is  clearly  illustrated  b e t w e e n s e c o n d g r o w t h T r e e s #1.1  by  ( F i g u r e 7)  of  and  pure  heartwood,  while  r i n g s from p i t h .  I n t h e o l d growth  ( F i g u r e 21) a n d #7 ( F i g u r e  23)  trees  represent  a t t a i n e d a maximum o f 1.77% t h u j a p l i c i n , maximum c o n t e n t  of  (Figure  0.323% i n #1.2  at  great v a r i a b i l i t y  (5) and S c h e f f e r  i n WRC  wood  decay.  has  only  studied,  10-15 #5  Tree  #5  extremes.  while tree  a  trees  #7  o f o n l y 0.28%. T h i s a g r e e s w i t h e a r l i e r  by Buckland  tree.  differences  #1.2  Tree  maximum o f o n l y 0.108%, a n d r e a c h e d t h a t v a l u e  suggests the  the  8 ) . T r e e #1.1 h a s a maximum t h u j a p l i c i n c o n t e n t the l a s t sample o f  thujaplicin  trees  i s more i n v o l v e d t h a n s i m p l y t h e age  This v a r i a b i l i t y  presented  In the  relatively  concentrations  conceivably weathering  at  WRC  wood h a s b e e n v a l u e d ) .  However,  that there  with  harvesting  much  old-growth  suggests that l e v e l of t h u j a p l i c i n s  case o f second growth stands,  where  had  a  results  ( 2 9 ) , b o t h o f whom f o u n d Perhaps  the  level  of  14  thujaplicin  i sa genetically  controlled  property,  and  c o u l d be s e l e c t e d f o r p r o p a g a t i o n w i t h t h i s p r o p e r t y As  s t a t e d , t h e new  GC  increment cores could The 1.8%,  technique  assist  maximum l e v e l s  used  i n such  The  possibility  protected  exists  their  that  extractive  i n mind.  non-destructive  selection.  of thujaplicin  exceed any p r e v i o u s l y r e p o r t e d  with  trees  reported  h e r e , a s up t o  i n t h e l i t e r a t u r e f o r WRC.  previous samples  researchers  from  had not  light,  and  that  photochemical decomposition of t h e t h u j a p l i c i n s  had occurred  described  result  reported  b y Coombs a n d T r u s t values  being  (8). This  would  lower than t h e a c t u a l values.  c o l o r i m e t r i c m e t h o d ( 1 7 ) assumes a c o n s t a n t  r a t i o of  gamma t h u j a p l i c i n ,  60%  thujaplicins.  with  gamma  making  up  Any d e v i a t i o n from t h i s r a t i o  of  could  Since  0%  thujaplicin be  false.  studied  from  However,  thepattern  concentration  to  t h e magnitude  of  the error  would cause i s n o t p r e s e n t l y  of  fairly  rapid  increase  of  i n t h e heartwood o f o l d growth t r e e s  t h r o u g h 23) d i f f e r s from t h e work o f MacLean and and  Swan a n d J i a n g  ( 3 1 ) , who  found  o l d e s t heartwood of t h e t r e e s they The  the  beta  and  the  results.  90%  gamma  very  low  that  of t h u j a p l i c i n  to this  known.  As  thujaplicin (Figures  Gardner  levels  17 (18)  i n the  studied.  o n e o l d g r o w t h WRC t r e e w h i c h d i d n o t h a v e h i g h  of e v i d e n t  total  ( A p p e n d i c e s 3 a n d 6 ) , t h i s a s s u m p t i o n i s shown  difference i nratios well,  varied  Also,  change  erroneous  t h e samples  i n the  the  a b s o r b a n c e maximum o f t h e s a m p l e , a n d g i v e  as  levels  ( T r e e #7) was s e l e c t e d f o r s a m p l i n g on t h e b a s i s  d e c a y . The f a c t  t h a t t h e t r e e showed s i g n s o f  decay  15  and  low  thujaplicin  thujaplicins the  content  p l a y a major r o l e  d e c a y was  thujaplicins  i n WRC  c a u s e d by t h e absence had  been  inactivated  remains a q u e s t i o n f o r f u r t h e r that t h i s tree  supports  the  decay r e s i s t a n c e . of by  thujaplicins, the  research. Also,  h a d r o u g h l y t h e same l e v e l s o f  d i d the other o l d growth t r e e s  theory  (Figure 35).  decay  that Whether or  the  organisms  i t i s noteworthy thujic  acid  as  16  CONCLUSION The new GLC method i s a s e n s i t i v e for analyzing extractives.  thujaplicins  and  Thujaplicin  research  genetically  associated  compounds  Thujic pattern  in  WRC  analysis.  t o t r e e v a r i a b i l i t y was f o u n d to  determine  controlled  i f this  property  could  to  be  variabiltiy prove  N o n - d e s t r u c t i v e increment cores would f u r n i s h for analysis  method  c o n t e n t seemed t o b e d i r e c t l y r e l a t e d t o  although tree  Further  convenient  The r e s u l t s o b t a i n e d b y t h i s method a r e c o m p a r a b l e  t o t h o s e o b t a i n e d by c o l o r i m e t r i c  age,  and  tree high.  is  a  informative.  enough  material  b y t h e new GLC method. a c i d was  found  as t h u j a p l i c i n s .  to  vary  in  generally  the  same  17  LITERATURE CITED Anderson,  A. B. a n d J . G r i p e n b e r g . 1948. Antibiotic s u b s t a n c e s f r o m t h e h e a r t w o o d o f Thu.ia plicata D. Don. I V . The c o n s t i t u t i o n of thujaplicin. A c t a . Chem. S c a n d . 2:644-650.  A u l i n - E r d t m a n , G. 1950. S t u d i e s i n t h e t r o p o l o n e s e r i e s . 1. T h u j a p l i c i n s and n o o t k a t i n . A c t a . Chem. Scand. 4:1031-1041. B a r t o n , G. M. a n d J . A . F . G a r d n e r . 1954. The c h e m i c a l of t h e acetone e x t r a c t i v e o f western r e d P u l p P a p e r Mag. Can. 5 5 ( 1 0 ) : 1 3 2 - 1 3 7 .  nature cedar.  — a n d B.F. M a c D o n a l d . 1971. The c h e m i s t r y a n d utilization of western red cedar. Dept. Fisheries and Forestry, Canadian Forestry S e r v i c e . Pub. No. 1023:13-19. 5.  B u c k l a n d , D. C. 1946. I n v e s t i g a t i o n s o f d e c a y i n w e s t e r n r e d cedar i n British Columbia. Can. J. Res. C24:158-181.  6. C a n a d i a n  Forestry Statistics.  7. Cook, J . W.  1982. S t a t i s t i c s Canada. p 3 3 .  , Raphael, R. A. a n d A. I . S c o t t . 1951. T r o p o l o n e s . P a r t I I . The s y n t h e s i s o f a l p h a , b e t a , a n d gamma t h u j a p l i c i n s . J . Chem. S o c . ( L o n d o n ) . 1951:695-698.  8. Coombs, R. W. a n d T. J . T r u s t . 1973. The e f f e c t o f l i g h t on the a n t i b a c t e r i a l a c t i v i t y of beta thujaplicin. Can. J . M i c r o b i o l . 1 9 ( 1 0 ) : 1 1 7 7 - 1 1 8 0 . 9. C o u n c i l o f F o r e s t I n d u s t r y S t a t i s t i c s .  1984. C 0 F I .  10. D o e r i n g , W. a n d L.H. Knox. 1953. S y n t h e s i s o f s u b s t i t u t e d t r o p o l o n e s . J . Amer. Chem. S o c . 75:297. 11. E n g l e r t h , G. H. a n d T. C. S c h e f f e r . 1954. T e s t s o f decay r e s i s t a n c e of four western pole s p e c i e s . USDA Forest Service, Forest Products Laboratory, M a d i s o n . Pub. No. 2006. 8pp. 1 2 . E r d t m a n , H. and J . G r i p e n b e r g . 1948. A n t i b i o t i c substances f r o m t h e h e a r t w o o d o f Thu.ia p l i c a t a D. Don. 2. The constitution o f gamma t h u j a p l i c i n . Acta Chem. S c a n d . 2:625-643. 1 3 . G a r d n e r , J . A. F. a n d G. M. B a r t o n . 1958. O c c u r r e n c e o f b e t a dolabrin (4-isopropenyl tropolone) i n western r e d c e d a r . Can. J . Chem. 36:1612-1615.  18  1 4 . G a r d n e r , J . A. F. , B a r t o n , G. M. a n d H. MacLean. 1957. Occurrence of 2,7-dihydroxy-4-isopropyl-2,4,6cycloheptatrien-l-one (7-hydroxy-4-isopropylt r o p o l o n e ) i n w e s t e r n r e d c e d a r Thu.ia p l i c a t a D. Don. C a n a d i a n J . Chem. 35:1039-1048. 15. J o h n s o n ,  16.  E. L. a n d A . J . C s e r j e s i . 1975. G a s - l i q u i d c h r o m a t o g r a p h y o f some t r o p o l o n e - T M S e t h e r s . Chrom. 107:p388. . 1980. W e a t h e r i n g t h u j a p l i c i n concentration i n western shakes. F o r e s t Prod. J . 30(6):52-53.  J.  e f f e c t on redcedar  17. M a c L e a n , H. a n d J . A. F. G a r d n e r . 1956. A n a l y t i c a l methods f o r t h u j a p l i c i n s . A n a l . Chem. 28:509-512. 18.  . 1956. Distribution of fungicidal extractives (thujaplicins and w a t e r s o l u b l e phenols) i n western r e d cedar heartwood. F o r e s t Prod. J . 6(12):510-516.  19.  . 1958. Distribution of fungicidal extractives in target pattern heartwood o f western r e d cedar. F o r e s t Prod. J . 8(3):107-108.  20. N a u l t , J . R. 1985. Distribution of thujaplicins in f a s t - g r o w n , second growth Thu.ia p l i c a t a Don. U n p u b l i s h e d r e s e a r c h r e p o r t , Dept. o f F o r e s t r y , UBC. 21.  1986. A c a p i l l a r y gas chromatographic method for thujaplicins i n extractives Thu.ia plicata Don. Unpublished research report, Dept. of F o r e s t r y , UBC.  22.Nozoe, T. Y a s u e , A. a n d K. Yamane. 1951. On t h e a c i d i c c o n s t i t u e n t s o f Thu.iopsis d o l a b r a t a . Occurence of alpha thujaplicin. Proc. Japan Acad. 27(1):15-17. 23.Raa, J . a n d J . G o k s o y r . 1965. S t u d i e s o f t h e e f f e c t s o f t h e heartwood toxin beta-thujaplicin on the m e t a b o l i s m o f y e a s t . P h y s i o l . P l a n t . 18:159-176. 24. R e n n e r f e l t , E. 1948. T h u j a p l i c i n , a f u n g i c i d a l s u b s t a n c e i n t h e h e a r t w o o d o f Thu.ia p l i c a t a . P h y s i o l . Plant. 1:245-254. 25.Roff,  J . W. a n d E. I . W h i t t a k e r . 1959. T o x i c i t y new tropolone, beta (7-hydroxy-4-isopropyl tropolone) w e s t e r n r e d c e d a r . Can. J . B o t a n y .  tests of a thujaplicinol occuring i n 37:1132-1134.  19  2 6 . R o f f , J . W.,  W h i t t a k e r , E. I . and H. W. E a d e s . 1962. Decay r e s i s t a n c e of western red cedar r e l a t i v e t o k i l n s e a s o n i n g , c o l o u r and o r i g i n o f t h e wood. Can. Dept. F o r e s t r y , F o r e s t P r o d u c t s R e s e a r c h B r a n c h , Tech. N o t e No.32:3-19.  27. Rudman, P.  1962. The causes of n a t u r a l durability in timber. Part IX: The antifungal activity of heartwood extractives i n a wood substrate. H o l z f o r s c h . 16(3):74-77.  28.  1963. The causes of n a t u r a l durability in timber. Part X I : Some t e s t s on the fungi toxicity o f wood extractives and related compounds. H o l z f o r s c h . 1 7 ( 2 ) : 5 4 - 5 7 .  29. S c h e f f e r ,  T. C. 1957. D e c a y r e s i s t a n c e o f w e s t e r n r e d c e d a r . J. F o r e s t r y . 55(6):434-442.  30.Sowder, A. M. 1929. T o x i c i t y o f w a t e r soluble extractives and r e l a t i v e d u r a b i l i t y o f w a t e r - t r e a t e d wood f l o u r of western red cedar. I n d . Eng. Chem. 21:981-988. 31.Swan, E. P.  and K. S. J i a n g . extractives in 53(5):844-846  32.  and j , A. F. G a r d n e r . 1969. The lignans of Thu.ia plicata and the sapwood-heartwood transformation. Phytochem. 8:345-351.  33. T r u s t ,  1970. Formation of heartwood western red cedar. TAPPI  T. J . and R. W. Coombs. 1973. of beta thujaplicin. 19(11):1341-1346.  34. V o g e l , A.  Antibacterial activity Can. J. Microbiol.  I . 1948. I n P r a c t i c a l O r g a n i c C h e m i s t r y . Longmans, G r e e n and Co., L o n d o n . 1948:843-845.  35. Z a v a r i n , E. and A. B. A n d e r s o n . 1956. Paper chromatography o f t h e t r o p o l o n e s o f C u p r e s s a c a e . J . Org. Chem. 21:332-335. 36.  37.  and R. M. S m i t h . 1959. P a p e r chromatography of t h e t r o p o l o n e s of Cupressacae: J . Org. Chem. 2 4 : 1 3 1 8 - 1 3 2 1 , S m i t h , R. M. and A. B. A n d e r s o n . C h a r a c t e r i z a t i o n of Cupressacae dicyclohexylamine salts. J. 24:1584-1585.  1959. t r o p o l o n e s as Org. Chem.  20  3 8 . Z a v a r i n , E., S m i t h , R. M . a n d A. B. A n d e r s o n . 1961. On t h e occurence of alpha thujaplicinol i n the h e a r t w o o d o f C u p r e s s u s pygmaea (Lemm.) S a r g . J . Org. Chem. 26:173-176.  21  TABLE 1.  GC SAMPLES ANALYZED WITH R E P L I C A T I O N  SAMPLE AVERAGE T H U J A P L I C I N S (% O.D.WOOD) NAME # RINGS TRIAL 1 TRIAL 2 TRIAL 3 AVERAGE FROM BETA GAMMA BETA GAMMA BETA GAMMA BETA GAM PITH SECOND GROWTH TREE # 1.1  OLD GROWTH TREE # 3  2.5 7.5 12.5 17.5 25 35 45  0 0 0 .07 .15 . 19 .08  .03 .02 .05 . 13 .27 .24 . 11  0 0 0 .04 . 15 . 21 .08  .03 .05 .06 . 15 .25 . 28 . 13  0 0 0 .08 . 16 .25 .09  .03 .04 .07 . 13 .28 .29 .21  0 0 0 .06 .15 . 22 .08  .03 .04 .06 . 14 .27 . 27 . 15  .06 .08 . 10 . 12 . 14 .22 . 30 .02  .07 .24 .50 .34 . 56 .38 .58 .04  .07 .04 .09 . 12 . 14 . 16 . 21 .33  .08 .27 .44 .33 . 51 . 39 .58 .04  .02 .08 .05 .09 . 11 . 15 . 18 .25  .08 .36 .48 .31 . 58 .38 .59 .03  .05 .07 .08 . 11 . 13 . 18 . 23 .20  .08 .29 .47 .33 .55 .38 .58 .04  40 125 210 310 410 475 558 610  TABLE 2,  COMPARISON OF DATA WITH LITERATURE VALUES COMPONENT  SOURCE OF DATA (3) (16) (18) (19) (31) (32) NAULT  ETHANOL:BENZENE EXTRACTIVES 13. 8  6.2-22.8  THUJAPLICINS (%)  THUJIC A C I D (%)  0.17-0.35 0-0.546 0-1.22 0-0.27 0-0.42 0.01-0.34 0.004-1.8  0.11-0.68  ANALYTICAL METHOD  GRAVIMETRIC GC COLORIMETRY COLORIMETRY PAPER CHROM. COLORIMETRY 0.017-1.024 COLORIMETRY AND CAP. GC  FIGURE  1.  SAMPLING  PROCEDURE  BREAST HEIGHT RADIAL CROSS SECTION  FIGURE  2.  RADIAL DISTRIBUTION OF ETHANOL:BENZENE EXTRACTIVES FOR SECOND GROWTH S I T E tfl  O > 0 0 r ^ c O t / ) < 4 - r o c M (aOOM 3 3 H J I 3AII,DVHIXa AH0-N3A0 NO a S S V H ) (%) S 3 A I 1 0 V H 1 X 3 3N3ZN3g:iONVH,L3  FIGURE  3.  RADIAL DISTRIBUTION OF ETHANOL BENZENE EXTRACTIVES FOR SECOND GROWTH S I T E *2  o o > o o r ^ ( O i n ^ - K ) c > i (aOOM 33H3 3 A I 1 D V H I X 3 AHCI-N3A0 NO CI3SVg) (%) S 3 A I I 0 V H 1 X 3 3N3ZN39:10NVH13  FIGURE  4.  RADIAL DISTRIBUTION OF ETHANOL:BENZENE EXTRACTIVES FOR OLD GROWTH TREES  (aOOM 3 3 H 3 3 A I J , D V H , L X 3 AHCI-N3AO NO a 3 S V 9 ) (%) S 3 A I I 0 V H X X 3 3 N 3 Z N 3 9 • 1 0 N V H I 3  24 22  t-i o a H  Q  §20  &w w 18 a; w > w 16 M  >  >  + +  H  E- H-t  U E-  <u  03 < E - ttJ X £W X  w  2 W Nl 2 W CQ ••  w  >03 Q I 2 W >  3 ° 3§  X E- Q W W  14  M  < -3  1  +  - J  12  - J  10  H  8  ^  + +  + + +  Q O W tr  +  +  W n 2 O m  +  td W 2 INI W 2  •n m w ow  + +  2  X  h a ow w o > o  6  f c-  12  2 >-3  <  wk cokn  CQ  400 600 AVERAGE * RINGS FROM P I T H HEARTWOOD SAMPLE + HEARTWOOD+SAPWOOD SAMPLE O 2  0  0  800 CO  27  00  (O  Q O  e CN>-t  m  -'OS E-  W «  h-l t d « >  O  t-H  CQ  X W  —o u u < CO  Z >H  C0>-< «  <  Z  o z o Q W  CO  < CQ  d  CM  d i  i — i — i — r  co s «o m <t io -  T  i—i—i—i—i—i—r  « r ^ o> «o- s.  — - — -  *  "1  1 — 1 — r t  10  N  ^  o o o o o o d d p  (aOOM 33Hi 3AI10VHIX3 AH0-N3A0 NO (I3SVH) 00 A9 SNIOndVPflHI %  O  FIGURE  7.  T H U J A P L I C I N CONTENT BY TWO METHODS VS. AVERAGE RINGS FROM P I T H FOR SECOND GROWTH TREE #1.1 HEARTWOOD + SAPWOOD  1  1  60 AVERAGE # RINGS FROM P I T H •BETA (BY GC) +GAMMA (BY GC) OTOTAL (BY GC) FIGURE _  8.  © 0.8  8 w  0.7 -  80  ^COLORIMETRIC  T H U J A P L I C I N CONTENT BY TWO METHODS VS AVERAGE RINGS FROM P I T H FOR SECOND GROWTH TREE #1.2 HEARTWOOD  HEARTWOOD + SAPWOOD  w 0.6 -  — >  o 0.5 "  xli < 03 EU X 2  t-i  i-t  w  J p.. >* < 03 »  0.4 0.3 -  l  ac z0.2 -  > Z  o °o.i  Q W W  <  0  •BETA (BY GC)  I  40 AVERAGE # RINGS FROM P I T H +GAMMA (BY GC) OTOTAL (BY GC)  — i  1  60 ACOLORIMETRIC  80  FIGURE  i W  9.  T H U J A P L I C I N C O N T E N T B Y TWO M E T H O D S ¥S A V E R A G E R I N G S F R O M P I T H F O R S E C O N D GROWTH T R E E # 1 . 3 HEARTWOOD  0.7  29  HEARTWOOD + SAPWOOD  W  « fa  0.6  — >  U0.S  CO <  Z  O M  «  Xo.4 W  •-3 Q C 3  O  l  H  W  33 Z  >0.2  z o Q  0.1 -  w  CO < CQ  1  —  •BETA  0 (BY  FIGURE  1  60 GC)  10.  A V E R A G E # R I N G S FROM P I T H +GAMMA ( B Y G C ) OTOTAL (BY  GC)  60  ^COLORIMETRIC  T H U J A P L I C I N C O N T E N T B Y TWO M E T H O D S V £ A V E R A G E R I N G S F R O M P I T H F O R S E C O N D GROWTH T R E E # 1 . 4 HEARTWOOD + SAPWOOD  60 •BETA  (BY  GC)  A V E R A G E # R I N G S FROM P I T H +GAMMA (BY GC) OTOTAL (BY  GC)  ACOLORIMETRIC  60  FIGURE 1 1 . ~ § 0 . 8  T H U J A P L I C I N CONTENT BY TWO METHODS VS. AVERAGE RINGS FROM P I T H FOR SECOND GROWTH TREE #1.5 HEARTWOOD  S  HEARTWOOD + SAPWOOD  W 0 . 7  w OS  fa —  >  ^  E-»  CO  Z n U  <  K  Eh * 0 . 4 • W  < ! OS  n i s z E-<  W  > 0 . 2  z o 0.1 a w  -  CO  <  —I  CQ  1  6 0  AVERAGE # RINGS FROM P I T H •BETA (BY GC) +GAMMA (BY GC) OTOTAL (BY GC) FIGURE 12. 0 . 8  Q  O  i fe  —  _,  6 0  ^COLORIMETRIC  T H U J A P L I C I N CONTENT BY TWO METHODS VS AVERAGE RINGS FROM P I T H FOR SECOND GROWTH TREE #2.1 HEARTWOOD HEARTWOOD + SAPWOOD  o.e H  w  >  ~ H  D  H  . 5  CO < Z OS  < « 0 . 3  -  o an z  > 0 . 2  O  z 00.1 Q W  CO  -  .  5 <o o DBETA  AVERAGE # RINGS FROM P I T H (BY GC) +GAMMA (BY GC) OTOTAL (BY GC)  8 0  ^COLORIMETRIC  FIGURE 1 3 .  a 0.B o  £  w 0.7 w  -  to  0.6  "  &- 0 . 3  ^  -  1  CO  <  z OS * 0 . 4  <w  T H U J A P L I C I N CONTENT BY TWO METHODS VS. AVERAGE RINGS FROM P I T H FOR SECOND GROWTH TREE #2.2 HEARTWOOD HEARTWOOD + SAPWOOD  H  5h  § 0 . 3  I  H  Z  >0.2 O  -  O0.1  -  z w  CO  <  i  CQ  60  AVERAGE * RINGS FROM P I T H •BETA (BY GC) +GAMMA (BY GC) OTOTAL (BY GC) FIGURE 14. Q 0 . B  O  £  60  ^COLORIMETRIC  T H U J A P L I C I N CONTENT BY TWO METHODS ¥ S AVERAGE RINGS FROM P I T H FOR SECOND GROWTH TREE #2.3 HEARTWOOD HEARTWOOD + SAPWOOD  w OS  w ~>  0.6  ~£o.  CO < Z OS i-t  U X  -  H  5  0.4  -  OS! 0 . 3 Q  -  z w >o.2 o z  -  j  Si  •"3  I  °ai Q  W  CO <  0  AVERAGE # RINGS FROM P I T H •BETA (BY GC) +GAMMA (BY GC) OTOTAL (BY GC)  60  ^COLORIMETRIC  FIGURE 15. § 0 . 8  T H U J A P L I C I N CONTENT BY TWO METHODS V£ AVERAGE RINGS FROM P I T H FOR SECOND GROWTH TREE # 2 . 4 HEARTWOOD  S  32  HEARTWOOD + SAPWOOD  WO.7 Cxi  « HH CO Z  U 0 . 5 < «  O  X Q . 4  M  E-  J ^  Q 0 . 3  D I X z E-> W  o* w  z  z  o 0.1  -  D W  CO  <  T  —  o  •BETA (BY GC) FIGURE 16. Q  0  T  4 0  AVERAGE # RINGS FROM P I T H +GAMMA (BY GC) OTOTAL (BY GC)  1  1 6 0  6 0  ^COLORIMETRIC  T H U J A P L I C I N CONTENT BY TWO METHODS V g AVERAGE RINGS FROM P I T H FOR SECOND GROWTH TREE #2.5  B  HEARTWOOD  O  ;HEARTWOOD I-+ SAPWOOD  W W tf 0.6  TA  W a* I—I w ECQ Z  O  M  05 E-<  M  W  <  «  O  0 . 8  <  0.4  X  --  0 . 3  oi 33  Z  * ^ 0 . 2 O O  0.1  -  a  w CO <  CQ  n BETA (BY GC)  20 AVERAGE # RINGS FROM P I T H +GAMMA (BY GC) OTOTAL (BY GC)  6 0  aCOLORIMETRIC  FIGURE 17,  2  §'••  -I-  T H U J A P L I C I N CONTENT BY TWO METHODS V g AVERAGE RINGS FROM P I T H FOR OLD GROWTH TREE #1  33  HEARTWOOD ' SAPWOOD  * 1.8 W •, to  7  «1.6 to  1.5 1.4 ''3 12  w-Eh  °  « 1.1  2  ux  i  O  '  H I  2 0.6 to >0.5 °0.4  OC  E-  o"  —I—  0.2  —I—  400  Q  < 0  •BETA (BY GC) FIGURE 18. Q 2 gl.» 1.8 H  600  AVERAGE # RINGS FROM P I T H +GAMMA (BY GC) OTOTAL (BY GC)  800  ^COLORIMETRIC  T H U J A P L I C I N CONTENT BY TWO METHODS VS AVERAGE RINGS FROM P I T H FOR OLD GROWTH TREE #2 HEARTWOOD!  SAPWOOD  to i 7  to)  « 1.6 1.4 1.3 5  ~ 2. to  CO <  H  1 , 2  2 « 1.1 O X 1 n W J 0.9 0<><fl. <P4°-  D £  I 2  8  '  0.8 > 0.5 §0.3 0.2 W 0.1  H  Q  CO  < •BETA  0  0  (BY  200 GC)  AVERAGE * RINGS +GAMMA ( B Y GC)  600 FROM P I T H OTOTAL (BY  GC)  *COLORIMETRIC  FIGURE 19.  T H U J A P L I C I N CONTENT BY TWO METHODS Y £ AVERAGE RINGS FROM P I T H FOR OLD GROWTH TREE #3  34  HEARTWOOD ' SAPWOOD  Ol.9 S 1 . B 1 . 7  W  gi.e 1.5  FE  ^^1.4  KH1.J  -  "ul.2 CO < , ,  ox: £j  1  W0.9  a, ><O.B -3  Q 0 . 7  §  2=0.6  E - W O . 3  O0.4 Z 0 . 3 ° 0 . 2 § 0 . 1  BOO  •BETA (BY GC) FIGURE 20. ~  AVERAGE # RINGS FROM P I T H +GAMMA (BY GC) OTOTAL (BY GC)  ACOLORIMETRIC  T H U J A P L I C I N CONTENT BY TWO METHODS Vg AVERAGE RINGS FROM P I T H FOR OLD GROWTH TREE #4  BOO  DBETA  AVERAGE # RINGS FROM P I T H (BY GC) +GAMMA (BY GC) OTOTAL (BY GC)  ACOLORIMETRIC  FIGURE 21  T H U J A P L I C I N CONTENT BY TWO METHODS VS AVERAGE RINGS FROM P I T H FOR OLD GROWTH TREE #5  200 AVERAGE # RINGS FROM P I T H • BETA (BY GC) +GAMMA (BY GC) OTOTAL (BY GC) FIGURE 22 O  o  1 fl  35  800 ^COLORIMETRIC  T H U J A P L I C I N CONTENT BY TWO METHODS VS AVERAGE RINGS FROM P I T H FOR OLD GROWTH TREE #6 HEARTWOOD ' SAPWOOD  1,s  3= 1.8 Oh 1.8 1.5 W. . rn  CO  Z  O 1.2 < OS 1 .1  Ox 1  as  zo.e >0.9 °0.4 §0.3 H0.1 CO „ < 0  CQ  —r-  400  AVERAGE # RINGS FROM P I T H •BETA (BY GC) +GAMMA (BY GC) OTOTAL (BY GC)  — i — 600 ^COLORIMETRIC  BOO  FIGURE 2 3 .  o o  T H U J A P L I C I N CONTENT BY TWO METHODS V g AVERAGE RINGS FROM P I T H FOR OLD GROWTH TREE #7 HEARTWOOD'  Q  SAPWOOD  1.5 — >1 WE-  1  -  co < * 1  Z  M  05 E-  1.  O X M W  o.  •J  < OJ°-  X20. E- W >0. °0. z  o < 0 CQ  1  0  •BETA (BY GC)  200  T-  ,  w  •  I•  1  400  AVERAGE # RINGS FROM P I T H +GAMMA (BY GC) OTOTAL (BY GC)  J  T  600 ^COLORIMETRIC  800  o a  ro  > W < W W -3  325 O W  Q >  w l  i—11> 2  O  H  kp as a w > o ^  s cha o »-3  O  Z O O  2  " 3 > z s  200  i  1  i  r  400 AVERAGE # RINGS FROM P I T H HEARTWOOD SAMPLE+ SAPWOOD CONTAINING  800 SAMPLEO  CO -4  1 1.2  1  1 1.6  1  J  r  T  2  2.4  2.8  LOG (AVERAGE # RINGS FROM P I T H ) HEARTWOOD SAMPLE+ SAPWOOD CONTAINING SAMPLEO  CO 00  M  0.7  a  Q O  0.6  ro  -H  CO  i  w w fa 0.5 ^ 2  > n H  o  <  •-H «  J EDH X < W  0.4  H  H  < EW CQ  Q I 2 W > O 2 O  W W H >  W o  a  H -9  EC  "J  S ><  ac PS  W n 2 O CO  0.3  0.2  O W  H  H  2  >  O O 2 *-3  f  2  t=d co  Q W CO < CQ  a  M  > <  > a w  0.1  T  200  1  400 AVERAGE # RINGS FROM P I T H HEARTWOOD SAMPLE+ SAPWOOD CONTAINING  r  600 SAMPLEO  800 CO CO  200 400 AVERAGE # RINGS FROM P I T H HEARTWOOD SAMPLE+ SAPWOOD CONTAINING  600 SAMPLEO  800  1.4 1.3  H  1.2 Q O O  1.1 1 0.9  ^> i—i ze « 0.8 u< 03 - 3 E-t Pu X m  <W 03 H  « Q I  0.7 0.6  < 2 0.5 2 O Q  to CO <  0.4 0.3 0.2 0.1  -4  +  +  4+  +  o  o o  1—*—I"' 0.8 1.2 1.6 2 2.4 LOG (AVERAGE # RINGS FROM P I T H ) HEARTWOOD SAMPLE+ SAPWOOD CONTAINING SAMPLE O 0.4  I l|0 2.8 DO  z I-H  o  1.7  a  ~1.6  H  11.5  H  »  1.4  H  ei.3  h  ei.2  h  o E-"  '•  <  Ed CQ  !x! X -3  a  •-3 f M  H  O O O O  z  +  0.9  >>  + +  §0.8 i  <  W -3  + +  1  1  < E-" X w  CO  o  1 1  I—I O •J tD X E-  1.8  O0.6  + +  >-3 z Z •-3 •-3 M Z -3  +  wko tr  §0.5  ^ 3  w 0.4  +  0+  $  -|  Z  o  tr tx) .. CO W  1  +  CO  0.2  *-3  w z  + +  tsi  0.1 0  T  r •fT I ~T~ T 4 8 12 16 ETHANOL:BENZENE EXTRACTIVES (%) (BASED ON OVEN-DRY EXTRACTIVE FREE WOOD) HEARTWOOD SAMPLE + SAPWOOD CONTAINING S A M P L E O  20  24 •Ik. CO  o o g W P=3  to W  > t—i EH <  Q  CS  O <  X ! W  U  >•  1 1 •-• "3  «  Q  I 2  O  33 EH  H  W > O  2 O Q W CO <  4  8 12 16 ETHANOL:BENZENE EXTRACTIVES (%) (BASED ON OVEN-DRY EXTRACTIVE FREE WOOD) HEARTWOOD SAMPLE+ SAPWOOD CONTAINING SAMPLE O  r  20  24  0.6  0.8 1 THUJAPLICINS (%) (BASED ON OVEN-DRY EXTRACTIVE FREE WOOD) HEARTWOOD SAMPLE + SAPWOOD CONTAINING SAMPLEO  Ot  o  FIGURE 34.  c  x •  «  «-•-  •  «  RADIAL DISTRIBUTION OF THUJIC ACID CONTENT FOR SECOND GROWTH S I T E #2  -  0  ) —*  o  o  o  r *  >  o  >  (  o  O •  i  o  r •  )  o  ^ •  -  o  •  r  o  o  •  c  N •  o  (dOOM 33H3 3 A I I 0 V H I X 3 AH0-N3A0 NO (I3SVS) (%) a i o v  DirnHX  «  •  o  o  200  i  r  400 AVERAGE # RINGS FROM P I T H HEARTWOOD SAMPLE+ SAPWOOD CONTAINING  600 SAMPLEO  0.30 0.28  -  _0:26  -  8 0.24 "0.22  -\  2  0.20  H  *£0.18  H  zolo.16  H  fa  w  I—I  £-t  O  X  3 0.14  H  3q0.12  H  W  Pu  o H  i  ^o.io  H  o  z 0.08  o  gO.06 CQ  H  0.04  -  0.02 0.00  BETA T H U J A P L I C I N D  AVERAGE Ht RINGS FROM P I T H AVERAGE BETA^-0GAMMA T H U J A P L I C I N +  0.60  Q O  0.50  s  Eel W 03  0.40  H  0.30  H  0.20  H  < 0.10  H  td  —  >  as  n  o  CO < 2 03 t-t E-<  o x; ft  >•  03 Q 2  I  2  o  Q w  CO  CQ  0.00 200 BETA T H U J A P L I C I N n  400  AVERAGE # RINGS FROM P I T H AVERAGE BETA^-^GAMMA T H U J A P L I C I N +  600 AVERAGE GAMMAA-A-  FIGURE 39.  BETA+GAMMA THUJAPLICIN CONTENT I S LOG (AVERAGE RINGS FROM PITH) FOR ALL TREES  o o o o o o d o o (CIOOM  3AII0VHIX3 AH0-N3A0 NO ( % ) N i o n d v r n H i vwwvo + v i s a  3 3 H 3  0 3 S V 9 )  52  APPENDIX 1. SAMPLE SITE  PHYSICAL DATA FOR OLD GROWTH TREES.  TREE #  PORT M c N E I L L  DBH (cm) # RINGS HEARTWOOD/SAPWOOD (AGE) BOUNDARY (RINGS FROM PITH)  1 2' 3 4 5 6 7  VANCOUVER ISLAND B.C.  HANEY, B.C.  100. 8 115.6 134.0 135. 6 130.4 116.8 54.2  APPENDIX 2. TREE #  RINGS INCLUDED IN SAMPLE  287 622 622 710 579 260 420  273 604 597 696 554 239 405  OLD GROWTH SAMPLE DATA  AVERAGE RINGS FROM PITH  RADIUS TO LAST RING (cm)  1- 40 41-100 101-160 161-220 221-250 251-273 274-287  20 70 130 190 235 262 280  5.9 17.0 36. 5 41.9 46. 1 48.6 50.4  1-124 125-244 245-334 335-424 425-514 515-574 575-604 604-622  62 184 289 379 469 544 589 613  4.4 16. 6 26.6 36. 6 46. 5 53.1 56.4 58. 6  1- 80 81-170 171-250 251-370 371-430 431-520 521-597 598-622  40 125 210 310 400 475 558 610  3.5 17. 5 33.5 45. 8 52.8 58. 3 64.8 67.3  54  OLD GROWTH SAMPLE DATA TREE #  RINGS INCLUDED IN SAMPLE  AVERAGE RINGS FROM P I T H  RADIUS TO LAST RING (cm)  1-100 101-250 251-340 341-430 431-520 521-610 611-670 671-696 697-710  50 175 295 385 475 565 640 683 703  6.7 26.7 35. 2 43.6 50.4 55.8 62.5 65.3 67.7  1-134 135-224 225-284 285-344 345-434 435-494 495-524 525-554 555-579  67 179 254 314 389 464 509 539 566  4.9 14.2 26.5 42.0 54.5 58.5 60. 5 62.5 63.8  1- 40 41-100 101-160 161-190 191-220 221-239 240-260  20 70 130 175 205 230 250  6.1 17. 6 35.9 47.4 52. 7 56. 3 59. 1  1- 30 31-150 151-240 241-300 301-360 361-390 391-405 406-420  15 90 195 270 330 375 397 412  4.8 10. 1 15.1 19. 1 23.1 24.6 25. 9 27. 1  55  APPENDIX 3.  EXPERIMENTAL DATA FROM OLD GROWTH TREES  ( A L L RESULTS % OVEN DRY EXTRACTIVE FREE WOOD) AVE. # EtOH: BETA GAMMA RINGS BENZ. THUJA- THUJAFROM EXTR. P L I C I N P L I C I N PITH  BETA+ GAMMA GAMMA /TOT. THUJAPLICIN  20 70 130 190 235 262 280  1.9 6.5 7.5 9.6 13.2 13.0 1.7  .034 . 133 . 179 . 194 . 145 .135 .033  .001 .204 .281 .349 .419 .520 .067  .034 .337 .460 .543 . 564 .655 . 100  .02 .60 .61 .64 .74 .79 .67  62 184 289 379 469 544 587 615  4.5 10. 1 15.2 13.4 13.1 14.0 15.6 1.1  .209 . 220 .135 . 134 .223 . 134 . 164 .021  .039 . 382 .732 .718 .747 .409 .809 .036  .248 .602 . 867 . 852 .970 . 543 .974 .057  40 125 210 310 410 475 558 610  3.2 5.9 7.4 11.2 13.3 15.0 16. 8 1.1  .007 .090 .098 . 381 .172 . 507 .342 .021  .061 . 288 .254 . 382 .693 .240 . 578 .030  50 125 295 385 475 565 640 683 703  7.2 13.0 16.4 15.4 19.0 16. 8 17. 6 17. 1 .6  . 119 . 218 . 142 . 252 .205 . 197 .106 . 165 .007  .201 .488 . 548 .318 .417 . 181 .469 .456 .008  COLOR. THUJIC THUJA- ACID + P L I C I N METHYL THUJATE . 170 .400 .454 .465 .635 .702 . 153  . 198 .457 .367 .494 . 586 .573 .097  . 16 .63 .84 . 84 .77 . 75 . 83 .63  . 243 . 528 .772 . 794 .952 1.079 1. 171 . 114  .488 . 527 . 465 . 688 1.024 .671 .960 .017  .068 .377 .352 . 763 . 865 . 747 . 919 .051  . 90 .76 .72 . 50 .80 . 32 . 63 . 58  . 178 . 347 .474 . 556 .763 .728 1.039 .091  . 304 .429 . 280 . 298 .388 . 382 . 387 .023  . 320 . 706 . 690 . 570 .622 . 377 . 575 . 621 .015  . 63 . 69 .79 . 56 . 67 .48 .82 . 73 . 51  .324 . 662 .666 .422 .658 . 325 .728 .883 .081  .490 . 554 .447 . 306 .320 . 238 . 401 .475 .022  56  EXPERIMENTAL DATA FOR OLD GROWTH TREES ( A L L RESULTS % OVEN DRY EXTRACTIVE FREE WOOD) AVE. # EtOH: BETA GAMMA RINGS BENZ. THUJA- THUJAFROM EXTR. P L I C I N P L I C I N PITH 67 179 254 314 389 464 509 539 566  6.3 10.0 9.8 10.0 22.8 15.7 17.0 15.8 2.7  6  20 70 130 175 205 238 250  7  15 90 195 270 330 375 383 412  BETA+ GAMMA GAMMA /TOT. THUJAPLICIN  COLOR. THUJIC THUJA- A C I D + P L I C I N METHYL THUJATE  .024 .000 .024 . 166 .072 .238 . 204 . 148 . 352 .219 . 173 .392 . 321 .294 .615 .466 1.308 1.774 .502 1.240 1.742 .270 .437 .707 .062 .010 .072  .00 .30 .42 .44 .48 .74 .71 .62 . 14  . 127 .680 .872 .831 1.000 1.216 1.186 1.063 . 134  2.9 6.4 7.8 11.2 12.4 12.4 2.4  .014 . 187 .347 .469 .587 .653 .055  .000 .014 . 146 .333 .260 .607 .372 .840 . 813 1.400 .663 1.315 .070 .125  .00 .44 .43 .44 .58 .50 .56  .161 .480 .647 .954 1.131 1.189 .139  .350 .936 .646 .694 .603 .613 .036  2.4 8.0 9.6 9.4 14.1 15.4 16.2 4.2  .040 .044 .078 .020 .004 . 121 . 201 .030  .000 .000 .016 .000 .000 .000 .077 .002  .00 .00 .17 .00 .00 .00 .28 .06  .061 .075 .109 .065 .082 .102 .228 .088  .306 .623 .545 .537 .728 .632 .561 .127  .040 .044 .093 .020 .004 .121 .278 .032  .660 . 920 .793 .553 .794 .868 .797 .679 .071  APPENDIX 4. SAMPLE S I T E  HORNE LAKE, VANCOUVER ISLAND, B.C. SHAWNIGAN LAKE, VANCOUVER ISLAND, B.C.  PHYSICAL DATA FOR SECOND GROWTH TREES  TREE #  1.1 1.2 1.3 1.4 1.5 2.1 2.2 2.3 2.4 2.5  DBH (cm) # RINGS (AGE) 46.8 44.5 37.8 51.6 44.9 64.6 63.7 56.0 47.8 52.7  50 44 52 51 63 68 52 71 42 77  HEARTWOOD/SAPWOOD BOUNDARY (RINGS FROM P I T H ) 44 39 46 46 58 60 46 64 36 72  58  APPENDIX 5. TREE #  RINGS INCLUDED IN SAMPLE  SECOND GROWTH SAMPLE DATA AVERAGE RINGS FROM P I T H  RADIUS TO LAST RING (cm)  161116213141-  5 10 15 20 30 40 50  2.5 7.5 12.5 17. 5 25 35 45  2.0 4.8 8.3 11.5 14. 7 17.4 20.3  1611162131-  5 10 15 20 30 44  2.5 7.5 12. 5 17.5 25 35  3.3 5.6 7.2 9.0 12.3 16.2  161116213141-  5 10 15 20 30 40 52  2.5 7.5 12.5 17.5 25 35 45  1.4 3.7 5.8 7.0 10.4 14. 5 19. 2  161116213141-  5 10 15 20 30 40 51  2.5 7.5 12.5 17.5 25 35 45  1.5 3.1 5.2 8.4 15.9 20. 1 23.5  1212631364151-  20 25 30 35 40 50 63  10 22. 5 27. 5 32.5 37. 5 45 55  3.0 5.2 8.5 11.1 12. 6 16.0 19.7  59  TREE #  RINGS INCLUDED IN SAMPLE  SECOND GROWTH SAMPLE DATA AVERAGE RINGS RADIUS TO FROM P I T H LAST RING (cm)  1263136414651-  25 30 35 40 45 50 68  12.5 27. 5 32.5 37. 5 42.5 47.5 55  3.7 6.3 8.2 12.3 14.9 21.1 30.3  11116213141-  10 15 20 30 40 52  5 12.5 17. 5 25 35 45  1.9 5.0 8.0 13.1 20.2 30.1  1263136414657-  25 30 35 40 45 56 66  12. 5 27.5 32. 5 37.5 42. 5 50 60  3.4 5.0 7.5 10.3 13.3 17.3 22. 3  1611162131-  5 10 15 20 30 42  2.5 7.5 12.5 17. 5 25 35  1.3 3.5 6.5 8.8 14. 2 19.2  1616671-  60 65 70 77  30 62. 5 67.5 72. 5  10.2 12. 7 15. 8 19. 8  60  APPENDIX 6.  EXPERIMENTAL DATA FOR SECOND GROWTH TREES  (ALL RESULTS % OVEN DRY EXTRACTIVE FREE WOOD) TREE #  AVE. # EtOH: BETA GAMMA RINGS BENZ. THUJA- THUJAFROM EXTR. P L I C I N P L I C I N PITH  BETA+ GAMMA COLOR. THUJIC GAMMA /TOT. THUJA- ACID + THUJAP L I C I N METHYL PLICIN THUJATE  2.5 7.5 12. 5 17.5 25 35 45  3.3 3.9 3.6 5.7 8.0 9.2 5.0  .004 .002 .013 .036 .055 .080 .014  .010 .010 .044 . 108 .225 .243 .077  .014 .011 .058 .145 . 280 .323 .091  . 72 .85 .77 .75 .80 .75 .85  .086 . 112 . 147 . 197 .488 .525 . 222  . 128 .310 . 216 .331 .703 .618 . 246  2.5 7.5 12.5 17.5 25 35  3.6 5.1 7.4 5.4 5.4 6.3  .024 .032 .036 .034 .018 .016  .032 .054 .073 .047 .016 .042  .055 .086 .108 .081 .034 .058  .57 .63 .67 . 59 .46 .73  . 109 . 148 . 180 . 193 .229 . 191  .312 .477 . 884 .612 .843 . 394  2.5 7.5 12.5 17. 5 25 35 45  5.2 4.6 5.3 7.2 7.4 9.8 8.6  .016 .058 .059 . 108 . 162 . 303 . 200  .005 .000 .001 .003 .028 .063 .024  .021 .058 .060 . Ill .190 . 366 .224  .25 .00 .02 .03 . 15 . 17 . 11  . 125 . 164 . 210 . 315 .348 .481 . 368  . 172 .445 .446 . 600 . 650 . 824 .504  2.5 7.5 12. 5 17.5 25 35 45  4.8 5.0 4.6 4.6 8.2 9.7 6.1  .021 .042 .054 .044 . 157 .292 .095  .014 .028 .022 .016 . 107 .233 .060  .035 .070 .077 .060 .264 .525 . 156  .40 .40 .29 .27 . 40 .44 .39  .078 . 116 . 108 . 115 . 325 .544 . 194  . 286 . 579 . 526 .393 . 772 .989 . 361  10 22.5 27. 5 32. 5 37.5 45 55  2.8 3.3 3.8 5.4 7.0 8.3 9.3  .022 .058 .089 . 122 .226 . 194 .242  .000 .000 .023 .047 . 150 . 154 . 184  .022 .058 . 113 . 169 .376 .348 .426  .00 .00 . 21 .28 .40 .44 .43  .030 .050 . 115 . 245 .390 .511 .710  .069 , 157 . 242 .407 .580 .661 .516  61  EXPERIMENTAL DATA FOR SECOND GROWTH TREES ( A L L RESULTS % OVEN DRY EXTRACTIVE FREE WOOD) TREE #  AVE. RINGS FROM PITH  EtOH: BETA GAMMA BETA+ GAMMA BENZ. THUJA- THUJA- GAMMA /TOT. EXTR. P L I C I N P L I C I N THUJAPLICIN  COLOR. THUJIC THUJA- ACID + P L I C I N METHYL THUJATE  2.1  12. 5 27.5 32. 5 37.5 42. 5 50 60  3.2 4.9 5.7 5.4 9.5 9.3 6.9  .043 .024 .052 .074 . 125 .166 . 137  .000 .073 . 109 . 170 .341 .240 . 299  .043 .097 . 161 .244 .467 .406 .436  .00 . 75 .68 .70 .73 .59 .69  .058 . 222 . 284 .299 . 511 .524 .397  . 215 .395 . 383 .357 .407 .295 . 144  2.2  5 12. 5 17.5 25 35 45  3.6 3.9 4.3 6.0 6.1 8.2  .079 .094 .152 . 206 .376 .315  .019 .040 .034 .044 .040 .000  .099 . 134 . 186 .249 .415 .315  .20 . 30 . 18 . 18 . 10 .00  . 137 . 128 .240 . 350 .466 .622  .205 . 282 .305 .444 .290 .232  2.3  12.5 27. 5 32.5 37. 5 42.5 50 60  3.7 4.7 5.2 6.3 7.5 8.9 8.6  .027 .028 .055 . 189 .171 . 152 . 300  .006 .018 .024 .016 .016 .034 .027  .033 .046 .080 . 205 . 188 . 186 .327  . 18 . 39 . 30 .08 .09 . 18 .08  .082 . 151 .250 . 266 .389 . 338 . 594  . 338 . 327 .438 . 614 . 616 .427 . 686  2.4  2.5 7.5 12. 5 17.5 25 35  4.0 2.4 2.8 5.9 6.2 6.0  .041 .007 .019 .070 .098 . 135  .017 .000 .011 .061 .056 .035  .058 .007 .030 . 130 . 154 . 169  . 29 .05 . 37 . 46 . 36 .20  .084 . 020 .038 .238 .299 . 284  . 116 .026 .064 . 305 . 317 . 302  2.5  30 62.5 67. 5 72.5  5.2 6.8 6.3 6.9  .054 .108 .046 .181  .046 . 105 . Ill .070  .099 .213 . 157 .250  . 46 .49 .70 .28  . 146 .355 . 336 .349  . 392 .440 .444 .404  APPENDIX 7.  LINEAR REGRESSION S T A T I S T I C S FOR GC v s COLORIMETRIC RESULTS  SLOPE  INTERCEPT  CORRELATION COEFFICIENT  994  .062  . 905  819  

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