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Distribution and characterization of organo-clay complexes in selected Lower Fraser Valley soils Parasher, Chander Dutt 1969

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THE DISTRIBUTION ORGANO-CLAY  AND  CHARACTERIZATION  OF  COMPLEXES I N S E L E C T E D  LOWER ERASER  VALLEY  SOILS  fey C H A N D E R  D U T T  P A ' R A S H E R  A T H E S I S SUBMITTED I N P A R T I A L FULFILMENT T H E REQUIREMENTS FOR MASTER OF S C I E N C E I N IN  THE  OF  T H E D E G R E E OF A(TR1CULTUR_  DEPARTMENT OF  SOIL  SCIENCE  We a c c e p t t h i s t h e s i s as conforming required  t o the  standard  THE UNIVERSITY  OF BRITISH COLUMBIA  September 12, 1969-  In  presenting  an  advanced  the I  Library  further  for  this  thesis  degree shall  agree  scholarly  at the University make  tha  p u r p o s e s may  h i s representatives.  of  this  written  i tfreely  permission  by  thesis  of  The U n i v e r s i t y o f B r i t i s h V a n c o u v e r 8, Canada  ,  of British  shall  $c>gvct. Columbia  copying  by t h e H e a d  I t i s understood gain  Columbia,  f o r reference  f o rextensive  be g r a n t e d  f o rfinancial  S^>\£  f u l f i l m e n t o f the requirements f o r  available  permission.  Department  Date  in partial  that  n o t be a l l o w e d  and  that  study.  of this  o f my  copying  I agree  thesis  Department o r or  publication  without  my  TABLE OE CONTENTS  PAGE ACKNOWLEDGEMENT  i  ABSTRACT  i i  SECTION 1  I. INTRODUCTION II. III-  LITERATURE REVIEW  . .  19  METHODS AND MATERIALS  29  IV. RESULTS AND DISCUSSION V- SUMMARY AND CONCLUSION VI. BIBLIOGRAPHY  .  5  ......  52 55  ACKNOWLEDGEMENTS  The a u t h o r wishes  t o express h i s deep sense o f a p p r e c i a -  t i o n t o t h e f o l l o w i n g p e r s o n s , w i t h o u t whose t i m e l y h e l p  this  t h e s i s would n o t have been p o s s i b l e ; to Dr. L. E . Lowe f o r h i s f r i e n d l y  h e l p and guidance  d u r i n g the course o f t h i s i n v e s t i g a t i o n , and Dr. 0. A. Howies, Chairman, Department o f S o i l S c i e n c e , to t h e members o f t h e Research Committee, Dr. P. M. Townsley and p a r t i c u l a r l y  D r . L . M. L a v k u l i c h who p r o -  v i d e d v a l u a b l e a i d i n connection with x-ray  diffraction  analyses. t o Mr. H e r b e r t L u t t m e r d i n g , P e d o l o g i s t , B r i t i s h Columb i a Department o f A g r i c u l t u r e f o r h i s h e l p i n l o c a t i n g the sampling  s i t e s , and l a s t l y , t h e f i n a n c i a l  support  by t h e N a t i o n a l Research C o u n c i l o f Canada d u r i n g t h e course o f t h i s work i s acknowledged.  ii ABSTRACT In the study o f the d i s t r i b u t i o n o f o r g a n o - c l a y t h i r t y - f o u r samples r e p r e s e n t i n g  complexes,  e i g h t s o i l types were c o l l e c t e d  from the Lower E r a s e r V a l l e y and the e f f e c t i v e n e s s o f the t h r e e methods, v i z . simple d i s p e r s i o n , i n s o n a t i o n were examined.  and c h e l a t i n g r e s i n  The use o f a c h e l a t i n g r e s i n was  found most e f -  f e c t i v e f o r q u a n t i t a t i v e s t u d i e s while- I n s o n a t i o n was f o r qualitative studies.  preferred  F o r d e t a i l e d c h a r a c t e r i z a t i o n o f the  o r g a n o - c l a y complexes e i g h t samples were chosen and u l t r a s o n i c a g i t a t i o n was The  used f o r i s o l a t i n g the o r g a n o - c l a y  complexes.  o r g a n o - c l a y complexes v a r i e d w i d e l y i n c h a r a c t e r i s t i c s .  The y i e l d o f complexes by simple d i s p e r s i o n , u l t r a s o n i c v i b r a t i o n and c h e l a t i n g r e s i n ranged  from 0.15  t o 10.42, 0.20  17.20 and 1.25 t o 25.70 p e r c e n t by weight, The  to  respectively.  o r g a n o - c l a y complexes were a n a l y s e d f o r t h e i r c o n t e n t  o f carbon, n i t r o g e n ,  i r o n , s i l i c o n , aluminum a l o n g w i t h  h y d r a t e s , humic (HA)  and f u l v i c  (FA) a c i d s .  The C/N  carbo-  ratio  the s e l e c t e d complexes v a r i e d between 5»5  and 17.0  h y d r a t e c o n t e n t accounted  p e r c e n t o f the comp-  l e x carbon.  f o r 3*3  t o 16.0  and  of  carbo-  The HA:FA r a t i o i n d i c a t e d t h a t the major p r o p o r -  t i o n o f the o r g a n i c component i n t h i s a s s o c i a t i o n was n a t u r e , except i n the case o f the P o d z o l i c i n which about 2/3  of  fulvic  B f h o r i z o n samples  o f the e x t r a c t a b l e m a t e r i a l was  i n the humic  fraction. X-ray  d i f f r a c t i o n , i n f r a r e d (IR) and d i f f e r e n t i a l  a n a l y s i s were a l s o conducted.  The m i n e r a l o g y  was  not  thermal observed  t o d i f f e r t o a g r e a t e x t e n t except i n the Ae h o r i z o n sample o f the O r t h i c P o d z o l and the B t g of the O r t h i c G l e y s o l where mont-  i i i morillonite  was  present  in significant  amounts.  I n most  samples examined i n t e r l a m e l l a r i n c l u s i o n o f the o r g a n i c was  also  matter  observed.  The d i f f e r e n t i a l t h e r m a l a n a l y s i s e x h i b i t e d a b a n d 320°C p r o b a b l y fraction. organic  o f the  due  t o t h e e l i m i n a t i o n o f some f o r m o f  The I R s t u d i e s  conclusive  evidence  ic  components and c l a y  organic  i n d i c a t e d the bonding of s i l i c o n to  components t h r o u g h oxygen l i n k a g e s ,  no  near  o f amide l i n k a g e minerals.  however, t h e r e  formation  between  was organ-  1. INTRODUCTION The  r o l e o f o r g a n i c m a t t e r and c l a y o c c u p i e s a p l a c e o f  c o n s i d e r a b l e importance  i n the realm o f s o i l  i n t e r a c t i o n o f t h e s e m a t e r i a l s t o produce  f e r t i l i t y , and  so-called  the  organo-clay  complexes i n s o i l s has an important i n f l u e n c e on physico-chemi c a l properties of In  soils*  the study o f s o i l  p r o p e r t i e s i n r e l a t i o n t o c r o p growth  t h e r e f o r e , the p r o c e s s o f o r g a n o - c l a y complex f o r m a t i o n m e r i t s due  attention.  In t h i s connection Jacks (46), stated,  u n i o n o f m i n e r a l and o r g a n i c m a t e r i a l t o form the complexes ( i s ) a s y n t h e s i s as v i t a l a s , and l e s s understood, appears perhaps  organo-clay  t o the c o n t i n u a n c e o f  than p h o t o s y n t h e s i s . "  t o be an overstatement,  Although  life this  n e v e r t h e l e s s the p r o -  c e s s o f o r g a n o - c l a y complex f o r m a t i o n i s important ing  "the  i n sustain-  o r g a n i c m a t t e r i n the solum which o t h e r w i s e i s l i k e l y t o be  l e a c h e d down q u i c k l y . S e c o n d l y , a l t h o u g h a c o n s i d e r a b l e amount o f work has been done on a r t i f i c i a l l y p r e p a r e d o r g a n o - c l a y complexes, v e r y  few  s t u d i e s have been r e p o r t e d on the n a t u r e o f o r g a n o - c l a y complexes as they o c c u r i n s o i l s under n a t u r a l c o n d i t i o n s .  I n the p a s t  many workers have devoted a g r e a t d e a l o f e f f o r t t o working pure m i n e r a l s and o r g a n i c compounds, which c e r t a i n l y has some i n f o r m a t i o n about ponents.  with  given  the i n t e r a c t i o n mechanisms o f t h e s e com-  However, the v a l i d i t y o f these s t u d i e s i n the  field  seems r a t h e r d o u b t f u l . T h e r e f o r e , t h i s p r e s e n t i n v e s t i g a t i o n was  undertaken  under  t h e heading, d i s t r i b u t i o n and c h a r a c t e r i z a t i o n o f o r g a n o - c l a y complexes i n d i f f e r e n t  soil  t y p e s t o i n v e s t i g a t e the n a t u r e o f  2. the n a t u r a l l y the  inter-relationship In  the  view o f the  essentially  objectives iveness and  occurring organo-clay  o r g a n i c and  preliminary nature  of the  investigation  of d i f f e r e n t  different  this  association  reagents,  and  through the  d i f f r a c t i o n and  mineral  of the  were t o  study,  fractions. field,  the  on  different  complexes w i t h r e s p e c t t o complexes and (3)» use  and  specific  ( 1 ) compare t h e  methods o f i s o l a t i o n  a s s o c i a t e d with these  with  to e l u c i d a t e  d e a r t h o f p r e v i o u s work i n t h i s  ( 2 ) , c h a r a c t e r i z e these  carbon  ray  of the  c o m p l e x e s and  effectsoils,  organic  i t s extractability  s e e k some i n f o r m a t i o n a b o u t of i n f r a r e d  d i f f e r e n t i a l thermal  spectroscopy,  analyses.  X-  3. •LITERATURE REVIEW The  difficulties  m a t t e r from soil in  soil,  colloids  theory  organic  encountered i n the e x t r a c t i o n of organic  serve  t o remind  i n t o organic  than  and i n o r g a n i c  components.  called  organo-clay  tempts  e x t r a c t i o n of organic  The  A review  This  complex f o r m a t i o n .  enon o f o r g a n o - c l a y  lowing  the separation of  components i s e a s i e r  i n p r a c t i c e , due t o t h e i n t i m a t e  and i n o r g a n i c  count.  one t h a t  matter  association i s often Therefore,  when one a t -  from t h e s o i l  complex f o r m a t i o n  of pertinent  association of  t h e phenom-  must he t a k e n i n t o a c -  literature  i s given  i n the f o l -  pages.  effectiveness of different  e x t r a c t i o n methods and  reagents.  A l t h o u g h t h e l a c k o f s a t i s f a c t o r y methods o f s e p a r a t i n g the  organic  has  long  component  been r e c o g n i z e d ,  given  to this  1786,  when A c h a r d  ate  problem.  humic a c i d .  alkali soil  from  may  the inorganic  surprisingly l i t t l e  Alkali  Consideration  matter  time  Keeping t h i s  ially  t h e sodium  the 83),  great  of organic  v a r i e t y of chemical  extraction of the organic  sodium h y d r o x i d e  i t to that  and i n o r g a n i c  isol-  caustic  properties of t o seek  milder  i n mind they  n e u t r a l reagents,  sur-  espec-  acids.  r e a g e n t s have been t e s t e d f o r  fraction  from  and t h e advantages and d i s a d v a n t a g e s  r e v i e w e d and d i s c u s s e d .  (12),  objective  t h e e x t r a c t i n g powers o f v a r i o u s  A  employed  the physico-chemical  veyed  salts  a t t e n t i o n has been  of the p o s s i b i l i t y  l e d Bremner and L e s s  methods o f e x t r a c t i o n .  of the s o i l  e x t r a c t i o n has been i n use s i n c e  (1), f o r the f i r s t  seriously affect  organic  material  soils,  (13,14,17,  o f these  critically  T h e r e a g e n t s commonly e m p l o y e d a r e  a n d two r e l a t i v e l y  mild  salts,  sodium  pyro-  4. phosphate and sodium f l u o r i d e , experimental  c o n d i t i o n s a r e seldom c l e a r l y  However, r e c e n t l y with  h u t optimum c o n c e n t r a t i o n a n d  reasonable  these  success  methods ( 9 5 ) , have been  and p r o b a b l y  duction  of artefacts,  organic  association  In  the present  investigation  forisolating  organo-clay  ployed  not  briefly Simple  Black Solonetz  about  ganic  reagent  Chelating It  silty  clay  hence, v e r y  work.  loam and f o u n d  little  little  liter-  The m e t h o d s a r e  type  and, t h e r e f o r e , l i t t l e  applicability  for isol-  However, t h i s  to a l l s o i l s .  a p p l i e d t h i s method b u t t h e i n t r o d u c t i o n i n h i s m e t h o d may h a v e p r o d u c e d  was  c a n be Tinsley  o f an o r -  artefacts.  Resins:  resin  prior  of the l a t t e r  cation  groups,  i s treated with  a  o f organic matter, the  extracted i s increased  significantly.  (14,16) r e p o r t e d t h a t t h e use o f t h e  exchange r e s i n  was v e r y  They a l s o  that i fa s o i l  to extraction  Bremner and coworkers synthetic  satisfactory  complexes i n good y i e l d .  i s g e n e r a l l y observed  chelating  tion.  direction,  Relatively  below:  i t s universal  also  acid  complexes.  em-  a n d i n some i n s t a n c e s t h e work r e p o r t e d may  on o n l y one s o i l  (83),  amount  clay-  (7)» h a s b e e n a p p l i e d t o a B n t h o r i z o n o f a  organo-clay  attempted said  of breaking  pro-  d i s p e r s i o n and d e c a n t a t i o n :  T h i s method  ating  significant  t h r e e methods have been  pertinent to the present  enumerated  employed  remains.  i s available,  be t o t a l l y  without  but the p o s s i b i l i t y  work h a s b e e n done i n t h i s ature  defined.  effective  Dowex A - l , w i t h i m i n o d i a c e t i c i n soil  claimed that t h i s  organic matter  reagent  extrac-  d i d not i n v o l v e the  5 .  risks  of artefaction  ( 9 5 ) also reported that  Yuan  tracted  comparable  (10),  observed  that  i s comparable  and an e x t r a c t d e v o i d  suggests  the p o t e n t i a l  resins  have a l s o been employed  i t s associated mineral  humus f r a c t i o n s  organic  Use  m a t t e r by t h e use  an o b s e r v a t i o n  that  colloids.  Cation  mat-  exchange  f o r the removal o f c a t i o n s  from  and i n t h e s e p a r a t i o n o f humic and f u l -  and Reeve ( 5 5 ) r e p o r t e d  that  c h e l a t i n g agents effective  m a t t e r from a P o d z o l i c B h o r i z o n .  that the extent  withtthe of  Bear  f o r dispersing organic  s o d i u m p y r o p h o s p h a t e ) were p a r t i c u l a r l y  ted  extraction.  acids,(60). Martin  of  was i n some  o f contaminants i s obtained.  o f such r e s i n  with  m a t t e r ex-  i n q u a n t i t y t o 0.5N s o d i u m h y -  i s usually high;  erials  isolated  by a l k a l i  the e x t r a c t i o n of organic  However, t h e a s h c o n t e n t  methods.  t h e amount o f o r g a n i c  to that obtained  chelating resin  droxide,  vic  the c l a s s i c a l  b y t h e u s e o f Dowex A - l c h e l a t i n g r e s i n  cases  of  associated with  of organic  (e.g.,  i n extraction  Evans  (31) repor-  matter e x t r a c t i o n tended t o r i s e  pH, a n d c h e l a t i n g r e a g e n t s  e x t r a c t e d more t h a n  others  c o m p a r a b l e pH v a l u e . of ultrasonics,: The  use o f u l t r a s o n i c s i n the study  o f o r g a n i c matter and  humus c o m p l e x e s a p p e a r s t o h a v e c o n s i d e r a b l e  potential,  but the  method has as y e t n o t been used e x t e n s i v e l y . It  was o b s e r v e d  (34),  tracted  by treatment  of soils  for  three  reagent  that  t h e amount o f o r g a n i c  with  0.1M N a ^ O ?  a n d 0.5N NaOH  h o u r s were i n c r e a s e d b y 20 t o 4 8 % p r o v i d e d  suspensions  Bremner ( 2 6 ) ,  were s u b j e c t e d  confirmed  this  to insonation.  observation  m a t t e r ex-  but found  the s o i l -  Edwards and that the  6. amount o f reagents  organic f o r 24  matter extracted  h o u r s were n o t  s i o n s were s u b j e c t e d before the  with  alkali  same a u t h o r s  (27),  used  content,  from and  soils  they  comparable Several  permits dants,  separation  significantly  (19),  ported  that  and  that  der  his laboratory  organic for  this  removing  lator, (9) utes ium  high  reported period  pH  the  probe-type  without  c o n d u c t i v i t y of  claimed  studied  crystal  soil  matter  give  of  soil  quite  the  time  t o be  shakunused  humified  a r a p i d method  sediments. soils  a 1500W.  carbonate  of  re-  ( 4 0 , 6 0 ) , have  insonation  of u l t r a s o n i c v i b r a t i o n of  However,  dispersion  of p a r t i a l l y  d i s p e rsion achieved  not  suspension,  separation  effective  does  time p e r i o d s ,  Other workers  d r i v e n by  oxi-  stable.  effective  dispersion of  hexametaphosphate-sodium  insonation  m a t e r i a l , and  for different  matter from  reasonably  the  1967,  In  vibrator  use  by  i n t e n s i t y s o u n d waves p r o d u c e d by  that  hour  without d i s s o l u t i o n of  were r e p o r t e d l y  organic  the  or  conditions.  reported  suspen-  f o r one  organic  inorganic  method d i d n o t  (66)  quartz  and  and  or  insonation  soluble  Olmstead  electric  the  and  kc)  (26,27,34) that  particles  d i s p e r s i o n f o r the  materials  quency and  texture  r e s u l t s were q u i t e v a r i a b l e w i t h  ing  ultrasonic  soil  obtained  using  these  sonic v i b r a t o r .  of organic  affect  with  f o r d i s p e r s i o n of  o r p e p t i z i n g r e a g e n t s and  suspensions  Bourget  of  20  to  insonation  of d i f f e r e n t  the  soils  sodium p y r o p h o s p h a t e .  a l s o commented t h a t  to  more t h a n t r a c e s  and  or  (18  w o r k e r s have c o n c l u d e d  acids,  shaking  markedly a f f e c t e d i f the  insonation  treatment  particles  was  to  by  high  fre-  a large  vacuum-tube  piezo-  oscil-  dispersion.  Barkoff  a 15  min-  by  soils  o r 60  suspended i n  s o l u t i o n was  more  sodcom-  7. plete  than  that  o b t a i n e d by  shaking these  suspensions  for  five  hours. The ful  use  i n not  stable  of u l t r a s o n i c  vibration  i n t r o d u c i n g any  suspension  and  for dispersion  contaminant,  probably not  bringing  appears  about  a  use-  fairly  breaking clay-organic asso-  ciations. Amount  of carbon  It  i s not  a s s o c i a t e d w i t h the  easy  to determine  amount o f o r g a n i c m a t t e r the  doubtful nature  which carbon  According "combined" must be plex,  amount o f t h i s  in- a l i q u i d  an  less work.  t h e manner i n  to separate the  t o 2.0  but  the  fraction,  was  has  "free"  will  field  free  of the  soil  also and  be  comthe  (4-0,46,47,50,  organic material o f the  liquids  free satis-  of density  ultrasonic  disper-  entangled  o v e r c o m e by  t h e n w a s h i n g and  boiling drying  reaggregation (61).  of carbon  sedimentation  can  form  d e p e n d on  the b e s t method o f r e l e a s i n g  entanglement  found  Short  and  i n the  r e p o r t e d i t t o be  reported that  \*/ere r e a s o n a b l e .  to prevent  percent  carbon  2 micron  c l a y - o r g a n i c complex and  aqueous s u s p e n s i o n  soil  (39),  s e p a r a t i o n of the  (39)  to  complex.  Many w o r k e r s i n t h i s  the  Greenland  with alcohol  ing  than  (40), i s probably  The  i n the  and  o f d e n s i t y i n t e r m e d i a t e between t h a t  and  b e t w e e n 1.8  material,  a c c u r a t e l y the  the p r o p o r t i o n of m a t e r i a l found  54,61), have t r i e d  sion  and  o r g a n i c m a t e r i a l some amount o f work i n some  i . e . , the  factory.  complex i t s e l f ,  to Greenland  done, and  material  precisely  i n v o l v e d i n c o m p l e x f o r m a t i o n , due  of the  i s present  complexes.  i n the  by H e n i n  and  complex expressed Turc  t o be  66.5%  i n a benzene-bromoform mixture  of  on  the  total  ( 4 6 ) , by specific  us-  8. g r a v i t y 1.75  f o r Rendzina  soils.  Khan ( 5 0 ) , working on  Podzol  and Chernozem s o i l s r e p o r t e d 89•6% and 85.2$ r e s p e c t i v e l y u s i n g sedimentation i n Toulet s o l u t i o n of s p e c i f i c  by  gravity  1.8.  Monnier and h i s a s s o c i a t e s ( 6 1 ) , used ethanol-bromoform o f specific  g r a v i t y 2.0  bon  silt  from  54.3%  tion  under o l d p a s t u r e .  and 68.1$  carbon  f o r s e d i m e n t a t i o n and r e p o r t e d 77*5$ c a r -  o r g a n i c carbon r e s p e c t i v e l y o f the t o t a l  from Rendzina  specific  soil  and Brown E a r t h s o i l s by u s i n g a " f l o t a -  s i e v i n g " method.  d i s p e r s i o n and  R o u l e t et a l . ( 7 1 ) , r e p o r t e d  Greenland  and F o r d (40) used  ultrasonic  s e d i m e n t a t i o n i n bromoform-petroleum s p i r i t  g r a v i t y 2.0  and  s t u d i e d organo-mineral  number o f s o i l s and r e p o r t e d 7 1 . 5 , 68.4, p e r c e n t o f the t o t a l s o i l carbon  97.8,  of  complexes i n a and 5 1 . 6  76.4,  from Red Brown E a r t h , Rend-  z i n a , L a t e r i t i c Red Earthy Solo.dized S o l o n e t z and S o l o n i z e d Brown s o i l r e s p e c t i v e l y i n the complex. S e v e r a l workers (40,46,50) have concluded  that free organic  m a t e r i a l ( i . e . , not complexed) i s i n a much e a r l i e r stage of c o m p o s i t i o n than the m a t e r i a l complexed w i t h c l a y .  de-  However,  t h e i r methods o f i s o l a t i n g complexes do not seem sound, and i t is  hard to t e l l  whether they are p r o d u c i n g new  use o f o r g a n i c l i q u i d s , Secondly,  or whether they are i s o l a t i n g  sometimes the d i s t i n c t i o n  gano-mineral  complexes by them.  between o r g a n o - c l a y and  or-  complexes i s not c l e a r l y e s t a b l i s h e d .  A g r e a t number o f s e p a r a t i o n methods have been used p a s t without  the  i n the  g i v i n g much a t t e n t i o n t o the a r t e f a c t s produced,  Such methods ranged chemical treatments.  from  simple d i s p e r s i o n i n water t o d r a s t i c  However, even the m i l d e s t o f these c o u l d  cause some s e p a r a t i o n of o r g a n i c m a t e r i a l from the m i n e r a l  com-  9. I n 1938,  ponent.  T y u l i n (85),  proposed  sodium c h l o r i d e , which p r o b a b l y colloids, release  and subsequently  some i r o n  some p a r t  o f the  +  organic  f o r the  technique Several his  satisfactory  layer. total  similar  finer  humus i n t h e  40-50  fractions  and the  10  top  cm a n d  cm l a y e r .  contained organic  i n the  clay fraction  ticle  size.  A similar  clay  size  with  the It  w h i c h may  use o f  used e l u t r i a t i o n and materials, but this (39).  Trofimenko and  appear a p p r o p r i a t e  the  magnitude  silt  fraction  33•5  to  55.2  percent  i n / t o p 10 cm percent o f the  o f the total  t h a t the  0.1-  a s e m i d e c o m p o s e d mass, b u t i n t h e  They  the  mineral  f u r t h e r mentioned t h a t the  humus o f a p a r t i c u l a r and i n c r e a s e d with  f r a c t i o n was  i n c r e a s i n g par-  was made b y A r s h a d a n d Lowe  t h e amount o f c a r b o n i n d i f f e r e n t more o r g a n i c  carbon  associated  fraction.  from the  not  soils.  material associated  They a l s o r e p o r t e d  and found  coarser clay i s evident  and a l l i e d  lower r e s u l t s  50-77-4  investigation  t o estimate  particles  this  c a r b o n was a s s o c i a t e d w i t h  least  who t r i e d  fine  contained  o f humins i n the  (7),  alkali  due t o t h e  and p a r t i c u l a r l y  surfaces o r microaggregates. percentage  (71),  amounts o f o r g a n i c  The c l a y f r a c t i o n  0 . 2 5 mm f r a c t i o n  with  c o n d u c t e d e x p e r i m e n t s on G i e c a u c a s i a  clay fraction  humus i n t h e  information  significantly  (3,4),  other workers  the  Therefore,  Some w o r k e r s  appeared t o give  They r e p o r t e d  soil  bonded t o o r g a n i c  + +  dilute  separation o f free organic  a s s o c i a t e (84),  with  t r e a t i n g with  fraction.  i o n s a n d a h i g h pH.  sieving  releases C a  the  a n d aluminum bonded m a t e r i a l and a l s o d i s s o l v e  m e t h o d s do n o t g i v e Na  shaking  literature  r e v i e w e d t h a t i t does  t o make a n y c o n c l u s i v e s t a t e m e n t  o f carbon present  i n the  organo-clay  about  complexes,  10. as  i t varies  at  least  on  and  should vary  from  source  c l i m a t e , v e g e t a t i o n and  different  ations tion the  of Organo-clay  does n o t  be  study  appear f r u i t f u l  to review  drawn o n l y t o t h o s e  of organo-clay  are  complexes.  made m e a s u r a b l e p r o g r e s s  ever,  field  the  is still  l a c k o f knowledge  complexes. sition  to  conducted  soil  fertility.  h e l d at the  be  important and  the  colloids  may  serve  extent  matter ing  w e l l understood, special  study He  on  complex  reHow-  p e r h a p s due  to  organo-clay compo-  the m i n e r a l  0.5.  alfalfa  organo-mineral  soil  of the  can the  fractions.  lignin, He  also  l e a f meal by  phenomenon was  gels i n  r e p o r t e d t h a t humus i s q u i t e  fertility..  affecting  l e a f m e a l , and  and  r e l e v a n t to  p r o p e r t i e s of  g e l s and He  also  loosely  a valuable criterion  factors  a maximum a t pH straw  Atten-  during recent years.  be  he  of s o i l  fertility,  between  gelatin,  soil or (30)  organic  r e p o r t e d that the  an  the  Ensminger  albumen,  increased with a c i d i t y claimed  i t to  h e l d humates i n  interaction He  claimed  reported that  cultivated.  capacity of montmorillonite with  alfalfa  This  a  composition  to which the  the and  public-  a p p l i e d to s o i l s .  Organo-clay  s u r f a c e s of these  in soil  quantity  studied  of the  (85)  loosely  the  not  t h e numerous  structure.  Tyulin  very  soils  These complexes appear t o have v e r y p e c u l i a r  and  relation  very  p a r a m e t e r on  studies directly  s e a r c h has this  not  Complexes.  i n which v a r i o u s techniques  will  of t h i s  and  depending  sources.  Characterization It  source,  mineralogy,  much i s known a b o u t t h e v a r i a b i l i t y from  to  combinstraw,  reaching  increase i n s o r p t i o n of  montmorillonite with  more p r o n o u n c e d i n a l f a l f a ,  composting.  probably  due  to  11. high nitrogen content. Khan ( 5 0 ) the  soil  separated free  o r g a n i c m a t e r i a l by  samples  i n T o u l e t s o l u t i o n s by  tation.  He  solutions with  2.45  less  and  used  than  1.80.  nique.  Brydon  and  It i s unlikely  his associate  c o m p l e x e s o f a Chemozemic a n d method o f f r a c t i o n a t i o n . and  less  tions  crystalline  and  o f o r g a n i c and  and  Nad  (4)  from  gano-mineral complexes The  tion  that  iron  matter  absence  e x t r a c t e d by  However, a n o t h e r f o r the  structure  development.  mainly  polyvalent  metals.  and  Their  (21),  on  smaller  size  bond-  of or-  colloids  as  dispersed minerals.  and  organic  iron-humic  S i m i l a r was who  frac-  Aleksandrova  the n a t u r e  der-  the  observa-  reported that  calcium,  c o n c l u s i o n was  linked  the percentage  of mineral t o the  fact  of organic  solvents increased considerably.  of workers  (28), put  They r e p o r t e d t h a t  forward a  and  concept  similar  subsequently  soil  microaggregates  con-  humified organic material  Their  Tyulin's  r e s p o n s i b l e f o r the  formation of aggregates  of clay  using  the  tech-  clay-humus  t h e medium o f c o m b i n a t i o n  alkaline  group  the  by  the alumino-  of these cations  criterion  sist  be  immersion  of the m i n e r a l w i t h the  of aggregation.  organic fractions. i n the  t o be  compounds o f h i g h l y  may  sep-  considered organo-mineral  reported through state  the complete  (18), studied  R u s s i a , r e p o r t e d a study and  decanthan  simple  soil  of  of l e s s  m i n e r a l components.  o f Chaudhry and S t e v e n s o n  aluminum, and and  inorganic  of v a r i a b l e  i n the  that  and  were c o n c e n t r a t e d i n t h e humate  phenomenon o f c o m b i n a t i o n  ivatives  gravities  They r e p o r t e d t h a t  clays  colloids  component was  this  Podzolic  c l a i m e d amino g r o u p s  ing  centrifuging  specific  a r a t i o n w o u l d h a v e b e e n o b t a i n e d by  immersion  linked  of microaggregate  through  (<25Q£) f o r -  12. mation through worker's  (4,21)  However, t h i s plex  cation bridge hypothesis  process  formation, but The  process  cess  on  the  coarse and  to the  the  cationic  adsorbed  wetting. and  and  readily  (86),  soils.  by A  revealed that s o i l s  allophane  adsorption  has a l -  form  clay pro-  a s u r f a c e phen-  form  a thin  film  Besides,  a separate  in  coagulum  phenomenon o f c o m p l e x  In the  surfactants (an-  dry  state  liquid  they  were  phase upon r e -  were s t r o n g l y a d s o r b e d  study  The  and  by  other  containing montmorillonite  0.65$  C,  oxygen  d i d not  allophane  showed  whereas s o i l s  showed g r e a t e r a d s o r p t i o n b u t  the  non-ionics  on m o n t m o r i l l o n i t e a n d  at  forma-  r e p o r t e d t h a t a n i o n i c s were  H-bonding to c l a y  substances  by  sat-  contain-  attain  an  maximum.  Hargitai  (45),  s t u d i e d the  m i n e r a l c o m p l e x e s on ganic  just  fractions.  r e l e a s e d to the  surfaces.  u r a t i o n w i t h humic ing  as  r e l e a s e d upon r e w e t t i n g .  were r e p o r t e d a d s o r b e d r i c h mineral  also  and  In contrast c a t i o n i c s not  (96),  d e s c r i b e d the  three d i f f e r e n t  nonanionic)  quickly  com-  of concretions.  s t u d i e d the  s t r o n g l y by  weakly h e l d and  soil  e t a l . (5),  colloid  composition  e t a l . (53),  formation.  p a r t i n the  complex f o r m a t i o n  humus s u b s t a n c e s  other  over-estimated.  complex f o r m a t i o n  surfaces of a l l mineral fractions  to  a d s o r p t i o n of microorganisms  w i t h m o n t m o r i l l o n i t e and  ionic,  be  However, A l e k s a n d r o v a  enter into  tion  a significant  should not  similar  complex  T h e y r e p o r t e d t h a t humus s u b s t a n c e s  Law  not  occupies  of organo-mineral  omenon.  f o r organo-clay  of organo-clay  so b e e n a t t r i b u t e d minerals.  l i n k a g e s appears  nitrogen.  the  effect  quality  However, t h i s  o f changes i n  of s o i l  study  organo-  organic matter  does not  and  appear sound  ordue  13.  t o t h e l a c k o f w e l l d e f i n e d o b j e c t i v e s as he l i m e d the s o i l and r a i s e d the pH from 5 - 5 t o 6.0.  He found t h a t the e a s i l y  avail-  a b l e n i t r o g e n i n c r e a s e d and the aluminum c o n t e n t d e c r e a s e d sharply.  I t appears hard t o b e l i e v e t h a t these changes a r e t a k -  i n g p l a c e due e n t i r e l y t o o r g a n o - m i n e r a l complexes. s e e l (72),  Scharpen-  conducted a t r a c e r study on o r g a n o - c l a y complexes  and c o n c l u d e d t h a t NH4 , A l +  +  +  +  ,  Ca  + +  , and F e  + + +  ,  ( i n increasing  o r d e r ) , b u t n o t H , N a , K , o r M g , a c t e d as b r i d g e c a t i o n s +  +  +  ++  i n m o n t m o r i l l o n i t e - h u m i c a c i d complexes.  However, the b r i d g i n g  mechanism d i d n o t operate w i t h k a o l i n i t e - h u m i c a c i d o r k a o l i n ite-fulvic Fe  + +  a c i d complexes.  Pe  and the complexes formed  was found more e f f e c t i v e  through c a t i o n b r i d g e s were l e s s  s t a b l e than the complexes formed X-Ray d i f f r a c t i o n  than  by hydrothermal  synthesis.  studies:-  P r o b a b l y t h e importance  of clay-organic interactions i n  the ceramic i n d u s t r y t o produce  m a t e r i a l s w i t h c o m p l e t e l y modi-  f i e d p r o p e r t i e s has l e d t o the use o f x - r a y d i f f r a c t i o n methods. I n t e r l a m e l l a r a d s o r p t i o n o f o r g a n i c compounds by montmorillonite easily  c o u l d be observed by x - r a y d i f f r a c t i o n methods q u i t e  (11,20,38,42,54,57,91,92).  However, x-ray  diffraction  a n a l y s i s does n o t y i e l d d i r e c t l y any i n f o r m a t i o n on the mechan( 3 6 , 4 3 ) have em-  ism o f t h i s a d s o r p t i o n .  S e v e r a l o t h e r workers  ployed x-ray d i f f r a c t i o n  f o r the c h a r a c t e r i z a t i o n o f organo-clay  complexes,  and p a r t i c u l a r l y  t h e former ( 3 6 ) , who p r e p a r e d the  complexes o f c l a y m i n e r a l s o f the m o n t m o r i l l o n i t e group  with  d i m e t h y l s u l p h o - o x i d e which had s p a c i n g s v a r y i n g from 18.21 t o o i9.ll  A and c o r r e s p o n d e d t o 2 l a y e r s o f t h e o r g a n i c compound.  I n t e r l a m e l l a r a d s o r p t i o n (74) o f f u l v i c  a c i d by N a - m o n t m o r i l l -  14. onite  was a l s o  observed.  studying naturally from  occurring organo-clay  the Bnt h o r i z o n o f a Solonetz  evidence  of interlamellar  pure  d i d n o t observe any matter. with  o r g a n i c compound.  mechanisms b u t e x t r a p o l a t i o n i n r e l a t i o n  Infrared  c o m p l e x e s d o e s n o t seem  These  s t u d i e s on  o f pure  tively  bonding  to naturally occurring  justified.  Spectroscopy:-  Although study  organo-  montmorillonite monoionically  s y s t e m s h a v e g i v e n q u i t e v a l u a b l e i n f o r m a t i o n on  organo-clay  while  obtained  s t u d i e s were c o n c e r n e d  complexes i n v o l v i n g m a i n l y  s a t u r a t e d and a s p e c i f i c  soil,  complexes  adsorption of organic  Hov/ever, most o f t h e s e clay  a n d Lowe ( 7 ) ,  However, A r s h a d  little  infrared  analysis  i s an e s t a b l i s h e d  c l a y m i n e r a l s and pure work h a s b e e n c a r r i e d  tool  i n the  o r g a n i c compounds, o u t on o r g a n o - c l a y  relacomplex-  es. When some s p e c i f i c with a clay  g r o u p s o f an o r g a n i c m o l e c u l e  m i n e r a l s u r f a c e on w h i c h t h e m o l e c u l e  the v i b r a t i o n s  o f t h e atoms c o m p o s i n g t h o s e  ified  will  and t h i s  infrared be  useful  papers A bonyl  radiation  result  i n the study  (29,73),  increase formation  i n intensity  frequency  observed  of adsorbed  should  The r e v i e w  mentioning. shifts  i n the car-  compounds a n d a n  o f t h e b o n d e d 0-H b a n d a t ^ 4 due t o t h e  o f hydrogen bonds w i t h Si-OH groups a t t h e edges o f  the m o n t m o r i l l o n i t e l a t t i c e . iates  are worth  be mod-  a t which  T h e r e f o r e , IR a n a l y s i s  group o f workers ( 3 5 , 5 1 , 5 2 ) group s t r e t c h i n g  groups w i l l  o f a d s o r p t i o n mechanisms.  o f a few workers  i s adsorbed,  i n a change i n w a v e l e n g t h  i s absorbed.  interact  (82), a t t r i b u t e d  such  However, T e n s m e y e r a n d h i s a s s o c shifts  to interlamellar  complexes  15of montmorillonite to  the  enhanced i n t e r a c t i o n s  Similar that  were t h e  this  yl  the  between the  adsorbed  effects  was  due  to  the  molecules.  a s s o c i a t i o n of the Thus t h e r e  f o r hydrogen b o n d i n g between  due  established carbonyl  i s no  confirm-  s u r f a c e and  carbon-  groups.  onite  i s w e l l understood,  but  also other  however, t h a t n o t  clay minerals  with  organic  have  shown t h a t m o n t m o r i l l o n i t e ,  compounds.  themselves r e a c t with form ved  interlamellar t o be  slower  W e i s s and  complexes.  i n others  face  charge d e n s i t y . (42,70)  actions  o f v e r m i c u l i t e and  pounds.  be  The formation cant  due  and  silicate  charged  role  the  has  special one  other  sheet,  edges, o f t h e  the  i s a l s o supported  with  amount o f  to lower  of the sheet  by  surother  lattice  be  greater  area.  quite  in  not  and  the  signifi-  c r y s t a l made o f (89,91)  on  adsorption  allophane be  re-  com-  •••••r^.c:v s u r f a c e  s u r f a c e may  to  obser-  organic  surface  should  s t r u c t u r e , and  gibbsite  kaolinite  the  complexes  of gibbsite  was  d i f f e r e n c e i n the  s e s q u i o x i d e s j . and  basal face  micas  s m a l l d i f f e r e n c e s i n the  s u r f a c e s and  of organo-mineral  and  montmorillonite.  s t r e n g t h o f a d s o r p t i o n may  of kaolinite-,  to t h e i r  very  due  (90,91,93,94)  process  to  montmorillonite  c o n s i d e r a b l y lower  kaolinite  sheet  observed  However, t h e  more d e n s e l y should  who  interaction  ammonium compounds,  to the  T h i s concept  workers  montmorill-  vermiculite, i l l i t e ,  However, t h e  due  in  h i s co-workers  i n comparison  d i f f e r e n c e seems t o be  only  participate  long chain a l k y l  This  The  r e p o r t e d these  exchangeable c a t i o n s .  evidence  It  As  and  f i n d i n g s o f T a h o u n e t a l . ( 8 0 ) , who  effect  group w i t h atory  with ketones,  area. silicate  unlike  the  carry a  charge.  become p o s i t i v e l y  charged  16. (70,77), high  pH  at  low  pH  values.  and  The  this  c h a r g e may  p o s i t i v e charge at  form p e r i p h e r a l complexes w i t h (2,62),  Several  other  anionic  polymers i s g r e a t e r  probably  decreases the  adsorption and  workers  of organic  alumina.  of  these  gin,  h a v e shown t h a t  i n the  cause very  silica  surface  area ori-  differences in their  in relation  place  heating.  organo-clay Spiel particle  b e t w e e n OH  ad-  h a v e u s e d IE. s p e c complexes  groups of  and  mineral  polymer.  been a c o n s i d e r a b l e  minerals  size  has  the  s h a p e and  size  effect  of the  bead i n the the  lower the  the  not  changes  on  with  differential  hole.  slower the temperature  taking  DTA. thermal  component m i n e r a l s ,  sample h o l e  and  Several  heating o f the  analysis and  Arnes  thermal curves  the  p o s i t i o n of  other  r a t e , the peak.  soil  b e e n much work done  applied differential  f r a c t i o n s of the  i n v e s t i g a t e d the  that  and  complexes i n c o n j u n c t i o n  et a l . ( 7 8 ) ,  thermal-couple  amount o f work done on  to dehydration  However, t h e r e  (8)  the  the  Thermal A n a l y s i s : -  T h e r e has  and  the  d e p e n d i n g upon t h e  c h a r a c t e r i z a t i o n of organo-clay  f u n c t i o n a l group o f the  Differential  observed  of  which  p o l y m e r and  (25,33,49,67,79,81),  hydrogen bond f o r m a t i o n  to  adsorption  behavior.  reported  on  the  of cations  the  i t to  (44,58,59,62).  p r o p e r t i e s and  significant  f o r the  on  presence  surface  troscopy  the  edges e n a b l e  a n i o n i c compounds  considerably,  A number o f w o r k e r s  and  relatively  compounds f r o m a q u e o u s s o l u t i o n by  materials vary  sorption  to  c o n d u c t e d many i n v e s t i g a t i o n s on  However, the  w h i c h may  the  zeta p o t e n t i a l of  G i l e s et a l . ( 3 7 ) ,  clay.  persist  workers  (6),  the  (65,78),  broader the  Allway  of  peak  studied  17piperidine-montmorillonite detailed  features  composition exothermic  interactions  o f the exothermic  and observed t h a t the  reactions  of the mineral montmorillonite. r e a c t i o n was a l w a y s  multiple  d e p e n d e d on t h e He f o u n d t h a t t h e  a n d a p e a k a t 700°C  g e s t e d a h i g h M g - m o n t m o r i l l o n i t e , a n d a t 4-50° a n d 500°Cy ted  an i r o n - r i c h m o n t m o r i l l o n i t e .  600°C ing  nitzer  (75)>  to the present investigation,  They r e p o r t e d  tion  coordination.  a n d H o f f m a n on humic c o m p o n e n t s  pertinent ing.  i n tetrahedral  2  They a l s o  reported  T h e work o f S c h -  though  phenolic  not quite mention-  due t o t h e e l i m i n a -  due t o t h e e l i m i n a t i o n  (76) that  contain-  appears worth  s m a l l c u r v e s n e a r 100°C  o f H 0 , 200 t o 3 8 0 ° C  sugges-  However, a p e a k a t a b o u t  s u g g e s t e d a member o f t h e m o n t m o r i l l o n i t e g r o u p  some a l u m i n u m  sug-  o f C00H+0H.  OH g r o u p s were more  stable  t h a n COOH b u t b o t h were e l i m i n a t e d b e t w e e n 250 a n d 4 0 0 ° C . Extraction The plexes  o f organic matter  extraction  has n o t been  information  from  t h e complexes:  o f o r g a n i c c a r b o n f r o m o r g a n o - m i n e r a l comstudied  i s available  i n detail  on e x t r a c t i o n ,  gents.  However, t h e work o f A r s h a d  tioning  i n this  tions ces  connection.  of organic matter  and as such v e r y  from  o r on e x t r a c t i n g  a n d Lowe ( 7 ) ,  They c a r r i e d only  fractions.  one s a m p l e a n d f o u n d  Organic matter  However, no c o m p a r a b l e and p o l y v a l e n t  different  ic  matter.  extrac-  differenclay  cations:  o r otherwise help i n complexing  Sodium pyrophosphate  men-  data i s available.  Some o f t h e o x i d e s o f m e t a l s h a v e b e e n r e p o r t e d organic matter  rea-  i s worth  out successive  i n t h e n a t u r e o f o r g a n i c components from  size  little  i s claimed to extract  this  t o complex  organic matter. complexed  organ-  18. Some w o r k e r s bably als et  solubilizes  and  from  and  that pyrophosphate  g e l s by  soils  (22,23)  Wyoming B e n t o n i t e  that  mechanism.  w h i c h have not  and  s t u d i e d the and  c l a y were n o t  organo-clay  carbon.  been l e a c h e d  organic  that  stable.  complexes are  the  met-  Nightingale and  organic  and  material.  interaction  reported  pro-  c h e l a t i n g entrapped  complexes of c a l c i u m  amounts o f d i s p e r s e d  workers  hydroxides port  organo-mineral  also reported  sodic  considerable other  have r e p o r t e d  r e l e a s i n g f r e e complexed o r g a n i c  a l . (64),  ter  (14,64),  of i r o n  mat-  contain Several hydroxides  complexes o f  iron  These workers d i d not formed through c a t i o n  re-  bridge  19. METHODS AND In sample The  any  scientific  i s a very  was  important  finding  a representative  p a r t o f the whole  experimentation.  mineralogy  this  purpose  the  soil  In dried  eight s o i l survey  great  personnel  a 2 mm  topographical I.  of organo-clay  selected  based  tion  carbon  and  investigated  of these  on  and  the  with opted  x-ray  iron,  complexes,  and  pass  The  are  classand  given i n  f o r studying  However, f o r  o n l y e i g h t samples  i n conjunction to  the  detailed were  distribu-  c o m p l e x e s were s u b j e c t e d t o  are  analysis:  The  clay  content  was  silicon  on  content.  infrared analysis  reagents The  along  methods  ad-  below.  e s t i m a t e d by  committee  thermal  with d i f f e r e n t  enumerated  size  the  differential  of carbon  Particle  Soil  sites,  complexes.  aluminum and  f o r analyses  recommended by  area. in  boxes.  s a m p l e s were u s e d  diffraction,  extractability  their  i n that  help  content.  These e i g h t s e l e c t e d spectroscopy,  for  along with vegetation  sampling  the v a r i a b i l i t y  to  the  s a m p l e s were g r o u n d t o  stored i n cardboard  thirty-four  characterization  g r o u p s were c h o s e n w i t h  The  inves-  Therefore,  working c u r r e n t l y  f e a t u r e s of the  These  distribution  soils  content.  h o r i z o n s a m p l e s were b r o u g h t  s i e v e and  of the  present  o f samples i n r e l a t i o n  organic matter  a l l , thirty-four  ification  Table  and  a t room t e m p e r a t u r e .  through  samples f o r the  to include a v a r i e t y  soil  of  investigation  main o b j e c t i v e o f s e l e c t i n g  tigation  MATERIALS  a h y d r o m e t e r method,  physical  analysis  as  (24).  Reaction: The  pH  of the  soil  water suspension  ( R a t i o 1 : 2 . 5 ) was  meas-  20. TABLE  Soil Subgroups  I  Series  Topography  Major  Langley  L e v e l t o depressional  Planteneum, Horset a i l , Sedges and Buttercups.  O r t h i c Concretionary Brown (Orthic Mini Humo-ferric Podzol)  Nicholson  L e v e l to dulating  A l d e r , Maple Braken f e r n .  O r t h i c Regosol (Orthic Eutric Brunisol)  Monroe  Orthic Podzol (Orthic PerroHumic P o d z o l )  Blaney  Undulating  Hemlock, C e d a r Douglas F i r .  and  Humic P o d z o l (Orthic FerroHumic P o d z o l )  Cardinal  Rolling  Hemlock, Maple Cedar.  and  A c i d Brown Wooded ( M i n i Humof e r r i c Podzol  Whatcom  Undulating  Maple and  Humic G l e y s o l ( O r t h i c Humic Gleysol)  Hazelwood  L e v e l t o depressional  Pasture  Orthic  Hatzic  Level  Mainly  Humic iated sol  EluvGley-  Gleysol  un-  Vegetation  and  B u t t e r c u p s , Thorny S u n f l o w e r , and o t h e r graminaceous p l a n t s .  Alder.  grasses  only.  grasses.  N.B. The names i n p a r e n t h e s e s a r e r e v i s e d n o m e n c l a t u r e s a c c o r d i n g t o t h e 1968 r e p o r t o f t h e N a t i o n a l S o i l S u r v e y C o m m i t t e e o f Canada. (Table I to V).  21. ured  w i t h a Beckman Z e r o m a t i c  Organic  induction  and  meter.  Carbon:  Carbon  with  pH  of the s o i l  furnace  different  a n d c o m p l e x e s was  and c a r b o n  extracting  analyzer.  agents  was  determined  However,  estimated  w i t h a Leco  carbon  by t h e  obtained Walkley  B l a c k wet c o m b u s t i o n m e t h o d ( 6 8 ) .  Nitrogen: T o t a l n i t r o g e n content by  a n d c o m p l e x e s was  obtained  a m i c r o - k j e l d a l method (68).  Methods o f i s o l a t i n g Simple  chemical  ferred salts  organo-clay  complexes:  dispersion:  Dispersion ing  of soils  a n d d e c a n t a t i o n was u s e d  treatments  t o a two  litre  a t any s t a g e .  with a view to a v o i d -  A 1 0 gm  sample was  g l a s s b e a k e r a n d washed f r e e  and o r g a n i c m a t t e r  of soluble  by d i s p e r s i o n i n d i s t i l l e d  water,  slow manual s t i r r i n g  and d e c a n t a t i o n o f the supernatant  tion.  3-4  I n many c a s e s  purpose and t h e c l a y tation  techniques  The battery  suspension nature speed  thus  o f t h e sample. centrifugation size  for  freeze drying.  solu-  by  sedimen-  (7)-  which u s u a l l y  clay  with  optimum f o r t h i s  f r a c t i o n s were s e p a r a t e d  o b t a i n e d were c o l l e c t e d  The p r o c e s s  The  glass  size  suspensions jars.  w a s h i n g s were f o u n d  trans-  was  took  continued  was  and t h e s u p e r n a t a n t were t r a n s f e r r e d  The f r e e z e d r i e d  containers f o r further  litre  t h e r e was no more  a b o u t a week, d e p e n d i n g u p o n t h e  The s u s p e n s i o n  fractions  till  in 6  study.  subjected to high solution  discarded.  to p l a s t i c  containers  s a m p l e s were s t o r e d i n  22. Ultrasonic  dispersion:  Ultrasonic (26,60),  for extracting  completely es  or  ly  below.  j u s t the  market.  sonic with  models of  supplied Forty  p o w e r o u t p u t 80 gm  soil  tube  was  placed  i n the  tank. The  give  pensions thus  to  to  a  The  f o r 15  stand  r e s u l t s , and  2 centrifuge  v o l u m e was  clear  supernatant  Inc.,  G.-40  100  N.  CI-P  ml  to  level  containers  small  and  s a m p l e s were u s e d f o r f u r t h e r  with  in  the  that  the  of water  short  while,  clay  in  which  using  litre and  glass  susbeak-  discarding  v o l u m e s were dried.  The  The  transfreeze  investigations.  resin;  Chelating  resins  have been u s e d under d i f f e r e n t  f o r d i f f e r e n t purposes, but  here the  use  an  size particles.  necessary.  freeze  Y.,  minutes.  centrifuging  These  Ultra-  centrifuge  then c e n t r i f u g e d  separate  in  capacity.  suspension  for a  many t i m e s a s  r e d u c e d by  solution.  into plastic  available  gallon  o b t a i n e d were c o l l e c t e d i n two  The  tions  a half  water.  insonated  r e p e a t e d as  ers.  Chelating  Industries  c o m p l e t e l y below the  better  No.  brief-  u l t r a s o n i c b a t h i n s u c h a way  s a m p l e was  p r o c e s s was  dried  distilled  i n the  i s described  study DisOntegrator  transferred  s a m p l e s were a l l o w e d  International  ferred  ml  t a n k had  not complex-  G e n e r a t o r M o d e l No.  The  t u b e was  The  appeared to  The  and  present  method  organo-clay  equipment are  Ultrasonic  s a m p l e was  a l o n g w i t h 50  the  a useful  However, i t i s  method u s e d  ultrasonic  by  watts.  tube  sample  The  However, i n t h e  s y s t e m No.  5  been r e p o r t e d  organic matter.  aggregates.  cleaner  A  has  understood whether i t breaks the  Different the  dispersion  of  assump-  chelating  the  23. agent  was made t o i s o l a t e t h e c o m p l e x e s  o t h e r methods. A 5 gm polythene  The method i s d e s c r i b e d b r i e f l y  soil  sample was  transferred  bottle  along with  0.88  200-400 mesh Na  in  form  ( 0 . 5 gm  2 5 ml d i s t i l l e d  bottle  f o r comparison  an end-to-end  shaker  below.  t o a 1 2 5 ml n a r r o w neck  gm c h e l a t i n g  r e s i n , Chelex  on o v e n d r y b a s i s ) .  w a t e r was  with  To t h e sample  a d d e d a n d s a m p l e s were  f o r 15 h o u r s a f t e r  100,  shaken  stoppering the  bottles. The and by  s a m p l e s were t r a n s f e r r e d  free high  soluble speed  centrifuging.  as n e c e s s a r y .  The c l a y  No.  till  fractions  of suspension  freeze  X-ray  A 15-20 pared  in  w i t h h e a d No.  no more s u s p e n s i o n  dried  continued  as l o n g  s e p a r a t e d by  cen-  was  240.  Inter-  The p r o c e s s  obtained.  was  The d i f f e r e n t  were c o l l e c t e d i n p l a s t i c c o n t a i n e r s  f o r f u r t h e r use.  d i f f r a c t i o n analyses  percent  suspension  in distilled  used  matter  of organo-clay  as  employing  f o r investigations.  c o m p l e x e s was  Ni-filtered  However,  t o s e e i f t h e p o o r r e s o l u t i o n was Secondly,  p a t t e r n s were  obtained.  micro  preslides.  and a  Phil-  GuKtx: r a d i a t i o n  due t o p o o r  t h e s l i d e s were h e a t e d  alone.  follows:  t o d r y a t room t e m p e r a t u r e  d i f f r a c t i o n unit  some o f t h e c a s e s ,  hours  were c o n d u c t e d  w a t e r a n d m o u n t e d on 27x46 mm  s l i d e s were a l l o w e d  i p s X-ray was  s a l t s were r e m o v e d  d i f f r a c t i o n studies: X-ray  The  The p r o c e s s was  s i z e p a r t i c l e s were  2 centrifuge  continued  and  and s o l u b l e  tubes  t h e s a m p l e a t 7 5 0 rpm f o r 3 - 3 m i n u t e s u s i n g an  trifuging national  organic matter  t o 100 m l c e n t r i f u g e  resolution  t o 500°C  for 5  e n t i r e l y due t o o r g a n i c  t h e c o m p l e x e s were g l y c o l a t e d  and  x-ray  24. After results, les. and  having  the organo-clay  Firstly, secondly  drogen x-ray  obtained  some i n f o r m a t i o n f r o m  c o m p l e x e s were a t t a c k e d f r o m  t h e attempt  iron  peroxide  was made t o d e s t r o y  oxides.  The complexes  treatment  diffraction  to destroy  oa.terns  then In  was  subjected to x-ray the interpretation  p l a c e d on m i n e r a l o g y .  w i t h HgGV) t o d e s t r o y dithionite ided  into  tassium urated cases  slides  s a m p l e s were a l l o w e d slides.  analysis.  Infrared  Study:  in  infrared  the study  A was a  pellet  infrared  1.3  oxides  (88),  emphasis first  f o l l o w e d by s o d i u m  citrate  o b t a i n e d were  divided  These m o n o i o n i c a l l y  into  two g r o u p s . while  f o r some t i m e  t h e o t h e r was  The  glycolated  and then  h a s been u s e d  sat-  In both  m o u n t e d on  s a m p l e s v/ere s u b j e c t e d t o x - r a y  spectroscopy  div-  b a t c h was s a t u r a t e d w i t h p o -  dif-  quite frequently  c o n f i g u r a t i o n s o f m i n e r a l m o l e c u l e s . The  i s described b r i e f l y  s m a l l amount o f o r g a n o - c l a y  mixed w i t h  complexes  t h e main  The samples t h u s  to stand  o f atomic  method adopted  results  i n t h e u s u a l manner.  A l l these  fraction  The  o f x-ray  o f s a m p l e s was g l y c o l a t e d  mounted on x - r a y  x-ray  t o remove i r o n  w i t h magnesium.  c o m p l e x e s were a g a i n one g r o u p  Secondly,  analysis.  The f i r s t  and the second  (88), and  T h e c o m p l e x e s were t r e a t e d  t o remove i r o n .  matter,  were s u b j e c t e d t o h y -  were o b t a i n e d .  organic matter,  two g r o u p s .  two a n g -  organic  organic matter  were t r e a t e d w i t h c i t r a t e - d i t h i o n i t e and  the foregoing  i n the following complex  anhydrous KBr thoroughly  cm i n d i a m e t e r  and about  s p e c t r a were r e c o r d e d  (determined  and then  1 mm  on an U n i c a n  pages. by  trials)  compressed  i n thickness. Instrument  into  The  model  25. SP.  200  G.  infrared  spectrophotometer  with  a prism-grating  interchange. In the  second  hydrogen peroxide  part organo-clay to destroy  s p e c t r a were r e c o r d e d  kaolinite,  organic matter  f o r comparison.  s p e c t r a o f pure m i n e r a l s lite,  c o m p l e x e s were t r e a t e d w i t h  illite  association  Differential In the 900  thermal present  ature  was  This about  the nature  mineral  study  thermal  was  on  organo-clay  unit  a t 15°C  was  vermicu-  taken.  from  These  identification  organic  fraction.  The  treatments  used.  complexes, The  "DUPONT"  change i n  temper-  per minute f o r b e t t e r r e s o l u t i o n .  conducted  of the  component.  successive  were a l s o  component a n d  of organic matter  study  infrared  analysis.  maintained  Extractability  infrared  feldspars obtained  i n conjunction with mineral  of mineral  differential  In addition  and  Ward's n a t u r a l s c i e n c e e s t a b l i s h m e n t  and  again  comprising montmorillonite,  chlorite,  r e s u l t s were u s e d  and  from  selected  complexes:  w i t h a view to g e t t i n g  combination organic  which are  of organic  carbon  was  some i d e a  fraction  with  e x t r a c t e d by  three  enumerated i n the f o l l o w i n g  section. Extraction A 0.5 along with stoppered  w i t h 0.1M  Na^P^Q-:  gm  s a m p l e was  10  ml  and  e x t r a c t a n t (pH  s h a k e n g e n t l y by  were s h a k e n o v e r n i g h t ter  solubilized  speed  transferred  by  centrifuging  on  about hand.  a mechanical  to a p l a s t i c 10).  hour.  The  tubes  ml  tube  were  Subsequently  the  shaker.  o r g a n i c mat-  s o d i u m p y r o p h o s p h a t e was f o r an  The  100  The  samples  s e p a r a t e d by  p r o c e s s was  high  continued  un-  26. til  no f u r t h e r  tract  extraction  was o b s e r v e d .  The volume o f t h e ex-  was r e d u c e d b y e v a p o r a t i n g a t l o w t e m p e r a t u r e  was  e s t i m a t e d b y wet c o m b u s t i o n  for  the next operation.  (68).  and carbon  T h e r e s i d u e was s a v e d  E x t r a c t i o n w i t h 0.1N NaQH: The hours by  r e s i d u e was t r e a t e d w i t h 0.1N NaOH a n d s h a k e n  on a m e c h a n i c a l  sodium  for  shaker.  The o r g a n i c c a r b o n  h y d r o x i d e was s e p a r a t e d b y h i g h s p e e d  one h o u r .  were f o u n d n e c e s s a r y .  specified  w i t h 0.1M  to.be  T h i s mixture  pyrophosphate.  method  outlined  tube  The s o l u b i l i z e d  overnight with  a n d e s t i m a t e d b y wet c o m b u s t i o n  iron,  free  sodium  c a r b o n was s e p a r a t e d b y h i g h as b e f o r e .  and S i l i c o n :  o f W e a v e r e t a l . ( 8 8 ) , was u s e d  f o r estimating  aluminum a n d s i l i c o n w i t h s l i g h t m o d i f i c a -  below. to a polyethylene centri-  a l o n g w i t h 5 ml c i t r a t e - b i c a r b o n a t e  s a m p l e was h e a t e d was  s i l i c a t e minerals.  o v e r n i g h t a n d t h e sample was w a s h e d  A 0 . 5 gm s a m p l e was t r a n s f e r r e d fuge  This concentration i s  (21), to dissolve  I r o n , Aluminum  extractable  tions  HF-HC-£ t r e a t m e n t :  The c a r b o n was e x t r a c t e d  centrifuging  Extractable  the  3-6 e x t r a c -  c a r b o n was e s t i m a t e d a s  t o 100 m l 0.1N HC-&.  optimum  was l e f t  chlorides.  The  Organic  col-  r e s i d u e was t r e a t e d w i t h HF-HC-& m i x t u r e p r e p a r e d b y  considered  speed  On a n a v e r a g e ,  Na^PgOnafter  a d d i n g 1 m l HF ( 4 8 % )  of  centrifuging  previously.  Extraction The  solubilized  T h e p r o c e s s was c o n t i n u e d u n t i l no f u r t h e r  o u r was o b s e r v e d i n t h e e x t r a c t . tions  for 5  t o 80°0 i n a water  a v o i d e d , t o a v o i d FeS f o r m a t i o n .  solution.  The  b a t h and h e a t i n g above T o t h e s a m p l e 0.1 gm  80°C  27. Na.2&2®i). powder was ute  and  then  repeated to  three times.  a water bath  5 ml  A  sample.  solution  The  r e s i d u e was  collected  washed w i t h  mixed t h o r o u g h l y .  conical to  flask  oxidize  and  any  The  a i r was  remaining  taken  to determine  tion  spectrophotometry,  Humic: F u l v i c A 0.5 ture  Acid  gm  iron,  o f IN NaOH a n d  (68)  was  used  f o r 5-10 ml  IN NaCl£ a n d The  bubbled  was  was  added  m i x e d , warmed i n subjected to  minutes.  high  The  super-  volumetric flask  supernatant  v o l u m e was  s a m p l e was  min-  solution  made t o 100  ml  to a 250  ml  transferred  through  f o r 4 hours  dithionite.  Suitable  aluminum and  silicon  and  o r more  aliquots by  were  atomic  absorp-  ratio:  sample  h u m i c a c i d was  subsequently  i n a 100  added t o the v o l u m e t r i c f l a s k . and  This process  s u s p e n s i o n was  ( 1 6 0 0 - 2 2 0 0 rpm)  was  c o n t i n u o u s l y f o r one  s a t u r a t e d NaCX s o l u t i o n  f o r 10 m i n u t e s a n d  centrifuging  natant the  the  stirred  f o r 5 minutes.  intermittently  flocculate  speed  added and  o f c o m p l e x was 1M  e x t r a c t e d w i t h a 5 ml  mix-  Na^P20- m i x e d i n e q u a l p r o p o r t i o n .  precipitated  a t pH  f o r e s t i m a t i n g the  2.0  and  carbon  wet  combustion  o f humic a n d  The  method  fulvic  acids. Carbohydrate A 0.3  content  gm  conical  flask  for  hour.  one  after  adding  clave  a t 15  to  cool  stored  and  sample  of  complexes:  o f c o m p l e x was  a l o n g w i t h 3 ml The 100  ml  p s i and then  erlenmeyer distilled 124°C  and  HgSO^ a n d  f l a s k was ELpO, and  f o r one  filtered.  in a refrigerator  of 72$  t r a n s f e r r e d to a 250  The  hour.  allowed to  covered with a h y d r o l y s e d i n an The  v o l u m e was  carbohydrates  ml  sample was  made t o 100  stand  beaker autoallowed ml  were d e t e r m i n e d  and by  28. u s i n g anthrone  method"'".  T h i s method i s n o t a good measure o f  c a r b o h y d r a t e s as i t measures o n l y hexoses, good index o f c a r b o h y d r a t e  I v a r s o n , K.C.,  however, i t i s a  measurement.  and Sowden, F . J .  1962.  S o i l S c i . 94,  245-250.  29. RESULTS AND General  characteristics  Table samples.  I I presents  o f samples: some p h y s i c o - c h e m i c a l  The s a m p l e s were a c i d i c  between 4 . 6 and 6 . 8 .  The c l a y  carbon  from  9.25  content  percent The  except  ranged  with  i n nature  content,  p r o p e r t i e s of the and v a r i e d  i n pH  n i t r o g e n c o n t e n t , and  2 t o 6 7 , 0 . 0 2 3 t o 0.830 a n d 0 . 1 1 t o  respectively.  organic carbon  decreased  the Orthic Podzol  was n o t o b v i o u s . depth  DISCUSSION  a n d Humic P o d z o l ,  Nitrogen  w h e r e a s C/N r a t i o  with depth  i n a l l profiles  where a u n i f o r m  trend  showed t h e same r e l a t i o n s h i p t o  d i d n o t show a n y d e g r e e o f u n i f o r m i t y  depth. Having  tention plexes  obtained this  was f o c u s s e d and f i n d i n g  preliminary information, further a t -  on t h e d i s t r i b u t i o n  suitable  of organo-clay  methods f o r c h a r a c t e r i z i n g  comt h e com-  plexes. Comparison The tion  e x t r a c t i n g methods o f o r g a n o - c l a y  e f f e c t i v e n e s s of simple  and c h e l a t i n g r e s i n  yield the  of three  o f the complexes,  dispersion,  treatment their  results  a r e summarized  ultrasonic  agita-  was c o m p a r e d i n r e l a t i o n t o  carbon  complexes r e p o r t e d as p e r c e n t  complexes.  content  of total  and t h e carbon o f  soil  carbon.  i n t h e f o l l o w i n g pages under  The  different  headings. Yield  o f complexes: The  sented  yield  i n Table  o f complexes  I I I and summarized below.  complexes i n the case ating  resin  was  o b t a i n e d by t h e t h r e e methods i s p r e -  of simple  dispersion,  The a v e r a g e  amount o f  i n s o n a t i o n and c h e l -  2 . 5 8 , 3.41 a n d 12.30% r e s p e c t i v e l y .  The y i e l d  TABLE II Some Characte : i s t i c s of S o i l Samples Depth in inches N % Clav % Ore?. C ."/ _i_H_  S o i l Subgroups  Horizons  Humic eluviated gleysol  Ah 0.9 Ahe (Aeg) 9-12.5 Bg (Btg) 12.5-21 BC 21-34 Cg 34+ Bfcc 0-1.5 Bfcc 1 1.5-15 Bf 15-27 C 27+ Ap 0-7 7-23 (Bm) C, C 23+ (II O 2 LF 3-2 H 2-0 Ae 0-2 Bf. (Bhf) 2-11  Orthic Concretionary Brown Orthic regosol Orthic Podzol  L  Bf'  Cg  Humic Podzol  2  LF FH Aeh Bhf Bf  Acid Brown Wooded Humic gleysol Orthic  gleysol  Cg Ap Bf  BC C Ah Btg C Ap Btg Bg  11-20 20+  C/N ratio  Textural class Loam S i l t y clay loam Clay Clay Clay loam S i l t loam S i l t loam Loam S i l t loam  5.50 5.75 6.30 6.40 6.70  17.0 40.0 67.0 53.5 27.0  9.25 3.64 0.65 0.30 0.23  0.83 0.33 0.09 0.07 0.034  11.1 11.2 7.2 4.5 C6C8  5.70 5.60 5.80 6.40  14.0 13.5 11.0 27.5  5.63 1 .60 0.54 0.11  0.314 0.129 0.045 0.023  17.9 12.4 12.0 4.8  5.90 5.80 6.10  11 .0 17.5 4.0  2.80 0.93 0.19  0.297 0.118 0.023  9.4 7.9 8.3  Loam Loam Sandy loam  6.0 5.1 2.0 6.2  2.15 2.62 3.34 0.68  0.053 0.083 0.139 0.076  40.6 30.1 24.0 9.0  Sandy loam Loamy sand Loamy sand Sand Loam Loam Sandy loam Loam S i l t loam S i l t loam S i l t loam S i l t y clay loam S i l t y clay S i l t y clay S i l t y clay loam S i l t y clay Clay S i l t y clay  — —  4.70 5.30 5.30 5.70  2.5-2 2-0 0-1 1-2.5 2.5-14 14+  4.60 5.20 5.50 5.80  11.0 12.5 6.1 10.0  2.47 7.90 3.08 1 .53  0.113 0.308 0.165 0.077  21 .9 25.7 18.7 19.9  0-2 2-10 10-27 27+  5.30 6.00 5.60 5.80  9.9 10.5 18.5 30.3  8.50 2.30 1.13 0.19  0.466 0.103 0.066 0.037  18.2 22.3 17.1 5.1  0-7 7-18 18+  5.60 6.00 6.80  42.5 51 .5 33.5  5.44 2.34 0.60  0.403 0.148 0.027  13.5 15.8 22.2  0-5 5-17 17+  5.30 5.80 6.60  45.3 47.0 50.5  5.21 1 .32 0.62  0.500 0.128 0.038  10.4 10.3 16.3  —— ——  31. TABLE I I I Yield Soil  o f o r g a n o - c l a y complexes o b t a i n e d by t h r e e e x p r e s s e d as p e r c e n t o f a i r d r y s o i l  Subgroups  Horizons  Yield Simple dispersion  Humic E l u v i a t e d Gleysol  Orthic Concret i o n a r y Brown  Ah Ahe ( A e g ) Bg (Btg) BC Og  Orthic  Humic  Regosol  Podzol-  Podzol  A c i d Brown wooded  Humic  Orthic  Gleysol  Gleysol  3.60 10.40  (%)  Ultrasonics  4.00 2.00 4.40  5.00  11.80  Bfcc-. Bfcc£ Bf C  1.12 1.65 2.00 2.00  1.20 2.50  Ap C, C^  0.80  0.80 2.40  tL  Orthic  0.64  0.56 3.20  (Bm) (IIC)  1.50 1.20  2.00  25.50 20.30 12.68 11.03 11.57 10.99 14.33 8.35 7.92 2.96  0.40  0.90 0.50 0.30 0.50  5.94 5.03 1.25 4.00  mm —  „  eg  —  0.30 0.30  ——  0.35 0.25 0.15  0.40  0.26  0.40  Ap Bf BC C  0.29  0.30 0.20 1.90 3.20  Ah Btg C  4.28 7.69 7.04  Ap Btg Bg  i.9.48  Average  13.97  18.71  —  0.60  ,LF HF Aeh Bhf Bf Cg  2.40 2.60  Chelating Resin  —  LF w xl Ae Bf, (Bhf) Bfi 2  methods  0.20 1.85  2.15  2.81  10.42  2.58  0.20 0.20  3.47 7.15 6.01 3-10 7.84  10.14 11.06  18.95  5.40 8.60  21.75 25.70 14.63 19.96 24.70 19.96  3.41  12.30  7-10 3.90 10.10 17.20  32. o f complexes d i d not but  roughly  ating  on  resin  an  agree  average  with  the  i t was  gave h i g h e r v a l u e s  clay  content  comparable.  due  probably  On  i n every the  case,  whole  t o h i g h pH  and  chelzeta  potential. From T a b l e o b t a i n e d by dispersion simple  chelating and  resin  ultrasonic  d i s p e r s i o n and  h i g h e r i n the seems t o be yield  I I I i t i s e v i d e n t t h a t the y i e l d  is No  case  simple  treatment. the  by  a  little  Chelating resin complexes as  f a r as  concerned. g e n e r a l t r e n d was  simple  i n s o n a t i o n and  e s was  observed  face.  However, t h i s  i n the  case  of chelating  ting  resin  this  the  d i d not  of the  chapter.  Percent  carbon  Table  complexes  was  as  f a r as  concerned  but  d i s p e r s i o n the  lower  o b s e r v a t i o n was  resin.  Data  complexes.  in  usually  interesting  was  i n the  higher y i e l d  not  of Table  the  equally true i n  after be  complex-  to the  I I I suggest  case  of  case  sur-  the  that chela-  simple d i s p e r s i o n investiga-  a critical  eval-  d i s c u s s e d a t the  end  carbon  i n the  complexes  ob-  average  carbon  content  complexes: the  percent  t h r e e methods.  o b t a i n e d by  treatment,  distribution  However, i n t h e p r e s e n t  a p p e a r t o be  IV p r e s e n t s the  the  h o r i z o n s i n comparison  t h r e e methods w h i c h w i l l  of t h i s  by  observed  i s f a r s u p e r i o r t o i n s o n a t i o n and  isolating  tained  higher than  However, t h e y i e l d s  a good method o f i s o l a t i n g  of  uation  treatment.  of u l t r a s o n i c  depth  tion  substantially  complexes  i n s o n a t i o n were c o m p a r a b l e , b e i n g  o f complexes w i t h  in  was  of  5.01,  to note  simple 5.33  and  t h a t the  The  dispersion, 4.70  ultrasonics  percent  complexes  and  respectively.  o b t a i n e d by  i n the resin It is  ultrasonic  33. TABLE I V Percent Soil  carbon  Subgroups  Humic E l u v i a t e d Gleysol  i n complexes o b t a i n e d  Horizons  Ah Ahe ( A e g ) Bg (Btg) BG  Og  Orthic Concret i o n a r y Brown  Regosol  Humic  Orthic  Gleysol  Gleysol  11.12 5.03 0.93 0.66 0.39  Ap C,  4.64 (Bm)  LP u n  0.47  2.19 1.43 —  2  LF HF Aeh Bhf Bf  5.20 2.66 1.38 —  Resin  10.50 4.60  0.70  2.00  0.50  2.60  2.69 0.35 0.38  5.23 2.19 0.95 —  6.16  11.94 11.11  4.41  8.71 13.20 5.09  -—  —  3-37  (Bhf)  10.24  11.11  10.97 7.70 —_  —  —  4.19 15.52 14.69 18.66  6.75 10.71 21.76  Ap Bf BC C  9-59 4.33 2.29 0.97  10.14  9.46  6.03 2.94 0.53  4.37  Ah Btg C  3.85 2.33  4.44  0.81  4.67 2.77  Ap Btg Bg  3.23 1.07 0.69  4.12 1.05 1.00  4.02 1.27 0.83  Average  5.01  5.33  4.70  OS  A c i d Brown wooded  11.16 6.39 0.32 0.61 0.60  3.08 0.43  og Podzol  Ultrasonics  1.28  Ae Bf,  Humic  Simple dispersion  9.97 4.43  2  Podzol  Carbon  6.39 3.10  c (no)  Orthic  Percent  methods  Bfcc, Bfcci Bf G d  Orthic  by t h r e e  9.03  2.29 0.75  —  9.26  18.39  0.68  7.63  1.86  0.31  0.66  34. treatment  contained  this  t r e n d was  were  examined. Percent  except  t h e h i g h e s t mean c a r b o n  not  c o n s i s t e n t when v a l u e s  carbon  i n the  t h e O r t h i c and  Humic P o d z o l ,  d i s p e r s i o n methods, except BC  zol  In  the  other  soil  Great  soils.  Podzolic  soil  the  cent  case  carbon  the  case  similar. resin to  the  complex from  and  very rapid  i n t h e Ae  i n comparison  to  resin  the O r t h i c Pod-  fractions  i n t h e Cg  the  in  horizon  coupled comparison complexes  h o r i z o n o f Humic  other horizons  except  o b t a i n e d by r e s i n  treatment  where  was  t o be  horizon.  However,  and  observed  solubilizes  lower  thereby  the  as r e s i n effects  to the  However, t h e  treatment,  were n o t  treatment  of the m i n e r a l  circumstances  Such a  of organic  seems more  possibil-  matter  seem so  t o b r i n g about  h y d r o l y s i s may  s p e c i e s and  clay  pronounced.  some  c o n t a c t o f sample w i t h and  due  o f the method f o r  d i s p e r s i o n does not  i t appears  quite  free'surfaces of  complexes.  splitting  per-  of organic matter  suitability  t o h i g h pH  to prolonged  of r e s i n  upon the n a t u r e  some f r a c t i o n  though simple  due  results  t h a t under c e r t a i n  c r e a t i n g new  q u e s t i o n as  study.  the  i n Bf  come i n c o n t a c t w i t h  c o m p l e x e s due  effect  of the  o f complexes  Similarly,  lytic  lower  samples  f o r a l l three  G l e y s o l o b t a i n e d by  carbon  of the O r t h i c P o d z o l  qualitative  The  case  except  percent  w h i c h may  raised  from  was  treatment  minerals,  ere  were s i m i l a r  soluble organic  I t i s hypothesized  h i g h pH  ity  The  for individual  o f t h e Humic P o d z o l  Groups,  However,  o f samples o f a l l p r o f i l e s  t h e movement o f c o m p l e x e s a p p e a r s  of these  in  case  t h e movement o f e a s i l y  with  in  i n the  h o r i z o n o f t h e Humic E l u v i a t e d  treatment.  to  complexes  content.  vary  organic  sev-  hydrowater. depending  fraction  as  35. well. Qarbon i n c l a y - o r g a n i c complexes as p e r c e n t o f t o t a l s o i l T h i s parameter formation.  carbon  i s v e r y i m p o r t a n t , b e i n g an i n d e x o f complex  I n t h e p a s t t h i s has been used v e r y f r e q u e n t l y i n  t h i s f i e l d , b u t a t some p l a c e s i t appears m i s l e a d i n g w i t h o u t • s p e c i f y i n g t h e o r i g i n , n a t u r e and m i n e r a l o g i c a l c o m p o s i t i o n along w i t h the nature of organic matter.  Therefore, keeping  t h e s e p o i n t s i n mind, t h e r e s u l t s o f T a b l e V a r e summarised below. The  average  c a r b o n o f t h e complexes as p e r c e n t o f t h e t o t a l  s o i l c a r b o n by s i m p l e d i s p e r s i o n , i n s o n a t i o n and r e s i n  treat-  ment, was f o u n d t o be 4.64, 6.34 and 2 2 . 1 3 % r e s p e c t i v e l y . t h e case o f s i m p l e d i s p e r s i o n and u l t r a s o n i c d i s p e r s i o n , v a l u e showed an i n c r e a s i n g t r e n d w i t h d e p t h .  In this  T h i s may be a t -  t r i b u t e d t o t h e most a c t i v e and s o l u b l e f r a c t i o n o f t h e humus moving downward t h r o u g h t h e solum and w h i c h t e n d s t o a s s o c i a t e , i t s e l f w i t h the m i n e r a l f r a c t i o n o f the s o i l .  However, t h i s  t r e n d seems t o be d i s t u r b e d by t h e o x i d e s o f i r o n , aluminum and o t h e r m u l t i v a l e n t m e t a l s w h i c h i s o b v i o u s from t h e Humic and O r t h i c P o d z o l P r o f i l e s where t h e a f o r e m e n t i o n e d not  sequence does  exist. Some w o r k e r s  ( 2 7 , 2 8 ) however, c o n s i d e r t h a t t h e m u l t i v a l -  e n t m e t a l s a r e a p o t e n t i a l s o u r c e o f complex f o r m a t i o n t h r o u g h what t h e y c a l l b r i d g e mechanisms.  T h i s a s p e c t needs f u r t h e r  e x a m i n a t i o n because t h e r e s u l t s o f T a b l e V appear t o c o n t r a d i c t this  assumption. The complexes o b t a i n e d by r e s i n t r e a t m e n t d i d n o t show any  s p e c i f i c t r e n d of d i s t r i b u t i o n w i t h depth.  The complex c a r b o n  36. TABLE V Organo-clay Soil  complex carbon as p e r c e n t o f t o t a l  Subgroups  Horizons  Percent Simple dispersion  Humic E l u v i a t e d Gleysol  Ah Ahe ( A e g ) Bg (Btg) BC Cg  Orthic Concret i o n a r y Brown  Bfcc,  Bfcci Bf C  Orthic  Orthic  Regosol  Podzol  -  d  Ap C, C^  (Bm) ( I I C)  Bfi eg 2  Podzol  Carbon  Ultrasonics  Resin  4.80  2.76 6.34 11.00 20.00  15-86 23.65 27.46 45.10 27.57  1.27 3.20 4.74 8.54  2.12 6.93 13.69 10.27  7-87 19-45 20.44 49.55  1.33 3.54 9.05  1.49 6.86 14.53  15.60 18.65 14.79  —  —  •a  Jtl Ae Bf, ( B h f )  Humic  carbon  0.78 0.98 4.05 7-33 27.13  —  LF  soil  LF HF Aeh Bhf Bf Cg  0.94 1.17 1.00 2.59  2.58 1.66 1.19 3.75  32.98 21.33 23.81 45.29 —.—  —  0.60  0.49 0.71 3.17  1.09 0.27  13.61 16.64  1.41  2.36  1.33 15.46  0.33 0.38 3.75 11.00  0.36 0.53 4.95 8.95  8.73 19.27 18.20 30.89  4.41 8.41  18.67 30.42 16.10  3.04  A c i d Brown wooded  Ap Bf BC C  Humic  Ah Btg C  3.03 7.66 9.50  Ap Btg Bg  1.74 7.68 11.60  8.03 27.66  15.40 23.77 26.73  4.64  6.34  22.13  Orthic  Gleysol  Gleysol  Average  8.88  37. as  percent  0.27  of t o t a l  2 7 . 6 6 and  and  ultrasonic  1.33  dispersion  seems w o r t h n o t i n g which i s quite sults.  c a r b o n v a r i e d between 0 . 3 3  soil  and  that  i n no  contradictory  plexes rather were n o t  than  sociates  restricted  At  also (84)  this  who  should  But  only  It  appeared  smaller  eight  the  w o r k e d on  stage  to  be  Ifc  f i g u r e exceed  49.6$  complexes,  to the  reof  into different  termed organo-mineral  the<"2/c f r a c t i o n .  since  the  com-  materials  Secondly, the  possib-  i n t r o d u c t i o n of  organic  r e s u l t s o f T r o f i m e n k o and  o r g a n o - c l a y complexes, are  his  as-  quite  r e s u l t s of t h i s i n v e s t i g a t i o n . i t seems a d v i s a b l e  about the  c h a r a c t e r i z a t i o n , and  detailed  on  to  exists.  mark s p e c i f i c a l l y  a  dispersion,  workers (40,46,50)  with other  a r t e f a c t s due  comparable w i t h the  to  case d i d t h i s  organo-clay  of producing  liquids  ples  simple  respectively.  densities for fractionating soils  groups which, t h e r e f o r e ,  for  r e s i n treatment  by  However, many o f t h e s e w o r k e r s u s e d h e a v y l i q u i d s  different  ility  49.55 percent  and  27.13,  and  t o make a c o n c l u d i n g  s e l e c t i o n of u l t r a s o n i c  about  Cutting  down t h e  re-  dispersion  number o f  sam-  eight. legitimate  one  when t h e  studies  within  to  cut  first  down t h e  p h a s e was  number o f  over, to  a reasonable period  samples  permit  of time.  more  In . a l l ,  s a m p l e s were c h o s e n f o r d e t a i l e d c h a r a c t e r i z a t i o n b a s e d  similarity  and  carbon content, Secondly,  dissimilarity  and  representing  insonation  characterization  of  III  that  Table  IV  these  was  complexes  preferred  complexes.  simple  samples i n r e l a t i o n to  a wide range  a f t e r examining the  quantitatively,  and  of the  in  properties.  q u a l i t a t i v e l y and  for further detailed  I t i s evident  from  Table  d i s p e r s i o n . i s a p o o r m e t h o d and  a  38.  slow process bring  about  of isolation  a n d i n some c a s e s  some h y d r o l y t i c  majority  o f the cases  possibly  due t o h i g h pH t h u s  from  t h e complex.  effects.  isolated  the use o f u l t r a s o n i c  erable.  I t should also  es,  t o be t h e b e s t  without  changing  of this  Organo-clay  differential  Table  be e m p h a s i z e d  of organo-clay  by u s i n g x-ray thermal  o f t h e complex-  was a l s o  to the other  an a d d i t i o n a l a d -  results  complexes.  diffraction,  analysis  infrared  and d i f f e r e n t  treatment  were  absorption,  extracting  reagents,  below.  analysis: of x-ray  q u a n t i t y except  Illite  diffraction  analysis are reported i n  examined, c h l o r i t e  i n t h e Ae h o r i z o n s a m p l e  V e r m i c u l i t e was o f s e c o n d was p r e s e n t  kaolinite  absent.  The amount  subjected to x-ray  t o observe  was f o u n d  to quantity.  percent,  o f amphibole  was a l s o  however, i nthe  s i g n i f i c a n t . The  diffraction  any e x p a n s i o n .  i n ma-  o f t h e O r t h i c Pod-  i n relation  o f 10-15  o f t h e Humic P o d z o l  c o m p l e x e s were a l s o glycolation  order  up t o t h e e x t e n t  was t o t a l l y  h o r i z o n sample  after  yield  VI and enumerated i n t h e f o l l o w i n g pages.  zol.  Cg  method was n o t  complexes o b t a i n e d by u l t r a s o n i c  I n most o f t h e s a m p l e s jor  that this  i n b r i n g i n g about d i s p e r s i o n  Speed o f i s o l a t i o n  diffraction The  fraction  d i s p e r s i o n was c o n s i d e r e d p r e f -  satisfactory  w h i c h a r e summarized X-ray  i nthe  method.  Characterization  characterized  to  c o n s i d e r i n g a l l o f these  t h e c o m p l e x e s much i n c o m p a r i s o n  methods examined. vantage  treatment  o f f the organic  f o r i s o l a t i n g maximum  b u t i t was f o u n d  appeared  f a r g r e a t e r amounts o f c o m p l e x e s ,  after  factors,  found  Resin  splitting  Therefore,  also  analysis  However, i n no  case  TABLE VI Clay minerals i n selected complexes. S o i l Subgroups Humic Eluviated Gleysol  Horizons Ah  Chlorite 3  Montmorillonite  Vermiculite  —  (Data based on x-ray d i f f r a c t i o n Mixed Layer  Illite  2  1-2  2  Feldspars 1  Comparison of X-ray data before and afte;r treatment. Lower peak heights probably due to Fe or some other interlamellar material i n 148 region which was l o s t on ^2^2 ^• '^ ment. Lower peak heights i n untreated samples probably due to Fe interference ceB  1-2  Cg Orthic Concretionary Brown  Quartz  Amphibole  analyses).  Not as complete collapse of vermicul i t e as i n treated sample when heated to 500 C and s l i g h t l y lower 14n spacing after h^C^ treatment.  Bfcc.  1  1  Orthic Podzol  1-2  Ae  a n d  1-2  Humic Podzol  Untreated complex gave 13. peak which became 14.28 after ^^02 c i t r a t e - d i t h i o n i t e treatment. 13. peak i s probably due to binding of the micelles together by organic matter which became broader on H-D2 treatment. Low peak heights i n both cases probably due to Fe interference or amorphous material.  Bhf  1-2  1-2  Cg  3-4  1-2  1-2  Lower peak heights i n untreated complex and 14.2°-peak shifted to 14.028 on h^O,, treatment. The high Background probably due to Fe and H2O2 treatment did not change 14.488 peaR probably due to the una c c e s s i b i l i t y of organic matter to H  Orthic Gleysol ** 5 4 3  2 1  65 %+ 65-40$ 40-205$ 20-10$ 10- 1$  2°2'  108 peak in untreated possible complex and 188 peak l o s t on "^02 treatment.  Btg Treatments  ^2 2 Q  a n d  c i  '  t r a  " ~ ' t 8  d i  t n i o n i  '  t e  (f° d e t a i l s see methods) r  40. was  such  expansion  observed.  Humic E l u v i a t e d G l e y s o l : The Ah h o r i z o n vermiculite, quantities the  148  and i l l i t e  of quartz  a n d 188  and f e l d s p a r s .  after  treating with  of organic matter. than  chlorite  observed  only  i n t h e 148  Concretionary  The B f c c chlorite present 148  n  with  H 0 2  suggesting  2  sample  slight  peak  interlamellar  c o n t a i n e d more  interstratification  verwas  Brown: o  n  sample  Quartz.  observed  An  c o n t a i n e d more v e r m i c u l i t e t h a n Amphibole  a n d f e l d s p a r s were a l s o  interlamellar  inclusion  b u t c o u l d n o t be a t t r i b u t e d  i n the  t o any  min-  Podzol: horizon  montmorillonite  13.608 due  gether the  z  However, t h e 18.8  regxon.  i n m i n o r amounts.  The Ae  was  i -  f o l l o w e d by m i n o r  Interlamellar inclusions i n  The C g  but very  chlorite,  species.  Orthic  at  r  10-15$  r e g i o n was  eral  o  2  to contain  as the major m i n e r a l s ,  miculite  Orthic  observed  r e g i o n were o b s e r v e d .  148  dropped to inclusion  sample was  Bf  and  2  14.9?8.  14.97^  sample  indications  a significant  amount o f  f o l l o w e d by v e r m i c u l i t e w h i c h e x h i b i t e d peaks  to organic and  sample c o n t a i n e d  I t was  components p e a k was  concluded  t h a t the  b i n d i n g the adjacent  attributed  t o F e , Mg  d i d n o t h a v e any m o n t m o r i l l o n i t e ,  of organo-clay  interaction  was  e n c e o f a h i g h amount o f m o n t m o r i l l o n i t e sample  appears q u i t e unusual  source  of  contamination.  13.608  and f o r e s t  micelles to-  or A l .  However,  although  observed.  i n t h e Ae fire  peak  The  some pres-  horizon  fighting  may  be t h e  41. Humic  Podzol: Neither  any  the  Bhf  or the  montmorillonite.  absent the  from  the  more t h a n  matter.  The  Cg  However, i t c o n t a i n e d  Orthic Podzol  14A* Cg  sample o f t h i s  r e g i o n was  samples. observed,  sample c o n t a i n e d  soil  contained  illite  which  was  Interstratification probably  due  a considerable  to  in  organic  amount o f  am-  phibole. Orthic  Gleysol:  The  Btg  sample c o n t a i n e d  some m o n t m o r i l l o n i t e  p e a k was  attributed  t o the  interlamellar  matter.  Therefore,  i t can  be  x-ray it  diffraction  should  organic crystal, thus  a l s o be  but  An  inclusion  m e n t i o n e d by  revealed  always r e s u l t  sometimes i t t e n d s t o b i n d the  normal  the  infrared  study  was  and  and  approach f o r mineral  complexes, complexes,  conducted to  P i g . 1 and and  (b)  the  to  with  micelles  and  of mineral  together,  2 represent  a view to observing  an  a i d i n mineral  i s interesting  I t was  and  (a) the  complexes a f t e r  infrared  infrared  2  found  of  an  use-  c h a r a c t e r i z a t i o n of  treatment  H 0 2 and  changes i n the  (specified  x-ray  b o n d i n g mechanisms  identification  s p e c t r a of pure minerals  It  inclusion  s u b s t a n t i a t e the  observe the  c o m p l e x e s were t r e a t e d w i t h  u s e d as  that  absorption analysis:  i n o r g a n i c components as w e l l .  red  summary  spacings.  organic  taken  18$  organic  i n expanding the  analyses  The  of  of  the  some u s e f u l i n f o r m a t i o n  diffraction  ful  way  remembered t h a t i n t e r l a m e l l a r  m a t e r i a l does not  reducing  Infrared  analyses  and  spectra  with  -^2^2'  s p e c t r a were  spectra.  Infra-  p r e v i o u s l y ) were a l s o  identification.  to note  that  the  of  infrared  spectrum  of  42.  25  WAVELENGTH p fe 7  3  10  12  14  ORTHIC CONCRETIONARY BROWN  Bfcc,  HUMIC PODZOL (Cg)  4000  FIG. I  3000  2000 •-  1750  .  1500  WAVENUMBER  1250  1000  750 650  Infrared spectra of complexes obtained by insonation. a.  Complexes.  b.  Complexes  a f t e r HgOg  treatment.  43. t h e complex o b t a i n e d from is  just  about  treatment used  a straight  with H 0 2  2  t h e B t g sample o f t h e O r t h i c line  i t gave a d i s t i n c t  i s very important  hedral  s h e e t and  1 0 . i s  A  sample and Cg very  different  tion  b a n d i n t h e 10 t o l l ^  bonded  t h e Ah  slight  r e g i o n where  silicon  may  was The  treating  of the B f  2  attributed  however,  that  o f t h e Ae  to mineralogy absent  t h e IB. s p e c t r u m  i s concluded that  under c e r t a i n  absorp-  have  been  exhibited  I t i s suggested  a  Podzol  a s t h e Ae  from  through  that  oxygen.  i n the 3 . 0 5 ^ r e g i o n . different  soil.  from  I t was,  how-  s a m p l e c o n t a i n e d mont-  the B f  2  sample.  I t was  noted  o f the complex o b t a i n e d from  IR a n a l y s i s  an a l m o s t  upon H 0 2  2  the  straight  treatment.  g a v e some i n t e r e s t i n g i n -  f o r m a t i o n when c o u p l e d w i t h x - r a y d i f f r a c t i o n . that  may  s a m p l e was  w h i c h became c o m p l e t e l y d i f f e r e n t It  a distinct  sample  2  s a m p l e o f t h e Humic P o d z o l a g a i n showed  line,  ob-  oxygen.  stretching  sample o f t h e O r t h i c  w h i c h was  also  sub-  10.6°/^ w h i c h became more p r o n o u n -  o f N-H  spectrum  to  G l e y s o l were n o t  be b o n d e d t o some o t h e r c o m p o n e n t s  infrared  morillonite  through  t h e s a m p l e w i t h B^G^*  no i n d i c a t i o n  octa-  o f the Ah h o r i z o n  silicon  C o n c r e t i o n a r y Brown B f c c  a b s o r p t i o n band around  ced a f t e r  spectra  s a m p l e showed  t o some o r g a n i c component  The O r t h i c  Cg  Infrared  s a m p l e o f t h e Humic B l u v i a t e d except  This  and o t h e r p o l y m e r i c  amount o f c a r b o h y d r a t e s were  association.  after  commonly  The r e g i o n 8 . 5  linkages.  of glucosidic-linkages  significant  served i n this  ever,  l o o p ( a term  a s i t p r o b a b l y c o v e r s aluminum  silicon-oxygen  typical  stances.  that  However,  i n chemical j o u r n a l s ) i n the 9«9 to l Q ^ r e g i o n .  region  There  o v e r a wide range.  Gleysol  I t i s suggested  c o n d i t i o n s g l u c o s i d e s c o u l d be b o n d e d t o  44.  WAVELENGTH' p  e  HUMIC ELUVIATED GLEYSOL  (Cg)  '8 I 2  ORTHIC  •1000  3200  .2000  1750  1500  1250  GLEYSOL (Big)  ICOO •  750 650 >  WM'ENUMBER  FIG.  I I " Iis^rared V  a. b«  spectra o f complexes obtained by insonation. Complexes. Complexes a f t e r B2 2 0  trea  '  fcmen  'k»  4-4-.  45. c e r t a i n m i n e r a l s and l i k e w i s e some a l k a n e s d i r e c t l y to t h r o u g h oxygen l i n k a g e s .  silicon  The p o s s i b i l i t y of c a r b o n y l groups  b o n d i n g t o s u r f a c e c a t i o n s o f c e r t a i n m i n e r a l s depending s u r f a c e charge cannot be r u l e d out.  There was  upon  no c l e a r c u t i n -  d i c a t i o n o f bonding o r g a n i c components t o m i n e r a l s through linkages.  NH-  However, the c o m p a r a t i v e l y low p e r c e n t o f o r g a n i c  m a t t e r makes i t u n l i k e l y t h a t f i n e d e t a i l s of s p e c t r a due  to  o r g a n i c components c o u l d be r e v e a l e d . D i f f e r e n t i a l thermal The  analysis:  complexes o b t a i n e d by u l t r a s o n i c d i s p e r s i o n were sub-  j e c t e d t o d i f f e r e n t i a l t h e r m a l a n a l y s i s up t o o n l y about due  t o the t e c h n i c a l d i f f i c u l t i e s w i t h the h i g h temperature  which p r o b a b l y would have g i v e n more i n f o r m a t i o n .  t i o n i n r e l a t i o n to mineralogy.  more  i n the case o f the Cg sample o f Humic P o d z o l .  T h i s was  t o o r g a n i c matter e l i m i n a t i o n .  A prominent  by S c h n i t z e r and h i s a s s o c i a t e ( 7 5 , 7 6 )  Extractability  pronounced  curve  probably  observed  a t 400°C due t o p h e n o l i c s  n o t seen i n the p r e s e n t i n v e s t i g a t i o n .  the dominance o f f u l v i c  absorp-  S m a l l peaks near 3 0 0 t o 3 2 0  were observed i n each sample but the curve was  was  cell  However, i t  s u p p o r t e d the r e s u l t s o f x - r a y d i f f r a c t i o n and i n f r a r e d  due  600°C  T h i s may  be due  to  f r a c t i o n i n the complexes.  of carbon from  complexes:  T a b l e V H X p r e s e n t s the carbon and n i t r o g e n c o n t e n t o f the complexes a l o n g w i t h the carbon e x t r a c t e d w i t h d i f f e r e n t in  succession.  from 5*5  "to 1 7 ,  The V a r i a t i o n  i n the C/N  reagents  r a t i o , which ranged  suggested t h a t the n a t u r e o f the o r g a n i c compo-  n e n t s i n d i f f e r e n t complexes a l s o v a r i e d . gen c o n t e n t o f the complexes appeared  In g e n e r a l the n i t r o -  to be h i g h and h i g h  C/N  TABLE VII C, N contents and C extracted with successive treatments from selected organo-clay complexes*  S o i l Subgroups Humic Eluviated Gleysol  Horizons Ah j.  4 2°7  Percent carbon recovered 0.1 M Na.P_0 0.1N After HF-HC1 Not treatment NaOH  8.00  50.0  13.8  25.0  11.2  6.50  37.5  6.3  27.1  29.1  %N  C/N Ratio  11.12  1.39  0.39  0.06  % C  0.1 M N a  P  extracted  Orthic Concretionary Brown  Bfcc.  4.43  0.26 17.04  54.5  6.8  19.9  18.8  Orthic Podzol  Ae  6.16  0.56 11.00  45.3  11.3  32.0  11.4  Bf.  13.20  0.83 15.90  53.9  1.9  26.2  18.0  Bhf  10.71  1.20  8.93  62.8  13.0  19.3  Cg  9.03  0.55 16.42  46.0  4.9 8.3  23.1  22.6  Btg  1.05  0.19  49.9  1.5  20.7  7.9  Humic Podzol  Orthic Gleysol  5.53  * Complexes were obtained by the use of Ultrasonic dispersion.  47. ratios  suggested  that organic  components i n t h i s a s s o c i a t i o n  may p e r h a p s i n c l u d e l o n g c h a i n It  was o b s e r v e d  fraction  BfcCg  extracted the largest  suggesting  residue,  with  (28)  over  more s t a b l e f o r m  was c o n c l u d e d  gesting  i n nature  m a t t e r a f t e r HF-  of the organic  high  This finding conclusions.  matter.  insufThe  suggested  fraction.  o f o r g a n i c matter exhigher  from  o f e x t r a c t a b l e i r o n , sug  through multivalent c a t i o n  link-  i s i n a c c o r d a n c e with. E d w a r d s a n d B r e m n e r ' s However, t h i s  anism and secondly,  the extent  is  understood.  not f u l l y  Characteristics  content  remainin  was l i k e l y  s o d i u m p y r o p h o s p h a t e was c o m p a r a t i v e l y a fairly  after  to that  i n t h e Cg samples  that the percentage  t h e complex f o r m a t i o n  still  2  o f t h e Humic P o d  The m a t e r i a l s  maximum amounts o f o r g a n i c  amount o f c a r b o n l e f t  samples w i t h  ages.  significant.  s i n c e t h e s i n g l e HF-HG&- t r e a t m e n t  comparatively  the  a n d t h e B h f sample  may w e l l be s i m i l a r  to liberate  tracted  from  Brown, t h e B f  the release of organic  was n o t v e r y  HF-HG& t r e a t m e n t  It  o f carbon  The amount o f c a r b o n e x t r a c t e d f r o m t h e c o m p l e x e s  HG& t r e a t m e n t  higher  pyrophosphate  t h a t m u l t i v a l e n t c a t i o n s may be i n v o l v e d i n com  w i t h NaOH a n d s i m i l a r l y  ficient  proportions  sample o f t h e O r t h i c C o n c r e t i o n a r y  plexing.  in  ^0% o f t h e o r g a n i c  on an a v e r a g e ,  sample o f t h e O r t h i c P o d z o l zol,  hydrocarbons.  o f t h e c o m p l e x e s was e x t r a c t e d b y s o d i u m  Pyrophosphate the  that  aliphatic  o f the organic  i s probably  and importance  fraction  not the only of this  mech-  mechanism  e x t r a c t e d from s e l e c t e d complexes.  Table ratio,  VIII  presents  FA a s p e r c e n t  t h e Humic A c i d  (HA):  of extracted organic  F u l v i c A c i d (FA)  matter and carbohyd-  48.  TABLE  VIII  C h a r a c t e r i s t i c s o f t h e o r g a n i c components e x t r a c t e d from s e l e c t e d complexes  Soil  Subgroups  Horizons  0.20 0.08  Humic e l u v iated Gleysol  Ah Cg  Orthic Concret i o n a r y Brown  Bfcc,  Orthic  Ae Bf  Humic  Orthic  Podzol Podzol  Gleysol  Humic A c i d : Fulvic Acid Ratio  2  Bhf Cg Btg  0.67 2.33 1.72  Fulvic Acid as % o f extracted organic matter  Carbohydrate-C as % of total complex carbon  83 93  7.7 109.0  100  6.4  60  30  12.6 6.8  *37  8.4  100  3.3  100  16.6  49rate  c a r b o n as  ratio  was  and  high  Bfcc2 of  s  a  the  m  Acid  Bhf  l  e  o  ^  fully  whereas the  o f the  of the of  and  100$  The  the  Btg  of the  significance  to  T h e r e was Podzolic no  t o be  their  indicated  samples  be  Orthic  due  to The  of the  Orthic  m a t e r i a l i n the  Fulvic  sample  observation  of the  the Cg  however,  and  total  horizon  complex  i n the  finer  of  the  anomalous p e r c e n t a g e  of  109  total  errors associated  to  the  fraction  soils.  the  data  However, t h e  complexes.  c o m p l e x e s was  higher  f o r the  silicon  i n Table  of the  The  support  p  and  IX.  p  and  the  con-  did  appear pyro-  extracted  in iron. Bhf  was  c a t i o n ';>  sodium  amount o f c a r b o n  Bf ,  Si in  carbon  to the  of carbon with  of  There  amount o f i r o n  i n samples h i g h  Bfcc ,  soil.  amount o f i r o n  extractability  with  carbon.  o f e x t r a c t a b l e F e , A l , and  between the  carbon  sample  c o m p l e x e s , w h i c h l e n d s no  from  by  percent  sample  to a n a l y t i c a l  a marked enrichment  related  from the  the  Cg  r e s p e c t i v e complexes i s given  mechanism t h e o r y .  phosphate  FA  of  samples.  amount o f e x t r a c t a b l e i r o n , ' a l u m i n u m and  of the  bridge  The  T h i s may  e x t r a c t s o f c o m p l e x e s and  inter-relationship  tent  due  of carbohydrate  Dithionite-Citrate  and  percent  Brown, t h e  of t h i s  percent  16.6$, b u t  w h i c h seems more l i k e l y  soils  HA:  sample o f t h e  i n these  horizon  organic  as  100$.  Humic P o d z o l .  Humic E l u v i a t e d G l e y s o l showed an  The  to  Bf^ horizon  sesquioxides  c a r b o n as  r a n g e d b e t w e e n 3«3  levels  30  FA  The  understood.  Carbohydrate  low  complex carbon.  Orthic Concretionary  e  contained  fraction.  not  case  sample  f  total  t o 2.33  concentration P  the  m a t t e r v a r i e d from  Humic P o d z o l  Gleysol  is  organic  lower i n the  Podzol the  of  r a n g e d f r o m 0.08  extracted FA  percent  This i s  (Table VII  and  50. and  VIII)  Podzol,  samples o f the O r t h i c  a n d t h e Humic P o d z o l  concretionary  respectively.  Brown, t h e O r t h i c  TABLE IX  Dithionite, extractable  Fe, A l and S i o f S o i l s and Complexes P e r c e n t i n S o i l s P e r c e n t i n Complexes  S o i l Subgroups Humic e l u v i a t e d Gleysol  Fe  Al  Si  Fe  Al  Si  Ah  2.20  1.28  0.42  2.33  1.60  0.53  OS  1.20  0.16  0.54  1.83  2.07  0.62  1.95  0.92  0.39  5.50  2.60  0.97  0.53  0.18  0.25  2.08  0.90  0.68  1.50  2.10  0.62  6.33  6.70  2.44  Bhf  2.10  3.12  0.74  4.83  6.60  1.70  Cg  0,98  1.38  0.45  4.00  3-20  1.37  Btg  2.40  0.50  0.68  2.00  0.37  0.64  Horizons  O r t h i c Concret i o n a r y Brown  Bfcc  Orthic  Ae  Podzol  Bf Humic P o d z o l  Orthic  Gleysol  2  2  52. SUMMARY AMD Thirty-four eight  soil  tribution The  great  groups,  expressed  v i z : - simple  dispersion,  i v e n e s s was a s s e s s e d . dispersion  soil  by i n s o n a t i o n ,  3.41;  a n d by c h e l a t i n g  carbon  insonation,  organo-clay  between 0.15  2.58;  represented  f o r t h e i r carbon  T h e amount  varied  which  f o r the d i s -  complexes and o t h e r c h a r a c t e r i s t i c s .  on t h e t o t a l  forisolating  soils  were c o l l e c t e d a n d s t u d i e d  of organo-clay  were u s e d  ple  eight  c o m p l e x e s were a n a l y s e d  was a l s o ods,  samples from  CONCLUSION  content  which  Three  meth-  basis.  and c h e l a t i n g  resin,  complexes and t h e i r e f f e c t -  o f complexes o b t a i n e d  by  sim-  a n d 10.42 w i t h a n a v e r a g e o f  between 0.20 and 1?.20  w i t h an a v e r a g e o f  r e s i n , b e t w e e n 1.25 a n d 2 5 . 7 0 w i t h an  average o f 12.30. The 0.47  percent  and 18.66 p e r c e n t  i n t h e c o m p l e x e s was o b s e r v e d w i t h an a v e r a g e o f 5*01  between 0 . 3 9 and 21.76 p e r c e n t  persion; by  carbon  ultrasonic dispersion,  w i t h an a v e r a g e o f 4 . 7 0 A very plexes,  important  expressed  dispersion,  with 22.13  an a v e r a g e  of organo-clay  soil  and c h e l a t i n g  carbon  a n d 1.33  by  com-  simple  r e s i n , was  w i t h an a v e r a g e o f 4.64; 0 . 2 7  o f 6.34,  percent  found  a n d 27.66  a n d 4 9 . 5 5 w i t h an a v e r a g e o f  respectively. It  i s felt  obtaining dispersion of  and 27.13  dis-  resin.  of the t o t a l  ultrasonic dispersion  between 0.33  and 18.39  parameter, v i z carbon  as percent  by s i m p l e  w i t h an a v e r a g e o f 5*33  and between 0.31  by c h e l a t i n g  between  that  the c h e l a t i n g  r e s i n i s a good a g e n t f o r  h i g h e r y i e l d s o f complexes which i s p r o b a b l y e f f e c t a n d h i g h pH.  complexes,  insonation  However, c o n s i d e r i n g  due t o a  the q u a l i t y  was c o n s i d e r e d t h e p r e f e r a b l e  method.  53. T h i s method a l s o  had the advantage  of relative  speed  and con-  venience. For characterization and  were f o u n d  to vary i n carbon,  aluminum and s i l i c o n from  different  cession, varied  only eight  content.  c o m p l e x e s were  nitrogen, extractable  b e t w e e n 5*5  different.  reagents used  T h e 0/N r a t i o  a n d 17.0.  sample,  nature, except  i n which about  i n explaining  carbohydrate and  The in  mineralogy  nificant lar  always  o f the Podzolic Bf material  f o r only  evidence  sigThe  3«3  carbon.  and i n f r a r e d  of the Orthic  s t u d i e s were a l s o  to differ  I n most  made.  t o any e x t e n t  except  Podzol and the BJfg-horizon o f  o f t h e samples  entrapment o f t h e o r g a n i c carbon  was a l s o  association  G l e y s o l where m o n t m o r i l l o n i t e was o b s e r v e d  amounts.  that  T h i s o b s e r v a t i o n may be o f some  was n o t o b s e r v e d  the Ae-horizon  the O r t h i c  i n this  c o n t e n t o f t h e complexes accounted  diffraction  indicated  t h e p r o c e s s o f complex f o r m a t i o n .  16.6% o f t h e complex X-ray  i n the case  i n succomplexes  two-thirds of the extractable  was i n t h e h u m i c f r a c t i o n . nificance  of these  T h e HA: F A r a t i o s  a m a j o r p r o p o r t i o n o f t h e o r g a n i c component was o f f u l v i c  iron,  T h e amount o f c a r b o n e x t r a c t e d  complexes w i t h d i f f e r e n t  was a l s o  selected  suggesting that  examined,  was a l s o  i n sig-  interlamel-  observed.  multivalent  cations  There  are not  t h e means o f c o m p l e x f o r m a t i o n a s i s r e p o r t e d b y some  w o r k e r s (27,28). Infrared  study also  gave  some i m p o r t a n t  i n f o r m a t i o n about  mineralogy  and suggested  some p o s s i b l e  some c a s e s  some e v i d e n c e  of glucoside linkages i n the 8.5-10.^  r e g i o n was a l s o  observed.  There  bonding  was a l s o  mechanisms.  In  some i n d i c a t i o n o f  5*bonding o f s i l i c o n  to organic  However, t h e r e  no  was  evidence  m a t t e r and c l a y m i n e r a l s , to  low c o n c e n t r a t i o n  compounds t h r o u g h o x y g e n l i n k a g e s . o f amide l i n k a g e s b e t w e e n  w h i c h may  of organic  organic  have n o t been r e v e a l e d  components  due  i n the complexes.  55.  BIBLIOGRAPHY 1.  Achard,  1786.  F.K.  Chemische Untersuchung des C r e l l s Chem. Ann.  2.  A h l r i c h , J.L. 1 9 6 2 . Aleksandrova,  391-404.  Bonding o f o r g a n i c p o l y a n i o n s t o c l a y minerals.  3.  2:  Torfs.  L.N.  1967.  D i s s . A b s t r a c t s 22,  2121.  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