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Diagenesis and thermal maturation of the Eureka sound formation, Strand Fiord, Axel Heiberg Island, Arctic… Allen, David Peter Beddome 1986

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DIAGENESIS  AND  THERMAL  STRAND  MATURATION  FIORD,  OF  AXEL HEIBERC  THE  EUREKA S O U N D  ISLAND,  ARCTIC  CANADA  by DAVID  A  PETER  BEDDOME  THESIS  SUBMITTED  IN  THE  REQUIREMENTS MASTER  ALLEN  PARTIAL FOR  OF  THE  FULFILMENT DECREE  OF  SCIENCE  in THE  FACULTY  (Department  We  of  GRADUATE  Geological Sciences)  the  required  UNIVERSITY  OF  Spring,  ©  STUDIES  a c c e p t this t h e s i s as. c o n f o r m i n g to  THE  OF  David  Peter  standard  BRITISH  COLUMBIA  1986  Beddome  Allen,  1986  OF  FORMATION,  In  presenting  degree shall for  at  of  thesis  THE  it f r e e l y  extensive  copying my  the  make  Head  this  available f o r of  Department  or  publication  written  permission!  (Department  of  of  this or this  Spring,  fulfilment  OF  BRITISH  reference  thesis by  for  his  or  thesis  for  Geological Sciences)  T H E U N I V E R S I T Y O F BRITISH 2075 W e s b r o o k Place Vancouver, Canada V6T 1W5  Date:  partial  UNIVERSITY  copying  my  in  1986  COLUMBIA  and  of  requirements  COLUMBIA, study.  scholarly her  the  I  agree  I further  purposes  shall  agree  may  representatives.  financial gain  for  be  an  that that  advanced  the  Library  permission  granted  by  It  is  understood  not  be  allowed  the that  without  ABSTRACT Nearly and  coals  N.W.T.,  were  in  thermal  present  1.0  and  nm  strata a n d  in  findings  make  from or  Na -enriched  waters  passed  laterally  adjacent  supported  by  offset  from  plot on  primarily  lower  segment  (based  mainly  phase  dawsonite  sandstones. and  An  as  105  analyses  Formation  thermal  been  parameters  illite  used  in  Island,  such  as  illite  illite/smectite mixed  in c o m b i n a t i o n  thermochemical  heat  modelling flow  and  anomaly  cores (where such  of  as  with  evolution  coals)  has  of  the  authigenic chemical that  higher  the  Na*  This  versus  depth  precipitated  conditions  the  arenites.  formation  under  in  concept  of  the  which  concentration  may  heated occurred)  reflectance values  on  phase  petrology  halite d i s s o l u t i o n  coals and  and  sandstone  existed whereby  vitrinite r e f l e c t a n c e  phytoclasts),  the  can  suggest be  reactions between  Textural  relationships  (calcite,  ankerite,  features  in  the  fluid chemistry  of  Heiberg  shales  into is  whereby  the  than  the  the  sodium  pores  of  the  halite  dissolves  have  been  as  1  mineral  diagenetic  last of  diagenetic  the  sandstones,  Peninsula, Axel  proportion have  Formation  I" .  Eureka S o u n d to  on  precipitates suggests  g  Clay  the  examination  dawsonite  high  as  rocks,  about  diapir  in t h e  (based  Kanguk  ratios,  lithologies  segment  Sound  waters. the  upper  rich  these  post-tectonic  permeable  an  along  inferences  both  a syn-  Eureka  paragenesis  pore  that  +  From  cement  to  of  outcrop  sharpness  their contained  The  metres  study.  peak  sandstone  modelling  suggest  continuous  examined  the  crystrallinity, layers,  3000  to  major  part  changes  the  clay  minerals  between  the  six p r i n c i p a l  aluminosilicates occured  the  attributed  siderite, dawsonite,  have  that  kaolinite and  suggest  since the  that  the  detrital  authigenic  7  clay variation minerals  their c h e m i c a l  quartz  at least  strata w e r e  ii  and  in  of  episodes  deposited.  rather  of  the than  environment.  sandstone  overgrowths)  in  and  cements dissolution  changing  pore  Table I. G E N E R A L  II.  GENERAL'STATEMENT  B.  STUDY  C.  GEOLOGIC  D.  PREVIOUS  A.  2.  2.  1  ,  ,  SETTING  7  MATURATION  Sample  3.  ,  Preparation  ....12  a.  Coal  b.  Phytoclast Pellets  Pellets  12 :  13 13  a.  Elemental  b.  Time-Temperature  Analysis  14 Model  14  DISCUSSION  16  Coalification Gradients  16  a.  Statistical C o n s i d e r a t i o n s  b.  Consideration  of  R max  c.  Consideration  of  Shifts in  Paleo-depth  of  Maximum  PETROLOGY  RESULTS  Q  19 Distribution  .  Pressure  Considerations  2.  Discription  Depth  20 22 25 27  Gradient  29  AND  35  DIAGENESIS :  Petrology  with  Coalification Gradient  Burial  Paleo-geothermal  1.  11 12  Analytical Techniques  SANDSTONE  ..2 2  WORK  a.  A.  .  AREA  RESULTS A N D 1.  III.  1  EXPERIMENTAL 1.  B.  Contents  INTRODUCTION  A.  ORGANIC  of  ............35 35  of  Authigenic  Minerals  a.  Principal A u t h i g e n i c  b.  Accessory Authigenic  iii  Minerals Minerals  41 41 50  B.  DISCUSSION 1.  Textural  2.  Fluid  55 Relationships  Chemistry a.  IV.  SHALE A.  C.  V.  Dawsonite:  MINERALOCY  Clay  AND  Chemical  Constraints  71  DIACENESIS  85 85  Sample  Preparation  a.  Oriented  b.  Unoriented  85  Samples  2.  Instrumental  3.  Analytical Techniques  87  Samples  88  Techniques  88 89  a.  Clay  Mineralogy  b.  Semi-quantitative  c.  Mixed-layer  d.  Sharpness  89 Mineralogy  90  Analyses Ratios  92  and  Illite  Crystallinity Index  96  RESULTS  96  1.  Clay  2.  Semi-quantitative  Mineralogy  3.  Percent  Illite/Smectite  4.  Illite C r y s t a l l i n i t y  5.  Sharpness  Mineralogy  Illite  in  96 • ,  97  Mixed-layers  Index  98 ~  103  Ratio  104  DISCUSSION  104  1.  Diagenetic  2.  Consideration  of  Shifts in  Clay  3.  Consideration  of  Variations  in  SUMMARY A.  67  EXPERIMENTAL 1.  B.  55  General  AND  Facies  and  Sub-facies  CONCLUSIONS  109 Parameters  Sample  with  Mineralogy  Depth  '.  113  with  Depth  115 118  Summary  118  iv  B.  Discussion  ,  1.  Subarial W e a t h e r i n g  2.  Subaqueous  3.  SedimentAVater  4.  S h a l l o w Burial  5.  Deep  6.  Syn/Post O o g e n i c  VI.  References  VII.  Appendices  Burial  120 120  Aggradation  and  Interface  Reactions (Diagenesis  (Diagenesis  (Diagenesis  Neoformation  120 A)  121  B)  121  C)  .  Reactions (Diagenesis  123 D)  .125 .......128 •  A.  Appendix  1:  Potassium Saturated  B.  Appendix  2:  Magnesium  C.  Appendix  3:  Non-Saturated  Clays  .144  D.  Appendix  4:  Heat Treated  Clays  145  Saturated  v  Clays  ...141  Clays  .....142 143  List of C  H  N  Elemental  Framework  Tables  Analysis  Petrology  of  Sandstones  D i s t r i b u t i o n of S a n d s t o n e Stratigraphic Section  Cements  Heat Capacity Coefficients and a n d E n t r o p y of D a w s o n i t e  Through  Standard  the  State  Enthalpy  N a m e s , C h e m i c a l F o r m u l a e a n d Free E n e r g i e s o f F o r m a t i o n o f t h e S o d i u m C a r b o n a t e s u s e d in t h e I n c l u d e d A c t i v i t y / A c t i v i t y a n d Partial P r e s s u r e D i a g r a m s Reactions, of  Free  Reactions  Energies  Used  in  of  the  Reaction and System:  LogKeg  H -Al +  + 3  -Na  +  Values -H O z  R e a c t i o n s , Free E n e r g i e s o f R e a c t i o n a n d L o g K e q V a l u e s o f R e a c t i o n s U s e d in t h e S y s t e m : H - A l - H 0 - C 0 +  Mineral Assemblages Species Analyses  Considered  in  +  the  3  2  2  Distribution  of  C o m p a r i s o n o f E u r e k a S o u n d F o r m a t i o n Fluid C h e m i s t r y w i t h t h e Fluid C h e m i s t r y o f O t h e r N a t u r a l S y s t e m s P o s i t i o n s o f ( 0 0 2 ) 1 0 / ( 0 0 3 ) 1 7 D i f f r a c t i o n Peaks f o r V a r i o u s % lllite in I l l i t e / S m e c t i t e V a l u e s ( m o d i f i e d f r o m R e y n o l d s and Hower, 1970) Variations  in  S m e c t i t e (060)  d-spacing  Through  Section  Semi-quantitative Clay U n d i f f e r e n t i a t e d lllite  Mineralogy  of  Studied  Section  with  Semi-quantitative Clay D i f f e r e n t i a t e d lllite  Mineralogy  of  Studied  Section  with  Variations  in  lllite  Crystallinity w i t h  Variations  in  Sharpness  Ratios  vi  with  Depth Depth  List o f Figure  1-  Location m a p showing Axel  Figure  2-  Heiberg  Simplified the  Island,  geologic  generalized  study  Figures area o n Kanguk  Peninsula,  3  N.W.T.. m a p of Kanguk  structure  Peninsula  in t h e s t u d y  showing  4  area.  Figure  3-  G e n e r a l i z e d stratigraphic s e c t i o n s h o w i n g lithofacies i n t e r p r e t a t i o n (Ricketts ef. al, pers. comm.) and section subdivisions (zones).  Figure  4-  Arithmetic plot o f mean m a x i m u m reflectance versus d e p t h s h o w i n g r e g r e s s i o n lines a n d c o r r e s p o n d i n g r - s q u a r e d values t h r o u g h t h e 3 p o s s i b l e p o p u l a t i o n s .  17  Figure  5-  S e m i l o g p l o t of m e a n m a x i m u m r e f l e c t a n c e v e r s u s d e p t h s h o w i n g regression lines a n d c o r r e s p o n d i n g r-squared values through t h e 3 possible populations.  18  Figure  6-  Hydrostatic pressure distribution through studied section a s s u m i n g a m a x i m u m d e p t h o f burial o f 5 5 0 0 m e t r e s .  28  Figure  7-  R e p r e s e n t a t i o n of t h e t e c t o n i c e v o l u t i o n o f E u r e k a S o u n d strata at S t r a n d F i o r d a s s u m i n g a m a x i m u m o f burial of 6 8 0 0 m e t r e s .  30 depth  R e p r e s e n t a t i o n of t h e t e c t o n i c e v o l u t i o n o f E u r e k a S o u n d strata at S t r a n d F i o r d a s s u m i n g a m a x i m u m o f burial o f 5 5 0 0 m e t r e s .  depth  Figure. 8 -  6  31  Figure  9-  G e o t h e r m a l gradient determination using Lopatin's (1971) m e t h o d a n d a s s u m i n g a m a x i m u m d e p t h o f burial o f 6800 metres.  32  Figure  10-  G e o t h e r m a l gradient determination using Lopatin's (1971) m e t h o d a n d a s s u m i n g a m a x i m u m d e p t h of burial of 5500 metres.  33  Figure  11-  R A K - 2 5 r o c k clan p l o t t e d c o m p o s i t i o n triangle.  (1954)  37  Figure  12a-  Energy  dispersive  spectrograph  of M g poor/free  ankerite.  43  Figure  12b-  Energy  dispersive  spectrograph  of M g p o o r  Figure  13-  A p p r o x i m a t e ankerite c o m p o s i t i o n r a n g e CaO-FeO-MgO-C02 ternary d i a g r a m .  Figure  14a-  Energy  Figure  14b-  Energy equal  o n a modified  Gilbert's  plotted  dispersive  spectrograph  of s i d e r i t e .  dispersive  spectrograph  of dawsonite  proportions  of N a a n d A l .  vii  ankerite. on a  43 44  46 showing  46  Figure  15-  V a r i a t i o n in d a w s o n i t e  a n d ankerite  proportions  with  47  depth. Figure  16-  Figure  17-  Diagram  of  Dawsonite  paragenetic heat  sequence.  capacity function  Ferrante  e t al. ( 1 9 7 6 ) .  Figure  18-  Plot  of  L o g [ A N + /A|_] +] v e r s u s  Figure  19-  Plot  of  Log[A |• a / A * 3  Figure  20-  Plot  of  LogPco  Figure  21-  Plot  of variations  with  variations  A  A  2  v  e  r  s  u  H  68 fit t o t h e d a t a  L  o  74  LogP Q . C  75  z  gA|-| 0  7  2  in ( 0 0 2 ) 1 0 / ( 0 0 3 ) 1 7  in %illite  72  L o g [ A ^ | + 3/A+3H*]  + ] versus  s  of  illite  peak  location  6  94  in i l l i t e / s m e c t i t e m i x e d - l a y e r  clays. Figure  22-  Plot  of v a r i a t i o n s  through  individual  distribution Figure  23-  Plot  being  of v a r i a t i o n s  through  individual  distribution Figure  24-  Plot  being  of variations  illite/smectite the Figure  25-  individual  Figure  26-  Plot ratio  Plot of  Figure  28-  Summary and  i n shale  composition  paleo-environments  99  with  with  depth  and  100  illite's  differentiated. in the percentage  o f illite  clays w i t h  in illite  of  in  depth  101  and through  RAK-25.  crystallinity t h r o u g h  in t h e 1.0:1.05  n m peak  section a n d individual  diagenetic fades  section  and  105  sharpness  diagram  o f early o f clay  minerals  stage  burial  106  paleo-environments.  in P-T s p a c e .  neoformation  source  and  illite's  paleo-environments.  through  27-  with depth  with  n o n differentiated.  paleoenvironments  of variations  Figure  paleo-environments  mixed-layered  Plot of variations individual  in s h a l e c o m p o s i t i o n  111  subaqueous under  aggredation  122  humid/tropical  conditions.  Figure  29-  Summary  diagram  of d e e p  Figure  30-  Summary  diagram  of post/syn-tectonic diagenetic  environment.  viii  diagenetic  environment.  124 126  List o f  Plates  M o r p h o l o g y , T e x t u r a l R e l a t i o n s h i p s , a n d Back S c a t t e r e d E l e c t r o n I m a g e A p p e a r a n c e of D a w s o n i t e a n d A s s o c i a t e d Minerals Morphology  and  Occurence  of  Kaolinite  Morphology  and  Occurence  of  Pyrite a n d  Rutile  M o r p h o l o g y and Textural Relationships Dawsonite and Quartz Overgrowths  Between  Textural Relationships Overgrowths  Between  Ankerite  and  Textural Relationships Quartz Overgrowths  Between  Calcite,  Textural Relationships Carbonates  Between  Dawsonite  and  other  Textural Silicates  Between  Dawsonite  and  Other  Relationships  Quartz  Ankerite,  and  Acknowledgements Sincere and  for  the  way  Barnes  thanks  enduring to  for  support  the  funding  the  guidance  was  instrumental  the  opportunity  the  G.S.C.,  suggesting Drs.  Ryan, helped would  Forman to the  my  of  the  me go for  were  in to  pursue  daughter, retain  my  forever.  A  reprographics  his  provided  final  members support  note  of  "expediting" during  that  was  my  Dr.  and  Financial  Engineering  Survey  of  especially grateful geology  the  grateful  extreme the  of  B.  when  by  study  and  reviews  Broster.  My  seemed  that  the  distribution  Resources  also  of  thesis son,  support this  is e x t e n d e d  I am  also  wife, Wiz, moral  and  with  for  of  needed  under  who  me  field  Calgary.  Esso  providing  Ricketts,  appreciation  in  Norris,  Brian  critical  it  Dr.  and  (I.S.P.G.)  Dr.  much  assembly  absence  provided  for  and  times  and  G.S.C. in t h e  Canada to  along  William  Geological  surplus  those  to  Logistic support  Berman a  extended  Sciences  thesis,  encountered  Bustin.  through  R.  were  this  Dr.  i n t e r e s t s in  I am  overseeing  s a b b a t i c a l leave.  Natural to  that are  Bustin's  involvement  topic.  Bustin for  thanks  a  I am  thesis  Barnes,  in  Dr.  the  early  sanity d u r i n g  patience  committee  by  Norris.  for  Marc  Additional  grant  thesis  Ainsley  frustrations  operating  my  W.C.  and  from  my  both  R.  obtained  K.  kindling  Dr.  during  provided  Dr.Donald  Bustin,  his  project  Canada  original  on  project.  was  is t h a n k e d  R.M.  and  the  to  headaches  the  project of  extended  many  overseeing  Council  additional  by  the  completing  for  Research  are  of  thesis  to  Robert  this  grateful  Canada  and  thesis for  Limited.  Note During Eureka S o u n d Formations informal Sound  t h e final s t a g e Formation  within  zones  nomenclature  new  group  the  Eureka  i n this t h e s i s .  Group  thesis t h e formal Sound roughly  D u e to the timing  it w a s n o t p o s s i b l e  strata  o f this  t o t h e Eureka  Eureka S o u n d  status a n d , t h e r e f o r e , Sound  Nomenclature  of preparation  was changed  the renamed  used  on  t o re-organize  t h e author  throughout.  xi  Group  status  (Miall,  correspond  of the change this t h e s i s  of the  in press).  .  to the  in t h e E u r e k a  t o incorporate the  has r e t a i n e d t h e f o r m a t i o n  status f o r  1 GENERAL  INTRODUCTION  GENERAL  Diagenetic sedimentology evolution  of  in that  3000 to  m  Formation  of  Eureka  changes different Sound  in  localized  heat  examine  the effects of  that  occurred  The  primary  peaks, The  primary  during  heat  looks  of illite  of  in  both  shale  Island  base  parameters  diagenesis and  the Eureka illite  and  made  Finally, to  Formation  clay d i a g e n e t i c thermal  changes  at Strand  crystallinity, s h a r p n e s s layer  to be  maturation.  chemical and  Sound  throughout  an o p p o r t u n i t y  thermal  sandstone  a  information.  area p r o v i d e  variations t o  coal  nearly  opportunity  across  for comparisons  maturation  in c o a l ,  First, t h e  w i t h an  of  make  Fiord.  ratio o f  illite  clays a n d vitrinite r e f l e c t a n c e .  are t o : and sandstone  mineralogy  and  diagenesis  studied section;  the paragenesis the geothermal  area;  Fiord  in i l l i t e - s m e c t i t e m i x e d  variations  2) d e t e r m i n e  on  include  this s t u d y  the  allows  and thermal  relates t h e s e  of  and chemical  Axel Heiberg  maturation  Fiord  of  C r e t a c e o u s - E a r l y Tertiary  S e c o n d , the abundance  at v a r i a t i o n s  considered  t h e Late  o n western  thermal  flow  the evolution  the thermal  an e x c e l l e n t d a t a  Strand  objectives  throughout  study  high  and  parameters  1) d e t e r m i n e  3) e s t i m a t e  diagenetic and  along  aspects  interest f o r diagenetic analyses.  section provides  study  depth  percentage  Fiord  c o m p l e x i t i e s in t h e S t r a n d  The present with  Strand  diagenetic parameters  flow  about  c h a r a c t e r i s t i c s of  of particular  Formation  inorganic  parameters  of  s t u d i e s are i m p o r t a n t  information  paleo-environments.  between  .  provide  along  this l o c a t i o n  examine  maturation  number  of continuous  number the  they  strata. A  Eureka S o u n d strata f r o m  and thermal  STATEMENT  of authigenic  gradient  and  minerals;  maximum  depth  o f burial  of strata  in t h e  4)  examine  t h e effect  thermal 5)  the diagenetic  shore  studied the  fluids  the present  of Kanguk  t o p of a ridge latitude,  1301 A—  Strand  The  environments.  extending  along from  longitude.  geologic  Fiord,  Formation Axel  the south 79°30'N  m  out along the  Heiberg  Island  (Figure  limb  1) T h e  of a syncline e x p o s e d  latitude,  91°30'W never  longitude,  exceeded  Peninsula showing  Geolpgical  3000  crops  Survey  Franklin ( T h o r s t e i n s o n ,  m a p of t h e study  approximately  that  Relief in t h e area  m a p of K a n g u k  District of  collected from  to  600 m.  the location  of C a n a d a  1971) should  along  Figure  of the  m a p sheet b e consulted  area.  SETTING  Eureka  predominantly  Sound  non-marine  Formation  strata o f t h e S v e r d r u p  Sverdrup  Basin  northern  margin  Basin  marine  clastic  of t h e North t h e basin  extends  American  craton  Arctic  occurring  (Balkwill,  s u c c e s s i o n is u p t o 1 3 0 0 0  for approximately  t o Late  sequence  of t h e Canadian  is a p e r i c r a t o n i c structural d e p r e s s i o n  its d e p o c e n t e r , Basin  is a Late C r e t a c e o u s  a n d nearshore  youngest  Sverdrup  Sound  and associated geology.  a smaller scale  GEOLOGIC  study were  Peninsula o n western  91°03'  is a g e n e r a l i z e d section  At  and chemical  s e c t i o n o f t h e Eureka  studied  for  pore  section was measured  79°14'N 2  from  continuous  south  has o n d i a g e n e s i s a n d  AREA  Samples of  in paleo-environment  maturation; and  model  STUDY  that c h a n g e s  1300 k m along  Eocene,  that  comprises the  Archipelago. The adjacent  1978; Miall, m thick. the north  to the  1 9 8 4 , in  press).  Regionally, the c e n t r a l part  of  Figure  1-  Location map Axel Heiberg  s h o w i n g study Island, N.W.T..  area o n  Kanguk  Peninsula,  4  _  -  u  CO  U.  «  c o  Z  C  CS  — c o  E  to E k_ o u.  o  a z  III  co  ~  o  o u.  w  E  £  a o CO  m to  X  O  4-inoB3Bt*J3-|  t/> o a  Foi  ^  •a  c <1)  **  CO 3  a —I  to E  Q  to  I  o  1 ~ 1  °  *~ to c  o u.  pu  ID  c  3  o  o  cn  LL  CO  O  CO  o  111  3  up  to  o 9 3 Ol  .  c CS  CD 1-  f- 3 I 0 X 0 U S> 0 — - | - «  Figure  2-  Simplified g e o l o g i c m a p of Kanguk Peninsula s h o w i n g the g e n e r a l l i z e d s t r u c t u r e in t h e s t u d y area ( m o d i f i e d from Thorsteinson, 1971).  E  the  Archipelago.  (Visean)  t o Early Tertiary  Geosyncline cratonic and  Basin's  to  uplifted  sediments  derived  (Balkwill, been  The  studied  the  framework  and  corresponding  Sound  Formation  basal  within  margins  Orogeny  7985,  margins  The contact has b e e n  into  Figure  Sound  dominated  disconformity overlying dominated comprise  between  strand  delta  plain.  shale.  facies o v e r l i e  sandstone-shale  wave  3 outlines  dominated  shales  shale  of the  sandstone  sequences  Each c o a r s e n i n g  stained  stratigraphy  a n d the overlying  as a n i n d i v i d u a l unit  marks  Eureka unit.  characterize upwards  prograding  d e l t a facies  form  section. The  of t h e first m a j o r  unit  lobe  of  a major and the  1 0 2 0 m o f t r a n s i t o n a l a n d fluvial  sequences  delta  the general  of the studied  dominated  T h e entire  ef al. (1975)  written pers. comm.) w h i c h  shale. T h e s e  upward  structural  different  235 m of marine  iron  Approximately  coarsening  bay subdelta-lobes.  t h e underlying  A thin  t h e marine  by Meneley  of  Formation.  t h e t o p of t h e wave  2 6 5 m o f marine  interdistributary between  delta  o f t h e Basin (Balkwill  t o Ellesmerian  sandstone-shale  t h e first 5 0 0 m o f s e c t i o n is i n t e r p r e t e d  a wave  a n d east  a number  the Kanguk  upwards  Paleozoic  (Devonian—Mississippian) and  ridge.  interpretations  s e l e c t e d at t h e b a s e  l i t h o f a c i e s of t h e E u r e k a  Franklinian  from  tectonic  (7985,  b y approximately  5 0 0 m of c o a r s e n i n g  i n part  roughly  positive  discussion.  between  Late  are reported  divided  paleo-environmental  in age from  written pers. comm.) T h e S v e r d r u p '  correspond  by Ricketts a n d M c l n t y r e  is m a r k e d  derived  t o the south  b y an intermittently  for the following  Formation.  Approximately the  terrains  section has b e e n  of the section  Kanguk  from  1978). T h e n o r t h e r n  paleo-environments  base  b y t h e Ellesmerian  a n d eastern  defined  B a s i n range  deposits  1 9 8 0 ; Ricketts a n d M c l n t y r e ,  southern  have  of t h e Sverdrup  a n d represent  strata  Bustin,  belts  Sediments  d e l t a i c a n d t r a n s i t i o n a l facies which  represent  1 0 2 0 m represents a n d overlying  a transitional  fluvial d o m i n a t e d  facies delta  AGE  H E I G H T A B O V E B A S E (Metres) GENERAL STRATIGRAPHY ROCK STRATIGRAPHIC UNITS IN T E R V A L T H I C K N E S S (Metres) PALEO-ENVIRONMENT LITHOLOGIC DISCRIPTION 1  1  >  2780  < ICC  111 770 DC LD  o  Interbedded fine to medium grained quartz arenites, coal (vitrain) and dark grey, friable shale; sandstones are commonly crossbedded and contain abundant chert and organics; shales are commonly coaly; sandstone cements include dawsonite, magnesium-poor ankerite, siderite, calcite, and kaolinite; dawsonite proportion generally increases toward top of section; segment consists of approximately 30 finingupwards sequences commonly capped with coals; fining upward packages range from 2 to 15 metres in thickness; coal seams are S3 metres in thickness.  2020  1020  CO 3 o UJ  Fine to medium grained quartz arenites interbedded with dark grey, friable shale; sandstones are well indurated and poorly to moderately sorted; shales consist primarily of kaolinite, illite and some chlorite; major sandstone cements are magnesium-poor ankerite, calcite and kaolinite; calcite proportion decreases toward top of section; minor coal seams of predominantly vitrain are present; section consists of approximately 45 coarsening upward packages ranging from 5 to 25 metres in thickness.  1000  o <  Moderately friable carbonaceous shale; blue-grey on weathered surface; minor sandstone horizons occur through out zone.  265  r-  UJ  a. o rr ui a. a. 3  500  Interbedded very fine to medium grained, poorly sorted quartz wackes, dark grey siltstones and carbonaceous shales; sandstones are moderately to well indurated; shales consist primarily of kaolinite and illite.  235 235  Interbedded dark- grey shale shale is moderately friable. 1  Figure 3-  and  Ricketts and Mclntyre (pers.  siltstone;  comm., 1 9 8 5 )  Generalized stratigraphic section showing lithofacies interpretation (Ricketts et al, pers. comm.) and section subdivisions (zones).  systems.  T h e final 7 7 0 m o f t h e s e c t i o n  upward These  sequences lithologies  commonly represent  Beaufort  Formation  although  it is n o t p r e s e n t  Locally, plunging 1971 the  part,  Gravity Sverdrup  Basin  confirmed however, support  Thorsteinson  o f a fluvial d o m i n a t e d  overlies t h e Eureka  broad  t h e structure  occur  over  (Trettin,  much  delta. T h e Formation  originally  doubly  1972; Thorsteinson,  and DeMille, 1964;  7985,  suggested  halite a n d , infact, later  o f halite i n t h e s u b s u r f a c e .  trending  o f t h e area a n d a r e , f o r  1 9 7 8 ; Ricketts a n d M c l n t y r e ,  t o find  deposits.  Sound  northwesterly  t h e axes of anticlines ( C o u l d  written  that  studies  Previous  field  direct o r indirect evidence  o f halite c o r e s  (1964),  Stott  (1977),  Balkwill  (1985,  written  pers.  pers.  comm.).  t h e diapirs  ofthe  b y Davies  (1973)  investigations,  in outcrop t o  i n t h e diapirs.  analyses  determined  (1969),  that  Balkwill  et al. (1982),  Fiord  Sound  Formation  b y Fortier. et al. (1963),  comm.).  at Strand  palynological  of t h e Eureka  is d e s c r i b e d  Bustin  have  dominate  with  accretion  of fining  area.  et. al. ( 1 9 6 3 )  unable  stratigraphy  Islands  Formation  a n d vertical  Peninsula,  diapirs  of a repetition  WORK  The Arctic  been  the presence  PREVIOUS  along  may be cored  the presence have  unconformably  evaporite  by Sobczak  coals  deposits  of Kanguk  1 9 7 1 ; Balkwill,  studies  plain  a n d synclines  localized  with  in t h e study  i n t h e area  ). C a r b o n i f e r o u s  Thorsteinson,  delta  elsewhere  anticlines  most  capped  are c o m p o s e d  has b e e n  (1985),  studies  considered  b y Ricketts a n d M c l n t y r e t h e Eureka S o u n d  Fricker  et al.  o f t h e Eureka  Maastrichtian  sediments  Balkwill  (.1975),  a n d Ricketts a n d M c l n t y r e  t h e base  (1985,  the Canadian  (1963), Tozer a n d  a n d Bustin ( 1 9 7 5 ) ,  Reidiger  In p r e v i o u s  throughout  (Bustin,  written  pers.  at S t r a n d  Fiord  Sound  1977). comm.),  were  Recent however,  d e p o s i t e d as  early  as t h e M i d d l e  Peninsula,  and. possibly  t h e base  of t h e Eureka  Santonian-Early  Campanian  Shenoceramus  ci.  a number  Riediger was  done  Bustin's depth  abundance  mapping  of evaporite  at S t r a n d  over  the.textural rocks  for  kaolinitization  to  about  Merino used  chemistry  Islands  a 2500  thermal  fossil  m thick  from  (1977;  determined  increase  this  b y Bustin  in R m a x  with  thermal  depth  Fiord.  exists  0  phenomenon  high  and  in press)  s e c t i o n at S t r a n d  of t h e coal.  Archipelago  been  in coalification levels  attributed  maturation  have  b y Bustin  n o systematic  Bustin  with  to the  conductivities  Regional  (in press)  coalification  revealed  a l o w o f 0 . 1 7 % at M a k i n s o n  of s a n d s t o n e s  f e w years. between changes  (1975),  textural  authigenic  Boles  diagenetic sodic  necessary  that  chemistry  a n d Franks  (1979)  to predict  of dolomite  t o chlorite  have  Inlet  received  demonstrated  phases  in p o r e w a t e r  relationships  of b i o t i t e  a n d shales  It h a s b e e n  of chlorite, conversion  conversion  produce  of t h e index  Formation  in t h e area w h o s e  Arctic  analyses  relationships  time.  example,  calcite,  diapirs  values vary  t h e past  information  through  at F o s h e i m  that  t o a high of  Fiord.  Diagenetic attention  east,  m a y b e as o l d as Late  o f variations  through  examined.  t h e normal  reflectance  examination  i n d i c a t e that  of t h e Canadian  vitrinite 0.70%  results  Sound  in t h e Arctic  (in press)  t h e interval  with  Formation  o n the presence  of t h e Eureka  A cursory  press)  over  interfered  levels  b y Bustin  (in  age, based  o f localities  (1985).  Sound  Further  patoontensiformis.  Coalification from  Early C a m p a n i a n .  a great  in numerous  it is p o s s i b l e a n d physical  reactions such  a n d kaolinite  (1978) also  t o facilitate t h e a n k e r i t i z a t i o n  o f calcite.  t o infer  e f al.  from  (1980), as t h e  t o chlorite a n d  a n d t h e reaction of anorthite  plagioclase.. Boles  studies of  conditions  and Hutcheon  diagenetic  deal of  predicted Recent  with  sodium  t h e fluid work  b y Surdam  (1984),  Moncure  addressed  the  of  Wescott  the  sandstone  al. (1984),  mechanics  aluminosilicar.es. quality  ef  Cotton  previously  distribution fluid  those  done  of  on  from  Tertiary  thermodynamics,  in  a general  equilibria.  Other  papers  that  those  Chave  (1960),  Siever  with  defining  phases  a "stable  involved  investigators  in  in  Papers  by  Foscolos  and  Foscolos  (1984),  literature  that  progressive Foscolos Hower  (1970)  calculating on  XRD  the  Wilson  to  assess  sandstones sense,  Texas. and  Crossey through  ef al. (1.984) the  Other  recent  (1977),  have  dissolution  t o , assess t h e  Pittman  past  to  and  ef  been  Kodama  of  reservoir  papers  on  Hurst  and  Irwin  (1974)  fluid  chemistry  relative  (1980)  proportions  analyses. C h a n g e s  in  1.0  and  and  and  White  determining  the  (1975b)  stabilities w i t h  Hutcheon  clay  chemistry  Hower ef  (1981)  other  origin  used  a  respect  to  used  authigenic of  (1965).  pore  mineral  fluids  Problems  stoichiometry  r e a c t i o n s have  ef al. (1976),  al. (1978),  Eberl  on  and  phase  California.  diagenetic  pore  locations. M e r i n o  examine  in  and  of  prompted  include  associated the  clay  many  similar analyses.  and  smectite  Srodon  of  to  and  Powell  written  other  al. ( 1 9 6 5 ) ,  avoid  Srodon  assemblages  authigenic  consider the  P o w e l l (1978),  and  porosity  east  strata f r o m  temperature  illitization of  and  of  Sarkisyan (1972),  has  of  authigenic  system"  low  the  and  d i a g e n e t i c analyses  Formation  s p e c i e s analysis  chemistry  of  used  studies  been  of  al. (1984),  (1983).  Thermodynamic have  (1983)  include  Hutcheon  ef  creating secondary  Valley  diagenesis  ( 1 9 8 2 ) arid  of  Seibert  (1984)  Hower  represent  shale diagenesis.  with  depth  Bruce have of nm  have  (1984).  illite peak  and  Bruce  changes  d i s c u s s e d by studies  relatively  from  in  by  (1978),  (1984),  Diagenetic  been  just  Taylor  fraction  smectite  shape  (1981),  and  a  Related  developed  Hancock  of  the  such  Burst  as  (1969),  Reynolds  and  sophisticated ways mixed-layered  XRD  the  clays  of based  analyses ( d e v e l o p e d  by  Weaver (1961) and Kubler (1966)) are commonly used (Foscolos et al., 1976) to index and predict diagenetic stages in strata. Clay diagenesis of the Eureka Sound Formation has been briefly examined by Bustin and Bayliss (1979) in the area of Fosheim Peninsula.  •  .  .  ORGANIC  Traditionally,  pressure  strata b y a n a l y s i n g o r g a n i c assemblages maximum been and  arid  temperature  shown  diagenetic  (pressure  1970;  maturation  once  conditions attained Foscolos  ef al.,  extracted  Clay  (Burst,  1969)  1978;  reflect b u t it h a s s i n c e  Hower  are equally  from  mineral  thought . to  1976,  clay m i n e r a l s  a n d temperature);  has b e e n  parameters.  were  ( p H , E h , c a t i o n activities,  clay assemblages  constraints  information  parameters  a c c e p t e d that  environment  environmment  unless  a n d inorganic  a n d pressure  is n o w c o m m o n l y  stable(?)  a n d temperature  ( D e Segonzac,  geochemical  of  related  MATURATION  ef al.,  1976)  as s e n s i t i v e t o t h e i r  etc.)  as t h e y  are t o t h e i r  physical  seefollowing  chapter.  A s a result,  the use  as g e o t h e r m o m e t e r s  and/or  o n the geochemical environment  geobarometers  are k n o w n  is l i m i t e d  (Hutcheon  e f al.,  1980).  The sequence vitrinite  1980;  indicator  ef al.  with  ef al.  although  retrograde  Unlike mineral  (1982)  have  shown  Fujii  ef al. (1982)  increases  temperature 0  analysis  a n d is, t h e r e f o r e ,  that  Studies R max  in t i m e  0  (after  1971;  maturation  a relatively  increases  a n d P r i c e ef al.  t h e r e f l e c t a n c e o f vitrinite. A s a result,  vitrinite  reliable  linearally a n d  a n d temperature.  o f vitrinite  Lopatin,  b y L o p a t i n (1971), D o w  (1985)  considered t o b e unaffected  in t h e H / C ratio  attained in a  reflectance ( R m a x ) of  metamorphism,  attained temperature.  increases, respectively,  (1980),  maximum  maturation  metamorphism  c o a l i f i c a t i o n is g e n e r a l l y  (1980)),  suppress  1982).  of the maximum  exponentially  the mean  a time—temperature  Middleton,  and Middleton  Hutton  for calculating t h e m a x i m u m  o f strata is b y m e a s u r i n g  not undergo  (1977)  method  a n d performing  Waples, does  preferred  Recent  have  studies b y  shown  b y pressure  that  (Hutton  a n d associated macerals m a y  if v i t r i n i t e  r e f l e c t a n c e is t o b e u s e d  as a reliable paleothermometer the variations types with  attention  must  (i.e.,  increases  in exinitic  in microlithotypes  be paid  by the investigator  component)  to  and vitrinite  depth.  This chapter the  close  maximum  examines  the studied section  depth of burial of the strata  inferences about  the thermal  and baric  for trends  in coalification,  and the geothermal  gradient  estimates  and makes  evolution of the section.  EXPERIMENTAL  Sample  Preparation  Forty samples m  of section.  R max  were  Both  kerogen  measurements  0  primarily from relative  coals  absence  from that  measurements  the  were  Coal  section  for R m a x  concentrates  (phytoclasts)  and coals  were  the upper half of the studied section  were  were  3000  examined. taken  grab—sampled at approximately 40—50 m intervals. The from the lower half of the section required  be made  collected  analysis from the approximately  0  of true. coal seams  that R m a x 0  chosen  on phytoclasts.  from approximately  Samples from  100—150  the lower  half of  m intervals.  Pellets  Coal samples were  pellets  were  prepared  initially crushed  approximately 850  using methods  with a mortar  jum. The less  than  850  to  U.S. mesh  was collected  and used  reduce  fxm fraction  larger fraction. by sieving with a 60 U.S. mesh than 60  modified  sieve.  from  the coal was then  Bustin (1977). The fragment separated  That portion  in the pellets.  size to from  that was finer  trie  A placed  1:3 m i x t u r e  of the < 8 5 0  in a h y d r a u l i c  minutes.  Once  applied  Buehler  P o l i s h i n g w a s left until with  R max  polished, hours  t h e samples  prior  immediately  to being  were  press  w a s attained  to cool  before  in o r d e r  a n d Transoptic® p o w d e r  I® p e l l e t  of 100 ° C  was allowed  measurements  0  Pneumet  a temperature  a n d t h e mixture  coal  and heated a pressure  under  pressure  the operator  to minimize  under  for 12—15  of  3.5 K P a w a s  f o r 15  minutes.  was prepared  the oxidation  left in a d e s i c c a t o r  w a s then  helium  to  proceed  o f t h e vitrinite. for n o longer  Once  than  48  analysed.  Phytoclast Pellets  Phytoclast and  Alpern  fragment 100%  (1977).  size  Shale  hydrofluoric  samples  using  were  was followed Silica  then  f o r 3 days.  product  a n d retaining  outlined  in t h e p r e c e d i n g  with  w a s next  placed  fraction.  paragraph  4  separated  the samples  silica w a s r e m o v e d followed  containing  any carbonates  tap water  Pellet p r e p a r a t i o n  Bostick  to reduce the  to remove  by leaving  o n coal pellet  from  in 1 litre b u c k e t s  rinses w i t h  coarse  modified  in a mortar  in o r d e r  removed  A n y residual  t h e fine  methods  initially c r u s h e d  a c i d a n d left f o r 2 4 h o u r s  periods. acid  prepared  were  3  T h e H C I bath  settling  were  t o 1 m m . Samples  hydrochloric  present. hour  concentrates  b y 24  in 4 8 %  by s i e v i n g t h e  the techniques  preparation.  Analytical Techniques All D2797,  samples  1980).  equipped  with  photomultiplier,  were  analysed  P o l i s h e d .pellets  in a c c o r d a n c e  were  a 50x o i l i m m e r s i o n and computer  with A S T M  procedures  (ASTM  examined  o n a Leitz M P V 2  microscope  objective,  10x ocular,  voltage  assisted  stable  data collector. T h e size  supply,  o f the limiting  aperture  used  a rate 1.515  of a p p r o x i m a t e l y was used.  recalibrated out  was 8 urn. Measurements  against  by more  Most  Fifty  R max 0  than  3 6 0 °/7  seconds.  measurements  the standard  were  taken  if t e l o c o l l i n i t e p r o p o r t i o n s  the  shale  samples.  the  theory  For a detailed measuring  reflectance  microscope  Elemental  Analysis  C  the  t w o sample  H N  elemental  vials t o e n s u r e are  indicated  One  1980).  of  analysis  o n figure  assumed  with  25 measurements.  index of  the system  of t h e optical  from  et al.  both  and redone. being  vitrinite w a s m e a s u r e d properties  and the mechanics  in  o f vitrinite,  of the  (1983).  the coals and t h e phytoclasts  to determine  being  If t h e c a l i b r a t i o n w a s  desmocollinite  low. Non-specific  description  Each s a m p l e  if variations  w a s analysed  e x i s t i n t h e H / C ratios o f  twice from  0.5%. The t w o samples  was chosen  chosen  separate  "masked"  for elemental  analyses  5.  of the methods  used  t o calculate t h e m a x i m u m  strata is L o p a t i n ' s  Lopatin's  assumptions, were  t h e strata. First,  a refractive  Model  in the studied  number  t h e s t a g e w a s r o t a t e d at  oil with  telocollinite with  were  t o Bustin  accuracy within  In a p p l y i n g  while  per sample  vitrinite r e f l e c t a n c e ,  sample  groups.  Time—Temperature  attained  refer  representative  for  taken  every  from  measured  A  Immersion  were  after  taken  0 . 0 2 % at t h e e n d of a r u n , t h e r u n w a s d i s c a r d e d  readings  behind  were  model  made  (1971)  t o the Eureka  regarding  time—temperature Sound  Second,  heat  flow  Strata  t h e t e c t o n i c history  f o r t h e sake o f s i m p l i c i t y t h e rates  t o b e uniform.  paleotemperature  a n d thermal  model  at S t r a n d a n d thermal  of subsidence conductivities  (Waples, Fiord a properties  a n d uplift a r e are a s s u m e d  to  be  constant (Lopatin,  maturation states  that  increase thus,  is  assumed  kerogen  in  1971).  to  an  of  the  constant.  maturation  temperature  defining  be  Third,  The  basic  premise  is s i m p l y  a function  will  in  10°C  exponential  activation energy  result  a  of  7  =  r  of  by  the  the  entire  L o p a t i n ' s TTl  time  doubling  relationship expressed  for  and of  range model  temperature.  the  of  An  maturation  level,  equation:  n  where, 7  =  to  temperature.  r  =  factor  f a c t o r by  increase  in  maturation  A  linear  time  temperature.  10°C  level  has  result  Lopatin's  in a  interval  equation  rate o f  fold  for  a  the  dependence  maturation  if o n e  doubling.in  index  ;  L  to  and  the  =  smallest n-index  nmax  =  largest  n-index  the  a given  i n c r e a s e in total  length  amount  = nmm  value value  of  maturation  maturity  (TTl)  ( A T ) n  <r ) n  where, nmin  each rate  maturation  every  increase of  10°C in  increase  in  value.  nmax =  increases for  a s s u m e s that  by:  TTl  of  1980).  maturation  exposed two  exponential  produces  between  been  the  r=2  (Waples,  temperature  package will  w h i c h the  of  r e l a t i o n s h i p exists  sedimentary heating  =  relates  temperature.  temperature  n  which  encountered, encountered.  of  of  time  heat. for any  any  that  a  Doubling  the  given  sediment  is  given  AT^ The  computer  (1971)  =  length  model  model;  used  expressed  of  in  as  time  this  study  of  T(t)  is t h e  deposition  temperature  and  t  being  =  rank  sub—bituminous approximately  was  (°C)  the  generally  A/high  as  time  1400  m  above  r e f l e c t a n c e values  change  in  at  the  (Fig.  both  the  improved points. 0.172  of  5)  R max 0  AND  in t h e  integrated  form  of  interval  /'.  Lopatin's  dt  of  time  with  t  being  0  the  time  DISCUSSION  when  and  t h e . data  example, the  the  semilog  versus  is  r  2  treatment  and  the  0.176  were  tested  two  it w a s  represent data for  found  two  assuming the  At decrease  Whether  this  determine  data w e r e  in t h e  B.  apparent  arithmetic  separate  from  later.  to  Both  the  phytoclasts  treatments  for  discussed  case,  second  to  is an  is  gradients.  each  and  assumed  values  not  curves  and  volatile b i t u m i n o u s  coalification gradient.  real o r  In  high  increasing depth  section there  measured  analysed.  were  to  the  depth  the  arithmetic  C  of  population  the  increase with  in t h e  population  upper  to  base  change  for  were  a single  semilog  For for  plots  first  coals  the  coalification gradient  number  representing namely  temperature  present.  bituminous  and  coalification gradient  semilog  a function  found  volatile  in t h e  fitting'  the  in  Gradients  Coal  A  uses  sediment  f2(T(t)-105)/10  RESULTS  Coalification  by  follows:  TTI where  spent  the  (Fig.  4)  treated  as  populations  of  lower that  'best and  points;  population. curve—fits  For  were  separate  populations  of  a  population  were  arithmetic  single  treatment.  By  assuming  17  ^—*v~t  3000  \  \ * \  A=C0AL -|- =PHYT0CLAST  ^  2500  \»  \ 2  \  \  4  \  2000 -  © to  CO  \  4 9 9  \  +  r :0.340  +  2  <  -  \  \  A  1500 -  2 : 0  \ V  m  © > o  '  \  \ \  N  \  \  N  \  cp  N  X  \  1000  \  +  \  \  \  N  +  \  \ N  500 -  i  1  0.5  0.4  1  i  1  1  1  r  0.6  1  0.7  1  1  1  T 0.8  1  R max 0  Figure  4-  A r i t h m e t i c p l o t o f m e a n m a x i m u m r e f l e c t a n c e versus d e p t h s h o w i n g r e g r e s s i o n lines a n d c o r r e s p o n d i n g r-squared values t h r o u g h t h e 3 p o s s i b l e p o p u l a t i o n s ( u p p e r p o p u l a t i o n c o n s i s t i n g primarily o f c o a l , l o w e r population consisting o f phytoclasts, single p o p u l a t i o n consisting of entire section).  1  1  0  0.1  0.2  0.3  0.5  R max Q  Figure 5-  Semilog plot of mean maximum reflectance versus depth showing regression lines and corresponding r-squared values through - the 3 possible populations (upper population consisting primarily of coal, lower population consisting of phytoclasts, single population consisting of entire section).  1.0  two separate populations, the r  2  values for the semilog plot were 0.484 (upper  population) and 0.318 (lower population). Corresponding arithmetic values were 0.49 and 0.34,  respectively.  Statistical Considerations  Given the low coefficient—of—determination (r ) values and relatively small 2  sample sizes, depth and thermal modelling of the studied strata using any of the above mentioned curves yield results with a good deal of uncertainty. The following sections, therefore, attempt to minimize this uncertainty by adjusting, where necessary, the various gradients such that they are in relative agreement with published local tectonic models. A literal interpretation of the r  2  statistic states that for an r  2  value of 0.49  (i.e., as seen in the arithmetic fit of the upper population) only 49.9% of the variability in R max values can be explained by the depth values. From the present 0  study this suggests that, at best, 50% of the variability in R max must be explained 0  in terms of some other variable(s). If the entire section was considered (r = 0.172, 2  semilog) at least 82% of the variability in R max would have to be explained in 0  terms of some variable other than depth. The following sections discuss a number of factors which are believed to contribute to at least some of the remaining variability in observed R max values. 0  Consideration  of  R max  A r i t h m e t i c fits fits f o r a n y g i v e n England  (1984)  histories  than  were  found  basement R max  have  Thermal rapid  did not extend below  created  sediment  loading  presence  hot  diapir  by  Balkwill  to  such  the rapid  similar from and  local depth  into  source  affecting  (1973) w h e r e  their  different  tectonic  in t h e s e  other  disequilibrium  of R m a x  conditions  were  sediment  Fiord  between but was  suggested  residence  other  accumulation  residence  to  times.  but for reasons  sediment  areas  with  values  0  A t Strand  diapirs  times  sediment  than  rates  were  were  deposition  while  the diapir  remained Upon  would,  resulted  is  b e transfered heat  attributed between  i n part  theoretically,  of sediments.  unrooted,  cease and the temperature  as i n d i c a t e d  disequilibrium  and unloading  becoming  is n o t u n i q u e  t o have  to  area. T h e c o n c e p t o f  thermal  and believed  would  related  t o diapirs  however,  rooted  likely  adjacent  of a diapir w h i c h  as r a p i d  is m o s t  in t h e s t u d y  of hornfels  Fiord,  is s u s p e c t e d  rock.  if it exists,  surrounding  effect  the surrounding  Fiord,  evaporite  and unrooting  would  Such  infilling a n d s h o r t  the formation  a n d the coals  at d e p t h  range  semilog  in studies by  the arithmetic relationship  t h e full  at Strand  of the numerous  emplacement  over  than  1978).  a phenomenum.  diapirs  In a d d i t i o n ,  thermal  1 2 0 m p e r m i l l i o n years),  disequilibrium  intrusions  where  as, a l t h o u g h  (Balkwill,  the  i n areas  better  reported  coalification gradients  and unloading  generally  been  considerably  at S t r a n d  (approximately  Thermal  basin  have  may b e possible  relatively h i g h long  t o be consistently  i n areas w i t h  0 . 3 5 % reflectance.  by rapid  disequilibrium  found  In g e n e r a l ,  flux w a s s u s p e c t e d .  t o values  been  (1985)  Fiord.  Depth  Similar f i n d i n g s  t o be arithmetic only  heat  restricted  interval.  and Moffat Strand  with  of t h e data w e r e  depth  and depth  0  Distribution  0  have a  Heat through  conduction  in t h e i s o l a t e d d i a p i r  from  derived the diapir from the would  drop.  This  theory  separation gradient  distance  in  rapid,  attained. The  an  Another  factor  away  from  coalification  as  with  however, kinetics  and  underlying  of  findings  that  dependent  than  completion  in  by  the  time  only  the  as little  these  also u s e d by  during  Price  the  versus  increment  were  depth  realized  geothermal  may never  to  to  be  10,000  be from  remains  to correspond  produce  explained  explained  of  the  a  strongly  reactions  a time  d e a l of time  line  t o a constant t e m p e r a t u r e  first  order that  (1983)  temperature  may proceed  vitrinite  to  r e f l e c t a n c e is dependant,  controversy  as  to  dependent  geothermometer, straight  suggested, •  r e a c t i o n . Barker's  than  rather t h a n  predict  kinetics p h e n o m e n a  short,  rather  of  log—linearly  have  using  defined  terms  reaction kinetics t o Barker ( 1 9 8 3 )  In  the  in  rate varies  'multi—order'  a good  r e f l e c t a n c e is an a b s o l u t e only  be  0  maturation  an a b s o l u t e ,  the coalification  K a r w e i l (1956)  (R max)  and  years.  of  in e x a m i n i n g  p r o c e s s is m o r e  a n d that  nevertheless  would  seen  could  early s t a g e s  r e f l e c t a n c e is an a b s o l u t e  0  be  first o r d e r  likely a  whether  R max  may  (1983)  maturation  as 1,000  authors  If  that as t h e  coalification gradient  the deviation  maturation  There  geothermometer.  find  process was  rocks  coalification process.  geothermometer. vitrinite  If t h e  of the  p r o c e s s is n o t p r o p e r l y  thermal  previously  to  process w h i c h  c o a l i f i c a t i o n is m o r e  is a f u n c t i o n  who  increases, the  surrounding  deviation  s t a t i n g that  the maturation  state  with the  distribution  Recent studies  that  its s o u r c e  diapir decreases.  contribute  Lopatin (1971)  level. that  believed  may  reaction kinetics,  maturation  the  W a l l i c k (1966)  distribution.  a time/temperature  temperature.  from  be a general  a log—linear  assumptions  Selig a n d  equilibrium  which  fundamental  first o r d e r  overlying  thermal  log—linear  by  i s o l a t e d diapir  result w o u l d  predicted  gradient  of  the sediments  sufficiently  the  is s u b s t a n t i a t e d  plo.t if  a  log—linear each given  increment.  plot  of  depth  This w o u l d  only  occur  under  throughout thermal  conditions of  Fiord  gradient  s e c t i o n is a p o o r  of  An enigma  of t h e R m a x 0  paragraph,  geothermal  and, therefore,  heat  flow  uniformed  gradient  through the  a log—linear coalification  and apparently  w a t e r s as b e i n g  reasons.  shifts  t h e primary  This  theory  First,  is g o o d  the R m a x  structural  0  associated geology.  in s u p p o r t  of  minor  have  been  a r e a is h i g h l y  Third,  suggest  a thrust  to produce  a thrust  fault w i t h  the observed  migration  diagenesis  explained  between  which may  through  in t h e R m a x  of such a structure was observed  are a l s o  in other  units  study  both  above  Second,  comm.).  0  findings  for a n u m b e r of  a considerable  shift  shift in  faults. T h e o c c u r r e n c e  improbable  fault  that  heated  the observed  factors  o f thrust  below of  in t h e c o a l i f i c a t i o n g r a d i e n t  (Ricketts a n d M c l n t y r e , pers.  would  values  0  lithostratigraphic continuity  break  e v i d e n c e that  be required  offset  of R m a x  by sandstone  1985) by the presence  fault in t h e s t u d y  there  number  a second  shift i n t h e c o a l i f i c a t i o n  in e x p l a i n i n g  is s u p p o r t e d  section. A  reveals  recognises fluid  factor  in coalification gradients  1983; England,  thrust  depth  distribution  discussion  discussion.  below  evidence  random  in t h e f o l l o w i n g  a major  distribution with  b e c o n s i d e r e d — h o w can the apparent  the observed  (Bustin,  would  and uniform  Gradient  to producing  Similar  or  Coalification  are d i s c u s s e d i n a later  included  no  in  coalification gradient.  areas  a consistent  assumption  b e explained? The following  contribute  and  must  at 1 4 0 0 m  diapir—derived  of  Shifts  examination  which  gradient  which  gradient  is n o t t o b e e x p e c t e d .  Consideration  the  geothermal  t h e s e c t i o n . A s is d i s c u s s e d in t h e f o l l o w i n g  conductivities and, therefore,  Strand  depth  a constant  t h e r e is  the studied amount  of  gradient.  o r has b e e n  section  throw N o field  previously  reported  in the literature..  Lithology and fracture primary control model  o n the observed  proposes  selective  stratigraphicaliy adjacent Nurkowski (1984) significant effect better aquifers  rather  than  in the coalification gradient.  horizontal migration of heated  permeable  have suggested  than shales  pore  that the heat carried  lithologies with the greatest shales. Again,  were would  seams  serve  as  extracted) the be observed primarily in  permeabilities; specifically, fractured  if thermal  be a shifting of the upper  (1984) and  by ground waters has a that coal  diapir—derived waters  The present  fluids from diapirs into  lithologies. Studies by Hitchon  (from which the phytoclasts  of the heated  the tight  result would  shift  o n the maturation of vitrinite. Given  maturation effect vitrinite from  controlled migration of fluids is believed to exert the  equilibrium was not attained,  curve  toward  higher reflectance  coals the  values and  a deviation from a log—linear curve.  The present and  phytoclast  sample support  is of a chemical, been  regarded  from  coals  studies  that there 0  from the elemental  analyses  the idea that the offset compositional, nature.  In the past,  is n o appreciable difference  values  obtained from  Increased  exinitic  in the vitrinite can result  reflectance.  Although  matured  also suggest  to have a  components  in R m a x 0  associated  in suppression  d o support  preferentially as a result  gradient  it has generally values  phytoclasts,  and even increased 0  than the phytoclast  extracted  however,  shown that  of R . In the present  H / C ratio  higher  these findings  that oxidative  in coal  (Table 1) of the coal  in the coalification  by Price ef al. (1985) and Fuji ef al. (1985) have  sample was found  have  rather than  and R m a x  always true. H/C  study's results  this is not proportions of  study the coal of  lower  the idea that the permeable  of being in contact  degradation of the coals  with heated  associated  with  recent  coals  waters  they  the horizontal  TABLE  C  H  N Elemental  1  Analysis of  Organic  Matter  (%)  Sample RAK-62-25 RAK-27-25  migration  of w a t e r m a y h a v e  . A final come  from  (Gretener, thermal  contribution  1981).  When  conductivity  of a package  lithotypes  occuring  below  10—20%  sandstone,  two  sedimentary  packages  a n d shale  (assuming,  is a linear c o m b i n a t i o n  (Moffat,  1985)).  Assuming  would  have  a bulk  60—65%)  packages  would  than  shale  that  thermal  (35—40%)  of approximately produce  2.8—2.9  difference  of u p t o 20°C/km  are c o n s i d e r e d , based  of course,  a n average  o n t h e relative  that  t h e average  this is t h e c a s e , 80—90%  shale  conductivity of in c o a l  thereby  thermal  This  in t h e g e o t h e r m a l that  the section and only  1.8—2.0  about  W/m°C.  and sandstone  producing  W/m°C.  if it is a s s u m e d  of section  of t h e c o n d u c t i v i t i e s o f t h e  1400 m, c o n s i s t i n g of approximately  conductivity  conductivities  in t h e c o a l i f i c a t i o n g r a d i e n t m a y  conductivities of the t w o segments  1 4 0 0 m , t h e s e c t i o n is c o n s i d e r a b l y r i c h e r  (approximately thermal  the offset  may be assigned to the package  conductivity individual  in thermal  complete  of sandstone  H/C 0.079 0.079 0.067 0.068  H 1.39 1.37 1.01 1.02  occurred.  to producing  the differences  proportions  Above  H_ 3.51 3.50 4.74 4.85  C 44.09 44.14 69.95 70.41  an average  difference gradients  heat  flow  bulk  in t h e r m a l between the  is u n i f o r m  throughout  the  s e c t i o n . If  stratigraphically envisage heat  an  flow.  likely a  offset The  rather  than  increase  The  0.127  population  Paleo—depth  calculated  of  of  model  the  resulting  shift in  of  section  the  the  model  from  =0.484)  the  is  possible  to  non—uniform  horizontal  coalification gradient  p e r m e a b i l i t i e s of  the  is  more  two  section.  used  rate (i.e.,  which  it is  from  coalification gradients  maturation  2  the  diapir,  later  R max)  determined  in this  with  0  from  study  increasing  assumes  from  a  an  temperature  studied section was, therefore,  as d e t e r m i n e d  the  (i.e.,  found  s e m i l o g analysis  of  to the  points.  Burial  extrapolating the level.  value  of  0.15%  or  0.20%  value  of  0.15%  R max  0  t e c t o n i c history  (r  zero—maturity  R max  observed  p r e — t e c t o n i c thickness of by  beneath,  is t h e  conductivities and  coalification gradient 0  The  the  in m a t u r a t i o n  %logR max/km  source  coalification gradient  the  because the  heat  than  thermal  plots  depth).  a  the  primary  rather  is that  decided to  exponential  to  the  result of  to,  It w a s semilog  upper  in  function  packages  be  adjacent  the  0  v a l u e s as  low  as as  sediment  from  coalification gradient  This  zero—maturity  (Middleton,  1982).  a previous  study  0.15%  do  a to  s e c t i o n of a  l e v e l usually The by  depth  which  study  B u s t i n (in  to  uses  a  press) has  the  Canadian  been  corresponds  corresponds  present  occur throughout  strata has  an  R max 0  zero—maturity  determined  that  Arctic  Archipelago.  Paleo^Jepth sediment (Figure  9).  may  have  of  burial  been  This w o u l d  calculations determined  eroded  suggest  a  from  above  the  that  as  studied  pre—tectonic thickness of  much  section the  as  4100  m  at S t r a n d  Eureka  Sound  of  Fiord  Formation  at S t r a n d  Previously sediments  are  Point where  values  A t Strand  meters  o n his  based  for  (1977) m o d e l .  a  The  coalification  position  done  rather  hundred burial  if t h e  maturation  flow  the  o f burial  was  determined,  which  gives  better  agreement  the  base  it w a s  the  was  present  b y the  and  b e estimated o f the  o f burial, f r o m  the  lower  more the  non—corrected  value  depth of  thermal realistic v a l u e  the  m . This  shallowest  o f 6800  adjusted  m with  for.  corrected  coalification gradient  which  position,  eight  possible  diapir-Wnduced  was  the  Sixty  calculated t o b e approximately  thickness o f 5200  b y shifting  coalification  only  diapir.  by examining  Bustin's  corresponded t o  that  maximum  3200  findings,  with  s e c t i o n . This  perhaps  upper  study's  maturation  of 0.50%  with  m from  o f a general  agreement  assumed  therefore,  Bustin (/n  o f approximately  o f the  absolute  A minimum,  depth  pre—tectonic  the  affected  and,  positioning  depth  than  was  flow  o f burial c o u l d  adjusted  thickness  value  May  t o determine a because  i n partial  Sound  and  determined.  diapir—induced  gradient  represent  minimal.  The  Peninsula  unable  area. T h e  are  for  m above  gradient  anomalies.  o f the  post—Eureka  o f u p t o 6000  coalification gradient  heat  the  Eocene  0  corrected  of high  attributes  a total  a Mid  until a n R m a x  upper  would  o f burial  studies w e r e  corrected  left  o f the  absolutely  depth  which  the  o f burial  were  depths  maturation,  section o f 1400  effects  maximum  gradient  t o the  slope,  metres  was  Fosheim  a pre—tectonic thickness  estimated  gradient  t o align  the  therefore,  from  and  m , respectively, were  previous  diapir—induced  In m o d e l l i n g  than  (1977)  paleo—reconstruction  curve  in the  in order  gradient.  the  the  2500  Formation  (1977)  Bustin  e f al.  and  Fiord  and,  lack o f d a t a .  the  b y Bustin  o f 3500  gradient  if c o r r e c t e d  pretectonic thicknesses of syn—  Eureka S o u n d  Island.  coalification  o f u p t o 6800 m .  reported  reported  press) r e p o r t s Meighen  Fiord  t o heat  possible  2500  meters,  value  is  previously  in  published  paleo—reconstructions  Maximum  A the  Pressure  Considerations  number  of assumptions  overlying  section. and  because  the modelled  shearing  stresses  is e q u a l  acceleration  to  at d e p t h  d u e t o gravity.  unknown  t h e hydrostatic  sediment  consisted  1967)) 4100  and second m  depth  hydrostatic. there  (Hobbs  p g h where  p  would  indicate  that  M P a f o r pure section  3  shale)  ( p = 2.25  at 5 2 0 0  lie s o m e w h e r e  pressures  between  pressure  that  the 5200 ( p = 2.5  m depth,  1967)).  t w o values  at t h e 1 4 0 0 m sandstone. shales  of t h e Eureka  sandstone).  at 2 5 0 0 (Clark,  (Figure mark  Values  depth  m of  c m  3  (Clark,  then  3  at  that t h e  t h e actual  6). T h e results ranges  from  Formation  s e c t i o n are  2.38 c m  Given  and sandstones,  Sound  at  r o c k a n d g is t h e  1 0 % porostiy 3  entirely  related  pressure  of t h e t w o l i t h o l o g i e s ,  these  to 100 M P a f o r pure  a n d 127 M P a (pure  c m  combination  hydrostatic  at t h e b a s e  with  to be  of the removed  assuming  m depth  are 5 5 M P a a n d 61 M P a f o r p u r e  Maximum  of t h e o v e r l y i n g  of the  that t h e  o f all c r e e p  T h e hydrostatic  of  (Balkwill, 1978)  the pressure  a relaxation  e t a / . , 1976).  1 0 0 % sandstone  a n d 2.42 c m  shale  has b e e n  high  it w a s a s s u m e d  By m o d e l l i n g  w a s calculated  of 1 0 0 % shale  t h e total  waters  distribution  at t h e b a s e  w a s relatively  As the lithologic proportions  actual strata c o n s i s t e d o f s o m e pressure  a n d pressure  t h e pressure  rate  is t h e d e n s i t y  pressure  first o f  t o estimate  is d i a p i r — d e r i v e d  was wholly that  the density  accumulation  source  it is a s s u m e d  Basin.  regarding  it p o s s i b l e  sediment  heat  at d e p t h  hydrostatic  (h)  strata m a k e  First,  pressure  of the Sverdrup  f r o m 95  t h e t o p of t h e respectively.  are 1 2 3 M P a (pure  28  Hydrostatic 40 0.0 -*-  Figure 6-  60  Pressure 80  in 100  Megapascals 120  Hydrostatic pressure distribution through studied section a s s u m i n g a m a x i m u m d e p t h o f burial o f 5 5 0 0 m e t r e s . Pressure brackets w e r e calculated using saturated bulk d e n s i t i e s f o r 1 0 0 % p u r e s a n d s t o n e a n d 1 0 0 % p u r e shale.  1 40  Paleo—geothermal  To  model  Gradient  the paleo-geothermal  history  of t h e strata m u s t  Sound  Formation  subsidence shown and  occurring  unit  Sverdrup  geothermal at S t r a n d  depth  burial.  of  Predicted the above  Formation  (corrected). . The Figures  The  70 M a with  uplift  paleo—temperature gradient  (i.e.,  w a s 75 ° C  1400 m  from  Going  terminated  from  gradient  a least  corresponding  squares  Lopatin's  calculated geothermal where  Fiord  based  Sound  a n d 10  a r e a is a l s o  regression  plotted  gradient analysis o f t h e (logCG).  is as f o l l o w s :  r = 0.98 2  gradient,  the maximum  t h e shift o c c u r s  of t h e section)  Sound  model  l o g coalification gradients  at Strand  used t o  using the corrected  for the calculated geothermal  at t h e p o i n t  t h e infilling o f  of t h e Eureka  the study  plain)  down  of t h e Eureka  9 (non—corrected) from  c e a s e d , as  d e l t a strand  comm.).  method)  generated  in figures  by performing  t h e base  infilling a n d  7 outlines t h e t e c t o n i c history  gradients)  G T G and l o g C G  the previously  basin  dominated  and erosion  GTG = 160.40*(logCG)-2.0411,  Using  strata o f t h e E u r e k a  8 outlines t h e t e c t o n i c history  numerical value  t h e burial  6 2 a n d 66 M a d e p o s i t i o n  Lopatin's (1971)  are s h o w n  ( G T G ) versus  method  t h e basal  d e p o s i t i o n a l a n d t e c t o n i c history  Fiord  between  Fiord  2 (the wave  Figure  (using  Figure  was determined  relationship  Fiord.  calculated geothermal  gradient  Lopatin's  (Ricketts a n d M c l n t y r e , pers.  (geothermal  9 a n d 10. A  (18.3°C/km) geothermal  Fiord.  mentioned  at Strand  unit  35 M a regional  gradients  curves  A t Strand  approximately  between  Basin at Strand  using  35 M a . B e t w e e n  shale)  at a p p r o x i m a t e l y  Formation  in  u p until  3 (the marine  calculate  on  deposited  by the disconformity  section the  were  be known.  gradient  a n d 45 ° C  attained  in t h e c o a l i f i c a t i o n at t h e t o p . T h e  Tectonic History Ma BP  7.0 J  Figure 7-  Representation of the tectonic evolution of strata at S t r a n d Fiord a s s u m i n g a m a x i m u m burial o f 6 8 0 0 m e t r e s .  Eureka S o u n d d e p t h of  Figure 8-  Representation of the t e c t o n i c e v o l u t i o n of strata at S t r a n d F i o r d a s s u m i n g a m a x i m u m burial o f 5 5 0 0 m e t r e s .  Eureka S o u n d d e p t h of  Figure  9-  G e o t h e r m a l g r a d i e n t d e t e r m i n a t i o n u s i n g L o p a t i n ' s (1971) m e t h o d a n d a s s u m i n g a m a x i m u m d e p t h of burial of 6800 metres.  Corrected Geothermal Gradients % R o Ma x 0.1  Figure  TO-  0.2  0.3  O.S  1.0  2.0  3.0  C e o t h e r m a l gradient determination using Lopatin's (1971) m e t h o d a n d a s s u m i n g a m a x i m u m d e p t h o f burial o f 5500 metres.  5.0  maximum TTl  model.  14°C 1400  m  mark.  R max)  temperatures  D i s c r e p a n c i e s in t h e t e m p e r a t u r e  to within  ±1  Lopatin's geothermal basic differences  to a number (i.e.,  gradient  will  using  Lopatin's  Barker's (1983) (0.80%  determined  o f f a c t o r s . First,  r =0.48) 2  values  m e t h o d are  R max) 0  from  of  burial v a l u e  value  obtained  a l s o b e s u b j e c t e d t o a d d i t i o n a l error. of  Barker's ( 1 9 8 3 )  discrepancies in t h e reported  (1971)  at t h e  the t w o  considering the poor  the depth  k m . A s a result, t h e t e m p e r a t u r e  in the assumptions  obvious  using  at t h e t o p o f t h e s e c t i o n a n d 8 3 ° C  0  c a n b e attributed  produce  of the section was 95°C  maximum  t h e coalification gradients  at b e s t  will  at t h e b a s e  Corresponding  (0.50%  models from  temperature  a n d Lopatin's  temperatures.  fits  is a c c u r a t e from Second, the  (1971)  models  SANDSTONE  An used  to  examination  determine  chemistry  in  the  information  samples  and  dispersive XRD  the  phases  the  of  the  was o b t a i n e d  based  of  the  on  from  both  of  Mm  DIAGENESIS  authigenic phases  cements  and  Formation  SEM—EDS  of  estimate from  gold  thin sections. Mineral  optical examination  examination  <20  of  Eureka S o u n d  optical examination  was  AND  relationships b e t w e e n  paragenetic sequence  spectrometry)  analyses  textural  sandstones  Textural  coarser  of  PETROLOGY  of  of  thin  coated  of  sandstones.  the  the  Strand  Fiord.  coated,  fractured  identification  polished  thin  been  fluid  of  sections, SEM—EDS  carbon  fraction  has  sections  the (energy and  RESULTS Petrology  Petrology of  16  thin  of  the  s e c t i o n s of  Eureka highly  Sandstone  samples  from  sandstone  horizons  without  procedure  was  lower  part  done  of  the  intervals  or  of  isolated  horizons  point  significant  grain  calculated  by  lower  exposure was  of  the  and  not this  any  section were  of  grained  sandstones  degree  of  consolidation permitted.  grains  obtained points  used  analysis of per  sample  (Solomon, per  sample  analysis  sandstones.  interval. This  samples were  samples  the  collected from  m,  400  grid  medium  from  1000  Modal  was  and  relative scarcity  study.  population  of  was determined  specific sample  as t h e  of  400  m  done  a minimum  identifying  1000  observing  because  specifically for  counting  the  Formation  c o n s o l i d a t e d , fine  section. Above  m  collected  as  Sound  taken  at  major  sampling  through  the  approximately Detailed  sampling  in this  study  were  not  framework  grains  was  done  to  that  1963).  ensure  Cement  as e i t h e r  a  and  80  by  statistically porosity  framework,  pore,  were or  cement. shapes  Roundness of  25  Rittenhouse of  25  for  grains  (1943).  grains  per  SEM—EDS  chosen  for  and  are only  outlines grains clan  sample.  the  while  counted from  the  per  et al.,  majority  of  altered  in t h i n  grains  (RAK—40)  mature range  the  more  16  on  to  quartz  of  11  varied  the  (1963)  measuring  compositionally  revealed  the  samples  complex  of  the  that  15%  each  along  sample  using  Gilbert's  all  samples  approximately  average  5%  section.  bulk  and as  is  the  and long  were  axis  chosen  samples  of  are  clay  in  with  the  were  studied  quartz  arenites,  its matrix.  the  Table  number  of  of  rock  composition  the  (1954) c l a s s i f i c a t i o n  monocrystalline on  of  the  the  samples,  2  scheme  detrital  quartz  submature  from  0.3-0.6  ( m o d e = 0.5)  (Krumbein  1943),  respectively.  Grain  roundness  is r e f l e c t e d  appears  to  by  sorting  improve  of  is  Chert  through  1963) primarily  as t h e  the  solution  and  commonly  1800  m  concavo-convex between  both  samples  are  sphericities w h i c h 0.53-0.91  moderate.  sorting  with  floating  lower  Texturally,  and  average)  included  from  pressure 1964).  on  grains  primarily  roundnesses  ef al.,  also  display  (Adams,  grain  Chert,  c o n t a c t s range  however,  grains  framework  material.  primarily  amounts  of  grains.  grain  (occurring  moderate  (77%  framework  Quartz—quartz  contacts of  average)  to  and  comparing  ef al.  texturally  demonstrates  framework  contacts indicating  overgrowths  sphericity  Krumbein by  Fifteen  of  section  sutured  section). The  (Rittenhouse,  by  determined  samples  mature.  Figure  the  (14%  appear  quartz  the  of  done  1982).  up  long  tables  most  wacke with  Fiord  makes  and  the  were  analysis.  sample.  polycrystalline  the  of  composition  Strand  the  sizes w e r e  of  analysis of  quartz,  of  6  whole—rock  framework  with  Seven  is a q u a r t z  determinations  grain  c o m p o s i t i o n a l l y very  The and  sample  Average  section  one  (Williams  sphericity  per  analysis  XRD  Thin rocks  and  In  increases.  ( m o d e = 0.75) general,  grain  37  Quartz + Chert 100-0-0  90-10-0  9 0-0-10  80-20-0  80-0-20  Feldspars  Rock  X - Y - Z : %Quartz-%Feldspar-%Rock |  Figure  11-  Fragments  fragments  | : Enlarged Area  R A K - 2 5 r o c k clan p l o t t e d c o m p o s i t i o n triangle.  on a modified  Gilbert's  (1954)  TABLE  Framework  2  Petrology  of  Sandstones  Sample  MxtlQ  PxtlQ  Plag  Kspar  SRF  Orgs  RAK-7 RAK-10  66 64 74 82 90  19 32 12  Tr Tr 2 Tr Tr  1 1 Tr  9 2 2  0 0  1 Tr Tr  0 0 Tr Tr tr Tr  0 0 1  Tr Tr 3 Tr 1  RAK-13 RAK-18 RAK-26 RAK-34A RAK-40 RAK-49 RAK-63 RAK-66 RAK-90 RAK-96 RAK-97 RAK-118 RAK-127  16 8 7 4 9 7  75 90 88 88 72 71 72 72 88 77  Tr Tr Tr 1 1 1 0  18 16 14 14 14 20  M x t l Q ( m o n o c r y s t a l l i n e quartz), P x t l Q ( p o t a s s i u m f e l d s p a r ) , SRF ( s e d i m e n t a r y  Detrital of  the  samples.  plagioclase  using  pairs  range  An  and  in  to  highly  be  value 0  in  display the  An , .  occurs  constitute  Plagioclase  grains  calculated  2  feldspars  4  times  than as  3%  twinning.  method  (Kerr,  from  to  indicating  12.5°  microcline  exceeding  extensive  18°  1%  altered  of  is t h e the  showing  dissolution.  of  abundant  Michel—Levy  diagenetically  sericitization and  to  more  characteristic albite  Degraded  amounts  is 3  ( p o l y c r y s t a l l i n e . quartz), rock fragments), O r g s  no  1977).  3 9 10 10 3 1 Tr  413 452 412 402 422 410  Plag (albite), K s p a r (organics/phytoclasts)  the as  total  framework  potassium  Averaged  plagioclase  in  feldspar.  of  extinction  feldspar,  All were  between  but  All feldspars  kaolinitization,  any  angle  compositions  potassium  detrital f r a c t i o n .  evidence  532 411 453 404  Plagioclase c o m p o s i t i o n s  dominant  total  7 2 2  0 3 3 1 Tr 2  0 0 0 Tr  Tr Tr Tr 0  Counts 414 407 436 525 410  0  9 3 Tr Tr  0 1 Tr Tr Tr  .  Chert 4 Tr 6 1  minor  never appear  Phytoclasts samples. 8%  in  Percentages  other  highly  are b e l i e v e d micro—porous pores  have  pores  form  chert  been  and  porosity  is p r e s e n t  calcareous  virtually to  as  in t h e  0% high  as  25%  Cements rock  volume.  as d e t r i t a l the  and  finer in  and  the  matrix  authigenic  commonly  by  the  samples  cleaner  of  to  the  as  16  much  than  3 outlines  the  subsequent into  that  the  as  and  contain  poorly  better  one—sixth  of  quartz  distribution the  detail.  this of  overgrowths,  carbonate  in  the  porosity  1% 20%  the  and is  values  occurrences  and  of  range  (e.g.  In  partially from  RAK—7)  (e.g.  RAK—118).  20%  of  matrix  observed  secondary  cement.  form  sandstones  sandstones  between of  oversized  spaces. Additional  sorted  sorted  constitute  growth  Total  pores  possibly these  appears  and  oversized  of  abundant  ankerite).  more  in m o r e  These  Oversized,  chert  Many  pore  porosity  section examines  minerals  this s t u d y .  associated with section.  the  and  generally  the  in  aluminosilicates and  secondary  and  out  later s e c t i o n .  sandstones  more  following  in m o s t  examined  a  aggregates  grained,  Usually no  The  in  ( e s p e c i a l l y calcite  clays. Table  section.  cements  crystal those  1985)  d i s s o l u t i o n of  in s i z e  sandstones,  dissolved carbonates  in a f e w  sandstones  through  is d i s c u s s e d  dawsonite in  from  pervasive  the  reduced  kaolinite  these  are  as  fragments  RAK—34A).  (Shanmugan,  by  opaque  trace a m o u n t s  is a b s e n t  feldspars to  from  (i.e.,  porosity  secondary  altered  as d i s s e m i n a t e d ,  range  samples  Primary irregular  occur  the  total  material  such  cements  through  morphology  of  the  TABLE  Distribution  Sample RAK RAK RAK RAK  7 10 13 18  RAK RAK  26 34A  RAK  40  RAK  49  RAK RAK RAK  63 66 90  QOG X,  x,  X(Tr),  x, x,  — —•  xr  of  Sandstone  Ankerite,  Calcite  RAK  96  2  Section  Pyrite  Clay  Other  X  •x, x,  FeO, FeO, FeO,  Kaolinite ,  —  X  X(Tr), X(Tr),  X  X(Tr),  — — — —  X(Tr),  —  FeO, FeO,  2  2  2  3  — —  -  3  2  3  Calcite 1 Dawsonite, Siderite(Tr), Ankerite(Tr), 2  X(Tr),  Through  — — — — '  1  Ankerite , 3 Calcite , 3 Calcite, 3 Ankerite , Calcite , Ankerite, 2  Xi Xi  Cements  Carbonate  — —. •— —•  3  3  3  2  — —  Kaolinite  2  3  2  3  2  3  FeO Rutile,  — — —.  FeO,  3  2  Calcite ^ 3 Ankerite , Dawsonite, Siderite Calcite Dawsonite , Siderite, 2  —  3  X  2  Kaolinite lllite 3  3  2  3  2  RAK  97  —  2  3  Kaolinite lllite  AnalcimeO Rutile  3  3  2  RAK  118  X(Tr),  X  Calcite , 3 Dawsonite, 2  2  Ankerite , Dawsonite, Fe—Calcite , Siderite 2  RAK RAK  127 129  x/ x,  3  3  —  2  2  1 = Determined Optically; 2 = Determined Tr=Trace; X = present; — = a b s e n t  using  XRD;  — — — 3 = Determined  — — — using  SEM—EDS;  Discription  A  of A u t h i g e n i c  total  sandstones. them  Of  t h e 13, only  6  for the purposes  principal authigenic  dawsonite. quartz are  o f 13 a u t h i g e n i c  as p r i n c i p a l a u t h i g e n i c  classified, the  Minerals  T h e remaining  overgrowths.  illite,  pyrite,  phases  observed  6 were  present  minerals.  The remaining  o f this  paper,  minerals 2  were  in t h e E u r e k a  in proportions  accessory-^uthigenic  oxide,  principal authigenic  calcite,  phases  minerals  sphene,  make  u p a less t h a n  Four  of  siderite, a n d  of kaolinite, a n d  occurring  analcime(?)  minerals.  ankerite,  consist  t o classify  m i n e r a l s are  as a c c e s s o r y — a u t h i g e n i c  are c a r b o n a t e s ;  rutile,  enough  authigenic  7  T h e accessory—authigenic minerals  iron  great  Sound  through  a n d chabazite(?).  1 % of t h e t o t a l  the section In g e n e r a l ,  a m o u n t of  cement.  Principal  Authigenic  CaC0 —  Calcite through  that of  minor calcite  never  amounts were  exceeds  of  also  v i s i b l e in t h e p o r e s  3  cement.  Like  around  from  2  in R A K — 1 3 ankerite  calcite  a n d fracture  filling  o p t i c a l l y b y its e x t r e m e l y SEM—EDS  for Ca. Well of a number  cement  high  analyses  revealed  developed  subhedral  of samples.  Calcite  crystals cement  cement.  Ca(Mg,Fe)(CO ) —  For example,  stains  Fe are s u b s t i t u t e d  1 0 % of t h e total  calcite,  as a v o i d  a n d c h a r a c t e r i s t i c {0112} t w i n n i n g .  samples.  distinguished  primarily  o f t h e s e c t i o n . It w a s i d e n t i f i e d (0.172)  Ankerite  Calcite occurs  3  most  birefringence  Minerals  Ankerite  is t h e d o m i n a n t  ankerite  comprises  o c c u r s as fracture  b y having  its cyrstal b o u n d a r i e s  generally and within  in a n u m b e r  u p t o 9 0 % of t h e t o t a l  and void  higher  cement  infillings.  birefringence  A n k e r i t e is and brownish  t h e crystals as s e e n  under  plane  of  polarized  light.  Furthermore,  generally  more  corroded  analyses s h o w 12).  carbonate  sections and  proportions  to be more  less  cement  than  i n part  areas. T h e b e s t Green saline  River  anhedral  the Ca—Fe  on SEM-CDS  Fe rich  m i d point  (Figure  o n the  than  o p t i c a l l y in t h i n  analyses o f p o l i s h e d  characteristic diffraction as s e e n  in f i g u r e  associated calcite  of t h e total cement.  8%  3  2  Dawsonite  d u e t o t h e relative lack known  Formation  peaks  (14a).  thin  at 0 . 2 7 9  Like a n k e r i t e ,  a n d o c c u r s in  Siderite occurs  as a p r i m a r y  and most  Other  studied  Gorge,  Tanganyika ef al.,  Through  occurrence  o i l shales o f C o l o r a d o  o c c u r r e n c e s of dawsonite  w a s initially difficult  of reported  s u c h as n a h c o i i t e ( M e d d a u g h  1975).  pore  appear  where  t o positively  o c c u r r e n c e s in o t h e r of dawsonite it o c c u r s  a n d Salotti,  with  other  Terlano,  lacustrine  and Young,  s y e n i t e tuffs  near  study  is f r o m t h e  1983; Smith  in weathered  ( H a y , 1 9 6 3 ) a n d in r h y o l i t i c i g n i m b r i t e s  in O l d u v a i Italy  1977).  the upper  sandstone  cement;  RAK—127.  Dawsonite  The  extremely  SEM—EDS  (Figure 13).  an EDS pattern  NaAlC0 (OH) —  carbonates  (Corazza  a n d thus  crystals.  (Plate 1a).  Dawsonite identify  near  Siderite displays  and produces  appears  or poor  identification w a s based  a n d X R D analyses.  siderite  a n k e r i t e crystals are  a s s o c i a t e d calcite  plots  diagram  section  Discrete siderite w a s n o t r e c o g n i z e d  3  0 . 1 7 3 nm  filling  ternary  FeC0 —  Siderite  generally  in thin  than  a n k e r i t e t o b e M g free  Siderite sections.  viewed  a n d anhedral  Ankerite's. composition  Ca—Fe—Mg  when  third  it c o m p r i s e s was only  of the section dawsonite approximately observed  is t h e m o s t  1 0 0 % of the c e m e n t  in t h e z o n e  in  5 and overlying  vertical distribution of d a w s o n i t e a n d ankerite appears  abundant sample sandstones.  t o b e i n v e r s e l y r e l a t e d . In  2 H  ~  o  Ca  O O  Mg  poor/free Ankerite  i H  c  Fe  3  O  O  i  i  p  —r 1o  6  4  KeV  Figure 12a- Energy  dispersive  spectrograph  4^  O O X w  ankerite.  Mg p o o r Ankerite  Ca  3H  of M g poor/void  2 H  co  c 3  1  H  Fe  O  O  i  1 — 1 — i — i 4  Figure  12b- Energy  dispersive  KeV  6  spectrograph  i — i  8  of M g p o o r  i  10  ankerite.  44  CaO-MgO-FeO-C0  • Figure 13-  2  A n k e r i t e c o m p o s i t i o n from this study  A p p r o x i m a t e ankerite c o m p o s i t i o n range p l o t t e d o n a CaO-FeO-MgO-C02 ternary d i a g r a m . C o m p o s i t i o n s are o n l y a p p r o x i m a t i o n s as d e t e r m i n e d b y E D S analyses.  general/  the  toward over  dawsonite  the  the  related  top  same  to  as  lower  that  SEM—EDS  of  shows  Dawsonite's  Na  crystal  occupying  by  the and  throat.  significance  is  with  wholly  Quartz S i 0 — 2  grained  samples  secondary fewer the  and  quartz on  100%  in  had  total c e m e n t  is m a n i f e s t e d  most  samples.  of  intergrowth this  of  greater  in  all  0.570  than  are  as e i t h e r  or  of  the  was  made nm.  whose  is  kaolinites. dawsonite.  roughly image  0.3385  amounts  of  cleaner 3—5  urn  RAK—18 both  most  primary  detrital q u a r t z  samples  that  of  light  birefringence  Plate 2 c ,  2d)  be  equal  of  dawsonite  two  minerals.  where  it  is  using  the  XRD  Dawsonite  is  chemical  time.  high  the  and  to  polarized  identifying  number in  decreases  believed  plane  than  scattered  (plate  overgrowths  relatively  in  showing  shown  5  later s e c t i o n .  for  dawsonite  'illitic'  is a p p r o x i m a t e l y  35%  is  occur  at  back  atomic  peaks  with  higher  dawsonite,  at  a  recognized  for  Confirmation  either  in  is  a c i c u l a r crystals. Its  a typical  zone  trend  this  technique  average  of  of  useful  morphology  overgrowths  overgrowths  cement  contacts  smaller  the  in  understood  Samples  approximately of  is  base  correspondingly  considerably  pattern  Syntaxial q u a r t z  which  porosity.  an  radiating,  most  1b  is  the  content  is d i s c u s s e d  dawsonite  but  difference  characteristic diffraction  not  the  aggregate  a pore  observed  quartz  far  ankerite  as  of  (0.172)  increases f r o m  significance  diapirs  A l . Plate  occasionally  to  the  the  The  and  revealing  quartz  found  15).  typical EDS  and  of  while  a  of  had  of  calcite's  a n a l y s e s are  (14b)  where  (Figure  sample  optical microscope  proportions  seen  section  proximity  the  per  clear, c o l o r l e s s a g g r e g a t e s  than  Figure  the  range  the  Under (ppl)  of  content  common  porosity  clay  in  or  the  in t h e oversized  matrix  generally  arenites.  The  and  overgrowths  grains. and  26.  the  average  Overgrowths Evidence  concavo-convex  and  medium  thickness can  comprise for  be up  additional  sutured  grain  2^  o o o  Fe  Siderite  CO  c 3  o O  Mn  8  6  4  (A. 10  KeV  14b- Energy  Figure  dispersive  8 -  O o o  X  w (0  o f siderite.  Al  78  spectrograph  "  5 -  Dawsonite  4 3-  •*—  C => O  o  21  Na  "  o-:  i  1  2  1  -  3  i  r  4  -I 5  KeV Figure  14a- Energy d i s p e r s i v e s p e c t r o g r a p h proportions of N a and A l .  of dawsonite  showing  equal  47 O O  *- 0  2 0  4 0  Percentage  Figure  15-  Variations depth.  in a n k e r i t e  60  of  total  and dawsonite  80  100  cement  proportions  with  PLATE 1  Morphology, Textural Relationships, and Back Scattered Ellectron Image Appearence of Dawsonite and Associated Minerals A.  Scanning electron micrograph of siderite (Sd) and quartz (Qu). Siderite occurs as a primary pore filling cement; polished thin section; back scattered electron image; RAK—97—25.  B.  Scanning electron micrograph of dawsonite (Dw), quartz (Qu), calcite (Cc) and plagioclase (Pg). Grey shade difference reflects the difference in average atomic number between these minerals; polished thin section; back scattered electron image; RAK—96—25.  C.  Scanning electron micrograph of acicular dawsonite (Dw) occupying a pore; calcite (Cc) occurs adjacent to an oversized pore; Dawsonite is associated with quartz (Qu) and potassium feldspar (Ks); secondary electron image; polished thin section; RAK—118—25.  D.  Scanning electron micrograph of dawsonite (Dw) intergrown with illite. Dawsonite (Dw) can also be seen replacing calcite (Cc) (see arrow); back scattered electron image; polished thin section; RAK—96—25.  Al Si O ( O H )  Kaolinite samples (Plate  2  as r e v e a l e d  2  s  of instances,  and Na—plagioclase. Optical  vermiform range  — Kaolinite booklets  habit  a n d very  in s i z e f r o m  occur  occasionally  occurs  Euhedral  2  pyrite  illite  dustings.  as an inter  growth  Pyrite o c c u r s  crystals w e r e  light  it is c l o s e l y a s s o c i a t e d  o f thin with  based  solely  calcite  very  t h e pyrite  fillings  resorbed o n its  kaolinite  crystals  coatings.  with  mineral  Individual  as r e v e a l e d b y illite crystals  previously,  ranging  appear  brown  sections under  through  the binocular  small,  crystals  illite(?)  also  plane  microscope  i n size f r o m  slightly  iron  the section. a n d in  3 to  translucent  11  (Plate 3a).  o x i d e s / h y d r o x i d e s are  polarized  light.  In m o s t  cases  ankerite.  Ti0 — 2  Rutile  a n d less c o m m o n l y  o n SEM—EDS  diagenetic  dawsonite.  Reddish  x  Rutile/Anatase(?)/Brookite(?) with  2 b ) . Individual  a f e w samples  both  FeO —  Oxides/hydroxides in a n u m b e r  with  observed  In p l a n e  polarized  stage  grain  in only  Mm.  association  associated with  As was mentioned  s e c t i o n . T h e crystals are g e n e r a l l y  recognized  (Plate  is a late  thin  Iron  as p o r e  identification of kaolinite w a s based  a n d as s p o r a d i c  as grain  FeS ^  Pyrite  occur  of the  Minerals  in pores  occasionally  are c l o s e l y  l o w birefringence  Like k a o l i n i t e ,  its o c c u r r e n c e  commonly  in m a n y  3 t o 4 Mm.  Accessory—authigenic  lllite—  are v i s i b l e  b y S E M analysis. T h e b o o k l e t s  2a) a n d , in a n u m b e r  K—spar  f l  analysis  with  of polished  occurs  as s m a l l  ankerite. thin  euhedral  Identification  sections  (Plate 3 b ) .  crystals in  o f rutile w a s  PLATE  Morphology  2  and Appearence  of Kaolinite  S c a n n i n g e l e c t r o n m i c r o g r a p h o f k a o l i n i t e (Ka) l i n i n g p o r e s ; s e c o n d a r y e l e c t r o n i m a g e ; f r a c t u r e d s a m p l e ; g o l d c o a t e d i m a g e ; RAK—96—25. M i c r o g r a p h o f a u t h i g e n i c v e r m i c u l a r k a o l i n i t e (Ka) o c c l u d i n g a p o r e a s s o c i a t e d w i t h q u a r t z ( Q u ) ; p l a n e p o l a r i z e d light; RAK—96—25.  space;  53  PLATE 3  Morphology  and  Occurence  of  Pyrite  and  Rutile  A.  C u b i c pyrite a s s o c i a t e d w i t h d a w s o n i t e ( D w ) a n d q u a r t z ( Q u ) as p l a n e p o l a r i z e d light; h o r i z o n t a l field = 0.19 m m ; RAK-118-25.  seen  B.  S c a n n i n g e l e c t r o n m i c r o g r a p h of rutile (Ru) a s s o c i a t e d w i t h a n k e r i t e p o l i s h e d thin section; back scattered electron image; RAK—96—25.  in  (Ak);  5V  NaAlSi O '2H 0—  Analcime study area  2  s  2  Analcime has  by Bustin (1977). In the present  previously been  reported in the  study, however, the occurrence  analcime is uncertain as it was identified in only one  sample based  pattern analysis from a single grain. Never was analcime observed in SEM fracture samples.  extreme trace  on an EDS  in thin section or  XRD analysis also failed to indicate the presence  analcime in any of the samples.  Certainly, if analcime is present  of  of  it only exists in  amounts.  DISCUSSION Textural  Relationships  Textural relationships between  authigenic minerals, where  present,  are outlined  below. Unfortunately, not all authigenic minerals display textural associations with all other authigenic sequence.  phases  A number of  and, therefore,  some  relationships are,  ambiguities exist  however, revealed  in the  paragenetic  by cement  associations  with quartz overgrowths.  Syntaxial quartz overgrowths coated  with kaolinite booklets or  crystals commonly project into pore spaces (Plate 4a, overgrowth formation p r e - d a t e d overgrowths are  also seen  b) suggesting  projecting into the oversized pores created  quartz overgrowths. Strong evidence overgrowth formation can be  seen  for calcite  illite occur  cementation  in plate 5a,b,  nucleus has not been  and quartz 'islets' within  Quartz by the  as coverings  on  post—dating quartz  which shows calcite  replacing a quartz overgrowth and its nucleus. Note that the  embayed contacts  that quartz  both kaolinite and dawsonite genesis.  dissolution of feldspars and chert grains. Veneers of  the overgrowth and the  dawsonite  cement  clay dust rim between  replaced by the calcite.  calcite and ankerite are  Both  extremely  PLATE 4  Morphology and Textural Relationships Between Dawsonite and Quartz Overgrowths A.  Scanning electron micrograph of dawsonite (Dw) post—dating quartz overgrowth formation. Note acicular and radiating habit of dawsonite; fractured sample; gold coated; secondary electron image;RAK—96—25.  B.  Thin section micrograph under crossed nicols showing same relationship as in plate 6a; dawsonite (Dw), quartz overgrowth; crossed nicols; horizontal field = 0.77 mm; RAK-90-25.  common. to  The  relative t i m i n g  inconclusive  formation  of  (Plate  b).  6a,  of  formation  textural relationships.  quartz It  overgrowths  is t h e r e f o r e  existed during  paragenetic  sequence  prior  of  the  framework  to  the  that  the  calcite  evolution  but  prior  to  most  two  of  of  is u n c e r t a i n  likely  stages  the  calcite  the  ankerite  formed  crystals w i t h i n  at least  precipitation  aluminosilicates  and  however,  replaces  concluded  formation  siderite  Ankerite,  as it  overgrowth  of  and  precipitation of  the  quartz  strata,  after  after  overgrowths  of  studied  due  early i n  the  the  dissolution  kaolinite  and  dawsonite.  Additional between were  the  carbonates  commonly  conclusive, in  textural  an  dissolution  crystals that  occasionally  observed  the  occurred  before  boundaries  calcite  theory  are  the  on that  is  other  drawn  suggests reaction. that  that  pre—dates euhedral calcite  two  the  of  the  are  b  Euhedral  calcite  relationships calcite  and  resorbed  kaolinite.  calcite  products  encased  or,  in  more  were  also evidence  precipitation/formation  aluminosilicates  aluminosilicate  are  x  s p a c e s . This  Ankerite  FeO^  not  FeC»  Kaolinite b o o k l e t s pore  and  Although  contemporaneous  crystals w i t h i n the  the  ankerite.  shows  either  framework  "ghost"  phases.  later s t a g e  dawsonite.  calcite  examining  anhedral  7a &  predates  dissolution  coincident with  a  Plates the  from  diagenetic  association with  suggesting  the  supports  the  in  relationship  ankerite  probably,  and  observed  this  dawsonite  information  as a n k e r i t e  grain  and  oversized  illite  and  dawsonite.  cement  pore  boundaries.  Plate can  be  seen  8a  demonstrates  both  with  an  the illitic  relationship covering  Kaolinite  booklets  and  dawsonite  can  between  kaolinite  and  dawsonite  suggests  syntaxial  or  the  kaolinite  pre—dates  be  the  between  and  as  an  seen  in  Plate 8 b .  that  intergrowth  dawsonite  dawsonite.  Figure  The  and 16  with  illite(?).  observed  relationship  k a o l i n i t e are outlines  Dawsonite  a  either  paragentic  (  59  PLATE 5  Textural  A.  Relationships  Micrograph  of  Between  ankerite  (Ak)  Ankerite  and  Quartz  replacing quartz  Overgrowths  overgrowth  and  the  nucleus (Qu). N o t i c e that t h e o v e r g r o w t h ' d u s t r i m ' (see a r r o w ) p r e s e r v e d in t h e c a r b o n a t e ; c r o s s e d n i c o l s ; h o r i z o n t a l f i e l d = 0.77 RAK-49-25. B.  Enlargement  of  plate  5a;  horizontal  f i e l d = 0.19  mm.  quartz is mm;  61  PLATE  Textural  Relationships  Between  Calcite,  6  Ankerite, and  Quartz  Overgrowths  Ankerite (Ak) altering to Calcite (Cc) euhedra within a quartz crossed nicols; horizontal field = 0.58 m m ; RAK—49—25. Enlargement  of  plate  13a;  horizontal field = 0.19  mm.  overgrowth;  (2  PLATE 7  Textural  Relationship  Between  Dawsonite  and  Other  Carbonates  S c a n n i n g e l e c t r o n m i c r o g r a p h of d a w s o n i t e ( D w ) s u r r o u n d i n g a c o r r o d e d ankerite (Ak) crystal. T e x t u r a l r e l a t i o n s h i p s u g g e s t s that t h e a n k e r i t e predates the dawsonite; g o l d c o a t e d fractured sample; secondary electron image; R A K - 9 6 - 2 5 . T h i n s e c t i o n m i c r o g r a p h similar t o plate 1 4 a s h o w i n g d a w s o n i t e ( D w ) r e p l a c i n g a calcite ( C c ) crystal; c r o s s e d n i c o l s ; h o r i z o n t a l f i e l d = 0.85 m m ; RAK-96-25.  PLATE 8  Textural Relationships Between Dawsonite and Other Silicates Scanning electron micrograph displaying textural relationship between kaolinite (Ka) and dawsonite (Dw). Relationship suggests that kaolinite is either pre— or syn—genetic with dawsonite; gold coated fractured samplesecondary electron image; RAK—96—25. Scanning electron micrograph of dawsonite (Dw) replacing both calcite (Cc) and plagioclase (Pg) and occurring with illite(?) (arrow), polished thin section; back scattered electron image; RAK—96—25.  sequence  based  o n information  derived  from  total c o m b i n e d  textural  information.  Fluid Chemistry  Chemical suggest  that  considerations  numerous  Eureka  Sound  and  pyrite,  for example,  and  Spears,  and/or  both  while  is,  reduction interface  and  in support  created  low.  t o b e mainly  favorable  Changes  controlled  siderite,  It is b e l i e v e d Fe  ,  near  formation.  increasing in b o t h  2 +  depth  the C 0  by the b i o c h e m i c a l  v  with  time  a n d Spears, 1 9 6 8 ) circulation,  ef al., 1 9 8 1 ) . although that  Pyrite  textural  the anaerobic  the sediment/water  Pyrite as C 0  2  (Curtis  conditions of  activity ( M a t s u m o t o  f o r pyrite  with  under  of restricted water  of e x c e s s  <0.35  t o facilitate t h e  activity ( C u r t i s  than  of siderite  formation 2  activity i n c r e a s e s  a n d sulfide  degradation  is b e l i e v e d  activities are  of organic  matter  diagenesis.  depths  early  overgrowth  precipitation  in t h e p a r a g e n e t i c  At the l o w temperatures  approximately  by conditions  in t h e p r e s e n c e  conditions  Initial q u a r t z shallow  sulfur  e x i s t e d in  activity h a d t o vary  to form  o f this is i n c o n c l u s i v e .  have  The presence  In o r d e r  sulfide  t o b e a n earlier p h a s e  activity d e c r e a s e s .  d u r i n g , early  is r e p o r t e d  l o w sulfide  w a y t o siderite formation  sulfide  believed  pyrite  chemistry  assemblage  Eh w a s l o w (i.e.,  high.  however,  mineral  deposition.  when  activity relatively  is f a v o r e d  suggested  o f sulfate,  of their  a period  a n d siderite,  a n d very  2  therefore,  give  formation  2  pore  circulation a n d elevated  Fe *:Ca *,  information  to  water  siderite  elevated  pyrite  For example,  non—restricted  fluid  suggests 2  depth.  of changing  strata s i n c e t h e t i m e  1968)) a n d F e *  of  authigenic  episodes  the  formation  of the observed  6 m g I" , 1  sequence  of shallow  significantly  is t h o u g h t  burial  lower  than  when  t o have  occurred  at relatively  silica  solubility  is g e n e r a l l y  t h e solubility  of quartz  is  the amount  o f silica  present in  Paragenetic Quartz  Sequence  Overgrowth  Calcite  _  Siderite Ankerite Pyrite Feldspar Dissolution Dawsonite Kaolinite  ?  mm  •  Figure 16-  -.  Diagram of paragenetic sequence  near  surface  solubility  a n d fluvial  is l o w q u a r t z  volume  of fluid  however,  more  mg I"  first e p i s o d e occurred water  increases  circulation  relatively  Although  when  t h e silica n e c e s s a r y  t o have  been  thought  t o have  precipitated  derived  by a combination  from  from  external  locally  of s o u r c e s  the dissolution  2)  silica  released  during  compaction  3)  silica  released  during  t h e illitization  arid  dawsonite  effects organic  matter  groups  from  the  larger  large Sound  of framework  amounts  Formation,  example,  Carothers  volatiles,  aliphatic  of coal  to the  quartz  as t h e 1  at 2 0 ° C t o  n o t referenced)). believed  <20°C  to  The  have  a n d near  surface  of  calcite  overgrowths m a y have  is  are  been  concentrations  such  chained  as t h o s e  that  of  functional  where  with  carboxylic  of  aliphatics  In r o c k s  can be exceedingly  demonstrated  kaolinite  maturation  in t h e c l e a v i n g  molecules.  organics,  of  by considering the  The thermal  a n d short  parent  shales.  precipitation  may be explained  t o result  chert;  solution;  in a d j a c e n t  diagenesis.  accepted  (1978)  of p r e s s u r e  aluminosilicates,  a n d alicyclic  a n d Kharaka  which  overgrowths  and micro—porous  of smectite  carboxylic acids,  carboxylic acid  later s t a g e  silica  as a result  and disseminated  quartz  including:  o n inorganic  is n o w c o m m o n l y  aromatic,  derived  of the framework  diagenesis  phenols,  silica  and temperature,  6 m g I"  source  t h e early  fluids,  aluminosilicates  and the presence  of o r g a n i c  from  were  to precipitate  1)  dissolution  depth  is, t h e r e f o r e ,  temperatures  where  proportional  to precipitate  1 9 8 0 (original  precipitation  conditions  unrestricted.  believed  The  increasing  of magnitude  a n d Blatt,  burial  burial  in q u a n t i t i e s  to be in solution  overgrowth  shallow  shallow  precipitate  b y an o r d e r  (Ehlers  of quartz  these  the rock. W i t h  silica is r e q u i r e d  during  produced  Under  through  at 1 0 0 ° C  1  .  will generally  moved  solubility of quartz 63  waters  from t h e r e are  i n t h e Eureka  high. For acid  concentrations Carboxylic Al  3  *  can exceed  acids,  to form  when  water  by an order  orders  magnitude  net of  effect  point  Al  where  *  3  when  through  the rock  believed  t o destabilize  1984)  a n d result  following  (possibly  e f al.  in solution  A s these  decrease  the solubility  demonstrated  increasing the  of carboxylic acids P^  Q  (Holland  o n the carbonate  increasing  aluminosilicates  (ankerite  t h e reverse  a n d Borcsik,  and presence  a n d Fe—calcite)  fluids  the A l  that  *  3  c o m p l e x is et al.,  dawsonite (see  is true: 1976).  the presence chemistry.  P  Sound  of  organic  While  the  the same  by buffering  acids c a n  the p H . ln the  2  calcite  solubility  The presence  increases  of dissolution  of pre—aluminosilicate—dissolution  i n t h e Eureka  sandstones  suggests  with features  carbonates that  the P C O  was  relatively  high  (Surdam  carbonate  precipitation  formation  of ankerite  ef al.,  m a y have  o f s m e c t i t e t o illite,  colloidal  oxides,  carboxylic acids  aluminosilicates. T h e iron  a number  transformation iron  1 9 8 4 ) a n d that  and destroying  to a  migrate  p H (Surdam  aluminosilicates  C O  absence  removal  t h e aluminosilicates  and possibly  to destabilize  with  the  constraints).  effect  of calcite  1984). T h e  al.,  is t o e n h a n c e  in s o l u t i o n  of kaolinite  also  tends  where  is  acid a n d by 3  et  —complexed  3 +  with the  in solution  +  acetic  destabilize  zones  chemical  has a p r o f o u n d  of carboxylic acids  Al  waters.  to bond  (Surdam  in s o l u t i o n  d u e t o changes  ( 1 9 8 4 ) have  presence  *  3  3  with  oxalic acid  encounter  o n Dawsonite:  of A l  complexed  with  formation  *, are k n o w n  3  a n d , thereby,  t o dissolve. eventually  o i l field  T h e mobility  of A l  in the precipitation  section  Surdam acids  they  complexed  the system  begin  of A l  when  the mobility  from  they  in s o m e  1  complexes.  of m a g n i t u d e  of increasing  aqueous  m g I"  in t h e p r e s e n c e  soluble  enhanced of  5000  of  sources:  the dissolution  and the dissolution  of biotite  necessary  Fe r e l e a s e d  of siderite,  were  during  buffering for the the  the reduction  and amphibole.  2  of.  Following the  in  dissolution Al  remained  it is b e l i e v e d  that  enough  in t h e s y s t e m  t o favor  the precipitation  post—aluminosilicate—dissolution  kaolinite  and dawsonite.  3  *  of t h e aluminosilicates  Dawsonite:  Chemical  The drawn  coefficients  a number  data necessary  of sources.  for the Maier—Kelly  taken  from  fit t o Ferrante the  Ferrante  ef al's  crystallographic  0.1 M P a ) (1978).  enthalpy Free  considered Carrels  First, t h e heat  heat  from  capacity  Helgeson other  phases  Corazza  capacity ( C p ) data  pressure  (1965).  (1969;  1978).  Before  of  -1661655.0  jnsupminus, Sup1,  of  -1675700.0  jn"  consistency,  the dawsonite  thermochemical  data  ef al., H°  data  the H°  in t h e d a t a s e t . H e l g e s o n  (Robie  (1977). T h e s t a n d a r d  state  taken  . in  1978).  used  derive  of dawsonite  adopted contrast  could  using  Robie  carbonate  were  to provide  a value  function  (298.15°K,  from  sodium  f o r all r e m a i n i n g  in o r d e r  collected  phases  were  be used  e f al. phases from drawn  with the  consistency with the  for the H °  of  corumdum  t o the calorimetrically derived  In o r d e r  was adjusted  for dawsonite  (S°). w e r e  for the additional  capacity  was calculated  a n d activity—activity d i a g r a m s  s e t it h a d t o b e a d j u s t e d  1  the heat  of dawsonite  and entropy  Thermochemical  to  2  17 s h o w s  volume  (C°)  used  function:  Figure  ef al.  (H°)  of formation  in t h e partial  data  (1976).  data. T h e m o l a r  of formation  energies  Helgeson  ef al.  data of  a n d Christ  of  t o c a l c u l a t e t h e stability o f d a w s o n i t e are  Cp = a+bT+c/T were  complexed  Constraints  thermochemical  from  organically  to provide  b y this  f o r internal  difference.  in t h e f o l l o w i n g  value  Table  distribution  4 presents the of  species  72  O o  CM  Data of Ferrante et al. (1976) o  CO  o  o CO •  3  o  aci  >»  o  N.  -  a  ca  O  ca <D  o  CO -  I  o  o T  ^"298  320  340  360  380  Temperature  Figure  17-  400  420  440  460  (Kelvin)  D a w s o n i t e heat c a p a c i t y f u n c t i o n Ferrante et al. ( 1 9 7 6 ) .  fit t o t h e d a t a  of  480  calculations.  The in  a  stability o f  series o f  distribution for and the and  the  of  7.  ratios,  is m o r e  5).  considered  Balanced  ,  18  through  Na*/H  in  Figures  under  low  to  the  these  Figures  diagrams  absence  18,  of  values 19  the  For  than  example,  previously  a recent  previously  undetected  Formation  of  a  u  but  c n  the  however,  has  Peace  not  been  strongly  20  may,  geologic  an  increase  size  dawsonite  (see  following  communication has  Oil  been  Sands.  some  pursued  influenced  that  the  River  have  demonstrate of  personal dawsonite  undoubtedly  this  realized  by in  field with  pH 1  on  topology  of  ri2vJ  Al  activity o f  has  unit  reults  P  and  in a a  +  /H  +  the  dawsonite  a..  +  of  species).  shown of  that  the  Gething  such  as  the  distribution  of  dawsonite,  *.  of  dawsonite  Figure  19  significant „.  u  3  6  Na  samples  3  ,  +  distribution  conditions Al  that 3  of  in T a b l e s Al  a.,  the  298.15°K  in  factors, however,  the  respect to  listed  ~,  in the  to  the  energies  suggest  Rottenfuser)  Stability  +  limited free  the  s e c t i o n re:  effect  performing  variations  , a,,  study.  loga^  the  in fact,  identified Other  and  are  on  P  (B.  controlling  in this  capacity coefficients  are  CO 2 conditions  heat  20  have  examined  to  and  and  was  prior  c o n t r o l that  water  through  temperature  carbonates  s t a b i l i t y analyses  activity o f 18  sodium  pressure  demonstrate  ratios, a n d  +  stability f i e l d . common  20  other  reactions, l o g K  reactions represented  c q  dawsonite  carbonates  (Table  Figures P  partial  species calculations. Due  MPa  various  relative t o  activity—activity a n d  sodium  0.1  dawsonite  The  to  21  increase  chemistry  are,  in of  the sea  co 2 ri (J w a t e r a n d t h e f l u i d c h e m i s t r y of a n u m b e r o f f o r m a t i o n w a t e r s are p l o t t e d o n f i g u r e s 1 8 , 1 9 a n d 20 t o illustrate t h e c h e m i c a l d o m a i n o f a f e w natural s y s t e m s 2  within  P  co  The assemblage  2  —a., H 0 2  reason was  to  a . , Al for  3 J  +  —a.. — H * Na +  performing  approximate  space. r  a distribution the  activities o f  of  species  aqueous  on  the  authigenic  species and  gases  in  o —  :  N  q  o  a 2  —  .  co  ••'/  :  —-// // / /  3  Thermonatrite  . _ _  _  •I  •  o  «vi  //  y  N a X O . 7H-0  /  /  //  //  7  I  /  /  /  // /  //'-.  CO • *" Z| I  o) O  //  2 r-  .-Jit*!™  o  Trona  6  Dawsonite  7'  o  o>  o  Nahcolite  a  q  SL  H 0*1 2  I  0.0  —  1.0  I  —  2.0  —r— 3.0  4.0  -r  —p— 6.0  5.0  1 8.0  7.0  i 9.0  Log »|l * a 8  H +  Figure  18-  Plot of  Log(A  N A  + / A [ • ] versus H  1 = Shannon Sandstone, Formation.  L o g [ A | • 3 / A H • ]. 3  A  2 = Ocean water,  Star=Eureka  Sound  " 10.0  75  Figure 19-  Plot o f L o g [ A | • 3 / A ^ + ] versus LogPco 2 - 1 = S h a n n o n and Blairmore Sandstones, 2 = O c e a n water, Star= Eureka Sound Formation. A  3  Dawsonite  Nahcolite  X  —  v.  j  N  V.  s  Trona  V  / i  s  N  Na C0 2  ^  \  1  !  ' i  3  o  OJ  Z  o  N.  <?' o CO  z  -2.20  -1.76  -1.32  Log a  Figure  20-  -0.88 H  -0.44  Q  2  Plot o f L o g P versus L o g A . 1 = S h a n n o n Sandstone, 2 = Blairmore Sandstone, 3 = O c e a n water, Star=Eureka Sound Formation. c  o  H  z  0  0.00  TABLE 4  Standard  Enthalpy  and Entropy  of Formation Capacity  AH°(298) ) / N -1956947.5  Heat  S°  computer  with progam  as a- g r a n d  program.  Limitations  d o exist,  For example,  considered  considered,  the program  2 9 8 . 1 5 °K w e r e  their  respective  As  and An  used  ankerite n  f o r runs  be  of such  Such  phases  temperatures.  at t e m p e r a t u r e s  at 2 9 8 . 1 5 ° K w e r e  done  using a  the chemical  system  all e q u a t i o n s  is p r e s e n t e d  in P e r k i n s  (Masters  as r e a c t i o n k i n e t i c s are n o t  handled  solid  solution  directly  phases  s u c h as  by t h e p r o g r a m .  had to be hand  When  calculated and added  o f s p e c i e s c a l c u l a t i o n s at t e m p e r a t u r e s albite a n d a n k e r i t e w i t h o u t  a treatment  served  _c_ 1563478.4  t h e versitility o f t h e c o m p u t e r  in addition,  Distribution  at 2 9 8 . 1 5 °K  at h i g h e r  a n d ankerite  cannot  such  also n o t p o s s i b l e w i t h  C p values.  a result, runs  activities  program,  energies  separately.  than  regarding  that treats  a n d solves  of t h e theory  non—trivial factors  a n d ankerite  t h e free  a n d Perkins)  reactions  however,  in t h e c o m p u t e r  albite—anorthite  Brown  description  b_ 0.37051717  of species calculations were  of inter—dependant  A formal  a, b a n d c H e a t  2  Distribution  (THB2:PATH.O,  matrix  simultaneously. Thesis).  t h e rock.  with  Coefficients  _a_ 14.8213156 .  capacity function: C p = a + b T + c / T  equilibrium  to  j/NK° 132.0  of Dawsonite  was beyond  as first Pure  albite a n d pure  greater than  this  for aqueous calcite  298.15°K.  calculated using  estimating  t h e s c o p e of  approximations  project.  species  replaced A n ^ ^  T h e free  the following  higher '  energies of  formula  of  ideal  TABLE 5  Names,  Chemical  Carbonates  Formulae,  Considered  a n d Free  in the Included  Mineral Natron Trona Thermonatrite  Energies  of Formation  A c t i v i t y / A c t i v i t y a n d Partial P r e s s u r e  Formulae Na C0 .10H O Na H(C0 ) «2H 0* Na CO «H 0 N a C 0 NaHC0 Na C0 '7H 0 NaAl(C0 )(OH) 2  3  3  Free  2  3  2  Sodium Carbonate Nahcolite (?) Dawsonite  of the Sodium  2  a  3  2  2  3  3  2  3  2  3  Energy (Kcals) -819.54 -570.40 -307.49 -250.4, -203.6, -649.12 -426.86„ 2  2  2  Diagrams  2  2  * T r o n a a l s o c o m m o n l y r e p o r t e d as N a C O • N a H C 0 • 2 H 0 1. R o s s i n i et al. ( 1 9 5 2 ) 2. S a e g u s a ( 1 9 5 0 ) 3. C a r r e l s a n d T h o m p s o n , u n p u b l i s h e d ( C a r r e l s a n d C h r i s t , 1 9 6 5 ) 4. R o b i e et al. ( 1 9 7 8 ) 2  3  3  2  mixing: u = Z u .x. + n R T ( Z x .Inx.) I I .  where:  ^.  and  n=  number  R=  8.417 joules/mole  T=  2 9 8 . 1 5 °K runs  within  intended  of t h e e n d m e m b e r  fraction  of solution  the considered that  system.  i  of e n d member i sites (?) °K  are i s o t h e r m a l a n d i s o b a r i c w i t h  species within  is o n l y  energy  the mole  computer  Equilibrium  t h e free  x.= i  All  =  II  s y s t e m is a s s u m e d It is i m p o r t a n t  pressures  r e s t r i c t e d t o 0.1  t o exist b e t w e e n  to note  that  all phases  the following  as a first approximation c a l c u l a t i o n as t h e fluid  MPa.  treatment  chemistry of the  TABLE  System:  H  +  —Al  +  6  3  - N a  - H  +  z  O  Reaction  AC  LogKeg  18.809 18.009 14.329 15.029 -2.529  -13.790 -13.203 -10.505 -11.018 1.854  15.789 15.389 13.549 13.899 5.120 -0.400 -2.240 -1.890 -10.669 -1.840 -1.490 -10.269 0.350 -8.429 -8.779 -12.769  -11.576 -11.282 -9.933  thermodynamic  and  T r o n a + N a * ( a q ) = 2 N a C 0 + H (aq) + 2 H 0 ( l ) T r o n a + N a * (aq) = 2 T h e r m o n a t r i t e + H * (aq) T r o n a + N a (aq) + 1 8 H O(l) = 2 N a t r o n + H (aq) T r o n a + N a (aq) + 1 2 H 0 ( l ) = 2 N a C 0 •7H OH-H (aq) Trona+2Al (aq) + 2 H O(l) = 2 D a w s o n i t e + N a (aq) + 5 H (aq) N a h c o l i t e + N a ( a q ) = N a C O + H (aq) N a h c o l i t e + N a ( a q ) + H O ( l ) = T h e r m o n a t r i t e + H * (aq) N a h c o l i t e + N a ( a q ) + 1 0 H O ( l ) = N a t r o n + H (aq) 2  +  3  2  +  2  +  +  +  2  3  2  3  +  2  +  2  +  2  +  +  +  3  2  +  +  2  Nahcolite + N a ( a q ) + 7 H O(l) = N a C O • 7 H O + H * (aq) Nahcolite + A l (aq) + 2 H - O ( l ) = D a w s o n i t e + 3 H * (aq) N a C 0 + H 0 ( l ) = Thermonatrite N a C 0 + 1 0 H 0 ( l ) = Natron Na C0 +7H 0(l) = N a C 0 »7H 0 +  +  2  3  2  3  2  3  2  2  3  3  2  2  2  2  2  2  3  2  N a C 0 + A I ( a q ) + 2 H 0 ( l ) = D a w s o n i t e + N a (aq) + 2 H ( a q ) Thermonatrite + 9 H O ( l ) = Natron Thermonatrite+ 6 H 0 ( l ) = N a C O ' 7 H 0 T h e r m o n a t r i t e + A l ( a q ) + H 0 ( l ) = D a w s o n i t e + N a (aq) + 2 H (aq) Natron = N a C 0 • 7H 0 + 3 H 0 ( l ) Natron + A l ( a q ) = D a w s o n i t e + N a (aq) + 2 H (aq) + 8 H O ( l ) N a C 0 • 7 H 0 + A I * (aq) = D a w s o n i t e + N a ( a q ) + 2 H *(aq) + 5 H 0 ( l ) T r o n a + H ( a q ) = 2 N a h c o l i t e + N a (aq) + 2 H 0 ( l ) 2  +  3  3  +  2  +  z  2  +  2  2  3  3  +  3  2  3  +  +  considered  system  computer  program  simplicity.  By  constrain  the  given  variable not  co 2  therefore,  , a., ™'  by  3  poorly  Ca  ,  +  2  .  constrained reduce  + /  pH,  Calcium  its activity w a s t h e  the  possible  assemblage to  c  D\KJ H  many  system  listed  a .„  , and  only  aqueous  one  of  the  a state 8  it  carbonate chosen all t h e  By v a r y i n g species  of  to  in T a b l e  molality was  considered.  determine  and  the  assemblage  a . Na +  2  2  limitations may  m o l a l i t y of  because  fixed  is very  considering the P  2  +  +  any  +  3  2  +  2  + 3  2  2  2  the  as  was  of  species molality  activities u n d e r  0.293 1.642 1.386 7.822 1.349 1.092 7.529 -0.257 6.180 6.436 9.361  unrealistic  possible  species the  -10.190 -3.754  to  activities f o r  independant c o n s i d e r e d that of  Ca  2  *  conditions  it w a s , where  was  TABLE  System:  Al  +  - H  3  +  7  - H  2  0 - C 0  2  Reaction T r o n a + C 0 ( g ) = 3Nahcolite + 1H O ( l ) 2Trona = 3Thermonatrite + 2 H O(l) + C O 2 T r o n a + 2 5 H O ( l ) = 3 N a t r o n + C O (g) 2  z  2  z  (g)  2  2  2Trona+16H 0(I) = 3 N a C 0 2  2  3  2  2  2  6.221 (aq)  +  12.529 5.120 -0.400 -2.240 -1.890 4.380 -1.840 -1.490 4.789 0.350 6.629 6.279 5.851 3.611 3.961 -5.451 11.891  2  3  3  2  2  Na C0 +7H 0(l) = N a C 0 «7H 0 N a C 0 + 2 A I ( a q ) + 5 H 0 ( l ) + C 0 2(g) = 2 D a w s o n i t e + 6 H * ( a q ) T h e r m o n a t r i t e + 9 H O(l) = N a t r o n 2  3  2  3  2  2  3  + 3  2  2  2  Thermonatrite + 6H O ( l ) = Na C O • 7H O Thermonatrite + 2Al (aq) + C O ( g ) + 4 H O(l) = 2 D a w s o n i t e + 6 H * (aq) Natron = N a C O • 7H O + 3H O ( l ) N a t r o n + 2 A l ( a q ) + C O ( g ) = 2 D a w s o n i t e + 6 H (aq) + 5 H 0 ( l ) N a C 0 • 7 H 0 + 2 A I (aq) + C 0 ( g ) = 2Dawsonite + 6H (aq) + 2 H 0 ( l ) 2  2  3  3  2  3  +  2  2  z  3  3  2  2  z  +  2  +  2  3  2  +  2  2  2Nahcolite = N a C 0 + C 0 ( g ) + H 0 ( l ) 2Nahcolite + 9H 0 ( l ) = Natron + C O ( g ) 2Nahcolite + 6H 0 ( l ) = Na C O • 7H O + C O ( g ) Thermonatrite + C O (g) = 2Nahcolite 2Trona=3Na CO + C O ( g ) + 5H O ( l ) 2  3  2  2  2  2  2  2  3  z  2  2  2  halite  (i.e.,  where  ' §Q 0  3  2  2  the source n a  |j  t e  ' ' 8' ' >  0  <  of N a * for dawsonite) n a  |j  t e  )  a n c  ^  thereby  salinity.  Fiord  were  1  are p r o p o s e d  pore  approximate  waters within  theoretically determined  analysis are p r e s e n t e d I"  begins  to g o into an u p p e r  solution  limit o n  1.386 -3.218 1.349 1.092 -3.511 -0.257 -4.860 -4.603 -4.290 -2.647 -2.904 3.996 -8.718  (i.e., solution  .  Post tectonic/late stage Strand  2.076 -7.838 -3.791 ^.561 -9.185 -3.754 0.293 1.642  2  2  3  LogKeqr  «7H 0 + C 0 ( g )  3  Trona+3 A l (aq j + 5 H O ( l ) + C O (g) = 3 D a w s o n i t e + 9 H N a h c o l i t e 4 - A l * (aq) + 2 H 0 ( l ) = D a w s o n i t e + 3 H * (aq) Na C0 +H20(l)=Thermonatrite N a C O - r - 1 0 H O ( l ) = Natron +  AC -2.831 10.691 5.171  in T a b l e  9. S o d i u m  at m i d s e c t i o n w i t h  P  t h e Eureka  to b e highly concentrations  Sound  Formation  saline. Results as h i g h  v a l u e s as h i g h  at  from the  as 95 t o 1 0 5 g  as 0 . 1 4 a t m . Similarity  TABLE  Components  Considered  8  in D i s t r i b u t i o n  T=298.15°K  of Species  P = 0.1 M P a  Components Dawsonite Alpha Quartz Kaolinite Ankerite Albite-90 Calcite Water Calcium ion  Formula NaAl(C0 )(0H) 3  2  2  brines  +  from  2  2  2  B 0  z  2  +  P = 0.1 M P a  Formula NaAl(C0 )(0H) SiO Al Si 0 (0H) NaAlSi 0 CaC0 H O Ca 3  2  z  2  2  5  2  3  8  3  z  2  such  believed  t o result f r o m  adjacent  diapir  attributed  5  3  concentrations  formed  2  3  Components Dawsonite Alpha Quartz Kaolinite Low Albite Calcite Water Calcium ion  Na  2  Si0 Al Si 0 (0H) CaFe(C0 ) NagCajAli i S i 9 O CaC0 H O Ca  T=333.15°K  high  Analyses  are c o m m o n  primarily  lakes. S o d i u m t h e liberation  cores. The presence  to the enrichment  of N a *  i n saline  enrichment  of N a *  upon  of dawsonite  lakes a n d f o r m a t i o n  in t h e Eureka  Sound  the dissolution  is, t h e r e f o r e ,  in c o m b i n a t i o n  with  +  strata is  o f halite  believed  relatively  water  high  from  to be P  , low  silicic  acid  activities,  and t h e eventual  destabilization of t h e carboxylic  acid—Al * 3  complex.  Distribution  o f s p e c i e s results  IOBQ .. > l o g K .. ° paragonite ° paragonite be  considered  t o explain  in  this  does  case,  quantification some  some  First,  suggested and  (STP)  pressure  is b e y o n d  diagrams  i n a range  t h e e f f e c t s that  silicic a c i d  from  have  assume  that  believed.  dawsonite  disregarded,  substantiated dawsonite  those  chemical  i n strata w h e r e  suggests  communications  state  in t h e r o c k dawsonite's  with  it h a s p r e v i o u s l y  as w e l l ,  possible  rocks  t h a n is  activity/activity  been  necessary t o  temperature  a n d pressure  a n d surficial  environments.  i n this s t u d y  it a p p e a r s  record  presence  overlooked. other  m a y in  2  The preceding  factors n o t c o n s i d e r e d  o r completely  although  sedimentary  day sedimentary  that  kinetics may,  the chemical conditions  at s t a n d a r d  abundant  possible  misidentified  by personal  that  Reaction  used in  solution.  o n t h e stability o f d a w s o n i t e  is m o r e  It m a y b e q u i t e  t h e literature.  therefore,  the program  inhibitors,  analysis  c o m m o n . in  shown  earlier,  Organic  must,  which  of paragonite  from  thermodynamic  run the  Reasons  consideration.  this s t u d y .  of present  activity, e t c ) have  for each  a system  As was noted  of paragonite  may be more scarcity  from  o n the absence  the precipitation of dawsonite  are f o u n d  Barring  either  dawsonite  absence  kinetics into  the preceding  b y its relative  partial  promote  control  the nucleation  Results f r o m  that  r  its p r e s e n c e .  o f this t h e o r y  w a y retard  insights.  r  n o t take r e a c t i o n  exert  indicate  irrespective of temperature.  paragonite's  thermodynamically f a v o u r s this s t u d y  also  This  than  reasonable t o  previously  has p r e v i o u s l y  been  s t a t e m e n t is  investigators  overlooked.  (i.e., Eh,  w h o have  identified  TABLE  Comparison  of  Eureka  Sound  Formation  other  Location Ocean Great  Water  Salt  Lake,  Utah  Fluid  Natural  Al  Na*  3  10,560  1.9  83,600  9  Chemistry  Systems  (mg  I"  LogAl *  +  with 1  Fluid  Chemistry  of  )  pH  3  the  H C 0  LogP "—CO  -  3  Ref. 2  0.27  8.1  140  -3.07  2  ' —  ?  7.4  251  ?  1  tr  ?  1  614 .  ?  1  Lake,  Calif.  137,580  •—  ?  —  Saline V a l l e y ,  Calif.  103,000  —  ?  7.35  9,450'  1.7  0.23  7.0  415  ?  2  Danby  Frio  Sandstone  Blairmore  Sandstone  31,500  4.1  0.61  6.8  140  -2.5  . 2  Shannon  Sandstone  6,300  0.6  -0.22  7.6  1.01  -1.7  2  *  *  *  *  *  *  117,000  0.0  -8.83  7.1  66.1  -1.99  Exp.  99,000  0.0  -6.63  5.8  297  0.14  Exp.  *  Upper Mid  Eureka Eureka  1. E u g s t e r 2. W h i t e ,  of  investigators cored  with  dawsonite. possible  Sound  and Hardie, 1965  The presence  Sound  to  second  implication  dawsonite who halite. As  the  1978  of  the  in  the  Eureka  suggest  that  the  In  this s t u d y ,  studied  calculate the  Sound  evaporite  halite  sandstones prevailing  preceding  is  thermodynamic  strata diapirs  modelled  contain  chemical  only  supports  treatment  the  findings  in  the  Arctic  as  the  source  1  conditions  authigenic which  is that of  other  Archipelago of  Na  Na-rich  allowed  the  are  for  the  phase  it  dawsonite  was to  precipitate  while  show  at t h e  that  precipitates saline  lakes  samples  favor  of  chemical the  point  Na  and  have  distribution the  the  keeping  all  other  where  In  thermodynamic  precipitation  in  addition,  In  other  calculated in the of  any  to  solution only  stability u n d e r  species program. conditions  phases  halite b e g i n s  concentration  formations.  Na-rich  phases  in  go  into  is as  high  those  the  words,  than  as  phases  with  the of  those  (i.e.,  solution  conditions  distribution  other  solution  that  halite). and  in  which  are  exception  present  present by  of  species program  observed  results  dawsonite  many  calculated  The  in t h e  in  day the  the pyrophyllite, do  not  samples.  SHALE  Clay about  mineral  strata.  Folscolos  In  ef al,  relationships to  clays.  (1976), does  and  the  (1970),  need  of  ef al ratio  (1981)  (Wilson  better  1981;  and  shown  parameters  in  and on  the  through  shown  role  that  studied  shown  diagenetic  as d e p t h  Perry  depth  and  information  (1970), that  parameters Eberl  of  and  burial  Hower  increases  Reynolds  and  burial  increases  the  layers  Gillot,  generally  1979;  so  Hower  decreases.  In  Sedimentology  detrimental  effects  characteristics have  play  relating  (1969),  of  the  recovery  clay m i n e r a l o g y  the  Millot  F o s c o l o s (1973),  1981),  clays  diagenetic  been  various  that  as  Perry  Davies,  reservoir  the  it has  illite.  that  1977;  and  (1970),  illite/smectite mixed  Pittman,  examines  and  crystallinity o f  have  clay minerals  chapter  have  genetic  (1976)  burial  DIAGENESIS  Segonzac  Burst ( 1 9 6 9 ) ,  (1976) and  De  ef al, of  by  Almon  understand  (1969),  depth  studies  AND  yield valuable  Hower  smectite present  authigenic  This  may Burst  between  Hower  studies  diagenetic  and  Foscolos  and  to  (1976)  example,  Research Group, and  by  sharpness  percentage other  studies  exist  For  analyses  MINERALOGY  of  detrital  increased  in  reservoir  mechanics.  and  variations  in  a  number  the  of ,  section.  EXPERIMENTAL  Clay  Sample  Twenty diffraction rock  Preparation  five  analyses.  fragment  shale  samples  Each s a m p l e  size to  were was  approximately  chosen  initially 5  mm . 3  from  ground The  100 in  m  intervals  a rock  samples  were  for  crusher then  to  x—ray reduce  washed  in  de—ionized by  the  water  rock  samples,  the  design  not  Once  dry,  each  placed  in  a one  in  water  eight  hours  1969), days. was  discarded  and  further  Before into  coarse  One  hundred  240  head  containing  and  crusher  made  from  one  sample  to  ground  8 cm  of  off  into  had  to  a  the  supernatant, a  remaining  powder  for  period  container out  and  of  the  slurry  was  set  aside  saturated  with  a cation  mortar  of um  to  8  and dispersed  hours.  for  the  cation  some  After  fraction (Jackson,  stand  solution  for  that  clays w e r e  <2.0 left  between  preparation.  agate  The  the  introduced  crusher  sample  in an  a  been  guarantee  water.  settle  completely  the  during  containing  separate  have  cleaning  next  de—ionized to  may  it i m p o s s i b l e . t o  fine  allowed  settled  clays w e r e  ml  the  rock  the  to  2.0jim)  and  medium  p l a s t i c test t u b e s  topped  to  2000  rpm  (after  when  the  was  which  10  to  14  supernatant  exchange  treatment  fractionation.  (0.2  at  taken  then  the  and  was  stirring a n d  clays  size  care  filled with  top  the  clay c o n t a m i n a n t s  litre b u c k e t  syphoned  Once  centrifuged  of  sample  the  any  Although  passed  by  were  solution  remove  crusher.  clays w e r e  the  to  10  cm  for  Brown,  1965  less t h a n  0.2  were  with  50  um  filled  to  de—ionized  minutes  and  (<0.2ym)  using  Jackson, fraction  an  sample  size fractions 1  cm  water.  1969). was  each  with  via  the  Samples  was  were  and  sample then  with  After centrifuging, off  centrifugation.  clay  IEC® c e n t r i f u g e  syphoned  separated  a  the  number supernatant,  reserved  for  later  treatments.  The that w e r e  coarse  f r a c t i o n of  subsequently:  1)  left  untreated;  2)  saturated  with  3)  saturated  with  K  and;  +  M g  2  +  .  each  sample  was  again  separated  into  three  portions  Cation  exchange  was accomplished  (1965) a n d Jackson test  tube  Cation  and flocculated  saturation  suspension removed  four  from  2  times  solution HCI  upon  drop  magnesium  was  solution  solution.  (i.e.,  It w a s n e c e s s a r y  in o r d e r  t o avoid  solution  until  in p l a c e  i n a 15 m l  KCI o r  MgCI ). 2  e x c e s s salts  9 5 % methanol  when  saturating  precipitating  the p H was between  of M g C I  Brown  a n d decanting the  Finally,  in 5 0 % methanol,  saturation w a s c o m p l e t e  desiccator  samples  over  and t w o a sample  Mg(OH)  with  out of  2  by adding 0.1N 3.5 a n d 4. T e n N  in t h e first c a t i o n — s o l u t i o n  2  were  bath.  an equal This  t o d r y at r o o m  volume  thinned  of water  was added  slurry w a s t h e n  temperature.  Once  pipetted  dry, e a c h  slide  giycolated.  were  ethylene  immediately  amount  o f t h e clay slurry.  and allowed  x—rayed a n d t h e n  Clay  the  was placed  Acidification was accomplished  2  volume  a glass s l i d e  x—rayed  of M g * .  was used  cation  the remaining  onto  in 9 5 % acetone.  by  Samples  Once to  by washing  t o t h e initial  outlined  by successively centrifuging  acidify t h e solution  acetate  Oriented  t o 25 m g of sample  in t h e 1 N c a t i o n — c h l o r i d e  addition  wise  techniques  in a 1 N c a t i o n — c h l o r i d e  the sample  t o first  +  Twenty  was completed  successive washings M g  (1969).  by following  glycol  after  o f interlayer  giycolated  being  by placing  t h e slides  for approximately removed  g l y c o l lost  from  through  24 h o u r s .  face—up  in a  T h e samples  t h e d e s i c c a t o r in o r d e r  evaporation  (Kunze,  vacuum were  to  minimize  1955; Srodon,  1980)..  Finally, for  2 hours  clays  saturated  at 5 0 0 ° C .  with  K* were  placed  A t t h e e n d o f this t i m e  in an e l e c t r i c  the samples  furnace  were  and heated  removed  and  placed  in a desiccator w h e r e  amount  of atmospheric  samples  were  again  they  water  were  resorbed  left  to cool.  This  b y clays u p o n  procedure  minimized the  cooling. Once  cool the  x—rayed.  Unoriented Samples  Unoriented oriented  sample  fine  powder.  and  x—rayed.  Instrumental  Voltage  with  42—48°  by scraping  blade  was then  a n d N i filter. Mg *  poured  saturated  x—rayed T h e scan  was 2°  2  were  the dried  material  off o f  a n d re—crushing  t h e clays  t o create a  into  aluminum  sample  a "welled"  were  samples  order  t o determine  percentage  were  used  index  (Kubler,  were  M g *  o f illite  t o examine  saturated  discrete  silicate  layer  0  diffractometer  o n all s a m p l e s  a time  precise  3—18° were  per minute  at 1/2°  f o r variations  constant  samples  were  identification.  through  Those  scanned with  (002)10/(003)17  ratio  28.  per minute  in illite/smectite m i x e d  1966) and sharpness  Mg *—glycol 2  between  of 1  scanned  a more  used  with  and glycol  2  also  speed  per minute  scanned  with  o n a Philips® x—ray  other of 2  s e t at 4 0 k V a n d 2 0 m A , r e s p e c t i v e l y .  2 d at a s c a n s p e e d  These  the  prepared  a razor  samples were  preparations  exchange  with  powder  and amperage  sample  were  holder  Techniques  source  saturated  mounts  This  All clay CuKa  samples  layer  a time  clays.  3—18°  had been 28 a n d  of 1  17 and 18°  T h e K * saturated  t h e s e c t i o n in t h e illite  for percent  that  illite  second. 28  in  location for calculating  o f t h e 1.0 n m p e a k s  used  those  seconds.  constant  between  reflection  than  a  All oriented  samples  between  using  samples  crystallinity  (Weaver,  1961).  determinations and  Unoriented minute was  in order  used  sample  preparations  t o examine  t o differentiate  were  scanned  between  50—58°  t h e (060)10 reflection. T h e p o s i t i o n  between  d i — a n d trioctahedral  of this  2:1 silicates  at 2 °  29  per  reflection  (Jackson,  1956).  Analytical Techniques Analytical into  techniques  the following  — Clay  layer  — Sharpness  analyses  have  been  divided  mineralogy.  analyses.  ratio  a n d illite  crystallinity  index.  Mineralogy Identification  locations following  o f clay m i n e r a l s different  sample  K a o l i n i t e — has (00/) d — s p a c i n g s by  cation  500 °C 2)  mineral  mineralogy.  — Mixed  1)  f o r s p e c i f i c clay  categories:  — Semi—quantitative  Clay  used  saturation  for 2  increases  produces in  o n changes Identification  in diffraction criteria w e r e  of 0 . 7 1 5 n m a n d 0.35 n m w h i c h peaks  dissappear  upon  peak as f o l l o w s :  are  unaffected  heating  at  hours.  of smectite present in intensity  l e a v e s this  treatments.  and glycolation. These  Illite— h a s a ( 0 0 1 ) d — s p a c i n g amount  was based  peak  1.0 n m w h i c h  (Reynolds  and sharpness  unaffected.  a (060) reflection  the 0.1525-0.1534  of  Jackson  &  Hower,  upon (1956)  slightly d e p e n d i n g  1970).  reports  that  o n the  T h e 1.0 n m p e a k  saturation with  at 0 . 1 5 n m w h i l e  n m range.  varies  K . +  Heating  dioctahedral  trioctahedral  illite  t o 500 ° C illite  has a (060) peak  3)  Chlorite—  has (00/) s p a c i n g s  vermiculite (Brown,  collapses  nm.  heating  After  n m while  Vermiculite— relative to  . 5)  500°C  of  of approximately  Brindley  result  (001) d—spacings 2  6) . M i x e d a later  clays—  1.4  sample  1.4 n m w h e n  will  at 1.4  collapse t o  in intensity. saturated  1980).  and collapses  persist  This  with  Mg *  at a  2  d—spacing  t o 1.0 n m w h e n  increases heated  to  (1980)  to 0.95—1.0  demonstrates  (00/) d — s p a c i n g s .  at 4 0 % relative saturated  nm when  h o w saturation  heated  with  For the purpose  for 2  different  o f this  humidity  are a p p r o x i m a t e l y  samples,  respectively.  study,  1.1—1.25  Giycolated  nm  samples  1.69 n m . of i l l i t e / s m e c t i t e  mixed  layers  is d i s c u s s e d in  Mineralogy  estimates  was determined  of t h e reflections  n m (chlorite),  samples.  increase  collapses  the identification  Semi—quantitative  height  3  section.  Semi—quantitative  each  smectite  and K*  t o approximately layer  non—Al *  vermiculite  3  4 0 % (Brindley,  giycolated  in d i f f e r e n t  1.1 n m f o r M g *  expand  and A l *  K*,  all 1.4 n m v e r m i c u l i t e will  vermiculite  3  with  with  hours.  at 500°C.  smectite and  has a (001) d—spacing  like v e r m i c u l i t e ,  cations will  for 2 hours  can be confused  all b u t n o n — A l *  treatment  chlorite  peak  for 2  hours  t o 500 °C  from  K*. Upon  t o 1.0 n m w h i l e  1.52 n m w h e n  Smectite—  with  t h e 1.4 n m c h l o r i t e  humidity  roughly  1.4 a n d 0 . 7 1 5 n m w h i c h  It is d i s t i n g u i s h e d  1 9 6 9 ) b y saturating  vermiculite  1.0 4)  a n d kaolinite.  of  o f t h e relative  by methods  at 0.7 n m (kaolinite),  a n d 1.7 n m ( s m e c t i t e )  A correction  outlined  factor  of 8 : 8 : 2 : 2 : 2  were  proportion  of each  type  in  b y Bayliss ef al. (1970). T h e  1.0 n m (illite), measured  was then  clay  1.4 n m  on M g *  multiplied  2  (vermiculite),  saturated  by the respective  peak  heights  to compensate  The  above  type p r e s e n t  mentioned  in a sample  between  mixed  smectite,  discrete  layered  polarization  procedure  b u t says  (Bustin  quantifies  nothing  a n d Bayliss,  only  about  h o w those  a n d d i s c r e t e clays. T o q u a n t i f y  illite,  1979).  the proportions  layer  illite/smectite present  Diffractograms  of M g saturated  clays  were  15.65—17.65°  26  be  at 15.78°  of each  clay  clays are d i s t r i b u t e d  the distribution  and mixed  was 1)  for Lorentz  of discrete  the following  technique  employed:  reflections  range.  examined  If d i s c r e t e s m e c t i t e a n d 17.65°  for reflections  a n d illite  were  present  respectively (Reynolds  26,  in the there  would  and Hower,  1970). 2) T h e ratio o f illite  3)  was  calculated  (i.e.,  X.j|. :1).  If,  tied  was  then  '  multipied  ^  l  m  )  o f this t e r m  of  '  t o t a  P  r  c  e  n  o f illite that  . w a s greater x  and  a new S  . mix  than  o r equal ^  S  unaccounted  e  than  t  will  8  normalized  b e referred  there  This  value  o f total  o f illite  °f  'H't  e  I  was calculated.  Intuitivly, 7  f o r if it h a d b e e n  in S  0  m  x  T h e difference  t o t  )  tot in t h e l/S in l/S) between  represented the  completely  the n e w S . mix  t o l/S m i x e d  would  . a n d S^ . w o u l d , mix tot  previously  (l j )  illite.  w a s assigned  .. T h e d i f f e r e n c e tot 4  present.  the sample  i n  smectite  s m e c t i t e (S,. J  of smectite  r  e  t o as ' X j ' .  t h e total clay c a l c u l a t i o n s  . a n d S . (the percentage mix mix ° layers  section)  to 1 smectite  w a s n o discrete  ' the percentage  o c c u r s as d i s c r e t e I  was then  layers.  o f l/S m i x e d a  layers ( s e e f o l l o w i n g  all t h e s m e c t i t e f r o m  b y X| t o d e t e r m i n e  The s u m of I  e  percentage If  value  u p in t h e i l l i t e / s m e c t i t e m i x e d  layers. '  a n c  This  it w a s d e t e r m i n e d  that  t h e total percentage  'mix  4)  value  t e  it w a s a s s u m e d  was  gave  sample.  t h e diffractograms,  present  mixed  for each The X-|jj  te  from  t o smectite in illite/smectite m i x e d  determined  that  have  therefore,  discrete  layers  t o b e less be  smectite was  not  present.  This  'residual'  smectite  mixed  in  small proportions  such  layers (i.e.,  r e c o g n i s e d . This of  both  Mixed  Hower  mixed  in mixed (1970),  produced  that  layer  study.  could  of % chlorite  at a p p r o x i m a t e l y  smectite  possible  to be  percentage  possible  in each  sample:  Two  mixed  different  were  layers  methods  the difference  was used  were  the proportion  in 28  of  (002)10/(003)17  peak  by  the author  to be a more  to  take  which  (Reynolds  of second  were  the percentage  the techniques  of  considered  order  between  illite  based  for determining followed  accurate  measure  account  coherently  of  (domain (Srodon,  %" c h l o r i t e study.  the percentage  The second  of  Srodon  28  method  of the  The former %—illite  of  in t h e 42—48°  o f illite.  method  is b e l i e v e d  as t h e latter  size b e i n g 1980)).  positions  the method  t w o reflections  1970).  of  in this  o n the positioning  and Hower,  peaks  D u e to the presence of  not possible  T h e first  of  Reynolds and  a n d third  and the determination  of the proportion  size' into  scatters x—rays  masked  layers.  as a m e a s u r e  'small domain  to determine  samples.  was, therefore,  in t h e illite/smectite m i x e d  (1980) w h e r e  layer c h l o r i t e / s m e c t i t e  1.4 n m a n d k a o l i n i t e at 0.71 n m t h e t r u e  chlorite/smectite  structure  present  other  was t o o weak  a n d a minimum  It w a s a t t e m p t e d  in giycolated  in  determines  reflection  been  shifts in t h e l o c a t i o n  the chlorite/smectite peaks  region  have  t o error,  of discrete  f o r t h e maximum  chlorite/smectite by using  of  illite  values  layer i l l i t e / s m e c t i t e a n d m i x e d  w h o used  as a m e a s u r e vermiculite  t h e (002)10/(003)17  layers a n d d i s c r e t e s m e c t i t e  in the current  chlorite  t o be attributed  Analyses  Both analysed  that  o f d i s c r e t e illite  layer  have  chlorite/smectite) or the presence  approach  l/S m i x e d  percentage  smectite w o u l d  that v o l u m e  Srodon  (1980)  neglects of' a reports  that  a small d o m a i n  location  a n d thus  Problems  obtained  > 8 0 % illite  d u e t o overlap  Using illite/smectite  introduce  Reynold mixed  from  contribute  additional  t o s h i f t i n g of t h e ( 0 0 2 ) 1 0 / ( 0 0 3 ) 1 7  error  associated with Srodon's  layers c o n t a i n i n g differentiated  size will  t o t h e analysis.  (1980)  t w o reflections  method  are that  in t h e 42—48°  for mixed range  28  cannot  be  o f the peaks.  and Hower's  (1970)  method,  layers w a s d e t e r m i n e d  t h e clay  peak  analyses with  the proportion  by comparing  the data  o f illite in  t h e diffractograms  of Reynolds  and Hower  (1970)  (Table 10). This  method  required  data. T h e objective linear equations position  theoretical data,  from which  t o have  the positioning  illite  peak.  a sigmoidal  of t h e s e c o n d  be assumed  of  Reynolds  was t o express their could  Although  a n d third order error  order  and Hower's  d a t a as a series o f  be determined  the data  distribution with  as t h e e x p e r i m e n t a l  it c a n o n l y  interpolation  proportions  j u s t i f i c a t i o n f o r fitting h i g h e r  in addition,  reported  a linear  of this i n t e r p o l a t i o n  of t h e (002)10/(003)17  (1970) appears and  performing  given the  of Reynolds  r e s p e c t t o illite reflection  polynomials  (i.e.,  associated with  peaks  proportion there  cubic)  is n o  to the  the data w a s n o t  that t h e r e l a t i o n s h i p is at b e s t  linear.  Example  A d i f f r a c t o g r a m i n d i c a t e s that n o r e f l e c t i o n s o c c u r at 15.78° 28, t h e r e f o r e , n o d i s c r e t e s m e c t i t e is p r e s e n t . M i x e d layer p e r c e n t — i l l i t e c a l c u l a t i o n s reveal that m i x e d layers are c o m p o s e d o f 8 5 % illite a n d 1 5 % s m e c t i t e . Therefore, Illite/smectite ratio = 8 5 : 1 5 N o r m a l i z e d ratio = 5.66:1  and Hower  %lllite  Figure 21-  in l / S  Mixed-Layers  Plot o f v a r i a t i o n s in ( 0 0 2 ) 1 0 / ( 0 0 3 ) 1 7 illite p e a k l o c a t i o n w i t h variations i n % i l l i t e in i l l i t e / s m e c t i t e m i x e d - l a y e r clays.  TABLE  Positions  of  the (002)10/(003)17  Diffraction  10  Peak  for Various  %  lllite  in I l l i t e / S m e c t i t e  Values  %  Data  of  lllite i n l/S 0 20  Reynolds  40  16.15  60 80 90 100  16.58 17.19 17.50 17.65  and  X|=  Total—clay  (002)10/(003)17: 15.78 15.87  Hower,  1970  5.66  c a l c u l a t i o n s reveal  that  the sample  is c o m p o s e d  5 5 % kaolinite 40% illite 4% smectite 1% vermiculite therefore, ltot=  and,  therefore,  ^tat 'mix  Total Total  40 -  =  Smix S j *X|= -  m  % %  x  4  23  l/S m i x e d layers = d i s c r e t e illite = l  t o t  I j + S j = 27% — l j = 17% m  x  m  m  x  x  of:  20  Sharpness  Ratio  Two the  degree  Weaver's to  to  of s h a l e  (1961)  Kubler's  measured  rather t h a n  Crystallinity  shape  Index  parameters  are u s e d  diagenesis in t h e studied  sharpness  ratio  of the reflection (1964)  at half  another  Illite  1.0 n m p e a k  the height  using  and  'illite  height.  it is m o r e  which  in this  section. These  compares  the height  at 1 . 0 5 n m a n d illite  crystallinity i n d e x '  A s scan  speeds  convenient  where  illite  approximate  p a r a m e t e r s are  of the peak  at 1.0 n m  crystallinity, w h i c h  t h e (001) peak  a n d chart s p e e d s  t o report  study t o  is  measured  w i d t h is  c a n vary  from  o n e study  crystallinity v a l u e s i n d e g r e e s  A20  millimeters.  RESULTS  Clay  Mineralogy  Appendices different sample  treatment.  1—3 s h o w From  and the section  kaolinite,  illite,  however,, s o m e  an e x a m i n a t i o n in g e n e r a l  and possibly variation  t h e diffraction  in t h e relative  restricted t o z o n e  through  zone  elsewhere.  (Table 11).  each  tables  each  of these  v e r m i c u l i t e persist  is a p p a r e n t l y  section  l o c a t i o n s f o r all s a m p l e s w i t h  was determined.  Chlorite  4 than  peak  4 while  Di—octahedral  T h e results  through  proportion  t h e clay  of  mineralogy  indicate  t h e entire  that  s e c t i o n . T h e r e is,  illite ( s e e f o l l o w i n g  s m e c t i t e is a p p a r e n t l y  2:1 silicates  persist  of  section).  less  through  abundant t h e entire  TABLE  Variations  in  Smectite  (060)  Height  d-spacing  Section  Tri—octahedral  (0.149-0.151)  (0.152-0.153)  — — •. — . — — — — —  0.1496 0.1499 .0.1512 0.1497  —  0.1511  — • —• —• — • — . — — —  0.1510 0.1507 0.1502 0.1505 0.1510  — '  0.1492 0.1501  Mineralogy  in T a b l e  decreased  with  increased.  At  12.  results General  increasing  the  approximately  of  total—clay  trends  depth  boundary  relative, p r o p o r t i o n s .  remained  Through  0.149  Semi—quantitative  their  nm)  0.1505 0.1510 0.1507  Semi—quantitative  listed  (in  Di—octahedral  656 748 892 919 1058 1070 1120 1268 1330 1551 1699 1830 2100 2173 2243 2358 2419 2967  are  11  Through constant.  indicate  through  between  zone  zones  zones The  percentages  2  major  that 4,  the  3 and and  as  3,  point  through  the  percentage  percentage  4 there  of  is a  sharp  and  illite  kaolinite of  the  interest  with  studied of total  section  kaolinite illite  reversal  in  proportions  respect  to  smectite  is that  smectite  was l o w (<2%)  Below  zone  4 there  approximately graphically  vary  interval.  Percent  of  trend  Smectite  to  in  layer  here  with  w a s that  Figure  with  increasing  depth.  of total smectite t o 22  demonstrates  depth.  both  through  the the studied  d i s c r e t e illite  a n d chlorite  i l l i t e / s m e c t i t e w a s relatively a b s e n t h o w t h e t h e relative  that  Mixed  through  were  this  proportions  o f clay  layers  of t h e diffractograms  was present in this r a n g e  a separate  minimize  permitted  to note  lllitel Smectite  in t h e s e c t i o n  assumed  t o t h e base.  23 i n d i c a t e s g r a p h i c a l l y  examination  o n e peak  In  high  constant  in the percentage  c o m p o s i t i o n s vary  4. M i x e d  Figure  t w o peaks  where  remained  increase  section the percentage of  depth.  An only  w a s a sharp  approximately  13 outlines t h e distribution of clay—types  The main  with  2/3 o f t h e s t u d i e d  and remained  h o w the sample  restricted t o z o n e same  the upper  4%, which  Table section.  through  in t h e 42—48° suggested,  the domain the amount  26  using  d i d the %—smectite  attempt  from  to determine  the application of  range  Srodon's  a value  (1980)  that  The absence  method,  that  layers  no  exceed 15%.  f o r t h e % — s m e c t i t e it w a s  through  and Hower's  revealed  in all s a m p l e s .  t h e s e c t i o n w a s large  attributable t o small d o m a i n  Reynold  study  in i l l i t e / s m e c t i t e m i x e d  size o f all s a m p l e s of error  the present  (1970)  s i z e . This  method  of  enough  assumption  %—illite  determination.  Figure were  24 illustrates t h e v a r i a t i o n s in t h e p e r c e n t a g e  calculated through  the section using  Reynolds  o f illite  and Hower's  with  (1970)  depth method.  that In  99  Figure  22-  Plot of v a r i a t i o n s in shale c o m p o s i t i o n w i t h d e p t h a n d through individual paleo-environments. K= kaolinite, 1 = total u n d i f f e r e n t i a t e d illite, V = v e r m i c u l i t e , C = chlorite and/or non-Al vermiculite, S = total smectite.  100  3000  ,500  H  5 0  1  1  1—-i  60  1  1  1  1  70  1  1  1  1  8 0  1  1  1  1  1  1  1—1—  90  Percent  Figure 23-  P l o t of v a r i a t i o n s in s h a l e c o m p o s i t i o n w i t h d e p t h a n d through individual paleo-environments. K= kaolinite, l = d i s c r e t e illite, l / S = illite/smectite mixed-layers, S = discrete and undifferentiated smectite, V = vermiculite, C = chlorite and/or non-Al vermiculite. '  100  101  Figure  24-  Plot of v a r i a t i o n s in the p e r c e n t a g e of illite in i l l i t e / s m e c t i t e m i x e d - l a y e r e d clays w i t h d e p t h a n d t h e i n d i v i d u a l p a l e o e n v i r o n m e n t s of R A K - 2 6 .  through  TABLE  Semi—quantitative  Mineralogy  of Studied  12  Section  with  Undifferentiated  Illite  (%)  H e i g h a/b  Kao  J!  Chi  Verm  Smec  656 748 892 1058 1070 1120  69 75 70 76 54 55  29 19 23 18 40 42  0 0 0 0 4 4  2 3 3 3  0 3 4 3 2 0  1268 1490  56  39  54 57 60 60 60 62 79 84 67 71 64  1551  1699 1755 1830 1866 2100 2173 2243 2419 2967  44  .  39  37 36 36 35 18 13 29 27 30  ? ?  3  ?  2  3  ?  3  ?  0 1 0 1 o 1 1 1 2 1 2  3 3 4 3 1 0 0 0 0  ? ? ? ? ?  2 2 1 •3  eight aJb = h e i g h t , a b o v e b a s e (metres). K a o = k a o l i n i t e , total s m e c t i t e , V e r m = v e r m i c u l i t e , C h l = c h l o r i t e  general,  the percentage  approximately sharp illite.  100%  increase Within  section.  o f illite  at t h e b a s e  in t h e percentage  zone  3 t h e illite  lll=  total  at t h e t o p of t h e s e c t i o n ( ~ 8 8 % ) of z o n e  4. B e l o w z o n e  4 there  of smectite a n d decrease  percentage  again  illite,  Smec =  increases t o is a - relatively  in the percentage  increases t o w a r d  t h e base  of  of t h e  T A B L E 13  Semi—quantitative  Mineralogy  of Studied  Section  with  Differentiated  Illite  (%) •  H a/b  Kao  lll(d)  Smec(d)  656 748 892 1058 1070 1120 1268 1490 1551 1699 1755 1830 1866 2100 2173 2243 2419 2967  69 75 70 76 54 55 56 54 57 60 60 60 62 79 84 67 71 64  29 20 0 0 41 42 43 44 0 37 0 36 35 0 0 0 0 0  0 0 4 3 0 0 0 0 1* o 1* 0 0 1* 1* 2* 1* 2*  H a / b = height above base (metres), discrete smectite, V e r m = vermiculite, layers i.e.,  Illite  Crystallinity  upper  A20 (Table  Verm  0 0 0 0 4 4 3 3 . 3 3 3 4 3 1 0 0 0 0  0 0 23 18 0 0 0 0 39 0 36 0 0 18 13 29 27 31  ?  2 2 1 3  K a o = k a o l i n i t e , lll(d) = d i s c r e t e illite, S m e c ( d ) = C h l = chlorite, lll/Smec= illite/smectite mixed  o r absent.  Index  2/3 of . the  were  section.  at t h e t o p o f t h e s e c t i o n 14). W i t h i n  Ill/Sm  2 3 3 3  (*) i n d i c a t e s maximum possible value ( 0 0 2 ) 1 0 / ( 0 0 3 ) 1 7 r e f l e c t i o n at 5 . 6 2 - 5 . 6 6 A w a s w e a k  Illite crystallinity values the  Chi  zones  found  t o decrease with  C r y s t a l l i n i t y values t o approximately  decreased  increasing depth from  through  approximately 0.85  0 . 3 3 A 2 0 at t h e b a s e  2 a n d 3, t h e crystallinity o f illite a p p e a r s  of zone  to show  no  4  relationship crystallinity  to  increasing d e p t h  throughout  (Figure  25).  and  is real  zones  2  values  show  3  Whether or  this  not  random  distribution  is d i s c u s s e d  in  a  of  illite  later s e c t i o n .  Sharpness Ratio  Sharpness ratio  increases  section  to  4,  however,  of  zone  ratio  more  or  less  approximately the  2  (Figure  linearly  1.60  sharpness  a simillar from  close to  ratio  trend  to  that  approximately  the  decreases  base  of  1.20  zone  linearly t o  of  illite at  4  crystallinity.  the  top  of  The  the  (Table  15).  Below  zone  approximately  1.05  at t h e  base  26)..  DISCUSSION  Shale and  analysed  diagenetic  temperatures in  a form  (i.e.,  increasing  Care  must,  attributable  attained will which  has  domain  the  be  Only the  been  temperature  therefore, to  the  clay c o m p o n e n t .  are  exist  from  detrital  diagenesis  after  low  majority o f unaffected  and  taken  of  pressure, when  component  grade  the  by  usually  metamorphic  detrital clay  its  in  pore  clay  from  attributable  and  no  longer  environment  chemistry,  analyses t o to  a detrital  pressures  chemical  water  interpreting  both  component  physical and  variations  those  contains  etc.).  differentiate the  results  diagenetic  component.  An that  of  paleo—environments  primary This  examination  control  does  not,  on  the and  producing  however,  shale c o m p o s i t i o n provenance, the  rather  observed  totally d i s m i s s  the  plots than  (Figures authigenic  distribution presence  of  of a  22  and  23)  indicates  mineralogy,  clay minerals diagenetic  with  exert depth.  component  .  Figure  25-  Plot of v a r i a t i o n s in illite crystallinity individual paleo-environments.  through  section  and  Figure  26-  P l o t of  v a r i a t i o n s in  the  through  section  individual  and  1.0:1.05  nm  peak  sharpness  paleo-environments.  ratio  TABLE  Variations in  Height  above  base  14  lllite C r y s t a l l i n i t y w i t h  (m)  Depth  lllite  Crystallinity  656 748 892 919 1058 1070 1120 1268 1330  0.55 0.85 0.77 0.50 0.65 0.34 0.45 0.49 0.46 0.40 0.50 0.45 0.49 0.49 0.50 0.70 0.75 0.73 0.67 0.55  1490 1551 1699 1755 1830 1866 2100 2173 2243 2358 2419 2967  In  these  p l o t s it  clay p r o p o r t i o n chlorite smectite and  4.  is  suggests  trends  if  that  seen  occur zone  that  illite  in  4,  in illite  l/S  at  gross zone  changes  kaolinite content  control on  mineralogy  zone trends  at t h e  boundary  sharpness  boundaries in  and  boundaries.  decreases through  increase sharply  layers at  in  (lithofacies)  crystallinity values,  mixed  lithofacies exert  the  primarily  kaolinite proportions  E n i g m a t i c shifts  percentage  0.65  can be  restricted to  and  Index  ratios (i.e.,  zone  and  in  example,, 4,  between  zones  clay diagenesis  For  reversals  and zones  3  the 3 and  parameters.  4)  also  TABLE  Variations  Height  •ove  base  in  15  Sharpness  Ratio  with  Depth  (m)  Sharpness  656 748 892  1.060 1.108 1.289 1.220  919 1058 1070 1120 1268 1330 1490 1551 1699 1755 1830 1866 2100 2173 2243 2358 2419 2967  Control,  in  chemistry  this c a s e ,  unique  to  Ratio  1.429 1.631 1.444 1.478 1.444 1.427 1.316 1.364 1.383 1.347 1.324 1.225 1.194 1.356 1.291 1.219 1.219  coming each  from  zone  (i.e.,  variations P.,  in  either detrital  P,-.-.  ,  mineralogy  or  fluid  [cation]).  112*-' ' \—U 2 Within evidence  to  example,  the  from of  the  illite.  top  each  zone,  support  the  i n c r e a s e s in of  the  and  in  some  diagenetic illite  section  Similarity, c o i n c i d e n t  cases t h r o u g h  overprinting  of  the  crystallinity, s h a r p n e s s to  the  base  increases and  of  zone  adjacent  there  detrital m i n e r a l o g y .  ratio 4  zones,  values  supports  d e c r e a s e s of  and  different  clay  For  %illite  diagenetic  is  in  l/S  alteration  minerals  over  specific  intervals  Before  examining  however, by  s u g g e s t s that  the diagenetic  it is first  Fades  1980  Glossary  strata a l o n g  there  of  r e a c t i o n s may  and some  b e taking  of t h e associated  the "diagenetic fades"  Kanguk  that  place.  problems, is r e p r e s e n t e d  Peninsula.  Sub—facies  and  Although  trends  necessary t o identify  the Eureka S o u n d  Diagenetic  possible diagenetic  exists  n o universally a c c e p t e d  (Bates  Geology  ef al.,  definition  1980) defines  of  diagenesis t h e  d i a g e n e s i s as:  'chemical, physical, a n d biological changes u n d e r g o n e b y a s e d i m e n t after its o r i g i n a l d e p o s i t i o n . . . e x c l u s i v e o f surficial a l t e r a t i o n a n d m e t a m o r p h i s m . . . . It e m b r a c e s the processes...that o c c u r under pressure (up t o 1 kilobar) a n d temperature ( m a x i m u m range o f 100 ° C t o 3 0 0 ° C ) that are n o r m a l t o t h e surficial o r o u t e r part o f t h e earth's c r u s t . ' The  temperature  however, (i.e.,  because  P>1Kb)  metamorphic fields, by  a n d pressure imply  and defined facies  a preferred  Winkler  they  constraints used that t h e l o w e r  without  regard  are delineated criteron  in this  limits  for marking  m a y be misleading,  of m e t a m o r p h i s m  t o phase  in P—T s p a c e  definition  stability f i e l d s .  by the mineral  are a b s o l u t e  Because  assemblage  the diagenetic/metamorphic  stability  boundary  is g i v e n  not without  fault.  (1967). ' M e t a m o r p h i s m has b e g u n a n d d i a g e n e s i s has e n d e d w h e n a m i n e r a l a s s e m b l a g e is f o r m e d w h i c h c a n n o t originate in a sedimentary environment.'  Although For than  Winkler's  example,  definition  if it is a s s u m e d  the sediment/water  precipitate apparent  just that  below  may perhaps that  interface  a 'sedimentary  then  diagenesis  the sediment/water  in h a v i n g  t o define  b e preferred  interface.  a 'sedimentary  it is still  environment' has e n d e d  once  It, t h e r e f o r e , environment'  extends pyrite  no  deeper  begins t o  n o w becomes a certain degree  of  cyclicity  is  introduced  diagenesis c o u l d a 'sedimentary space  into  perhaps  trying be  environment'.  relative t o  to  and  diagenesis)  relatively  u n s u c c e s s f u l . This  if  Figure  indicates the  based is  on  laumonite,  f a c i e s in  t h a n just  temperature  range  illite crystallinity v a l u e s derived  O.32A20  (Sagon  O.56A20  (Frey  ef  and  maximum  95 ° C  rather t h a n  al,  in  shown  be  Hower, water  and  the  some  to  rigorous  deliniation  as  of  of  definition  diagenesis  to  1970),  O.64A20 derived  the  layers have  peak  morphology  less—than-reliable  i n d i c a t o r s of  on  factors  I n a c c u r a c i e s are  such  in  of P—T  of  (islam  and  1970)).  previous  chapter  strata a p p e a r  As  (i.e., to  of  more  a result,  a  units f r o m boundry  Using on  been  investigators  Hesse,  to  have  function  the  (i.e.,  attempted  diagenesis/ankizone  (i.e.,  1983), the  coal  lie  which  (i.e.,  within diagenetic,  27).  sharpness been  ratios a n d  used  to  parameters, pressure  as v a r i a b l e  especially prevalent  c a t i o n c i r c u l a t i o n is less  then  is a  ef al,  (Figure  illite,  that  chemistry  the  studied  space  crystallinity o f  nanometre  the  O.43A20  the  and  crystallinity values).  (Chennaux  from  1.27Kbars)  parameter  previous  assemblages  pumpellyite)  as  mark  mineral  scheme  parameters  fact that  of  illite  varied  used  P—T  other  morphology the  terms  (i.e.,  Segonzac,  1980),  dependence  1978). and  been  illite/smectite m i x e d One  maturation  de  of  pressure  ankimetamorphic,  substages. to  and  pressures  Traditionally, smectite  terms  have  and  temperatures of  a more  definition  facies subdivision  peak  lawsonite, prehnite,  the  they were  f a c i e s in  1.0nm  primarily d u e  delineate  of  27  Winkler's  it c o n t a i n e d  pre—metamorphic  pre—metamorphic  a n k i z o n e = illite,  diagenesis.  improved  establish a  ankizone  defined  define  metamorphism.  Attempts  have  to  restricted. For  in  delineate  however,  and  cation  proportion  diagenetic  have  temperature  recently due  a c t i v i t i e s (Eberl  pre—ankizone  of  stages  e x a m p l e , variations  in  to  been their  and where [KVother  Figure  27.  P l o t of  diagenetic  facies  in  P-T  space.  cations]  are  known  [K /Na +Ca +  of  +  2 +  ]  to  are  have  to  Additional diagenetic  the  activity of  problems  expandable  material m a y  contribute  stages  observation  of  is a f f e c t e d  (Srodon,  1978,  suggested simply  therefore,  illite  on  nm  of  0  the  Strand  Fiord. of  the  ef  nm  scheme As was section  of  peak  to  diagenesis  ef al  rock  than  360 ° C of  mentioned  (1976) to  al  Srodon  ratios  l/S  a  be  commonly  of  a  The  present  (1970) t o  previously,  is a p p r o x i m a t e l y  mixed  of  based  be  in  and this  the  (001)  present  It is,  therefore,  depth  are  layers  and,  chemistry. more  than  Thus, just  classification s c h e m e  error.  using  cation  of  with  lithology  micaceous  R max 0  criteria.  independence  of  diagenetic sub—classification scheme  superior. ef al.  and  (1980)  support  1984).  the  delineated  dependence  delineate  early  component  parameters  function  would  the  width  Eberl,  fluid and are  to  Foscolos  findings  the  and  morphology  parameters  less  parameters  during  the  smectite content  matter,  Foscolos  Low  the illitization  c o n t r i b u t i o n s of  a maturation—temperature  be  retard  (1976) and  morphology  in f o r m a t i o n  temperature  appears  et  Broekstra's (1984)  1984;  morphology  organic  Hower  source  less  sharpness  s u b — f a c i e s are  on  said by  composition  in t h e  rocks to  to  peak  and  al.,  1.0  diagenesis parameters.  (1978)  clay  and  hm  and  variations  extreme  values  classification  amount  variations  peak  using  temperatures  Weaver  assigning  1.0  R max  base  the  clay  Hower  Foscolos  Weaver  crystallinity a n d  vitrinite m a t u r a t i o n by  at  to  1.0  is  on  in s o l u t i o n .  +  chemistry  the  v a r i a t i o n s in  Diagenetic Because  to  reflections of  temperature, based  by 1984;  that  layer  that  r e f l e c t i o n s of  because  K  illite  arise w h e n  diagenesis.  noting  Eberl a n d  crystallinity o f  in  peak  by  sub—stages. A c c o r d i n g  variations  middle  significant effect  suggested  smectite while the  directly, related  a  1.0%.  the Near  study,  define  mean the  the  therefore,  of  uses  the  d i a g e n e t i c s u b — f a c i e s at  maximum top  defined  the  reflectance  at  section the  the R max 0  decreases to  t o a m i n i m u m " of approximately  eodiagenesis  (i.e., w h e r e  R m a x = 0.5—1.5%). parameters  (i.e.,  R max=  (i.e.,  illite  thermal  0  values w o u l d  clay p a r a m e t e r s diagenetic  of  An  problems  include:  below  expected  zone  with  of these  shales  clay  seems  a more  increasing  by the meso—  As was mentioned 0  reasonable  where  t o late  the R m a x that  v a l u e s are  the measured  diagenetic stage  accurate measure  a n d that t h e of the  primary  than  trends  in overlying  that  ratio  must  a number  b e considered.  a n d increase  are t h e o p p o s i t e  of  to what  These  in illite crystallinity is g e n e r a l l y  depth). in illite  between  zones  proportion  i n t h e l/S m i x e d  layers  accounted  a n d 4?  3  can be answered  in part  b y c o n s i d e r i n g t h e effects of  depth.  factors believed  i n clay d i a g e n e s i s  Depth  2 4 , 2 5 a n d 2 6 i n d i c a t e that  in t h e s h a r p n e s s  decrease  questions  with  diagenesis parameters  4. ( S u c h  clay variation with  The shifts  t h e c o a l s exists  approach  Parameters  of figures  at t h e b o u n d a r y  detrital  stage defined  diagenesis.  t o a lower—than—true  Clay  a decrease  H o w is t h e s h a r p  Both  in  regarding  W h y is t h e r e  for  with  It, t h e r e f o r e ,  i n this c a s e ,  examination exist  2)  retarded.  Shifts  problems  index  the diagenetic  correspond  (i.e.,  crystallinity o f u p t o 0.4 A 2 0 ) c o r r e s p o n d  correspond  may,  brackets  0  stage.  Consideration  1)  purposes  disequilibrium  b e l i e v e d t o b e slightly  R max  t o early m e s o d i a g e n e s i s  0  because  R max  <0.5%)  These  1.0—1.5%) t o early t e l o — ( R m a x > 1 . 5 % )  0  earlier,  0  For comparative  o  clay  R max  0.48%.  parameters units.  to be responsible for producing are h i g h e r  Previously  P^Q  proposed  and P theories,  H  Q  the observed  in the z o n e  s u c h as a shift  3  from  dioctahedral be  smectite  discounted  trioctahedral  to  in this  2:1  c a s e as  silicates are  Late d i a g e n e t i c increase  et  the  Hurst  responds  to  'opening'  illite  weakened  whereby  order  to  under  an  and  is that  layers  from  by  K*  favor  the  and  be  is g e n e r a l l y  1977)  must  that  of  accepted C 0  Eberl ( 1 9 8 4 )  its interlayer  elemental  indicates  production  and  cations  lost or  (Bustin,  section.  the  Srodon  units  peaks  matter  interlayer  may  neutrality,  hydrated  organic  'opening'  two  (060)  entire  through  between  interlayer  of  the  (1982) and  bonds  could  of  environment  Irwin  charge  sufficiently  examination  absent  increasing acidity  preserve  octahedral  an  smectite between  decarboxylation  a c i d i t y of  (1980),  al  trioctahedral  and  . Foscolos  2  suggest  spaces. The  rearrangement  that  result  tetrahedral  substituded  other  within  the  conversion  of  illite t o  sodium—rich  conditions.  An  i n c r e a s e in  illite  of  sheets  with  retrograde  to  are  cations. tetra—  In  and  illite—smectite P.-.-.  ,  C O 2  therefore, illite the  can  produce  changes  crystallinity, s h a r p n e s s cation  and  3  chemistry  supports  is k n o w n  to  the  be  in t h e  ratio  and  is c o r r e c t . T h e  stable under  low  pH,  which  parameter  trends  is t h e  presence  Studies  illitization  notes  that  transformed kaolinite  by  under  to  Eberl a n d  conditions  under  Low  zones  2  may of  Hower  of  sufficiently  illite.  through  i n c r e a s e in environment  theory  and  3,  of  +  for  have  P.,  ^.  M  \J  2  conditions  u  observed ~  n 2U  also  Denoyer  +  the  shifts  de  that  as  that 2  kaolinite  by  the  in clay  between  smectite  Segonzac  smectite will  retard  given  in  within zones  K —poor  differential  suggested  cations], supported may  reflected  conditions.  the P  be  l/S v a l u e s  was acidic and  [K*7H ]  (1978)  illite in  will  kaolinite p r o p o r t i o n s  a possible  hydrated  [K " / o t h e r  low  account  elevated  lattice w h i c h  proportion  the  second  4.  the  i d e a that  A  and  illite crystal  resist  3  w i l l resist  (1970)  being  persistence  i l l i t i z a t i o n of  zones  of  smectite.  also  Consideration  of  As  Variations  was mentioned  paleo-environments trends the  produce  depth  of another.  trends  differed of the  chlorite  what  from,  sandstones  than  of f l o w  rather t h a n  in the z o n e some  which  the trends  appear  energy  in b u l k  may suggest  of  that  represent  production  o f o n e clay at  may, however,  exist w h i c h  t o represent  zone.  Likewise,  diagenetic reactions  in paleo—environment  that  such  the chlorite occurring  First, a u t h i g e n i c  Granted  the sandstone  and presence  shale mineralogy  each separate  authigenic. origin.  between  boundaries and  as  with  deepening  and competence.  suggests  4 sandstones.  Depth  the diagenetic  changes  deal of evidence  is o f detrital  detected  that  Chemical microenvironments  more  t h e basin, dissipation  with  d u e t o t h e c o i n c i d e n c e o f clay  rather t h a n  in mineralogy  good  Mineralogy  variations in clays w i t h i n  may be nothing  A 4  it is b e l i e v e d  authigenetic  intrazonal  Sample  previously,  in d e t r i t a l m i n e r a l o g y  expense  of  in  that  a n d adjacent  Mg—poor/free the bulk  t h e fluid  through  chlorite was not  chemistry c o u l d  shales, b o t h  fluid  chemisty  have  the absence .  ankerite (see previous  formation  zone  chapter) in,  was depleted  in  Mg.  Second occur  a n d third, under  previously  conditions of higher  Strand  Fiord.  Group  of s o u t h w e s t Texas,  temperature  For example,  range  M g  2+  2  +  and F e * 2  believed to b e derived  +  diagenetic  temperature  B o l e s a n d Frank that  3.5Mg  2  chloritization reactions  a n d M g activity t h a n  (1979)  the following  o f 150—200°C  3.5Fe The  reported  vs t h e 54—100°C  +  +  9 H  2  0 +  t h e illitization of  o b s e r v e d at  in a s t u d y  of the Wilcox  chloritization reaction occurred  3Kao=  necessary for the conversion from  found,  are said t o  range  at S t r a n d  Chlorite+ of kaolinite  14H  over a  Fiord.  +  t o chlorite was  smectite. Magnesium  c o n c e n t r a t i o n s in  the  Eureka  the  diagenetic  M g  2  Sound  void  +  second  strata f r o m  formation  to  of  extremely  Strand  c h l o r i t e as  Mg  2  zone  converted  4  to  is  presented  illite a n d  by  smectite + This  reaction,  low  K*  as w e l l ,  activity m a y  must have  be  (i.e.,  believed to  <5%  produces  Hower  c h l o r i t e as  are  ankerites from  poor  +  chloritization reaction w h i c h  through  Fiord  Mg  the  et al  the  be  too  section  in F e — M g  observed  are  by  promote  found  solution  trends  (1976) w h e r e  low to  to  be  sites).  in clay  A  mineralogy  s m e c t i t e is  follows: K =  illite +  +  quartz +  d i s c o u n t e d as  contributed  to  the  chlorite  previous  producing  the  section modelled  problems  in clay  that  diagenesis  parameters.  A chlorite also  final is  factor w h i c h  restricted to,  associated with  section w h i c h humid pH).  to  arid o r  Additonal  environment An  may  alternatively  chlorite  and  depositional  and  a  suggest  low  [K*]  humid  kaolinite through  if  delivered  a Mg—enriched  aggradation (1970) f o u n d the  Gulf  of  transport  M g  2  by  +  a trend  c o a s t that  (i.e.,  4  distances were  the  environment degraded  rock  (Zen,  greater  and and  mineralogy  similar t o  was  interpreted  as r e f l e c t i n g  c h l o r i t e is  Rex  the  the  be  the  silicated were  study  Perry  and  detrital  in  short.  the  zone  1966).  close to  from  that t h r p u g h only  trends  still f o r m by  an  Martin,  terrain was  2:1  moderate  in a  and  the  from  soil,  observed  degraded  A  The  provenance  distance w o u l d  silicates.  in  4.  neoformation 1959;  chlorite could 2:1  or  chlorite source  time  the  elsewhere through  leaching of  from  is that  zone  occurs  also p r o d u c e  if t h e  transport  than  come  chlorite  through,  minimal  could  of  source  A l : S i ratio  terrain  whereby  kaolinite  could  a high  zone  proportion  in either  this c a s e ,  source  environment  of  conditions  and  detrital o r i g i n  constant  a change  temperate  Alternatively, to  of  the  lesser a m o u n t  k a o l i n i t e , in  of  supports  4  Hower  in a w e l l  mineralogy.  from  Basically,  117.  an  increase  change  in  in t h e  chlorite and  d i s c r e t e illite  depositional environment  from  content  middle  and  was outer  found  to  neritic t o  correspond offshore.  to  a  SUMMARY  AND  CONCLUSIONS  General Summary  The  major  1) T h e o f f s e t the  in t h e c o a l i f i c a t i o n  preferential  horizontal  permeable  units  Additional  minor  come  from  contain  2)  conclusions drawn  Low r high  with  bulk  values  heat  migration  seams  thermal  a n d sandstones) to producing  however,  these  tectonic  models.  before  reduction  o f diapirs w i t h  t h i c k n e s s of  t o lie b e t w e e n subject  these  5200  in heat  offset  to  into adjacent  diapirs.  are t h o u g h t  the lithologies  Eureka  equilibrium  flow  Sound,  and 6800  to  that  m.  at t h e t o p o f t h e s e c t i o n  were  Low r  2  values  to a moderate  calculated  Barker ( 1 9 8 3 )  and 14°C,  with  the organic  to b e associated  at d e p t h .  and possibly  agreement  is r e c o r d e d  t o the cessation of  is t h o u g h t  Beafort, from  degree  with  of t h e c o a l i f i c a t i o n g r a d i e n t s  o f 18.3°C/km  to be 45°C  are a t t r i b u t e d  their source  thickness values  modelling  gradient  stratigraphically  between  thermal  t h i c k n e s s e s are in relative  4) T i m e - t e m p e r a t u r e  waters  +  primarily  matter.  t h e diapirs  gradients  area is a t t r i b u t e d  the observed  from  3) T h e p r e — t e c t o n i c  are as f o l l o w s :  Na —enriched from  t h e coalification gradients  the unrooting  geothermal  of heated  from  flow  study  in t h e s t u d y  conductivity differences  w a s a t t a i n e d . This  thought  the present  gradient  contributions  the organic  2  matter  (coal  from  methods  respectively.  the coalification  of  uncertainty,  previously  suggest  in t h e s t u d i e d  using  Strata is  that a  strata.  of Lopatin  Mid—section  proposed  Temperatures (1971) a n d  maximum  .  temperatures methods.  Six  section.  These  Also  pyrite,  of  calcite.  The  generations  precipitation  ankerite.  (possibly  8)  Second  The  precipitation minerals  dawsonite diapirs.  of  are  for  is  the  A l  the +  3  to  thought  to  into  siderite,  accessory  same  gradients  actual  these  temperatures.  from  kaolinite  authigenic  recognized  in  of  to  of  the  kaolinite  are  also  the  studied  and  quartz  phases  which  the  diagenetic  calcite  formed  in  precipitation  sandstones.  initial  precipitation  framework  and  dawsonite.  Initial  sequence  but  late  studied  the  recognized.  overgrowths  the  in t h e  prior  quartz  to  of  sandstones  dissolution  is  synchronous  precipitate  dissolution back  the  sequence  the  early  coalification  these  prior the  of  calcite  after  to  the  diagenetic  kaolinite  and  the precipitation cycle dawsonite  ankerite.  dawsonite  thought  of  precipitation  prior of  in  calcite,  are  precipitation  generation  precipitation  free  after  the  using  sphene.  diagenetic  relatively  the  after  release  to  tectonically)  and  calculated  approximations  ankerite,  overgrowths  formed  post  responsible  rutile  were  from  detected  a number  first g e n e r a t i o n  but  Both  are  calcite  occurred  were  in t h e  prior  of  p r e c i p i t a t i o n . of of  early  values  2  as first  dawsonite,  quartz  but  r  serve  phases  second  aluminosilicates  respectively,  low  only  illite,  x  formed  83 °C,  the  present  FeO ,  first  7) T w o  to  include:  generations  The of  due  authigenic  overgrowths.  6) T w o  and  temperatures  principal  include  75 °C  Again,  calculated  5)  of  of  the  solution!  originate  with  as t h e  from  the  Na*  precipitation  Al* —organic 3  aluminosilicate The  the  dissolution  of  for  kaolinite.  complexes  eventually  necessary  of  destabilize the  halite  and  precipitation in  adjacent  of  9) T h e  distribution  of  clay minerals  and  c h e m i c a l variations  clay  minerals.  support  the  with  between  However,  is b e l i e v e d  l i t h o f a c i e s rather the  within  diagenetic  depth  alteration  separate  of  illite  than  to  reflect  the  diagenetic  lithofacies there  and  primarily  alteration  is e v i d e n c e  illite/smectite mixed  detrital  layers  of  to with  depth.  These  above  summarize  the  Formation  at  mentioned  diagenetic Strand  and  conclusions  are  sedimentologic  used  in t h e  following  developement  of  the  section  Eureka  to  Sound  Fiord.  Discussion  Diagenetic and  physiochemical  These 1)  events  Eureka  the  high  Sound  occurred clay  zone  4  been  relatively  where  Subaqueous  number  previous  recorded  of  other 2:1  the  3  in . t h e  chapters Eureka  suggest  Sound  area  in  the  is  had  that  strata  at S t r a n d shales,  on  Fiord  that  conditions.  than  to  delivered  Aggradation  kaolinite  2:1:1  silicates.  may  be  subaerial  and  minerals  be  A  of  possible  Neoformationwithin  occurred  to  the  6  separate  at S t r a n d  bio-  Fiord.  As  if  of a  the  its  paleogeography  is b e l i e v e d ,  exception,  the  due  to  sediment  result, t h e basin  of  only  would  however,  transport  have  is s e e n  distance  in had  minimal.  Prior t o  different  these  it  to  detrital o r i g i n  degradation  the  erosion  humid  and  modifications  control  predominantly  chlorite  clay  poor  source  kaolinite  and  short  degraded of  Although  under  types  degraded  the  are  the  Formation  percentage  been  of  events  Weathering—  the  major  from  include:  Subaerial  source  2)  analyses  minerals  the  deposition  sedimentary while  still  and  burial  environments in  the  water  a  121  column  a n d at t h e s e d i m e n t / w a t e r  aggredation form  of Na ,  smectite  enriched  K  depleted  +  Al * / S i * 3  Sediment/Water during  relatively not with the  of M g  zone  ratio  4  Interface diagenesis  as s u l f i d e of. sulfate  concentration  Burial  solution  resulted  subsequent  occurring.  A s a result  elevated  C 0  2  partial  surface  b u t rather  generation  also o c c u r r e d  very  little, at this  therefore, pressure.  where  if a n y , F e * time.  under  in zone  First  t h e Eh w a s  high.  Pyrite  a n d siderite d i d  gave  w a y t o t h e latter  increased  o n passing  progressed and,  as  the  was being  Also  case, t h e  during primarily  t h e early in t h e  rearrangement w a s  liberated  calcite  of reduced  pressure  i n this  w a s still  o r n o lattice  generation  Eventually,  from  ceased.  overgrowths.  conditions  4 there  where  o f silica  2  Rapid  conditions  compaction  little  2  a n d siderite  t h e smectite-illite transformation dehydration  +  (Figure 2 8 ) .  of siderite  quartz  in a M g  of chlorite.  of methanogenesis.  mobilization  Second,  pyrite  a n d P.-.-.  A s sediment  B)-  environments.  2:1:1 silicates  the former  the precipitation  o f first  waters  formed,  near  occurred to  A)- Both  (Diagenesis  to the zone  in t h e t h e early  of smectite  ratio  +  activity relatively  2  however,  reduction  formation  time  +  A under  2:1 silicates  enriched  +  of kaolinite  activity d e c r e a s e d  first s t a g e  at this  +  2, 3, a n d 5  lead t o t h e production  Reactions  (Diagenesis  the formation  K +Na  by the degraded  2  and F e *  stages o f s h a l l o w burial  into  -poor,  and low K / H  o f Fe d e c l i n e d  Shallow  +  First, i n z o n e s  by t h e degraded  2  neoformation  synchronously,  depth  + 2  +  environment  l o w (<0.35v  form  in M g  a n d possible  a high  formed  4)  a n d illite  4 aggredation  was  and C a  +  in z o n e  flocculation  3)  K ,  +  interface.  b y t h e illite  which  Fe  +  2  precipitated  activity a n d  Subaqueous Aggradation and Neoformation Ul  o z < z  Humid/Tropical  UJ  > o CC Q.  Kaolinite, Chlorite and degraded 2:1:1 a n d 2:1 s i l i c a t e s  Flocculation rapid of  and  deposition Kaolinite  Aggradation Na,  of  C a , and Mg by  degraded  silicates  z E <  2 Degraded  lllite  Smectite Kaolinite Chlorite (zone  Figure 28-  4 only)  Chlorite  (zone  4)  S u m m a r y d i a g r a m o f early stage s u b a q u e o u s aggradation and n e o f o r m a t i o n o f clay minerals u n d e r humid/tropical source conditions.  5)  Deep Burial (Diagenesis C)-  During  to  Orogeny,  the  onset  maximum were  of b e t w e e n  It w a s u n d e r began  dissolution  of  Al * .  Second  3  dissolution  of  Within and  a) Z o n e s  2 and  P..  n  2  illite b)  U  2  lead  +Ca  P,~~  porosity  also  in  C,  high  intra-zonal  to the following  partial  2  2  ],  and  4 and 5- conversion  Possible  up to  in the with  this stage 29).  in  Prior t o t h e  at t h e Fe*  expense associated  2  pressures.  variations  in fluid  phenomena:  of smectite-illite transformation +  time  within the  during  increasing  C 0  of  complexing  precipitated to  at this  activity r e s u l t e d  (Figure  prior  to a  temperatures  occurred  response  just  buried  pressures  organic  ankerite  continued  stage,  enhancement  carboxylic acid  diagenesis  3- retardation  d u e t o elevated  Zones  smectite and  [K*/Na*  Hydrostatic  section with  however,  carbonates  permeability  and l o w  that  strata w e r e  aluminosilicate dissolution  t h e shales d u r i n g  chemistry  of the  cementation  the aluminosilicates,  t h e illitization of  m.  diagenetic  aluminosilicates through  calcite  generation  6800  as i n c r e a s e d  the framework  previous  burial  the studied  and  conditions  to occur  generation  with  with  these  the framework  association  the  5500  t o 1 2 7 M P a at t h e b a s e  sandstones  of  the Eurekan  depth  close  95 ° C .  of  the deep  retrograde  due to  conversion  of  elevated  smectite  to  [H*/K*].  of smectite  t o illite  due to  lower  P  H U  than  2  the  previous  liberation of Toward formed  stages. Fe* the  2  Conversion  of  previous  in t h e s m e c t i t e - i l l i t e  e n d of  diagenesis  as silica c o n t i n u e d , t o b e  illitization  of  C  s m e c t i t e in t h e a s s o c i a t e d  to  ankerite  through  the  transformation.  second  released  carbonates  into  shales.  generation solution  quartz  through  overgrowths the  progressive  in  124  Deep Burial (Diagenesis C)  zo UJ  H CO Q  Carboxylic acids -»-AI-*-AI-complex Dissolution of . framework aluminosilicates Calcite+Fe—Ankerite+Ca  Figure  2 9 - Summary  diagram  of deep  burial d i a g e n e t i c  environment.  6) SyiWpost Orogenic diagenetic  events  parameters the  maturation  complications the  that  leave  of t h e Eureka  thermal  created  Eurekan  Orogeny  b y heat  Heat  organic  matter.  Not- only  t o selectively mature  with  the most  the  the  net +  of  enriched  organically  began  the  of o r i g i n  as uplift  complexed  Al  t h e halite  +  pressure  and erosion  rooted  f o r that t o their  o n the  waters from  t h e diapir  was associated  v.s. t h e phytoclasts)  but the  in the sandstones.  Due to  o f t h e diapirs)  they  concentrations  as w e l l b e g a n  t o i n c r e a s e as  during  the deep  p H a n d liberate  P _ _  that  t o favor  Al *  burial back  3  was enriched t h e near  were  diagenesis  into  in b o t h  synchronous  stage  solution. The Na  +  and  precipitation  (Figure 30).  during  resulting  of the overlying  high  t o t h e diapirs i n  signature  which  were  core  produced  3  conditions  of  paragenetic  o f t h e strata  presence  from  the progression  relatively s i m p l e  the coals  point,  a n d free  diagenetic  of the maturation  of t h e i r  changing  a n d kaolinite  thickness  remained  (i.e.,  a sufficiently high  dawsonite  with  in t h e s e q u e n c e  w a s t o create an e n v i r o n m e n t  under  sufficiently  trace  in N a *. A l u m i n u m  Hydrostatic C  vitrinite  strata (i.e.,  to destabilize with  result 3  that  permeable  source  mobilization  diagenetic  U p u n t i l this  d i d t h e circulation of the heated  left a m i n e r a l o g i c  water's  greatly  Al  also  Fiord.  However,  by proximity  alteration  o n the many  relatively u n i f o r m  t h e strata's  created  a significant  tend  waters  anomalies.  altered  anomolies  produced  had been  flow  imprint  at S t r a n d  a n d associated diapir  history. area  prominent  Formation  o f t h e strata  i n t h e strata w h i c h  the  the most  Sound  created  flow  D)- It is t h e s y n - a n d p o s t - o r o g e n i c  Reactions (Diagenesis  diagenesis from  D was lower  t h e Eurekan  strata. T e m p e r a t u r e s ,  period source  immediately at d e p t h .  than  Orogeny  tended  o n the other  following  uplift  T h e strata b e g a n  during  while  diagenesis  to  hand,  reduce remained  t h e diapirs  to cool  only  once  Syn/post O r o g e n i c (Diagenesis D)  TOI  111  CO  Na —  Na-  from  diapir  Kaolinite and  z  dawsonite Destabilized  <  ^  Al-complex  Na  CO  AL  LU K+Smectite--^—Illite  =  I CO  Figure  30-  Summary diagram environment.  of post/syn-tectonic  diagenetic  127 the  diapirs  toward  began  shallower  to  separate f r o m  depths.  their s o u r c e  and  migrate  further  upwards  REFERENCES  Almon,  W.  American  R., a n d D a v i e s , D. K., 1 9 8 1 , F o r m a t i o n d a m a g e a n d t h e crystal c h e m i s t r y of clays: In: F. J. 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H.  of s e d i m e n t a r y r o c k s : in A s s o c i a t i o n of P e t r o l e u m  Fluids in S u b s u r f a c e G e o l o g i s t s M e m o i r 4,  p.  F. J. a n d G i l b e r t , C . M . , 1 9 8 2 , P e t r o g r a p h y : an i n t r o d u c t i o n t o of r o c k s in thin s e c t i o n , S e c o n d E d i t i o n , W . H . F r e e m a n a n d p..  D., a n d P i t t m a n , E. D., 1 9 7 7 , A u t h i g e n i c clays i n s a n d s t o n e s : r e c o g n i t i o n a n d i n f l u e n c e o n r e s e r v o i r p r o p e r t i e s a n d p a l e o e n v i r o n m e n t a l analysis: J o u r n a l of S e d i m e n t a r y P e t r o l o g y , v. 4 7 , n o . 1, p. 3 - 3 1 .  G . F., 1976, P e t r o g e n e s i s S p r i n g e r - V e r l a g , 334 P.  of  metamorphic  rocks:  Fourth  edition,  140  Zen,  E.,  1959, Clay mineral-carbonate relations of S c i e n c e , v. 257, p. 2 9 - 4 3 .  in  sedimentary  rocks: American  Journal  141  APPENDICES  P r e p a r a t i o n : SAMPLE  K  s a t u r a t e d  7 .0 -  7.9  RAK RAK  15-25  7 . 19 7 .22  RAK  20-25  7 .25  RAK  23-25  7 . 19  30-25  7 . 15  33-25 38-25  7 . 17 7 .22 7 . 18  RAK  42-25 43-25  RAK  45-25  7 . 18  RAK  46-25  RAK RAK RAK RAK  9-25  RAK  50-25  RAK RAK  53-25 57-25  7 .20 7 . 10  RAK RAK  60-25 67-25  7 . 19 7 . 19  RAK  68-25  RAK  71-25  7 .22 7 . 22  RAK  76-25  7 . 19 7 .22  RAK  78-25  RAK  112-25  7 .05  RAK  125-25  7 . 19  SAMPLE RAK 9-25 RAK 15-25  K  7. 22  RAK RAK  20-25 23-25  RAK  30-25  7. 25 7. 25 7 . 19  RAK  33-25  7 . 17  RAK  38-25  RAK RAK  42-25 43-25  7 .22 7 . 19 7 .22  RAK  45-25  7 . 19  RAK  46-25  7. 22  RAK  50-25  RAK  53-25  RAK  57-25  7. 22 7 . 10 7. 22  RAK  60-25  RAK RAK RAK  67-25  7. 2 0 7 .25  68-25 71-25  7 .20 7. 28  RAK RAK  76-25 78-25  7. 20 7 . 19  RAK  112-25  RAK  125-25  7. 05 7. 25  +  10.0 -10.9  11.0-11.9  -  10 . 10 10 . 0 4 10 . 10 10 . 4 6 10 . 16 10 . 10 10 . 10 10 . 1 1 10 . 10 10 . 10 10 . 10 10 . 10 10 . 10 10 . 10 10 . 10 10 . 10 10 . 5 2 1 0 . 16  8 .0-  - , -  8.9  9 . 0 -  14.0-14.9 14.02  -  '-. -  14.25 14 . 2 5  15.0-15.9  . -  --  - . -  14.25 14.25  -  1 4 . 14 14.25 14 . 2 5 14 . 2 5 14  .48  -• -  -  10 . 10  e t h y l e n e  13 . 0 -• 1 3 . 9  12.99  - • -  9.50  12 . 0 - 1 2 . 9  ' -  11 . 0 5  10 . 10 10 . 10  -  s a t u r a t e d  7 .. 0 - • 7.9 7. 22  9 . 0 - 9 . 9  -  7 . 22 7 . 22 7 .22  P r e p a r a t i o n :  8 . 0 - 8 . 9  16 . 0 - 1 6 . 9  . • -  ft>  (/>  c' > 3  UI 01  T3 T3 (D 3  c g. x' —1  g l y c o l 9.9  •v  o  10.0- 10.9 10. 10 10. 04 1 0 . 16 10. 22 1 0 . 16 10. 10 10. 10 10. 10 10. 10 10. 10 1 0 . 10 10. 10 10. 10 1 0 . 11 1 0 . 10 1 0 . 11 10. 10 1 0 . 16 1 0 . 10 1 0 . 10 10. 10 10. 10  11  0  1 1 9  -  13. 0- 13.9  14.0-14.9  15.0-15.9  -  -  -  15.36  -  -  1 1 . 40  -  12. 0 - 1 2 . 9  "  -  -  -  14.25  -  -  _  14.25  -  14.25 14.25 14.26 14.25 14.48 14.48 14.37 14.25  -  - ' _  14.48  -  _  _  _  -  _  -  -  14.25  _  -  -  _  -  16. 0 - 1 6 . 9  - • . • • -  ST CL n ft)  -<  —k  P r e p a r a t i o n : SAMPLE RAK RAK  Mg  s a t u r a t e d  7.0-  7.9  RAK  20-25  7.25  RAK  23-25 30-25  n/s 7 . 19 7 . 19  RAK  33-25 38-25  RAK  42-25  7.  RAK RAK  43-25  n/s  45-25  7.21  46-25  7.22  RAK  50-25  7.  RAK  53-25  7.20  RAK  57-25  7.  19  RAK  60-25  7  .20  RAK  67-25  7 . 19  RAK  68-25  RAK  71-25  7. 20 7 . 19  RAK  76-25  n/s  RAK RAK  78-25 112-25  7.20  RAK  125-25  7 . 22  SAMPLE  7.9 7.0 7 . 19  9-25 15-25  RAK  20-25  7 .25  RAK  23-25  RAK  30-25  n/s 7 .. 2 0  RAK  33-25 38-25  7 .20 7 .22 7  7 . 22  RAK  42-25  RAK  43-25  RAK RAK  45-25 46-25  7 .. 1 9 7 23  RAK  50-25 53-25  7 . 10 7 . 19 7. 22  19  -  RAK  57-25 60-25  RAK  67-25  RAK RAK  68-25  7.. 10 7 .22  71-25  7 .22  • -  RAK  76-25  n/s  n/s  RAK  78-25  7.. 2 0  RAK  112-25  RAK  125-25  RAK RAK  7 .. 1 9  7 .. 18  -  14.72  -  n/s  - .  10  -  12.27  10. 10 10. 10  11 . 0 5  12.62  -  1 0 . 11  e t h y l e n e  -  10. 10 10. 10 .  10  10  10. 10 n/s 10. 04  -  10. 10  12.27  11 . 9 4  12.80  n/s  11 . 7 8  -  -  14.37  -  14.72  -  n/s  n/s  11.78 r  -  ' • -  12.62  n/s  -  n/s  -  -  14.72 14 . 2 5 n/s  n/s  t4.25  -  -  --  - ' -  --  • - . -  -  n/s  n/s  -  -  -  14.97  n/ s  ---  --  14.25  -  -  --  14.48  n/s  • . -  n/s  14.73 14.48  12.27  •  -  14.25  17.0-17  n/s  --  14.25  14.25  •  n/s  14.25  --  -  .78  14.72 n/s  n/s  -  11.78 11  n/s  -  10. 10  -  -  -  -  -  -  16.0-16.9  -  12.81 n/s  n/s  n/s  15.0-15.9  14.25 14.25  -  1 0 . 10  -  8.9  14.0-14.9  -  n/s  n/s  -  13.0-13.9  12.62 n/s  1 0 . 10 n/s  --  8.0-  10  12.0-12.9  n/s  -  +  11.0-11.9 11 . 6 3  n/s 1 0 . 16  -  -  1 1  10 1 0 . 34  --  -  s a t u r a t e d  10 10.  n/s  -  -  10.0- 10.9  9.9  -  -  19  RAK RAK  RAK  -  n/s  RAK  Mg  9:0-  n/s  19  RAK  8.9  -  7.22  RAK  P r e p a r a t i o n :  8.0-  7 . 19 7 . 19  9-25 15-25  -  g l y c o l  9.09.40  n/s  n/s  9.9  10.0-- 1 0 . 9 10 04 10  04  10  28  10. 19 10 16 10 . 10 04  10. 10 1 0 11 10 10 10 10  10  10  10  10 10. 1 1 1 0 .. 1 0 10 10 n/s  -  -  10  -  -  10  04 10  12.0-12.9  -  n/s  n/s  10  11.0-11.9  -  -  - . .  -  -  n/s  -  -  -  • -  .  -. -  14.0-- 1 4 . 9 14 . 7 2  -  n/s  -  -  13.0-13.9  -  -  , -  n/s 14 . 6 0 14 . 2 5  15.0-15.9  • -  1 6 . 0 - 1 6 . 9  -  16.36  17  .67  -  16.99  17  .67  n/s  n/ s  n/s  15.36  16.99  -  16.83  -  14 . 2 2 14 . 4 8  -  14 . 4 8 14 . 14 14 4 8  -  16.06  -  14 . 7 2  -  -  25  -  -  15.23  -  -  16.99 , 1 6 . 0 9 16.99  -  n/s  n/s  n/s  n/s  n/s  -  12.27  -  14. 25  -  16.99  -  -  -• -  -  16 . 9 9  n/s  -  -  -  15.78  14  -  15.23  14 . 2 5  14 . 7 2 14 7 2  17.0-17.  -  16.99  17  .67  -  -  -  17.32 n/s  -  -  Preparation: SAMPLE RAK 9-25 RAK  15-25  RAK  20-25  RAK RAK  Non-cation 7.07.9 7 .19  saturated 8.08.9 8.84  9.0-  9.9  10.0-10.9  -  10 . 16 10 . 2 8 10 . 1 0 10 . 16  -  10 . 16  -  -  23-25  7 .19 7 .19  -  30-25  7 .19  -  •  33-25  7 .10  38-25  7 .19  RAK  42-25  7 .22  1 0 . 10 10 . 1 0  RAK  43-25  7 .25  10 . 11  RAK RAK  45-25 46-25  7 .19 7 .22  1 0 . 11  RAK  50-25  7 .19  10 . 10  RAK  53-25  7 .20  10 . 1 0  RAK  57-25  7  RAK  60-25  7 .19  RAK  67-25  7  RAK RAK  68-25  RAK  76-25  7 .20 7 .20  RAK  78-25  7 .22  RAK  1 12-25  RAK  125-25  -25  -  -  9.60  -  -  7 .20  14.0-14.9 14 . 14  -  -  14 . 7 2  -  -  14 . 14 14 . 4 8  -  -  -  -  14 . 2 5  -  -  -  -  -  -  10 . 10  11 . 3 3 -  1 0 . 11  11 . 7 8 -  to . 1 0  -  -  14 - 2 7 14 . 14  -  - .  14 . 3 7 14 . 2 5  -  -  10 . 10  -•  14 . 2 5  -  -  12 . 2 7 -  14 . 2 5  -  -  -  17.0-17.9  -  -  -  -  14 . 4 8  -  10 . 1 0  - ' -  -  .  14 . 4 8  -  16.0-16.9  -  14 . 2 5  -  -  15.0-15.9 -  -  14 . 4 8  -  10 . 1 0 -  13.0-13.9  -  -  10 . 10 10 . 1 0  .20 7 .20  -  -  10 . 0 4  .15  12.0-12.9  11 . 7 8 -  10 . 1 0  RAK RAK  7 1  11.0-11:9 -  -  -  -  -  -  -  -  -  -  -  -  -  -  -  -  -  • -  -  -  -  -  -  -  -  -  -  z o •? >  cr C  Preparat  ion:  SAMPLE RAK 9-25  Non- c a t i o n 7.0^ 7.9 7 . 16  saturated 8 . 0 - 8 . 9 -  RAK RAK  15-25 20-25  7 . 22 7 . 19  -  RAK  23-25  RAK  30-25  7 . 22 7 . 19  -  RAK  33-25  -  RAK  38-25  7 . 10 7 . 11  RAK  42-25  7 . 22  RAK  43-25  7 . 19  RAK  45-25  7 . 19  RAK RAK  46-25  7 . 22  50-25  RAK  53-25  7 . 10 7 . 20  RAK  57-25  RAK  60-25  RAK RAK  67-25  RAK  71-25  RAK RAK  76-25 78-25  RAK RAK  68-25  •  ethylene  9 . 0 - 9 . 9  .  -  -  glycol  10.0-  10. 10. 10. 10. 10. 10. 10.  10.9 04 04  11. 05  10 16  10.  10  10.  10  -  7 . 20 7 . 22 7 . 20  -  -  -  112-25  7 . 25 7 . 22 -  -  1 1  -  125-25  7. 20  -  10. 10  -  10  -  10. 10 10.  -  10  io. ' 0 -  -  10. 10  -  -  1 0 . 10 1 0 . 11 10.  13.9  -  1 1 . 48 -  10. 0 9  -  -  1 1 1 1  13.0-  -  04  10. 10  7 . 15 7 . 20  12.9  12.0-  10  10.  10.  11.9  11.0-  •  -  -  .12. 27  -  12 . 8 0 -  14.0-  -  14.9  14 . 4 8 14 . 7 2 14. 72 14. 0 2 14. 25 14. 24 14. 25 14. 25 14. 25 1 4 . 14 14 . 4 8 14. 48 14. 25 14. 48  15.0-15.9  -  15.50 -  • -  -  -  14. 72 -  -  -  -  -  -  _  -  _  -  -  16.83 16.06  -  17.0-17.9  -• -  32 2.* •<  -  -  -  1 3 . 19 -  -  16.0-16.9 -  TJ fD  -  -  -  -  -  -  -  •-  -  -  16.99 16.36  - ' -  -  -  -  -  .U  P r e p a r a t i o n : SAMPLE  s a t u r a t e d  7 .0-  7.9  +  15-25  RAK  20-25  RAK  23-25  RAK  30-25  RAK RAK  33-25 38-25  RAK  42-25  RAK  43-25  RAK  45-25  RAK  46-25  RAK  50-25  RAK  53-25  RAK RAK  57-25 60-25  RAK RAK  67-25 68-25  RAK  71-25 76-25  500  8.. 0 -  -  n/s  n/s  n/s  n/s  -  ' -  -  -  -  -  n/s n/s n/s  n/s  n/s n/s  n/s  n/s n/s  n/s  n/s  RAK  125-25  -  -  RAK  23-25  RAK  30-25  RAK RAK  33-25  s a t u r a t e d  7 .07.9 7 . 22  T n/s  38-25 42-25  RAK RAK  45-25  RAK  46-25  RAK  50-25  RAK RAK  53-25 57-25  -  RAK  60-25  -  RAK RAK  67-25  -  68-25  -  - •  RAK  71-25  RAK  76-25  RAK RAK  78-25 112-25  RAK  125-25  +  e t h y l e n e  0-  8.9  '  -  -  n/s  -  RAK  43-25  8  7.21  -  9 .9  -  +  ' n/s -  -  -  -  10  n/s n/s  n/s  -  n/s  n/s  n/s  n/s  n/s  n/s  n/s  h/s  -  -  degrees  C  for  two  n/s  n/s  n/s  -  -  -  -  -  13 . 0 - 1 3 . 9  14.0-14.9  15 . 0 - 1 5 . 9  16 . 0 - 1 6 . 9  17 . 0 - 1 7 . 9  hours  11 . 0 - 1 1 . 9  12.0-12.9 -  -  -  -  -  -  -  n/s -  -  10.  10  10. 10.  10 10  -  10.  10  _  10.  10  10.  10  10 10.  10 10  -  n/s  n/s  -  n/s  n/ s  . -  -  n/s  n/s  n/s n/s  10  n/s  n/s n/s  -•  n/s  12  10  14.25  n/ s n/s  10.  10.  -  n/s  10.  10 10  n/s  -  n/s  -  n/s  --  10.  n/s  -  -  n/s  n/s  •  -  _  n/s  -  -  -  n/s r  -  _  •  -  -  -  n/ s  n/s  -  14'.02 14.24  -  14.25  _  14.25  _  1 4 . 14  _  -  .14.48  _  14.48  _  -  _  _  _  _  _  -  -  14.28  _  _  _  n/s  n/s  _  _  _  -  14.25  n/s  -  _  _  n/s  n/s  -  -  _  n/ s  -  _ _  -  -  -  _  _  n/s  -  10  10.  -  14.48  n/s  -  n/s  n/s  04 10  15  14.48  .  n/s  1 0 . 10 10.04  -  14.  -  n/s n/s n/s  n/s  n/s  -  n/s  n/s  -  n/s  -  -  n/s  -  -  -  -  n/s  -  -  n/s  -  n/s  14.25  10  n/s  •-  n/s  -  -  n/s  -  n/s  n/s  -  -  ~ n/s  10  500  10  n/s  n/s  -  -  n/s  n/s  - '.  -  n/s  n/s  n/s  1 0 . 0 - 1 0 .9  10.  -  14.25  •  10  n/s  -  n/s  "  -  n/s  n/s  -  n/s  10  9 . 99  n/s  n/s  ' -  n/s  g l y c o l  9 . 0 -  -  -  -  10.  -  17 . 0 - 1 7 . 9  -  -  n/s  n/s n/s n/s n/s  -  16 . 0 - 1 6 . 9  -  -  n/s 10.  15 . 0 - 1 5 . 9  1 4 . 14  n/s  10  n/s  n/s n/s  n/s  -  20-25  10  -  -  RAK  10.  -  78-25  SAMPLE RAK 9-25 RAK 15-25  10.  -  1 12-25  K  10.  n/s  RAK  ion:  -  14.0-14.9  -  -  n/s  10  13 . 0 - 1 3 . 9  -  n/s  n/s  10.  12.0-12.9  -  1 0 . 16 n/s 10.  n/s  11 . 0 - 1 1 . 9  16  -  n/s  n/s  10.9  n/s  n/s  n/s  -  10.  -  -  hours  10.11 10.04  -  n/s  two  10.0-  -  n/s  n/s  for  -  n/s  -  C 9. 9  9 . 0 -  n/s -  n/s  RAK  P r e p a r a t  degrees  8.9  -  9-25  RAK RAK  RAK  K  _ _ _  _  n/s  n/s  _  _  -  _  _ _  _  _  _  _  _  _  _  _  _  _  _  _  -  -  _ _  -  -  

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