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Manganese chemistry in the Fraser estuary De Mora, Stephen John 1981-12-31

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MANGANESE CHEMISTRY IN THE FRASER ESTUARY by STEPHEN JOHN^DE MORA B.Sc,  The U n i v e r s i t y  of Wales, 1976  A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE  REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY in  THE  FACULTY OF GRADUATE STUDIES  (Departments of Chemistry and Oceanography)  We accept t h i s t h e s i s as conforming to the r e q u i r e d  THE  standard  UNIVERSITY OF BRITISH COLUMBIA March 1981  ©  Stephen John de Mora, 1981  In  presenting  requirements of  B r i t i s h  i t  freely  agree for  this for  an  a v a i l a b l e  that  I  understood  that  f i n a n c i a l  by  his  that  or  be  her or  s h a l l  The 2075  U n i v e r s i t y Wesbrook  Vancouver, V6T  1W5  of  B r i t i s h  Place  Canada  the  s h a l l  and  study.  I  copying  granted  by  p u b l i c a t i o n be  the  University  the  of  allowed  \r Columbia  of  make  further this  head  representatives.  not  c/C<r<i^  of  at  of  L i b r a r y  permission.  Department  f u l f i l m e n t  the  extensive  may  copying  gain  degree  reference  for  purposes  or  p a r t i a l  agree  for  permission  scholarly  i n  advanced  Columbia,  department  for  thesis  It  this  without  thesis  of  my  is thesis my  written  i i  ABSTRACT  The  Fraser  varying  flow  manganese ranging  4 t o 12  ppt.  peak . does  dissolution  of  excess  i s derived  metal  Desorption  waters,  especially may  release  dissolved  manganese  amorphous of  water  manganese  surface  water  waters  the  content, and  having  distribution dilution  and  water  be which  salt the  wedge bottom  manganese  extent  by t h e  with  enriched  to the i n s i t u  reduction  eventually  entrainment  salt  wedge  determines  in  Thus,  mixing  levels  the  explained  in  terms  intersect  at  the  the  t h e peak  downstream  low manganese  and  into the  increase  Further  decrease.  can  estuarine  This  lesser  downstream  relatively  curves  wedge.  the  salinity.  to  the  in  subsequent of  a  sediments.  from  to a  due  The toe  causes  concentrations  conservative  bottom  concentration  interstitial  oxides.  concentration  manganese  The  to the advancing  concentrations  from  dissolved  saline  p a r t i c u l a t e manganese.  influenced  some  manganese  river  with  be  of  outflowing  manganese  nor  the  and  salinity  desorption  i n the toe of the s a l t  also  a  data  from  due  under  of d i s s o l v e d  at  results  the estuarine  resuspended  times  field  result  from  value  o r d i s s o l u t i o n of manganese  concurrent  mixing  Experimental  suspended  five  distribution  a maximum  t h e d i s s o l v e d manganese  enrichment  of  surface  not  riverborne  sediments  enhances  The  investigated  consistently exhibited  this  bottom  was  regimes.  from  suggest  Estuary  causes  dissolved of  two  manganese  peak. The both  dissolved  the surface  removal  of  and  oxygen bottom  alkalinity  may  generally waters occur  of  behaves  conservatively in  the Fraser at  low  Estuary.  salinity,  The  however,  alkalinity  exhibits  salinity  range.  replicated  theoretically  only  considered  as a  process.  The of  the  The  two  alkalinity Strait  seasonal  conservative surface  step  behaves  related  through  distribution  when  mixing  most  of  in  of  pH  the  The  pH  be  surface  is  and d i s s o l v e d oxygen  to primary  productivity  the  can  c o n s e r v a t i v e l y i n the surface  of Georgia.  variations  behaviour  waters display  and  mixing  processes. The of  distribution  the S t r a i t  Fraser  River  o f d i s s o l v e d manganese  of Georgia water.  i s determined  Bottom  manganese  concentrations  manganese  from  manganese the  particulate  manganese  may  and/or  to  have  result  by  increasing  from  the resuspension  profiles  of  concentrations  sediments.  in  suspended with  the o x i d a t i v e p r e c i p i t a t i o n of bottom  of  dissolved  variations of  of  dissolved  remobi1ization  seasonal  Depth  waters  the d i l u t i o n  Concentrations  column.  indicate  by  enhanced  reductive  are determined  of the water  manganese  This  due  sediments.  a t mid-depths  stability  depth.  the  waters  mainly  in surface  of  iv  TABLE  OF  CONTENTS  PAGE  ABSTRACT TABLE  OF  i i CONTENTS  LIST  OF  TABLES  LIST  OF  FIGURES  iv viii ix  ACKNOWLEDGEMENTS 1.  2.  Introduction  1  1.1  The  1.2  Manganese  1.3  The  Fraser  Estuary  1.4  The  Strait  of  Estuarine  Environment  Case  1  Studies  3 8  Georgia  10  Methods 2.1  2.2  3.  x iii  Sea  12 Water  12  2.1.1  Sampling  2.1.2  Temperature,  2.1.3  Alkalinity  2.1.4  Total  2.1.5  Dissolved  2.1.6  P a r t i c u l a t e Metal  Sediment  Programme and  Oxygen  16  pH  Suspended  16  Particulates  18  Manganese  19  Analyses  23  Samples  25  Collection  2.2.2  Interstitial  2.2.3  Ammonium  2.2.4  Total  Metal  2.2.5  Grain  Size  and  12  Salinity,  and  2.2.1  Alkalinity 3.1  Samples  pH  Introduction  and  Storage  Water  Oxalate  25  Analyses  Extraction  Content  of  26 of  Sediments  Sediments  29  Analysis  Distribution  27  31 in  the  Fraser  Estuary  33 33  3.2  3.3  3.4 4.  Results  38  3.2.1  Alkalinity  3.2.2  Dissolved  3.2.3  pH D a t a  Data  40 42 44  3.3.1  Distribution  of A l k a l i n i t y  3.2.2  Distribution  of D i s s o l v e d  3.2.3  Distribution  o f pH  44 Oxygen  49 50  Summary  59  Distribution  4.1  Preamble  4.2  Field  4.4  Oxygen  38  Discussion  Manganese  4.3  Data  i n the Fraser  Estuary  61 61  Data:  Aqueous  Samples  61  4.2.1  Dissolved  4.2.2  Particulate  Manganese  65  4.2.3  Particulate  Aluminium  67  4.2.4  Total  Field  Data:  Manganese  61  Suspended P a r t i c u l a t e s Sediments  4.3.1  Interstitial  4.3.2  Ammonium  4.3.3  Total  Acid  4.3.4  Grain  Size  .  67  '  69  Water  Oxalate  69  Digest  71  Digest  72 73  Discussion 4.4.1  74  Distribution  of  Suspended  Particulate  Material 4.4.2  The  74  Dissolved  Manganese  Maximum  at  Low  Salinity 4.4.3  The R o l e in  77 of Suspended P a r t i c u l a t e  Establishing  the  Dissolved  Manganese Manganese  vi  Peak 4.4.4  79  The  Role  of  Estuarine  Establishing 4.4.5  Dissolved  4.4.6  Manganese Kinetic  4.5  A  Model  for  Bottom  the Dissolved  Manganese  Manganese  Removal  Behaviour:  Sediments i n Peak  Processes  99  Thermodynamic  and  Considerations Manganese  102  Behaviour  i n the  Fraser  Estuary 5.  Manganese  104  Distribution  5.1  Preamble  5.2  Surface  5.3  Time  5.4  Profiles  5.5  Summary  Conclusions  7.  Bibliography  APPENDIX  A:  i n the S t r a i t  of Georgia  110 110  Distribution  Series  6.  89  of Manganese  at Station  at Stations  110  15  1,  3,  120 and  25  124 127  and  Future  Work  128 133  Summary  of S t a t i o n  Positions  and  Sampling  Programme  140  A.l  Station  Positions  i n the S t r a i t  of G e o r g i a  140  A.2  Station  Positions  i n the Fraser  Estuary  141  A.3  Water  A. 4  Sediment  APPENDIX  B:  Sampling  Data  Programme  Sampling Summary  Programme  of Aqueous  B. l  Dissolved  B.2  Particulate Constituents  B.3  Time  B.4  142 143 Samples  144  Constituents  Series  56.3,  Cruise  Tidal  Data  144 163  of Bottom Waters C o l l e c t e d a t 78-16 for  Station  ( O c t . 1978)  Steveston  and  171 Deas  Island  during  vii  Cruise APPENDIX C.l  78-16  C: Summary  Waters 12/78 C.2  -  Station  Analyses  Sediments  Profiles  Sediments of  Interstitial Collected  C.3.1  Total  Acid  Total  Dissolved  Complete Collected Size  in  Jan  Digestion  Interstitial  Collected  Estuarine  (May 1 9 7 9 )  Grain  in  172  79-12  Collected  C.6  15  Cruise  Feb  29/79  Sediments  Digestion  Manganese Waters  174 Following  an  Ammonium 174 174  Only  and  Salinity  of  Estuar ine  Profiles  in  Sediments  i n J a n 1980 Analyses i n J a n 1980 Data  173  from  Extraction  Acid  Interstitial  C.5  Profiles  Manganese  of Estuarine  Complete  C.3.2  172  a n d F e b 6/79'  Oxalate  C.4  Data  Manganese  Dissolved Waters  C.3  of Sediment  Dissolved  171  ( O c t . 1978.)  175 of  Estuarine  Sediments 176 177  vi i i  LIST  I  Daily  Average  River II  during  Seasonal Rate  Analysis  IV  Replicate  V  Rate  of  the  Fraser 14  Daily  Average  Discharge  River  15  Reference  Manganese  and  Materials  Aluminium  24  Analyses  of  an  Sediment  Comparison  Salinity  PAGE  Cruises  i n the  of C e r t i f i e d  Surficial VI  Estuarine  Extremes  Estuarine  TABLES  Discharge  of the F r a s e r  III  OF  of  29  Total  Sediments and  Mn  and  A l Content  Collected during  Concentration  of  in  Cruise  the D i s s o l v e d  Estuarine 79-12 Manganese  Maxima  78  VII  Mixing  VIII  Comparison  Experiments  Manganese  X  The  Mn:Al  81  of the  Particulate  IX  30  Mean  Manganese  i n the Fraser Ratio  in  Collected  i n May  1979  Dissolved  Manganese  Riverborne with  "Excess"  Dissolved  Estuary  Surficial (Cruise  Data  Suspended  from  82 Estuarine  79-12) Station  Sediments 97  25.  126  ix  LIST  1  Conservative estuarine members  and  mixing  (Liss,  2  The  lower  3  Hydrograph (Station  FIGURES  PAGE  non-conservative of  single  river  behaviour  and  sea  during  water  end  1976).  Fraser of  No.  OF  2  River the  valley.  Fraser  08MF005)  River  measured  at  (Water  Survey  f o r 1978-1979  Hope of  Canada,  1978  4  Station  locations  i n the S t r a i t  of G e o r g i a .  13  5  Station  locations  in the Fraser  Estuary.  13  6  Alkalinity 78-04,  7  8  and  7  data  78-11,  Dissolved  78-16,  and  78-04,  pH  p l o t t e d versus 79-01,  9  The  profile  10  The  pH  and  of  single  water  79-01,  and  salinity  15,  mixing  Estuary of  one  Data  theoretical  dilution  curve  mass  the Fraser  of  are taken  two  Estuary step  the end from  for  pH by  and  f o r the water  The  properties  78-04.,  78-16.  sea water  from  as a  41  Cruises  generated  are taken  mixing  for  curve  e n d members  the  salinity for  79-12.  Cruise  the  of  versus  43  dilution  end members.  waters  Cruises  79-12.  the Fraser step  for  39  plotted  at Station  theoretical  waters a  78-16,  salinity  79-01.  data  Cruises data  9  p l o t t e d versus  oxygen  78-16,  11  1979).  Cruise for  members  Cruise  and  78-16.  in  surface  considering two  river  properties  of  78-16. pH  generated  process.  51  Data  in  by  53 surface  considering  f o r the  intermediate  water water 55  X  12  The  theoretical  waters a  the 13  step  e n d members  Theoretical and  Estuary  assuming  o f one  Data  values that  Cruise  with  the  sea of  water  56  i n the  by  Cruise  carbon  three  properties  f o r the water  calculated  considering  f o r pH  fresh  surface  79-01.  generated  from  in  by  water  curve  are taken  pH  generated  from  dilution  e n d members.  pH  f o r the water  are taken  mixing  for  of f r e s h  Data  of the Fraser  water  14  mixing  theoretical  single  curve  Estuary  e n d members.  wedge  the  step  e n d members  The  a  of the Fraser  single  water  dilution  salt  considering and four  sea  properties  of  78-16.  from  the  dioxide  57  alkalinity was  100%  saturated. 15  Dissolved Cruises  16  17  78-04,  for  78-04,  Cruises  Particulate Cruises  Total  21  Total  aluminium  62  versus  salinity  and 79-12.  plotted  79-01,  versus  66 salinity  and 79-12.  concentrations  68 plotted  78-16 a n d 79-12.  concentrations  particulate  Mn:Al  78-04,  manganese  Cruises  79-01,  data  78-16,  salinity for  plotted  69 versus  concentrations  for  78-16 a n d 79-12.  Particulate Cruises  78-16,  plotted  for Cruises  suspended  Cruises  data  versus  and 79-12.  particulate  salinity  total  20  78-04,  plotted  79-01,  aluminium  suspended  Particulate  data  78-16,  manganese  versus 19  manganese  Particulate  for 18  58  78-04,  ratios  78-11, data 78-16,  75 plotted  78-16,  versus  79-01,  plotted and 79-01.  salinity for  and 79-12.  versus  salinity  85 for 87  Dissolved plotted  the  56.3,  Schematic  for  78-16  concentrations,  bottom  waters  from  only.  f o r the transport  of manganese  through  Estuary. diagram  of the  d i s s o l v e d manganese  Cruise  Manganese  salinity,  Cruise  diagram Fraser  of  Particulate  versus  Station Flow  and  longtitudinal (ppb) and  distribution  salinity  (ppt) from  78-04.  Surface  distribution  manganese-  in  the  of  salinity  Strait  of  and  Georgia  dissolved  during  Cruise  78- 01. The in  distribution the S t r a i t  of  salinity  of Georgia  Surface  distribution  manganese  in the  and d i s s o l v e d  a t 1 and of  Strait  5 m,  salinity  of  Cruise and  Georgia  manganese 78-07.  dissolved  during  Cruise  79- 01. Surface  distribution  manganese,  and  Strait  suspended  of Georgia  during  Dissolved  manganese-  salinity  for  salinities  greater  Time  series  Station  15  of  salinity,  particulate Cruise  than  from 20  ppt  Profiles  of  concentrations  January  1978  suspended for  Station  plotted  Cruise  i n the  versus  79-12  with  only.  of d i s s o l v e d manganese from  manganese  79-12.  concentrations  samples  dissolved  concentrations  t o June  1979.  particulate 15,  at  Cruises  manganese 78-16  and  79-07. Profiles  of  dissolved  manganese  concentrations  in  interstitial Cruises  78-01  Profiles manganese  of  waters and  of  sediments  from  Station  15,  79-02.  dissolved  concentrations  and  suspended  for Station  3,  particulate Cruise  79-07.  xi i i  ACKNOWLEDGEMENTS  I his  would  like  continuous  t o thank  my  assistance  supervisor, and  D r . E.V.  patience  with  Grill,  this  for  research  project. Data the  collection  help  of  M.  graduate  students  mention  to  cooperation in  I  Oceanography the  to  in  Barb  been  impossible  A. R a m n a r i n e .  his  sense  I appreciate  to  without  Similarly, give  o f humour  the assistance  an  several  honourable  and e n t h u s i a s t i c o f B.  MacDonald  i n the estuary.  H. H e c k l  for  particular  Ltd. kindly  constructing  the  loaned  bottom their  various  water  teflon  pieces  sampler.  digestion  of  Seakem  bombs f o r  analyses.  gratefully  discussions  for  the cores  particulate I  and  have  a s s i s t e d , but I wish  at sea.  thank  equipment,  Storm  A. Hay  collecting  a t sea would  acknowledge  and h e l p i n g  f o r a l l that  D r . T. P e d e r s e n  to maintain  needs  n o t be  my  said.  sanity.  for  "valuable"  Finally,  thanks  1  1^  1.1  The E s t u a r i n e  Cameron  with  refers  only  river  runoff  and  fresh  point  sea  water  water  which  an  estuary  as  "a  which  has a  free  connection  which  sea  water  is  measurably  deriving  from  land  type  estuary  precipitation  of view,  define  of water  within  to a positive and  (1963)  body  sea and  with  chemical  Pritchard  coastal  t h e open  diluted  Environment  and  semi-enclosed  INTRODUCTION  produces  (Pritchard,  exceed  the estuary  drainage".  This  1952)  where  evaporation.  i s a mixing  compositional  From  zone  of  gradients  a  fresh  (Burton,  1976). Chemical and  ionic  gradients  strength  arise  and  when  high  metals,  n u t r i e n t s and suspended  having  high  these  trace  extent  of  Several  pH  metals, mixing  studies  concentrations are  differs  from  river  water  zone  is  of  and  Liss  by  that by  with  (1976)  sea water  low  trace  with  water  sea  sediment.  salinity indicate  through  i n an  index  the  estuary  processes. salt  matrix  concentration most  electrolytes.  "conservative  The  that  mixing  salt  of  of  measurements.  of the r i v e r  low  pH  of s e v e r a l  constituents  physical  the  mixes  suspended  the s a l i n i t y  t o be a  having  b u t low c o n c e n t r a t i o n s  the composition  of sea s a l t ,  determined  non-conservative  strength  of the major  solely  ensures  estuarine  by  most  although that  sediment,  nutrients  cited  be c o n s i d e r e d In  ionic  water,  concentrations  c a n be m o n i t o r e d  determined  Furthermore,  can  and  river  of the Thus,  in  mixing  salinity  mixing".  chemistry,  the concepts  of  conservative  behaviour  a r e important  i n examining  and  chemical  2  Salinity  Salinity  F i g u r e 1 C o n s e r v a t i v e and non-conservative behaviour during estuarine mixing of s i n g l e river and sea water end members ( L i s s , 1976).  gradients.  A component i s s a i d t o behave c o n s e r v a t i v e l y i f the  concentration  of  that  component i n the e s t u a r y depends s o l e l y  upon the extent of mixing between s i n g l e r i v e r and sea water end members.  G r a p h i c a l l y , the c o n c e n t r a t i o n of  a  given  component  would vary l i n e a r l y with s a l i n i t y and may e x h i b i t a p o s i t i v e (A) or n e g a t i v e  (B) slope depending upon the r e l a t i v e c o n c e n t r a t i o n s  i n r i v e r and sea water {see F i g u r e 1 ) . Departure  from  this  theoretical  n o n - c o n s e r v a t i v e behaviour, component  is  that i s , the  line  while  levels  curve  above  the  indicates  concentration  a f f e c t e d by chemical and/or b i o l o g i c a l  Values below the i d e a l mixing component  mixing  indicate  the  processes.  removal  theoretical  of  of  dilution  the line  i n d i c a t e an e s t u a r i n e i n p u t . Chemical catagorized  constituents as  in  "dissolved"  or  natural  waters  "particulate".  are  often  Proposed  by  3  (1952), " d i s s o l v e d " m a t e r i a l  Goldberg  et  defined  as  that  nominal  pore  size  retained may is  al.  on  the  include in  true  material of  500  but  type  of  may  due  present  to  or  may  Case  Manganese  be  and  depending  are  in  the  1978)  a is  component  material  the  estuarine  between  in  which  environment independently  these of  the  factors the  two  components dissolved  concentrations  and  to  the  biological  be  the  can  cause  particulate  adsorption  organisms. from  may  flocculation  phases  dissolved  by  are  they  the  efficient and  the  precipitation,  or  upon  elements  metals  material  p a r t i c u l a t e components  released  iron  Furthermore,  Hem,  the  with  onto  Alternatively,  particulate  matter  processes.  Studies  waters.  1956;  as  variations  between  from  Geochemically  solubility  filter  dissolved  speciation  while  absorption  material  Manganese  metals.  the  well  hydrodynamic  d i s s o l u t i o n , desorption  1.2  as  within  to  flocculation,  particulates  by  method,  chemical  material  by  dissolved  a  "particulate"  interaction  Interactions of  component  through  particulate constituents  change  due  processes.  and  The  ligands  deposited  transfer  this  colloids  stimulate  1976).  constituents and  while  processes  dissolved also  (Burton,  passes  operationally  solution.  the  can  By  and  Physico-chemical affect  nm  filter.  polymers  which  is  may  are the  biochemically subject pH  and  oxides  and  scavengers influence  estuarine  of  the  environment.  active  to  drastic  Eh  conditions hydroxides  other  metals  concentrations Factors  transition changes  in  of  natural  of  these  (Krauskopf, of  toxic  controlling  the  4  distribution  of  al.,  Sholkovitz,  1977;  either  by  the  in  e s t u a r i e s are  precipitation  colloidal removal  iron  iron of  as  hydroxide  iron  chemistry  1978).  of  may  Iron  humates  While  accompanied  manganese  i s not  understood  is  and/or  species.  be  well  by  removed by  in  the  (Boyle  from  et  solution  flocculation  some  instances  manganese  of the  precipitation,  necessarily coupled  to  that  of  iron. Several  field  indicating  wide  behaviour  of  St.  Lawrence  dissolved Estuary  Estuary  However,  in  behaves  field  a  (Subramnian  case  of  low  one  given  both  over  a  source  d i s s o l v e d metal,  et  1977;  Morris  a l . , 1979).  relative salinities al.,  to  and  they  and  which  salinities  et  may  conducted  Conservative  observed  in  1976) et  Liss  (1976),  to  the  and  Moore  chose  the  a l . , 1979).  ignore  that  dissolved  two  processes  be  an  conservative  occurring increase  dilution  indicating  ( H o l l i d a y and  a l . , 1978;  Secondly,  indicating  been  1976;  conservative  at  al.,  Liss,  Firstly,  observed of  low  behaviour.  d'Anglejan,  indicate  of  estuary.  concentration  been  their  elevated  salinities.  studies  or  and  as  have  has  Holliday  non-conservatively  identified, in  at  estuarine  manganese  questionable  concentrations  manganese  ( H o l l i d a y and  the is  Most  of  variations in  Beaulieu  assessment  studies  a  removal  Liss,  Duinker  deficiency mixing  that  of  has  (Graham  et  et  in  manganese have  concurrently the  manganese  curve  has  been  there  is a  local  1976;  Evans  a l . , 1979b; dissolved  been  been  found  a l . , 1976;  et  Wollast  manganese at  higher  Duinker  et  1979b). The  peak  manganese  concentration  has  been  attributed  to  5  desorption (1976) that  from  in  the  particulate  Narragansett  contact  mixing  with  experiments  (1979b)  could  suspended  Estuary,  could  that  the  in  from  i n the Calico  may  overlying  supply  Direct  measurements  manganese crude  flux  from  found  2  day"  1  the sediments  i s  t h e lower  reported  Scheldt  1978),  Bay  Estuaries of  oxide  o f some  rivers  et a l .  from  riverine  balance  i n t h e Newport  manganese.  proposed  as  a  (1979)  They  manganese have  that  Bay, r e s p e c t i v e l y ,  (1976)  (1979b)  source.  shown  dissolved  a l . ,  possibly  (Graham (Duinker  (1978)  estuaries.  in  manganese  Sholkovitz  h i smixing  ferric  o f manganese,  reaches  f o rthree  constants  Duinker  material  c o n s i d e r e d t o be t h e m a j o r  Narragansett  However,  respectively.  o f 2 + 1 ^ug  et a l .  released  Rivers,  with  et  was  found  cm"  were  manganese. indicated  day" ,  2  a  while  1  on t h e o r d e r o f  .  Precipitation dioxide,  water  (1973)  a l . ,  the p a r t i c u l a t e  acted  Graham  e s t i m a t e s by D u i n k e r cm"  that  et  Estuary.  and Chesapeake  estuarine by  Mn  and  mass  and Eaton  Creek  Graham  o f manganese  f o r the excess  (1978a)  sediments  (1979)  the  sediments  Sanders  5 4  i n t h e Columbia  considering  estuarine  suspended  the release  et al.(1977)  by  and C u t s h a l l  t h e Tay and Rhine  not account  Subsequently,  in  Evans  Sholkovitz  not detect  Evans  alone  sea water by  material  Furthermore,  in  Bay.  30 t o 6 0 % o f t h e r i v e r b o r n e  upon  1 jjg  material  Georgia  et  a l . ,  et a l . humates  This (Windom  1976),  are very  manganese  mechanism et and  Since  removal h a s been  a l . ,  1971),  t h e Rhine and the  low (Mantoura  dissolved  to the catalytic  h a s on t h e o x i d a t i o n  hydrous  process causing  1979b).  attributed  experiments  as  stability et  manganese  effect  and p r e c i p i t a t i o n  which of Mn  a l . ,  removal hydrous 2 +  from  6  aerated  water.  The et  general  al.  model  (1977) nutrient  manganese  dioxide  upper of  manganese  waters  of  to  the  reaches  of  the  quantities  of  during  estuary  a  by  estuary.  This  in  the  remobi1ization  into  overlying  low  Since  surveys  an  material  Newport  conducted  by  attained  episodic or  a  This  biological material  the  was  salinity  concentration.  particulate  balance  particulate  as  deposited  comparable  either  precipitates  reductive  peak.  mass  the  There,  a  the  Evans  s i m i l a r to  the  and  by  cycle.  may  also  Estuary Evans  in  et  the  deposition continual  was al.  upper  of  large  supply  of  material. this  (1979) escapes  sediment. dissolved introduced  dissolved  the  by  manganese  zone  a  process  in  flux  order  an  may  the  be  Gulf of  estuarine  in  (1977)  and  riverborne  remobilized of  St.  magnitude  field  p a r t i c u l a t e manganese  restricted  wedge  that  Sundby  detritus  from  Lawrence higher  Yeats  coastal causes  than  a  that  rivers.  early  River  offshore,  estuarine  manganese  or  hypothesis  suggested  Such  Many  salt  manganese  proposed  Extending  a  by  of  dissolved  riverborne  manganese  they  Fraser  reinforced  from  (1977),  were  estuary.  maximum  be  reaches  i s c a r r i e d upstream  the  proposed  manganese  lower  the  exporting  which  the  maintains  contribute  al.  Dissolved  sediment  may  behaviour  r e c y c l i n g mechanism  the  Desorption  et  in  a  from  recycling  bedload  trap.  manganese  reaches  manganese  involved  estuarine  particulate  of  to  was type  the  surface  proposed estuary,  to  studies  measurements  waters.  A  field  involved only,  programme  i n v e s t i g a t e manganese as  classified  by  and  the  either often in  the  chemistry  in  scheme  of  p50*N  Squami sh River  Port Mann  Vancouver" Annacis^ I  s  l  a  n  d  F o r t  Langley  49°—  0 123^  MILES  '  I KM  —I  8  Cameron Evans  and et  Pritchard a l .  (1963),  (1977).  particulate  manganese  would  established  be  recycling examined metal in  model to  into  the  mixing  zone  the  strait  the  system.  1.3  The  2), km  long  3  River  illustrated  discharge  rate  discharge  rates  while  (7000-8500  to  lm  Hodgins  Also  The  of and  sediments  contributing of  Georgia  incorporates  water.  bottom  estuarine in  the  Furthermore,  significant  of  dissolved  features  Strait  in  and  waters of  the  would  be  dissolved  was  included  high  salinity  sediment  q u a n t i t i e s of  southwest  Fraser of  River  discharge Survey  of  in Figure  3  which at  (approximately melt  early  the  less (1974)  in  within  manganese  to  The  Hope  depicts for  watershed  i n most  neap  classifies  a  varies  Packman,  1978  and  1979).  variations  1978  and  occur  1400  and  and  the  the  3  for  1978  m /sec)  range  during  (Hoos  2  at  (Figure  i s approximately  700  are  Columbia  seasonal  Hope  in June  estuary  km  Canada,  drastic  snow  which  rate  to  measured  British  233,000  is subject  tides. or  r e c y c l i n g model  which  potential  area  (Water  3  in  the an  m /sec)  semi-diurnal  the  surface  determine  River  daily  rapid  Tides  tides  by  mean  2370 m / s e c  March  the  i t often  Estuary,  drains  The  test  Estuary  Fraser  and  since  contribute  is supplied  Fraser as  may  to  to  distribution  both  waters.  Fraser  Fraser  1974). was  of  in  their  overlying area  The  present.  evaluate  study  The  were  and  1979 The  in  flow  daily  average  1979.  Minimum  in February  causes  the  and  freshet  years.  mixture from  of 5m  diurnal during  and  spring  tides. the  Fraser  Estuary  as  a  unique  9  Figure  3  Hydrograph  (Station No. 08MF005) 1978 a n d 1979).  for  of  the  Fraser  1978-1979  River  (Water  measured  Survey  of  at  Hope  Canada,  10  example  of  a  Pritchard, The  1963),  penetration  discharge water but  may  of the s a l t  intrude  flushed  wedge  of the t i d e .  the salt  of s a l t  depends  as f a r upstream  the freshet  river  bifurcates  numerous  confined  lesser  t o t h e main  85% o f t h e  1.4  is  estuary  each  upon  Trending situated  of  river  D u r i n g w i n t e r months  salt  does  Island  not  a t New  Westminster  channels  arm,  10  downstream.  t o 15 m d e e p ,  This  which  southeast-northwest,  between  Vancouver  the  Island  Strait  and  of  the  via  and  narrow  passages  an  average  (Waldichuk, Under  Juan  de  Fuca  (Figure  width  the broad  Furthermore,  of  of  Strait  4).  33  definition  Georgia  i t can  be  (Pritchard,  approximately time  f o r 80  and  Columbia  a t both  ends,  i n the north v i a  The b a s i n  km  is  i s 220  a mean  km  depth  long  o f 156 m  1957).  Strait  estuary  was  Georgia  British  south  numerous  study  of Georgia  in  the  divides  accounts  Ocean  to  2)  upstream  and f u r t h e r  and has c o n n e c t i o n s t o the P a c i f i c  any  (Figure  extend  mainland  the  cycle.  flow.  The S t r a i t  with  and  tidal  the rate  as A n n a c i s  wedge  (Cameron  Steveston. The  into  statified  which  and the s t a t e  during  past  to  moderately  1952).  of f r e s h  of Fraser  Waldichuk  (1957)  River  as  The runoff  water  a  to  be  an  positive  Fraser  River  entering  is  ( Waldichuk,  the physical  (1963) estuary.  fjord-like contributes  the s t r a i t  i n the s t r a i t  discharge  reviewed  and P r i t c h a r d  considered  classified  80% of t h e t o t a l  t h e volume  16 m o n t h s  is  o f Cameron  and a t  equivalent 1957).  oceanography  of the  11  Strait  of  Georgia  circulation intensive  to  in  the  strait  sea  water  from  the  and  de  mixes  through  Juan  Fuca  the  southern  this  masses  Water  northern  is  Fuca  wind.  The of  circulation  tides  the  contribute,  winters, p a r t s of  to  of  cause  strait, mixing  the  the  surface  by  outflowing Fraser water.  an  influx strong  compensating  flow  rather  than  "pure"  of  water  mass  this  i n the  late  intrudes into the  summer  is  formed  mass  Intermediate Strait  of  This  passages,  However,  In  the  the  saline  depth  Strait  Water  as  southern  formed  passages.  Intermediate cold  the  Strait.  causes  de  with  replaced at  characteristics  the  the  counter-clockwise  portion  Winds  form  water  from  During  winter.  s u r f a c e waters  being  Bottom  saline  and  southern  the  mainly  Juan  two  specific  general  runoff  affect  passages  these  the  and  entrains  these  in  the  layer.  Brackish water  tides,  the  waters  brackish  attributed  the  mixing  especially surface  and  Water  water  the of  oceanic  be  sea  exits  entrained  tidal to  River  a  water  action  in  mixture  of  water.  The  vary seasonally. autumn the  may  Georgia.  dense  mixing  months in  as  a  also  zone  warm,  these be  water of  highly  channels. formed  in  12  2_;_  2.1  Sea  Water  2.1.1  1979  Samples  Sampling  sampling  programme  and  required  fourteen  period  oxygen,  pH,  parameters  alkalinity,  particulate suspended  provides field  a  areas For  divided  the  three  and  this  in  seventeen  temperature, particulate  some  May  salinity, manganese,  instances  the  total  illustrated  of  in Figures A.l  cruise  and  4  and  A.2.  dates,  5;  the  Appendix  ships  A.3  used  and  Fraser  the  River  Estuary,  considerations  Westminster  to  Station  Fraser  of  regimes. of  Sand  near  Estuary  programme.  was  i n v e s t i g a t e d can  be  as  defined  extending  by  from  New  Heads  Georgia  15,  River  discharge  area  functionally  geographic  (3)  flow  discussion  regions:  Strait  estuary  1979).  of  (2)  sampling  average  iron,  and  in Appendices  summary  purposes  (1)  varying  were  until  visited.  into  The  monitored  1978  concentration.  recorded  complete  January  Throughout  l o c a t i o n s are  are  from  cruises.  and  particulate  positions  extended  dissolved  aluminium  Station  the  Programme  The  month  METHODS  the  Sand was  Attempts Table  investigated were  I gives  Fraser  investigated  Heads  River (Water  five  made  to  an  indication  at  Hope  Survey  on of  times  during  sample  under  the  of  the  daily  days  that  Canada,  1978  and  13  49°N  Figure  Figure  4  Station  5  Station  Locations  Locations  in  in  the  the  Strait  Fraser  of  Georgia.  Estuary.  14  TABLE  I Daily  Average  Fraser  Mar  22,  1978  951  78-11  Jul  19,  1978  4730  78-16  Oct  17, 18 19  1978  1950 1880 1840  79-01  Jan  4,  1979  816  79-12  May  30, 31  1979  7160 7120  daily  dates  and  discharge  cruises  were  run-off, as  Water bottom  ppt  in both  collected January  extensive  river  was  as  were  In  during  Im a  flow  the below range  periods  of  the  discharge in  the  1978;  however,  rates  i n May  made  Estuarine low  river  levels,  and  salinities Salt  minima  and  freshet.  surface  waters.  in  and  II.  peak  of  maxima  in Table  intermediate  bottom  cruises  high in  from  obtain  and  wedge  lm  from  above 0  to  samples  were  ice conditions  i t impossible  30  to  in get  1979.  systematic  conducted.  twice  approaching  to  seasonal  presented  different  surface  the  the  are  collected  so  data  Four  Passage  at  during  and  of  conducted  was  the  values rates  twice the  during  3  78-04  The  River  D a i l y Average Di scharge R a t e a t Hope ( m / s e c )  Dates  C r u i se Number  once  D i s c h a r g e Rate of the Estuarine Cruises  surveys  a l l , 26 occupied  of  the  Strait  of  s t a t i o n s from  Texada  (Figure  however,  5);  Georgia  Island  to  were  Boundary  complete  depth  15  TABLE  II Seasonal Extremes i n the D a i l y Average Rate of the F r a s e r R i v e r  Discharge  D a i l y Average Discharge R a t e a t Hope ( m / s e c )  Dates  3  Feb  5,  1978  736  Jun  8,  1978  6970  Mar  3,  1979  694  Jun  9,  1979  8390  profiles  were  and  25.  The  in  1978  but  With  one  on  nine  other  required Therefore, frame  the  a  Dual  casts  profile  were  was  separate  250  and  a  were ml  bottom  performed  a t lm and  cruises.  were  Since  5m  3,  15  depths  Station  which  the e n t i r e  et a l . , 1979a), of  bottles  other was  15  at  by  those  the samples was  mounted  simultaneously.  in  was  a  second  an  mechanism  stations the were  the was  aluminium  which nylon  where  total  on  could rope.  a  depth  suspended  collected  piggy-back  of  parameters.  on  of a  of  bottle  water  means  one  contents  recovery  mounted  self-tripping samples  collected  complete  i n s t a n c e s where  measured,  bottle  tripped  samples  to ensure  NIO  In  1979  bottles.  for surface  obtained.  particulates  bottle  with  activated  water  measurement of  sampled  S t a t i o n s 1,  occasions.  (Duinker  pair  equipped be  necessary  matter  for  NIO  locations:  were  lm d u r i n g  exceptions  were  four  stations  at  polypropylene  particulate  also  only  few  bottle  at only  remaining  investigated  litre  obtained  using the  a  NIO  16  River collected was  water with  also  a  of  ice  differentiated the  plastic  necessary  presence  in  data  2.1.2  Specific  file  some the  and  Guildline  at of  reliability  the  of  2.85  Temperatures  were  nylon on  Cruise  Om  opposed  and  This  79-01  depths to  were  method  due  to  the  can  are  be  recorded  lm.  Oxygen  oxygen  were  measured  Department  (1979)  70)  samples  their  as  (Station  rope.  since  techniques  and  of  data  by  standard  Oceanography.  are  presented  in  and  47  (1980).  Briefly,  were  determined  by  Winkler  titration  1966)  and  8400  conductivity  salinities  Salinometer.  ratio  of  to  The  measured lower  a  0.100  or  °C  were  +0.01  Supplementary  with  were  conductivity:salinity  recorded  thermometers. measured  Langley  Bucket  UBC  the  to  reversing  and  45  Model  corresponds ppt.  as  the  Carpenter,  a  B)  Reports  a  stations  samples  salinity,  Autosal  on  Salinity,  concentrations  (Carritt  Fort  river.  (Appendix  details Data  from  bucket  NIO  employed  departmental  the  on  Temperature,  procedures  a  at  from  Temperature,  oxygen  samples  limit  for  relationship salinity measured  estuarine  Beckman  with  of with  temperatures  RS5-3  Portable  Salinometer/thermometer.  2.1.3  Alkalinity  Samples salinity bottles The  f o r pH  into  and  and  Nalgene  pH  alkalinity  were  polypropylene  50  drawn ml  after  those  wide-mouth  and  250  for ml  respectively. pH  samples  and  standard  buffer  solutions  were  placed  17  immediately After  into  ambient  measured  a  at  bath  a  pH  and  solution  prepared  near  0.008695 M  Model 7.5  potassium  according the  in situ  correction  factor  of  0.0114  situ  measurement. corrections, pH  the  measurements  4°C  the  Anderson  0.0100N  of  HC1  resultant  was  pH  Electrodes potassium  until  was  measured  were  by  calculated  from  phthalate  Mattock the  alkalinity where  graphically At  low  by  =  2.500 =  -  activity  t+  at  H  plotting  salinities,  salinity  a  approached  As  in  a  buffer  by  applying  with  That  aliquot  of  pH  temperature of  in  situ  laboratory i s , ' 25  of  Model  pH  a  difference  refrigerator  i n the  4  pH with  also  alkalinity,  ml  sample.  GS  near  solution  The  recommended  degree  a  (1946).  Beckman  buffer  units.  analysis  at  hydrogen  at by of The  Meter. a  0.05M  prepared  as  i n meq/1,  was  expression:  a ^ t  for  +0.03 pH  100ml  (1963).  f„+ = h y d r o g e n Values  were  temperature  stored  standardized  hydrogen  described  be  a  on  Electrodes  phosphate  per  the  Robinson to  was  disodium  associated  subsequent  added  pH  (1963).  units  control.  the  standard deviation)  were  and  M  calculated  and  i s estimated to  approximately  0.03043  was  pH  (one  samples  Meter.  dihydrogen  errors  precision  Alkalinity  method  pH  temperature  Including  pH  temperature  attained,  to Mattock  (1969),  in  a  no  was  GS  with  Gieskes  between  with  equilibrium  Beckman  phosphate  by  water  temperature  with  standardized  a  of  (a */f„*) w  hydrogen  data was  0.0  ppt.  ion  ion a c t i v i t y  varying  f+ w  1250  from  coefficient  salinities  were  Anderson  Robinson  assumed  to  and  approach  estimated  1.0  (1946). as  the  18  Six 30.7  replicate  ppt) with  a  analyses mean  alkalinity  standard  deviation  of  analyses  of a r i v e r  water  mean  alkalinity  +0.01  meq/1.  2.1.4 T o t a l  Total by  the  of  +0.01  of the piggy-back  into  washed  a  possible  after  graduated  and  cylinder  polycarbonate  400  The  nm.  filtration water. water  glass  unit  The  filter  t o remove  frozen  for storage.  distilled  deionized  then  temperature to  +0.01  mg  filtration filter  left  were  a of  in  were  of  a  a  in  by  500 m l  size  rinsed  small  as  preweighed  distilled with  funnel  a  pore  were  complete  As soon  through  washed  prepared  The via  a nominal  rinsed  determined  bottle.  filtered  aliquots  placed  Bla'nks  emptied  cylinder  further  filters  a  Weights  Mettler  obtained  were  to attain  and humidity.  f o r an hour  Blanks  was  overnight  were  deviation  were  was m e a s u r e d  having  and  small  the  on  with  of  into the deionized  aliquots  petri  dish  filtering  of and  300 m l o f  water.  Subsequently hours,  a  O.Oppt)  (1972).  glass  suction  filters  sea s a l t ,  were  t h e volume  bottle  with  yielded  six replicate  a standard  and Buckley  400 ml  and then  Nuclepore  of  concentrations  sampler  dried  collection  of  Particulates  Cranston  contents  (salinity  meq/1  Similarly,  yielded  particulate  of  sample  2.11  (salinity  1.26 meq/1  suspended  of  meq/1.  sample  Suspended  method  of a sea water  H20  oven  negligible.  were  recorded  Balance.  °C f o r t w o  with  ambient  at least  Weights  manner  deionized The  a t 60  equilibrium  in a similar  in distilled  dried  after  twice  prior  to  soaking the  water.  precision  (one  standard  19  deviation)  of  the  sediment  weight  ranging  from  0.50 t o 6 0 0 . 0 0 mg.  +5 m l .  This  indicates  concentrations had  suspended  2.1.5 To for  loads less  sources  processing  acid-cleaned hot  pore  varying  minimize  water.  a precision  prior  6N  size  volume  between  i n samples was  250 m l  5 a n d 2% f o r s e d i m e n t  4 t o 2 4 0 0 mg/1.  than  4 mg/1.  To  of contamination,  then  450  of  Only  four  equipment  trace  This process  several  times  metal  involved  samples  nm,  were d e c o n t a m i n a t e d  i n 5% p o t a s s i u m  necessary samples  rinsing  was  first  with d i s t i l l e d deionized  GA-6 M e m b r a n e F i l t e r s ,  dihydrogen  with  a  nominal  by s o a k i n g a t  phosphate  least  and then  in  d e i o n i z e d water. avoid  possible  problems  settling  of p a r t i c u l a t e  contents  o f an NIO b o t t l e  PVC j u g .  As soon  sea  water  was m e a s u r e d  and  then  the  decontaminated of  storage  to use.  HC1  of  minutes  distilled  ml  water  from  and  Gelman M e t r i c e l  thirty  +0.05 mg  D i s s o l v e d Manganese  the  with  The  was  material  was  suction  After  into  the  complete  an a c i d - c l e a n e d 64oz  collection  filtered  discarding  f i l t r a t e was s t o r e d  Nalgene  polypropylene bottles  amount  of  the  after  sampler,  differential  t h e volume of the  i n a 2 1 polypropylene graduated  filters. the  i n the  were e m p t i e d  as p o s s i b l e  sample  sample,  associated with  filtered  which  sea  previously  t h e f i r s t 100  to  300  i n a c i d - c l e a n e d 500 m l  h a d been  water.  through  cylinder  rinsed  Aqueous  with a small  samples  were  acidified  t o a pH o f a p p r o x i m a t e l y 1.5 w i t h 2 m l o f c o n c e n t r a t e d  HC1  stored  and  storage  f o r some  at  room  months  temperature prior  to  until  analysis  analysed. was  Although  unavoidable,  20  depletion onto  of  soluble  container  Experiments thirty  by  days  samples  was  no m a n g a n e s e  Blanks  were  were  deionized  mentioned  f o r sea water  technique  iso-amyl  chlorine again  Specific noted  ppb  (parts  water  acid-cleaned  plastic  petri  with  of  filtering  600  and f i l t r a t e  In  by  following  that  ml  of  processed  as  and  back  foranalysis into methyl  dissolved basis,  billion  a  the  b y AAS  atomic  three  manganese  (NaDDC),  i s _ug/l,  o r 10"') i g n o r i n g  was  extracted into  acid  t h e manganese  i s o - b u t y l ketone  follow.  stage  by Thomas a n d  extracted  manganese  that  flame  described  brief,  the procedure  on a v o l u m e per  to  (IAA),  NaDDC  although  by  diethyldithiocarbamate  finally,  details  determined  and sea  from  determined  (1978).  sodium  water;  that  river  (AAS)  similar  acetate  extracted  problem. after  sea  was  extraction  with  a  samples.  manganese  with  be  adsorption  indicated that  the f i l t e r s  spectrophotometry  chelated  or  analysed.  at  water,  and G r i l l  in  until  absorption  (1977)  to  (1978)  occurred  stored  prepared  distilled  Grill  anticipated  et a l .  loss  temperature  Dissolved  by p r e c i p i t a t i o n  t o a pH o f 1 . 6 .  filters  a t room  not  Subramanian  acidified  The dishes  walls  manganese  First  (MIBK).  i t should  concentrations they  was  were  are recorded  the small  be  as  conversion  factor. All  organic  tetrachloride, solvents. for  I A A a n d MIBK,  In the case  a l l analyses.  daily  by  solvents  required, were  redistilled  o f IAA, a s i n g l e  A 1 0 % (W/V) NaDDC  dissolution  of  that  reagent  from  i s  carbon  reagent  2 1 b o t t l e was  recycled  s o l u t i o n was p r e p a r e d grade  NaDDC  in  grade  fresh  distilled  21  deionized with  water  carbon  A IM T r i s  reagent  grade  deionized  water  concentrated  the  A  After  concentrated extracted a  into  acid  buffer  was  ammonia  water  was  water  and  deionized  water.  combined,  giving  solution  a  phase  30 m l N a l g e n e  with  carbon  HCl  to  distilled  t o an  Erlenmeyer  6.80  t o 7.05  f o r 15  minutes  extraction  The combined  twice  These  polypropylene  phase  v i a pipette repeated  organic  extracts  4  with  5 ml o f  ml a l i q u o t s o f  aqueous 1.5,  was  was  first  with  near  with  minutes  for  was t r a n s f e r r e d  f o r one m i n u t e  pH  s o l u t i o n and  The manganese  mixing  5  The  then  distilled  with  i n 100 ml  and d i l u t e H C l .  o f IAA.  by s h a k i n g  7.5  was made  t o the range  funnel.  10 m l a l i q u o t s  distilled  5 m l o f NaDDC  o f t h e NaDDC  Following  organic  of  transferred  ml o f IAA by v i g o r o u s  t h e upper  in  decontaminated  o f 5 ml e a c h  stirrer.  remained  chlorine gas.  of sample  solution  20  addition  chlorine  with  addition  back-extracted  acid-cleaned  the  t h e pH was a d j u s t e d  chlorine  phase  by t h e d i s s o l u t i o n o f  o f 1 ml c o n c e n t r a t e d  saturated  magnetic  with  organic  extractions  t h e pH t o a p p r o x i m a t e l y  Acid  a 125 ml s e p a r a t o r y  twice were  Tris  into  separation,  the  was p r e p a r e d  Following  as above.  water  buffer,  with  and a d j u s t i n g  450 ml a l i q u o t  flask. Tris  buffer  by t h e a d d i t i o n  deionized  until  by s u c c e s s i v e  tris-hydroxymethylaminomethane  HC1.  tetrachloride batches  decontaminated  tetrachloride  colourless.  solution,  and  extracts  were  and s t o r e d  bottle  for  i n an  subsequent  analysis. Later, beaker. the  the  After  sample  concentrate  the addition  pH t o 7 a s b e f o r e ,  was  o f 1 ml o f T r i s  t h e sample  was  emptied buffer  transferred  into and to  a  glass  adjusting a  25  ml  22  mixing  cylinder.  together final  o f 20 m l .  Following  t h e a d d i t i o n o f 5 m l o f MIBK,  the  measured  was  Nine  limit  concentration  ppb  (4.5%).  who  recovered  from  o f 102%.  this  main  These  of  method  100%,  the recovery of Brooks  dependence, estuarine a  factor  thereby  analyses. of  rarely  on a  and t h e blank. prepared treatment  exceeded  the  of a sea water  90,  a standard  standard  with  a  a d d i t i o n s o f 2.2 p p b  agree  sea  with  water  those  o f 4.0% a t t h e 2 p p b  the  with  of  Grill  level  rate  of a single (1967)  and  may  after  manganese  exhibit  a  source  concentration  is  approximating  extraction  concentrating  i t has  manganese  closely  introducing a potential Secondly,  consuming  extractable  an e f f i c i e n c y  et a l .  the  with  d e v i a t i o n o f 0.12  of Georgia  values  sample  97.8%.  First,  recovered  as that  curves  an  Water  reagent  t o t h e same  i s l a b o r i o u s and time  consistently  such  nm  a baseline  the  a  phase  into  a t 279.6  calibration  Strait  a precision  attributes.  whereas  for  Blanks  incremental  extraction efficiency  two  measured  standards  o f 2.66 p p b g a v e  reported  While  from  determinations  Five  efficiency  (1978)  aspirated directly  corrected  manganese  for  Spectrophotometer.  concentrates.  replicate  were  minutes  give  o f 0.1 p p b .  mean  manganese  was  15  to establish  determined  s u b j e c t i n g aqueous  detection  and  Absorption  were  were  sample  phase  aspirated  absorbances  Concentrations  minute,  and the absorbance  Atomic  MIBK  the  1  organic  flame  AA-4  saturated  for  to  added  volume  shaking  water  was  deionized  Techtron  an  solution  distilled  air-acetylene  as  o f NaDDC  sufficient  separation,  an  0.5 m l a l i q u o t  with  vigorous  by  A  technique salinity  of error i n  the metal i s well  by  above  23  detection  limits;  virtually  eliminates  2.1.6  moreover,  Particulate  Particulate were  determined  following (1958). added acid acid  an  to  overnight  Metal  flame  ml  an  a  hydrofluoric  vented  acid  was  perchloric  acid-cleaned,  and aluminium absorption  procedure  After  acid  dried  30  and  iron  modified acid  the  oven  at  80°C.  ml  under  diluted Nalgene  of  vessels  4 ml of  were  next  ml  nitric  perchloric  infra-red  t o 10  were  The  until  The  Riley  mixture  addition  the reaction  was  from  bombs.  lamp  acid,  evaporated  concentrations  spectrophotometry  digestion  infra-red  generated.  hydrofluoric  in  iron  in teflon  under  that  effects.  nitric:perchloric  placed  were  matrix  atomic  o f a 4:1  i s i n a n MIBK m e d i u m  Analyses  digestion  evaporated  concentrated  remaining  by  filters  fumes  possible  manganese,  acid  Five  was  any  the metal  placed  day  the  lamps.  and  The  stored  polypropylene bottles  in  until  analysed. Manganese resulting  digests  absorbances for  at  279.6  iron.  the with  To  f o r manganese was 396.3  were  evaluated  perchloric  for possible  flame  and  nm.  nm  or  with  and  filter  absorbances  the  372.3  nm  a  nitrous  the  measured  blanks.  were  (Varian  calibration  the  and measuring  248.5  corrector from  aspirating  In a l l c a s e s  f o r reagent  background  by  determined  analyses, background  i n 10% test  at  determined  air-acetylene  corrected  deuterium  concentrations standards  flame  were  manganese a  nm  an  Aluminium  oxide-acetylene absorbances  into  were  corrected  BC-6).  curves  For  of  The metal  acid. volatile  losses  during  the  digestion,  24  TABLE  I I I A n a l y s i s of C e r t i f i e d  Reference  C a n a d i a n Rc>ck S a m p l e (% d r y v/ e i g h t )  Element  SY-2  MRG-1  Mn MnO R. V .  ( 1  0.136+0.003 0.175 0.17  >  Al Al O/ R. V.< '  0.256+0.009 0.330 0. 32  3.98+0.51 7.52 8.50  a  1  6.86+0.40 13.0 12.12  4.40+0.30 6.29 6.28  Fe Fe^O? R. V . ' ' 1  (1)  1  ml  of a  treated  in  the  mean  recovery  97.0  + 7.1%  _ug  50 mg  f o r Mn  digested. relative  (Abbey,  5 ppm  Mn  1980)  and  F o r 15  250  replicate  d e v i a t i o n s were  and A l r e s p e c t i v e l y .  ppm  Reagent  Al  was  analyses,  9 9 . 5 + 3.8% a n d blanks  were  0.3  of  the  respectively. both  the  6.8%  Rock  results,  standard  precision  reference  of Canadian The  manganese,  with  and s t a n d a r d  certified  samples  Value  p r e s c r i b e d manner.  determine  technique,  solution  rates  a n d 1.1 _ug To  Recommended  standard  Materials  for  accuracy  m a t e r i a l s were  Standards  presented  d e v i a t i o n s o f 2.2%  (MRG-1)  and  iron,  SY-2 in  and  and  Table  (MRG-1) 13%  analyzed. MRG-1  III,  a n d 3.5% (MRG-1)  About were  indicate  (SY-2) f o r and  5.8%  25  (SY-2) give  for  good  aluminium.  agreement  The  non-systematic  may  result  from  aluminium to  as  ,ug/kg  in  of  2.2  Sediment  2.2.1  devices  jjq/1,  the  by  aluminium  ppm  material  on  a  particulate  again  and  Abbey  iron  (1980).  determinations  manganese, but  not  weight  metal  in  have  ignoring  • text  refer  dry  of  basis  the  or  to  been the  and  referred  conversion  particulate, metal  basis sea  iron  metal  concentrations  but  rather  actual  water.  Samples  and  Storage  information and  in  volume  ppb  Collection  All  a  throughout  of  manganese  recommended  concentrations  instead  in  concentrations  values  of  effects.  on  Thus,  particulate  the  measured  concentrations  concentrations  discrepancies  units,  were  factor.  with  matrix  Concerning  The  sample  regarding  sites  of  collection  sediments  is  dates,  summarized  in  sampling Appendix  A. 4 . Shipek the  Fraser  the in  grab  bucket a  samples  Estuary. were  Gravity 79-02. shipment  These to  near  cores were  the  Repeated  were  failed  However,  cores  in whirl-pak  from  selected  samples  from  polyethylene  stations  the  bags  centre and  in of  stored  4°C. taken  stored  at  at  Station  ambient  15  on  (winter)  Cruises  78-01  and  temperatures  for  laboratory.  attempts  Estuary  obtained  Representative  placed  refrigerator  were  due were  to  at  gravity coring  the  coarse  collected  by  sandy  divers  in  the  nature in  Fraser  River  of  sediment.  the  February  1979  and  and  26  January  1980.  sediment,  capped  surface.  These  loss  A  plastic  t o p and bottom c o r e s were  of i n t e r s t i t i a l  Samples  of  collected standard  bottom at  At  the  After  the  thawing  cores  where  Finally,  the sediments  and f r o z e n  until  plastic  sediment  (1967).  The  water  been  acid-cleaned  were  was  soluble  Mn  2 +  and  Gaudette  the  periods  decreases  to from  and  +  the  to prevent  t h e sandy  core  sediment. were  1 9 8 0 by  opening  possible  after  3 cm  segments  described stored  as into  long and  sections. some  i n the f o l l o w i n g  in  polyethylene  grab  section. whirl-pak  Analyses  extracted  of  the  type  squeezed  from  t h e samples  described  under  pore  in Section which  using  by  nitrogen  (nominal  for filters  Reeburgh  gas  size  through 450  2.1.5) had  a  nm,  directly  previously  dried.  the  the length  atmosphere.  interstitial t h e work  of a i r exposure 2  the  to  determination  soon  divided  to minimize  (1978),  i n Mn  from  polypropylene bottles  taken  exposed  as  filters  described  30 m l N a l g e n e  as p o s s i b l e  in January  was  were  AN-450  into  Care  Water  samples  as  into  subsequently analysed.  squeezer  Acropor  pretreated  as  pushed  at depth.  and  were  Interstitial  Interstitial  Gelman  as cores  were  squeezed  a s soon  salinity  necessary,  were  2.2.2  time  storage bottles  samples  bags  for  was  and t r a n s p o r t e d  by d r a i n a g e  water  laboratory,  collection,  in situ  frozen  water  t h e same  glass  core-liner  water  Although has been  of Sanders  the  sediments  oxidative  suggested  (1978b)  are too brief  concentrations.  of time  loss  by  indicates  to cause  of  Lyons that  appreciable  27  Upon  squeezing,  removed  via  a  RefTactometer known this  stored  Manganese  (Varian curves  acidified  2.2.3  To  extract  ammonium  oxalate  three  About  100  oxalate two  of  hours  and  a  few  +0.5  water  drops  analysis determined  102 of  ppt,  at  of  was  concentrated manganese.  by  aspirating  AAS into  by an  279.6  a deuterium  on  sample  of d i s s o l v e d  directly  absorbance  Oxalate  amorphous  air-acetylene  nm.  Background  background  manganese  /  0.2M  they  treated oxalic  After were  through sediment  was  then  Extraction  manganese  were  polypropylene solution  Type  purposes.  with  measurements  were  measurement  of only  interstitial  water  Endeco  Although  accuracy  water  from  corrector  calibration  standards  prepared  water.  pass mg  i n an  the c o n c e n t r a t i o n s evaluated  (1964).  hours,  to  brown  1.5  corrected with  samples  Schwertmann  mortar  the  from  sea  placed  an  remaining  f o r subsequent  Ammonium  sediment,  for  the  "BC-6) a n d derived  and  indicated  interstitial  were  the i n t e r s t i t i a l  f o r comparative  and measuring  absorbances  of  the s a l i n i t y .  c o n c e n t r a t i o n s were  acidified  flame  in  of  drops  pipette  to approximately  and  the  samples  pH  adjusted HC1  Pasteur  sufficient  The  few  to estimate  salinity was  a  acid  Nalgene  suction  in  iron the  oxides  dark  (pH 3.0) were  oven  an  140  nylon  mesh  placed  i n an  bottle.  with  A  50  shaken  through  0.2M  at 110°C  pestle  ( 1 0 5 ^um  ml  the  following  dried  agate  the  and  opening).  acid-cleaned  the suspension filtered  from  reagent  with  a No. was  Sediments  and  sediments ground  added,  of  aliquot  100  ml  of the  vigorously for  Nuclepore  filters  28  (with  a nominal  beaker.  pore  size  The b o t t l e  o f 400 nm)  and f i l t r a t i o n  deionized  unit  an a c i d - c l e a n e d were  distilled  was  quantitatively  transferred to the f i l t e r .  made  up t o a v o l u m e  o f 100 m l  volumetric  acid-cleaned was  stored The  oxalate-leachable  described  in  15  NaDDC/MIBK Section  evaluated  from  extraction  of  oxalate/0.1M  oxalic  subjecting the  procedure,  a  complete The  replicate The  manganese  50  analyses  blank  with  standards  The  from  blanks  using  a  concentration by  0.1M  were  AAS  previously  prepared  ml a l i q u o t o f t h e w o r k i n g  similar ammonium  determined  oxalate  solution  by to  described. technique  of a sediment  presented  in  manganese  a standard  had a manganese  sample.  curves  filter  by f l a m e  concentrates,  solution.  Reagent  p r e c i s i o n of the  results,  ppm  acid.  procedure  oxalate-leachable 111  calibration  an  dish.  extraction  digest  in  The  was a n a l y s e d  2.1.5 f o r s e a w a t e r  was  Nalgene  stored  bottle.  petri  sediment  100 m l  manganese  ml a l i q u o t o f t h e o x a l a t e  was  plastic  times  The l e a c h a t e  then  polypropylene  i n an a c i d - c l e a n e d  the  and  teflon  few  a l l resistant  i n an a c i d - c l e a n e d flask  100 m l N a l g e n e  following  t o ensure  rinsed a  with  polypropylene  water  into  was  sample  Table  content  deviation  concentration  IV,  estimated  from  from  five  the Fraser  Estuary.  indicate that  t h e mean  on a d r y o f 5 ppm o f 2 ppm  weight  (4.4%). based  basis The  on a  was  reagent 100  mg  29  TABLE  IV R e p l i c a t e  Manganese Estuarine  cm  Ammon i u m Oxalate Res i s t a n t Mn (ppm)  Total Mn (ppm)  112 105 118 108 111  375 397 478 466 454  487 502 596 574 564  4.58 4.81 5.34 5.27 5.40  111  434  545  5.08  4.8  45.3  47.5  0.36  4 . 4%  10.4%  8.7%  7.2%  Mean S t d Dev RSD  The the  digestion for black  Total  Metal  was  with  residue, after  analysed  samples presumed  of Sediments  f r a c t i o n of the sediment f o r manganese  in Section to  the digestion  this  refractory  organic  were  filtered  through  size  Ammon i urn Oxalate Res i s t a n t A l (%)  and  nitric/perchloric/hydrofluoric  particulate  remained  Content  oxalate-resistant  filter  of an  Ammonium Oxalate Leachable Mn (ppm)  1 2 3 4 5  2.2.4  Analyses  Metal Concentration ( o n a d r y wes i g h t basis)  Sample 80-56.2  3-6  and Aluminium Sediment  o f 4 0 0 nm) p r i o r  be  2.1.6.  resistant  procedure  material  seemed  Nuclepore  to analysis  by  aluminium  acid  organic  excessive,  AAS.  as  On some  a n d , where  filters  retained  (with  by  after  described  occasion  a  material,  t h e amount o f the  digests  a nominal  Dilution  up  pore to  a  30  TABLE  V C o m p a r i s o n o f T o t a l Mn a n d A l C o n t e n t i n S u r f i c i a l E s t u a r i n e S e d i m e n t s C o l l e c t e d d u r i n g C r u i s e 79-12  Mn ( p p m )  Stat ion  79-12-  1840 330 514 498 542 425 447 477  Al  '  B  A  346 524 551 591 468 480 509  10.4 7.22 8.72 6.99 5.55 5.41 6.07 5.86  A  3 15 53 54 55 56 59 65  ( 1  ( %) ' ' 1  C  7.30 4.74 5.44 5.48 5.03 5.29 5.48 5.21  Column Column  A T o t a l HNO^/HClOy/HF d i g e s t i o n o n l y B Mn concentration: Sum of oxalate e x t r a c t a b l e and r e s i s t a n t metal Column C A l c o n c e n t r a t i o n : O x a l a t e - r e s i s t a n t m e t a l only (1) Concentrations m e a s u r e d on a d r y w e i g h t b a s i s  factor  of  10 was  concentrations working  necessary  were  within  i n some the  sediment  comparative from  purposes  Cruise  79-12  oxalate  extraction.  two  procedures  concentrations. basis,  extraction. the  linear  range  100 mg  samples  were  nitric/perchloric/hydrofluoric  weight  to ensure  final  defined  metal  by  the  standards.  For  the  cases  sum  of  acid  A comparison i s given  Column  Manganese  metal  by a n a c i d  oxalate-leachable  V  manganese  in  with  without  by  aluminium on  prior  i n column  and o x a l a t e - r e s i s t a n t  the prior  content  concentrations,  recorded  ground  without  together  digest  concentrations,  digested  mixture  of t o t a l  i n Table  A gives  determined  also  of d r i e d ,  a  dry  oxalate B, a r e  components  31  and  agree  within  deviation) column  with  C  values  are  components  of  was  values.  While  oxides  (such  susceptible manganese  determined  not  aluminium as  to  dissolution.  with  i n the a n a l y s i s  of  estuarine  sediment  and  and  of  standard  total  resistant  2.2.5  Grain  size  remove  sea s a l t ,  cause  some  +  0.36%,  deviation  shown  Size  lower  amorphous may  be  contributions  from  by  that  Mean  five  f o r Mn  replicates  i s t h e sum  This and  were  and 434  indicates  7.2%  standard of  as  following  concentrations  respectively.  was  Section  and aluminium  the r e l a t i v e  i s only  in  digestion  analysing  IV).  materials  samples  acid  of 10.4%  that  technique  f o rA l .  deviation  oxalate-leachable  8.7%.  Analysis  analyses by  the  (Table  manganese,  described  the  oxalate-extractable  reference  r e s i d u a l manganese  fractions,  Grain  of  determined  5.08%  , i t c a n be  the  f o r the  some  digestion  particulate  precision  deviations  relative  method  the  ppm  from  include  Canadian  of  was  + 45.3  account  by  aluminosi1icates  also  in  oxalate-resistant extracted  Consquently,  certified  extraction  for  some  standard  components.  oxalate  standard  may  (one  concentrations  the  extracted  may  while  However  only  this  gibbsite),  2.1.6,  a  Aluminium  aluminium  and be  technique  p r e c i s i o n of the s i n g l e - s t e p  indicated  ppm  any  may  concentrations  evaluated  an  A.  from  analysed  sedimentary The  i n column  the sediments;  oxalate  these  the p r e c i s i o n of the  were  Carver  centrifuged  cementation  carried (1971). and  out using  the dry  Sediments  oven-dried  were  a t 40°C.  of the f i n e - g r a i n f r a c t i o n  sieving washed This  to may  of the c l a y  32  minerals. with  ambient  sieved brass  After  by  temperature shaking  sieves.  weighed.  allowing  Each  for  the and 15  sediment  samples  to  humidity, minutes size  equilibrate  they  were  through fraction  a  overnight  weighed graded  was  and  series  dry of  subsequently  33  2L  3.1  ALKALINITY  chemistry  and  hydrogen  proton  and  DISTRIBUTION  pH  affect  ion  IN  THE  titrate  sea  of  FRASER  ESTUARY  water  to  necessarily  includes  less  than  the  Since  the  first  pH  =  pH  -log  The  pH  defined  =  [HCO^j  on  the  + H 0  =  2  =  H  +  +  HCOi  HCOj  =  H  +  +  CO^"  B(OH)  3  carbonate  H^COj  H^CO^  H  +  in  + + H.,0  OH=  B(OH),;  +  to  titration constants  carbonic  small,  acid.  only  oxygenated  [B(OH)£]  interrelated  a  2  required  This  of  is  boric waters.  +  [OH"]  -  [H ] +  activity  CO (aq)  C0 (aq)  is  the  :  reactions: =  constant  the  in  dissociation  acids  2[COy]  are  by  =  +  alkalinity  defined  CO^(g)  ions  point.  with  reflects  alkalinity  hydrogen end  measurement  present  The  considered  by  ion  dependence  H^O  weak  be  hydrogen  mutual  the  acids  most to  anions  solution  H  a^=  and  bicarbonate  is a  alkalinity  1970). of  pH  in  (a i)  Alkalinity where  need  are  the  dissociation of  The  acid  amount  a l l weak  acids  and  weak  the  the  contribution  Alkalinity  while  Morgan, as  parameters  processes.  the  and  defined  carbonic  important  concentration  (Stumm  operationally  are  several  deficiency  solution  and  PH  Introduction  Alkalinity  of  AND  +  H  +  and  because borate  of  their  systems,  as  34  As  a  consequence  influencing perturb  the  the  pH  respiration  in  a  water.  the  in  photosynthetic to  sea  or  decrease  the  above  concentration  of  via  of  dissolved  Thus,  carbon  o x i d a t i v e decay  pH.  uptake  of  equilibria,  of  or  evasion  to  the  carbon  dioxide  organic  Alternatively,  processes  carbon  dioxide  generation  matter dioxide  atmosphere  results loss  by  the  pH  causes  rise. A  number  have  been  the  Columbia  of  conducted.  (Pelletier  in  Chesapeake  salinity  in  1979;  such  This  having  lower  a  and  Lebel  mixing  of  estuarine  to  be  St.  and  waters  conservative  Lawrence  apparent of  the  the  pH  of  in  Estuaries  Pelletier,  zone  a l .  of  hydrogen a  occurs pH  Estuaries  Morris  ion  way  as  when  sea  and  has  1980).  non-conservative James  River  (Mook  and  estuarine  concentration  to  develop  water  been  a  in  1975;  in  waters  varies  pH  mixes  observed  Koene,  minimum  wih the  with at  river Scheldt,  Wollast  et  low  water Rhine  a l . ,  1979;  behaviour  to  1978 ) . et  a l .  (1978)  processes.  a  i n d i s s o l v e d oxygen  organic  carbon  levels.  They  (DOC)  suggested  increase  concentrations  of  in DOC  They  attributed  biological  sudden  found  observed  initial  the  salinity.  decrease  was  1972)  investigations  that  et  alkalinity  Bay.  indicate  Morris  the  a l . ,  (1979)  the  Several  Tamar  et  Lebel,  Wong  behaviour  of  Alkalinity  (Park  and  However,  and  studies  found  the  content,  concentrations that  ionic  minimum an  and,  halophobic  strength  thereby  pH  this  associated  increase a  peak  plankton  in dissolved  in chlorophyll encountering  disintegrated, releasing  supporting  a  large  with  population  a high of  35  oxygen-utilising proposed with  that  They  function data  of  for  and Koene(1975)  resulted  the  rapid  and  river  model  dissociation  supposition  water  with  allowed  Since  Fraser  from  second  this  that  salinity. the  Mook  verified  titrating  mathematical  Alternatively,  minimum  of the f i r s t  acid.  experiments, a  t h e pH  salinity  carbonic  bacteria.  their  River,  model  i t  is  constants  with  sea water, them  increase  laboratory  and  developed  to calculate  was  used  worth  of  pH  to  as a  examine  d i s c u s s i n g i n some  detail. Several water  parameters  sample.  apparent  o f Edmond  constants and G i e s k e s +  0.032786T  pK^  =  2902.39/T  +  0.02379T  = chlorinity  T  = absolute  Koene  applicable  a t low  pK'  y  =  =  Using  0 < CI  -  defined  6.4710  a the  via  the  -  0.19178C1 / 1  0.4693C1 / 1  3  '  3  water  the  0.032786T 9.0  following  expressions  0.02379T  <  0.005  from  a /D 2  - 14.8435  -0 . 0 8 9 2 1 C 1 / 1  2  ppt  to  6.4980  evaluate  dioxide, the  -  -  0.7531C1 / 1  2  ppt pK)  bicarbonate  carbonate  of the f o l l o w i n g e x p r e s s i o n s =  acid  of  temperature  +  of carbon  calculated  [CO,]  determine  -14.7122  of the  the above r e l a t i o n s  concentrations c a n be  +  0 < CI <  2902.39/T for  temperature carbonic  pH  salinities:  3404.71/T for  pK^  (1975)  the  (1970):  3404.71/T  CI  to c a l c u l a t e  of  =  and  means  and  pK;  where  ion  salinity  dissociation  expressions  Mook  The  are required  (Skirrow,  and  i o n and  alkalinity 1975):  pK^,  the  carbonate (CA)  by  36  [HCOj]  = a^K) D  [coy]  =K  where  D = CA/Ca^K^ CA  The  total  inorganic  Q = TC/CA, (a^  Hence,  y  + 2K  K'* ) 2  carbon  [HCOJ]  3  Q =  D  = [HCOj ] + 2 [ C 0 / ]  = [co ]-+  TC  If  K \  +  content  (TC) i s d e f i n e d by:  [coy]  then:  + a R ; + K'  )/(a„K;  A  the  pH  can  be  + 2R', K > )  calculated  from  the  quadratic  expression: a^,+ In Koene  a^K],  (1 - Q) + K', K'^ (1 - 2Q) = 0  calculating (1975)  inorganic  the  assumed  carbon  estuarine that  were  the  alkalinity.  carbonate  brackishness, estuary  a r e thus  given  bCl*,  CA  =  (l-b)CA +  bCA^  TC  =  (l-b)TC,+  bTC,,,  could  /  subscripts  Titration  contribution giving  b to represent  the  extent  (salinity)  in  of the  f and m denote  the values  of fresh  and  e n d members r e s p e c t i v e l y .  TC^.= Q^CA^ a n d T C « = determine  implement  mixing  and t o t a l  conservative.  f o rborate  and  by t h e e x p r e s s i o n s :  (l-b)C3y+  Cj = { ( l - b ) Q , X  the  Using  =  marine  To  corrected  Cl  Since  were  Mook  alkalinity  t h e CA a n d T C a t a n y c h l o r i n i t y  where  they  then  distribution,  the t i t r a t i o n  content  alkalinities  pH  two  Q CA^;  Q f o rany p o i n t + bQ }/{(l-b)X M  the model, water  Mook  masses  a n d d e f i n i n g X = CA^/CA^,  m  i n the estuary + b}  and at  by:  Koene  constant  (1975)  considered  temperature.  The  37  properties  of  alkalinity  and  carbon be  the  end  pH  (which  content).  evaluated  intermediate  members  The  and  alkalinity estuarine  that  River  documented in  Prolific  surface  bottom  waters  generation  and  by  sufficiently estuarine The same  organisms  water,  to  model  also  temperature,  dissociation temperature The will  be  in  of  discussed  this  data,  together  to  importance  water.  be  in  used  to  with of  a  to  of  the  be  valid Wong  may  for (1979)  in  the  biological is  well  depletion supplied  Carbon  residence  to  dioxide  reactions  occur  times  of  consequence. two  end  members  throughout i s not  the  acid  pH  The  in  model  data.  d i s c u s s i o n , have processes  the case,  may  reaches  and  pH  be  matter  the  chapter.  biological  behaviour  organic  the  lower  alkalinity  brief  at  dioxide  hydration  this  examine  minimum  carbon  its  that  the  then  estuaries  oxidized.  carbonic  distribution  will  sea  of  salinity  in  be  mixing  when  not  mentioned,  considerable  hence,  constants  (1975)  the  and  of  However,  and  may  assumes  and  may  however,  cause  compared  be  pH  could  non-conservatively  Alternatively,  rapidly,  isothermal.  may  sediments  inorganic  salinity  conservative  carbon  important,  and  salinity,  total  the  productivity  1976)  waters.  of  behaved  More  any  of  previously  alkalinity  (Head,  at  the  were:  shown.  assumption  As  Estuary.  influences.  clearly  inorganic  waters.  postulated James  total  pH  development  the  defined  establishes  theoretical  salinities  and  also  the  Unfortunately,  explicitly  have  the  estuary  is  the  vary of the of  an  apparent  with estuary.  Fraser Mook  Estuary  and  Dissolved been  both  Koene oxygen  included  in modifying  the  pH  due of  38  3.2  Results  3.2.1  Alkalinity  The  alkalinity  cruises.  The  Figures 79-01,  6a  through  behave  6d  for  inspection  At  the  any  time  alkalinity even  reflect appears  waters  versus  was  measured  salinity,  are  Cruises  78-04,  78-11,  to  October It  though  have  of  the  reveals  a  1978  linearly  fits  predicting observed.  on  four  presented in 78-16,  below  salinity  at  one  cruise  cruise  to  this  the  data.  and  This  that  the over  would  the  data  alkalinity deviations  linear  next.  The  That  to  i s to  function  slope  of  which  sampling other  i s most  a  the  linear  may  depth  than  to  evident  in  2  a to  is  cases  ranged  in  actually  relationship  are  8 ppt.  the  the  alkalinity  alkalinity  those  of  that  result  While  initiated  specific  not  range  relationship  below  such  is  complete  consistently  range  i n most  water  appears  alkalinity  values  from  the  establish  river  a  relationship  to another,  i n the  general  6c).  salinity  in  linear  feature  salinity  i n the  the  on  of  range.  Furthermore,  of  i t impossible to  Variations  a  Extrapolation  salinities  which  salinity  variations  however,  water  number  alkalinity  being  Figure  the  Furthermore,  evident  renders  higher  fresh  the  wide  in  to  78-16,  on  sampled. the  a  effect  noted,  dependent  salinities  year  there are  scatter  be  data  influences.  (Cruise  should  the  over  little  some  of  persists  temporal  introduce  one  estuarine  plotted  conservatively  salinity  from  the  respectively.  features.  best  of  results,  Cursory  say,  Data  paucity  varies of  data  value. are  apparent  from  a  from  minimum  of  39  0  5  10  15  20  25  30  SRLINITY (PPT)  35  5  10  15  20  25  30  'SRLINITY (PPT)  F i g u r e 6c C r u i s e  78-16  5  10  15  20  35  25  30  SALINITY (PPT)  F i g u r e 6b C r u i s e  F i g u r e 6a C r u i s e 78-04  0  0  0  5  10  15  20  78-11  25  30  SRLINITY (PPT)  F i g u r e 6d C r u i s e  35  35  79-01  FIGURE 6 A l k a l i n i t y data p l o t t e d versus s a l i n i t y f o r C r u i s e s 78-04, 78-11, 78-16, and 79-01. Symbols: • data at a l l depths for S t a t i o n 15; O data at a l l depths f o r other s t a t i o n s i n the Strait of Georgia; A surface samples in the Fraser E s t u a r y ; O bottom samples i n the F r a s e r E s t u a r y .  40  0.81  meq/1  78-07). were day  (Cruise  However,  observed sampling  values  decrease  term  than  i s evident  into  meq/1  1.31  meq/1  t h e same  the f i n a l  meq/1  (maximum  (minimum  magnitude  day  alkalinity  (Cruise  of a  three  dropped  from  value  value  1.17)  0.85).  to  This  6c.  of  the range  On  the  1.0  in Figure  alkalinities  to f a l l  78-16.  than 1.0  of  f l u c t u a t i o n s of  i n October  greater  less  t o a maximum  Cruise  programme  Maximum tends  short  during  always  alkalinities  78-04)  sea water 2.0  i n the S t r a i t  t o 2.2  meq/1,  of  Georgia  depending  on  the  salinity.  3.2.2  Dissolved  Oxygen  Data  . „  The  dissolved  oxygen  data  from  versus  salinity,  78-04,  78-16,  include  data  As  a r e shown  79-01, from  best  waters  of the F r a s e r  estuary  data  salt 7b)  Cruise wedge  i n bottom  through  of  7a a n d  behaviour  79-12 waters that waters  7b)  (Figure  collected the with  and  7d).  of  plotted  for  Cruises  7c a n d  7d  Georgia.  7c, the d i s s o l v e d  the lower  (Figure  7d  Figures  Non-conservative  waters  78-16  indicated  conservatively  conservative  surface  Estuary,  the S t r a i t  Figures  Estuary.  Cruise  during  from  (Figure  the  during  estuary  exhibited  in  7a  respectively.  throughout  illustrated  generally  in  in Figures  79-12,  stations  oxygen  observed  and  the Fraser  i n the  behaviour reaches  dissolved salinities  was  of the  throughout  However,  during  surface  extensive  Cruise oxygen less  the  78-16 behaved  than  27  including Station  15,  ppt. Samples exhibit  from  scatter  the S t r a i t  throughout  of Georgia,  the year.  Non-conservative  behaviour  41  0  5  10  15 20  SALINITY  25  30  35  5  10  15 20  SALINITY F i g u r e 7c C r u i s e  25  30  (PPT) 79-01  5  10  15 20  SALINITY  (PPT)  F i g u r e 7b C r u i s e  F i g u r e 7a C r u i s e 78-04  0  0  35  0  5  10  15 20  SALINITY F i g u r e 7d C r u i s e  25  30  35  (PPT) 78-16  25  30  35  (PPT) 79-12  FIGURE 7 D i s s o l v e d oxygen data p l o t t e d versus s a l i n i t y f o r C r u i s e s 78-04, 78-16, 79-01, and 79-12. Symbols: • data at all depths f o r S t a t i o n 15; O data at a l l depths at other s t a t i o n s i n the S t r a i t of Georgia; A surface samples i n the F r a s e r E s t u a r y ; O bottom samples i n the F r a s e r E s t u a r y .  42  occurs  because  biological  dissolved  pH  In  March  staying River of  are  in  range  as  at  Strait  of  pH  than  similar In trend  throughout  have  the  exhibit  a  i n the  surface  at  by  waters  Strait  curve near  pH  waters  of  can the  be  salinity  lower  the  Figure  seen  Georgia,  values  of  both  of at  than  the  pH  the those  1978  can  waters  two of  only,  end  the  members  2 ppt.  The in  salinities  of  the  be  in  samples  Strait  although  range  15.  decreases  8c)  pH The  pH  'observed  at  Strait  lower  features  these  pH  Fraser  in October  Bottom  the  the  wider  Station  7.8  little,  estuary.  salinity  15.  8d.  i n the  surface  for a  in  the  than  near  salinities  deep  of  varied  the  at  79-01,  through  However,  distinct  Station  uniform  in  River  ( C r u i s e 79-01,  specify  pH  minimum  higher  1979  to  pH  mixing  15.  collected  pH  Fraser  depth  At  those  available  depth,  to  three  pH  waters  reflects  were  78-16,  8a  values  surface  column  the  the  pH  Station  data  and  The  with  January for  of  water  pH  i n the  pronounced  8a)  The  salinities  8b)  Georgia.  ppt. to  more  lower  appear  23  7.77.  Considering  decreases  estuary  are  a  Figure  those  deeper  Figure  distinguished.  exhibits  influenced  78-04,  in Figures  mid-salinities  higher  Considerably  were  at  ofthe  78-16,  to to  Cruises  salinity  c h a r a c t e r i z e d by  observed  characteristic  values  7.56  similar  evident  (Cruise  versus  from  ( C r u i s e 78-04,  very  were  measurements  plotted  the  Georgia  scatter  pH  1978  were  values  are  Data  Estuarine 79-12  concentrations  processes.  3.2.3  and  oxygen  to  the less  values  Georgia.  same  general  insufficient minimum. surface observed  data Waters  and in  at the  43  0  5  10  15  20  SALINITY  25  30  (PPT)  0  5  10  15  20  SALINITY  25  30  (PPT)  F i g u r e 8c C r u i s e 79-01  5  10  15  r  20  SALINITY  F i g u r e 8a C r u i s e 78-04  0  i—i—i—I  35  25  30  35  (PPT)  F i g u r e 8b C r u i s e 78-16  35  0  5  10  15  20  SALINITY  25  30  35  (PPT)  F i g u r e 8d C r u i s e 79-12  FIGURE 8 pH data p l o t t e d versus s a l i n i t y f o r C r u i s e s 78-04, 78-16, 79-01, and 79-12. Symbols: • data at a l l depths f o r Station 15; O data a t a l l depths a t other s t a t i o n s in the Strait of Georgia; A surface samples in the Fraser E s t u a r y ; O bottom samples i n the F r a s e r E s t u a r y .  44  immediate  vicinity  comparable. available The  data  considerably surface seems  Very  few  however, water  data  than  salinities  for salt  wedge  are  waters a r e  t o p t o bottom for  for salt  both  at  other  column  in  with  water  the  time  Fraser  of  indicated  the  a decrease  again  when  apparent  5 ppt.  respect bottom  than  As a g e n e r a l  8d),  of Georgia, are  near  estuarine  wedge  salinity.  higher,  is  at a salinity  available  any  the S t r a i t  T h e pH m i n i m u m  waters  i s lower  Figure  River  to  pH.  waters;  for  surface  observation,  River  and S t r a i t  year.  pH of  Measurement  o f pH w i t h  depth.  Discussion  3.3.1  Distribution  While observed  1980),  (Pelletier (1979)  alkalinity alkalinity  and  relationship  behaviour (Park  and  found  a  more  linearly  with  i n the Fraser  (1979) observed  in  constant  at  low  alkalinity  1979;  Lebel  complex the  below  The  apparent  salinities  to  been  St.  Lawrence  and  Pelletier,  River.  a salinity  i s similarly  the  has  relationship  James  salinity.  River  attributed  of  e t a l . , 1972) a n d  Lebel,  salinity  was n e a r l y  increased  behaviour  Alkalinity  conservative  Wong  Wong  of  i n the Columbia  Estuaries  then  are  t h e water  though  79-12,  throughout  t o be h o m o g e n e o u s  were  through  3.3  estuarine  t h e pH  Georgia,  (Cruise  scattered.  of a corresponding  values  n o pH d a t a  1979  collected more  even  month.  f o r May  were  water  Heads  Unfortunately  for this  samples  for  of Sand  of  between  Here, 5  ppt  the but  alkalinity/salinity complicated. non-conservative either  removal of  45  alkalinity  or  the  In  examining  the  to  explain  the  consider  has  error  (2)  removal  (3)  mixing  been  knowledge  and  of  H  78-04  water  behaviour  water  of  of  various  sources.  possibilities  alkalinity.  exist  Points  to  The  hydrogen  Robinson  (1946)  Rogers, were  former  1.0  as in  to  0.88  and  procedure  0.1  0.1 meq/1  salinities made  of  and  Robinson  Anderson  for  at the  low  which  H  Anderson  0.0  f^-h  was  ppt  and  Considering be  0.913  water  corresponded  f *,  from  approached  to  fresh  requires  salinities  manner. have  taken  to  Cruises  and  0.885,  alkalinities  the  0.0  the  (1946)  alkalinity  f^+ w e r e  salinity  this  alter  of  must  outside  coefficient,  very  ppt  such  intercept  relationship.  purposes,  the  determined  by  a  Mean 0.78  low were  would  using  1973).  approximately than  and  sources  measurements  Values  values  was  salinities  various  ion a c t i v i t y  f„*  comparative  low  computation  however,  in order  at  salinities  determinations at  technique  78-16,  at-low  from  these  overestimated  sample  method  from  number  alkalinity  alkalinity/salinity  For  more  the  recalculated  the  and  of  approach  respectively,  of  of  (1946);  and  that  water a  method  salinity.  to be  the  since  the  with  assumed  of  standardised.  Robinson  f tmay  Estuary,  in alkalinity  f o r which  varies  fresh  anomalous  (1)  considered  range  Fraser  of  include:  Errors be  mixing  Gran  may meq/1. greater  the  respectively  However, the  the  measured 0.0  ppt  a of  Fraser  River  Anderson  procedure  for duplicate  overestimate  than  of  method  titration  values meq/1  alkalinity  (Gieskes  analyses  suggesting  by that  alkalinity alkalinities intercept  and  each the by  may  be  (Figures  46  6b  and  6d).  between the  the  two  The  of the  to  the  be  is  (1979)  However, losses  this  exceeds  alkalinities  at  low  relationship.  be  behaviour  real  bearing  in  the  rather  of  alkalinity  than  i n mind  Fraser  fresh  considered by  the  an  at  artifact  limitations  Estuary  water  and  should  not  Moreover,  of  (Figure  6)  alkalinities  of  occur  of may  may  be  alkalinity  at  explanation  for  et  magnitude.  anomalous  Pelletier  with  Taking  are  alkalinity,  in  starts  of  which  to  Estuary  non-conservative  and  may  be  are  which behaviour  discharge  to  an  boron  calcite  be the wastes  calcite attained.  the  by  at  Fraser least  into  an  account, for  zone. of  rapidly and  are  that  explanation  components  removed  Koene  to  that  unlikely  introduced  of  respect  mixing  and  indicate  salinities  Hoos  may  Mook  observations  initial  increase.  p o l l u t a n t s which  establishments  these  the  by  with  respect  seems  an  estimated  several non-carbonate  some  as  (1980)  high  (1969)  precipitation  There  waters  relatively  a l .  alkalinities  carbonate  Calculations  estuarine until  of  precipitation  and  undersaturated  carbonate  strength  calcite  Lebel  Garrison  was  removal  behaviour.  supersaturation  and  for  agreement  imated.  (1975)  several  linear  since  non-conservative  order  a  i n t e r p r e t e d to  salinities  River  to  give  Nevertheless,  non-conservative  alkalinity  Wong low  conform  to  H  required  exaggerated  overest  i -r r e q u i r e d  for  f^* values  methodology.  data,  value  i s 0.946.  apparent  salinity  the  techniques  calculated  salinities  low  Also,  the as  Packman  into  the  the  ionic  (1974)  Fraser  responsible. alkalinity. while  titration  organic  list River  for  the  Laundry compounds  47  with  titratable  from  several  While  boron  estuaries  f u n c t i o n a l groups  industries, especially  has  been  (Liss  shown  and  during  estuarine  however,  the concentrations  the a l k a l i n i t y  Suspended  were  attributable  to  the  salinity.  1965; S i e v e r ,  water  would  cause  exchange in  this  8.29  samples an  study,  meq/lOOg.  Mangelsdorf American a  Pharo  (1977),  rivers  suspended  concentration cation  insufficient any  load  capacity  capacity  present  values  (1965),  5.6  total  suspended  with  increasing  i n October  While  were  cited  the  from  by  meq/1  f o r the a l k a l i n i t y i n the suspended  6.73 t o  capacities  fresh  gives  anomaly. may  and for  Considering water  a  maximum  a  cation  f o r the Fraser  load  cation  Sayles  1978, and assuming  2  This  not measured  maximum  this  be sites  alkalinity.  ranging  exchange  o f 50 m e q / l O O g ; 1 x 10"  must  acceptors  t o 47.4 m e q / l O O g .  o f 20 mg/1,  of only  to account  carbonate  from  exhibit  a c t as proton  sediments  total  Alkalinity  would  alkalinity.  River  alkalinity  ion-exchange  to determine  reported  reported  have  may  of  Kennedy  measured  exchange  exchange  (1972)  load  to  great.  contributions  minerals  cases,  necessary  since  rapidly  sedimentary  f o r Fraser  In a l l  waters.  the  in  of the organic  materials  considered  1968) w h i c h  ranging  sediment  certain.  sediment  are acidified  .Also,  i s less  unfiltered  overestimation  capacities  industry.  non-conservatively  because  clay  products  the fate  decreases  possible  effluents  t o be e x c e s s i v e l y  suspended  Firstly,  when  on  i n the  1972),  be  behaviour  Two  examined. (Garrels,  may  concentration  t h e wood  these  have  performed  non-conservative particulate  of  would  be f o u n d  behave  mixing  sediments  measurements  to  Pointon,  material  affect  may  River,  Secondly,  contribute to  48  the  titration  carbonate  material  Mixing observed could the  of  However,  water  from  hypothesized.  Fraser  River  into  to  with  Secondly, subject  water the  evident  to short  i n t h e upper  behaviour  mixing  of  unlikely higher to  as  the r i v e r  (Figure  water  6c)  can  by  slope  initial  intersection  of the  intersection  points  for  dilution  alkalinities respectively. processes the  may  less  linear  near  curves  with  end  1 meq/1  the a l k a l i n i t y  establish different  low a n d h i g h  salinity  ranges.  the related  influences. alkalinity time  of  This  alkalinities  two  7 and  were  seem  always  behaviour 1978  intersecting  linear  would  well  as  14  having  do  conservative  alter  For  observed water 1  indicate  mixing  of  example,  fresh than  not  the  the p o i n t  ppt are  greater data  complex  October  input  as  of  long,  would  of c o n s e r v a t i v e for  is  storm  is sufficiently  members and  and  water  relationships. of  input  I f the residence  water  curve  salinities  than  However,  in fresh  models  t o be  geographic  alkalinity.  as  the  However,  T h i r d l y , data  mixing  two  outlets  the river  water  interpreted  water  manifestation  extrapolation  Variations  the  a  varying  e n d member. be  be  fresh  relationships. of  may  fresh  appears  of the e s t u a r y  with  measured  predicted  1978,  generate  several  estuary.  fluctuations.  reaches  waters  since  than  i n October  could  sewage  discernable  of a l k a l i n i t y  river  of  of  i s unknown.  and  of a l k a l i n i t y  no  term  sources  the major  the  behaviour  only,  concentration  relationship  b u t a number  non-conservative  is  various  Firstly,  itself  discharge  salinity  the  i n the p a r t i c u l a t e m a t e r i a l  alkalinity/salinity  be  drains  alkalinity.  curves  meq/1 what for  49  3.3.2  Distribution  Data  from  biological natural  the  waters. due  to.the  oxygen  saturation from  depths  saturation  on  the  i n bottom from  supersaturated  waters and  departure  conservative  reaches  of  scatter  exhibited  resulted  from  Except  during  (Figure  7).  result  from  with  respect  indicate the  Variations  the  that  salt  production summer, oxygen  in  bottom  in  to  oxygen,  Fraser  the  there  during  salt  wedge.  The  using  samples  levels  fell  Station  15  thereby for  from to  55%  were  indicating the  surface  the  percentage  calculated  7b).  the  below  waters  slight in  Similarly,  freshet  the the  (Figure  7d)  production. the  the  dissolved  waters  oxygen  of  the  data  estuary from  also  Estuary  less  the  may  than  27  of  behaves Estuary  river  the be  Cruise  behaves  Fraser  of  of  i s minimal,  evidence  oxygen  content  dependence  salinities  i s no  for  (Figure  d i s s o l v e d oxygen  in  decrease  oxygen,  behaviour  in  in  accounted  surface  waters  at  the  at  temperature  wedge  and  depths  freshet,  the  the  5m  primary  the  in  15.  data  d i s s o l v e d oxygen  oxygen,  Station  estuary  by  intense  conservatively  Although  the  of  was  of  This  influence  f r e s h water  with  to  the  matter.  78-16  While  respect  activity.  of to  organic  Cruise  photosynthetic  lower  tend  saturated  with  from  of  (1970).  1  illustrate  concentration  during  100%  Oxygen  Georgia  oxidation  Weiss  were  •Samples  of  Concentrations  surface  all  Dissolved  Strait  processes  expressions  of  water  solubility. undersaturated  78-16  (Figure  7b)  conservatively  in  ppt.  Thus,  except  biological  primary  during  utilization  the of  50  3.3.3  The  Distribution  distribution  Georgia  exhibits  sampling  time.  o f pH  o f pH  a number  Four  i n the Fraser of g e n e r a l  distinct  estuary  and S t r a i t  of  f e a t u r e s r e g a r d l e s s of the  trends  which  will  be  discussed  separately are: (1)  d e p t h - r e l a t e d pH  (2)  pH  distribution  of  Georgia  pH  distribution  (3)  variations i n the surface waters  of the  Strait  i n the s u r f a c e waters  of t h e F r a s e r  estuary (4) The  pH pH  i n the s a l t  profile  at  wedge Station  15  illustrates  the o b s e r v a t i o n s mentioned  there  l o w pH  with  are depth  stations that  was  depresses The  the  1979  the  pH  and  agree  l o w pH  values  observed  with  generation  and  productivity  both  8c) occur  water  pH  i n the  uniformly  The d e c r e a s e  o f pH  Georgia  carbon  of 8.8,  than  low  measured  Tully  this  and  occurred  time  of  to primary  because  phytoplankton at  that  of  Strait  to the surface.  are higher  maxima,  9)  3.2.3  biological  of  (Figure  at a l l  influences,  dioxide  which  Georgia  shows  water.  The  those  Strait  1978  Section  the surface. the  related  (Figure  in  and r e f l e c t s  of s u r f a c e waters  variations  salinity,  in  situ  of the  processes.  January  below  the year  in  t h e pH pH  seasonal  oxygen  consistent  throughout  i s ,  mixing  values  i n October  pH  productivity  values  winter  observed  mixing  I n May  1979  a t any o t h e r Dodimead  i n areas  time  the  of  (1957).  in high  (Figure  associated  concentrations. depresses  brings  and  8d) year  Their  with  high  High  primary  carbon  dioxide  51  8.2  FIGURE 9 The  concentration coupled  with  leads to an  pH p r o f i l e  at' S t a t i o n 15, C r u i s e  but e l e v a t e s the pH. complex  incoherent  Patchy  mixing p a t t e r n s distribution  of  biological  activity  i n the S t r a i t  of  surface  hence  apparent s c a t t e r i n the d i s s o l v e d oxygen and to  78-16  pH;  Georgia the  pH data with r e s e c t  salinity. A  Estuary  distinct was  pH minimum i n the s u r f a c e waters of the F r a s e r  observed d u r i n g a l l four e s t u a r i n e c r u i s e s .  there are more data  available  October  be examined i n d e t a i l  1978  will  from  Cruise  78-16,  i n order  Because  data  from  to e l u c i d a t e  f e a t u r e s common at a l l times. As  illustrated  i n F i g u r e 8b,  from the F r a s e r R i v e r Georgia  the  (with a mean pH of 7.85)  (with a pH of 8.06)  a s a l i n i t y of 1.5 Tamar,  ppt.  Scheldt  the mixing of  of  r e s u l t e d in a pH minimum of 7.72  at  has  and  waters  the S t r a i t  Such a s i t u a t i o n and  surface  been  Rhine e s t u a r i e s (Mook and  observed Koene,  in 1975;  52  Morris to  e t a l . , 1978; W o l l a s t  v a r i a t i o n s i n the carbonic  biological In model  o f Mook  from  a n d Koene  the  (1975)  f o r pH w h i c h  Fraser  t h e pH  River. at  and  conservative  properties.  members  was  were  used then  constant  or •to  salinity  total  to establish  from  and the  field  equilibria.  are  alkalinity  system  is  data  3.1, t h e m o d e l  carbonate  carbon  The s a l i n i t y ,  theoretical  with  in Section  inorganic  are required  o f t h e pH m i n i m u m , t h e  compared  As d i s c u s s e d  any  Alkalinity  end  dissociation  to i n v e s t i g a t e the o r i g i n  curves  computes  acid  processes.  order  dilution  i  e t a l . , 1979) and a t t r i b u t e d e i t h e r  treated  a n d pH  considered  as  o f two to  be  sothermal. Although  the  discussion  indicates  that  these  Estuary,  the  model  starting  point  first and in  conditions of  Mook  one  f o r sea water  Figure  10.  processes  f o r surface  1.0  were  ppt  either  properties  of  taking  alkalinity  subset.  Sea water  near  Heads.  Sand  trend  for  values  except  than  calculated that  pH  pH  with  ideal  a salinity  1.0  occurs  curves mixing  less  than  each  mimics pH  by  data  collected  indicated that  at a higher  The  defined  by s a m p l e s  waters  by  meq/1.  in  i n the surface  a  water  characterized  of a l l samples  data  provide  for river  then  field  Fraser  the d i l u t i o n  than  defined  3.3.1  Considering  were  were  with  t h e minimum  data.  subsets  e n d members  the  does  represent  greater  a n d pH  Comparison  to  two  or  properties  in  (1975)  to generate  Samples  water  met  Koene the  in Section  two e n d m e m b e r s  into  the fresh  t h e mean  of  meant  waters.  less  n o t be  used  are  divided  alkalinity,  may  waters,  were  These  alkalinity  and  f o r the a n a l y s i s  of a l l the s u r f a c e  of  the  measured  and  lower  53  0  5  10  15  20  SRLJNJTY  25  30  35  (PPT)  FIGURE 10 The t h e o r e t i c a l d i l u t i o n curve f o r pH i n s u r f a c e waters of the F r a s e r E s t u a r y generated by c o n s i d e r i n g a single step mixing of one sea water and two r i v e r water end members. Data f o r the water p r o p e r t i e s of the end members are taken from Cruise 78-16. Fresh water end members: s a l 0 ppt, a l k 0.87 meq/1, pH 7.82; s a l 0 ppt, a l k 1.07 meq/1, pH 7.84. Sea water end member: s a l 24.787 ppt, a l k 1.85 meq/1, pH 8.04. Temp=12.5 C. V e r t i c a l l i n e s r e p r e s e n t measured pH v a l u e s +0.03 pH u n i t s . c  s a l i n i t y than a c t u a l l y Adjustments  of  observed. the model were made i n attempts  the approximation with measured pH achieved  by  process.  An  considering  alkalinity  dilution  curve  Theoretical  estuarine  i n t e r m e d i a t e water mass was  of 7 ppt,  intermediate  the  values.  end pH  in  of  1.09  Figure  member  with  calculations  meq/1, 11  Some  mixing  and  river  generated  improve  success  was  as a two step  d e f i n e d with a s a l i n i t y pH  represents  both  to  in  of  7.83.  mixing  The  of  and  sea  this  manner  this water.  c l o s e l y agree with measured v a l u e s than d i d those r e s u l t i n g  more from  54  a  single  stage  developed  as  processes The  indicated low  no  sudden  the  On  and  oxygen  saturation  productivity,  inorganic  successful reasonable  the  pH  in  be  agreement  the  between  to  in  the  not  the  the  seems  Figure  surface  7b  waters  behaviour  was  exhibited  Minimal  primary  be  necessary  and  may  theoretical  of  estuary  would  This  types  (1978) in  conservative, model.  the  a l .  100%.  carbon  of  et  throughout  in October,  application  due  conservative  anticipated  still  estuary.  decrease  near  to  is  presented  contrary,  levels  the  Morris  data  waters  minimum  minimum  by  oxygen  surface  as  the  concentration  salinity.  the  observed  proposed  dissolved  observed  total  as  a m p l i f i c a t i o n of  biological unlikely.  However,  extensively  Further  at  dilution.  hence  account and  for the  for  the  observed  pH  values. The waters  model in  was  January  generated  by  marine  members  end  values.  have  minimal,  pattern  more  The features  which  Firstly,  the  comparable with  biologically However,  Fraser  Since the  waters  the  pH  a  of  is  the  to  than  Since  the  oxygen  produced oxygen  by  deficit  dioxide  could  waters  20%,  have  different  not  replicate  this  of  time  waters surface are  this must  been  a  sea  Estuary  in  12)  three  suggests  surface  bottom  at  surface  (Figure  could  dilution  observed  to  with  again  Fraser  from  10  carbon  but  step  estuarine  curves  activity  accord  lower  in  water  minima  single  in  pH  dilution  River  d i s t i n g u i s h them pH  examine  biological  lack  than  salinity.  respect  to The  developed  complex  bottom  used  1979.  mixing  measured been  also  would mixing  water.  exhibit  two  (Figure  8).  waters  of  a  undersaturated indicates  decrease generated  the  that pH.  outside  55  0  5  10  15  20  SALINITY  25  30  35  (PPT.)  FIGURE 11 The t h e o r e t i c a l d i l u t i o n curve f o r pH i n s u r f a c e waters of the F r a s e r Estuary generated by c o n s i d e r i n g the mixing as a two s t e p p r o c e s s . Data f o r the water p r o p e r t i e s of the end members and intermediate water mass are taken from C r u i s e 78-16. F r e s h water end member: s a l 0 ppt, a l k 1.07 meq/1, pH 7.84; Intermediate water body: s a l 7.000 ppt, a l k 1.09 meq/1, pH 7.83; Sea water end member: s a l 24.787 p p t , a l k 1.85 meq/1, pH 8.04. Temp=12.5°C. V e r t i c a l l i n e s represent measured pH values +0.03 pH u n i t s .  the  estuary.  Secondly,  the  r e g a r d l e s s of the s a l i n i t y . October  1978  and  to  some  measurements a r e a s s o c i a t e d quantities  of  bottom  localized  geochemical  reactions  with  (1975)  was  used  clay to  pH  This  remains  i s evident  extent with  relatively  particularly  i n May 1979. the  uniform  Because  resuspension  of  in  these large  sediments,  the pH may be i n f l u e n c e d by a  buffering  system  minerals. determine  The the  due  model extent  to  ion-exchange  of Mook and Koene to  which  mixing  processes alone c o u l d a f f e c t the pH. There are d i f f i c u l t i e s  i n d e f i n i n g an a p p r o p r i a t e sea water  end member and i n comparing the c a l c u l a t e d pH r e s u l t s with  field  56  r  i—i—i—i 0  5  10  15  20  SRLINITY  25  30  35  (PPT).  FIGURE 12 The t h e o r e t i c a l d i l u t i o n curve f o r pH i n s u r f a c e waters of the F r a s e r E s t u a r y generated by c o n s i d e r i n g a single step mixing of f r e s h water with three sea water end members. Data f o r the water p r o p e r t i e s of the end members a r e taken from Cruise 79-01. Fresh water end member: s a l 0 ppt, a l k 1.15 meq/1, pH 7.84; sea water end members: s a l 30.315 ppt, a l k 2.11 meq/1, pH 8.15; s a l 28.386 ppt, a l k 2.04 meq/1, pH 8.00; s a l 29.407 ppt, a l k 2.07 meq/1, pH 7.94. Temp=6.0°C. Vertical l i n e s represent measured pH values +0.03 pH u n i t s .  data.  The  sites  pH data  were c o l l e c t e d on d i f f e r e n t days at v a r i o u s  i n the F r a s e r  discrete Figure  dilution 13  Estuary curve.  represent  and The  possible  e s t u a r i n e bottom waters.  hence  may  represent  t h e o r e t i c a l pH values ideal  mixing  curves  a  shown i n i n the  Samples from C r u i s e 78-16 were used t o  d e f i n e water p r o p e r t i e s of a s i n g l e r i v e r with  not  end  member  together  four s a l i n e end members. Theoretical  the h i g h e s t observed  pH  results  s a l i n i t y end values.  generated member  bear  by mixing r i v e r water no  resemblance  with  t o the  However, t h i s i s to be a n t i c i p a t e d s i n c e  the s a l i n e water p r o p e r t i e s were d e f i n e d by bottom water  (196m)  57  i—r 0  5  10  15  20  SALINITY  25  30  35  (PPT)  FIGURE 13 The t h e o r e t i c a l d i l u t i o n curve f o r pH i n the salt wedge of the F r a s e r Estuary generated by c o n s i d e r i n g a s i n g l e step mixing of one f r e s h water and four sea water end members. Data f o r the water p r o p e r t i e s of the end members are taken from Cruise 78-16. Fresh water end member: s a l 0 ppt, alk 1.09 meq/1, pH 7.84. Sea water end members: s a l 12.114 ppt, a l k 1.32 meq/1, pH 7.80; s a l 22.901 ppt, a l k 1.72 meq/1, pH 7.79; s a l 26.740 ppt, a l k 1.93, pH 7.75; s a l 30.968, a l k 2.16, pH 7.56. Temp=12.5°C. V e r t i c a l l i n e s represent measured pH v a l u e s +0.03 pH u n i t s .  from  Station  f i e l d data. by s a l t  15.  samples  stages  most important  in  with  varying  salinities  f e a t u r e i s the u n i f o r m i t y of  the  calculated  cases i n F i g u r e 13, b i o l o g i c a l processes i n the  7b),  the  pH  Strait  Since the  d i s s o l v e d oxygen a p p a r e n t l y behaves c o n s e r v a t i v e l y in. the (Figure  The  range.  of Georgia cause the low pH of the s a l i n e end member.  wedge  the  representing  the d i l u t i o n curve f o r bottom waters.  over most of the s a l i n i t y For  remaining curves b e t t e r approximate  In these cases, the s a l i n e end members were d e f i n e d  wedge  possible  The  salt  oxygen u n d e r s a t u r a t i o n c a l c u l a t e d f o r  58  CO  LU _ 5  -  r  H  0  5  1  1  10  1  15  1  1  20  25  SALINITY  1  30  (PPT)  1  35  FIGURE 14 Theoretical pH values c a l c u l a t e d from the alkalinity and assuming that the carbon dioxide was 100% saturated. Symbols: • data at a l l depths for Station 15; A s u r f a c e samples i n the F r a s e r E s t u a r y ; ^ b o t t o m samples in the F r a s e r E s t u a r y .  these waters must r e s u l t water  from  outside  from the a d v e c t i o n  the e s t u a r y .  d i o x i d e i s i n s i g n i f i c a n t and behaves  conservatively.  may  explained  be  by  oxygen-depleted  In s i t u p r o d u c t i o n  the t o t a l  Thus,  of  i n o r g a n i c carbon  of carbon content  the pH of the s a l t wedge water  conservative  mixing  without  invoking  geochemical b u f f e r i n g e f f e c t s . A  second  waters was  method  examined.  of The  calculating  the pH  of the  t h e o r e t i c a l pH can be determined  the a l k a l i n i t y assuming that carbon d i o x i d e i s 100% each p o i n t carbon  i n the e s t u a r y .  content  conservative calculated  at  each  behaviour. using  the  estuarine  s a t u r a t e d at  T h i s e s t a b l i s h e s the t o t a l point  removing  Carbon  expressions  the  dioxide of  Skirrow  from  inorganic  p r e r e q u i s i t e of saturation (1975) and  was the  59  resulting  pH c a l c u l a t i o n s f o r C r u i s e  14.  a l l cases,  In  observed the  values  carbon  calculated factor  evade  from  the a l k a l i n i t y  t o 4.1.  in  for  atmospheric  situ  this  carbon  dioxide  dioxide  carbon  outside  attain  higher  than  levels  supersaturated  the estuarine to  by  dioxide  the estuary waters  at a  equilibration  a  either  does n o t rate  fast  with  the  concentration.  year,  most  these  overestimation  of the s a l i n i t y  the  of  the  of  A l t e r n a t i v e l y , data  Except  during  horizontal  the  freshet, in  calculated advection  estuary.  Only  dissolved  oxygen  a t low s a l i n i t i e s .  To a  may  during  the  t h e summer  in estuarine  78-16  samples;  cannot  (Figure  be  6c) c a n  dissolved  oxygen  Estuary.  The  waters  results  wedge  depleted months  waters  to  relationships.  Fraser  of oxygen  attributed  removal  Cruise  the  for salt  be  o f low s a l i n i t y  intersecting linear  conservatively  undersaturation  from  alkalinity from  conservative  Deviations  anomalies  alkalinity  possibility  exhibits  range.  are evident  alkalinity  i n t e r p r e t e d a s two  behaves  the a l k a l i n i t y  relationship  extent  ignored.  of  the  through  however,  the  from  Figure  underestimates  Carbon  a n d pH w e r e  from  were  procedure  indicates that  or advected  waters  linear  certain  the  this  values  in  Summary  behaviour  be  This  these  Throughout  an  that  pH  concentrations.  t o the atmosphere  enough  3.4  indicating  dioxide  o f 1.3  produced  theoretical  78-16 a r e shown  water  i s the  modified  from  also oxygen from  outside  concentration  by  biological  processes. Throughout  the  year  surface  waters  of the F r a s e r  Estuary  60  exhibited be  a pronounced  replicated  dilution; water  theoretically  gives  waters  relatively advection  reasonable  throughout  uniform  pH.  estuary.  The  Georgia,  both  at depth  and a t  facilitates measurements  to  the  the  of  pH  wedge  single  an  observed have  of  pH  a  values.  low  c a n be e x p l a i n e d  sea water surface,  stage  intermediate  oxygen-depleted  the  formation  explanation  i n the surface  m a s s m u s t be f o r m e d  entering  with  cannot  and by t h e  water  from  i n the S t r a i t  i s  of  influenced  by  processes.  Postulating  Discrete  salt  mixing  the  water  involving  agreement  the  outside  biological  dilution  T h e s e pH v a l u e s  and subsequent  This  by c o n s i d e r i n g a s i m p l e  h o w e v e r , a two s t e p  mass  Bottom  pH m i n i m u m a t l o w s a l i n i t y .  water  vertical  can  will  an i n t e r m e d i a t e  observed  waters  v i a the salt  advection.  manganese c h e m i s t r y  of  by m i x i n g  properties  the estuary  of  be  alkalinity  of the F r a s e r salt  Estuary.  attained only  The c o n s e q u e n c e s  mass  and  wedge a n d r i v e r  wedge b e c o m e s  be e x a m i n e d  water  pH This  water.  i f sea water  modified  prior  of such a process  i n the following  chapter.  on  61  MANGANESE  4.1  DISTRIBUTION  IN THE  FRASER  ESTUARY  Preamble  The  Fraser  varying and  flow  Estuary  regimes  particulate  was  investigated  (see S e c t i o n  manganese  five  2.1.1).  are tabulated  in  times  Data  under  for dissolved  Appendices  B.l  and  B.2, r e s p e c t i v e l y . While manganese  this in  chapter  the  deals  Fraser  Estuary,  particulate  concentrations  concentrations  are included  some  4.2  features  Data:  4.2.1  Dissolved  Dissolved plotted for  Figures of  Georgia.  Chapter of  15c  5 which  manganese In  13.0  higher  15d  than  data  deals  1978  they  a r e shown  are useful  will  with  in  in Figures  79-01, data  and  aluminium  in  explaining  be d i s c u s s e d  estuarine 15a  79-12,  collected  the temporal  through  15d  respectively.  throughout in greater  and  waters,  spatial  the  Strait  detail  in  distribution  strait. (Cruise  in  78-04,  i n the r i v e r  concentrations those  suspended  particulate  concentrations  78-16,  concentration  ppb,  total  behaviour.  include  i n the  March  manganese to  78-04,  These  for  of  Manganese  salinity,  and  the chemistry  Samples  manganese  versus  Cruises  Aqueous  data  and  since  of manganese  Field  p r i m a r i l y with  the  Figure water  i n the bottom surface  was  15a)  i n the range  waters  waters.  the d i s s o l v e d  being  Strait  9.97  somewhat of  Georgia  62  0  5  10  15  20  25  30  S R L I N I T Y (PPT)  F i g u r e 15a C r u i s e  35  0  5  10  15  20  30  SRLINITY-(PPT)  F i g u r e 15b C r u i s e  78-04  25  35  78-16  "1—r 0  5  10  15  20  25  30  S A L I N I T Y (PPT) F i g u r e 15c C r u i s e  79-01  35  0  5  10  15  20  25  30  35  S A L I N I T Y (PPT) F i g u r e 15d C r u i s e  79-12  FIGURE 15 D i s s o l v e d manganese data p l o t t e d versus s a l i n i t y for C r u i s e s 78-04, 78-16, 79-01, and 79-12. Symbols: • data at a l l depths f o r S t a t i o n 15; O data at a l l depths at other s t a t i o n s i n the S t r a i t of Georgia; A surface samples i n the F r a s e r E s t u a r y ; O bottom samples i n the F r a s e r E s t u a r y .  63  samples,  as e x e m p l i f i e d  by  concentration  o f 4.12  ppb  to  minimum  of  a mid-depth  the  surface  although, respect  dissolved  the  waters  Appendix  few B  dissolved should  salinity  data  to  are  2.93  manganese  be  t h e sample  noted  samples  similar  dilution  from  ppb  was  both  pattern  incomplete  estuary.  o f 17.6  A  with  maximum  evident  in the  o f 4.028 p p t . for  Fraser  river  ppb.  Estuarine  that  were  surface decreased  Estuarine  the  available  levels  a  ppt) which  series  in  concentration  for data).  1.97  a  range  exhibited  26.837  ppb.  followed  salinity  at a  15,  (salinity 0.37  cases,  manganese  Very  range  bottom  i n both to  surface  and  Station  which  Cruise  concentrations bottom  increased  the samples  78-11.  were  were  waters  with  (See in  the  exhibited  salinity.  c o l l e c t e d on  a  It  flooding  tide. During Estuary  in October  collected recorded Cruise  t h e week  daily  at  78-16.  typical  fell  15b).  manganese Surface  (Cruise  from  this 18.8  reflection collected showed  of  that  seen were  exhibited  during  a  time  a  two on  the d i s s o l v e d  series  B.2  to  ppb,  River  waters  at  dissolved  a t Anchor manganese  data  Station  a  value  during  was are 70,  manganese more  the c r u i s e  exhibited  March.  greatest  These  as  Fraser  samples  dissolved  4.45  in  i n the  of  2).  period  different  series  cruise  B . l and  i n the Fraser  that'  sampling  ppb  day  (Figure  time  estuarine  concentrations waters  Langley  observed  to  78-16),  in Appendices  Surface  similar  to the three  Fort  During  of those  pattern  B.3)  1978  sequentially  concentrations  (Figure  prior  a  mixing  That  i s , dissolved  low  salinities.  manganese  days. Station  maxima,  Bottom 56.3  concentrations  a  samples (Appendix ranged  64  from  2  varied  to  5-  from  8  ppt)  which  water  slack.  but as  as  ranged  in a  23  ppb  from  to  While  the  a persistent  Concentrations near  0.5  levels  ppb  in  at  maximum  exhibited samples  ppb.  March  Cruise  at other  Station  with  t o 18.0  manganese  the  dissolved  manganese  salinity  collected  associated  with  near  the  day t o  occasion.  to a  minimum  the bottom  Station  15  to are  with  t h e same  Three  had a  of  surface  stations.  salinity In  sediment  of  these loads  were from  6.412  ppt  a l l cases,  anomalously  waters Also,  four  samples ranging  were  trend  of  concentrations  concentrations  the  and a t the  the exception  ppb.  suspended  that  water  25.6  by  of  15c) mimic t h e  followed  B.2).  sample  content  at other  was  of  one  exception  river  15d)  manganese  exhibited  high  the  (Appendix  a dissolved  values  in  the year,  fourth  day  dropped  Figure  the  (Figure  and  exceeding  with  79-12 of  manganese  each  from  79-01,  in January.  53  The  Data  remained  profile  from  on  increased  (Cruise 1978  dissolved  ppb.  waters  5 ppb  times  varied  56.3  5.  content  h i g h e r by  from  from  riverine  3.6  manganese  was  Data  but  1979  last  observed  in surface  depth  12  a t low  of  salinities  and  to  wedge  upstream  A complete  was  p p t ) but  (8  and d i s s o l v e d  concentrations  in Chapter  in  that  the f i r s t  t o 4.9  samples  58.3,  slack  mid-depth  January  observed  dissolved  16.1  4 ppb  in detail  Data trend  near  station,  ppb.  profile  ( 2 6 t o 27  the toe of the s a l t  indicate  both  absolute  i n the range  discussed  on  samples  salinity  low w a t e r 7.58  15  cruise. next,  basin,  ppt during  at Station  from  another  small  6.03  salinity  i n t h e low  collected  Data  from  obtained  in high  t o 10  were  situated high  ppb  high,  comparable samples relative  were to  65  surface the in  waters  collected  data  from  Cruise  Fraser  River  water  dissolved observed  manganese  waters  79-12,  maximum  exhibited  near  Particulate  Particulate salinity, 78-04,  are  78-16,  differing  on'  a l l  (2)  these  rates,  few  ppb.  The  waters  was  bottom  than  samples  did  respectively.  few  surface  estuarine  which  e n d member  concentrations  exponentially  with  a reflection  Cruise  are  of  evident  78-11 a r e a l s o  concentration  varies  samples  absolute  include:  manganese  surface  Although  of f e a t u r e s  from  versus  16d f o r C r u i s e s  t o the next,  data  observations  River  plotted  16a t h r o u g h  a number  particulate  curve,  The  concentrations,  one c r u i s e  The  Fraser  5  estuarine  higher  in Figures  from  discharge  the  concentrations  salinity.  depicted  with  (1)  ppt.  of  Manganese  occasions.  consistent  12  manganese  vary  the remainer  around  i n the surface  79-01 a n d 79-12,  concentrations the  clustered  concentrations  of a comparable  4.2.2  Considering  d i s s o l v e d manganese  mainly  at a salinity  collected  elsewhere.  the  considerably  follow  decreasing salinity  in  a smooth either  dilution  linearly  depending  upon  or the  cruise. (3)  bottom which  samples  exhibit  are independent  very  of both  high  concentrations  salinity  and  station  salinity  near  25 p p t ,  location. One is  sample  presumed  water  from  to reflect  sampler  may  Cruise  78-04,  a sampling  n o t have  with  a  error.  tripped  until  That  is>  the  bottom  i t l a y on t h e b o t t o m ,  66  T  T 0  5  10  15  20  25  0  30  5  15  20  25  30  S A L I N I T Y (PPT)  S A L I N I T Y (PPT)  F i g u r e 16a C r u i s e  10  F i g u r e 16b C r u i s e  78-04  78-16  o LO .  LO .  <> I  0  CQ O _ o _J Q_C\I  o  T T o _1 C D co  •_  LU I—  Q_  o  c r  _|  <!>  CJ QlLO  CE  <!>  0  5  10  15 20 25  30  S A L I N I T Y (PPT) F i g u r e 16c C r u i s e  79-01  35  0  5  10  15  20  25  30  35  S A L I N I T Y (PPT) F i g u r e 16d C r u i s e  79-12  FIGURE 16 P a r t i c u l a t e manganese data p l o t t e d versus s a l i n i t y f o r C r u i s e s 78-04, 78-16, 79-01, and 79-12. Symbols: • data at a l l depths f o r S t a t i o n 15; O data at a l l depths at other s t a t i o n s i n the S t r a i t s of Georgia; A surface samples i n the Fraser Estuary; <> samples i n the F r a s e r E s t u a r y . b o t t o i n  67  thereby  collecting  4.2.3  salinity, 78-04,  are  shown  distribution  4.2.4  during  the  or  in  May.  On  surface  78-16  are  of  17d  versus  for  respectively. of  magnitude  displays  variation  both  In  Cruises Although  higher,  features  the  similar  Fraser  contrast,  in  the  River  and  estuarine  decreases  particulate estuarine  surface  in  samples  concentrations  data  particulate and  follow  October both  Particulates  79-12.  presented  in 1978  waters  suspended  material  station  The  evident  the  Fraser  and  from  the  decreased  location.  results, 18a for  River  186  to  suspended  rapidly  waters which  concentrations  in Figures  trends  occasions  bottom  the  through  orders  exponential  suspended  Estuarine  nor  two  plotted  p a r t i c u l a t e manganese.  Suspended  Concentrations mg/1  sediments..  p a r t i c u l a t e manganese.  Cruises  salinity,  of  samples.  Total  Total  17a  79-12,  considerable  linear  for  Figures and  concentration  the  evident  suspended  p a r t i c u l a t e aluminium  is  water  follow  as  concentrations,  generally  distribution  aluminium  Again  are  of  There  in  79-01,  concentrations  bottom  well  aluminium  78-16  the  as  P a r t i c u l a t e Aluminium  Particulate  to  bedload  were  in  and the  mg/1  exhibited r e l a t e d to  from in load  initial high  versus  respectively.  particulate  sediment the  measured  plotted  18b,  ranged 540  were  11.1  metals. to  24.1  the  following  in  estuarine  mixing  zone.  concentrations  neither  the  of  salinity  68 o  ID  CD " CM  51 Q_ Q_cr> -—-  o  _)  cr  CO Q_ Q_co  _  <!>  <>  0.  O  0  CD  _  cn CE  o  o  AA A  o o  0  5  10  15 20  SALINITY  25  30  5  35  (PPT)  —i—i—r  10  15  20  SALINITY F i g u r e 17b C r u i s e  F i g u r e 17a C r u i s e 78-04  25  30  35  (PPT) 78-16  o r-  CD .in  Q_ Q_  O O  0  5  10  15 20  SALINITY F i g u r e 17c C r u i s e  25  30  (PPT) 79-01  35  5  10  15 20  SALINITY F i g u r e 17d C r u i s e  25  30  35  (PPT) 79-12  FIGURE 17 P a r t i c u l a t e aluminium data p l o t t e d versus s a l i n i t y for C r u i s e s 78-04, 78-16, 79-01, and 79-12. Symbols: • data at a l l depths f o r S t a t i o n 15; O data at a l l depths at other s t a t i o n s i n the S t r a i t s of Georgia; A surface samples i n the F r a s e r E s t u a r y ; O bottom samples i n the F r a s e r E s t u a r y .  69  0  5  10  15 20 25 30  SALINITY  0  35  5  10  15 20 25 30  SALINITY  (PPT)  35  (PPT)  F i g u r e 18b C r u i s e 79-12  F i g u r e 18a C r u i s e 78-16  FIGURE 18 T o t a l suspended p a r t i c u l a t e c o n c e n t r a t i o n s p l o t t e d versus s a l i n i t y f o r C r u i s e s 78-16 and 79-12. Symbols: • data at a l l depths f o r S t a t i o n 15; O data at a l l depths at other s t a t i o n s i n the S t r a i t s of Georgia; A s u r f a c e samples i n the F r a s e r E s t u a r y ; O bottom samples i n the F r a s e r E s t u a r y .  4.3 F i e l d Data: Sediments  4.3.1 I n t e r s t i t i a l Water Interstitial  water  S t a t i o n 15  and  various  dissolved  manganese  was sites  e x t r a c t e d from c o r e s c o l l e c t e d at in  the  concentrations  Fraser  and  Estuary.  salinities  The  i n the  i n t e r s t i t i a l waters of the e s t u a r i n e sediments are presented  in  Appendix C. The  dissolved  was s i m i l a r  manganese p r o f i l e  i n the i n t e r s t i t i a l  water  i n two cores c o l l e c t e d a t S t a t i o n 15 (Appendix C l ) .  A subsurface maximum of 3.85 and 4.81 ppm, f o r cores 78-1-15 and  70  79-2-15, The  respectively,  concentration  approximately In  manganese 1979  1 ppm  three  (Appendix  C.2).  subsurface  a l l  the  in  the core  depths,  All  this  time.  subsurface  of  divers  reaches  sediments t o an 57.2  dissolved  the  manganese  and  from even  was  samples,  in February  of  56.2  6 t o 9 cm  Fraser profiles  displayed  6.30  ppm  Station greater  depleted  concentration  was  cores. water  by  Station  Station  a maximum  estuarine  relatively  C.4  Station  at  cm  and  exhibited  dissolved  manganese  from  with  one  exhibited  both  ppm  section.  two  a t 19 t o  59.0  were  degree.  In  i n manganese  of o n l y  126  ppb  in  section.  but  (Appendices  lower  cm  depth  sea  sediments  from  waters  dissolved  6 t o 9 cm  1980  10.9  t h e 50  collected  i n the  Sediments  maxima:  comparison, at  estuarine Cores  of  6  with  and  different  Interstitial  enriched  river  stations  displayed  cm.  from  i n the 3 t o  regularly  the bottom  with  waters  Estuary  22  near  enrichment.  from  observed  decreased  comparison  interstitial  was  core  low d i s s o l v e d  and C.5).  and S t a t i o n  The  exception, 4.4  ppm  59  were  in January  concentrations  waters  of  sediments  depleted  in  Station  a t 9 t o 12  by d i v e r s  manganese  Interstitial  57.2  maxima:  collected  56.2, cm  and  again 5.7  from  manganese  at  displayed  two  ppm  a t 24  to  27  cm. The  interstitial  collected of  the core  profile  was  was  to determine  preserved i n the sampling  the length  interstitial  salinity  primarily  i n sediments  throughout of  i n 1980,  water  from  Station  of the c o r e .  waters  increases  67  measured whether process.  indicates  In g e n e r a l , downstream.  for  the The  integrity salinity  fresh  the salt  cores  water content  However,  the  71  salinity may  profile  display  Station  and  a  56.2,  4.3.2  a t some  subsurface  Appendix  Ammonium  Oxalate  collected  selected  samples  presented In  to  an  extractable  1979,  riverine  surface  74.0  ppm  f o r marine  with  a concentration  extractable May.  The  surface  from  upstream  advance  similar  The  Steveston with 30  (Station  of  80.2  and  trend  and  Appendix  C.4;  of  the 161  near  ppm  showed  ppm,  Sediments  1980  were  Results  are  the  site  at the surface manganese  a mid-depth and  of  ppm  to  at Station  53,  trend.  contained  was  in  70.8  the 168  of  ppm  the time,  and  more  previous  layers.  at the  Sediments furthest exhibited  133  ppm  i n sediments  maximum  bottom  respectively.  t o 130  in  at this  oxalate  to this  1980  collected  wedge  at the surface 81.9  125  range  sediments  of e x t r a c t a b l e  56.2)  i n the  in subsurface  salt  79-12  ammonium  from  in January  in riverine  60.5,  of  d i d not conform  sediments  ppm  i n January  extraction.  sediments. ppm,  Cruise  respectively.  to values  156  Station  concentrations  cm)  to  profile  57.2,  during  obtained  decreased  collected  than  Grab  concentration  o f 153  concentrations:  depth.  cores  a n d C.5  surface  concentration  collected  a Shipek  generally  sediments  150  regular  (Station  oxalate  C.3  sediments  and  with  the  manganese  no  Digest  ammonium  manganese  Surface  minimum  from  i n Appendices May  follows  C.5).  Sediments  subjected  stations  of  243  of the core  at near ppm  (27 t o  72  4.3.3  Total  Manganese the  ammonium  data  No  aluminium ' In  was  manganese in  May  January  from  and  fairly  67.0)  The r e s i s t a n t  in  aluminium  As  the oxalate  mentioned 79-12 were  without  prior with  fractions;  fraction.  unlikely  higher This  a  Accordingly, oxalate  of  than  Mn:Al  manganese  the  total  aluminium  observed that  i n only  obtained  of  acid  and  At  the  and  oxalate total  samples  should  during  digestion  concentrations  the oxalate  for  291 t o  aluminium  resistant  concentrations  t h e ammonium  proportion  and  collected  leachable  oxalate  from  profile.  samples  the  (Stations  4.46 t o 5 . 2 1 % .  the  ratios  values.  sites  Manganese  extraction are overestimates maximum  concentrations in  extraction.  indicates  significant  to  residual  time.  ranging  from  2.2.4,  subjected  however,  consistently  extracts  t h e sum  estuary,  ppm.  manganese  The  at three  of both  Section  oxalate  total  manganese  e x t r a c t a b l e manganese  in also  lowest  varied  estuarine  o f 468 t o 5 9 1  Steveston.  uniform the  These  350 t o 5 1 9 ppm  5.03 t o 5 . 4 8 % a t t h i s  56.2 t h e c o n c e n t r a t i o n s  paralleled  the  in  from  i n the range  1980, t h e r e s i d u a l were  of the sediments.  varied  near  determined i n  C.3 a n d C . 5 .  1979  but  observed  were  concentration  contents  ranged  sediments  Station  i n Appendices  evident  content  ppm.  agreed  fraction  was  60.5,  Cruise  resistant  compiled  concentration  316  concentrations  manganese  trend  56.2,  aluminium  collected  total  surface  and  resistant  sediments giving  Digest  oxalate  are also The  Acid  be  were  resistant digestion aluminium.  subjected  to  considered  73  4.3.4  Grain  Grain  Size  size  collected  i n May  selected  core  January sizes sand  Fraser grain  River size.  locations  and  less  fine-grained Station  53  core.  than  Sediments estuarine percentage  most at  were  seaward  53)  had  a  finer  uniform  sediments higher  10%  varied core,  but the  and  of  63 urn. in  the  i n terms  entirely  in  grain  than  sediments  almost  Surficial  on  divers  mean  of  of  sand,  from  deeper  percentage  e s p e c i a l l y the manganese-rich  the surface  mud.  relatively  by  and  the percentages  surface  consisted  of the r i v e r i n e  sediments of  the  contained  also  with  the  to the material  May,  and  are  sediments  Grab  obtained  C.6  together  estuarine  a Shipek  sediments  1% mud.  15  which  the sediments The  refers  and  material,  Examination that  mud  on  with  i n Appendix  sediments  (Stations  79-12)  from  Estuary  These  performed  deviations  i n January  containing  from  where  were  (Cruise  Tabulated  standard  a n d mud, Both  1979  sections  1980. and  analyses  of  sediments  mud.  and  estuarine  little  through  Station  56.2,  below  cm  24  intervening  revealed  the length was  were  layer  cores  of the  exceptional.  s i m i l a r to  contained  a  other high  74  4.4  Discussion  4.4.1  Distribution  An  understanding  material the can  although, vary  be  Price  the  waters  aluminium  content  and C a l v e r t ,  estuarine  particulate  total  This  suspended  (Hydes  19) s u g g e s t s of  and L i s s ,  to  and  versus  the  months.  material  According when  suspended  sediment  load  estuary,  leaving  primarily  most  i s deposited the  Sachs,  Price,  1980).  low  of  suspended  p a r t i c u l a t e aluminium in  salinity  be  load  used  as  Estuary  (1980),  this  fraction  of the  reaches  of the  i n the upper and  particulate  the Fraser  to Milliman  silt  to the  sediment  may  of the sand  size  and  from  Plots  can  grain  the c o n t r i b u t i o n  is negligible.  that  periods  1977),  material,  material  and  precipitates  terrigenous  non-freshet  Sholkovitz  behaviour  of p a r t i c u l a t e  suspended  composition  in  particulate  p a r t i c u l a t e s (Spencer  aluminium  concentrations  corresponds  in detail.  i n the  1973;  concentration  indicator  manganese  i n d i c a t o r of t e r r i g e n o u s  of the suspended  dissolved  during  useful  mineralogical  Although  (Figure  a  the aluminium  distribution  an  c a n be e x a m i n e d  of  A l t e r n a t i v e l y , the concentration  may  with  of suspended p a r t i c u l a t e  the d i s t r i b u t i o n  i n v e s t i g a t e d by c o n s i d e r i n g  aluminium  1970;  before  Estuary  concentrations.  Particulate Material  of the behaviour  i s necessary  Fraser be  of Suspended  clay  fraction  in  suspension. The shows with  a  concentration strong  Milliman  discharge  in  of  dependence (1980), January  suspended  material  on t h e d i s c h a r g e lowest  and  March  values while  in river  rates. occur  In during  maximum  water  agreement minimal  values  were  75  i  0  10 20 30 40 50 60 TSP (MG/L)  F i g u r e 19a  Cruise  0  70  r  20 40 60 80 TSP (MG/L)  F i g u r e 19b  78-16  Cruise  100 120 140 (X10 ) Y  79-12  FIGURE 19 Particulate aluminium concentrations plotted versus t o t a l suspended p a r t i c u l a t e c o n c e n t r a t i o n s for Cruises 78-16 and 79-12. Symbols: • data at a l l depths f o r S t a t i o n 15; O data at a l l depths at other s t a t i o n s in the Straits of Georgia; A s u r f a c e samples i n the F r a s e r Estuary; Obottom samples i n the F r a s e r E s t u a r y .  measured  in  May.  concentration exhibits  of  Regardless riverine  considerable  effects  on  the  river  due  persists in  October  year,  particulate  flow.  Pretious  (1972) reported  suspended  load  Bridge  were  (Figure  2)  observed where  and at and  in  the that  as f a r  ebb-tidal Downstream  t i d a l e f f e c t s and d e p o s i t i o n as  widens  the  the  material  variations  to stronger  trifurcates  f r e s h water Steveston  of  were g r e a t e r than f l o o d - t i d a l d i s c h a r g e s .  v a r i a t i o n s occur the  time  reflecting  upstream as the Port Mann discharges  the  suspended  scatter  hydrodynamics of the r i v e r tidal  of  at New  surface  as  Westminster. far  to Sand Heads i n May,  Since  downstream riverine  as data  76  exhibit  considerable  Suspended in  October  with  particulate  1978  salinity  suggesting  the  rapidly  with  Cruises  salinity  samples  in  resuspension  bottom  suspended  of  This  the  of  only  of  30  decreased  increased  samples  behaves  indicate May  similar  1979  (Cruise  material  decreases  zone  but,  apparently  at  behaves  the  (26.095  to  suspended  During load  (1980)  near-bottom  water  slack  of  an  was  had  mg/1.  to  mg/1.  63  range  as  of  26.922 ebbing  at  and  5.60  a  51 ppt)  tide mg/1  maximum Steveston  on  total  8  to  concentrations  of  waters the  during  Cruise  (Appendix  from  the  high  salt  salinity  particulate  at  to  with  suspended  of  suspended  12  ppt  amount  tide mg/1  the a  in  high  at  salinity  water  flood  salinity  of  day, 26.530  concentrations  flood  but  approximately  following  sediment during  low  s t a r t e d to  collected  at  to  contrast,  64  on  high due  56.3  year  suspended  The the  the  mid-flood  tide  By  from  only  Station  ebbing  ranged  observed  waters  an  ppt) 8.33  highest  observations  during  exhibited  throughout  The  Anchor  somewhat  to  mid-flood.  Milliman  material  Estuary  material  at  series  salinity  loads  material  low  (26.969  concentration  then  with  time  water  sediment  linearly  mixing  ppt,  Fraser  sediments.  measured  indicated that  slack  initial 10  the  suspended  sediment  coincided  bottom  In  waters  decrease  data  79-01.  surface  ively.  of  wedge  suspended  particulate  the  than  concentrations  B.3).  and  the  18a)  aluminium  of  in  in  Figure  the  78-04  greater  Bottom  78-16  that  concentration  salinities conservat  78-16,  Particulate  during  79-12),  concentrations  (Cruise  conservatively. behaviour  scatter.  tide  at  times  the ppt. in of  77  the  year  other  4.4.2  The  at  most  striking  plots  mixing  this  time  zone  peak  independent VI).  the r i v e r Both  varies from  the  daily  might  case  conducted  studies  data  discharge  expected,  the  o f t h e maximum  in  a t which  several  3 ppt i n the  Estuaries  (Duinker  t h e manganese  16  at three  Fraser  exhibiting peak.  water  upon t h e to  be  of the r i v e r  maximum  manganese  concentration  dissolved this  other  were  Beaulieu  is  temporal  Also, in  maximum  Estuary  the  variations dissolved  these  two  to  estuaries.  i n the Fraser  approximately  25  but  above.  exceed  salinity  et a l .  Newport  from  ppb  6  to  Thus,  Estuary  in  o f t h e manganese  concentrations The  and  (1977)  Estuary.  maximum  and Newport 100  Peak  the Rhine and  ranging  manganese  observed  mentioned  Evans  i n the s a l i n i t y  concentrations  ppb  i n both  the  with  (Holliday  i n t h e Newport  similar  agree  exhibited at a  at salinities  times  occurs  manganese  estuaries.  e t a l . , 1979b).  different  Estuary  comparable  studies  rate  i n the  the  appear  t h e d i s s o l v e d manganese  concentrations  observed  the  of  4 t o 12 p p t d e p e n d i n g  1 9 7 6 ) a n d a t 5 p p t on two o c c a s i o n s  ppt  dissolved  concentration  available  the s a l i n i t y  manganese  approximately  Scheldt  a l l the  water.  and  Liss,  in  Salinity  The s a l i n i t y  average  be  varies with  concentration  of  from the  the establishment  dissolved  observed  a t Low  1 5 ) i s t h e maximum  but  As  Maximum  of the e s t u a r y .  value  of  concentration in  the freshet.  feature  (Figure  of sampling  (Table  during  The D i s s o l v e d Manganese  manganese initial  than  are  manganese  Estuaries  i n the other  are case  78  TABLE  VI  Salinity  Cruise Number  and C o n c e n t r a t i o n Max ima  R i v e r Mean D i s . Mn (ppb)  Di scharge Rate (m /sec) 3  78-04  951  78-16  1900  79-01  816  79-12  7140  The  of  source  controversial. anthropogenic River,  some  Island Since  sewage this  sewage  effluent,  and  representative River. of 0.04  0.03  al.,  Fraser  origin  of  are into  plant treats water  mg/1.  mg/1  and  These  levels; from  River  (Figure  the excess  manganese  5)  discharge  the m /s  manganese  of the  from  daily during  reported.  should the  somewhat  1971/72  i s considered  from higher  discharge  (Tanner  t o the flow an  Fraser  ranging  average  Consequently,  be  concentrations  content are  Iona  industrial  data into  the  Fraser  the  been  manganese  i n comparison  3).  remains for  sewage,  manganese  3  arm  have  these  concentrations  are insignificant  12.280  discharged  dissolved  t o 12.9  14.4  domestic  however,  1.67  8.804  the main  runoff,  total  23.9  unavailable  (Figure  of the anthropogenic  0.06  varying 1973),  data  plant  4.028 4 - 8  dissolved  of the e f f l u e n t  storm  riverine  rates,  excess  (1977) r e p o r t e d  to  t o 0.08  than  the  Higgs  9. 24  treatment  S a l i n i t y of Mn Maximum (ppt)  7  15.1  of manganese  Manganese  17.6  6.61  Although  analyses  Max imum D i s . Mn (ppb)  11.2  this  input  of the D i s s o l v e d  rate  et of  anthropogenic  t o be  improbable.  79  But,  as o u t l i n e d  Firstly,  the  particulate  manganese  To  The R o l e  may  natural  be  the metal  of Suspended  the Dissolved  determine  material  sources  released  from  dissolution  may  be  exist.  suspended  or  released  will  be  biological  from  estuarine  of  mixing  (2)  comparison  the  o f t h e mean particulate  ratios total  Experiments with  dissolved  sea  and  versus  were  samples  with  waters  were  bottom  samples  particulate  maximum,  a  number  sea  mixed. were  manganese  concentration by  of  riverborne  with  "excess"  collected water  The  Mn:Al  bottle each  mixtures  filtered  Surface  and  with  would  sampler.  immediately  and  respect  and  a  bottom  in the Fraser The  of the surface remaining  river  indicate  (fresh)  stations  of  Enhancement of  i n the mixture,  at three  from  aliquots  salinities.  concentrations,  interaction.  NIO  particulate  i n the estuary.  mixing  of varying  water  were  concentration  salinity  o n e NIO b o t t l e  samples  manganese  suspended  concentrations  the double of  the  performed  particulate/dissolved (saline)  in  manganese  manganese  river  suspended  manganese  variations  (4)  Peak  experiments  dissolved (3)  Manganese i n  examined:  (1)  contents  Manganese  the importance  suspended  water  Particulate  i n developing the dissolved  points  River  two  by d e s o r p t i o n ,  Secondly,  Establishing  to  1,  sediments.  4.4.3  of  Chapter  material  processes. bottom  in  complete and  bottom  surface processed  and as  80  described  i n Chapter  Results precision in  presented  of  and  the  filter  of  with  similar  the  no  definitive,  filter  and  95  cut-off  of  release manganese riverine estuarine  pore  of  This  4  and  the  mixing  agrees  of  with  (1979)  and  manganese  Moore  et a l .  manganese  water  was  from  collected (salinity  Metricel  a nominal  nm  dissolved  and a  that  t o be  Petersen Nuclepore  present  in  this  t o 450  n o t meant  (1979) f o u n d  with  100  through  was  the  in 98  River  true  t o 102% Beaulieu  molecular  weight  respectively.  5  c o n c e n t r a t i o n was sediment,  nm)  of  nm),  the  Kremling  manganese  filters  of  is  passing  400  450  to  analysis  of  experiment  of  VCWP  dissolved  a Gelman  range  with  the  precision  size  manganese  agree  a Millipore  Since  the  size  size  10  nm.  through  pore  single  does  through  100  filtered  in  a  through  3 x 10  second  simply  Sholkovitz  within  % of the d i s s o l v e d  passed  A  While  Similarly  waters  of  of  (nominal  reported that  t o 100  size  measurable  (nominal  solution.  from  observed.  refiltered  mixture  the r e s u l t  who  the  d e s o r p t i o n nor d i s s o l u t i o n  was  agreed  colloids  concentration.  (1978)  was  pore  filter  that  contribute  within  manganese c o n c e n t r a t i o n s  anticipated no  that  (1979b).  with  indicates  those  experiments  a nominal  Membrane  indicate  dissolved  manganese  concentration  technique  VII  Thus,  of the mixtures  manganese  GA-6  waters.  et a l .  One  with  particulate  results  Duinker  agreed  sea  riverborne  in Table  the technique,  the mixture  river  2.  performed  particulate monitored from =  10  Fort  to  examine  material.  after  introducing  Langley,  p p t , pH  The  into  = 7.75,  possible dissolved 25.7g o f 800ml  temperature  of =  81  TABLE VII  Mixing  Experiments  Sample  Salinity (ppt)  1  Sur f a c e  1 . 324  1  Bottom  Dis. Mn (ppb)  12.6  27.427  1.. M i x t u r e  8.43 10.7  14.376  1  Ideal  2  Surface  0.107  2  Bottom  9.458  12.7  4.783  10.7  10.5  2 Mixture 2  Ideal  3  Surface  8.67  10.7  0.0  9.25  3 Bottom  1.0  9.00  3 Mixture  0.5  9.13  3  Ideal  9.13  3 Ref i l t e r e d (100 nm)  10°C).  The  however, three ppb  sediment  the  weight  hours.  after  4  The  hours  Although  these  observed  in  sediment  was  was was  9.29  not  dried  measured  only  after  and  then  fell  estuary, 1.7  ppm  on  are the a  dry  to  to  oven  d i s s o l v e d manganese  concentrations the  prior  the  drying  experiment; at  concentration  40  ppb  considerably manganese weight  110 rose  after  20  higher  that  released basis.  °C to  for 60  hours.  from  Although  those the i t  82  T A B L E V I I I C o m p a r i s o n o f t h e Mean R i v e r b o r n e S u s p e n d e d P a r t i c u l a t e Manganese with " E x c e s s " D i s s o l v e d Manganese i n the Fraser Estuary  Cruise Number  Mean P a r t i c u l a t e Manganese (ppb)  78-04  9.13  78-16  be  possible  could  observed  data  evaluate  the with  mean  source  that  the  two  four  sufficient  estuarine  suspended  of d i s s o l v e d  which end  manganese dissolved  dissolved  refers  Total  balance  the riverborne  mg/1  suspended metal  i n October particulate  to account  manganese,  occur  as a  were  particulate  f o r the  result  VIII  "excess"  the  as  a  River  dissolved  observed  of c o n s e r v a t i v e  to  compares  i n the Fraser  where  between  examined  material  Table  concentration  to the d i f f e r e n c e  would  cruises  manganese.  p a r t i c u l a t e manganese  manganese  ( 1 0 t o 24  sediment  maxima.  from  "excess"  and  that  riverborne  potential  the r e s u l t s to suspended  i n the estuary  not r e l e a s e  manganese  Field  12  to scale  observed  i t i s evident  material  12  222  concentrations 1978),  3.5  9.24  79-12  not  8  14.3  79-01  may  "Excess" Dissolved Manganese (ppb)  amount  mixing  of  members. dissolution  during  Cruise  manganese  could  be  of the r i v e r b o r n e 79-01  excess.  achieved  only  could  not account  During with  suspended  Cruise  particulate  f o r the 78-04  near-complete  observed the  mass  d i s s o l u t i o n of  83  the  manganese  unlikely only but  i n the  since  the  manganese also  suspended  bound  that  sufficient  riverborne  manganese  the  ratio  of  to  concentration  versus  normalizes  the  data  terrigenous  material  in by  suspended  particulate  and  zone would  salinity, shown  100  in  ppb  Figure  a  particulate  manganese  bulk  of  ratio  during  manganese  in  suspended  suspended  drastic  This  constituent  can  distribution  Estuary of  aluminium  1979).  this  total  78-11,  through  rejected.  of  be the  material  non-freshet  i n the  decrease  The  x  10"  and 3  .  79-01  Data  are  from  ratios, 78-16,  F i g u r e ,20e,  initial of  at  The very  Cruise  plotted  79-01,  and  the  Mn:Al similar,  are  Samples  less  p a r t i c u l a t e Mn:Al  salinities  78-16  versus  79-12  respectively.  concentrations  suspended  d i s c e r n i b l e decrease  78-11, 12  Mn:Al  p a r t i c u l a t e aluminium  were no  20a  78-04,  d i s s o l v e d manganese peak.  to  involves  size  the  in  maxima.  data  unreactive  grain  release  particulate  suspended  78-04, 10  field  While  Fraser  reflected  for Cruises  displayed the  an  oxides  ratio. Suspended  with  be  the  dissolved  (Sholkovitz,  material,  therefore,  the  78-16  particulate  Estuary.  i n the  amorphous  not  supply  c o n s t i t u t e s the  v a r i a t i o n s i n the  behaves c o n s e r v a t i v e l y  Mn:Al  which  includes  be  particulates could  suspended  to aluminium,  seem t o  79-12  observed  suspended  Fraser  would  and  examining  the  material  the  the  salinity,  influenced  months,  of  and  from C r u i s e s  suspended  the  This  material  Data  to develop  concentration  mixing  organic  a l t e r n a t i v e method  plotting  the  to  material.  particulate fraction  r e s i d u a l manganese.  indicate  An  suspended  than ratios  corresponding  ratios  for  falling  i n the  show more  to  Cruises  scatter  range and  84  0  5  10  15  20  SALINITY  25  30  35  (PPT)  5  10  15  20  SALINITY F i g u r e 20c C r u i s e  25  30  (PPT) 78-16  5  10  15  20  SALINITY  25  35  5  10  15  30  35  (PPT)  F i g u r e 20b C r u i s e  F i g u r e 20a C r u i s e 78-04  0  0  20  SALINITY F i g u r e 20d C r u i s e  78-11  25  30  (PPT) 79-01  35  85  in  — I CC CELO C L  0  5  10  15  20  25  30  35  SALINITY (PPT)  F i g u r e 20e C r u i s e  79-12  FIGURE 20 P a r t i c u l a t e Mn:Al r a t i o s p l o t t e d versus s a l i n i t y f o r C r u i s e s 78-04, 78-11, 78-16, 79-01, and 79-12. Symbols: • data a t a l l depths f o r S t a t i o n 15; O data a t a l l depths a t other s t a t i o n s i n the S t r a i t of Georgia; A surface samples i n the F r a s e r E s t u a r y ; O bottom samples i n the F r a s e r E s t u a r y .  Mn:Al  r a t i o s i n the s a l t wedge were lower than those i n s u r f a c e  waters of comparable differences  salinity.  between  the  This  riverborne  m a t e r i a l and the resuspended sediment. f u r t h e r i n the f o l l o w i n g s e c t i o n . 20e)  differ  content  of  considerably  somewhat the at  suspended This w i l l  time  compositional particulate be  times.  particulate (Figure  is  particularly  evident  suspended p a r t i c u l a t e Mn:Al salinity  increases,  but  in  ratio higher  (Figure  The aluminium  material  varies  19), and t h e r e f o r e , Mn:Al  r a t i o s e x h i b i t s c a t t e r due t o v a r i a t i o n s i n g r a i n s i z e This  discussed  Data f o r C r u i s e 79-12  from data a t other  suspended  this  indicates  the  effects.  r i v e r i n e samples.  tends salinity  to  increase  samples occur  as  The the  i n the  86  Strait salt  of  Georgia.  wedge  ratios  in  observed  are  also  surface at  periods  of  in  total plots  of  between  total  the  the  Cruises  78-16  (Figure seem  conservative  plotted  due  fraction  to  to the  Riverborne dissolved  79-12),  total  sediment  levels,  waters  during  suggest from  measured  resulted  the  manganese  The  anomalously associated (1980)  greater the  freshet  for  mixing  when  high  maximum from the  manganese  zone  l i e above  79-12  acts  the  was  not  particulate  a  source  of  suspended  levels  are  from  high  as  Station  53  suspended  similarly mg/1,  which  times  however,  dissolved  with  400  the  the  freshet.  possibly  samples  in  these  total  Cruise  through  results  certain;  the  freshet  to  the  the  indicated  evident both  c o n t r i b u t i o n of  observed than  At  of  less  during  surface  not  corresponded  initial  material the  (Figure  79-01.  Data  from  p a r t i c u l a t e components,  was  that  curve.  during  were  and  i s somewhat  suspended  M i l l iman  than  maximum  significance  overwhelming  high.  concentrations, loads.  21b)  mixing the  78-04  The  samples  with  and  behaviour  concentration  to  manganese  exceptionally  greater  21a  Cruise  those  absolute  salinity  concentration.  to  the  the  versus  dissolved  the  though  manganese  total  the  magnitude  similar  As  for  in  even  are  conservatively.  waters  concentration  zone  in  differences,  behave  surface  would  of  these  should  conservative  data  year,  dissolved  21c),  maximum  mixing  ratios  discharge.  Figure  the  the  Despite  d i s s o l v e d manganese  manganese  of  in  lower  p a r t i c u l a t e Mn:Al  high.  orders  i f the  interaction  the  times  are  Finally, an  quite  waters  other  concentrations during  Suspended  in he  high surface  attributed  (Cruise  manganese sediment suspended offshore to  the  87  LO  o  ^OJ  -i\  CQ J\ Q_ CL —in — z: —12 CE \ 1  o 1—  1  in i—i—i—r  0  5  10  15 20  25  30  S R L I N I T Y (PPT)  Figure  0  35  5  10 15 20  30  35  SRLINITY (PPT)  F i g u r e 21b C r u i s e  21a C r u i s e 78-04  25  78-16  i—r 0  5  10  15 20  25  30  S R L I N I T Y (PPT)  F i g u r e 21c C r u i s e  35  79-01  FIGURE 21 T o t a l manganese data p l o t t e d versus s a l i n i t y f o r C r u i s e s 78-04, 78-16, and 79-01. Symbols: • data at a l l depths f o r S t a t i o n 15; O data at a l l depths at other s t a t i o n s in the S t r a i t of Georgia; A surface samples i n the Fraser E s t u a r y ; O bottom samples i n the F r a s e r E s t u a r y .  88  resuspension The  dissolution  suspended for  of bottom  anticipated  Riverine  sediment  the  on  dissolved  sediment  loads  geochemical particulate cannot  be  suspended in  often mass  exhibits  particulate  For supply al.  these  (1977)  reasons,  proposed  sediments  following  this  the  elevated wedge  and  a t low  waters  case  dissolved  times  Mn:Al  10  the with  even  at least  manganese complete The  manganese  two o c c a s i o n s . sediments Evans  remobilized  of manganese one in  sediments.  A  suspended  total  was  the  1.7  significantly  manganese  of  only  mg/1.  with  manganese.  concentrations  alone.  manganese.  bottom  Estuary,  with  suspended  dissolved  dissolved  i n the Fraser  waters  as 24  not change  estuarine  the reduction  manganese  on  the  to account f o r  to  particulate  salinity  agree  riverborne  "excess"  does  of  manganese  released  Estuary  of the year,  ratio  account  processes  the c o n c e n t r a t i o n of  that  interstitial  of  to  times  waters  water  between  suspended  Finally,  overlying  be  a t some  likely  insufficient  i n the range  riverborne  dissolved  mixing  in the Fraser  and e s t u a r i n e  of a l lthe  a maximum  saline  balance  manganese  the estuary.  fresh  basis,  peak  fall  that  and  from  other  indicates  in estuarine  a dry weight  manganese  n o t be at  physical  suspended  attained  dissolution  of  from  would  observed  evidence  in mixtures  results  manganese  material  enrichment  Experimental  concentrations  ppm  or d e s o r p t i o n of manganese  particulate  t h e manganese  year.  sediments.  oxides. would both  must et from  Should  anticipate the  salt  89  4.4.4 the  Role  Dissolved  In of  The  of E s t u a r i n e Manganese  examining  t o be (1)  considered dissolved  Sediments  in Establishing  Peak  the estuarine  t h e d i s s o l v e d manganese  aspects  Bottom  sediments  maximum  as a p o t e n t i a l  source  in the surface  waters,  five  concentrations  in salt  wedge  in  the  are: manganese  waters (2)  dissolved  manganese  interstitial (3)  ammonium  waters  oxalate  concentrations  of estuarine  extractable  sediments  manganese  in  estuarine  sediments (4)  variations  in  the  Mn:Al  ratios  in  estuarine  sediments (5) Most  mass  balance  c a l c u l a t i o n s f o r manganese  studies  of the  manganese  waters  have  (1976)  reported  compared few  the at  to  samples  Bottom  focussed  waters  manganese various  in  the s a l t  sediments (Figure  15).  Fraser  River  from  only  1.97  restricted  distribution  on  indeed Although water t o 2.93  waters. in  in Narragansett to s a l i n i t i e s Estuary  through  in  Graham bottom  Bay;  greater  were  et a l . waters  however,  these  than  ppt.  collected  the complete  estuarine  to  27  determine  salinity  range  year.  dissolved  wedge do  waters  of the  surface  concentrations  i n the Fraser  times  Elevated  the  enhanced  surface were  on  distribution  manganese  several a c t as  occasions the source  the d i s s o l v e d during ppb,  concentrations  Cruise five  suggesting  78-11  samples  the  manganese  concentration  (Appendix  water  observed that  of extraneous  manganese  bottom  were  in  B . l ) ranged collected  90  near  Steveston  salinity  of  salinity were salt  19.580  i n these  obtained wedge The  (Figure than was  exhibited concentrations  few  salt  15d)  than  bottom  waters  higher  than  salinities i n the surface  7 ppb  were  ranging  from  ppb  in this 10  with  the  samples  the toe of the  Cruise  79-12  concentrations  higher  salinity.  with  the s a l t  series  and  salinity,  (Figure  a  This  salinity  15b)  manganese  waters  waters  concentrations  than  20  previous  week,  observed  t o 14.295  the  ppt.  In  exhibited  While  River  peak  during  salinity,  ppt.  of the F r a s e r  range  estuarine  of comparable  greater  2.282  salinity  at  from  respectively.  following discussion ebbing  station  Numbers  tide,  data  refer  from  56.3  particulate  this  the  wedge  Station  suspended  22b  26.969  increased  were  as  manganese cruise  at  comparison,  concentrations  ppb.  among  time  an  at a  during  waters  78-16  in surface  and  On  after  of comparable  dissolved  near  Included  versus  shortly  bottom  Cruise  the  8 and  dissolved  for  ppb  because  obtained  waters  in  waters  partial  evident  exhibited  18.8  concentrations  between  surface  13.3  site.  samples  during  at  concentrations  bottom  wedge  content  possibly  flooding tide  observed  especially  salinities  samples,  as  25 p p t .  Similarly,  as  manganese  the c o l l e c t i o n  in  particularly  high  a  The  e x h i b i t e d d i s s o l v e d manganese  observed  greater  bottom  on  passed  ppt.  as high  Cruise  (Appendix manganese  are presented  used  to identify  to these  the bottom  p p t and a d i s s o l v e d manganese  78-16  is a  B.3). data,  The  plotted  in Figures water  22a  samples i n  figures.  water  (1) h a d a  concentration  of  salinity 3.62  of  ppb.  91 (O <$\ o CQ  4  Q_ CL  0  CO  .o  CM  CC CE CL  o  —i  J  2  5 0  5  10  15  20  25  30  0  35  5  10  15  20  25  30  35  SRLINITY (PPT)  S R L I N I T Y (PPT)  F i g u r e 22b P a r t i c u l a t e Mn  F i g u r e 22a D i s s o l v e d Mn  Manganese and Particulate FIGURE 22 Dissolved c o n c e n t r a t i o n s , p l o t t e d versus s a l i n i t y , f o r bottom waters from S t a t i o n 56.3, C r u i s e 78-16 o n l y .  The  suspended  particulate  manganese  content  was 6.30 ppb.  A  sample (2) with a s a l i n i t y of 22.925 ppt had an anomalously high d i s s o l v e d manganese particulate  content  manganese  (12.6 ppb)  content  and  a  (5.60 ppb).  particulate  47 ppb, r e s p e c t i v e l y .  concentrations  Suspended  remained  had  high,  t o 4.5 ppb.  ( 4 ) , the s a l i n i t y and  t o former l e v e l s , 26 ppt and 3 ppb,  particulate  ebbing t i d e on the f o l l o w i n g decreased  (3)  of 8 t o 10 ppb and 25 to  As the t i d e f l o o d e d  d i s s o l v e d manganese returned  initially  slack  from 8 t o 12 ppt with d i s s o l v e d and suspended  manganese  respectively.  suspended  Samples c o l l e c t e d  from the toe of the s a l t wedge d u r i n g low water s a l i n i t i e s ranging  low  38  to day  49  manganese ppb.  ( 5 ) , the  While one sample  concentrations  However, d u r i n g an concentration  had  (2) behaves anomalously,  92  these  data  indicate  concentrations associated upriver 78-11,  in  with  from  sediments  Steveston.  the  year,  that  waters  by  (1977),  two  concentrate Subsequent by  the  may  dissolved  via  t h e manganese  estuarine  sediment  1979; in  Fraser  1979  to tidal  scouring  during  Cruise  as  waters  may  be  into  overlying  (Evans  the  could  sediments  could  to tidal  or  waters  Manganese into  bioturbation. from  the  scouring. been  reported  concentrations Sanders,  Some c o r e s from  occur  introduced  have  e t a l . , 1977;  waters.  then  (or d i s s o l v e d )  manganese  interstitial  be  wedge et a l .  sediments.  also  estuaries  1980  salt  Evans  could  diffusion  et a l . , 1979).  by  the  estuarine  interstitial  water  desorbed  several  the  the  dissolved  throughout  l i e i n the  in  of  due  wedge  suggested  in  molecular  significant  the lower  1978a;  considerably  in  Eaton,  collected reaches  to  both of the  enriched  in  manganese.  While  some  concentrations the  generally  must  interstitial  and January  had  that  oxides  dissolved  waters  Estuary  dissolved  in  from  and E l d e r f i e l d  February  due  salt  Firstly,  resuspended  elevated  interstitial  manganese  are  observed  released  resuspension  Secondly,  exhibit  be  of t h i s  waters  Sediments  in the  manganese  in interstitial  overlying  indicate  of manganese  release  also  of manganese  mechanisms.  turbulent  dissolved  occurs  metal  reduction  was  dissolved  waters  resuspended  data  the source  The  bottom  This  field  enrichment  sediments.  elevated  previously.  manganese and  the  estuarine  as d i s c u s s e d  Thus,  that  ppm  samples  ranging range  from  were  analysed 19  t o 126  measured  had ppb  dissolved only,  manganese  concentrations  i n the i n t e r s t i t i a l  waters  of  93  sediments C.2)  from  Stations  and a g a i n  from  Thus,  some  levels  enriched  Station  interstitial  concentrations  estuarine into  waters  may  exhibiting  relatively  (less  150 p p b ) .  than The  volume  dissolved  estimated  of 1:10  1 2  with  3  of i n t e r s t i t i a l  the  area  of This  the  would 2  reported  Fraser  water river  water  (Eaton,  al.,  1979b)'. The d i f f u s i v e  be  lead  the  water  from  be  those  cores  manganese  can  be  manganese c o n c e n t r a t i o n i n and a  River  2), i s approximately•90.0 1978 and 1 9 7 9 ) ,  (4.5 x 1 0  dilution  Since the Fraser  channel affected  dissolved  Thus,  waters  necessary.  b e 2.0  dissolved  to account f o r  i n the surface  (Figure  would  to  depleted.  removed  water.  an o r d e r of magnitude  1979)  would  of Canada,  f o r N a r r a g a n s e t t Bay  Bay  time,  been  River  would  correspond to a  ug/cm /day,  same  over  of these  would  i s a p p r o x i m a t e l y 10 mg/1  15 km b y 300 m  interstitial  waters  the d i s s o l v e d  manganese  magnitude  required  Survey  1/yr  of  interstitial  at Mission  1/yr (Water  approximately  have  dissolved  of d i s s o l v e d  waters  measured  of  waters  (Appendix C.5).  low c o n c e n t r a t i o n s  assuming  interstitial  10  of  the  (Appendix  Incorporation  overlying At  1979  1980  orders  waters.  manganese e n r i c h m e n t  by  discharge, x  three  i n the i n t e r s t i t i a l  interstitial  factor  exhibit  in  enrichment.  the  waters as  considerable  the  i n January  much  waters  i n February  56.2  as  interstitial  manganese  /  5 6 . 2 a n d 59  1 0  90.0 x 1 0 '  Assuming  by t h e s a l t  wedge i s  cm ), the net  exchange  2  l/cm /yr 2  o r 5.5  manganese  greater  than  ml/cm /day. 2  efflux diffusive  of  55  fluxes  1976),  Chesapeake  and t h e R h i n e / S c h e l d t E s t u a r i e s  (Duinker et  flux  (Graham e t a l . ,  that  (F) of d i s s o l v e d  manganese  from  Fraser  94  Estury  sediments,  manganese,  c a n be  a  lower  estimated F  where  D,  2 x 10"  the  concentration a  depth  of  February flux  7.5  cm  diffusion  overlying  dissolved Fraser  the  resuspended  release  The  water  to  be  taken  increases  manganese  t o 11 j u g / m l a t  at  This  gives  a dissolved  manganese  The  discrepancy  between  calculated from  cannot  enrichment  from  Station  flux  be  solely  the  desorption  or  56.2  that  waters  into  responsible  surface  in  indicates  interstitial  in  estuarine  in  The  bottom  the observed  the resuspended  decrease  advances.  the  to  increase  slight  wedge  of  f o r the  waters  of  the  Estuary.  significantly  in  C.2).  supply  collected  of manganese  manganese  Accordingly,  the  dissolved  previously  salt  law:  1979).  2  and  first  of  D  < <  value  rate  is  in sediments  (Appendix  the  coefficient,  i n the i n t e r s t i t i a l  1979  molecular  from  Fick's  of a p p r o x i m a t e l y 0 . 3 ug/cm /day.  this  the  (Eaton,  2  using  for  = -(dc/dx)  diffusion  cm /sec  6  limit  ionic  i n t h e pH high  d i s s o l u t i o n of  sediments  manganese  material  strength  surface  waters  at Station  associated  with  resuspended  from  the analyses  contribute  enrichment.  may  occur  in  water  manganese  53 d u r i n g bottom  as  Manganese  response  or, alternatively,  of the bottom  dissolved  must  manganese  due  to the  the s a l t  wedge  concentrations  Cruise  to  79-12  sediments  observed  were,  (see  also  Section  4.4.3). Results suggest occur.  that It  transported  of  the estuarine  the removal  o f manganese  should  noted  through  be the  Fraser  that  from  bottom  these  the s u r f i c i a l  Estuary  as  sediments  sediments sediments  bedload  may are  material  95  rather  than  being  varies  little  down  possible  to  content  Mn:Al  ratio.  in  the estuary  (Appendix  C.6),  of  sediments  ammonium  concentration  trend  was o b s e r v e d  1980  riverine  130  ppm  Steveston 80.2  sediments May  oxalate  decreases  (Appendix  in  both C.5).  Steveston  i n May  concentrations  levels  further  manganese  the  dropped  were  and  125 t o  1980.  to  102  of  having  concentration  at  content  At and  downstream  i n manganese,  found  higher  C.3)  i n January  A greater  was  manganese  concentrations  collected  73 ppm.  and  the estuary.  Westminster  had  be  i n terms of  (Appendix  depleted  1 5 3 ppm,  with  sites  manganese  New  size  should  extractable  1979  from  of approximately  associated  May  Sediments  1979 were  e x t r a c t a b l e manganese,  possibly  oxalate  a n d 161 t o 168 ppm  respectively.  i t  extractable  Leachable  collected  1979  the grain  s y s t e m a t i c a l l y down  in  ( S t a t i o n 56.2) t h e s e  ppm,  from " d i f f e r e n t  o f ammonium  sediments  January  of  because  surface  This  in  Moreover,  compare  their  The  deposited.  Station  53,  of f i n e - g r a i n e d  ma t e r i a 1. Pharo  (1972) a l s o  ammonium  oxalate  relative  to sediments  in  these  91.2  ppm,  higher hours  sediments  collected ranged  respectively.  in this  near  from  The  the  in Fraser  River  Sand Heads.  1 7 6 t o 226 ppm  absolute  content  sediments  Concentrations and from  concentrations  e x t r a c t i o n time,  of  4 hours  88.0 t o may  compared  be to 2  study.  t h e amount  surficial  downstream  differences in  e x t r a c t a b l e manganese  due t o h i s l o n g e r  While in  reported  from  o f ammonium  sediments Steveston  oxalate  collected (with  extractable  in  May  the exception  1979 of  manganese decreases  Station  53),  96  ammonium in  oxalate  sediments  extractable  from  Stations  from  upstream  locations  not  related  to  C.6).  i n the Rhine  physical  mixing  of  Forstner,  1975).  However,  Fraser  Estuary  transport  manganese  may  composition estuary.  Such  difference the  total  oxalate of and  the total  downstream,  riverborne  Cruise ratios ratios always  common  ranging  either  from  exceeded  oxalate  and suspended  x  10~  sediments  extractable  mineralogical  account  of the for  The  the and  ammonium  upstream  55. lower  x 10'  3  observed  Estuary  (Table  sampled 20e).  during display  IX).  Mn:Al  this  time  at Since  t h e bottom  Estuary  ratios  function  than  collected  i n the Fraser  as a  1980).  collected  the Fraser  i n t h e Mn:Al  i n the r a t i o  near-bottom  C.3).  Sediments  (Figure  3  the  89 t o 9 8 % a n d 62 t o 7 8 %  Station  9.77  in  reaches  also  i n sediments  to  the differences  variations  lower  i n the sediments.are  5.89  the  and  r e s i s t a n t aluminium  constituted  throughout  (Muller  occur  the  (Appendix  from  attributed to  oxalate  in  the  particulate material  10.0  not  bottom  (Milliman,  v a r i a t i o n s may  content  stations  i n suspended  source,  in  particulate material.  79-12 f r o m  (bedload)  variations  concentrations  ratios  does  are  (Appendix of  sediments  i n t h e ammonium  respectively,  Mn:Al  has been  only  sediments  aluminium  content  seaward  r e s i s t a n t aluminium  The in  aluminium  metal  is  t h e ammonium  variations  the  process  higher  i n sediments  of the sediments  because  to  are  size  freshet  mineralogical  between  These  the  be r e l a t e d the  observed  and marine  this  the increase  of  C.3).  Estuaries  riverine  sediments  Alternatively,  in  and Elbe  during  of  grain  variations  sediments  concentrations  54 a n d 55 t h a n  (Appendix  t h e mean  Downstream  manganese  may  share  a  be due t o  of the g r a i n  size  97  TABLE  IX  The Mn:Al R a t i o i n S u r f i c i a l E s t u a r i n e C o l l e c t e d i n May 1979 ( C r u i s e 79-12)  Stat ion Number  Mn:Al (x  the  result  As  loss  of  Mn:Al  1980  values  ratios (Figure  in  particulate  78-16  (Figure  bottom  20c).  20c)  tend  to  the 10.2  should  material  may  be  to  x  sediments.  ratios exceed  10" )  the  explained  sediments  true  oxalate  that  salt  by  values  are  lower  than  particulate  low  wedge  due  extraction.  estuarine  noted the  for  again  3  in  be  in  the  ammonium  observed  It  in  ratios during  resuspension  found Cruise  of  these  sediments.  A  mass  balance  hypothesis  that  dissolved  manganese  waters. 2),  (8.85  3  Mn:Al  during  generally  material the  will  aluminium  these  processes  mentioned,  in January  However, the  diagenetic  previously  obtained to  of  Ratio 10 )  17.7 4.57 5.89 7.12 9.77 7.85 7.36 8.14  3 15 53 54 55 56 59 65  or  Sediments  The  the  Fraser  i s approximately  1978  and  1979).  river  water  for  manganese  estuarine to  sediments  maintain  River 90.0  was  c a l c u l a t e d to  could  sufficient in  observed  maximum  discharge,  measured  at  Assuming  i s approximately  10 the  1 2  1/yr excess  10 ^ug/1  (Water  Mission  Survey  of  VIII),  the  surface (Figure Canada,  d i s s o l v e d manganese (Table  the  supply  the  x  test  in  efflux  the of  98  excess  manganese  oxalate by  would  extractable  approximately  be  9.0  x 10  manganese 65  ppm  (Appendices  a r e t r a n s p o r t e d from  Assuming  that  physical lO  processes  kg  1 0  would  enhancement. transport (1972) to  be  between act  required  through  the F r a s e r  x  these  values  as a  10*  source  of  derived the  the  manganese from  manganese  coupled  to  Estuary.  the  This  desorption  interstitial  oxides.  The  occurrence  extractable  to  f o r 1978  rather of  than  1.4  x  manganese  of  bedload  o r 1979, P r e t i o u s  passing  New  kg/yr.  J O  these  Steveston.  bedload  measurements  10  as  the observed  bottom  Westminster The  agreement  sediments  in  waters  the  situ  downstream  manganese  suggest  of  could  sediments  the  of  in  the  salt  may  be year  wedge  salinity. to  be  i n the Fraser occur  due  resuspended release  processes  decrease  may  appears  concentrations  reduction such  the  waters  of  excess  waters  comparable  concurrent  high  content  in  of  the  Throughout  enrichment from  that  surface  manganese  manganese  having  to  general  annual  i n the bottom  with  due  a  C.5)  chemical  sediments.  dissolution)  manganese  by  from  the  resuspension  dissolved  water  in  surface  tidal  together  data  bottom  content  (or  sediments  the  dissolved  in  Enhanced  that  field  estuarine  levels  x  observed  c o n c e n t r a t i o n of  exceeds  bedload  o r 1.5  suggests  and  decreases  manganese.  Summarizing, dissolved  tons/yr  no  Estuary  the p o t e n t i a l  16.2  an  are  sediments  C.3  to balance  there  c o n c e n t r a t i o n of  Westminster  results  in the estuary,  Although  estimated  New  decrease  be  The  in surficial  sediments  this  kg/yr.  5  to  bottom  of  some  of  dissolved  amorphous  manganese  i s further  suggested  the  ammonium  in estuarine surficial  oxalate  sediments,  99  together  with  observed  in  calculated in  the  bedload  enriched into  with  the  Fraser  subsequent  environment.  Such  1979b).  may  to  to  lead  the  The  due  humate  distribution  mechanisms  dissolved  occur  this  D i s s o l v e d Manganese  Two  that  bottom in  a  of a  of  Removal  to  in  the  will  are  introduced  satisfies  manganese  the. t r a n s f e r  be  thermodynamic  1976  of  the  throughout  discussed  in  processes from  and  with  has  a  in  a l .  Field  observed  cause  mixing of  recycling  established  variations  the  experiments the  mechanism  interaction  manganese  and/or  model  plays  an  proposed  by  (1977) .  s t u d i e s have of  in  should et a l . ,  hydroxide to  from  estuarine  dioxide  shown  Regardless  role  the  i n the  (Duinker  iron  been  solution  1978).  manganese  manganese  considerations  association  manganese  of  component  important  in  manganese  Processes  dissolved/particulate  been  the  waters  be  which  dissolved  this  chemistry  wedge  must  manner  involved,  et  of  transport  salt  water  mechanism  precipitation  flocculation  (Sholkovitz,  Evans  Finally,  balance  bedload  the  particulate  Alternatively,  removal  of  mass  than  1972).  water  Estuary.  lower  Section.  4.4.5  the  manganese,  surface  estimates  sediments  particulates.  achieve  indicate  overlying  observed the  with  data  these  suspended  (Pretious,  the  in  required to  agrees  Estuary  While  ratios  riverborne  system  Fraser  Mn:Al  manganese. in three  Narragansett  Bay  The  rivers (Graham  removal  of  in Georgia et  i n the  dissolved (Windom  a l . , 1976)  and  et  estuarine  manganese a l . ,  i n the  has  1971),  Rhine  and  100  Scheldt  Estuaries  manganese  was  reaches  the  the  of  (Duinker  shown St  et  to  behave  Lawrence  Beaulieu Estuaries  a l . , 1979b).  conservatively  (Subramnian  (Holliday  However,  and  and  dissolved  in  the  d'Anglejan,  Liss,  1976;  lower  1976)  Moore  et  and a l . ,  1979). The  Fraser  Considering from  the  solution  theoretical waters  Estuary,  the  dilution the  1).  Subsequent  removal  line water  Plots suggest  any  redefined  cause  curve  of  reaches the  of  total  this  evidence  ideal in  situ  particulate Fraser  suspended  of  water  Georgia at  to  member  low  Fraser  examine may  manganese of  the  the  mixing  the  theoretical  order  reaches  versus  year  of  i n the  the  the  below  below  be peak.  estuary  theoretical of  Strait  of  water.  manganese the  year  end  considering  salinity  lies  removal  influx  In  at  lower  category.  Strait  l i e above  falling  manganese  mixing  positive  the  low  the  initial  i n the  by  for  time  the  values  generated  Similarly, would  by  and  members.  salinity  processes  dissolved  at  data,  end  that  manganese  throughout  two  second manganese,  curve  dissolved  consistently  low  with  of  no  salinities this  the  indicated  dilution Georgia  data  this  dissolved  dilution  observed  manganese  as  a  a  for these  redefined  of  to  for Fraser River  Since  field  curve  be  line  been  dissolved  would  develop  mixing  has  conforms  distribution  would  (Figure  salinity  Estuary  salinity  removal  when  at  examined  (Figure  15)  intermediate in  terms  of  curve. production  deviations  from  manganese. Estuary  for  of the  This two  particulates  particulate  theoretical  holds  reasons.  behave  manganese  true  i n the  Firstly,  conservatively  mixing lower since in  the  101  surface  waters,  any  increase  concentration  indicates  concentrations  of d i s s o l v e d  same  order  16)  manganese  that  occur,  distributions components  i n the  Manganese  Mn:Al  for  ratios  such  Mn:Al  during ratios  ones.  This  following  either  (Figure  precipitation the  particulate  increase  of bulk  manganese  data  fairly  (Figure  ratios  be  20)  is  more  fully  ratio  at  show  no  for particulate  uniform.  time  the  estuary.  Mn:Al  This  20e); however,  at this  alter  the  (Figure  and h y d r o l o g i c a l p r o c e s s e s will  also  of  this  The Mn:Al  remain  would  reaches  the f i e l d  salinity  concept  waters  does  the  estuary.  the removal  in  the  Mn:Al  lower  oxidative with  t o be  rather  was  the  probably than  developed  dissolved  not  increase due  to  chemical in  a  remain  iron  of  humates  significant behaves  manganese  of the F r a s e r  precipitation  manganese ratios  of  reaches  colloidal  not appear  particulate  particulate the  would  waters  with  coprecipitation  the  the  the  chapter.  by  oxides,  and  However,  affect  interactions  behaviour.  Recapitulating, surface  to  the  are of the  salinity  oxidative  i n the lower  the freshet  sedimentological  Secondly,  manganese  versus  insufficient  however,  in surface  case  solution.  manganese  estuary.  salinities;  material  of  the  dissolved  precipitation  evidence  the  the  particulate  the f r e s h e t .  manganese  dissolved/particulate  particulate  higher  of  is  from  during  should  i t  the  and p a r t i c u l a t e  of p a r t i c u l a t e  suggests  Any  removal  of magnitude except  distribution  in  process.  conservatively  relatively  Estuary,  manganese and/or  constant  from  or  hydrous Instead, and  the  throughout  102  4.4.6  Manganese  Behaviour:  Thermodynamic  and  Kinetic  Considerations  Wollast pH  and  and  noted  of  the  in  Rhine  distribution  and  dissolved  with  They  assumed  that  pH  the  salinity  acid  (Mook  low  dependence and  Koene,  concentration  both  Estuaries  corresponded the  of  Scheldt  minimum  manganese  of  the  developed the  1975)  due  dissociation  and  suggested  resulted directly  from  pH.  Accordingly, behaviour  of  explained  they  manganese  in  terms  exist  MnOOH,,MnO^), sulphate  in  Eh  =  on  1.012  -  field  the  and  Rhine  equilibrium manganese associated determined dissolved dissolution  Scheldt  levels with the  +  suggesting  the  that  if  log  This which  (MnCOj,  the  and  following  1972):  pO* agreed  with  dissolved concentrations controlled  in  be  chloride  concentrations  these  500  manganous  maximum  results  by  changes  estuaries  ppb  where  oxides  by  the  could  phases  with  (Breck,  of  manganese  solid  Eh  couple  that  waters  solubility  estuary  pairing  0.030  However,  anoxic  determine  d i s s o l v e d manganese  ion  E s t u a r i e s are  (greater  manganese of  O^/H^O^  0 . 0 5 9 pH  an  various  defined  the  conditions.  by  of  d i s s o l v e d manganese data  in  to  equilibrium relationships.  account  They  based  observed  simple  into  model  mixing  concentration  taking  Calculated  during  a  equilibrium with  ions.  relationship  developed  of  c a l c u l a t e s the  should  in the  the  pH  carbonic  enhanced  low  model  (1979) d e t e r m i n e d  the  maximum.  constants  the  that  variations  that  a l .  d i s s o l v e d manganese  manganese to  et  in  the  some  in  the cases)  concentration  carbonate. from  associated  the with  Hence,  in the  high are is the  reductive riverborne  103  suspended  particulate material.  Similar Fraser  calculations  Estuary  indicate that  concentrations In  contrast  always  equilibrium  the  concentration  are  t o redox  than  and  rate  partial  Morgan  Such  pH v a l u e s  and  were  intense  2  *  oxidation  adsorption  biological  It  precipitation residence During  in estuarine  suggesting  oxidation  estuary  peak  waters.  at  a  that  the  cannot  Furthermore,  slightly these  two  higher features  dioxide  8.5  hours.  environment  during  periods  surfaces.  demonstrated  may  of  due t o  However,  experimentally  catalyse  manganese  that dioxide  waters. that  well  significantly months,  only  than  within  i n the marine  Estuary  pH  i n Stumm a n d  greater  observed  the  v i a an a u t o c a t a l y t i c r e a c t i o n  (1979)  been  cited  both  (Figure 8d).  manganese  noted  upon  a t pH v a l u e s  oxygenation  proceeds  be  depends  Experiments  only  activity  onto  has  summer  occurs  encountered  in estuarine  times  the  remains  be  i n the Fraser  a l .  should  Estuary  manganese  that  processes  precipitation  throughout  of oxygen.  are rarely  et  Fraser  the d i s s o l v e d  manganese  exhibited  Wollast  the  values.  interrelated.  photosynthetic  The  manganese  of  maximum  indicated  measurable  dissolved  from t h e  by t h e l o w s o l u b i l i t y  processes  pressure  was  data  i s determined  o f manganese  (1970)  field  calculated equilibrium  and  t h e pH m i n i m u m  not d i r e c t l y The  Mn  Thus,  d i s s o l v e d manganese  salinity  7)  with  observed  exceeded  (Figure  dioxide.  attributed  the  t o the p o l l u t e d Rhine,  well-oxygenated  manganese  performed  in estuaries substantiated,  longer  waters  in  than  f o r which the  waters  in the Fraser  Narragansett  manganese  Bay  have  Estuary. have  a  104  residence  time  The  and  Rhine  order  of  to  Fraser  the  cycle  a  of  Scheldt  few  days  (Hodgins,  times  are  too  process residence  4.5  A  The general  which  1974).  short  to  time  of  hydrodynamics  data  of  particulate  Fraser  the  manganese.  environments  (river,  three  components  simple  flow  (Figure  the  and  Estuary  residence  both  the  field  occur. where  considering  for  area  and  a l l the  into  and three  manganese  into  sediments),  the  a  and  dissolved  the  illustrates  to  Georgia  accounts  and  is  chemistry  of  sea)  tidal  Estuary  by  manganese which  compares  longer.  Fraser  particulate  23)  of  the  each  dioxide,  Strait  on  This  Fraser  summarized  dividing  estuary  the  the  distribution After  times  with  is considerably  in  a l . , 1976).  precipitation  the  Estuary  (dissolved,  diagram  to  briefly of  salt  manganese  Behaviour  model  in  of  significant  be  et  respectively.  although  to  water  (Graham  residence  flushed  confined  will  the  features  is  allow  f o r Manganese  field  have  Thus,  the  month  months  respect  descriptive  observed  two  i s probably  the  Model  and  with  one  Estuaries  Estuary  supersaturated  This  approximately  a  transport  of  0  manganese  through  the  interactions  and  other  studies.  case  included  for  dashed  system. lines  Solid  represent  Interactions  completeness  but  will  be  in  lines  represent  processes the  discussed  reported  "sea" in  observed  the  have  in been  following  chapter. Dissolved no  through  the  Fraser  perceptible oxidative precipitation  nor  coprecipitation  flocculated concentration  manganese  colloidal at  low  passes  iron salinity  oxyhydroxides. arises  due  Estuary  The to  the  with with  maximum release  of  105  RIVER  ESTUARY  SEA  dissolved  dissolved  dissolved  part  iculate  i  i  i i I  i i  T  particulate  particulate  sediments  sediments  sediments  F I G U R E 23 F l o w d i a g r a m f o r t h e t r a n s p o r t o f m a n g a n e s e through the Fraser E s t u a r y . Solid lines represent observed interactions while dashed lines represent processes reported in other estuaries.  manganese  from  the  suspended  particulate  Following the  river  and  the  of  manganese  in  the  r i v e r ,  seems  with  Both  in  bed  load  a  the  and  as  the  than  from  be  and  particulate  estuary  particulate  due  to  riverborne  changes  resuspension  during  redeposited  the  in  in  the  generally  of  of  ebb-tidal as  manganese  manganese  concentrations  waters  flooding river  some  Tidal  wedge to  of  the  enhanced  salt  material  decreases  of  conservatively. causes  rather  material.  reaches  the  sediments  this  sediments  deposition  upper  hydrodynamics behaves  bottom  estuarine particulate  flows.  Most  discharge  of  rate  tide. estuary,  such  can  be  s u r f i c i a l considered  sediments to  be  comprise  transported  106  through  the  bottom  sediments  waters  system.  of t h e s e  Diagenetic  concentrate  sediments.  releases  these  desortion  or d i s s o l u t i o n  sediments in  water  causes  Fraser  salt  maximum River  wedge.  water  a  distribution Estuary.  conservative  the  with  the  wedge. from  estuarine  interstitial  of d i s s o l v e d  sediments  The c o n c u r r e n t  these  resuspended  manganese  indicates  observed  water  must  which  be  the  dissolved  results  from  the mixing  satisfies  the  which  into  throughout  intersect  from  the  overlying  observed  c a n be c o n s i d e r e d  curves  water  introduced  manganese  distribution  concentration  waters  that  manganese-enriched  dissolved  dilution  salt  manganese  evidence  bottom  of  in  the  r e s u s p e n s i o n of the  in the surface  manner  This  manganese  of  in  wedge.  water  This  in  Tidal  into  the available  manganese  manganese  the enrichment  of the s a l t  Thus,  of  waters  processes  surface  the  Fraser  to consist  of  at the s a l i n i t y  c o r r e s p o n d i n g to the d i s s o l v e d  two and  manganese  max imum. Data bottom' occur  from  waters,  and  (Figure  highest  subsequent  discharge  causes  concentration increase  in  the s a l t  conservative Furthermore, the  the  78-16  i n the t o e of the s a l t  waters  from  Cruise  surface  in  the  surface The  with  dilution  with  wedge.  mixing salinity  curve process  manganese  into in  the  the  waters  mixing  river  indicate  Vertical  entrainment  salinity.  this  dissolved  an • i n c r e a s e  wedge  15b)  that  in  concentrations  advection  of  outflowing  dissolved  corresponds  forms  and d i s s o l v e d  at  low  a discrete manganese  river  with  of manganese-enriched  observed  these  manganese  concurrently  water  the  an water  with  the  salinities.  water  mass  at  concentrations  107  corresponding case  during  Fraser  Cruise  River  development 5  to  6  9  ppb.  water  to  ppt  and  These the  becomes  the  the  salt  peak  can  Although obtained  at  been  ppb  in  for  manganese  observed  at  4  (Figure  Maximum  ppb)  of  causes  a  salinity with  therefore,  samples  from  the  range  of  to  ppt  different  8  occurs and  10  for  of  the  the  toe  mixing  increase  with in  low  mixing  manganese decrease.  wedge  were  concentrations the  the  establishes  Subsequent  the  water  with  in  concentrations  suggests  the  dissolved  released  ppt.  model  sea  diagram  saline  eventually  toe  and  manganese  and  relatively  the  6  with  schematic  waters  this  salinity  not  would  and  20  to  enriched  in  manganese. of  the  Accordingly,  a  Inflowing  4  surface  between  of  establishes  downstream  of  salinity  Water  salinity  and  the  salinities.  with  these  of  to  dissolved  enrichment  concentration,  on  a  higher  illustrated  water  water  having  d i s s o l v e d manganese  waters  depending  on  to  time,  wedge  estuary.  1  24).  dissolved  lead  (with  this  the  Salt  Georgia  the  mixing  could  Intermediate  78-04 the  Considering  concentration  of  approximate  and,  mass  distribution  river  bottom  this  Entrainment  saline  concentrations  waters  observed be  peak.  conservative  Water  of  sediments.  manganese an  of  curve  with  wedge.  at  of  order  Cruise  enriched  involves  22  Strait  in  of  15b),  bottom  dilution  mixing  from  dissolved  have  with  manganese  d i s s o l v e d manganese  outflowing  the  (Figure  processes  resuspension the  78-16  longitudinal  manganese  of  a  the  "Intermediate"  the  concentrations  of  an  Subsequent  conservative  of  water  of  from  those  the  days  varying state  salinities  of  the  different may  be  tide  may or  be  position  d i s s o l v e d manganese  explained  either  by  in  the  maxima  short  term  108  Surface 9.97 11.1 1 1 . 4 , 1 6 . 2 16.6 17.6 17.2 14.8  14.5/13.4(4.12  0.0  7.6 / 1 2 . 6 / 2 6 . 8  0.0  CM)' 2 ^ 0  _  2^2 —  4^0  —  —  5^3  5^9  10 _ - 2 0  —  —  y  —  ^  11.7  13.0//14.7 /10.2 7.68 6.91 3.28 2.52 2.77 4.49 1.43  0.0  0.0^14.4^21.3  Annacis Island 65  63  23.4 24.6 27.4 28.3 28.4 29.7 30.3 Bottom Steveston  Deas Island 61  59  58  57 56 Station  Sand Heads  55  54  53  15  FIGURE 24 Schematic diagram of the longitudinal d i s t r i b u t i o n of d i s s o l v e d manganese (ppb) and s a l i n i t y (ppt) from Cruise 78-04. Salinity values a r e u n d e r l i n e d and contoured. The water depth a t S t a t i o n 15 i s 177 m but v a r i e s i n the range of 6 t o 20 m f o r S t a t i o n s 53 t o 65.  variations  i n the F r a s e r  vertical  advection  d i s s o l v e d manganese Seasonal  of  River salt  manganese wedge  concentrations  variations  waters  explained  with  comparable salinities.  processes.  with the pH d a t a .  water.  i n terms  features Finally,  manganese  The  i n s u r f a c e waters f o r both these parameters i s best of a  two s t e p mixing p r o c e s s .  While t h e  manganese peak occurs a t a higher s a l i n i t y than the pH these  by the  i n the a b s o l u t e c o n c e n t r a t i o n of the peak  d i s s o l v e d manganese data concur  distribution  or  but d i f f e r e n t  (Table V I I I ) may a l s o be c o n t r o l l e d by such The  content  with  a r e both  caused  by entrainment  d e s p i t e the n o n - l i n e a r v a r i a t i o n respect  to  salinity,  this  minimum,  of s a l t wedge of d i s s o l v e d metal  behaves  109  conservatively chemical bottom  i n the  reactivity  sediments.  surface appears  waters to  be  of  the  Fraser  restricted  to  Estuary the  and'  estuarine  110  §-L  5.1  MANGANESE  portions 1978  one  and  1979.  month  OF G E O R G I A  surface  (Figure  of  4),  distribution 26  A  "surface"  off  of water  southern  a n d May  by  parameters  located  i n both  the dates of approximately  refers  t o samples  was a l s o  Cruise  78-07.  Complete  1,  on n i n e  the  constituents  c o l l e c t e d from depth  during  mouth.  Data  were 15  period  concentrations  fordissolved in  a  depth  Station  the study  manganese  are tabulated  a  profiles  other  dissolved  strait  c o l l e c t e d from  Furthermore,  occasions  determined the  3, 1 5 , a n d 2 5 .  how  river  was  throughout  of samples  to determine  particulate B.2,  and  preceded  discharge  suite  investigated  varied  January  periods  River  stations  at Stations  order  the central  during  sampling  of t h e F r a s e r  where  during  obtained was  of Georgia  These  of  of lm.  5m  throughout  (Table I I ) .  the basis  depth  conducted  extremes  The  and  Appendices  suspended B . l and  respectively.  5.2 S u r f a c e  Some for  were  of the S t r a i t  seasonal  in  IN THE STRAIT  Preamble  Cruises  on  DISTRIBUTION  D i s t r i b u t i o n of Manganese  difficulties  surface  synoptic programme.  waters  as  two  i n the i n t e r p r e t a t i o n of the data  i n the S t r a i t days  The wind  processes  within  short  variations  term  exist  were  required  a f f e c t s both  the brackish  of Georgia.  the  surface  i n t h e wind  The data  t o complete circulation layer.  pattern,  the  are  not  the sampling and  mixing  Therefore,  due t o  distribution  of  Ill  water  parameters  mixed  e f f e c t s of The  for  Fraser  the  the  Strait  in  River of  of  28a).  stations  in  to  northwest  trends  are  the  North  and  i n d i c a t i n g the the  1957).  tend  Heads.  The this  regular  for  from  influence River  the  show  the  cruise.  of  fresh  the  water  i s evident  in  waters  (Figures  25a  be  associated  salinity area;  7  however,  2)  these  outlined  show  Squamish  (Figure  with  increases  reasons  Station  of  to  This  to  of  data  Fraser  tend  source  surface  southeast  necessarily  of  major  in  Sand  Furthermore,  Arm  the  salinities of  will  e x i s t i n g during  salinity  vicinity  not  as  layer  (Waldichuk,  Lowest  previously. salinities  acts  Georgia  through  the  surface  a l l conditions  distribution  the  the  depressed  River  and/or  during  summer  falling  in  months. Salinities range in  of  50  27.989  January  mixing to  and 60  This  cruise  30.316  were  a  surface  with  almost The  exclusively same  holds  during  Cruise  is  major  source  of  were  of  observed  in  78-07  the  the  this  the  by  i n May  In  1979  wind  speeds  rates  of  of  contrast,  (Figure the  28a). Fraser  samples  the  manganese  salinity  for  (Figures  The  Fraser  surface  highest Sand  is  c o l l e c t e d from  26d).  manganese  of  Georgia  intense  Wind  dissolved  for  of  the  3).  (Figure  vicinity  from  cruise.  the  Accordingly,  Strait  time.  discharge  of .  true  dissolved  Georgia.  at  (Figure  distribution  5m  Strait  maximum  high,  resulted  observed  period  of  the  This  during  were  were  throughout  runoff  recorded  depth the  waters  27a).  River  sampling  28b).  ppt,  (Figure  coincided  determined through  surface  salinities  during The  the  Fraser  knots  lowest  to  1979 low  the  River  in  25b a  River  waters  in  concentrations  Heads.  Dissolved  112  Figure  25b D i s s o l v e d manganese ( p p b )  FIGURE 25 S u r f a c e d i s t r i b u t i o n of s a l i n i t y and dissolved manganese i n t h e S t r a i t o f G e o r g i a d u r i n g C r u i s e 7 8 - 0 1 .  113  F i g u r e 26a  Salinity  (ppt), 1 m  F i g u r e 26b D i s s o l v e d manganese (ppb), 1 m  114  F i g u r e 26c S a l i n i t y  (ppt), 5 m  F i g u r e 26d D i s s o l v e d manganese (ppb),  5 m  FIGURE 26 The distribution of s a l i n i t y and d i s s o l v e d manganese i n the S t r a i t of Georgia a t 1 and 5 m, C r u i s e 78-07.  115  F i g u r e 27b D i s s o l v e d manganese (ppb) FIGURE 27 Surface d i s t r i b u t i o n manganese i n the S t r a i t of Georgia  of s a l i n i t y and d i s s o l v e d d u r i n g C r u i s e 79-01.  116  Figure 28b Dissolved manganese  (ppb)  117  F i g u r e 28c Suspended p a r t i c u l a t e manganese (ppb) FIGURE 28 Surface distribution of s a l i n i t y , dissolved manganese, and suspended p a r t i c u l a t e manganese i n the S t r a i t of Georgia d u r i n g C r u i s e 79-12.  manganese l e v e l s g e n e r a l l y river  mouth,  that  decreased  i s , they  with  decreased  d i s t a n c e ' from with  the  an  increase i n  Data f o r S t a t i o n 7 i n d i c a t e a secondary source  of d i s s o l v e d  salinity.  manganese d u r i n g the summer ( F i g u r e s 26b and 28b). may  be a s s o c i a t e d with water from B u r r a r d  more probably  originates  in  the  Inlet  discharge  Squamish R i v e r or the North Arm of the F r a s e r Station  3  also  This  ( F i g u r e 4 ) , but  from  either  i n d i c a t e s a l o c a l i z e d source  In comparison to waters  locations,  of  similar  the  River. of d i s s o l v e d  manganese, but t h i s was e v i d e n t d u r i n g C r u i s e 78-07 o n l y 26b).  source  salinity  at  (Figure other  the waters at S t a t i o n 3 were e n r i c h e d with d i s s o l v e d  118  manganese  t o a depth  o f 10m.  The  source  of  this  manganese  is  in fairly  low  o f 1.36  ppb  unknown. Intense levels were but  mixing  January  of d i s s o l v e d manganese measured  Island.  In  throughout  occurred  River  Cruise  the  i n May  northwest  for  t h e d i s s o l v e d manganese. o f d i s s o l v e d manganese  salinity  values  dilution the  and southwest  i n the southern  lower  curve  Texada  Island.  extreme  of  manganese The was  less  rates  Strait  surface  than  0.5  were ppb.  portions  analyses  on s a m p l e s resulted Suspended  sea  water  particulate  of suspended  For  represents while  stations at  near either  dissolved  in Section  particulate select  the  5.4.  manganese  samples  from  were c o n s i s t e n t l y  approach  the  detection  of Georgia  were  performed  when  manganese  29).  members  concentrations values  in  different  While  to  curves  of Georgia  northern end  water  mixing  curve  be e x a m i n e d  manganese  River  (Figure  have  will  79-12  i n measureable  of  salinities  evident  of the S t r a i t  the S t r a i t  Cruise  are  salinity  79-12 o n l y .  throughout from  trends  Georgia  these  manganese  low  two d i s t i n c t  the  This  Texada  to periods  of Fraser  with  analyzed, As  hence  Georgia  near  dissolved  25 p p t , t h e u p p e r  the  of  (Figure 28b).  versus  distribution  for Cruise  and  These  of  observed  1979, c o r r e s p o n d i n g  generates  than  concentrations.  cruises  limit, only  Thus,  were  rates  i s associated  the  determined  other  greater  Values  of the S t r a i t  the d i l u t i o n  the  plot  27b).  highest  of Georgia  79-12,  resulted  portions  1 ppb  discharge  the S t r a i t  During  than  contrast,  concentrations Fraser  less  1979  (Figure  i n the southern  concentrations  high  in  high  river  discharge  concentrations.  levels  mimic  the d i s s o l v e d  119  20 22 24 26 28 30 32 34  SALINITY  (PPT)  FIGURE 29 D i s s o l v e d manganese c o n c e n t r a t i o n s p l o t t e d versus s a l i n i t y , f o r samples from C r u i s e 79-12 with s a l i n i t i e s greater than 20 ppt o n l y . Symbols: • S t a t i o n 15, + northern s t a t i o n s , X southern s t a t i o n s .  manganese v a l u e s r e f l e c t i n g t h e i r common However,  the  suspended  increasing s a l i n i t y oxidative  source  (Figure 28c).  p a r t i c u l a t e Mn:Al r a t i o i n c r e a s e d w i t h  ( F i g u r e 20e).  precipitation  of  This could  dissolved  result  manganese  from  the  and/or  the  r e l a t i v e l y r a p i d s e t t l i n g of suspended p a r t i c u l a t e m a t e r i a l with low manganese c o n t e n t . The processes  data  cannot  may  be  p r e c i p i t a t i o n of Estuary,  this  specifically occurring.  manganese  process  was  could  indicate  While not occur  significant  observed in  which  in  of  oxidative the  with  Fraser  the S t r a i t of Georgia  d u r i n g the summer due to the l o n g e r r e s i d e n c e time of the together  these  water  high d i s s o l v e d oxygen c o n c e n t r a t i o n s (Figure 7d)  and pH v a l u e s near 8.5 ( F i g u r e 8 d ) .  Furthermore, the o x i d a t i v e  120  precipitation  onto  fine-grained  material  coarse-grained material of  that  lead  5.3  Time  in  30.-  data  the  surface  is  derived  manganese  indicate a  and bottom from  the  variations length  of A  79-07  waters At  depth  the  coarser  p a r t i c u l a t e Mn:Al Lawrence  develop  Yeats  than  concentration  distance  a  indicate suspended  above  the  e t a l . , 1979).  for Station  differs  15  due  are  to  illustrated  variations  source, o f d i s s o l v e d manganese Manganese  River.  in  flux  in  manganese  of manganese  from  time  water  samples  and  shows  79-12 20 m  intermediate  of  the  collected  that  of  was  to  and t h e  River. i n the  the sediment. may  water  due  sampling  concentrations  content  the  surface  occur  the Fraser  i n t h e manganese  s e r i e s of  within  of  f o r both  i n the d i s s o l v e d  waters  a t the time  content  that  i n the  Variations  these  the s a l i n i t y  dissolved  indicate a  sediments.  in  St  some 1977;  data  waters.  d i s s o l v e d manganese  Cruises  of  processes  layer  the F r a s e r  i n both  Elevated  case,  of  in  15  concentrations  differences  waters  ratio  settling  i n the suspended  (Sundby,  bottom  Mn:Al  result  location.  The  mean  The  may  i n the absolute  settling  at Station  minerals  higher  i n the Gulf  d i s s o l v e d manganese  Figure  station  profiles  interface  Series  The  increase  manganese-rich  sediment/water  a  Subsequent  differential  particulate  of c l a y  to a decrease  b u t an  Vertical such  having  sediment.  could  manganese  ratio.  the surfaces  be  bottom  In  this  associated  in contact  with  with the  near  the bottom  during  significant  enrichment  occurs  sediments.  depths,  the  dissolved  manganese  121  Depth  (m)  FIGURE 30 Time s e r i e s of d i s s o l v e d manganese c o n c e n t r a t i o n s a t S t a t i o n 15 from January 1978 t o June 1979.  122  concentrations higher  in  the  variations  winter in  development leads  exhibit  to  of  a  the  100  m  was  While could  the  Vertical obtained  the  reason  do  advected  suspended and  and  concentrations  except  in  the  particulate  in  due  October  compared  to  to  ppb)  was  5.4  ppb  and  the  ppb  m  150  suspended  in April.  to  at  profiles  for  two  unknown,  the  depths  interface  enhanced  (Figure were  due  manganese  particulate anomalous  31)  in both  Firstly, level  The with  salinity  manganese  similar  values.  associated  This  and  seasonal  intermediate  been  79-07  The  a  50  this  is  particulate  differences.  (1.6  Secondly, at  salinity  conform  mixing  levels.  observed  anomaly  oxidative  intensive  manganese  the  to  sediments.  April,  occurred  However,  to  sediment/water  and  suspended  due  below  local  78-16  respectively.  dissolved  from  of  is  low  processes  had  which  uniformly  from  a  summer  layer  water  underlying  Cruises  the  i f the  concentration  profiles  in  The  southern  enhanced  this  to  the  mixing  not  due  be  via  concentrations  for  generated  the  during  Georgia  mid-depth  1978  m  to  column.  brackish  have  be  higher  May  be  from  to  may  in  manganese  diffusion  of  20  tend  summer  water  and  surface  Strait  due  manganese  horizontally  where  a  Levels  the  the  10  mid-depths  causes  elevated  pattern. profile  at  of  d i s s o l v e d manganese.  winter  depths  during  between  the  Depletion of  than  of  concentrations  precipitation  The  exits  Waters  pycnocline.  during  pycnocline  and  variations.  stability  formation  manganese-rich  manganese  months  the  the  channels.  seasonal  in  lower a  of  sample  surface  in  form  waters  concentration of  10  in  may  October  variations  salinity  manganese  were  ppt  content be  24  ppt,  April. was  4.4  indicative  123  0  PRRT. 1 2 J_mJ  PRRT.  MN (PPB)  of  short  term  from  fluctuations  a  concentrations .from  sediment/water  mentioned,  been  i n t e r f a c e where bottom  elevated  the bottom sediments.  manganese  in  the  in  and  dissolved  manganese  conditions  the  ppm  79-02.  range  The  profiles  waters with  oxides  a l . , 1969;  at  from of  ( F i g u r e 32) a  subsurface  These c h a r a c t e r i s t i c  manganese  ( L i et  Cores were obtained  interstitial  a t a depth of 3 t o 6 cm.  i n d i c a t e the r e d u c t i o n of anoxic  discharge  i n bottom waters at S t a t i o n 15 i n d i c a t e a f l u x of  exhibit concentrations maximum  7  79-07  i n the r a t e of sediment  S t a t i o n 15 d u r i n g C r u i s e s 78-01 dissolved  6  resuspended.  previously  manganese  5  A l t e r n a t i v e l y , t h i s water may have  local  sediments had been As  4  Profiles of suspended p a r t i c u l a t e manganese f o r S t a t i o n 15, C r u i s e s 78-16 and 79-07.  from the F r a s e r R i v e r . advected  3  F i g u r e 31b C r u i s e  F i g u r e 31a C r u i s e 78-16 FIGURE 31 concentrations  1 2  0  3 4 5 6 7 I 1 1 L  MN (PPB)  depth  profiles due to  Holdren e t a l . , 1975).  124  DIS. 1 I  MN  DIS.  (PPB)  1  2 3 4 5 6 7 I I I I L  2  MN  3  4  (PPB) 5  F i g u r e 32b C r u i s e  F i g u r e 32a C r u i s e 78-01  6  7  79-02  FIGURE 32 P r o f i l e s of d i s s o l v e d manganese c o n c e n t r a t i o n s i n interstitial waters of sediments from S t a t i o n 15, C r u i s e s 78-01 and 79-02.  S o l u b l e manganous ion may be i n t r o d u c e d due t o the resuspension  into  overlying  of sediments and/or molecular  waters  diffusion.  5.4 P r o f i l e s a t S t a t i o n s 1, 3, and 25 Depth  profiles  of  S t a t i o n s 1, 3, and 25. similar  and  illustrates  showed  than  manganese  P r o f i l e s a t the northern little  seasonal  were obtained at locations  variations.  a r e p r e s e n t a t i v e example from S t a t i o n 3.  concentrations (less  dissolved  of d i s s o l v e d manganese  at  mid-depths  1 ppb), bottom waters e x h i b i t e d enhanced  to d i a g e n e t i c processes  i n the sediments.  were  F i g u r e 33a While the were  low  l e v e l s due  The f l u x of manganese  from the sediments e n r i c h e d waters 50 m above the bottom.  125  0  DIS.  2  MN ( P P B )  4  6  8  10  12  0  14  PRRT. 2  4  6  MN  (PPB)  8  10 12 14  F i g u r e 33b P a r t i c u l a t e Mn  F i g u r e 33a D i s s o l v e d Mn  FIGURE 33 P r o f i l e s of d i s s o l v e d and suspended p a r t i c u l a t e manganese c o n c e n t r a t i o n s f o r S t a t i o n 3, C r u i s e 79-07.  The  concentrations  steadily the  of  suspended  particulate  manganese  i n c r e a s e d with depth a t t h i s time ( F i g u r e 33b).  data  oxidative  do not c l e a r l y  i n d i c a t e whether t h i s r e s u l t s from the  precipitation  of  resuspension  manganese  of bottom sediments.  in  situ  and/or  IX).  I t i s worth n o t i n g that t h i s area  of manganese nodule formation Concentrations at  Station  25  observed i n the northern 1.0  ppb  were  observed  X)  sediments  i s a known s i t e  i n the S t r a i t of G e o r g i a .  of d i s s o l v e d manganese i n the  (Table  the  These f i n e - g r a i n e d sediments  have a h i g h e r Mn:Al r a t i o than observed f o r e s t u a r i n e (Table  Again,  were  generally  p o r t i o n of the only  higher  strait.  i n February 1979.  suggest t h a t there may be a s i g n i f i c a n t  water  f l u x of  than  Levels  column those below  Bottom samples manganese  from  126  TABLE  X  Dissolved  Manganese  D i s s o l v e id  Depth (m)  the  sediments.  intense (Figure levels  4),  during water  river and m  i n the Cruise  i n the  curve)  the  1 1 1  76 37 55  0 1 2  99 02 09  at  --  secondary due  cause  to  the  different In  the  of  coupled  p r o x i m i t y of high  such  Figure  the  the  from  Samples  mixing  Strait  mixing with  of  83 62 41 94 44 23 44 36 89  Boundary  dissolved  dilution  29,  79--12  manganese,  Similarly,  of  (ppb)  5 2 2 1 1 1 1 1 1  •  c o n c e n t r a t i o n s g r e a t e r than  bottom.  25.  10 87 46 46 46 23 14 14 09  manganese  section  curve).  1 0 0 0 0 0 0 0 0  relatively  distinguished  (upper  Station  79--02  source  mid-depths.  79-12.  be  manganese  above  43 86 69 55 41  northern  can mouth  2 2 1 1 1  mixing  may  observed  manifest  81 64 39 81 72  This  vertical  78- -07  2 2 1 2 1  --  from  M a n g a n e s e C o n c e n t r a t i c )ns  78- -01  . 1 5 10 25 50 75 100 150 Bottom  Data  with  Passage  manganese  p r o c e s s e s may curves of  be  observed  Fraser  Georgia  River (lower  processes  south  of  the  salinities  above  30  ppt  3 ppb  were  collected  1  127  5.5  Summary  The waters is  distribution of the S t r a i t  the  major  determined Secondary at  sources 7  by  of manganese  of S t . Lawrence of d i s s o l v e d  Levels intense  tidal  of  summer.  These  are  during  discharge)  discharge. the  summer  and S t a t i o n  dissolved  of Georgia sediments  is  3.  manganese  similar  a c t as a  manganese  the pycnocline causes  from  to  the  significant  concentrations  processes  may  which  i n the northern  at mid-depths are  of the during  enhanced  i n the southern  d i s s o l v e d manganese  processes  Concentrations  r e m o b i l i z a t i o n o f manganese  bottom  below  mixing  manganese  surface River  the river  enhanced  dissolved  mixing  dissolved  the  manganese.  depleted  winter  Similarly,  for  of  by v a r i a t i o n s i n t h e s t a b i l i t y  are  in  the Fraser  observed  River  the S t r a i t since  Concentrations determined  were  have  Thus,  metal.  dilution  due t o r e d u c t i v e  sediments.  manganese  indicates that  this  the  waters  concentrations  source  of  ( p o s s i b l y Squamish  Bottom  Gulf  dissolved  of Georgia  source  largely  Station  the  of  for  and southern  t h e summer b u t  causes  at mid-depths  differ  column.  concentrations.  passages  be m a n i f e s t  water  even  enhanced  during  i n the d i l u t i o n Fraser  extremes  River  the  curves mixing  of the S t r a i t  of  Georgia. Finally, indicate from  profiles  of  suspended  increasing concentrations  the  resuspension  oxidative of bottom  with  precipitation sediments.  of  particulate depth.  This  manganese  manganese may  result  and/or  the  128  6_;_  The  Fraser  varying  zone. to  The  the  appeared Two  examined,  estuarine  the  seem  an  of be  cannot  at  other  that  mixtures  of  fresh  and  from  physical  manganese  on  dissolved sediment  a  geochemical particulate cannot  be  Suspended initial does  not  dry  saline  fall  under  manganese  initial  mixing  from  cruise  the  one  Fraser  excess  out  River  manganese  material  of  the  and  in  for  i n the  at  and some the  and  between  times  suspended  manganese the  the  significantly  year,  i n the  alone. only  River 1.7  account  to  as  even  for  24  mg/1.  estuary.  the  A  suspended manganese  with  complete  manganese.  conservatively  particulate  ppm  suspended  dissolved  particulate  behaves  suspended  to  results  riverborne  "excess"  of  with  Estuary 10  manganese  concentrations in  released  of  would  Experimental  agree  Fraser  estuarine  the  processes  range  suspended this  year.  manganese  the  dissolution  freshet,  the  waters  basis,  that  riverborne  account  mixing  balance  particulate  change  to  dissolved  peak  a l l  zone  ruled  insufficient  manganese  mixing  this  weight  mass  of  of  water  often  attained  dissolution  varied  in estuarine  manganese loads  the  suspended  from  times  indicates  suspended  be  during  mechanism  evidence  sediment  of  riverborne  significant  observed  anticipated  in  peak  sources  times  dissolved  independent  manganese  unlikely  enrichment  this  be  potential  possibility  may  observed  five  sediments.  desorption  particulates  maximum  of  to  namely,  bottom  While or  but  rate.  A  salinity  F U T U R E WORK  investigated  consistently  specific  AND  was  regimes. was  next  discharge were  Estuary  flow  concentration  CONCLUSIONS  Mn:Al  in  the  ratio  The c o n c e n t r a t i o n  129  of  total  least  manganese  two  also  well-oxygenated,  oxides  associated  field  observed  in  dissolved  the  of  influenced  (or  to  having  situ  of  these  estuarine these  the  salinity Fraser  on a t Estuary  d i s s o l u t i o n of  suspended  i n the s a l t salinity.  manganese  p a r t i c u l a t e s i s not  high  in  i s suggested oxalate  surficial  sediments,  lower  Fraser  a  manganese  estimates  of bedload  transport  also  downstream  be  due  decrease in  ratios  in  suspended  required  i n the system  to  content  Mn:Al  bedload  in the Fraser  sediments  occurrence  in riverborne  balance  of  The  observed  achieve  tidal While  manganese  with  the c a l c u l a t e d  in  of i n t e r s t i t i a l  together  Furthermore,  surface  the  may  manganese  particulates. mass  to  oxides.  general  of  content  enrichment  extractable  than  in  resuspended  the release  manganese  estuarine  Estuary.  of d i s s o l v e d  by  levels  manganese  these  by  from  coupled  manganese  extent  ammonium  sediments  the  manganese  concentration  exceeds  be  from  of amorphous  the  Enhanced  concentrations  processes  year  to  dissolved  be d e r i v e d  wedge  appears  lesser  may  the  responsible,  a  the excess  waters  dissolution)  reduction  the  that  sediments  primarily  in  riverborne  Throughout  waters  desorption  waters  the reductive  surface  of comparable  be  because  suggest  manganese  resuspension  in  data the  bottom  must  with  sediments.  waters  Finally,  a t low  thermodynamically.  The  bottom  a maximum  occasions.  remains  favoured  exhibits  agrees  Estuary  to with  (Pretious,  1972). The waters  of  dilution  distribution the curves  Fraser which  of  dissolved  Estuary  manganese  consists  of  two  i n t e r s e c t at the s a l i n i t y  i n the  surface  conservative and  manganese  130  concentration The of  water river  The  corresponding  properties  water  entrainment  conservative surface  member  curve  dioxide,  the  the  Despite  exhibit  relatively may  be  the  Fraser  behaviour  of  at  alkalinity; strengths  manganese  may  the  year  wedge.  low  salinities  the  high  between  in  salinity the  the the  region  sea  water  end  to  manganese  salinity. respect  reaches  of  the  estuary  did  manganese.  Furthermore,  also  conservatively  short  tend during  estuary. oxygen  the  behaved Mn:Al  ratios  precipitation  residence  errors  to  alkalinity  range  salinities  may in  the  in  be the  exaggerate  time  of  of  the in  remained manganese waters  in  technique  the  extent the  Fraser  calculated  for  salt  in  estuarine  summer waters  of  these  wedge  months  water  is modified  low  of  ionic  oxygen The  waters  the  removal  removal.  Estuary.  oxygen-depleted  the  at  Anomalous  the  dissolved  the  During  conservatively  estuary.  a t t r i b u t e d to  freshet,  of  behaves  the  in  horizontal advection  processes.  salt  at  with  oxidative  salinity  conservatively  dissolved  the  mixing  establishes  particulate  the  of  the  water  low  lower  dissolved  to  the  low  undersaturation  the  the  The  due  however,  Except  the  in  toe  by  maximum.  Estuary.  most  behaves  of  constant.  undetected  in  at  determined  the  mixing  maximum  suspended  Throughout through  waters  particulate and  curve  supersaturated  removal  region  from  observed  subsequent  being  are  bottom  dilution  manganese  surface  suspended this  mixing  d i s s o l v e d manganese  peak  water  this  from and  saline  The  the  this  of  waters.  results  not  with  of  to  also oxygen  results from  outside  concentration by  from  of  biological  131  The surface which  distribution waters  persists  variations constants observed Koene  pH  estuary and  pH  throughout  the  the  minimum  waters  acid  can  only  are  depleted  be  as  two pH  consistent with  dependence  of  the  the  from  the  Strait  of  sampling  oxygen  concentrations  related  primary  productivity  metal  for  determined in  the  the  strait.  stability Depth increasing  are of  the  the  Fraser  to  of  waters  have  reductive  determined  profiles  of  by  Mook  waters  the  from  and  of  the  the  salt of  low wedge  oxygen  River  the  during  January  period.  The  seasonal  a  1978 the  pH  and  variations  processes.  manganese  in  i s the  the  major  surface source  Concentrations Fraser  enhanced  of  of  the  conservatively in  mixing  of  However,  collected  River  dissolved  r e m o b i l i z a t i o n of  Concentrations  water  were  Georgia.  dilution  to  dissociation  advection  displayed  and  zone  Estuary.  time  dissolved  the  Bottom due  this  Strait  by  sediments.  mid-depths  of  that  mainly  concentrations the  throughout  in  the  attributed  Finally,  observed  behaved  dissolved  this  process.  alkalinity  Georgia  indicated  surface  extending  of  waters  the  period  Strait  distribution  in  model  in  mixing  1975).  the  Georgia  May  The  The  by  Fraser  until  to  1979.  Koene,  horizontal  outside  month  and  values  from  seventeen  initial been  stage  the  salinity  has  replicated  a  the  to  This  waters  Data  in  year.  mixing  uniform  respect  minimum  (Mook  when  is considered  relatively  with  salinity  carbonic  (1975)  pH  displays a  in of  of  dissolved  seasonal  are  discharge manganese  manganese manganese  variations  of  in  from at the  column. suspended  concentrations  with  particulate  depth.  This  manganese  may  result  indicate from  the  132  oxidative bottom  precipitation  future  a consequence  removal  appropriate  of a l k a l i n i t y  of  has  Estuary.  Manganese  influenced  been  by  sediments.  wedge.  waters  of  of  distribution  of  in  order  chemistries  may  be  chemistry and with  However, of t r a c e  suspended the  to  coupled  to  should  from in  i n both of  establish to that  c a n be  desorption  waters,  similar  of  of manganese  determined  Zn) i n  sediments  components a r e examined  wedge  should  t o which in  work, only  The  the salt  extent  in this  and  the  bottom  sediments  the  of the  influence  the  in  anoxic  anticipated.  the waters  estuarine  of  N i , Pb,  be  be  estuarine  waters  may  surface  Fraser  examined  by  estuarine  might  the  Since  resolve  may  the p o s i t i o n  oxides  the More  i n the  be  of  Secondly,  waters  (Co, Cu,  as demonstrated metals  employed  within  1978).  metals  metals  particulate  sediments.  Hem,  enrichment  determined  Estuary.  metals  1968;  waters  zone.  influenced  manganese  manganese  such  be  indicate  mixing  surface  sediments  sediments  other  interstitial  in  to determine  hydrous  (Jenne,  data  avenues  salinities.  processes  several  significant  enhancement  and  to those  of  dissolution  causes  enrichment  Thirdly,  low  three  t o behave c o n s e r v a t i v e l y  particularly  in relation  might  at  Accordingly, these  detail,  natural  shown  presented,  Firstly,  techniques  diagenetic  concentrations  or  the r e s u s p e n s i o n of  i n the i n i t i a l  alkalinity  manganese  greater  suggested.  analytical  behaviour  zones  of the r e s u l t s  r e s e a r c h c a n be  possible  salt  and/or  sediments.  As  the  of manganese  the  the  when  be their  Fraser  estuarine dissolved  in conjunction  133  7.  BIBLIOGRAPHY  Abbey, S., ( 1 9 8 0 ) . 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An i m p r o v e d L i m n o l . O c e a n o g r . , 12, 163-165.  interstitial  of the in coastal  Advan.  Geophy.  water  sampler.  R i l e y , J . P . , ( 1 9 5 8 ) . The r a p i d a n a l y s i s o f silicate m i n e r a l s . A n a l . C h i m . A c t a , 1_9, 4 1 3 - 4 2 8 .  rocks  and  Sanders, J.G., (1978a). The s o u r c e s o f d i s s o l v e d manganese t o C a l i c o Creek, North C a r o l i n a . E s t . Coast. Mar. S c i . 6, 231-238. Sanders, J.G., (1978b). The s o u r c e s of d i s s o l v e d manganese t o C a l i c o Creek, North C a r o l i n a : A reply. E s t . Coast. Mar. Sci. 7, 5 7 9 - 5 8 0 . Sayles, F . L . and Mangelsdorf, P.C. J r . , (1977). The e q u i l i b r a t i o n of c l a y m i n e r a l s w i t h sea water : exchange r e a c t i o n s . G e o c h i m . C o s m o c h i m . A c t a , 4_1, 9 5 1 - 9 6 0 . Schwertmann, U., (1964). Differenzierung der E i s e n o x i d e des Bodens durch Extraktion mit Ammoniumoxalat-losung. P f l a n z e n e r n a h r . Dung. Bodenkunde, 105, 194-202. Sholkovitz, E.R., ( 1 9 7 6 ) . F l o c c u l a t i o n o f d i s s o l v e d o r g a n i c a n d i n o r g a n i c matter d u r i n g mxing of r i v e r water and sea water. G e o c h i m . C o s m o c h i m . A c t a , 4_0, 8 3 1 - 8 4 6 . S h o l k o v i t z , E.R., ( 1 9 7 8 ) . T h e f l o c c u l a t i o n o f d i s s o l v e d F e , Mn, Al, Cu, N i , Co and Cd during estuarine mixing. Earth P l a n e t . S c i . L e t t . 41, 77-86. Sholkovitz, E.R., (1979). Chemical and physical processes controlling the chemical composition of suspended material i n t h e R i v e r T a y E s t u a r y . E s t . C o a s t . M a r . S c i . 8, 5 2 3 - 5 4 5 . S h o l k o v i t z , E.R. a n d Price, N.B., (1980). The major-element chemistry of suspended matter i n t h e Amazon estuary. G e o c h i m . Cosmochim. A c t a , 44, 163-171. S i e v e r , R., ( 1 9 6 8 ) . and s e a water.  E s t a b l i s h m e n t of e q u i l i b r i u m between E a r t h P l a n e t . S c i . L e t t . 5, 1 0 6 - 1 1 0 .  clays  Skirrow, G., (1975). The dissolved gases-carbon d i o x i d e , In " C h e m i c a l O c e a n o g r a p h y " , ( J . P . R i l e y a n d G. S k i r r o w , e d s . ) . Vol 2, A c a d e m i c P r e s s , L o n d o n , p p . 1 - 1 9 2 . S p e n c e r , D.W. a n d S a c h s , P.L., (1970). Some aspects of the distribution, c h e m i s t r y and mineralogy of suspended matter  138  in  the  Gulf  of  Maine.  Mar.  Geol.  9,  117-136.  Stumm, W. a n d M o r g a n , J . J . , ( 1 9 7 0 ) . "Aquatic W i l e y & S o n s , I n c . , New York, pp. 583.  Chemistry",  Subramanian, K.S., C h a k r a b a r t i , C.L., Sueivas, J.E. I . S . ( 1 9 7 8 ) . P r e s e r v a t i o n o f some t r a c e m e t a l s o f n a t u r a l w a t e r s . A n a l . Chem. 50, 4 4 4 - 4 4 8 .  and in  John  Maines, samples  Subramnian, V. a n d d'Anglejan, B., (1976). Water c h e m i s t r y t h e S t . L a w r e n c e e s t u a r y . J o u r . H y d r o l . 29, 3 4 1 - 3 5 4 . S u n d b y , B., coastal  (1977). Manganese-rich particulate matter m a r i n e e n v i r o n m e n t . N a t u r e , 270, 417-419.  in  of  a  Tanner, G., Trasolini, G. a n d N e m e t h , L . , ( 1 9 7 3 ) . A s t u d y on wastewater characteristics of greater Vancouver sewage treatment plants a n d m a j o r s e w e r s . EPS R e p o r t 5-PR-73-11, E n v i r o n m e n t a l P r o t e c t i o n S e r v i c e s , P a c i f i c R e g i o n , pp. 223. T h o m a s , D . J . a n d G r i l l , E.V., (1977). The effect of exchange reactions between Fraser R i v e r sediment and sea water on dissolved Cu and Zn concentrations in the Strait of G e o r g i a . E s t . C o a s t . M a r . S c i . 5, 4 2 1 - 4 2 7 . Tully, J.P. and Dodimead, A . J . , ( 1 9 5 7 ) . P r o p e r t i e s of the water i n the S t r a i t of G e o r g i a , B r i t i s h Columbia, and influencing f a c t o r s . J . F i s h . R e s . B d . C a n a d a , 1±, 241-319. U n i v e r s i t y of B r i t i s h Columbia, ( 1 9 7 9 ) . D a t a R e p o r t 45, British Columbia Inlet Cruises 1978. U.B.C. Institute of O c e a n o g r a p h y . , p p . 68. ( U n p u b l i s h e d m a n u s c r i p t ) . U n i v e r s i t y of B r i t i s h Columbia, ( 1 9 8 0 ) . D a t a R e p o r t 47, British Columbia Inlet Cruises 1979. U.B.C. Department of O c e a n o g r a p h y . , pp. 77. ( U n p u b l i s h e d m a n u s c r i p t ) . W a l d i c h u k , M., Georgia, 321-486.  (1957). British  P h y s i c a l oceanography of Columbia. J . F i s h . Res.  the Bd.  Strait Canada,  of 14,  Water  Survey of Canada, measured at Hope sheet.  (1978). Fraser a n d M i s s i o n , B.C.  River discharge Computer p r i n t o u t  rate data  Water  Survey of Canada, measured at Hope sheet.  (1979). Fraser a n d M i s s i o n , B.C.  River discharge Computer p r i n t o u t  rate data  W e i s s , R.F., ( 1 9 7 0 ) . The solubility of nitrogen, oxygen and a r g o n i n w a t e r a n d s e a w a t e r . D e e p S e a R e s . 1/7 , 7 2 1 - 7 3 5 . Windom, H.L., Beck, K.C. a n d S m i t h , R., (1971). t r a c e metals t o the A t l a n t i c Ocean by three r i v e r s . S o u t h e a s t e r n G e o l o g y , 1_2, 1 6 9 - 1 8 1 .  T r a n s p o r t of southeastern  139  Wollast, R., B i l l e n , G. A n d D u i n k e r , J . C , ( 1 9 7 9 ) . B e h a v i o u r o f manganese i n the Rhine and Scheldt Estuaries. I. Physico-Chemical aspects. E s t . Coast. Mar. S c i . , 9, 161-169. Wong,  G.T.F., (1979). Alkalinity and pH Chesapeake Bay and t h e James River O c e a n o g r . 24, 9 7 0 - 9 7 7 .  Y e a t s , P.A., S u n d b y , B. a n d Bewers, J.M., r e c y c l i n g i n c o a s t a l w a t e r s . M a r . Chem.  i n the Estuary.  (1979). 8, 4 3 - 5 5 .  southern Limnol.  Manganese  140  APPENDIX  A  Summary  APPENDIX  of S t a t i o n  A . l Station  Stat ion Number  1< 2 3< 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25< 26  1  ( 1  1  > i >  >  Positions  Positions  (1) C o m p l e t e stat ions  i n the S t r a i t  North Lat i tude  of  Programme Georgia  West Longitude  49° 49° 49° 49° 49° 49° 49° 49° 49° 49° 49° 49° 49° 49° 49° 49° 49° 49° 49° 48 48° 48° 48° 48° 48° 48°  26.0' . 21.8' 16.6' 18.5' 18.5' 18.5' 18.5' 14.2' 14.2' 14.2' 14.2' 09.9' 09.9' 09.9' 05.6' 05.6' 05.6' 01.3' 01.3' 57.0' 54.4' 57.2' 54.2' 54.5' 49.5' 45.2'  124° 124° 123° 123° 123° 123° 123° 123° 123° 123° 123° 123° 123° 123° 123° 123° 123° 123° 123° 123° 123° 123° 123° 122° 123° 122°  depth  profile  taken  0  >  and Sampling  27.5' 09.0* 48.4' 42.0' 34.0' 27.5' 21.5' 21.5' 27.5' 34.0' 42.0' 34.0' 27.5' 21.5' 21.8' 27.5' 34.0' 27.5' 18.5' 18.5' 18.2' 07.0' 09.0' 53.5' 01.0' 48.0*  at  these  APPENDIX  A.2  Station  Stat ion Number  •  50 51 52 53 54 55 56 56.3 57 58 58.3 59 60 61 62 63 64 65 67 70  Positions  i n the Fraser  North Latitude  49° 49° 49° 49° 49° 49° 49° 49° 49° 49° 49° 49° 49° 49° 49° 49° 49° 49° 49° 49°  06.00' 06.00' 06.00' 06.25' 07.18' 07.93' 07.44' 07.00' 06.60' 06.45' 06.60' 06.85' 07.85' 08.90' 09.35' 09.30' 10.32' 12.28' 12.70' 10.8'  Estuary  West Longitude  123° 123° 123° 123° 123° 123° 123° 123° 123° 123° 123° 123° 123° 123° 123° 122° 122° 122° 122° 122°  20.0' 19.30' 18.78' 18.00' 16.00' 14.0' 12.0' 11.2' 09.6' 07.55' 07.45' 05.5' 03.85' 02.0' 00.1' 57.1' 55.35' 53.88' 53.20' 34.0'  142  APPENDIX  Cruise  A.3  Water  Sampling  Ship  Dates  Programme  S t r a i t of Georgia  Fraser Estuary  Stn  1978  78-01  Jan  9-12  CFAV  78-04  Mar  22  78-07  May  29-30 CFAV  Endeavour  78-10  Jun  30  CSS  Vector  78-11  Jul  19  Brisk  78-12  Aug  10  CSS  Vector  78-13  Sep  21  CSS  Vector  78-16  Oct  16-20  CSS  Vector  78-20  Dec  CSS  Vector  CSS  Vector  CSS  5  Endeavour  X  X  Vector  X X  X X X  X X Stn  1 X  X X  1979  79-01  Jan  2-5  •  79-02  Feb  6  79-05  Mar  13  CSS  Vector  79-07  Apr  4-5  CSS  Parizeau  79-12  May  28-31  CSS  Vector  MV  Pandora  X II  Stn  X 25  X X X  Stn  3 X  X X  X  15  143  APPENDIX  Collection  Shipek Grab  A.4  Sediment  Date  Sampling  Programme  Station Number  Depth (m)  Salinity (ppt)  51 52 3 15 53 54 55 56 59 65  100 50 420 212 35 13 11 11 11 11  29.925 29.825 30.939 30.714 30.027 28.143 0.0 0.0 0.0 0.0  190 215  30.225 30.631  7 9 9 15 13 13 18 17 16 13  27.143 25.439 23.619 21.288 11.579 13.101 0.0  Jan  12/78  May May May  28/79 29/79 30/79  Gravity Corer  Jan Feb  12/78 6/79  15 15  Divers  Feb  29/79  Jan  22/80  Jan  25/80  56.2 57.2 59.0 56.2 57.2 59.0 60.5 62.2 62.5 67.0  144  APPENDIX  B Data  APPENDIX  Cruise  78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01  Stn  1 .0 1 .0 1 .0 1 .0 1 .0 1 .0 1 .0 1 .0 1 .0 2 .0 2 .0 3 .0 3 .0 3 .0 3 .0 3 .0 3 .0 3 .0 3 .0 3 .0 4 .0 4 .0 5 .0 5 .0 6 .0 6 .0 7 .0 7 .0 8 .0 8 .0 9 .0 9 .0 10 .0 10 .0 11 .0 11 .0 12 .0 12 .0 13 .0 13 .0 14 .0 14 .0  (1)  Summary  of Aqueous  B.l Dissolved  Samples  Constituents  Depth (m)  Temp ( °C)  Salinity (ppt)  Oxygen (ml/1)  PH  1 5 10 25 50 100 200 300 390 1 5 1 5 10 25 50 100 200 300 392 1 5 1 5 1 5 1 5 1 5 1 5 1 5 1 5 1 5 1 5 i 5  5.98 6.28 7.23 8.04 8.22 8.95 9.23 9.02 N A 5.83 5.87 6.73 6.78 6.73 7 .73 8.54 8 . 72 9.19 9.25 N A 5.73 5.65 5. 57 5.73 6.16 6.40 7.34 7.34 7.41 7.61 5.50 5.65 4.91 4.93 5.01 •5. 05 5.41 5.45 5. 67 5.71 5.72 7.36  27.582 27.812 28.659 29.242 29.585 30.233 30.910 31.098 31.098 27.405 27.405 28.350 28.303 28.309 28.804 29.744 30.321 30.910 31.107 N A 26.597 26.615 26.618 26.666 27.588 27.766 28.229 28.607 28.243 28.528 26.731 26.831 26.351 26.344 26.429 26.339 26.593 26.596 26.694 26.738 21.857 28.361  6.78 6.68 6.07 5. 39 4.86 3.89 3.52 3.30 3.00 6.85 6.85 6.63 6.63 6.60 5.86 5. 01 4.78 3.47 3.48 N A 7.01 7.08 7.04 7.00 6.59 6.44 5.99 5.96 6. 06 5.88 6.99 6. 93 7.22 7.23 7.20 7.26 7.01 7.01 6.99 7.00 6.80 6.15  7.73 7.73 7.71 7.72 7.69 7.64 7.64 7.60 7.60 7.76 7.77 7.76 7.78 7.78 7.73 7.68 7.69 7.62 7.62 " N A 7 . 76 7 . 77 7.76 7 .77 7.74 7.77 7.75 7.74 7.69 7.67 7.77 7.78 7.77 7.78 7.74 7.78 7.74 7.75 7.76 7.74 7.70 7.74  N A  = No  1  Analysis  Alk D i s Mn (meq/1) (ppb) 2.03 2.09 2.15 2.10 2.12 2.21 2.20 2.26 2. 22 2. 04 2 . 00 2.04 2.22 2.05 2.06 2.11 2.13 2 .17 2.19 N A 1.96 1.96 1.96 1.96 2 . 00 2.00 2.03 2.05 2.03 2.04 1.97 1. 97 1.93 1.94 1.94 2.03 1.95 1.95 1.97 1.95 1.84 2.02  2.60 1.43 0.82 0.49 0.47 0.41 1.07 1.78 6.81 2.53 N A 1.14 2.53 1.21 0.48 0.39 0.64 0.52 1.50 7.91 4.08 N A 4.12 N A 2.25 N A 2.02 N A 2.65 N A 3.12 N A 3.57 N A 3.34 N A 3.22 N A 3.47 N A 9.29 N A  145  Cruise  78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01 78-01  Stn  15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 16. 0 16. 0 17. 0 17. 0 18. 0 18. 0 19. 0 19. 0 20. 0 20. 0 21. 0 21. 0 22. 0 22. 0 23 . 0 23. 0 24. 0 24. 0 25. 0 25. 0 25. 0 25. 0 25. 0 25. 0 25. 0 25. 0 26. 0 26. 0 51. 0 51. 0 52. 0 52. 0  Depth (m)  Temp (° C)  1 5 10 25 50 100 150 188 1 5 1 5 1 5 1 5 1 5 1 5 1 5 1 5 1 5 1 5 10 25 50 100 150 210 1 5 1 100 1 50  6. 37 6. 77 7. 45 7. 62 7. 66 7. 51 7. 69 N A 5. 49 5. 68 5. 44 5. 52 5. 96 6. 12 7. 00 7. 32 5. 83 6. 22 6. 18 6. 28 7. 39 7. 41 7 . 41 7. 48 7 . 25 7. 37 6. 94 6. 97 7 . 57 7. 60 7. 57 7. 54 7 . 63 N A 7. 53 7. 57 N A N A N A N A  Salinity (ppt) 26 27 28 29 29 30 30 30 25 26 26 26 27 26 27 28 25 26 26 26 29 29 29 29 29 29 28 28 28 29 29 29 30 30 29 29 20 29 23 29  .014 .165 .308 .636 .886 .051 .138 .225 .630 .467 .553 .613 .024 .993 .937 .652 .382 .736 .497 .620 .706 .658 .555 .619 .213 .309 .102 .059 .923 .604 .793 .899 .039 .143 .822 .823 .702 .925 .734 .825  Oxygen (ml/1) 6.63 6.36 6.00 5.70 5.55 5.74 5.59 5.23 7.02 6.98 • 7.04 7.02 6.63 6.63 6.15 5.96 7.00 6.74 6.73 6.68 5.90 5.90 5.89 5.83 6.01 5.94 6.16 6.25 5.76 5.70 5.70 5.75 5.70 5.52 5.79 5.77 N A N A N A N A  pH  7.72 7.76 7.73 7.75 7.75 7.78 7.77 7.76 7.76 7.74 7.76 7.76 7.78 7.77 7.74 7.75 7.71 7.73 7.74 7.73 7.73 7.73 7.74 7.73 7.74 7.74 7.72 7.74 7.69 7.70 7.71 7.72 7.73 7.73 7.73 7.74 7.69 7.72 7.69 7.70  Alk meq/1 1.99 2.04 2.13 2.11 2.10 2.31 2.18 2.14 1.93 1.98 1.97 1.94 1.97 1.97 2.02 1.93 1.93 2.00 1.77 1.98 2.10 2.18 2.10 2.14 2.09 2.09 2.07 2.03 2.08 2.10 2.15 2.23 2.14 2.13 2.11 2.12 1.74 2.13 1.84 2.12  D i s Mn (ppb) 8.63 7.55 1.96 1.56 1.04 1.84 1.38 2.44 5.52 N A 3.80 N A 3.26 N A 5.01 N A 6.76 4.85 5.51 4.66 2.03 4.43 1.99 1.77 2.54 2.22 2.81 2.64 1.39 2.81 1.72 1.76 1.37 1.55 N A 1.55 4.16 3.07 8.82 4.87  146  Cruise  78-04 78-04 78-04 78-04 78-04 78-04 78-04 78-04 78-04 78-04 78-04 78-04 78-04 78-04 78-04 78-04 78-04 78-04 78-04 78-04. 78-04 78-04 78-04 78-04 78-04 78-04 78-04 78-04 78-04 78-04 78-04  Stn  15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 53.0 53.0 54.0 54.0 55.0 55.0 56.0 56.0 57.0 57.0 58.0 58.0 59.0 59.0 61.0 61.0 63.0 63.0 65.0 65.0  Depth  (m)  1 5 10 20 25 30 50 75 100 150 177 1 12 1 16 1 20 1 13 1 17 1 17 1 6 1 12 1 12 1 16  Temp  CO  8.66 8.59 8.57 8.01 7.87 7.84 7.86 7.93 7.96 8.09 N A 7.44 7.41 6.74 6.80 6.81 6.78 6.54 6.53 6.54 6.33 6.59 6.50 6. 36 6.33 6.09 6.14 6.05 6.11 6.08 6.11  Salinity  (ppt)  26.837 27.356 27.379 28.424 29.085 29.551 29.789 29.951 30.019 30.187 30.296 12.634 29.712 7.649 28.469 5.970 28.392 5. 364 27.495 4.028 24.622 2.226 23.425 2.055 21.378 0.039 14.444 0.0 0.0 0.0 0.0  Oxygen  pH  (ml/1) 6.81 6.52 6.73 6.90 5.68 5.74 5.60 5.79 5.73 5.45 5.55 7.24 5.42 8.00 5.72 8.22 5.70 8.27 5.84 8.43 6.18 8.62 6.18 8.60 6.43 8.88 7 .22 8.90 8.91 8.91 8.92  Alk  meq/1 7 .71 7 .77 7 .72 N A 7 .60 N A 7 . 63 N A 7 .71 7 .69 7 .68 7 . 58 7 . 63 7 . 64 7 .69 7 .60 7 .60 7 .58 7 .62 7 .59 7 .64 7 . 60 7 .65 7 . 60 7 .60 7 .65 7 . 56 7 .70 7 .66 7 .68 7 .73  N A 1.99 2.02 N A 2.08 N A 2.12 N A 2.13 2.13 2.16 1.52 2.10 1. 37 2.06 1.37 2.07 1.32 2 . 01 1. 20 1. 92 1. 24 1.88 1.26 1.82 1.22 1.59 1.31 1.20 1.18 1.19  D i s Mn  (ppb)  4.12 N A 1.29 N A 1.33 N A 0. 37 N A 0.87 1.01 1.43 13.4 4.49 14.5 2.77 14.8 2.52 17.1 3.28 17.6 6.91 16.6 7.68 16.2 10.2 11.4 14.7 11.1 13.0 9.97 11.7  147  Cruise  78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07 78-07  Stn  1. 0 1. 0 1. 0 1. 0 1. 0 1. 0 1. 0 1. 0 1. 0 2. 0 2. 0 3. 0 3. 0 3. 0 3. 0 3. 0 3. 0 3 .0 3. 0 3 .0 4. 0 4. 0 5. 0 5. 0 6. 0 6. 0 7. 0 7 .0 8. 0 8. 0 9. 0 9. 0 10. 0 10. 0 11. 0 11. 0 12. 0 12. 0 13. 0 13. 0 14. 0 14. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 16. 0 16. 0 17. 0  Depth  (m)  1 5 10 25 50 100 200 300 324 1 5 1 5 10 25 50 100 200 300 420 1 5 1 5 1 5 1 5 1 5 1 5 1 5 1 5 1 5 1 5 1 5 1 5 10 25 50 100 150 180 1 5 1 .  Temp  CO  13.26 12.21 10.80 9.50 8.87 8.44 8.95 9.15 N A 13.37 12.94 12.60 12.12 10.47 8.85 8.33 8.35 8.79 9.00 N A 12.09 11.85 12.70 12.19 11.91 10.94 12.71 10.86 12.61 10.15 12.35 11.61 12.41 12.24 12.41 12.45 12.45 11.42 13.79 13.05 12.41 12.24 13.55 13.23 10.21 8.74 9.16 8.69 8.81 N A 12.96 13.03 12.91  Salinity  (ppt)  26.165 26.912 28.590 29.445 29.717 29.979 30.743 30.942 30.966 26.015 26.176 25.918 26.810 28.627 29.450 29.743 30.072 30.622 30.872 30.975 26.629 26.806 24.975 25.959 25.027 27.183 18.256 26.855 20.440 27.992 25.379 27.330 21.641 27.315 25.844 25.845 22.995 27.193 21.472 24.537 21.641 27.315 19.574 21.894 28.551 29.519 29.901 30.165 30.552 30.643 22.082 22.170 20.224  Oxygen  pH  (ml/1) 7.96 9.16 6.70 5.32 4. 59 4.05 3.33 2 . 24 2.63 7.71 7.80 9.17 9. 38 6.98 5.06 4.55 4.73 4.16 3.15 3.73 9.02 9.43 8.29 8.18 7.33 6.69 7.49 5.89 7.55 5.78 7.45 7.84 7.49 5.96 8.26 8.23 8.06 8.66 7.94 8.46 7.49 5.96 8.43 8.60 6.07 5.18 5.18 5.00 4.67 4.22 8.70 8.66 8.79  Alk  meq/1 8 .32 8 .36 7 .96 '7 .70 7 .58 7 .51 7 .51 7 .48 7 .48 8 . 30 8 .28 8 .39 8 .31 7 .97 7 .64 7 . 56 7 .62 7 .60 7 .51 7 .58 8 .33 8 .32 8 .29 8 . 25 8 .15 7 .99 8 .27 7 .83 8 .25 7 .83 8 .24 8 .09 8 .25 8 . 02 8 .36 8 .37 8 .27 8 .21 8 .39 8 .35 8 .20 7 .86 8 .40 8 .43 7 .88 7 .69 7 .76 7 .70 7 .68 7 .65 8 .39 8 .40 8 .42  1.91 1.95 2.00 2.06 2.03 N A 2.06 2.08 2.24 1.90 1.87 1.85 1.95 1.99 2.06 2.00 2.01 2.11 2.11 2.13 1.95 1.87 1.85 1.90 1.70 1.92 1.35 1.91 1.43 1.91 1.81 1.95 1.81 2.00 1.59 1.85 1.70 1.95 1.21 1.82 1.63 1.94 1.48 1.65 1.95 1.99 2.04 2.06 2.07 2.07 1.69 1.69 1.63  D i s Mn (ppb) 2.88 2.26 1.04 0.45 0.25 2. 65 1 07 0.71 5.70 40 36 84 54 54 61 02 34 30 80 02 80 .41 .54 92 4.96 1 69 6 53 3 66 4 73 1 15 4 58 1 89 4 52 1 83 3 01 2 96 4 55 1 65 4 23 2 45 6 41 2 96 7 95 11 7 4 96 2 14 6 06 6 20 2.48 8.57 5.35 5.35 7.03  148  Cruise  7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - 07 7 8 - •07  Stn  17. 0 18. 0 18. 0 19. 0 19. 0 20. 0 20. 0 21. 0 21. 0 22. 0 22. 0 23. 0 23. 0 23. 5 23. 5 24. 0 24. 0 25. 0 25. 0 25. 0 25. 0 25. 0 25. 0 25. 0 25. 0 26. 0 26. 0 53. 0 54. 0 55. 0 56. 0  Depth (m) 5 1 5 1 5 1 5 1 5 1 5 1 5 1 5 1 5 1 5 10 25 50 100 150 218 1 5 1 1 1 1  Temp (° C) 1 1 . 54 1 2 . 87 1 2 . 75 1 1 . 33 9. 96 1 2 . 17 1 2 . 02 N A N A 1 0 . 56 9. 48 1 2 . 00 1 1 . 79 1 1 . 85 1 1 . 62 1 1 . 21 1 1 . 21 1 0 . 19 1 0 . 07 1 0 . 02 9. 78 9. 73 9. 36 9. 40 N A 9. 49 9. 49 N A N A N A N A  Salinity (ppt)  Oxygen (ml/1)  pH  24.321 21.065 21.086 23.394 28.619 21.808 24.058 21.491 21.552 26.270 29.215 22.639 23.447 23.665 23.891 29.219 29.222 28.132 29.274 29.473 29.697 29.854 30.306 30.428 30.616 30.243 30.251 0.364 0.271 0.0 0.0  8.03 8.24 8.14 6.43 5.84 7.99 7.57 7 .94 8.04 6.86 5.76 .7.69 7.94 8.14 8.10 7 .44 7 .49 6.12 6.12 5.99 5.84 5.77 5.31 5.34 5.18 5.44 5.45 7.71 7 .78 7 .79 7 .80  8.19 8.39 8.39 8.05 7 .86 8.19 8.24 8.35 8.33 8.00 7.83 8.22 8.25 8.28 8.28 8.15 8.16 7.92 7.91 7.89 7 .88 7.86 7 .81 7.81 7.79 7.82 7.82 7.95 7.96 8.01 8.01  Alk meq/1 1.81 1.63 1.63 1.65 1.95 1.69 1.79 1.69 1.69 1.85 1.99 1.68 1.74 1.72 1.74 2.00 2.07 1.95 1.96 2.00 2.00 2.02 2.06 2.06 2.07 2.07 2.04 0.82 0.83 0.85 0.81  D i s Mn (ppb) 5.73 6.44 6.59 6.50 4.55 6.21 5.05 6.50 5.97 1.77 1.24 6.86 4.91 4.70 4.70 2.96 2.96 2.43 2.26 1.69 1.55 1.41 0.99 1.02 2.09 1.18 1.36 5.06 2.81 3.24 3.39  149  Cruise  Stn  78-10 78-10 78-10 78-10 78-10 78-10 78-10 78-10 78-10  15. 15. 15. 15. 15. 15. 15. 15. 70.  Depth (m) 0 0 0 0 0 0 0 0 0  1 5 10 25 50 100 150 188 0  Temp (°C) 16.17 16.22 14.94 10.47 9.45 9.21 9.05 N A N A  Salinity (ppt)  Oxygen (ml/1)  14.626 23.399 26.711 29.205 29.837 30.217 30.512 30.652 0.0  6.82 6.95 6.97 5.28 4.65 4.51 4.27 4.22 N A  N N N N N N N N N  pH  Alk meq/1  D i s Mn (ppb)  A A A A A A A A A  N A 1.85 1.97 2.08 2.10 2.12 2.14 2.15 1.19  4.40 3.36 0.98 0.93 0.49 0.52 0.55 5.83 4.28  150  Cruise  78-11 78-11 78-11 78-11 78-11 78-11 78-11 78-11 78-11  Stn  58.0 58.0 55. 5 55.5 56.2 56.2 56.4 56.5 56.6  Depth  Temp  (m)  CO  1 9 1 9 1 9 9 9 9  N N N N N N N N N  A A A A A A A A A  Salinity (ppt) 0.0 0.0  o.o •  19.580 0.0 18.463 4.887 10.016 2.380  Oxygen (ml/1)  N N N N N N N N N  A A A A A A A A A  N N N N N N N N N  pH  Alk meq/1  D i s Mn (ppb)  A A A A A A A A A  0.96 0.96 1.00 1.65 0.93  1.97 2.03 2.93 13.3 2.78 11.0 5.96 10.3 6.71  1.61 1.01 1.27 0.89  151  Cruise  Stn  78-12 78-12 78-12 78-12 78-12 78-12 78-12 78-12 78-12 78-12 78-12 78-12  15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15.  Depth (m) 0 0 0 0 0 0 0 0 0 0 0 0  0 1 5 10 20 25 30 50 75 100 150 194  Temp ( °C) 19.1 19.12 16.76 13.67 11.46 10.41 10.09 9.37 9.84 10.16 9.70 N A  Salinity (ppt)  Oxygen (ml/1)  PH  19.917 19.685 24.026 26.749 29.104 29.391 29.509 29.668 30.057 30.364 30.683 30.622  N A 6.80 6. 79 6.06 4.82 4.58 4.34 4.20 4.14 4.10 4.10 4.01  N A 8.39 8.24 8.05 N A 7.68 N A 7.58 7.65 7.68 7.69 7.69  Alk meq/1 N A 1.69 1.85 1.99 N A 2.09 N A 2.09 2.11 2.14 2.14 2.15  D i s Mn (ppb) N A 3.36 2.60 1.91 N A 0.67 N A 0.17 0.23 2.81 0.81 3.44  152  Cruise 78-13 78-13 78-13 78-13 78-13 78-13 78-13 78-13  Stn  1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0  Depth (m) 5 10 25 50 100 200 300 351  Temp ( °C) 13.19 11.92 10.94 9.91 9.50 9.00 9.03 N A  Salinity (ppt)  Oxygen (ml/1)  26.726 28.225 28.807 29.450 30.231 N A 30.932 30.208  6.55 5.06 4.32 3.70 3.55 3 .18 3.13 3.79  pH N N N N N N N N  A A A A A A A A  Alk meq/1 N N N N N N N N  A A A A A A A A  D i s Mn (ppb) 0.39 0.28 0.36 0.33 0.0 0.53 0.0 3.78  153  Cruise 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16  Stn 70. 0 70. 0 70. 0 70. 0 70; 0 70. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 50. 0 50. 0 50. 0 53. 0 53. 0 53. 0 53. 0 53. 0 53. 3 53. 6 53. 6 54. 0 54. 3 54. 3 54. 3 54. 3 55. 0 55. 3 55. 5 56. 0  Depth (m) 0 0 0 0 0 0 1 5 10 25 50 75 100 150 196 1 5 10 25 50 75 100 150 1 5 10 25 50 75 100 150 187 188 1 1 141 1 11 1 11 1 1 1 9 1 1 10 1 1 1 1 1 1  Temp (°C) 12. 3 12. 3 12. 3 12. 3 11. 7 11. 5 12. 71 12. 48 11. 72 10. 40 9. 88 10. 16 10. 11 9. 71 N  A  12. 86 12. 69 11. 16 10. 12 10. 15 10. 14 9. 93 9. 73 12. 88 12. 79 11. 09 N N N N N N N  A A A A A A A  12. 5 12. 9 10. 0 11. 8 10. 2 11. 7 10. 8 11. 6 11. 6 11. 8 10. 3 11. 9 11. 9 10. 3 12. 0 12. 0 11. 3 11. 7 11. 3 11. 3  Salinity (ppt) 0.0 0.0 0.0 0.0 0.0 0.0 24.416 26.739 29.271 N N  A A  29.937 30.143 30.752 30.968 22.594 25.527 28.408 29.387 29.769 29.982 30.232 30.706 24.160 25.337 28.297 29.390 . 29.806 . 30.037 30.285 30.747 30.963 N  A  21.3.48 25.236 30.564 11.329 29.591 7.063 29.645 6.171 16.255 11.677 28.951 9.887 11.572 29.236 8.852 7.054 1.411 1.535 0.703 0.628  Oxygen (ml/1) N N N N N N  A A A A A A  pH  Alk meq/1  D i s Mn (ppb)  N  A  N  A  1.17 1.08 1.07 1.06 1.06 1.05 1.84  18.8 14.0 8.63 7.89 6.03 4.65 4.64 0. 67 0.70 0. 34 0.25 0.87 0.83 1.56 3.62  7 .93 7 .86 7 .85 7 .94  6.63 5.91 4.96 3.99 3.64 3.82 3.89 3.65 3.49 6.91 6.69 4.49 3.80 3.87 3.96 3.95 3.60 6.94 6.88 4.47 3.78 3.80 3.96 3.86 3.60 3.46  N N N N N N N N  N  A  6.71 6.89 3.74 6.79 4.00' 7.00 4.03 7 . 22 6.52 6.81 4.31 6.77 6.68 4.19 6.99 7.12 7.49 7.46 7.58 7.58  8 .00 7 .87 7 .75 7 .60 7 .52 7 .61 7 .60 7 .59 7 .56  N  A  2.00 2.05 2.09 2.11 2.12 2.13 2.16 N N N N N N N N  A A A A A A A A  8 .06 8 .05 7 .67 7 .56 7 .60 7 .62 7 .62 7 .58 7 .57  1.82 1-.86 1.93 2.Q0 2.04 2.04 2.06 2.09 2.11  N  N  A  A A A A A A A A  A  7 .99 8 .03 7 .59 7 .88 7 .65 7 .79 7 .62 7 .80 7 .91 7 .86 7 .62 7 .80 7 .80 7 .60 7 .87 7 .86 7 .74 7 .72 7 .79 7 .75  1.71 1.87 2.15 1.25 2.09 1.10 2.06 0.92 1.47 1.24 2.03 1.21 1.18 2.07 1.05 1.09 1.08 1.09 1.07 1.07  N N N N N N N N  A A A A A A A A  2, 15 1. 06 0.44 0.33 0.61 1.44 1.03 0.69 4.94 4 86 3. 33 0.67 2.29 5, 50 2, 49 6, 03 2, 42 6, 01 4, 50 4, 88 2, 02 5, 30 5, 57 2, 33 5, 99 6, 87 5, 65 6, 50 5, 52 4.77  154  Cruise  78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-1678-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16  Stn  57 . 0 57. 0 57. 5 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 58 . 3 58. 3 58. 3 58. 3 58. 3 58. 3 58. 3 58. 5 58 . 5 59. 0 59. 0 60. 0 60. 0 61. 0 61. 0 62. 0 62. 0 63. 0 63. 0 56. 0 55. 0 54. 0 53. 0 51. 0  Depth (m)  Temp (° C)  12 11. 3 13 11. 3 13 11. 3 11 11. 3 1 11. 3 11 11. 3 15 11. 3 9 11. 3 8 11. 3 9 11. 3 8 11. 3 7 11. 3 7 11. 3 7 11. 3 7 11. 3 8 11. 3 8 11. 3 9 .. 1 1 .3 9 11. 3 9 11. 3 1 11. 3 1 11. 3 9 11. 6 15 11. 2 12. 0 1 13 11. 2 13 11. 2 13 11. 2 14 11. 2 13 11. 2 11 11. 2 1 11. 2 16 11. 2 1 11. 2 16 11. 2 1 11. 2 12 11. 2 1 11. 2 17 11. 2 1 11. 2 13 11. 2 1 11. 2 1 11. 2 1 11. 2 1 11. 2 1 11. 2 1 11. 2  Salinity (ppt)  Oxygen (ml/1)  pH  24.986 24.382 20.762 26.969 0.570 22.925 20.677 11.859 8.303 11.993 11.023 12.114 12.558 10.873 9.810 9.531 8.658 26.095 26.740 26.922 0.874 0.874 26.530 23.394 0.039 22.820 22.901 22.858 22.813 21.706 4 .171 0.003 22.139 0.0 0.786 0.0 0.0 0.0 0.0 0.0 0.0 0.0 2.282 6.379 14.295 12.697 15.095  5.18 5.26 5.60 4.85 7.56 5.23 5.40 6. 21 6.48 6.08 6.30 6.33 6.19 6.49 6. 50 6.60 6.66 4.84 4.86 4.71 N A 7.57 5.41 5.46 7.56 5. 51 5. 51 5.51 5.54 5.57 7.12 7.66 5.53 7.66 7.52 7.72 7.72 7.71 7.66 7.67 7.73 7.70 7.41 7.26 6.95 6.90 6.73  7.74 7.75 7.79 7.72 7.78 7.77 7.78 7.79 7.80 7 .81 7.80 7.80 7.81 7.80 7.80 7.78 7.78 7.75 7.75 7.75 N A 7.83 7.75 7.80 7.82 7.79 7.79 7.82 7.82 7.80 7.77 7.86 7.79 7.84 7.78 7.88 7.80 7.82 7.80 7.79 7.84 7.81 7.74 7.87 7.97 7.94 7.95  Alk meq/1 1.89 1.84 1.66 1.96 N A 1.77 1.63 1.26 1.24 1.37 1.27 1.32 1.34 1.30 1.22 1.22 1.19 1.91 1.93 1.93 N A 1.07 1.87 1.76 0.85 1.71 1.72 1.72 1.67 1.72 0.93 0.92 1.69 0.89 0.88 0.86 0.86 0.86 0.85 0.85 0.87 0.87 0.92 0.98 1'.36 1.24 1.35  D i s Mn (ppb) 4.59 N A 5.48 3.62 10.6 12.6 8.62 ' 8.55 8.80 8.29 9.77 8.59 8.75 8.42 8.27 9.42 9.51 4.95 4.28 4.28 4.97 4.83 2.67 6.03 6.49 6.67 7.00 7.61 6.78 7.58 7.83 N A N A 5.47 6.40 4.54 3.98 3.98 4.08 4.08 4.65 4.54 7.17 7.11 6.92 7.64 5.44  155  Cruise  Stn  78-20 78-20 78-20 78-20 78-20 78-20 78-20 78-20 78-20  15. 15. 15. 15. 15. 15. 15. 15. 15.  0 0 0 0 0 0 0 0 0  Depth (m)  Temp (°C)  Salinity (ppt)  Oxygen (ml/1)  PH  Alk meq/1  1 5 10 25 50 75 100 150 186  8.64 8.66 8.62 9.01 9.07 9.15 8.91 8.42 N A  28.885 28.878 28 .831 30.034 30.180 30.346 30.418 30.467 30.560  5.67 5.58 5.47 4.30 4.18 4.18 4.43 4.61 4.62  7.71 7.71 7.70 7.66 7.67 7.69 7.68 7.70 7.70  N A N A N A N A N A N A N A N A N A  D i s Mn (ppb) 0.83 0.93 1.07 N A 0.83 0.69 0.69 1.16 2.54  156  Cruise  7979797979797979797979797979797979797979797979797979797979797979797979797979797979797979797979797979797979-  01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01 01  Stn  1. 0 1. 0 1. 0 1. 0 1. 0 1. 0 1. 0 1. 0 1. 0 1. 0 1. 0 2. 0 3. 0 3. 0 3. 0 3. 0 3. 0 3. 0 3. 0 3. 0 3. 0 3 .0 3. 0 4. 0 5. 0 6. 0 7. 0 8. 0 9. 0 10. 0 11. 0 12. 0 13. 0 14. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 16. 0 17. 0 18. 0 19. 0 20. 0 21. 0 22. 0 23. 0 24. 0 25. 0  Depth (m)  Temp (° C)  Salinity (ppt)  1 5 10 25 50 75 100 150 200 300 362 1 1 5 10 25 50 75 100 200 300 350 422 1 1 1 1 1 1' 1 1 1 1 1 1 5 10 25 50 75 100 150 200 1 1 1 1 1 1 1 1 1 1  7. 15 7. 14 7. 18 7. 28 7. 49 8. 45 9. 32 9. 18 9. 16 9. 29 N A 7. 28 7. 32 7. 32 7. 36 7. 33 7. 34 8. 73 8. 86 8. 16 8. 95 9. 05 N A 6. 53 6. 46 6. 49 6. 27 5. 98 7. 17 7. 00 7. 31 6. 05 5. 75 6. 15 5. 60 5. 75 5. 95 7. 07 7. 33 7. 27 7. 23 7. 33 N A 5. 93 5. 78 5. 2 5. 9 5. 7 6. 5 7. 1 7. 1 7. 0 7. 3  2 9 . 636 2 9 . 614 2 9 . 572 2 9 . 6,55 2 9 . 733 2 9 . 976 3 0 . 571 3 0 . 841 3 1 . 015 3 1 . 144 3 1 . 180 2 9 . 687 2 9 . 623 2 9 . 632 2 9 . 613 2 9 . 601 2 9 . 655 3 0 . 078 3 0 . 530 . 3 0 .769 3 1 . 029 3 1 . 084 3 1 . 110 2 9 . 213 2 9 . 303 2 9 . 294 2 9 . 003 2 8 . 527 2 9 . 355 2 9 . 414 2 9 . 508 2 8 . 788 2 8 . 565 2 9 . 150 2 8 . 368 2 8 . 694 2 8 . 844 3 0 . 092 3 0 . 326 3 0 . 346 3 0 . 348 3 0 . 389 3 0 . 447 2 8 . 745 2 8 . 599 2 7 . 989 2 8 . 750 2 8 . 745 2 9 . 050 3 0 . 230 2 9 . 591 3 0 . 316 2 9 . 963  Oxygen (ml/1)  pH  Alk meq/1  6.21 6.19 6.14 6.11 5.98 4.71 3.72 3.53 3.37 3.13 3.27 6.19 6.13 6,07 6.06 6.06 6.08 4.30 4.13 4. 68 3 . 63 3.52 3 . 71 6.14 6.26 6.21 N A 6.04 5.95 6.16 5.96 6.66 6.72 6.45 6.53 6. 32 6.14 5.68 5.57 5.65 5. 58 5.54 5.40 6.70 6.75 6.81 6.20 6.54 6.31 5. 74 5.74 5.68 5.16  7.69 7.68 7.68 7.69 7.63 7.63 7.60 7.63 7.60 7.58 7.60 7.69 7.70 7.69 7.48 7.70 7.68 7 .64 7 .63 7.65 7.63 7.62 7.65 7.74 7 .72 7.73 7.73 7.68 7.75 7 .75 7.75 7.72 7.70 7.68 7 .68 7.69 7.66 7.67 7.67 7.70 7.67 7.66 7.66 7.72 7.71 7.69 7.67 7.68 7.71 8.06 7.68 8.10 8.14  2.05 2.05 2.05 2.05 2.05 2.07 2.10 2.12 2.13 2.13 2.15 2.05 2.05 2.05 2.06 2.05 2.06 2.08 2.11 2.12 2.13 2.14 2.14 2.04 2.04 2.03 1.99 2.02 2.05 2.05 2.02 2.02 2.01 2.03 1.99 2.02 2.01 2.08 2.08 N A 2.11 2.11 2.11 2.03 2.02 2.00 2.05 2.04 . 2.04 2.12 2.08 2.11 2.08  D i s Mn (ppb) 0.67 0.64 0.56 0.45 0.49 0.45 0.26 0.60 0.0 1.01 4.79 0.64 0.45 0.67 0.45 0.45 0.45 0.23 0.34 1.57 1.61 1.29 8.14 1.29 0.82 0.71 1.01 2.11 0.23 0.0 0.67 1.79 2.11 1.43 3.37 3.05 3.19 2.08 1.36 1.72 1.43 1.51 1.90 1.90 2.29 3.15 4.26 3.01 1.68 1.36  2'. 19  1.36 1.18  157  C r u i se  79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01. 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01  Stn  26.0 15.0 50.0 50.0 51.0 51.0 52.0 52.0 53.0 53.0 53.3 53.3 53.6 53.6 54.0 54.0 54.3 54.3 55.0 55.0 55. 3 55.3 55.3 55. 5 55.5 56.0 56. 0 56.0 57.0 57.0 57.5 58.0 58.3 58.5 61.0 63.0 65.0  Depth (m) 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 14 1 1 1 1 10 1 1 9 1 1 1 1 1 0 0  Temp (° c)  Salinity (ppt)  Oxygen (ml/1)  pH  6. 9 5. 1 5. 5 5. 5 6. 1 6. 2 6. 3 6. 3 5. 9 5. 9 5. 8 5. 9 5. 8 6. 0 6. 40 6. 22 5. 21 5. 30 2. 76 2. 73 2. 07 N A 2. 30 1. 35 1. 90 2. 38 N A 2. 40 1. 75 N A 1. 50 1 . 30 1 . 36 0. 92 0. 91 0. 2 0. 2  3 0 . 315 2 6 . 998 2 7 . 962 2 7 . 873 2 9 . 407 2 8 . 659 2 9 . 200 2 8 . 991 2 8 . 346 2 8 . 247 2 8 . 471 2 8 . 507 2 8 . 386 2 8 . 4 54 2 9 . 024 2 8 . 899 2 8 . 382 2 8 . 506 1 6 . 490 1 5 . 859 1 4 . 010 2 8 . 280 1 3 . 945 1 2 . 820 1 0 . 971 1 4 . 593 2 5 . 397 1 5 . 677 1 0 . 018 2 1 . 587 8. 804 8. 111 8. 141 5. 834 1. 193 0. 155 0. 060  5.87 6.37 6.32 6.32 5.08 6.10 N A 6.10 6.19 6.20 6.13 6.13 '6.05 6.21 4.61 6.02 6.41 5.05 7.78 7.86 8.04 5.73 8.07 8.17 8.43 7.93 6.50 7.78 8.49 7.04 8.68 8.76 8.72 9.07 9.78 N A N A  8.15 7.92 7.97 7.93 7.94 7.93 7.96 7.95 7.94 7.94 7.95 7.98 8.00 7.99 7.98 7.95 7.93 7.92 7.89 7.88 7.87 N A 7.89 7.87 7.82 7.87 N A 7.89 7.85 N A 7.83 7.82 7.80 7.76 7.79 7.82 7.84  Alk meq/1 2.11 1.99 2.04 2.02 2.07 2.05 2.07 2.06 2.03 2.02 2.04 2.04 2.04 2.05 2.06 2.05 2.03 2.03 1.59 1.57 1.51 2.02 1.49 1.46 1.38 1.52 1.93 1.57 1.34 1.79 1.30 1.25 1.26 1.19 1.11 1.14 1.15  D i s Mn (ppb) 1.36 7.53 6.70 6.45 3.23 5.27 3.60 4.38 5.23 5.15 4.99 4.38 5.43 5.19 4.22 4.74 5.52 5.19 16.9 16.9 20.6 9.57 N A 19.3 20.6 17.7 8.84 17.4 18.6 10.9 23.9 21.9 20.6 21.5 16.5 14.9 15.3  158  Cruise  79-02 79-02 79-02 79-02 79-02 79-02 79-02 79-02 79-02 79-02 79-02 79-02 79-02 79-02 79-02 79-02 79-02 79-02  Stn  15. 15. 15. 15. 15. 15. 15. 15. 15. 25. 25. 25. 25. 25. 25. 25. 25. 25.  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0  Depth (m)  Temp  CC)  Salinity (ppt)  Oxygen (ml/1)  1 5 10 25 50 75 100 150 215 1 5 10 25 50 75 100 150 188  5.81 5.83 6.06 6.73 7.40 N A 6.76 6.83 N A 7.05 7.18 7.36 7.45 7.22 6.92 6.88 6.88 N A  27.835 28.095 28.804 29.869 30.432 30.607 30.615 30.667 30.631 30.071 30.180 30.262 30.314 30.401 30.448 30.560 30.654 30.834  6 .87 6 .76 6 .64 5 .92 5 .32 5 .57 5 .79 5 .73 5 .75 5 .61 5 .61 5 .39 5 .36 5 .49 5 .82 5 .78 5 .73 5 .65  pH  N N N N N N N N N N N N N N N N N N  A A A A A A A A A A A A A A A A A A  Alk meq/1 2.04 2.04 2.07 2.10 2.14 2.14 2.14 2.14 2.14 2.11 2.11 2.11 •2.11 2.11 2.12 2.12 2.12 2.13  D i s Mn (ppb) 3.90 2.89 2.57 2.07 1.01 0.51 2.34 0.87 2.30 1.10 0.87 0.46 0.46 0.46 0.23 0.14 0.14 0.09  159  C r u i se 79-05 79-05 79-05 79-05 79-05 79-05 79-05 79-05 79-05  Stn 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0  Depth . (m)  Temp  1 5 9 14 29 54 104 154 192  7.25 7.45 7.32 7.09 7.46 7.37 7.32 7.22  CO  N  A  Salinity (ppt)  Oxygen (ml/1)  pH  20.066 28.723 28.971 29.373 30.099 30.300 30.524 30.608 30.705  7.32 7.08 6.99 5.78 5.62 5.45 5.45 5.09 5.01  7.73 7.83 7.75 7.76 7.68 7.72 7.72 7.70 7.67  Alk  meq/1 N N N N N N N N N  A A A A A A A A A  D i s Mn (ppb) 11.0 2.35 1.84 2.80 1.74 3.12 1.94 2.43 6.20  160  Cruise 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07' 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07  Stn 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 56. 3  Depth (m)  Temp (°C)  Salinity (ppt)  Oxygen (ml/1)  1 5 10 25 50 100 200 300 350 372 382 392 396 398 400 401 1 5 10 25 50 75 100 150 156 166 176 180 182 184 185 0  8.65 8. 52 7.96 7.54 7.66 7.40 7.75 7.34 7.28 7.27 7.29 7.22 7.24 7.23 7.26  29.314 29.326 29.505 29.927 30.260 30.549 30.789 30.749 30.769 30.762 30.745 30.769 30.769 30.771 30.770 30.769 10.599 29.161 29.295 29.906 30.130 30.265 30.281 30.355 30.374 30.493 30.618 30.648 30.671 30.692 30.716 2.676  11.33 10.68 8.41 6.02 5.12 5.27 4 .62 5.18 5.12  N  A  7.48 8.20 8.08 7.59 7.49 7.60 7.58 7.60 7.55 7.49 7.34 7 .34 7.33 7.36 N  A  5.3  N N N N N N  A A A A A A  pH  Alk  meq/1  8.31 8.28 8.09 7.65 7.57 7.60 7.56 7.61 7 . 60  2.06 2.07 2. 07 2.07 2.07 2.08 2.09 2.09 2.10  N N N N N N  N N N N N N  A A A A A A  A A A A A A  5.11 8.72 8.89 8.44 6.13 5.72 5.92 5.93 5.84  7.59 7.93 8.23 8.10 7.71 7.65 7.70 7.69 7.69  2.10 1.27 2.06 2.06 2.07 2.09 2.10 2.10 2.10  N N N N N N  N N N N N N  N N N N N N  A A A A A A  4.90 8.76  A A A A A A  7.60 7.63  A A A A A A  2.11 1.01  D i s Mn (ppb) 1.21 1.26 1.31 0.50 0.69 0.78 0.45 0.83 3.11 4.34 4.96 8.43 9.00 8.76 9.47 8.95 10.7 1.19 0.97 0.31 0. 36 0.74 0.78 1.59 3.73 4.06 4.91 6.43 5.72 5.58 6. 96 10.6  161  Cruise  79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12 79-12  Stn  1. 0 1. 0 1. 0 1. 0 1. 0 1. 0 1. 0 1. 0 1. 0 2. 0 3. 0 3. 0 3. 0 3. 0 3. 0 3. 0 3. 0 3. 0 3. 0 3. 0 4. 0 5. 0 6. 0 7. 0 8. 0 9. 0 10. 0 11. 0 12. 0 13. 0 14. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 15. 0 16. 0 17. 0 18. 0 19. 0 20. 0 21. 0 22. 0  Depth (m)  1 5 10 25 50 100 200 300 351 1 1 5 10 25 50 100 200 300 350 420 • 1 1 1 1 1 1 1 1 1 1 1 1 5 10 25 50 75 100 150 182 192 202 206 208 210 211 1 1 1 1 1 1 1  Temp  CO 14.00 13.86 12.23 10.32 8.97 7.78 7.54 7.50 N  A  14.42 14.00 13.65 10.89 8.75 8.03 7.60 7.57 7.44 7.41 N  A  13.91 13.90 14.74 17.83 13.64 14.10 13.91 13.90 15.60 15. 94 15.82 12.13 13.17 11.41 8.60 8.92 8.99 8.85 8.83 7.88 7.80 7.77 7.78 7.77 7.75 N  A  13.46 14.34 13.79 11.45 12.98 13. 54 11.44  Salinity (ppt)  Oxygen  28.534 28.574 29.058 29.715 30.061 30.321 • 30.723 30.791 30.791 26.012 24.789 24.779 28.506 29.893 30.138 30.409 30.710 30.749 30.773 30.939 26.509 22.220 16.695 15.177 18.445 18.613 19.090 27.222 17.705 15.682 17.500 13.082 24.234 29.418 30.048 30.303 30.382 30.459 30.749  7.08 7.15 6.99 5.83 4.90 4.82 4.78 4.57 4.47 6.87 6.89 6.95 6.69 5.22 4.83 4.90 4.87 4.84 4.86 4.87 6.99 6.98 7.54 7.29 7.08 7.68 7.19 6.65 8.99 9.59 9.29 6.99 7.09 6.33 5.03 5.25 5.28 5.26 5.06  N N N N N N  A A A A A A  30.714 11.933 20.316 11.959 18.447 17.901 18.249 26.491  pH  (ml/1)  N N N N N N  A A A A A A  4.92 7.53 8.79 8.13 6.54 7.12 7.68 6.58  Alk  meq/1  8.38 8.38 8.29 8.01 7.83 7.72 7.72 7.69 7.69 8. 38 8.36 8.36 8.31 7.83 7 . 75 N  A  7.83 7 . 71 7.70 7.77 8.32 8.29 8.31 8.28 8.19 8.36 8.28 8.28 8.62 8.69 8.64 8.09 8.25 8.02 7.73 7.79 7.80 7.80 7.79 N N N N N N  A A A A A A  7. 64 8.35 8.60 8.52 8.07 8.23 8.36 8.03  N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N  A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A  D i s Mn (ppb)  0.68 0.72 0.38 0.55 0. 30 0.30 0. 34 1.44 3.63 2.32 3.38 1.10 0.63 0.17 0.17 0. 04 0.25 0.76 1.77 18.4 1. 94 5.70 9.91 10.7 8.37 8. 62 10.2 1.18 11.0 13.4 10.6 9.66 3.80 0.46 0.10 0.30 0.46 0.50 1.30 1.70 2.60 2.70 2.90 3.20 3:00  3.80 15.9 8.02 12.1 7.90 10.0 8.97 3.13  162  Cruise  79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12  Stn  23. 0 24. 0 25. 0 25. 0 25. 0 25. 0 25. 0 25. 0 25. 0 25. 0 25. 0 26. 0 15. 0 15. 0 50. 0 51. 0 51. 0 51. 0 51. 0 52. 0 52. 0 52. 0 53. 0 53. 0 53 .0 53. 0 56. 0 59. 0 65. 0 15. 0 15. 0 15. 0 15. 5 15. 0 50. 0 52. 0 53. 0 53. 0 53. 3 53. 6 54. 0 54. 3 54. 6 55. 0 55. 3 55. 5 56. 0 56. 6 57. 0  Depth (m)  Temp (° C )  Salinity (ppt)  Oxygen  1 1 1 5 10 25 50 75 100 150 229 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 100 1 1 1 11 13 13 14 14 11 11 12 11 13 10 13  12 .23 10 .48 12 .31 10 . 50 10 .04 9 .94 9 . 34 9 .17 9 .17 9 .11  25.472 29.916 22.618 28.315 29.151 29.530 30.375 30.573 30.577 30.635 30.741 25.377 9.558 11.747 12.842 9.085 12.280 16.544 16.061 7.481 8.176 3.154 0.053 0.563 6.412 0.054 0.0 0.0 0.0 10.416 10.267 8.986 6.294 30.590 11.400 5.890 0.0 30.027 29.610 28.604 28.143 27.887 14.013 0.0 17.801 0.0 0.0 0.0 0.0  6. 64 6.10 7.12 6.28 5.99 5.89 5.42 5.27 5.28 5.24 5.05 6. 59 8.02 7.79 7.53 7.64 8.18 8.79 9.04 7.79 7.48 7.84 8.06 7.89 7.38 7.99 8.09 8.29 8.24 8.74 8.59  8.08 7.96 8.15 7.97 7.93 7.93 7.84 7.82 7.82 7.81 7.73 8.02 8.33 8.30 8.23 8.19 8.37 8.58 8.64 ' 8.18 8.04 7.97 8.11 8.00 7.94 8.10 8.14 8.06 8.14 8.48 8.41  N  N  N  A  11 .11 12 .51 12 .79 12 .65 12 .10 12 .32 15 .23 15 .44 11 .30 10 .8 10 .4 10 .7 10 .6 10 .8 11 . 0 11 .20 6 .50 10 .65 13 .75 10 .86 13 .52 13 .0 9 .01 12 .90 11 .1 11 .3 9 .0 N N  A A  N N N N N N N N  A A A A A A A A  9 .3  pH  (ml/1)  A  8.35 N  A  8.52 7.76 8.25 5.33 5.41 5.59 5. 64 5.61 6.83 8.24 6.50 8.24 8.25 8.28 8.28  Alk  meq/1  A  8.36 N  A  8.43 8.08 8.15 7.79 7.80 7.79 7.78 7.79 7.85 8.15 7.86 8.16 8.15 8.17 8.15  N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N  A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A  D i s Mn (ppb)  3.87 2.22 5.83 2.62 2.41 • 1.94 1.44 1.23 1.44 1.36 1.89 4 .18 10.5 12.7 13.9 13.8 14.4 10.8 10.6 6. 91 6.13 9.30 16.1 18. 0 25.6 17.4 6.63 5.27 N  A  12.1 12.5 N  A  9.55 N  A  14.6 5.97 10.1 6.26 6.13 10.7 12.4 11.1 16.7 5.33 18.7 4.83 4.50 4.20 N  A  163  APPENDIX B.2 P a r t i c u l a t e  Cruise 7878787878787878787878787878787878787878-  04 04 04 04 04 04 04 04 04 04 04 04 04 04 04 04 04 04 04 04  Stn 53. 53. 54. 54. 55. 55. 56. 56. 57. 57. 58. 58. 59. 59. 61. 61. 63. 63. 65. 65.  Depth (m) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0  1 12 1 16 1 20 1 13 1 17 1 17 1 6 1 12 1 12 1 16  Sal (ppt) 12.634 29.712 7.649 28.469 5.970 28.392 5.364 27.495 4.028 24.622 2.226 23.425 2.055 21.378 0.039 14 .444 0.0 0.0 0.0 0.0  D i s Mn (ppb) 13 .4 4 .49 14 .5 2 .77 14 .8 2 . 52 17 .1 3 . 28 17 .6 6 .91 16 .6 7 .68 16 .2 10 .2 11 .4 14 .7 11 . 1 13 .0 9 .97 11 . 7  Constituents  P a r t Mn (ppb) 3.84 3.38 4.45 3.13 4.69 3.51 4.87 5.24 4.79 14.5 5.18 5.47 5.15 4.64 6.76 5.55 9.41 8.67 10.2 10.6  P a r t Fe P a r t A l TSP (ppb) ( p p b ) (mg/1) 274 199 347 158 371 202 378 318 370 979 380 375 412 325 710 377 558 537 606 654  298 292 384 256 400 303 446 436 405 1440 424 512 446 423 557 493 679 701 789 849  164  Cruise  787878787878787878-  11 11 11 11 11 11 11 11 11  Stn  58. 58. 55. 55. 56. 56. 56. 56. 56.  0 0 5 5 2 2 4 5 6  Depth (m) 1 9 1 9 1 9 9 9 9  Sal (ppt) 0.0 0.0 0.0 19.580 0.0 18.463 4.887 10.016 2.380  D i s Mn (ppb) 1.97 2.03 2.93 13.3 2.78 11.0 5.96 10.3 6.71  P a r t Mn (ppb) 53.4 72.2 47.9 96.6 45.9 56. 9 100.0 107.0 103.1  P a r t Fe P a r t A l (ppb) (ppb) 2810 4190 2540 5780 2580 3160 5370 5640 6240  5050 6770 4430 9310 4490 5410 9100 9730 10260  TSP  165  Cruise  Stn  78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16  70.0 70.0 70.0 70.0 70.0 70.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 50.0 50.0 50.0 53.0 53.0 53.0 53.0 53.0 53.3 53.6 53.6 54.0 54.3 54 . 3 54.3 54.3 55.0 55.3 55.5 56.0 57.0 57.0 57.5 56.3 56.3 56. 3 56.3  Depth (m) 0 0 0 0 0 0 1 5 10 25 50 75 100 150 196 1 5 10 25 50 75 100 150 187 188 1 1 141 1 11 1 11 1 1 1 9 1 1 10 1 1 1 1 1 1 12 13 13 11 1 11 15  Sal D i s Mn (ppt) (ppb) 0.0 0.0 0.0 0.0 0.0 0.0 24.416 26.739 29.271 N A N A 29.937 30.143 30.752 30.968 24.160 25.337 28.297 29.390 29.806 30.037 30.285 30.747 30.963 N A 21.348 25.236 30.564 11.329 29.591 7.063 29.645 6.171 16.255 11.677 28.951 9.887 11.572 29.236 8.852 7.054 1.411 1.535 0.703 0.628 24.986 24.382 20.762 26.969 0.570 22.925 20.677  18.8 14.0 8 .63 7.89 6.03 4.65 4.64 0.67 0.70 0.34 0.25 0.87 0.83 1.56 3.62 2.15 1.06 0.44 0.33 0.61 1.44 1.03 0.69 4.94 4.86 3.33 0.67 2.29 5.50 2.49 6.03 2.42 6.01 4.50 4.88 2.02 5.30 5.57 2.33 5.99 6.87 5.65 6.50 5.52 4.77 4.59 N A 5.48 3.62 10.6 12.6 8 .62  P a r t Mn (ppb) 13 . 5 19 .3 15 .5 13 .6 12 .4 12 .6 3 . 00 1 .70 0 .70 0 .70 1 .10 1 .00 1 .10 1 .40 5 .60 1 .60 1 .10 0 .60 0 .80 1 .10 1 . 30 1 .10 1 . 50 2 . 60 3 . 20 2 .90 1 .10 2 .80 6 .50 4 .40 7 .20 3 .70 7 . 50 5 .90 6 .20 4 .90 6 .40 5 .70 5 .40 7 .40 7 .00 10 .0 11 .6 11 .8 12 .1 13 .1 11 .7 19 .9 6 .30 21 .1 5 .60 28 .7  P a r t Fe P a r t A l TSP (ppb) ( p p b ) (mg/1) 932 1134 921 772 650 625 130 45. 4 4. 0 1. 7 7. 4 25. 7 24. 9 31. 5 326 42. 2 9. 8 3. 3 3. 3 11. 3 37. 3 26. 3 25. 0 129 160 132 9. 4 156 346 244 407 202 421 320 329 296 349 317 327 368 356 609 746 684 703 905 780 1320 431 1870 501 1750  1270 1610 1340 1140 961 907 223 73 4 1 11 42 40 57 475 61 20 7 3 15 60 40 27 212 274 232 13 275 512 442 558 384 583 471 490 433 510 471 494 533 491 857 1050 996 914 1370 1240 1870 569 2030 583 2730  2. 29  6. 17  3. 59 3. 67 2. 00 4. 59 6. 44 7. 53 7. 67 5. 60 7. 44 6. 25 6. 12 7. 20 6. 28 5. 75 6. 40 6. 41 6. 92 9. 92 12. 71 12. 24 13. 71 19. 88 15. 20 31. 28 8. 33 24. 08 8. 75 42. 71  166  Cruise  78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16 78-16  Stn  56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 56. 3 58. 3 58. 3 58. 3 58. 3 58. 3 58. 3 58. 3 58. 5 58. 5 59. 0 59. 0 60. 0 60. 0 61. 0 61. 0 62. 0 62. 0 63. 0 63. 0 56. 0 55. 0 54. 0 53. 0 51. 0  Depth  Sal  D i s Mn  (m)  (ppt)  (ppb)  9 8 9 8 7 7 7 7 8 8 9 9 9 1 1 1 9 15 1 13 13 13 14 13 11 1 16 1 16 1 12 1 17 1 13 1 1 1 1 1 1  1 1 . 859 8. 303 11. 993 1 1 . 023 12. 114 12. 558 10. 873 9. 810 9. 531 8. 658 26. 095 26. 740 26. 922 0. 874 0. 874 0. 874 26. 530 23. 394 0. 039 22. 820 22. 901 22. 858 22. 813 21. 706 4. 171 0. 003 22. 139 0. 0 0. 786 0. 0 0. 0 0. 0 0. 0 0. 0 0. 0 ' 0. 0 2. 282 6. 379 14. 295 12. 697 15. 095  8 .55 8 .80 8 .29 9 .77 8 .59 8 .75 8 .42 8 . 27 9 .42 9 .51 4 .95 4 .28 4 .28 5 . 61 4 .97 4 .83 2 .67 6 . 03 6 .49 6 .67 7 .00 7 .61 6 .78 •7 .58 7 .83  Part  Mn  (ppb)  N N  A A  5 .47 6 .40 4 .54 3 .98 3 .98 4 .08 4 .08 4 .65 4 .54 7 .17 7 .11 6 .92  46.6 45.6 45.5 45.9 33.7 30.4 26.6 24.1 28.0 34.0 49.0 37.8 39.7 18.3 16.9 8.60 4.50 11.8 12.2 9.80 10.7 9.40 9.80 8.80 10.3 13.1 6.90 11.5 14.9 14.7 16.6 16.1 14.8 11.9 14.7 14.1 11.4 10.5 4.40  N  A  N  5 .44  A  2.70  Part  Fe  Part  Al  (ppb)  (ppb)  2870 2930 2830 2870 2170 1790 1620 1510 1710 2070 3100 2440 2460 1280 • 1110 1160 236 798 7.03 637 713 630 685 598 582 698 399 594 842 789 911 902 798 636 812 711 734 679 337  4700 5070 4680 4560 3300 3240 2750 24 2.0 2920 3440 5230 4220 4350 1780 1770 1680 380 1130 917 954 1090 1050 1120 981 735 1080 592 828 1120 1160 1320 1290 1170 943 1190 1100 1010 980 495  N  A  128  N  A  215  TSP  (mg/1)  56. 08 62. 86 62. 82 47. 00 40. 12 35. 32 30. 24 35. 48 43. 67 64. 16 51. 32 56. 36 20. 16 5. 60 14. 48 11. 96 11. 24 14. 24 12. 60 14. 12 12. 64 1 1 . 25 12. 49 7. 71 1 1 . 12 16. 20 14. 69 18. 32 14. 04 15. 84 12. 96 14. 75 13. 00 1 1 . 80 1 1 . 43 5. 76 6. 68 5. 56  167  C r u i s e Stn  79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01 79-01  15.0 50.0 50.0 51.0 51.0 52.0 52.0 53.0 53.0 53.3 53.3 53.6 53.6 54.0 54.0 54.3 54.3 55.0 55.0 55.3 55. 3 55.3 55.5 55.5 56.0 56.0 56. 0 57 . 0 57.0 57.5 58.0 58.3 58.5 61.0 63.0 65. 0  Depth (m) 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 14 1 1 1 1 10 1 1 9 1 1 1 1 1 0 0  Sal (ppt) 26.998 27.962 27.873 29.407 28.659 29.200 28.991 28.346 28.247 28.471 28.507 28.386 28.454 29.024 28.899 28.382 28.506 16.490 15.859 14.010 28.280 13.945 12.820 10.971 14.593 25.397 15.677 10.018 21.587 8.804 8.111 8.141 5.834 1.193 0.155 0.060  D i s Mn (ppb) 7.53 6.70 6.45 3.23 5.27 3.60 4.38 5.23 5.15 4.99 4.38 5.43 5.19 4.22 4 . 74 5. 52 5.19 16.9 16.9 20.6 9. 57 N A 19.3 20.6 17.7 8.84 17.4 18.6 10.9 23.9 21. 9 20.6 21.5 16.5 14.9 15.3  P a r t Mn (ppb) 1.60 1.50 1.60 0.90 1.20 1.00 1.20 1.20 1.10 1.30 1.60 1.70 1. 50 1.50 1.10 1.10 1.10 5.40 5.50 6.08 22.3 5.38 5.57 5.55 6.10 16.9 6. 55 9.21 17.3 8.28 7.38 8.07 7.48 8.64 11. 3 7.79  P a r t Fe P a r t A! (ppb) (ppb) 124 111 124 60. 96. 75. 87. 93. 89. 98. 114 101 97. Ill 97. 96. 96. 295 355 363 1400 414 389 393 417 1110 447 653 1160 574 520 563 521 564 659 467  1 5 4 8 8 6 0 2 1 3 3  182 168 192 109 142 112 141 147 142 153 161 153 158 181 153 145 148 549 526 488 2270 577 561 507 548 1710 595 915 1790 824 679 784 721 788 877 465  TSP (mg/1)  168  C r u i se S t n  79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07 79-07  3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 56.3  Depth (m) 1 5 10 25 100 200 300 350 382 392 396 398 400 401 1 5 10 25 50 75 100 150 156 166 176 180 182 184 185 0  Sal (ppt) 29.314 29.326 29.505 29.927 30.549 30.789 30.749 30.769 30.745 30.769 30.769 30.771 30.770 30.769 10.599 29.161 29.295 29.906 30.130 30.265 30.281 30.355 30.374 30.493 30.618 30.648 30.671 30.692 30.716 2.676  D i s Mn (ppb)  P a r t Mn (ppb)  1.21 1.26 1.31 0.50 0.78 0.45 0.83 3.11 4.96 8.43 9.00 8.76 9.47 8.95 10.7 1.19 0.97 0. 31 0.36 0.74 0.78 1.59 3.73 4.06 4.91 6.43 5.72 5. 58 6.96 10.6  0.70 0.70 0.70 0.90 1.00 2.70 3.30 4.10 4.50 8.70 8.80 9.20 9.40 10.5 5.40 0.30 0.30 0.60 1.00 1.30 1.20 4.40 1.90 1.60 1.90 2.30 1.90 2.20 2.40 10.2  P a r t Fe P a r t A! (ppb) (ppb) 13.3 14.7 9.8 4.5 9.4 10.7 11.9 15.8 21.0 25.9 33.3 31. 5 33.1 37.6 319 5.0 1. 7 2.8 11.3 39.0 26.1 48.5 84. 3 79-2 68.5 91.2 70.8 79-3 80.3 545  22 26 18 4 13 4 14 23 28 27 34 45 51 60 414 11 4 2 14 74 37 78 132 128 103 118 111 122 142 834  TSP (mg/1)  169  Cruise  Stn  79-12 1. 0 79-12 2. 0 79-12 3. 0 79-12 4. 0 79-12 5. 0 79-12 6. 0 7 .0 79-12 79-12 8. 0 79-12 9. 0 79-12 10. 0 79-12 11. 0 79-12 12. 0 79-12 13. 0 79-12 14. 0 79-12 15. 0 79-12 16. 0 79-12 17. 0 79-12 18. 0 79-12 19. 0 79-12 20. 0 79-12 21. 0 79-12 22. 0 79-12 23. 0 79-12 24. 0 79-12 25. 0 79-12 26. 0 79-12 15. 0 79-12 15. 0 79-12 50. 0 79-12 51. 0 79-12 51. 0 79-12 • 5 1 .0 79-12 51. 0 79-12 52. 0 79-12 52. 0 79-12 52. 0 79-12 53. 0 79-12 53. 0 79-12 53. 0 79-12 53. 0 79-12 56. 0 79-12 59. 0 79-12 65. 0 79-12 15. 0 79-12 15. 0 79-12 15. 0 79-12 15. 5 79-12 15. 0 79-12 50. 0 79-12 52. 0 79-12 53. 0 79-12 53. 0  Depth (m) 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 100 1 1 1 11  Sal D i s Mn (ppt) (ppb) 28. 534 26. 012 24. 789 26. 509 22. 220 16. 695 i s : 177 18. 445 18. 613 19. 090 27. 222 17. 705 15. 682 17 .500 13. 082 11. 933 20. 316 11. 959 18. 447 17. 901 18. 249 26. 491 25. 47 2 29. 916 22. 618 25. 377 9. 558 11. 747 12. 842 9. 085 12. 280 16. 544 16. 061 7. 481 8. 176 3. 154 0. 053 0. 563 6. 412 0. 054 0. 0 0. 0 0. 0 10. 416 10. 267 8. 986 6. 294 30. 590 11. 400 5. 890 0. 0 30. 027  0. 68 2. 32 3. 38 1. 94 5. 70 9. 91 10. 7 8. 37 8. 62 10. 2 1. 18 11. 0 13. 4 10. 6 9. 66 15. 9 8. 02 12. 1 7. 90 10. 0 8. 97 3. 13 3. 87 2. 22 5. 83 4. 18 10. 5 12. 7 13. 9 13. 8 14. 4 10. 8 10. 6 6. 91 6. 13 9. 30 16. 1 18. 0 25. 6 . 17. 4 6. 63 5. 27 N A 12. 1 12. 5 N A 9. 55 N A 14. 6 5. 97 10. 1 6. 26  P a r t Mn (ppb) 2. 00 1. 70 1. 30 1. 40 1. 10 4. 50 5. 60 3. 10 1. 90 3 .00 1. 20 1. 80 5. 20 2. 30 19. 0 23. 7 2. 10 13. 50 13. 8 9. 60 5. 60 5. 20 3. 40 0. 90 3. 20 1. 40 30. 4 19. 10 11. 60 25. 4 8. 40 4 .60 5. 00 63. 9 91. 3 232 301 248 256 286 183 233 188 13. 6 16. 1 15. 2 54. 6 2. 00 11. 9 140 134 13. 9  P a r t Fe P a r t A l TSP (ppb) ( p p b ) (mg/1) 20. 7 0. 0 0. 0 0. 0 7. 1 146 263 117 74. 0 127 0. 0 76. 1 260 85. 6 69. 7 101 84. 6 624 647 381 287 231 181 26. 7 119 45. 0 102 51. 3 508 93. 2 364 227 198 2960 333 10700 8180 13600 13700 13500 8150 11000 10900 576 673 636 2450 72. 0 520 6780 7730 566  64 1 11 0 24 283 457 209 134 205 0 159 468 197 1750 2130 180 1180 1170 719 491 334 249 68 211 88 2670 1640 989 2270 634 392 359 5560 8310 20500 13700 22200 22900 25200 16100 21100 11500 1120 1290 1190 2280 140 968 9540 6440 1140  1. 76  5. 10 27. 2 19. 4 12. 5 26. 9 9. 06 8. 34 8. 57 87. 1 117. 287. 540. 530. 600. 368. 220. 274. 209. 14. 7 17. 5 63. 1 13. 3 171. 186. 15. 6  170  Cruise  Stn  79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12 79- 12  53. 3 53. 6 54. 0 54. 3 54. 6 55. 0 55. 3 55. 5 56. 0 56. 6  Depth (m) 13 13 14 14 11 11 12 11 13 10  Sal D i s Mn (ppt) (ppb)  P a r t Mn (ppb)  P a r t Fe P a r t A l TSP (ppb) (ppb) (mg/1)  29. 610 28. 604 28. 143 27. 887 14. 013 0. 0 17. 801 0. 0 0. 0 0. 0  151 334 790 525 771 207 1360 17 5 225 N A  6870 21500 37800 25600 53200 8830 63600 7020 9630 N A  6 .13 10 .7 12 .4 11 .1 16 .7 5 . 33 18 .7 4 .83 4 . 50 N A  8410 35900 34600 28100 20100 17200 63700 12000 16700 N A  236. 984. 1530. 929. 946. 285. 2400. 296. 246. 309.  171  APPENDIX B.3 Time S e r i e s o f B o t t o m W a t e r s C o l l e c t e d a t S t a t i o n 56.3, C r u i s e 78-16 ( O c t . 1978)  Date  Time D e p t h (m)  18 18 18  1115  Sal D i s Mn (ppt) (ppb)  1350  11 11 15  26. 969 22. 925 20. 677  3. 62 12. 6 8. 62  18 18 18 18 18 18 18 18  1425 1431 1441 1500 1505 1522 1539 1556  9 8 9 8 7 7 7 7  11. 859 8. 303 11. 993 11. 023 12. 114 12. 558 10. 873 9. 810  18 18 18 18 18  1617 1624 1739 1753 1804  8 8 9 9 9  19  1151  9  P a r t Mn (ppb)  P a r t Fe P a r t A l TSP (ppb) (ppb) (mg/1)  6. 30 5.60 28.7  431 501 1750  569 583 2730  8 .33 8 .75 42 . 71  8. 55 8. 80 8. 29 9. 77 8. 59 8. 75 8. 42 8. 27  46.6 45.6 45.5 45.9 33.7 30.4 26.6 24.1  2870 2930 2830 2870 2170 1790 1620 1510  4700 5070 4680 4560 3300 3240 2750 2420  56 .08 62 .86 62 .82 47 .00 40 .12 35 . 32 30 .24  9. 531 8. 658 26. 095 26. 740 26. 922  9. 42 9. 51 4. 95 4. 28 4. 28  28.0 34.0 49.0 37.8 39.7  1710 2070 3100 2440 2460  2920 3440 5230 4220 4350  35 .48 43 .67 64 .16 51 . 32 56 .36  26. 530  2. 67  236  380  5 .60  4.50  APPENDIX B.4 T i d a l D a t a f o r S t e v e s t o n and Deas I s l a n d C r u i s e 78-16 ( O c t . 1978)  Date  Height at Atkinson (m)  Time a t Steveston  during  Time a t Deas I s l a n d  Oct.  1 8 , 1978  1.1 4.4 2.7 4.2  0140 0805 1400 1910  0225 0810 1430 1920  Oct.  19, 1978  1.1 4.4 2.8 4.0  0215 0900 1445 1950  0300 0905 1505 2000  172  APPENDIX C Summary o f S e d i m e n t  Data  •APPENDIX C l D i s s o l v e d Manganese P r o f i l e s i n I n t e r s t i t i a l W a t e r s - S t a t i o n 15 S e d i m e n t s C o l l e c t e d J a n 12/78 and Feb 6/79  78-]L-15  Core Section (cm)  79-:1-15  Di s s o l v e d Manganese (ppm)  Core Sect ion (cm)  Di s s o l v e d Manganese (ppm)  0-3  1.82  0-3  3.02  3-6  3.85  3-6  4.81  6-9  3.15  6-9  3.19  9-12  2.87  9-12  2.95  12-15  2.64  12-15  2.58  15-18  2.59  15-18  2.12  18-21  2.36  18-21  1.61  21-24  2.17  24-27  1.28  24-27  2.02  •31-34  1.01  27-30  1.98  38-41  1.12  30-33  1.88  45-48  0.85  33-36  1.85  52-55  1.21  36-39  1.64  39-42  1.51  42-45  1.19  45-48  0.99  48-51  0.71  173  APPENDIX C.2 D i s s o l v e d Manganese P r o f i l e s i n I n t e r s t i t i a l W a t e r s o f E s t u a r i n e S e d i m e n t s C o l l e c t e d F e b 29/79  Station  56 2  Depth (cm)  57 2  D i s Mn (ppm)  59 0  Depth (cm)  D i s Mn (ppm)  Depth (cm)  D i s Mn (ppm)  0-3  4.61  0-3  0.077  0-3  35.5  3-6  7 . 50  3-6  0.048  3-6  37.0  6-9  0.126  6-9  6-9  10.9  9-12  6.58  9-11  0.087  10-13  25.0  12-15  4.82  11-14  0.019  13-16  19.0  15-19  3.28  14-17  0.019  16-19  7.7  19-22  6.30  17-20  0.048  19-22  5.6  22-26  6.27  174  APPENDIX C.3 C o m p l e t e A n a l y s e s o f E s t u a r i n e 79-12 (May 1979)  C.3.1 Total E x t r a c t ion  Stat ion  3 15 53 54 55 56 59 65  Acid  Digestion  Ammon iurn Oxalate Leachable Mn (ppm)  Ammonium Oxalate Resistant Mn (ppm)  70.8 153 74.0 72.2 102 130 125  804 275 371 477 519 366 350 384  C.3.2 T o t a l A c i d D i g e s t i o n  Stat ion  3 15 53 54 55 56 59 65  Following  Mn (ppm)  1840 330 514 498 542 425 447 477  Sediment from  an  Ammonium  Total Manganese (ppm)  Cruise  Oxalate  Ammonium Oxalate Resistant A l (%)  7.30 4.74 5.44 5.48 5.03 5.29 5.48 5. 21  346 524 551 591 468 480 509  Only  Al (%)  10.4 7.22 8.72 6.99 5.55 5.41 6.07 5.86  Am. Ox. R e s . A l as % of T o t a l A l  70 66 62 78 95 98 89 89  175  APPENDIX C.4 D i s s o l v e d Manganese a n d S a l i n i t y P r o f i l e s i n I n t e r s t i t i a l W a t e r s o f E s t u a r i n e S e d i m e n t s C o l l e c t e d i n J a n 1980  Core  Station  Sect ion  (cm)  Number  57.2  Salinity (ppt)  62.5  Dis. Mn (ppb)  Salinity (ppt)  0-3  28.2  75  6.8  3-6  24.0  75  2.9  N  6-9  21.5  40  3.5  N D  9-12  19.9  25  4.5  N D  12-15  19.2  N D  4.8  N D  15-18  17.9  N D  5.9  N D  18-21  18.1  45  6.7  N D  21-24  18.1  45  8.2  N D  24-27  18.9  N D  9.1  N D  27-30  19.7  N D  59.0  1.  Dis. Mn (ppb)  25 D  1  62.2  0-3  19.6  175  12.2  3-6  13.7  100  10.0  6-9  14.2  N D  8.9  N D  9-12  14.0  N D  8.5  N D  12-15  15.0  25  N D = not d e t e c t e d ,  concentration  N D 5  N D  < 25 ppb  176  APPENDIX C.5 C o m p l e t e A n a l y s e s o f E s t u a r i n e C o l l e c t e d i n J a n 1980  Station Sect ion (cm)  Interstitial Salinity (ppt)  Water  D i s . Mn (ppm)  Sediments  Ammon iurn  Ammon iurn  O v a l a f o VyAct -Let L c  O v a ia f o  80.2 111 106 142 178 243 218 212 93.5 81.9  316 434 352 442 425 472 430 413 395 373  4.46 5.08 4.98 6.21 5.86 6.95 6.26 5.68 5.62 5.59  161  '291  4.45  133  346  4. 94  168  293  5.21  156  347  5. 38  150 •  342  5.50  Leachable Mn (ppm)  UAd±aL c  Resi stant Mn (ppm)  Ammon i urn Ova 1 a f o U X d l a i c  Resi stant A l • (%)  56.2  0-3 3-6 6-9 9-12 12-15 15-18 18-21 21-24 24-27 27-30  26. 6 23.0 24.4 24.2 25.6 25.8 26.0 26.8 22.8 20.5  0.88 3.2 4.4 4.2 3.0 2.3 4.7 5.7 4.6  28.2 19.4 17.8 14.9  N N N N  D D D D  0.7 .0.9 0.9 0.9 1.0 1.1 1.0  N N N N N N N  D D D D D D D  60.5  0-3 3-6 6-9 9-12  1  67.0  0-3 3-6 6-9 9-12 12-15 15-18 18-21  1. N D = n o t d e t e c t e d ,  concentration  < 25 ppb  177  APPENDIX C.6 G r a i n  Stat ion Number  79-12-15 79-12-53 79-12-54 79-12-55 79-15-56 79-12-59 79-12-65 80-56.2 80-56.2 80-56.2 80-56.2 80-56.2 80-56.2 80-56.2 80-56.2 80-56.2 80-56.2 80-57.2 80-57.2 80-57.2 80-59.0 80-59.0 80-60.5 80-60.5 80-62.5 80-62.5 80-62.5 80-67.0 80-67.0 80-67.0  1.  Size  Data  Sect ion (cm)  % Sand  % Mud  Mean G r a i n S i z e (mm)  Standard Deviation  SS SS SS SS SS SS SS 0-3 3-6 6-9 9-12 12-15 15-18 18-21 21-24 24-27 27-30 0-3 6-9 15-18 0-3 6-9 0-3 6-9 0-3 6-9 15-18 0-3 3-6 15-18  98.62 89.53 99.92 99.69 99.75 99.93 99.86 99.97 89.67 56.14 41.36 44 . 50 38.47 47.87 78.62 99.49 99.90 99.97 100.00 100.00 99. 91 99.94 99.92 99.97 100.00 99.97 100.00 99.96 100.00 100.00  1.38 10.47 0. 08 0.31 0.25 0. 07 0.14 0.03 10.33 43.86 58.64 55.50 61. 53 52.13 21.38 0.51 0.10 0. 03 0.00 0.00 0.09 0. 06 0. 08 0.03 0.00 0.03 0.00 0. 04 0.00 0.00  0.1842 0.1677 0.3424 0.2329 0.3045 0.2836 0.2938 0.2353 0.1789 0.0225 0.0109 0.0125 0.0094 0.0174 0.0993 0.2983 0.2940 0.3936 0.3472 0.3724 0.2774 0.2643 0.2335 0.2287 0.3648 0.3603 0.3900 0.'3589 0.3545 0.3551  0.6693 0.3569 0.7560 0.7436 0.6787 0.6933 0.7299 0.7406 0.3292 0.0763 0.0709 0.0762 0.0710 0.0664 0.1401 0.7308 0.7539 0.7363 0.7436 0.7400 0.7529 0.7489 0.7247 0.7330 0.7132 0.6967 0.6893 0.7280 0.7331 0.7654  1  SS = S h i p e k Sample  

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