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An investigation of ligand-exchange as a method for the extraction and concentration of dissolved organic… Pocklington, Roger 1964

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AN I N V E S T I G A T I O N  OP L I G A N D - E X C H A N G E A S  A METHOD F O R T H E E X T R A C T I O N AND C O N C E N T R A T I O N OF D I S S O L V E D ORGANIC M A T T E R FROM SEAWATER  by  ,  ROGER F O C K L I N G T O N B.A.,  Oxford  University,  1961  A T H E S I S S U B M I T T E D I N P A R T I A L F U L F I L M E N T OF T H E R E Q U I R E M E N T S FOR T H E D E G R E E OF  M A S T E R OF S C I E N C E in  the  Department of  Chemistry  We a c c e p t required  and I n s t i t u t e  this  thesis  as  of  Oceanography  conforming  to  standard  T H E U N I V E R S I T Y OF B R I T I S H C O L U M B I A September, 1964  the  In the  r e q u i r e m e n t s f o r an  British  Columbia, I  available mission  for extensive be  cation  of  w i t h o u t my  Department  by  for  the  I  the  further  Head o f my  Columbia,  agree for  that  of  not  per-  scholarly  Department  shall  of  make i t f r e e l y  or  t h a t ; c o p y i n g or  f i n a n c i a l gain  ci  fulfilment  University  shall  this thesis  permission-  The U n i v e r s i t y .of B r i t i s h V a n c o u v e r 8, Canada Date  study.  Library  I t i s understood  this thesis written  and  in partial  degree at  that, the  copying of  granted  representatives.  this thesis  advanced  agree  for reference  p u r p o s e s may his  presenting  be  by publi-  allowed  ABSTRACT  The t e c h n i q u e as  a possible  of  organic  of  method  for  compounds  used  to  from d i l u t e  the  extract  resins  solution in  applied  extraction  from  the  natural  This  of  work demonstrated ions.,  the  2M K H g P O ^ case  sorption  i n Ni(NH organic  i n the  from  was  for  ligands  amino-acids The  optiwere  amino-acids  seawater.  strong  sorption  and Cu(NH_)  first-stage  bonding the  of  citrate,  and a l a n i n e (4)  form  and  of  to  b y Dowex A - l i n  by i n o r g a n i c  of F e ( i i i )  Fe(iii) by  the  the  displace-  reagents:  30$ a m m o n i a  in  the  forms.  3  concluded that  the  the  of glutamate  3 3  utility  forms  experiments  the  )^. a n d C u ( N H ^ )  case  of Ni(NH_)  It  and  especially Fe(iii),  g l y c i n e and glutamate  o f jjhe  metal  seawater.  (l)  tartrate,  ment  concentration  C-labelled  r e s i n Dowex A - l (2)  same r e s i n  anions  from s m a l l - s c a l e  chelating  (3)  and  seawater.  transition-metal  form  investigated  seawater.  synthetic  found  was  in transition  carboxylate  mum c o n d i t i o n s to  extraction  dissolved in  Cation-exchange were  ligand-exchange  the  method  extraction  is of  of  marginal  organic  ligands  i i  The r e l a t i o n s h i p tabulated plexes  of the  S t a b i l i t y Constants  with  organic  ligands  is  experimental  results  of Transition-metal briefly  discussed.  to  com-  ACKNOWLEDGMENTS  I advice  wish  and  for,use of  to  thank Dr.  supervision the  facilities  Oceanography,  including  was  by the  supported  and of  P.  M. Williams for  Prof. the  Q.  Pickard  Institute  ship-time.  National  L.  This  Research  his  of work  Council.  iv T A B L E OP C O N T E N T S  I.  INTRODUCTION  Page  1.  The D i s s o l v e d O r g a n i c  2.  Methods o f E x t r a c t i o n o f from Seawater  3.  The T h e o r y  and  II.  Matter  Practice  of  Seawater  Organic  1  Compounds 5  of  Ligand  Exchange  7  E X P E R I M E N T A L METHODS AND M A T E R I A L S  1.  Treatment  of  the  Resins  2.  Analytical  3'.  Radio-Carbon Techniques  15  4.  Seawater  Samples  16  5.  Column O p e r a t i o n  17  Procedures  III.  1.  The E f f e c t Metal  11  of  13  EXPERIMENTAL  Seawater  RESULTS  Upon 'Resins  Form  in  Transition-  $  19  2.  Measurement  of  the  Ion-Exchange  3.  Measurement  of  the  Ligand-Exchange Capacities  4.  Extractions  from N a t u r a l  5.  E x t r a c t i o n of M e t a l - L i g a n d Complexes  31  6.  Elution  32  of  Seawater  Ligands IV.  Capacities  DISCUSSION  20 22 26  33  v Page APPENDIX  s^EFERENCES  37  vi I N D E X OF T A B L E S  Table  following  .1  Organic  Matter  in Natural  Waters.  2  2  Organic  Matter  in Natural  Waters.  2  3  Organic  Matter  in Natural  Waters.  2  4  Representative Aqueous  5,< 6  Organic  Material  Sediments.  Oceanographic Taken.  Data  2  on Seawater  The E f f e c t o f S e a w a t e r Upon R e s i n s T r a n s i t i o n - M e t a l Form. Equilibrium Capacity Various Forms.  8  Sorption of Amino-Aclds in F e r r i c -Form.  10  Samples 16  7  9  from  of  Dowex A - l i n  of  log  11- .  M  19 on  21  b y Dowex A - l  E l u t l o n f r o m Dowex A - l , F e ( i i i ) Values  in  23 Form.  32 39  page  vii  . /  I N D E X OP F I G U R E S  . following  Figure 1  . Apparatus  for  2  Self-Absorption  3  Citrate  4  Cruise  Correction  Sorption 62/13  12  Ligand-Exchange.  and  Sample  :  15  Curves.  22  Elution. E:  Sorption  of 28  Glutamate. 5  Sorption  of M e t a l - L i g a n d Complexes.  6  Displacement  of  Glutamate  by  7  Displacement  of  Glutamate  by Ammonia.  Phosphate.  31 32 32  page  I. 1.  The D i s s o l v e d  Analyses the  ocean  have  the  past,  and  of  wet  lie  described  range  1963).  7  carbon of  0.2  i n the  clt.) .  These  were  carbon  and  0.03  nitrogen and  mg N / L  (1964)  method  for  organic  the  carbon  in  mg C / L , a n d r e q u i r i n g o n l y a 5 n i l  analysis  to  it,  accompany  compounds  should every  enable  report  from seawater,  a  very  check.  Taking centration  variants  (STRICKLAND  0.54  to  reproducible  i s o l a t i o n of' o r g a n i c  necessary  by  Total dissolved organic  range  in  in  R e c e n t l y , MENZEL a n d VACCARO  20 * 0.1  organic  solution  3^0 mg C / L o b t a i n e d  to  by m i c r o - K j e d a h l methods  a rapid  to  in  investigators  T h i s m e t h o d , 6j| a m o d i f i c a t i o n o f  sample.  the  organic  Seawater^  o f d i s s o l v e d and p a r t i c u l a t e  0.1  range  total  i n the  PROVASOLI,  loc.  measurement  of  values  i960)  (PROVASOLI,  a  total  b e e r i made b y a n u m b e r  determined  PARSONS,  the  the  combustion methods.  values,  have  O r g a n i c Compounds o f  of  1961;  (DUURSMA,  INTRODUCTION  of  a* f i g u r e :  of  1 mg C / L f o r  dissolved organic  carbon  the  average  throughout  conthe  ocean,  9 with |.  a total  ocean  volume o f  1.37  x 10  cubic  kilometers  •  ^ The d i s s o l v e d " p o r t i o n o f the o r g a n i c m a t t e r i n s e a w a t e r i s d e f i n e d a s t h a t w h i c h p a s s e s a t y p e HA M l l l i p o r e f i l t e r (Millipore F i l t e r Corp., Bedford, Mass.) of 0.45 pore s i z e . R  1  -  (SVERDRUP  et  a l . ,  1942),  2  -  the  total  metric  tons.  mass  of dissolved  organic  12 carbon  is  1.37  10  greater  than  the  particulate  and  the  comparable  1.5  x 10"  metric  annual  tons  hundred  times  plants,  ca_.  largest  quantity" of  1:5  10  x  detrital  than  the  metric  1 0  is  a factor  carbon  of  organic  1953)  a l . , annual  tons  carbon  *•  it  is  1963)  i960).  upon t h i s  of  one  production of  (FOX,  ten  (PARSONS,  production of phytoplankton  (RILEY et  greater  This  land-  Thus  the  planet,  out15  side  of  metric  that tons  In""sediments  the  1963),  (HUNT,  (1957)  VALLENTYNE  and  molecular nature  of  is  soil,  estimated  dispersed  reviewed the organic  at  i n the data  matter  3.8  x  10  ocean.  available  i n lakes  on  and  oceans  (1963)  have  i  up t o  May  covered  1956.  some  3 summarize January for  o f the the  1964,  with  some  from  The o r g a n i c portant BAYLOR  to  constitutes  a  has  matter  d i s s o l v e d In the and g e o c h e m i c a l  shown thiat  "reservoir"  the  which  culate-form by bubbling Induced coming a v a i l a b l e In  a d d i t i o n to  as  the  and  Included of  organic  sediments.  both b i o l o g i c a l  (1963)  examples  2  through  r i v e r values  some  1,  Tables  f r o m M a y 1956  data  gives  PRGVJ&SOLI  literature.  l a k e and  Table 4  reported  and  more r e c e n t  literature  comparisons  matter  (1961)  DUURSMA  a  source  potential  of  dispersed can be  ocean  organic  converted  food  for  value  marine for  im-  processes.  b y wave a c t i o n ; food  is  matter  to  hence  partibe-  organic-ems.  zooplankton,  TABLE ORGANIC  SOURCE  1  M A T T E R I N N A T U R A L WATERS  MATERIAL  AMOUNT mg/L  METHODS  REFERENCE  by e f e t . i m a ^ i b n ' o f the products of oxidation  CREACH  solvent  ext.  KOYAMA &  at^pH  '  ORGANIC ACIDS French coast  Puget Sound Pacific Ocean  citric": malic formic  0.0025 0.0055 .0.0068  a c e t i c , formic, l a c t i c jgly'colie sat..and unsat. fatty acids C _ . to 10  0.1 1.4 0.02 0.11  Lake water  to  3  J  (1) co-precip. w i t h Fe(0H)o (2) s o l v e n t ext. w i t h CHC1_, C S ; G . L . C . of^Me esters  1959 ^  WILLIAMS,  1961  P  laurlc,stearic, palmitic, myris t i c , myristo- , 4 to lelc, palmitoleic, oleic, linoleic, linolenic d,icarboxylic hydroxy a l i ^ phat.ic acids  by  E t 0 a n d b y CHClo T H O M P S O N ,  '20  Gulf of Mexico  1955  up t o  Unpol;- - v a l e r i c , . b u t y r i e . , l u t e d \. pyruvic, lactic, s t r e a m s ••.•.suc:cihic,,ma:leic  13  ethyl acetate ext.SLOWEY, a t p H 2, G . L . C . JEFFREY & o f Me e s t e r s HOOD, 1962  5 ethyl acetate . . ext. of a c i d i f i e d • evaporate' .  O'.C to 0.60  SHAPIRO,1957 " ,1958 ...  c o n t i n u o u s l i q u i d - . L A M A R &'. : l i q u i d ext. .with -GOERLITZ, buta.nol.  TABLE  2  ORGANIC MATTER I N N A T U R A L WATERS SOURCE  MATERIAL  AMOUNT mg/L  METHODS  REFERENCE  CARBOHYDRATE South Atlantic  arabinose equiv.  Long Island  carbohydrate  North Sea  carbohydrate humic a c i d s  Offshore California  galactose, glucose, mannose  Lake water  sucrose glucose  0.0  0.5  to  2.6.  1.5  to  N-ethyl zole  carba-  N-ethyl zole  carba-  1958  up t o  0.005  WANGERSKY,  1959  fluorescence  ethanolle  0.014 to 0.035  ANDERSON & GEHRINGER,  KALLE,1962  ex-  DEGENS  et  ^a^^Aniof^r1964 vacuum evap. residue  0.01  a l . ,  ,  d e i o n i s e d w a t e r VALLENTYNE to dryness i n & WHITTAKER, vacuo 1956  V I T A M I N E S AND HORMONES m jAg/L English Channel  B  Sargasso Sea  B  A table North Sea offshore  of  12 12  cobalamine plant growth substances  0.2  to  0.1,;tP  2.0'  phenol ext.; b i o a s s a y -,.  0.2  direct assay  bio-  _  COWEY,  MENZEL & SPAETH, 1962  equivalents i n seawater i s to • . . . i n PROVASOLI, I963 3.4 as I.A.A.  1956  be  found  ether extracBENTLEY, t i o n o f p H 5? I960 Avena b i o a s s a y  TABLE  ORGANIC  SOURCE  MATERIAL  3  MATTER I N NATURAL  WATERS  AMOUNT  METHODS  REFERENCE  PROTEIN Surface seawater  aspartic acid theonine serine glutamic acid  Black Sea, coastal  tyrosine  Gulf of Mexico, deep sea  glutamic acid amino acids  FREE  Offshore, South Calif.  AMINO  glutamic acid a spartic acid glycine serine oc-alanlne leucine  hydrolysed,  HC1/NH-,  pHl,  de-  i o n i s e a by i o n exchange, paperc hroma t p g r a phed  ca .  7  TATSUMOTO, 1961  STARKOWA, residue after evap. i n vacuo 1962 extracUTed by h o t 80$ EtOH c o - p r e c i p . Fe(OH) ,PARK et desalt., acid 3 - i . , T962 a h y d r o l . b y 6N H C 1 , r e s o l v e d by i o n exchange a  ACIDS  1.2 2.3 12.1 8.5 6.4 5.5  evaporated to dryness i n vacuo DEGENS e t w i t h N HOT; a l . , I9OT e x t r a c t e d by ethanol; resolved by i o n - e x c h a n g e chromatography  TABLE  REPRESENTATIVE  SOURCE  ORGANIC  MATERIAL  4  M A T E R I A L FROM AQUEOUS  AMOUNT  SEDIMENTS  METHODS  REFERENCE  HYDROCARBONS Gulf  of  n  JHexlco  series,  STEVENS  M . W . 310 t o  1956  450, mostly odd n o s . C B a s i n s ; .hydrocarbons S. C a l i f . Lake sed-i iment North Italy  0.05  0.64$  KETO-ACIDS  FATTY ACIDS Recent  to  "  ORR & E M E R Y  1956  ppm  0.18  ext. by r e f l u x COOPER, MeOH-KOH, acidified, ext. CClu, esterified, G.fi.C.  1962  to  0.44 0.008 t o 0.07  Petroleum Water PHENOLIC Offshore Calif.  ACIDS  p-hydroxybenzoic, vanillic,  ca.  10  chromatographic analysis  DEGENS e t a l . , 19BT  ext. with ethanol  1959 b  syrlngic AMINO  ACIDS  assorted FREE  20-350  SUGARS  various Lakes o f glucose, N. Italy sucrose, maltose  k  I s o l a t i o n b y r e - POVGLEDO, a c t i o n w i t h 2,4- 195? a dinitrophenylhydrazine  s a t . , o d d 1.05 to & e v e n n o s . 6.92  Ancient  et : a l . ,  ~~  1-400  2900  70$  POVOLEDO,  —  TABLE 4 REPRESENTATIVE  SOURCE  continued  ORGANIC M A T E R I A L FROM AQUEOUS  MATERIAL  AMOUNT ppm  METHODS  SEDIMENTS  REFERENCE  CAROTENOIDS  20,000 yr. old lake  carotenoids 27.8 x a n t h o p h y l l s 23.0 CHLOROPHYLL  South Calif.  extracts VALLENTYNE, c h r o m a t o g r a p h e d 1957 b  DERIVATIVES  intermediate i n structure between c h l o r o p h y l l and p o r phyrins of petroleum  ORR e t 1958  a l . ,  there  Is evidence  organic growth as  (LUGAS,  compo'urfds  i n s o l u t i o n i n seawater  of phytoplankton.  important  even determining  the  succession  and b o t h  the presence  i t s d i s t r i b u t i o n have  of  seawater  assay  that  tracts  plant  (i960) e x t r a c t e d ether-soluble coleoptile  substances  (ABELSON,  may b e limiting  f o r cobalamlne algal  species,  variations  by the  bioassay  ( l o c . c i t . ) showed b y b i o were  present  i n ex-  waters  of the English active  i n the  Channel  "Avena"  test.  escaping  bacterial  incorporated  these  into  i s a useful  or animal  the  sediments  indicator  are subsequently  of the  subjected  1959).  The forms  in  demonstrated  w h i c h were  matter  to which  the  o f t h e N o r t h S e a , a n d POCKLINGTON  H) a n d i t s s u r v i v a l  temperatures  the  growth and i n f l u e n c i n g  for certain  substances  waters  i s eventually  influence  v i t a m i n and o f  BENTLEY  straight-growth  metabolism  Ti(iv),  been  from inshore  The o r g a n i c  (Table  2).  growth  of offshore  proven  of this  in  that  as f a c t o r s  A requirement  has been  (Table  nutrients  phytoplankton  of species.  i t s equivalent  1957)  Organic micronutrients  as t h e Inorganic  and  or  1958J S A U N D E R S ,  Cr(iii)  seawater  may a c c o u n t  i n w h i c h many m e t a l and, especially,  are uncertain. f o r some  cations  Pe(iii),  Complexes w i t h  species.  e.g.  exist  i n solution  organic  The b i n d i n g o f  Al(iii),  ligands  potentially  - 4 t o x i c c a t i o n s by organic  l i g a n d s has a b e n e f i c i a l e f f e c t  upon l i f e - p r o c e s s e s i n n a t u r a l waters, as has been r e cognised  i n the development of a r t i f i c i a l media f o r algae  (PROVASOLI et a l . , 1957 J JOHNSTON, 1963)•  - 52»  Methods  Of cular the of  of  the  nature  first  Extraction of  several of  is  the  the  1 mg C / L o r  obstacles  to  Compounds  the  dissolved organic  problem of  less  Organic  Seawater  study  of  the  matter  in  seawater,  efficiently  from an aqueous  from  extracting  solution  mole-  quantities  containing  4 3 x  10  times  sufficient seawater  of  the  then of  must  organic  provide  be  for  open  Methods  order  chemical analysis,  litre  ocean  an have  been  desalting  by  ion-exchange,  various  methods  JEFFREY  a n d HOOD  that  (see have  been  (1958).  promising  method  as  must  so  be  include  and  latter  removed  samples  length  solvent  ex-  absorption,  and  absorption  3). E v a l u a t i o n s (1955)  authors  the  of  the  and  concluded  h y d r o x i d e was  95$ o f  which  the  charcoal  made b y JOHNSON The  quantities  minimised.  electrodialysis, 1,2  obtain  decomposition  seawater  action,  tried  with ferric  it  the  to  i n containers  activated  Tables  co-precipitation  placed  extraction  co-precipitation,  clay minerals  when  bacterial  traction,  on  Moreover,  are  for  for  that  In  accelerates  surfaces  required  salts.  processed.  matter  from the  time  much i n o r g a n i c  material  of  taken  as  total  the  most  organic  14 carbon  from a  concentration that  a  removed The  C - l a b e l l e d aged factor  maximum o f  only  from seawater  problem  of  of  10,000. 60% o f  the  iron  culture  More recent  the  by F e ( 0 H )  removing  algal  3  total  giving work  organic  precipitation without  a  indicates  carbon  is  (WILLIAMS,  altering  the  1964).  organic  - 6 material  presented  exchange  resins  tion,  the  strong all  for  inorganic  resin  for  ions  to  3 ml seawater)  volume w i t h this  inorganic other  ions  methods  of  of a  extraction  medium,  directly as  volume  of  the  i n columns,  processing ocean.  plus  large  final  resin solution  conclude  that  traces  concentrated  through  of  by  offers a  operation,  volumes  The use  the  fixed and  of water  the  drawn  of  ion-exchange  resins  than  as  de-ionisers,  should  proportion  of  resin,  rather  difficulty  eluate  the  however,  system  room t e m p e r a t u r e  a much s m a l l e r  overcome  proportion  co-precipitation.  ligand-exchangers,  require  removed anions.  removal of  initially  simple uniflow  from the  of  ( l ml mixed  authors to the  high  Ion-  concentra-  organic  from the  only for  resins  advantages  the  doubling of  l e d the  useful  e.g.  of  the  from samples  The use  possibility  40$ o f  arising  and  simple  of  a combination  de-3alt seawater  washings,  m e t h o d was  to  use  and weak a n i o n - e x c h a n g e r plus  blank  required  prior  showed t h a t  cation-exchanger  the  Regarding the  desalting  same a u t h o r s  The h i g h o r g a n i c of  problems.  of  a high organic  washings.  and  blank  hence and  large  - 7 3.  The T h e o r y and  Practice  A transition has  the  power  molecules vent  to  (HELFFERICH, for  chosen  i n the  ligands  of  organic  metal-ligand extracted  is  so  complexes  of  a  in stability.  Selectivity is  that  i n the  seawater,  through  the  of  resin  and  from  metal advan-  seawater  between  a  ligands  can  very  low  is  a  pro-  the  concentra-  with  only the  organic  metals  possible,  inorganic  be  specific  of a metal  thus  sol-  the  ligand with different  vary  case  that  Complex f o r m a t i o n  and  neutral  several  ligands  possible  pair,  resin  and r e p l a c e  offers  e v e n when a t  i n which the  and  solvation s h e l l of  chelation  ligands,  as  This process  solution.  interaction different  ionic  sorption  quantitatively tion  from s o l u t i o n anions  i n the  Strong  Ligand-Exchange  ion i n a cation-exchange  function  1961).  the  solution. perly  sorb  which can  molecules  tages  metal  of  so  ions  ligands  pass  are  re-  tained. The washing of  ligands  this  free  c a n be of  ligand-exchange.  c a n be ing  with  inorganic Ligands  solutions,  strong  centrations  of  from the  Ions,  sorbed  d i s p l a c e d by a s o l u t i o n o f  l i g a n d , by b r e a k i n g  buffer  recovered  the  By s e l e c t i n g  c a n be  adjusted,  same  from d i l u t e  a more  both  a suitable  so t h a t  a  solution  bond  metal  complexwith  and  metal  after  process  strongly  metal-ligand  or by e l u t i o n o f  acid.  by the  resin,  ligand ion,  polydentate  con-  ligand a  sorbed  from a d i l u t e  concentrated  loc.  ligand-exchange  extraction,  from  the  tion  must  results  for  be  against which  a  give  loss  be  displaced  ligand  by  (HELFFERICH,  loss  and  of  capacity.  of  against of  ligands,  ligand-exchanger  dentate,  3/g bidentate  nickel.  cations  complexing  carboxylic acid  i n the  the  type expense of  consistent  capacity  one  the  ligand-exchange  a metal-ion  Dowex A - l i n  or  (e.g.  in a  strongly  D o w e x 5 0 W) c a n e x e r t  (e.g.  a  resin  metal.  coordination positions  though  has  compete  (Dowex A - l ) at  resin  moreover,  by u s i n g a  loss,  solu-  Protection  the  metal-ion  in  from the  the  maximum c o o r d i n a t i o n number  a  metal  resin.  obtained  reduction  cation-exchanger  for  complexing  for  the  For example,  chemistry  means  ions  i n the  iminodiacetate  consequent  a  other  external  c a n be  resins  some  with  metal  highly selective  or  o f the  as  solution  the  C G 50)  successful  capacity!  with  metal-ion  be  ligand-exchange  ligands  protection  acidic  of  i n the  blocking  to  Loss of metal  ions  is  metal  is  metal  Amberlite  of  raonodentate  by ion-exchange  Gation-exchange  as  solution will  displacement  avoided.  in a  the  then  resin  displaced  of  -  cit.).  If of  solution of  8  with  the  the  stereo-  N?^$ii).-fp^f''functioning for  only three  mono-  tridentate  l i g a n d per  atom  The l i g a n d - e x c h a n g e  capacity  (L.E.C.)  of  a  - 9 -  N  3 free  positions  \  \  resin able  i n metal-ion form, coordinative sites  1962 b)  c a n be  of  the  number of  the  metal of  fixed  bonds  Previous the  to  exchange  resin  ion-exchange  the  resin)  and  (HELFFERICH, capacity•  used  ligand  compounds  1952b,  1957, 1958) f i r s t  through. form,  a mixed aqueous  the  number  exchange  organic  in Fe(ili)  passed  Z is m  the  resin.  from  i n bisulphite-form to  Dowex 5 0 , F e ( i i i ) from  avail-  volume o f r e s i n  the  t h a t p - d i k e t o n e s were  resin,  monoketones  the  to  workers have  (1952 a,  exchange  of  maximum c o o r d i n a t i o n number m i n u s  bonds  extraction of  noted  number  number o f a v a i l a b l e c o o r d i n a t i o n p o s i t i o n s  SJOSTROM  then  unit  the  lig  (the  fixed  per  c a l c u l a t e d from  X  where N„ i s m  d e f i n e d as  to  form,  sorb  whilst  used an  by a  a column  and  anlonHe  cation-  cX - d i k e t o n e s  used  caffeine  solution.  ketones.  retained  L a t e r he sorb  aqueous  for  and of  antipyrine  s o l u t i o n , a»d subsequently  eluted  - 10 -  the  caffeine  3N  removed by the  stability  Cu(i) a  from  HC1. of  on the  saturated  liquid  over  nitrate. MULLER and  water,  ammonia  for  patented  an a n i o n - e x c h a n g e  of  (1961, form  to  from  both  ligand the tion  resin  sorb  was  1 9 6 2 b)  the  dilute  of  that  of  with  by  that  silver  QIESEN  and  purification absorption  The most is  the  with  con-  detailed  o f HELFFERICH  A m b e r l i t e CO  50  in  Ni(ii)  ligand 1,3-diaminopropan-2-ol  aqueous and  ammoniacal  30% a m m o n i a  selectivity with  concentration.  obtained  by p a s s i n g  separation,  system  and  hydrocarbons  pretreated is  be  Ag(i)  previously activated  who u s e d  bidentate  d i s p l a c e d by  reversal  process  solution.  ligand-exchange  1962 a,  resin  of  (1958)  polyhydric alcohols  aqueous borax a  THOMAS  to  measured  complexes  unsaturated  tfcie r e c o v e r y , of  (195*0  i n gasoline  anion-exchange  concentration  study  amine  of  antipyrine  WALTON  resins.  separation  Anqther  centrated  and  hydrocarbons  an  (1959)  l e a v i n g the  STOKES a n d  i n cation-exchange  patent  on  with  solutions.  i n accordance  increasing  total  This with solu-  - 11 II. 1.  E X P E R I M E N T A L METHODS AND M A T E R I A L S  Treatment The  of  the  cal  used  cross  in  this  acidic  sulphonic  acid  linkage,  spherical  beads,  "Baker  Analysed"  reagent  from  J.  T.  C G 50:  a weakly  acidic,  carboxylic  work  were:  type  with  100-  Baker  Chemi-  Co.  Amberllte crylic  100-200 mesh b e a d s ;  type;  Haas R e s i n o u s  Products  graphic  by  Grade  Dowex A - l : a diacetate but  resins  strongly  divinyl-benzene  200 m e s h ;  Resins  cation-exchange  D o w e x 50W - X 8 : a 8$  -  from  The m a t e r i a l directly quality  groups.  the  varied  The  Chromato-  as  the  cross-linkage  and  to  "Dowex C h e l a t i n g  Baker  as  "Bio-Rad  stated,  be  Resin  Chel.  This  ca.  form.  supplied  Dow C h e m i c a l C o . , a n d batch.  as  Anal.  product  imino-  not  Na  batch  was  was  beads were 50-100 mesh,  experimental  it  with  to  manufacturer, from  copolymer  found  available and  supplied  characteristics  spherical was  by  b y Rohm  styrene-diy-inylbenzene  active  The  manufactured  Mallinekrodt.  swelling  3% D V B .  Division,  polymetha-  resin  A - l " from  is  J.  Resin-Chelex  the now  T.  100"  from  Calbloohemsv. (a)  Conditioning  and  ,  were c o n d i t i o n e d  The  resins  Storage by a l t e r n a t e  cycles  - 12 with  2M s o d i u m h y d r o x i d e a n d  washed  between  washingswere same t y p e and  cycles with  clear.  of glass  sion  fracture  the  ethylene little  b)  t h y m o l added  metal  were  to  the  i n the  until  shown by S p o t which  until  performed i n the  the in  the  sorption  Sodium hydroxide  r e s i n bed because  then  the  Tests  i n the  synthetic  i n h i b i t the  Resins  to  the  was  expan-  Na f o r m  could  Na f o r m i n  poly-  seawater,  metal  salt  effluent (FEIGL,  was  the  that  1954  s i z e was  by washing through  Forms  run  through  concentration i n the  and back-washed was  a  fungi.  Transition-metal  equalled  washed  with  growth of  i n Na f o r m u n t i l  effluent  c o n t r o l o f mesh graded  the  stored  under  resin  The r e s i n b e d was water  used  (Pig. l ) .  M s o l u t i o n of  water-washed  led  were  containers  A 0.5  the  was  and  column.  Conversion of  the  water  conversion of H form to  The r e s i n s  of  column as  by u p - f l o w through  during the  distilled  C o n d i t i o n i n g was  e l u t i o n experiments  passed  2M h y d r o c h l o r i c a c i d  feed.  with  free  of metal  a).  For experiments  desirable, Standard  the  ion  distil-  resin  Sieves.  as in  beads  100  ML R E S E R V O I R  \  CONSTANT. H E A D  NON-DRAIN RUN-OFF  /  FLOWMETER RESIN  BED  NEEDLE  RECT RUN-OFF  FIGURE  It  A P P A R A T U S FOR L I G A N D - E X C H A N G E  VALVE  - 13 2.  a  Analytical  )  Procedures  The P r e p a r a t i o n o f a S y n t h e t i c The  HARVEY  Seawater  f o r m u l a o f LYMAN a n d F L E M I N G ,  (1955) w a s u s e d t o p r e p a r e a s y n t h e t i c  The  A . R . grade  and  made u p t o v o l u m e t o g i v e a w a t e r  S $*=34.33. b)  salts  The pH a f t e r  acids  water  solutions..  (SCHLENKER  The samples  water  s o l u t i o n was added  agent  prepared  and a l l reagents  70 g  a d d i n g 125 m l c o n c e n t r a t e d and f i n a l l y  The f l a s k  adapted  T o a 25 m l s a m p l e  by d i s s o l v i n g  acid,  1953)  10 m l o f a m a n g a n o u s  was l e f t  ( l V g hours  the  oxidation.  diluting  the  s o l u t i o n heated  t o 6o°C,  were  brought  of the  sea-  sulphate  t o one l i t r e  re-  of tartrate) oxalic  s o l u t i o n was f o r one  to  acid  and the excess  with  for ten  i n the water-bath  25 m l o f s t a n d a r d  sea-  H ^ S O ^ a n d 125 m l 85$  i n the water-bath  i n the case  for  M n S O ^ . ^ H g O i n 500 m l  20 m l o f a p o t a s s i u m p e r m a n g a n a t e  added and t h e m i x t u r e l e f t hour  o f C i t r a t e , T a r t r a t e and  a n d RIEMANN,  Q  minutes.  was 8.00*0.05.  aeration  3 °C i n t h e w a t e r - b a t h .  water.  o f C I $ e =19.00,  was b y a method f o r t h e d e t e r m i n a t i o n o f  fruit  phosphoric  water  i n Seawater  Analysis  water,  seawater.  were d i s s o l v e d i n d i s t i l l e d  The Q u a n t i t a t i v e A n a l y s i s Oxalate  to  as given by  complete was a d d e d ,  oxalate  - 14 titrated  c)  against  KMnO^ f r o m  Spot^est f o r A m i n o - a c i d s I n Three  5 citrate paper for  standardised  drops  buffer  of a  were  solution and the  minutes  spotted  to  be  tested  intensity  standards.  Proline  (FEIGL,  of  The l i m i t  comparison with  duced w i t h  110°C  at  b).  7 cm c i r c l e  N o . 595)  i n the  w h i c h was  oven. the  of  detection  paper  good t o  determined as  The l i m i t  was ±  by the  of  filter  then  dried  of  dried  the  again,  compared  10 ppm a n d  with the  5$. purple  compared w i t h of  i n pH  One d r o p  c o l o u r p r o d u c e d was  nitroprusside,  1954  Seawater  on a  was a d d e d ,  standards was  mlcroburet.  1% s o l u t i o n o f n i n h l d r i n  (Schleicher & Schuell  five  a  detection  was  colour  pro-  standards 10  ppm.  3.  15  -  Radio-Carbon Techniques Fifty  ( 1 . 7 mg)  microcuries  of DL-Glutamie  Acid-1-  14 C, ml  s u p p l i e d by N u c l e a r C h i c a g o ,  of d i s t i l l e d  solution  was p i p e t t e d  seawater,  giving  555 * 1 . 1 1  with  water.  into  edge.  dryness under  r i m to  an  not  the  for  20 L c a r b o y  sample  prevent  not  for  to  be  counts  the  the  spread  were  of  corrected  low l e v e l  taken  was  counting rate.  factor  counted  was  w h i c h h a d a wax  co-incidence or r e g i s t e r  dpm/ml by m u l t i p l y i n g by a  glutamate  circle  solution  l a m p , a)tid, w h e n c o o l ,  as  to  counted  the  read  the  from  backwhich  of counting employed. standard  geometry  corrected  for  Flow  losses,  The cpm/ml were  s e l f - a b s o r p t i o n and counter  samples  filtered  ( N u c l e a r C h i c a g o M o d e l D - 4 7 Gas  s i g n i f i c a n t at  sample  of  was c a u t i o u s l y e v a p o r a t e d  The measured  The c o u n t i n g e r r o r of  each  Infra-red  a G e i g e r Tube  ground but  stock  dpm/ml.  The l i q u i d  under  Detector).  were  each  on a n i c k e l - s t e e l planchjet  the  10 m l , o f t h i s  s o l u t i o n 5.785 x 1 0 " M i n  a  drawn i n s i d e the to  100  A portion,  A 1 ml p o r t i o n of plated  was d i s s o l v e d i n  deviation corrected  and converted  counts  of  to  weighed  a c a l i b r a t i o n curve  (Fig.  2).  14 The curves acid  were  standards  tially  prepared at  weightless  by c o u n t i n g  various samples.  C-labelled  d i l u t i o n s from  seawater  aminoto  essen-  FIGURE  2>  SELF-ABSORPTION  CORRECTION  CURVES  - 16 4.  Seawater  All trated to  Samples  glass-ware  nitric  absorb  reagent  acid,  nitric  acetone  then  ographic  most  boiling  filled  with  then  three  final  concentap-water  Three washings w i t h  followed;  redistilled  rinsings  with  water.  The s e a w a t e r , the  briefly  fumes.  double-distilled  below  was c l e a n e d w i t h  active  details,  c o l l e c t e d i n van Dorn b o t t l e s p o r t i o n of the  T a b l e 5) w a s r u n  photic  zone  initially  from (ocean-  into  4 L R  conical  flasks,  filters  o f 0.45  boys. fied a  then  filtered  pore  Carbon-l4 t r a c e r with  HC1.  into  was a d d e d  When p o s s i b l e t h e  deep-freeze d u r i n g the  activity.  size  through  return  t y p e HA M i l l i p o r e  20 L g l a s s and the  or  contents  carboys were  trip  to  plax  reduce  car-  acidi-  placed  in  bacterial  TABLE 5 OCEANOGRAPRTC DATA ON SEAWATER S A M P L E S T A K E N Cruise No. 62/7  Station No.  Latitude and Longitude  L o c a t i o n Date a n d Depth Sample T°C Time to Depth P.S.T. Bottom  Pac3-2  48°13'N 127 25'W  W e s t o f 29.3.62. m. Vancouver 2580 Island 0815-1400  Q  50  8.0  31.70  7.64 4.2  10.5.62. 2700 1020-1130  50  8.87 32.68  7.91 4.2  72  50  8.0  50  9.36 32.36  6.20  8.3  2.8  3.4  0.28  7.6  2.8  5.24  8 . 1 4 2.6  "  Pac3-3  47°20'N 130°55'W  N . E . Pacific  62/14  QC-1  50°51'N 126°25'W  Queen 20.5.62 Charlottel510-l6l5 Str.  63/16  Pacl-7  47°59*N 127°30'W  N . E . Pacific  8.5.63 morning  2616  "  "  "  "  "  Juan de Fuca Str.  3.4  161  J u a n d e 7-5.62. F u c a Str.1615-1800  48°15*N 123 10*W  ,  32.65  48°20'N 123°50»W  JF1-1  Acidification t o pH  7.9  JFl-3b  11.5.63 128 afternoon  1000 50  31.84  34.42  8.8131.25  6.0  pH  m. 5G  62/13  "  0 ml/£  5.83  4.0  - 17 5.  Column O p e r a t i o n The column d i a m e t e r ,  formity chosen  of  resin  for  the  beads  the  plus  meter  capacity  to  appeared  A constant  the  of  head  flow  and  uni-  feed,  were  The V o i d Volume  where  effluent  expressed  to  on the  feed  of flow feed  was  as  of  at  ensure reserflow-  feed.  The  or  ligands  Breakthrough  mM f e e d / m l  Volume o f E f f l u e n t  was  and a  ions  the  fluid  The bed  settle  needle-valve  rate  point  i n the  (.B.C.)  B.C.  of  and a l l o w e d to  a constant  used  Capacity  size  by d r a i n i n g .  a glass-in-tefIon  ensured  first  measured  back-washed  adequate packing. voir  and r a t e  length,  volume o c c u p i e d by i n t e r s t i t i a l  c o l u m n , was  briefly  bed  optimum column o p e r a t i o n .  (VilV.) i . e . in  -  resin  Breakthrough  Void - Volume  -  X R e s i n Volume  where  M =•  Passage in  the  used  of  feed  effluent  to  this  w h i c h was 3).  Molarity o f  removing the  •:  equalled  estimated  of  continued  s t a g e was  The Degree  fraction  was  the  feed  that  the  until  the  i n the  feed.  Equilibrium  from the  concentration  effluent  o f Column U t i l i s a t i o n  Capacity history  l i g a n d from the  feed,  capacity (E.C.),  (see  (D.C.U.),  c o l u m n p a c k i n g w h i c h was  ion or  The  that  effective was  Fig.  in  defined  as  M  -  the  ratio  of  the  expressed  as  a  breakthrough  was  defined  found city  as  defined  and  B.C. = — E.C.  of Ligand  equilibrium  the  ratio  x  1 0 0  capacities,  %  Exchange C a p a c i t y of  i n column o p e r a t i o n as  -  percentage.  D.C.U.  The U t i l i s a t i o n  1 8  the  to  equilibrium capacity  the  ligand-exchange  i n Section 1 - 3 , expressed  U.L.C.  =.  (U.L.C.)  E.C. 1 L . E.C •  x  100  as  %  a  capapercentage.  - 19 III.  1.  The E f f e c t  of  EXPERIMENTAL  Seawater  RESULTS  upon R e s i n s i n  TransItIon-metal  Form Synthetic  seawater  water-washed  resins  mine whether  the  of  seawater.  of  the  1954  a)  resin in  and  i n t r a n s i t i o n metal  m e t a l w o u l d be  The e f f l u e n t  metal  was r u n t h r o u g h  i o n by the  was  beds  form  of  to  deter-  d i s p l a c e d by the tested  appropriate  for  spot  the  (FEIGL,  changes  In the  c o l o u r and volume o f  bed were a l s o  looked  for.  Table Of  cations  presence  test  The r e s u l t s  the  are  the given  6. the  resins  and  N i ^ H ^ ^  forms,  the  t r a n s i t i o n metal  tested,  only  adequately i o n by the  Dowex A - l , i n  resisted cations  Fe(lii)  displacement of  seawater.  of  TABLE  6  THE E F F E C T O F SEAWATER UPON R E S I N S I N T R A N S I T I O N - M E T A L RESIN  Amberlite  RESULT  FORM  D o w e x 50W-X8  Fe(iii)  C G 50  effluent test for  yellow; Fe(iii)  strong positive w i t h 0.5$ K ^ P e . ( C N )  Ni(ii)  effluent green; strong p o s i t i v e t e s t f o r N i ( i i ) w i t h 1$ e t h a n o l i c d i m e t h y l g l y o x i m e (2)  Ni(ii)  effluent Ni(ii)  Ni(NH-)u z  green;  positive  effluent blue-green i n s m e l l i n g o f ammonia  3  Dowex A - l  FORM  c a . 5 ppm F e ( i i i ) i n WTTen r e s i n b e d w a s i n b u f f e r e d t o t h e pH o f F e ( i i i ) was no l o n g e r i n the effluent  Fe(iii)  test  for  colour,  effluent. itially seawater, detectable  Ni(ii)  positive test for Ni(ii) in effluent Ni(NH ) no. d e t e c t a b l e N i ( l l ) i n e f f l u e n t 3 3 n o r ammonia b y N e s t l e r ' s r e a g e n t (3) Cu(ii)  'l)  2) ,3) k)  detection  " " "  not e l u t e d In q u a n t i t i e s great enough.to give the c o l o u r of 'hydrated G.u(il) i o n to effluent b u t d e t e c t a b l e a s c a . 10 ppm b y 0.5$ r u b e a n i c a c i d T n m e t h a n o l  limit  1  " 3 " 0.5 " 0.1  ppm ppm ppm ppm  6  - 20 2.  The Measurement  Two m e t h o d s •equilibrium through  Ion-Exchange  were  capacity,  used,  and  the  the  Capacities  first  to  second to  give  the  give the  break-  capacity.  In  the  e q u i l i b r a t i o n procedure,  volume o f graded effluent of  of  resin  was n e u t r a l ,  a transition  the  colour of the  the  end-point.  titrated  salt,  hydrated  This  measured  i n Na f o r m was w a s h e d then  metal  a  against  using the metal  until a  solution  persistence  ion in solution  e q u i l i b r a t i o n procedure  the  was  of as slow.  if  In  the  column technique  capacity, were  successive  used  portions  washed by d i s t i l l e d  resin,  Na f o r m ,  to  until  of  water  the  obtain the  the  metal  through  first  trace  breakthrough salt  solution  a  bed  of  the  of  the  colour  of  •i  the  hydrated  effluent. band the  of  t r a n s i t i o n metal  The c o l o u r e d l e a d i n g - e d g e  converted  exchange.  studied are Dowex A - l  value  0.33  also  of  the  i n d i c a t e d the  for  the  in  the  advancing progress  two t y p e s  of  of  resin  given below.  experiments of  resin  The r e s u l t s  •An E . C . o f tion  i o n was v i s i b l e  O.318 with  mM/ml was  found from  2M N i S O u . This 2+ mM C u C N H ^ ) ^ / m l Na f o r m  is  equilibra-  lower than  quoted  by  the  the  - 21 manufacturer, pected pH  to  but  vary  the  capacity  with different  -  of  the  metals  resin and  may b e  at  ex-  different  levels  The B . C . w i t h 0.1M N i S O ^ exchange  of  was  favourable  very  alkali  metal  was  ion for  with this  identical,  transition  resin,  as  the  so  the  metal  ion  D.C.U.  was  100$. There in  the  metal  conversion forms.  calculated sured  was  of  from the  CO  form r e s i n  60$  reduction  in resin  D o w e x A - l , Na f o r m , the  resin  to  volume transition  i n other  k n o w n E . C . o f Na f o r m a n d  volumes  (Table  forms  was  the  mea-  7).  50  Equilibration Na  to  The E . C . o f  relative  Amberlite  50  gave an E . C . o f  (manufacturer  quoted TABLE  3.5  3.06  mM N i ( i i ) / m M  meq/ml).  7  E Q U I L I B R I U M C A P A C I T Y OF DOWEX A - l I N V A R I O U S RESIN  FORM  . RELATIVE VOLUME  FORMS  EQUILIBRIUM CAPACITY meq/ml  Na  1.00  0.318  H  0.45  0.71  0.53  0.60  Ni(ii)  0.60  0.53  Cu(ii)  0.53  0.60  Fe(iii)  .  - 22 .3.  The Measurement  o f L i g a n d - E x c h a n g e C a p a c i t i e s I n Columns  a)  Dowex A - l , F e ( i i i )  form,  xylate  anions  solution i n synthetic  from  The r e s i n , glass  gave  50  column w i t h  synthetic  carboxylic  m l , was  poured  fritted-glass  seawater  a negative  Allquots  dilute  was u s e d  until  test  the  into  base,  was t h e n  run through  of the  effluent  were  method d e s c r i b e d  was  continued after  a 1.7  in Section III-2. breakthrough  to  Passage  synthetic  seawater  feed,  then washed w i t h  distilled  water  ligand the  •  was t h e n  results  •  for  obtained  .  are  4  The r e s u l t s  of  the  effluent  are  m l , the  the ml/min.  of  AgNO^.  by  feed The  displace the  effluent  Elution acids  the  used  of  the  and  below.  M.  titrations  of  the  aliquots  of  shown i n F i g . 3 .  With a r e s i n volume of 30  to  until  The o r g a n i c  given  •  C i t r i c . - J S i £ t e £ l i S 6 x 10 —. * : i r " " - • -v\  the  C l ~ with  attempted.  and  5  equilibrium.  flushed with  test  8  c o l l e c t e d and a n a l y s e d  was  a negative  with  r e s i n at  resin  gave  cm I . D .  h a d a pH o f  the  carbo-  seawater.  The s o l u t i o n o f  acid  the  extract  and washed  effluent  for F e ( i i i ) .  to  50  ml and a v o i d  b r e a k t h r o u g h v o l u m e f o u n d was  180  ml  volume of giving  -2 a B . C . of 0.79  x  10"  O.167 2  x 10  mM/ml was  mM/ml.  From the  estimated.  g r a p h an E . C . o f  The D . C . U .  w a s 2.1.2$  FIGURE  3:  C I T R A T E SORPTION  AND E L U T I O N  1300  - 1200 - 1100  - 1000  _ 9OO  - 800  -700  - 600  - 500  -  400  L  300  \- 200 Equilibrium  FEED  l>c$o  kb~o  6o'o  800  1000  1200  E F F L U E N T VOLUME m l  W  AOXJ  i4'oo  EDiUTE  1600  i8bo  - 23 and  the  U . L . C ,  l i g a n d assumed  Citrate at  a  was  eluted,  concentration  In HC1,  a  eluted  Tartaric  the  resin  A saturated at  one  so  but  2 x  the  the  10'  feed  solution of  quarter  also  Fe(iii)  that  a more  brought  1.32$.  was  of  by  the  dilute Fe(iii)  1M H g S O ^  feed.  acid, off  0.O1M  the  resin.  10"3M.  5 x  The B . C . was from  times  experiment,  citrate  acid,  along with  thirteen  repeat  tridentate,  feed  mfd/ml,  2  was  boric  not  but  Fe(iii)  continued pH 4,  acid,  concentration  to  was  equilibrium.  eluted  with  removed  tartrate  only a  trace  of  iron.  Oxalic  This as  to  5 x  acid,  make  10~^M.  l i g a n d removed evaluations  of  Fe(iii)  from the  capacity  resin  so  readily  impossible.  Amino-acids  Dowex A - l , F e ( i i i ) aeids  from  procedure for  was  the  amino-acids  III-2. two  solution  Table  other  in  8 gives  ligands,  was  synthetic  same a s  i n the  form,  for  seawater.  was  results  glycolic  to  sorb The  carboxylic acids.  effluent the  used  acid  as  for and  given the  in  aminocolumn The  test  Section  amino-acids  acetylacetone.  and  TABLE SORPTION LIGAND  OP A M I N O - A C I D S B Y DOWEX A - l I N F E R R I C - F O R M  FEED CONC. M  (1)  1x10  glycine (bidentate)  '  p H OF P E E D C A P A C I T I E S D.C.U. AND R E S I N B?C. E.C.  -P c  _3 glutamate 5x10 (tridentate)  -2  1.3x10  -2  1.0x10  -3,,,  proline 5x10 (bidentate)\ glycolic acid  \  8  '1x10  -R  -2  acetyl/p\4xlO~ acetone^ ' (bidentate)  2  (1) (2)!  > U.L.C  8  0.002  0.009  8  0.013  0.040  32.5  6.6  5  0.011  0.039  28  6.5  3  0.011  0.091  12  45.5  8  no  retention  8  no  retention  8  0.08  22 -  Not e l u t e d b y pH 4 b o r i c acid buffer Iron readily the r e s i n  removed  from  2.25  -  b)  24 -  Dowex A - l , N i ^ N H . ^ ) ^ f o r m ,  labelled  glutamate  dissolved  was used  i n synthetic  t o sorb  Re-  seawater.  -2 The was  run at  feed,  1 x 10  M In glutamate,  1 ml/min through  E.C.  was 0 . 0 4 0 mM/ml f r o m w h i c h a D . C . U .  the  glutamate  the  feed.  capacity  Spot  tests  i n a volume h a l f  detected  'wi(ii)  during  elution.  c)  A m b e r l i t e C G 50 i n N l ( N H ^ ) ^  glutamate  from  fed at  column. through  virtually  effluent  M solution  The c o l o u r  displaced.  passage  -2  1 ml/min through  green  displaced  that of  i n the  effluent  f o r m was u s e d  to  sorb  seawater.  A 1 x 10 was  o f 33.3$ a n d  A m m o n i a , 30$,  calculated.  from t h e r e s i n  i n a 1 cm  w a s 0.0133 m M / m l a n d  column.  o f 7.55$ w e r e  dpm/ml)  15 m l o f t h e r e s i n  I.D.  U.L.C.  Breakthrough  (1110  glutamate  i n a 1 cm I . D .  bed changed ammonia,  occurred  and the r e s i n  o f 10 b e d - v o l u m e s  C-labelled  the resin  as, first  Breakthrough  history  14  of the resin  to white  zero,  of  from  then  n i c k e l , was  immediately,  hence B . C .  was f u l l y - l o a d e d  of feed.  w a s 0.0833 m M / m l ,  blue,  after  The E . C . from t h e from which a  U.L.C.  of  2.7$ w a s c a l c u l a t e d , a s s u m i n g t h a t o n l y o n e m o l e c u l e  of  g l u t a m a t e was a t t a c h e d  t o each  nickel  atom  i n the  resin.  - 25 Ammonia  and N i ( i i )  out  experiment,  the  "no d e t e c t a b l e his to  were  of  with  nickel  this  not  concentrated  from  effluent  through-  (1962b) s t a t e s  the  bed o c c u r r e d "  passed  i n the  as  eluant,  but  Dowex A - l I n C u ( N H ^ )  mM/ml^p||g^.ower Cu(ii)  from  than  effluent.  of  ligands.  f o r m was  seawater.  for NifNH^)^  i n Dowex A - l h a d b u t  attachment  in  gluta-  -I  l a b e l l e d .glutamate  that  resin.  m a u v e w h e n 30$ a m m o n i a w a s  m a t e was  i n the  though HELFFERICH  loss  experiments  detectable  one  used  to  sorb  The B . C . was form,  free  h -Re-  0.0033  presumably  position for  because  the  - 26 4.  Extraction  from N a t u r a l  Glutamic tracer water  In the as  the  acid,  highest  Seawater  labelled  experiments  -  14  with  C , was u s e d  on e x t r a c t i o n from  degree  of  as  natural  column u t i l i s a t i o n  sea-  |thd  ine f f e c t i v e • l i g a n d exchange c a p a c i t y had been shown i n t h e small-scale tests with this ligand. Some l a t e r e x p e r i ments  were  performed w i t h  S e a w a t e r was  the  in Section III-4.  pH o f  seawater  the  seawater  base at  10 m l a l i q u o t s for  counting of  metal  of  the  was a d j u s t e d  to  effluent  the  C. added  the  with  were  de-  2M Na.OH.  of  The  column  with  10 m l / m i n  taken at  1 ml samples  as  laboratory,  i n a glass  a controlled rate  duplicate  d i s p l a c e d from  Cruise  On r e t u r n  w a s r u n t h r o u g h tike r e s i n  fritted-glass  14  c o l l e c t e d and t r a c e r  ;  scribed  DL-Alanlne-l-  and  intervals  and t e s t i n g  for  resin.  62/7 Water  c o l l e c t e d at  S t a t i o n Pac  5 0 m l o f Dowex A - l , F e ( i i i )  form,  in a  3-2  was r u n  V4"  I.E.  through column.  Q  .The f e e d , s o l u t i o n w a s 5.785 x 1 0 ~ ° M o l a r . a n d h a d 4 0 3 . 2 ±= 14.8 three  days  storage  dpm/ml. at  p H 3.4  immediately  and e q u i l i b r i u m  had  giving  feed  passed,  was a c i d i f i e d  The l o s s was after  an E . C . o f to  p H 3.9  6.95  25$. only  in  glutamate  of activity  after  Breakthrough occurred six  x|^0~^  litres mM/ml.  of  feed  When  by HC1 and r u n t h r o u g h  thj&  freshly  - 27 prepared tained  Pe(iii)  giving  an E . C . of activity  a column c a p a c i t y  15.0  in  form r e s i n b u f f e r e d  10"^  x  samples  showed t h a t  presumably  as  92$ w a s  7*65 x 10"  of  mM/ml  mM/ml b y e x t r a p o l a t i o n .  of  experiment  pH 4,  to  the  feed  counted  a c t i v i t y was  CO^ due  to  at  lost  bacterial  reand  Lower  the  end  of  from the  the  feed,  oxidation,  during  at  JFl-3b,  processing.  62/13  Cruise  Samples and  Samples  batch  C and D at  t||e  run  through  extractions.  this  of  this  previously  through  the  reconstituted was  sorbed  column  Station  3-3-  The  8 x 10"^  C o . was  resin  i n "V^" I.D. failure  batch  of  was  resin,  used  o f D were columns. attributed  which  form than  was the  used.  remaining half  manufacturers'  in Fe(iii)  from the  capacity  second  A , B , C and h a l f  i n c o l o u r when i n F e ( i i i )  S a m p l e E a'riljl t h e run  Pac  n e g l i g i b l e and the  low c a p a c i t y  much l i g h t e r batch  Station  Samples  100 m l o f  R e t e n t i o n was the  taken  o f D o w e x A - l p r o v i d e d b y Dow C h e m i c a l  for  to  A , B and E were  of  mM/ml by  first  x 10"^  batch  Some 8$$  form.  second h a l f 4.13  of  of  o f Dowex A - l of  the  feed  Sample D, g i v i n g  mM/ml,  extrapolation.  Sample D were  and E . C . o f  a ca_.  - 28 -  Despite a c i d i f i c a t i o n to pH 2.6 aind f r e e z i n g , only i'i  h a l f the added a c t i v i t y was present i n Sample E a f t e r days storage.  18  The seawater sample, brought to pH 4 . 1 ,  was run through 200 ml of Dowex A - l , F e ( i i i ) form, i n a " V ^ " I . D . column.  The f i n a l l e v e l of counts i n the  ent was one t h i r d of the feed.  :  efflu-  The l e v e l of a c t i v i t y i n  the feed d i d not decrease during the r u n .  The r a t i o of  a c t i v i t y r e t a i n e d by the r e s i n to the amount fed was 88.6$, g i v i n g a column c a p a c i t y of 5.13 x 10  mM/ml from which  6  an E . C . of 17.35 x 10" ( F i g . 4) . Cruise ,62/14  mM/ml was estimated by e x t r a p o l a t i o n  .  I t was hoped that by using r e s i n of smaller p a r t i c l e s i z e , f u l l s o r p t i o n by a smaller t o t a l q u a n t i t y of r e s i n c'^ld be achieved. Dried beads of Dowex A - l , F e ( i l i ) form, were ground i n a mortar, then graded by Hydraulic Separation (HAMILTON, 1958).  A l l p a r t i c l e s smaller than 230 mesh were washed  away .and a l l greater than 130 mesh were l e f t behind. A 50 ml p o r t i o n of the 130-230 mesh f r a c t i o n was used i n a V 4 " I . D . column to sorb  l2  * C - l a b e l l e d glutamate from water  c o l l e c t e d at S t a t i o n QC-1, brought to pH 4.5 and run at 5  ral/min.  FIGURE C R U I S E 62/13 S O R P T I O N OF  4 SAMPLE  E  GLUTAMATE  - 29 This  smaller  improve the reached 3.48  extraction.  after  x 10"  3L had  of  '-•  Eighteen l i t r e s glutamate  resin,  after  half  10"^  mM/ml.  volumes  tracer  buffered  the  with  glutamate was  One 18L through  not  feed  was  an E . C . of  only  Station  Pac  and  giving  was  distilled  only twice that  of  attained  o f C l " by  of  of  traced  Pac  followed  5$ o f  Only  the the  ligand  30$ a m m o n i a ,  water.  x  10.4  Six"bed-  D i s p l a c e m e n t :of the  d i s p l a c e d and  sample  column.  an E . C . o f  free  two bed-volumes of  I.D.  7.6>  50 m l o f  run through 3/^"  form. -  m, pH  e q u i l i b r i u m was  passed,  water.  f r o m 1000  V  1-7  the  concentration  in  feed. ,  1-7  water  was  fun  50 m l o f D o w e x A - l , .NiCNHg)^ f o r m , i n b a t c h e s o f After  washed.free  each  batch  of C l  with  30$ a m m o n i a .  By t h i s  of  feed,  the  was  p H 8, i n a  had  distilled  el'uate  seawater  added,  to  feed  :  sorbed  of  T h e r e s i n was w a s h e d  attempted  2.5L.  giving  c o l l e c t e d at  immediate  by two bed-volumes  the  passed,  the  did  c o l u m n s o f Dowex A - l i n N i ^ H ^ ) ^  B r e a k t h r o u g h was  was  mesh r e s i n  Equilibrium with  seawater  run through  the  finer  mM/ml.  6  Samples  with  of  63/16  Cruise  were  amount  sorbed  of  feed  had  distilled  method,  passed,  water  then  displacement  concentrated  fifteen  the  of  resin  eluted one  times,  was  was  with quarter achieved  - 30 14 The e x t r a c t i o n using  the  same t y p e  of  of  C-labelled alanine  resin,  unbuffered.  was  Fifty  attempted mierocuries  14 (0.76  mg)  water  and added  4.74  tion  of DL-Alanine-1to  18L o f  C was filtered  x 10~ M i n a l a n i n e 7  with  t h y m o l was  added  through  m l o f Dowex A - l , N i ( N H  60  as  dissolved in seawater  distilled  to  give a  6ll6 d p m / m l .  preservative.  solu-  A little  The s e a w a t e r )  fomr»%|n  was r u n 3 a V ^ " I.D.  3 3 column, after 3.16 25$  at  a rate  o n l y 800 x 10 ~  of  the  of  ml of  mM/ml. sorbed  2 ml/min. feed  had  E q u i l i b r i u m was past,  On p a s s a g e feed  2% i n t h e  70  appeared  30  ml and  an  overall concentration  of  giving  an E . C . o f  100 m l o f  i n the  void  2M a m m o n i a , volume  ml of ammoniacal e l u a t e , only three  times  achieved  that  of  giving of  the  feed.  - 31 5.  E x t r a c t i o n of Metal-Ligand To d e t e r m i n e  existing  in  whether  seawater  could  Complexes  m e t a l - l i g a n d complexes be  extracted,  pre-  3 bed-volumes  of  14 a  solution of  through X8,  two  both  gible  C - l a b e l l e d glutamate  separate  D o w e x 50W s i n c e  e q u i l i b r i u m was volume o f  attained  feed.  0.35  the  has  the  passage  a much h i g h e r  cations  of  come b y c o m b i n i n g t w o V i j " m l o f Dowex 5OW-X8, of  90  eluted  column to  The a c t i v i t y i n the  effluent,  tween  showed t h a t  the  two b e d s ,  c o l u m n was  89$,  and by the  capacity  Fe(iii)  feed,  form,  i n samples  97$,  displaced  first  sorbed by the  retention  is  than  T h i s was  the  Fe(iii)  second,  bed-  resin  enabling F e ( i i l )  and  and  extrapolation.  that  be  negli-  immediate  o n l y one  seawater.  100-200 m e s h ,  first  of  columns,  m l o f Dowex A - l , Na f o r m , from the  was  86.7$ o f t h e  mM/ml by  disadvantage  r e s i n by the  run  R e t e n t i o n was  breakthrough  * 10"^  D o w e x 5OW-X8 i s  from  p H 8.  Dowex A - l r e t a i n e d  an E . C . o f  Dowex A - l b u t  to  after  was  o f Dowex A - l a n d Dowex 5 0 W -  ml beds  i n Na f o r m b u f f e r e d  with  giving  50  i n seawater  of  the  giving  180  second  plus  ligand  second.  taken  by the  over-  from  be-  first an E . C . of  6 ca.  32  the  best  of  x 10  mM/ml b y e x t r a p o l a t i o n  performance  r e s i n was  of  required.  any  system,  ( F i g . 5). but  a  large  T h i s was . quantity  FIGURE  5  S O R P T I O N OF M E T A L - L I G A N D  A. B.  Between the two Final effluent  COMPLEXES  columns  - 32 6.  The E l u t i o n  of  Ligands  A number  of  r e a g e n t s were  whether  they  Pe(iii)  form,  agents  were  m a t e 'Ind Fe(iii)  would displace without  run  the and  also  through  effluent  glutamate eluting  beds  was  tested  of  of glutamate.  the  for  determine  f r o m Dowex A - l ,  resin  tested  to  metal. loaded  the  The r e s u l t s  The with  gluta-  presence  are  given  re-  of in  Table  9. . Of  the  reagents  2M K H g P O ^  ( F i g . 6)  resin  expanded,  and  bed  t h e r e was  tion  Glutamate CG 150 i n ammonia  ammonia of  the  effect  had  the  there  was  some d i s p l a c e m e n t  retention of  was  which also  and  it  displaced  the  but  served  i n the  to  eluate  the  beads.  was  less  bed  to  disadvantages  positions  regenerate was  never  strong  clog,  due  Weaker ammonia, efficient  of  than that of  to  as  an  the  better  2M, d i d not eluting  30$  by  (Fig.  than  increase  metal.  Amberllte  resin  i n ammonia. to  Fe(iii)  the  forms  the  occupa-  f r o m Dowex A - l a n d  copper-ammonia  c o n c e n t r a t e was  caused resin  and  better  on r e - c y c l i n g due  coordinating  nickel-ammonia  Concentration fold  none p r o v e d  but  poor  by phosphate  tried,  7).  threeThe  in  volume  have  agent.  30$  this  TABLE  ELUTION  FROM DOWEX A - l , F e ( l i i )  Fe(iii)  REAGENT  O.IM  ammonia  2M 6M  9  FORM  TEST  GLUTAMATE TEST (1)  no i r o n d e t e c t a b l e ent (2)  in  efflu-  d i t t o , but a 100$ r e s i n bed volume  increase  3M N H ^ C l  negative  iron  3M N H . C l +• 6M N H ^ , pH 9  iron faint dipyridyl  O . I M NaOH  negative  IM b o r i c pH 4  acid,  no  iron  test  for  1  iron  eluted  0.2 M c i t r a t e , pH 5  effluent yellow in Fe(iii) positive  O . I M HOOC.Na  negative  O.IM  in  c* - i x -  by (3]  for  negative  not  colour,  negative 11  HOOCH  O.IM o x a l i c acid  tested  effluent strongly  not  yellow, Fe(iii) positive  tested  O.IM disodium oxalate 2M N H , , H P 0  iron positive dipyridyl  O.IM  negative  o  KH PO^  ca,  2M KH_PO„  (1)  10  oc-oc'-  positive  ppm  feed concentrated X70  Fe(iii)  qualitatively by C activity.  nir.hldrin  (2)  test  with  (3)  test for Fe(ii) with of F e ( i i i ) ; l i m i t of  I  by  spot  test;  quantitavely  by  4  for  Fe(iii)  K^Ee(CN)j ; i l m i t  of  o< - c * J - d i p y r i d y l d e t e c t i o n 1 ppm.  detection after  1  ppm.  reduction  FIGURE  6  DOWEX A - l , F e ( i l l ) DISPLACEMENT  FORM  OF GLUTAMATE B Y PHOSPHATE  L 8000 ELUTE  2MKH„P0, L  7000  - 6000  EH  W L-5000  3  fe w H  4000  3000  r-2000 0.1  FEED 1000  w "A S H  _^—•-=200  400  p-  600 EFFLUENT  j - — i — j  800 VOLUME  M  KHgPOi  W  E L  U  ,  / \3v  ll  1000  - ML  WASH  1  1200  i  distilled water  n  1400  iOO 1800  FIGURE  7  DOWEX A - l , N 1 ( N H ) 3  DISPLACEMENT  -1-1200 1 x  3  FORM  OF G L U T A M A T E B Y AMMONIA  ELUTE  WASH  FEED 10~ M glutamate 2  pH 8  2 M NH,  borate  H looo Feed  Level  100 E F F L U E N T VOLUME - M L  2E0  - 33 IV. As a method of  organic  to  be  (1)  for  compounds  a very  the  e x t r a c t i o n and  from seawater,  impractical for Of the  DISCUSSION  the  low c a p a c i t y  ligand-exchange  following  cation-exchange resin,  resins  concentration proved  reasonss used,  was a b l e ,  o n l y Dowex A - l ,  in Fe(iii)  or  ni(NH~) 3  form,  to  by the (2)  resist  cations  displacement of  the  metal  from the  resin  seawater.  The b r e a k t h r o u g h  and  extraction  of  level  many o r d e r s  were  of  3  glutamate  equilibrium capacities  from n a t u r a l of magnitude  seawater  for  at  lower than  the  the  the  10  M  capacities  _3 obtained  i n the  Hence g r e a t e r complete lower (3)  quantities  extraction  of  experiments  o f r e s i n were  in Fe(iii),  sorption Ni(NH  of  ligands  sorbed,  could  not  removing the HELFFERICH  of  of  M level.  for  the  ligand  at  be  was a b l e  to  forms  was  proven,  so  strong  that  d i s p l a c e d from the  ligands,  resin  or  u s i n g overmuch d i l u t e  (1962  b)  in his  the  successful  once  without  metal,  use  b y Dowex  3  were  l,3-diaminopropan-2-ol  tions  10  from seawater  )_ and Cu(NH_)  l i g a n d - m e t a l bonds  also  the  required  smaller quantities  3 3 the  at  concentration. Though the  A-l  small-scale  eluant.  extractions  from aqueous and ammoniacal high-capacity  solu-  resin Amberlite  - 34 CO 5 0 ,  but  A-l  regards  as  degree  of  capacity  this  resin the  compared  retention  unfavourably  of  the  column u t i l i s a t i o n and in  experiments  with  metal  use  of  glutamate  w i t h Dowex  by the  resin,  ligand-exchange in  solution  in  seawater. o . The most of  promising procedure  high-capacity  A-l  of  the  Dowex 50W-X8 i n F e ( i i i )  i n Na f o r m i n  tention  was  2^1 p r o p o r t i o n  97$ of  the  to  feed  and  Thus  5 ml of  combination  f o r m w i t h Dowex  g i v e an  an E . C . f o r  overall  re-  glutamate  of  6 ca.  32  should  x  mM/ml.  1G~  be  sufficient•to  occurring  glutamate  sample  seawater.  the  of  resin  bed  extraction  is  and  no g r e a t e r  than  0.5 m l / m i n , extraction.  plete  utilisation must  both  be  and  hence  plete  sorption.  factor  This  the  eluant  were  trated  in a void  jxg of  bed  would a  resins  naturally-  effective  that  complete,  the  L.E.C.  20L  length  of  sharpness  of  a  column of  flow-rate  the  time  of  s o r p t i o n would the  degree  was be  displacement  of  be  for  effeccom-  l i g a n d by  then  the  glutamate  volume o f  ca.  100 m l / g i v i n g  com-  capacity  required the  for  column  o n l y 0.005$  of  less  required  ligand-exchange  r e s i n would  the  the  require  feed  increasing  negligible i.e.  But  that  c o n t r o l l i n g the  assumes  1000ml of If  24  however,  0.5 cm a n d  greatly  100$.  tive,  Note,  than  and wash-out  the  combined  ( D E G E N S et_ a _ l . , 1 9 6 4 ) f r o m a  a 5 ml r e s i n  I.D.  the  a  sorb  the  could  be a  the  concen-  200-fold  - 35 concentration. placement would a  and  with  be  3.5$  However,  that  Hence the exchange  expectation  organic  was  realised.  ful; for from  was  the  of  be  that  a  anions  and  first-stage  concentrated  ligands  of  metal  ion,  ligand  complexes  be  from s o l u t i o n s c o u l d be  transition  m e t h o d was  might  resin  the  of  molecules  concentration  a higher-capacity  or  diseluant  from 20L o f  only  metal, form could  the  on  7$-fold  Z$$> o f i n o r g a n i c  neutral  However, i t  removed  small quantity  concluded that  seawater.  traction  glutamate  in transition  extract  It  the  factor  X7$, s o 300oml o f  only  solution containing  resin  not  Thus  s o l u t i o n would  in a  concentration  2M K H ^ P O ^ w a s  required.  salt  the  from concentrates  cationefficiently  from seawater  not  of  organic  compounds to  the  lower s a l i n i t y without  the e.g.  .  success-  applicable  used for  of  salts.  ex-  where  displacement  extraction  of  re-dissolved  metalFeCOH)^  co-precipitates.  This  i n v e s t i g a t i o n was  t i c a l . p u r p o s e •• of  the  do  indicate,  the  ultimate  dissolved organic  metal-ligand  however, systems  interest  matter  that  the  can be  .known s t a b i l i t y c o n s t a n t s  undertaken  of  for  a purely  attached  seawater.  behaviour  of  to  the  The these  pracnature  results resin-  approximately predicted  of m e t a l - l i g a n d complexes  from and  - 36 1957)  by  the  A few  sample  treatment  due  calculations  to are  R . J . P . WILLIAMS given  in  the  (1953).  Appendix.  - 37 APPENDIX  Some C a l c u l a t i o n s  A simple  (1953)  can  formation fixed when  equation  used  to  between any  pH.  a metal  predict  of  the  Ligand-Exchange  by R.  the  ligand  ion M reacts  base  to  derived  and  From c o n s i d e r a t i o n  conjugate k  be  Relating  degree a  of  P. of  WILLIAMS complex  given metal  the  with a  J.  at  equilibria  a  set  ligand L which is  a c i d HL o f  dissociation  up the  constant  , a M  +  nL  ^  ML  -j-  nHL  ^  n L +•  n  tiH  he obtained the expression  - - •  - -1  a  N  where K tion  n  of  , the the  overall  complex  stability  ML  was  n  constant  defined  [ M I  The  degree  to  which the  [ML J / [ M ] ,  is  a  stant  of  tration t  the of  function  complex,  the  metal  ligand  K  not n  , but  acid,  L nJ ML  log K -t- n l o g k - n logLHJi- n logLHLI* l o g for  ~—  QMj  the  forma-  as  Go"  ion  is  complexe.d,  only  of  the  also  •  of  [HL], and  the of  i.e.  stability pH, the the  conconcen-  acid  I n t h e s e , and subsequent e x p r e s s i o n s , charges for the sake of s i m p l i c i t y of p r e s e n t a t i o n .  are  omitted  - 38 dissociation  constant  inter-related. the  k  of  two o r more u n i t s  where  C is  the  an  expression ,  for  at  [HL]  the  is  lower than  initially  three  a fixed  acid  concentration  acid  oC'  tion,  of  ligand  pH i s  ligand  The l a s t  The e f f e c t  concentration  of  .  added  to  negligible i f the  the the  pk .  the  Then  Q  system.  -oc ')  be  JHL}=C, per  litre  Otherwise  new d e g r e e  p r e v a i l i n g p H , must  (1  are  pH i n s o l u t i o n o n  i n gram e q u i v a l e n t s  involving  [HL] =  quantities  of  dissocia.  used!  .0  where 10  cx' =  The e q u a t i o n  log  p  -  n  for  P  n  k a  the  a  Io"P + l O ^ a H  IML~]/|M]  calculation of  + n pH + n l o g 1 0  -pH  +  is  1 0  now  -pk ^*  nl o g —=— C  M  =  where  the  stant  of  ence  to  term the  the  p  for  complex K  n  of  the  the  original  1957)  is  L  M  cummulatlve s t a b i l i t y  (BJERRUM,  used  C  a  in  n— ]  con-  prefer-  expression.  [ n~l ML  Some v a l u e s  of  log  c a l c u l a t e d as  above,  LMJ for  m e t a l - l i g a n d systems  comparable  with  those  studied  - 39 experimentally, constants ligand  of  acids  otherwise  are  given i n Table  complexes are  as  the  it  found by  type to  plexing  to  the  resin the  of  n  group  of  the  p H 8,  From T a b l e  in  i f  seawater,  active  ligand free  on t h e  basis  in of the  of  the at  a  (glu),  a  ligand  di-carboxyllc concentration  H form of the  resin,  ions  com-  competing  for  2.88  g l u j  [Cu(ii)] and  the  ion  10,  1.25  [Mg(ii)]  CG 50,  metal  and compared w i t h  with Mg(ii)  LCu(ii)]  Now i f  the  glutarate  A m b e r l i t e C G 5©>  at  [Mg(li)  ligand is  [ML1/[M!  Cu(ii)  log  which the  may b e made  consider  active  I.E.C.  Cu(ii),  ligand.  log  unless  experiment.  example,  comparable  equal  (loc. cit.)  w o u l d be w e r e  some p r e d i c t i o n s  For  acid  degree to  same w h e n t h e  calculated values  results  the  the  of a resin  solution, the  f r o m BJERRUM  of  indicated.  complexed i s  group  A l l stability  and d i s s o c i a t i o n c o n s t a n t s  quoted  Assuming that is  10.  =  3.06  [Mg(ii)]  meq/ml, the —  0.10  I.E.C.  meq/ml,  of Amberlite  the  concentration  TABLE 10 VALUES OF LOG [M]  a IMINODIACETATE (Ida)  pH  pk. 9.12  4.0  0.70  M  n  logp  Fe(iii)  1  12.0  2  20.0*"  %  Ni(ii)  8.0  12.0 4.0  Cu(il)  S.o  GLUTARATE (glu)  2  5.06  3.5  lxlO"  3  -10  9.45 10.68  1  8.26  2.99  2  14.6.1  4.07  1  7.34  2  11.97  1  7.99  1  10.55  2 l 2  16.20  5.28  13.56 2.94  0.52  4.0  Cu(ii)  1  2.40  1.84  4.0 8.0  1x10  6.73  1  1 Mg(ii)  8.0 3.94  J>oJ  Mg(ll)  8.0  2  log  8.0  4.0  TARTRATE  1  1  8.0 4.0  n  Fe(lii)  1  2.88 1.08  O.52  1  1.25  1  18.06? 14.82  1  15.12  1  8.12  TABLE 10  -  continued  [«%]  VALUES OP LOG a  PK  GLUTAMATE 3  9.95  [M]  pH  lxlO"  1x10  3  ...  M  8.0  Fe(iii)  ,-8  1x10*  n  logp  1  12.10  1  -2  Nl(ii)  1 2  0.53  AMMONIA  t  estimate  9.20  2  PERRIN,  n  12.0 12.0  1958  [MLJ  M  7.15 2.15  5.90 10.34  1 Ni(ii)  log  1.95 2.43 5.67  1  2.80  2.90  2  5.04  5.24  3  6.77  7.07  4  7.96  8.36  5  8.71  9.21  6  9.74  9.34  -  [ou(ii)glu-Tj  then  __ glUjj  [Mg(li)  1.3  =  Compare t h i s  with  of  Dowex A - l , a t  the  I.E.C. p H 8,  resin of  the  40  -  o  10°  x  Iminodlacetate  ions  the  a concentration  H form of the  with Mg(ii)  (Ida),  resin,  active equal  group  to  the  complexing C u ( i i ) ,  competing for  the  ligand.  at  Prom  10,  Table  Fcu(ii)  ida-,1  log  ti—  log  [ M g ( i i ) Ida,"] — - — - ±  = S  -  A L  {_Cu(ii)J  9.23  =  =  0.52  UMg(iiQ if  [ c u ( l i j ] = 0.60 m e q / m l ,  if  [Mg(ii)]  0.10,  -  as  the  I.E.C.  above,  rcu(ii)ida-r)  o f Dowex A - l , a n d  then  = 3.1 * 10  x  9  CMg(ii)ida^) Thus, both  though these  Mg(ii)  is  the  degree to  ligands  is  greater  complexed w i t h  is  10  is  i n accord with  times  greater  diacetate-type displacement  the  resin,  which C u ( i i )  the  i n the  than  of  experimental  complexed  degree to  ligands,  3ame  case  the  is  the  which  disparity  iminodlacetate, fact  that  the  Ni(ii)  and C u ( i i )  which  imino-  Dowex A - l , much more r e a d i l y  of F e ( i i i ) ,  by  i o n s by  resisted the  -  Mg(ii)  Ions  resin,  A m b e r l i t e CG 50. It  (1)  seawater than  may a l s o  higher  Ni(ii) by  of  41  be  pH l e a d s  and C u ( i i )  d i d the  infered to  for  -  that:  greater  preference  iminodiacetate,  OH , w h i c h w o u l d b e a p p r e c i a b l e  metals  at  pH 8 o r  above as  and f o r  must  be  with  higher  (2)  lower concentration [ML^/EMH.  ions  from the  (C  ^=  of  metal  1 x 10  whereas  though  for  the  Fe(iii)  a competing  of  Pe(iii), competition  divalent  even at  factor  also  pH 4 ,  increasing  pH.  of  values metal  considered  glutarate-type  those  Thus resin  ) might  ions,  of  ligand acid those  of  without  lower  successfully  to  which  small-scale  retained,  from s o l u t i o n s ligands  ligands  i n the  be  leads  lower  removed  experiments, displacement  concentration,  sorbed,  without  dis-  -3 placement readily  of metal,  retained  example, diacetate  compare at  and F e ( i i i )  at  the  from l e s s the  the at  level,  would  concentrated  IMLJ/IMI  pH 8 w i t h glutamate  10  values  values  different  for  not  be  solutions.  of F e ( i i i ) Fe(iii)  so For  imino-  tartrate  concentrations:  -  42  -  log 0.70  iminodiacetate  --  10.68  . .  ••.  -3 1 x 10  tartrate  15.12  1 x 10" _3 ,  «  for  metal a  with  the  than  displacement  resin,  that  without  pH  the  better  of  the  of  a  chosen  sorbed  with  l i g a n d but  For example,  in  the metal-ion,  [ML l/[M] n  less  than  consider  f r o m Dowex A - l , N i ( i i )  n  that the  form,  ammonia  Of t h e  t  log  [Ml  1  7.99  0.53  1  5-67  2  3  7.07  0.70  glutamate  of  ligand  12:  iminodiacetate  The L . E . C .  to  d i s p l a c i n g the  L  t The L . E . C .  of  a conclusion  l i g a n d bound  also  complex.  choice  results.  s h o u l d be  of glutamate  at  be  experimental  resin-metal  ammonia  not  2.15  8  lower concentration;  complexing reagent  displacement by  at  the  the  i n the  greater of  would  experiments  For  7.15  1 x 10"  glutamate  keeping  8.12  1 0  1 x 10  glutamate  Hence  -nrr-  H form of  the  Dowex A - l , N i ( i i )  resin. form.  Thus but  2N a m m o n i a might  glutamate  also  It lated data  stability  any  of  ligands  observed  i n the  Displacement i n the  and to  choosing  loss  investigations  of  experiments,  from  acid dissociation  pair,  ligand acid for  without  resin,  eluate.  metal-ligand  of  from the  similar calculations  a guide  system,  future  was  constant  concentration  elution in  that  could provide  glutamate  some N i ( i i ) .  detected  appears  resin-metal and  remove  was  -  3  should displace  b y 2M a m m o n i a  and N i ( i i )  4  of  the  constant  most  pH o f  tabu-  suitable  solution  the  sorption  and  of metal  from the  resin,  ligand-exchange.  - 44 REFERENCES A B E L S O N , " P . H . , 1959. Geochemistry of organic " R e s e a r c h e s i n G e o c h e m i s t r y " , p p 79-103.  substances.  A N D E R S O N , W . W . a n d J . W . G E H R I N G E R , 1958. Physical Oceanographic, b i o l o g i c a l and c h e m i c a l d a t a . South A t l a n t i c coast of the United States. MA "Theodore N . G i l l " C r u i s e 6 a n d 8. Spec. S c i . Rep. Fisheries  N o . 265, p p I-99 a n d N o . 303, p p 1-227-  B A Y L O R , E . R . a n d W . H . S U T C L I F F E , J r . , 1963. D i s s o l v e d organic matter i n seawater as a source o f p a r t i c u l a t e food. L i m n o l . O c e a n o g r . , 8, 369-372. B E N T L E Y , J . A . , i960. P l a n t g r o w t h hormones i n marine phytoplankton, zooplankton and seawater. J . Mar. Biol.  A s s . U . K . , 39, 433-444.  B J E R R U M , J . e t a 1., 1 9 5 7 - . ^ ^ | S t a , b i l . i £ y . g - o n s t a n t s " , C h e m i c a l S o c i e t y S p e c i a l P u b l i c a t i o n s , " N o . 6'. a n d N o . 7 (1958). C O O P E R , J . E . , 1962. Fatty acids i n recent and ancient sediments and petroleum r e s e r v o i r waters. Nature, 193,  744.746.  COWEY, C . B . , 1956. A preliminary investigation variation of vitamin B i n ocean and c o a s t a l J . M a r . B i o l . A s s . U . K . , 35., 609-620. 1  2  of the waters.  C R E A C ' H , P . V . , 1955. Q u e l q u e s c o m p o s a n t s de l a m a t i e r e o r g a n l q u e de l ' e a u de mer l i t t o r a l e . Helio-oxydation dans l e m i l i e u m a r i n . C o m p t e s r e n d u s , 2 4 l , 437-439. D E G E N S , E . T . , J . H . R E U T E R a n d K . N . F . SHAW, 1964. B i o c h e m i c a l compounds i n o f f s h o r e C a l i f o r n i a sediments and s e a w a t e r s . G e o c h i m . C o s m o c h i m . A c t a . , 28, 45-66. D U U R S M A , E . K . , 1961. Dissolved organic and phosphorus i n t h e s e a . N e t h e r l .  1-141.  carbon, nitrogen J . S e a R e s . , 1,  E R D M A N , J . G . , E . M . M A R L E T T a n d W. E . A N D S O N , S u r v i v a l o f amino a c i d s i n marine s e d i m e n t s .  124, 1026.  1956. Science,  F E I G L , P . , 1954. "Spot T e s t s " , a . V o l . I-Inorganic application b. V o l . II-Organic application, Elsevier. 4th E d .  - 45 F O X , D . L . , i960. Perspectives A n n a l . N . Y . A c a d . S c i . , 90,  i n marine  617-621.  G I E S E N , J . a n d F . M U L L E R , 1959. C h e m . A b s t r . , 54, 13017a.  biochemistry.  U.S. Pat.  2,916,525.  H A M I L T O N , P . B . , 1958. Ion-exchange chromatography o f amino a c i d s . E f f e c t o f r e s i n p a r t i c l e s i z e on column performance. A n a l . C h e m . , 30, 914-191. HARVEY, H . W . , Sea W a t e r s " .  i960.  "The C h e m i s t r y a n d F e r t i l i t y o f C a m b r i d g e U n i v e r s i t y P r e s s , 2nd E d .  H E L F F E R I C H , F . . , 1961. 'Ligand Exchange': a novel separation technique. N a t u r e , 189, 1001-1002. I962 ( a ) L i g a n d E x c T T a n g e . I . Equilibria.  J.  A m . C h e m . S o c , 84, 3237-3242.  of  ligands  1962 (b"T L i g a n d E x c h a n g e . having different coordinative  I I . Separation valencies. J .  A m . C h e m . S o c , 84, 3242-3245. 196^~~(c) New  "Ion Exchange".  McGraw-Hill,  York.  H U N T , J . M . , 1962. Some o b s e r v a t i o n s o n o r g a n i c m a t t e r i n sediments. Paper presented a t the S c i e n t i f i c S e s s i o n , 25 y e a r s o f H u n g a r i a n O i l , B u d a p e s t . J E F F R E Y , L . M . a n d D . W . HOOD, 195,8. Organic matter i n seawater: a n e v a l u a t i o n o f v a r i o u s methods f o r i s o l a t i o n .  J . M a r . R e s . , 17, 247-271.  J O H N S T O N , R . , 1955. B i o l o g i c a l l y a c t i v e compounds i n t h e sea. J . M a r . B i o l . A s s . U . K . , 34, 185-195. I963. S e a w a t e r , th"e~ n a t u r a l m e d i a f o r phytoplankton. Part I . General aspects. Part I I . Trace metals and c h e l a t i o n . I b i d . , 4 3 , 427-456. K A L L E , K . , 1962. D i s s o l v e d o r g a n i c components i n s e a w a t e r . K i e l . M e e r e s f o r s c h , 18, 128-131. ( i n german). K O Y A M A , T . a n d T . G . T H O M P S O N , 1959. Organic acids o f seawater. P r e p r i n t s 1st I n t . O c e a n . C o n g . , 925. L A M A R , W . L . a n d D . F . G O E R L I T Z , I963. Characterization of c a r b o x y l i c acids i n u n p o l l u t e d streams by gas chromatography. J . A m . W a t e r - W o r k s A s s o c , 55., 797-802. L U C A S , C . E . , 1958. E x t e r n a l metabolites and p r o d u c t i v i t y . R a p p . P r o c . V e r . , C o n s . P e r m . I n t . E x p l . M e r . , 144,  155-158.  - 46 M E N Z E L , D . W . a n d J . P . S P A E T H , 1962. Occurrence o f vitamin B I n t h e S a r g a s s o S e a . L i m n o l . O c e a n o g r . , J _ , 151-154. 1  2  M E N Z E L , D . W . a n d R . F . V A C C A R O , 1964. of d i s s o l v e d organic and p a r t i c u l a t e L i m n o l . O c e a n o g r . , £ , 138-142.  The measurement carbon i n seawater.  O R R , W. L . a n d K . 0. E M E R Y , 1956. Composition of organic matter i n marine sediments: p r e l i m i n a r y data on h y d r o carbon d i s t r i b u t i o n i n basins o f f S. C a l i f o r n i a . Bull. G e o l . S o c . A m . . , 67, 1247-1258. O R R , W . L . , K . 0. EMERY a n d J . R . G R A D Y , 1958. ,,Preservation of chlorophyll derivatives i n sediments(S. California). B u l l . A m . A s s o c . P e t . G e o l . , 4j2, 925. P A R K , K . , W . T . W I L L I A M S , J . M . P R E S C O T T , D . W . HOOD, (a). Amino a c i d s i n d e e p - s e a w a t e r . S c i e n c e , 138,  I962 531.  P A R K , K . , L . W . L A T I M E R a n d D . W . HOOD, I962 ( b ) . U s e of c a t i o n exchange r e s i n s i n the a n a l y s i s o f seawater. P a p e r r e a d a t 25th A n n l . M e e t i n g A m . S o c . L i m n o l . Oceanogr., Oregon S t a t e U n i v e r s i t y , C o r v a l l i s , Oregon.  A u g u s t 26-31, 1962.  P A R S O N S , T . R . , 1963. Suspended o r g a n i c m a t t e r . "Progress i n O c e a n o g r a p h y " , V o l . 1, e d . M . S e a r s , M a c m i l l a n , N . Y . P E R R I N , D . D . , .1958. S t a b i l i t y o f complexes amino a c i d s . J . C h e m . S o c , 3120-3128.  o f Fefril) and  P O C K L I N G T O N , R . , 1961. The scope o f s o l v e n t - e x t r a c t i o n of seawater constituents. Thesis f o r Part I I ,B . A . (Hons.). Oxford U n i v e r s i t y , England. P 0 V 0 L E D 0 , D . , 1959 (a) Sulla pre3enza d i chetoacidi nei sediment! d i a l c u n i l a g h i d e l l ' I t a l i a Settentrionale. M e m . 1st. I t a l . I d r o b i o l . , 11, 113-132. 1959 (b) S t u d y o f o r g a n i c compounds i n lacustrine deposites. I n t e r n . V e s . T h e o r e t . Angew. L i m n o l . V e r h a n d . , 1 4 , 256-262. i960. H a t u r a , c o n c e n t r a z i o n e e m e t o d i d i studio d i a l c u n i compost! n i n i d r i n p o s i t i v i presenti n e l l ' acqua d i a l c u n i l a g h i d e l l a I t a l i a Settentrionale. M e m . 1st. I t a l . I d r o b i o l . , 12, 289-334. PROVASOLI , L . , I963. Organic regulation o f phytoplankton fertility. " T h e S e a " , e d . M . N . H I L L , V o l . 2, 165-219. P R O V A S O L I , L . , J . J . A . M c L A U C H L I N a n d M . R . D R O O P , 1957. The development o f a r t i f i c i a l media f o r m a r i n e a l g a e . A r c h . M i k r o b i o l . , 25, 392-428.  - 47 RILEY, J . , 1953. Gons. Perm. I n t e r n . E x p l . M e r . , 19, 85-89. See Fox (i960). SAUNDERS, G . W . , 1957. I n t e r - r e l a t i o n s of d i s s o l v e d organic matter and phytoplankton. B o t . R e v . , 23> 389-409. SCHLENKER, H . H . and W . RIEMAN, 1953. Determination of m a l i c , t a r t a r i c and c i t r i c acids i n f r u i t by i o n exchange chromatography. A n a l . Chem., 25, 1637. SHAPIRO, J . , 1957. Chemical and b i o l o g i c a l studies on the yellow organic acids of lake water. Limnol. Oceanogr., 2, 161-179. 1<558. Yellow a c i d - c a t i o n complexes i n lake water. Science, 127, 702-704. SJOSTROM, E . , 1952 (a) Separation of aldehydes from ketones. Svensk. Kern. T i d s k r . , 64, 15O-I56. C . A . , 49, l 4 8 3 f . 1952 (b) U t i l i z a t i o n of i o n exchangers i n a n a l y t i c a l chemistry• separation of ketones. Svensk. Kern. T i d s k r . , 64, 301-305. C . A . , 47, 4248c. 1957T Separation of caTTeine from a n t i pyrine by means of c a t i o n exchanges i n the f e r r i c i r o n form. A n a l . Chim. A c t a . , 16, 428-430. 1958. IoninvaihTokemian v i i m e a i k a i s l s t a t u t k i m u s - t u l o k s i s t a ja n i i d e n s o v e l t a m i s e s t a . Suomen K e m i s t i l e h t i , 31B, 110-115. S L O W E Y , J . F . , L . M . J E F F R E Y a n d D . W . HOOD, 1962. The f a t t y a c i d content of ocean water. Geochim. Cosmochim.  Acta.,.26,  607-616.  S T A R C K O W A , N . D . , 1962. Qualitative composition of organic m a t t e r d i s s o l v e d i n sea and o c e a n s e d i m e n t s . Tr. Inst. O k e a n o l . , A k a d . N a u k S S S R , 54_, 22-30. C . A . , 58, 5378h. STEVENS, N . P . , E . E . BRAY a n d E . D . EVANS, carbons i n sediments of Gulf of Mexico. A s s o c . P e t . G e o l . , 4©, 475-983.  1956. Bull.  HydroAm.  S T O K E S , R . H . , a n d H . F . W A L T O N , 1954. M e t a l - a m i n e complexes i n ion-exchange. J . A m . C h e m . S o c , JjS, 3327. STRICKLAND, J . D . H . and T . R . PARSONS, i960. A manual o f sea w a t e r a n a l y s i s . F i s h . Res. Bd. Can., B u l l e t i n  N o . 125, p p 81-85.  S V E R D R U P , H . V . , M . W . JOHNSON a n d R . H . F L E M I N G , 1942. "The O c e a n s : t h e i r p h y s i c s , c h e m i s t r y and g e n e r a l biology". Prentice-Hall.  - 48 T A T S U M O T O , M . , W. T . W I L L I A M S , J . M . P R E S C O T T a n d D . W . H O O D , 1961. On t h e a m i n o a c i d s i n s a m p l e s o f s u r f a c e seawater. J . M a r . R e s . , 19, 89-96. THOMAS,  G. L . ,  6593d.  1958.  U . S . Patent  2,865,970.  O.A.,  53,  V A L L E N T Y N E , J . R . , 1956. Epiphasic carotenoids i n postg l a c i a l lake sediments. L i m n o l . O c e a n o g r . , 1_, 252-262. 1957 (a) The m o l e c u l a r n a t u r e o f organic matter i n lakes and oceans, with l e s s e r r e f e r ence t o sewage a n d t e r r e s t r i a l s o i l s . J . Fish. Res.  Bd.,  C a n . , 1 4 , 33-82. 1957  (b)  Carotenoids  i n a 20,000  year o l d sediment from S e a r l e s Lake, California. A r c h . B i o c h e m . B i o p h y s . , 7©, 29-34. 1957 (c) Sedimentary c h l o r o p h y l l d e g r a d a t i o n p r o d u c t s i n s u r f a c e muds f r o m C o n n e c t i c u t l a k e s . C a n . J . B o t . , 35_, 35. V A L L E N T Y N E , J . R . a n d R . G . S . B I D W E L L , 1956. l a t i o n between free sugars and sedimentary i n l a k e muds. E c o l o g y , 37, 495-500. VALLENTYNE, J . R . a n d J . R . WHITTAKER, presence of free sugars i n f i l t e r e d 124, 1026. W A N G E R S K Y , P . J . , 1959. I s l a n d Sound. Bull.  94.  The r e chlorophyll  1956. On t h e lake water. Science,  Dissolved carbohydrates Bingham Oceanogr. C o l l . ,  W I L L I A M S , P . M . , 1961. Organic acids i n Pacific waters. N a t u r e , 189, 219-220. 1964. Unpublished r e s u l t s from communication. W I L L I A M S , R . J . P . , 1953. Metal B i o l . R e v . , 28, 381-415.  ions  i n Long 17, 87Ocean private  i n biological  systems.  

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