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The radioactive determination of uranium in sea water Wong, Robert 1950-12-31

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THE RADIOACTIVE DETERMINATION OF URANIUM IN SEA WATER.  In P a r t i a l F u l f i l l m e n t For The Master*s Degree In Chemical Oceanography  by Robert Wong, B.A.  UNIVERSITY OF BRITISH COLUMBIA (October, 19.50.)  2  THE UNIVERSITY OF BRITISH COLUMBIA VANCOUVER,  CANADA  TRY  October 2,  To Whom I t May This  1950.  Concern: i s to c e r t i f y that  the t h e s i s  entitled  "The R a d i o a c t i v e D e t e r m i n a t i o n o f U r a n i u m i n S e a W a t e r " b y Mr. R o b e r t Wong m e a s u r e s up t o t h e r e q u i r e d of the Master's t h e s i s i n t h i s  Department. Yours  -ew  truly,  standards  THE  RADIOACTIVE DETERMINATION  -OF URANIUM IN SEA -WATER7"""  ABSTRACT.  The the  determination of  order of parts  carried  out  by  per  o f the  measurements.  in equilibrium.  use  o f an  activity  aluminum) b e i n g a d d e d .  of the  concentration.  The 3.0$  method i s t e s t e d  of  ity  method b u t  approximately  The  u r a n i u m i s d e t e r m i n e d as  A, v a r i a n c e of the  use  by  of  1.  Such  amounts:, i s separated  co-precipitators.  alpha-particle a measure o f i t s  two  e f f i c i e n c y of the  50$.  been  separation  control tests.  f o r these t e s t s substantiates the  of  radio-  i o n - e x c h a n g e r and  i n a r a d i o a c t i v e l y pure s t a t e w i t h the i r o n (and  The  i t s isotopes; i n such s m a l l  accomplished w i t h the  the  usually  e m p l o y e d e x c e p t when t h e  known t o be  u r a n i u m and  amounts o f u r a n i u m  h u n d r e d m i l l i o n has  indirect radioactive  measurements c a n n o t be elements are  small  the  valid-  extraction  was  I  INTRODUCTION  I t i s presumed that the ocean came into being as soon as the Earth cooled below the condensation point of water, and since that time i t has been receiving substances leached and eroded from the continents.  Some of these substances  have made the journey from the continent to the ocean and back again several times and may continue to do so. However, i n the case of the radioactive substances which cease to exist a f t e r a time, a l i m i t to t h i s phenomena e x i s t s .  The  non-radioactive sediments may come and go, but a l l the radioactive elements, whether of long or short l i f e , cannot exist eternally but aire t r a n s i t o r y . I t i s then also true that uranium cannot exist forever. The determination  of minute traces of uranium which  are present i n nearly a l l materials has received scant attent i o n e s p e c i a l l y when one considers the quantity of data a v a i l able concerning the radium content of a l l types of matter. In a few radioactive problems the uranium i s present i n s u f f i c i e n t amount f o r determination by standard procedure.  chemical  In the majority of radioactive problems, p a r t i -  c u l a r l y those of interest to tho geophysicist, such as the determination  of geologic time and the production of radio-  active heat, equilibrium i n uranium-238, thorium series has been established.  uranium-235,  Equilibrium i n the  uranium-238 series i s established i n less than 10 3  and  years;  g e o l o g i c a l l y a very s h o r t p e r i o d of t i m e .  The o t h e r  two  s e r i e s a t t a i n e q u i l i b r i u m i n much l e s s than 1©^ y e a r s .  If  the uranium-238 s e r i e s i s i n e q u i l i b r i u m , the measurement of radon i s e q u i v a l e n t t o a d e t e r m i n a t i o n of the uranium o r of  any member of i t s s e r i e s .  An extremely  s m a l l amount of  the gas&ous radon, the d i s i n t e g r a t i o n product o f radium, can be e a s i l y separated from the o t h e r members o f the and measured by i t s i o n i z i n g  series  effect.  PREVIOUS WORK H i t h e r t o no standard a n a l y t i c a l method f o r measuring uranium w i t h the necessary degree o f s e n s i b i l i t y has been known, e l e c t r o m e t r i c methods f a i l i n g i n the case o f  extremely  minute amounts of uranium owing t o i t s v e r y weak a c t i v i t y . A d e t e r m i n a t i o n suggested by J o l y method proposed  by Walker ( 2 ) , was  (1), using a c o l o r i m e t r i c undertaken  40 y e a r s  The q u a n t i t y o f uranium expected from t h e radium  ago.  content  amounted t o over one m i l l i g r a m i n the 8 grams of sample but the a c t u a l weight o f uranium a c t u a l l y present was milligrams.  .6  However, he a s s e r t s t h a t about one h a l f of the  uranium present might have been l o s t i n the chemical  opera-  tion. In  1930  Herculano  de Carvalho  (3) measured the amount  of uranium i n t h e water from some s p r i n g s i n P o r t u g a l u s i n g the c o l o r i m e t r i c method w i t h f e r r o u s cyanide and found  quan-  —6 t i t i e s o f about 10~  grams per l i t r e .  Where l a r g e samples  of water are a v a i l a b l e and the s o l i d content i s low,  the  u r a n i u m c a n be a  considerably  small f r a c t i o n  c o n c e n t r a t e d by e v a p o r a t i o n  o f i t s o r i g i n a l volume  substances d i s s o l v e d  before the  s a l t s per l i t r e ,  the problem o f f i n d i n g the minute difficult.  ( 4 ) , h a s d e v e l o p e d an o p t i c a l  method o f  d e t e r m i n i n g u r a n i u m by c o m p a r i n g t h e f l u o r e s c e n c e violet  light  of fused  sodium f l u o r i d e  in ultra-  b e a d s , t o w h i c h known  and unknown amounts o f u r a n i u m h a v e b e e n a d d e d . glass  In  30 and 40 grams o f  amount o f u r a n i u m i s t h e r e f o r e much more Hernegger  other  i n the water begin to c r y s t a l l i z e .  s e a - w a t e r , however, w h i c h h o l d s between dissolved  into  He u s e d a  s p e c t r o g r a p h o f v e r y h i g h l i g h t - g a t h e r i n g power a n d  by p h o t o g r a p h i n g t h e c h a r a c t e r i s t i c uranium f l u o r e s c e n c e and  b a n d - s p e c t r a due  comparing the i n t e n s i t i e s  t h o s e f o u n d w i t h t h e c o n t r o l s o f known u r a n i u m The method i s c l a i m e d t o e a s i l y d e t e c t amounts a s 10 ^  grams.  with  content.  uranium i n as  small  In collaboration with Karlik (5),  measurements o f t h e u r a n i u m c o n t e n t w h e r e i n t h e u r a n i u m was  to  o f o c e a n w a t e r o f Norway  c o n c e n t r a t e d f r o m samples o f  one  -6 liter  o r more, gave  gram u r a n i u m p e r  consistent  results  averaging  1.5x10  liter. PRESENT WORK  The  sea water samples  through glass-wool f i l t e r s which would a d v e r s e l y change  resin.  alkaline  The  a s o b t a i n e d were  to eliminate  any  solid  influence the e f f i c i e n c y  s e a w a t e r sample  ex-  slightly  hydroxides from  column unchanged,the 5  matter  of the  a s o b t a i n e d was  and hence t o p r e v e n t c o l l o i d a l  p a s s i n g t h r o u g h t h e exchange  filtered  pH  was  a d j u s t e d t o 4 by Each through  the  seawater o r  higher valence  Ag^etc,  control  HCl.  sample was  then  pumped  i o n exchange column c o n t a i n i n g IR-120 i n t h e U-238, U 2 3 4 , U235 and  s o d i u m f o r m and  u r a n i u m was  the a d d i t i o n of p u r i f i e d  i o n s were c o n c e n t r a t e d  then  e l u t e d along with  other divalent or on t h e  other  w h i c h f o r m complex i o n s w i t h  resin.  i o n s such  NaCN.  The  The a s Fe  complex  was  t h e n decomposed by  evaporating with  Purified  A l C l ^ was  t h e n added to t h e  solution  boiling  s o l u t i o n was  precipitated with  concentrated  By  precipitation,  and  the  NH^OH.  F e C l ^ and  cipitated  this  u r a n i u m was  adaptations  T h i s p r e c i p i t a t e was  from the  determination  U-234 are  procedure  then  g i v e n by  Urry  procedure,  separated  U - 2 3 8 and  from a l l the  other radio-elements  The  is  t h a t a l l the  need o n l y be  ionium,  and  reagents actinium.  s o l u t i o n are used as the  carrier  c i p i t a t i o n of the uranium.  the  i s the  important  The  sequence o f  The  l a y e r " of l e s s than  iron  free  and  of uranium,  aluminum i n t h e final  c o n c e n t r a t i o n by  principle  pre-  these  o f t h e method  because  uranium r e q u i r e s a  a c e r t a i n t h i c k n e s s and  a g i v e n mass f o r a g i v e n a r e a .  by  co-precipitation  agents i n the  r a d i o a c t i v e measurement o f t h e  l e s s than  (6) f o r t h e  i t s i s o t o p e s U-235  of c o - p r e c i p i t a t o r s .  carriers  pre-  treated with  the use  thorium,  also  o f s m a l l amounts o f u r a n i u m .  In t h i s  such  ^SO^.  i f i n macro-amounts o r c o - p r e c i p i t a t e d i f i n  micro-amounts.  and  the  concentrated  and  "thin  consequently  For very  uranium c o n c e n t r a t i o n s i t i s p o s s i b l e to separate  of  low the  iron  plus  aluminum f r o m t h e u r a n i u m and t o r e t u r n  portion  o f the former as c o - p r e c i p i t a t i o n s , which  i n a much h i g h e r c o n c e n t r a t i o n The and  only  final  a  small  results  factor.  p r e c i p i t a t e of the oxides of iron,  uranium i s d r i e d ,  i g n i t e d , and w e i g h e d .  aluminum  The p r e c i p i t a t e  i s g r o u n d and s p r i n k l e d  on an a d h e s i v e  surface  t o form a  t h i n l a y e r and t h e r a t e  a o f emission o f the a l p h - p a r t i c l e s  from the uranium i s determined p h o t o g r a p h i c a l l y . of  The r a t e  e m i s s i o n i s a d i r e c t m e a s u r e o f t h e number o f atoms o f  uranium present  i n the thin  layer.  PRINCIPLE OF ION-EXCHANGE Our separation  u s e o f a n i o n exchange r e s i n i n t h e i n i t i a l  o f uranium from s e a water warrants a b r i e f b u t  necessary discussion the  nature o f o u r exhaust To  it  due t o t h e d i f f i c u l t i e s  illustrate  i s necessary only  synthetic that  bases. reactive  to substitute  ordinary  a large,  that w i l l  trade  a c i d groups as p a r t  The r e s u l t The i o n  a c i d s and  i t will  possess  o f the r e s i n molecule.  I n any  can replace  groups t o produce i n s o l u b l e cations  i n equations  ions.  insoluble  I f t h e r e s i n i s a c a t i o n exchanger,  resins,  insolu^ble,  o f one o f t h e i o n s  are a c t u a l l y large,  case o t h e r c a t i o n s  taining  o f i o n exchange  double decomposition.  a type o f r e a c t i o n  exchange r e s i n s  sea water.  the reactions  molecule i n place  illustrate  depicts  solution,  a r i s i n g from  t h e hydrogen o f these  "resin salts".  As a s o l u t i o n  i s p a s s e d t h r o u g h a column c o n t a i n i n g  7  acid con-  large  numbers o f released  c a t i o n exchange r e s i n p a r t i c l e s , hydrogen i o n s  from the  absorbed.  As  r e s i n ' s a c i d g r o u p s , and  a r e s u l t , the  riched with metallic ions. the  sodium i o n s  first all  treated with  of the  when t h e  as  on  the  the  becomes  i n our  r e s i n with  reactions  The  other m e t a l l i c ions  exchange  and,  mass a c t i o n . these  at  equilibrium,  The  ions  between i o n s which a r e i s the  rate  t a k e s the A'-r  m BX  i n s o l u t i o n and  of the  the  mass a c t i o n  other  the  metathesis law  AX  +  the  Kerr  (7)  B*  +  8  of  reactions in  which holds  solu-  for  exchange t a k e s p l a c e porous g e l  equation:  m_  (B )  of  i s approached.  law  p a r t i c l e s having a  form of the  BX =  do  a l l homogeneously d i s p e r s e d  e x c h a n g e r s where a l l o f t h e  interior  as  g o v e r n e d by  at which equilibrium  In general, granular  There-  d e f i n i t e com-  double replacement o r are  Then,  centers,  c h i e f d i f f e r e n c e s between r e a c t i o n s  compounds w i t h  tions,  are  replace  in solution.  into chemical reactions  reactions  resin is  sodium i o n s .  i o n e x c h a n g e r e s i n s f o r m compounds w i t h  compounds.  cation  sodium c h l o r i d e to  active  separate  case, the i s , the  are  en-  necessary to  sodium form, t h a t  s o l u t i o n s passes over the  p o s i t i o n s which enter  the  I f i t i s not  a s o l u t i o n of  hydrogen ions  sodium r e p l a c e s fore,  c a t i o n r e s i n bed  from a s o l u t i o n s  exchanger i s used i n the  m e t a l l i c ions  are  a  _ _  in  structure,  An fact  equation of t h i s  type  t h a t t h e d i s t r i b u t i o n o f two  depends upon t h e d i l u t i o n ;  expresses the  well-known  i o n s of unequal  t h e more d i l u t e  charge  the ^solution,  t h e g r e a t e r t h e p r o p o r t i o n of t h e h i g h e r v a l e n c e i o n i n t h e exchanger. In the  i o n e x c h a n g e as i n o t h e r c h e m i c a l  reactions are r e v e r s i b l e ;  d i r e c t i o n we  have t h e  that  i s , i n the  have r e g e n e r a t i o n .  it  i s recommended t h a t a 10% s o l u t i o n o f N a C l  will and  i n the  displace thereby  I n our p a r t i c u l a r  sodium c y c l e ;  r e j u v e n a t e ...the r e s i n .  confronted with the d i f f i c u l t y  seen from  exchanged form,  AX,  it  may  I t was  be  i s lowered our  resin  e x a c t l y how  the  be t h e  t h a t we  regenerant resin are  have a p p r e c i a b l e  equilibrium by  re-  W i t h s e a w a t e r , we  exhaust  solution.  equation that  t h e i n c r e a s e i n B.  exchange c a p a c i t y i s now  t h e r e f o r e e s s e n t i a l t o conduct  determine the  said that  our  IR-120  sodium from t h e  sodium i o n s i n our  Hence i t c a n be  direction  case w i t h  i n o t h e r words, t h e  a l l cations other than  amounts o f r e g e n e r a n t  forward  e x h a u s t i o n and t h e r e v e r s e d  we  generant  equilibria,  experiments  Or lower.  to  capacity of the resin varies  c o n c e n t r a t i o n o f sodium i o n s i n t h e exhaust  the  with  solution  because our d e t e r m i n a t i o n of uranium i s q u a n t i t a t i v e .  Furthe  more, c a p a c i t y v a r i a t i o n s u n d e r s u c h  been  recorded  i n the  literature. PRINCIPLE OF  There  conditions|has not  i s a fundmental  CO-PRECIPITATION d i f f e r e n c e between t h e  chemistry o f extremely s m a l l amounts of the and t h a t o f the weighable q u a n t i t i e s  radio-elements  i n chemical  analysis.  Thus, the c o n d i t i o n f o r c o - p r e c i p i t a t i o n i s not so much one o f isomorphism as the f o r m a t i o n of a p r e c i p i t a t e  consisting  o f a compound whose anion forms an i n s o l u b l e compound w i t h the r a d i o - e l e m e n t . Paneth (8)  is  F a j a n ' s r u l e as  as f o l l o w s :  s t a t e d by Hevesy and  " A c a t i o n w i l l be absorbed by a  difficult  s o l u b l e s a l t when i t forms w i t h the a n i o n of the  absorbing  s a l t a compound, the s o l u b i l i t y of which i n the  solvent i s  small."  i n v o l v e d and t h a t absorption. radio-elements  The l e s s the s o l u b i l i t y of the compound of t h e absorbent,  In the f o l l o w i n g t a b l e ,  (Table 1) most o f the  are i s o t o p e s of the c o - p r e c i p i t a t o r s  other element, of the s e r i e s . elements  the s t r o n g e r w i l l be the  F o r example,  or of one  of the  radio-  c o - p r e c i p i t a t e d w i t h bismuth, the C and E p r o d u c t s ,  i s o t o p e s o f bismuth, the remainder are i s o t o p e s o f polonium. The v e r y short l i v e d " C " products o f t h a l l i u m need not be removed. Table 1 C o - P r e c i p i t a t i o n of the Radio-Elements (9) Element added and precipitated  Radio-elements p r e c i p i t a t e d as i s o t o p e s or c o - p r e c i p i t a t e d  Ce (as B i (as  Io UX UY—Ac R a A c — T h MsTh? RaTh RaA RaC R a C RaE Po—-AcA ACC A c C — ThA ThC T h C  oxalate) sulphide)  Pb (as s u l p h i d e ) Ba (as sulphate) Fe (as Hydroxide)  RaB RaD AcB ThB Ra—AcX—MsTh. ThX U-238 U234 U-^35  10  <^  EXPERIMENTAL"  Evaluation of A simple figure  1, was  experimental  Amberlite  120,  data t o construct a l a r g e r o f uranium i n sea w a t e r . 10  column, as  inches long with  venient to handle  and  and  A g l a s s c o l u m n 1.5  afforded excellent  entrainment  of  The  sufficient determination  inches i n  conused  sintered-glass plug  and  or  other  channeling of  the  avoided.  joint  and  attached to t h i s  c o l u m n by means o f  each p r o j e c t i n g p a r t of t h e T-tube  f i t t e d w i t h a p i e c e of rubber  t u b i n g and  a Hoffman  clamp f o r r e g u l a t i o n o f f l o w a t t h e d e s i r e d r a t e . a t the top f i t t e d w i t h a three-way T-tube as 1 completed  the apparatus.  p r o v i d e d f o r escape o f e f f l u e n t tions,  diameter  v i s i b i l i t y was  r e t e n t i o n of regenerant  I n such a column, p a c k i n g  A T - t u b e was  figure  the  A  prevented  a rubber  in  a medium p o r o u s p l u g w h i c h m o s t  p r e l i m i n a r y experiments.  r e s i n was  also to obtain  column f o r our a c t u a l  f o r these  solutions.  illustrated  constructed t o t e s t the performance of  exchange r e s i n ,  and  Resin.  and  f o r entrance  operation.  Connections  The  downflow r a t e was;  clamp a t t h e b o t t o m o f t h e A strip  of ruled  A  stopper  illustrated  arms o f t h i s  solutions  one  controlled  T-tube opera-  controlled  o f t h e s e were r e by t h e  Hoffman  c o l u m n s e r v i n g a s an  outlet.  o r c o o r d i n a t e p a p e r was  11  in  i n downflow  u p p e r T - t u b e were  by means o f p i n c h c l a m p s and when a n y moved, t h e  screw  i n back-wash o r u p f l o w  of exhausting to the  was  pasted  a l o n g t h e s i d e , t h e c o l u m n was terms o f l i n e a r milliliter the  calibrated  s c a l e u n i t s by p i p e t t i n g  successive  10  s a m p l e s o f w a t e r on t o p o f t h e g l a s s p l u g  s c a l e r e a d i n g o f t h e m e n i s c u s was  T h i s was  conveniently i n  recorded  each  and time.  done a f t e r t h e b o t t o m o f t h e c o l u m n had b e e n  filled  w i t h w a t e r up t o t h e p l u g w i t h t h e c l a m p s o f t h e T - t u b e From t h i s  d a t a a n a v e r a g e "column f a c t o r " ,  the h e i g h t its  of  t h e number by  which  o f a s e c t i o n o f column must be m u l t i p l i e d t o g i v e  volume,  were then  closed.  was  obtained.  calculated  R e s i n bed v o l u m e s  directly  s c a l e u n i t s between  in  from the product  the l i m i t s  milliliters  o f t h e number  o f t h e bed and t h i s  column  factor. Two  r e s e r v o i r s were r e q u i r e d , one a s a s o u r c e  s o l u t i o n t o be t r e a t e d , and t h e o t h e r t o f u r n i s h  regenerant  for  the r e s i n .  the  s o l u t i o n s were f o r c e d t o t h e t o p o f t h e column b y ed  pressed  Since  t h e f l o w must be c o n t r o l l e d a c c u r a t e l y ,  a i r under a constant  arrangement  t h e r e was  relatively  120 c o n t a i n e d  maintain^by  introduction  into  r e s i n was  column t h r o u g h  T-tube  1,  sufficient  measured  corn-  moisture  out d i r e c t l y  so t h a t  Thus  before  t h e column u s i n g t h e exchanger as r e c e i v e d .  slurried  first  a funnel.  d e s c r i b e d , t h e c o l u m n was 50 t o 70 p e r c e n t  a  l i t t l e s w e l l i n g upon w e t t i n g .  a g i v e n d e s i r e d volume was  The  pressure  i n m e r c u r y a s shown i n f i g u r e  Amberlite  of  i n a b e a k e r and washed i n t o  A f t e r t h e column was  charged  washed a t a r a t e s u f f i c i e n t  bed e x p a n s i o n . 12  T h i s was  the  as t o cause  done i n o r d e r t o  Figure  1.  EXPERIMENTAL COLUMN.  Pinch  clamps  NOTATION FOR  1. E x h a u s t 2.  Drain  3.  Rinse  4. L e v e l  FIGURE 1 — - E X P E R I M E N T A L  Solution.  control  5. I o n - e x c h a n g e 6.  Porous  7.  Effluent  8.  Backwash  9.  Regenerant  resin-  plug  1 0 . Compressed a i r 11. Regenerant  solution  Amberlite  IR-120  COLUMN  remove t h e f i n e s w h i c h r e m a i n i n t h e r e s i n s when T h i s r e s i d u e was removed t o p r e v e n t downflow o p e r a t i o n .  proper  the bed.  i t was s i m p l e t o o b s e r v e  been reached  excessive resistance t o  The b a c k w a s h was c o n t i n u e d u n t i l t h e  f i n e s h a d b e e n washed f r o m technique  shipped.  when t h i s  a n d prevent.; i. t h e l o s s  flow regulation.  I n t h e g l a s s column c o n d i t i o n had  o f t h e l a r g e r p a r t i c l e s by  The p r o p e r  backwash caused t h e  r e s i n p a r t i c l e s t o move up a n d down f r e e l y w i t h i n t h e b e d a n d this  served t o c l a s s i f y  particle  s i z e from  t h e bed h y d r a u l i c a l l y  t o p t o bottom.  improved o p e r a t i n g c h a r a c t e r i s t i c s The was c a r r i e d repeated  of the resin.  backwash w h i c h p r e v e n t e d  each exhaustion  packing o f the r e s i n ,  cycle.  When t h e backwash was  i t was n e c e s s a r y t o d e t e r m i n e  w h i c h c a p a c i t y d a t a were c a l c u l a t e d . that  classification  o u t u s i n g d i s t i l l e d w a t e r a n d b a c k w a s h i n g was  after  completed,  Such a  i n increasing  r e p r o d u c i b l e b e d volume r e s u l t s  t h e b e d volume  I t has been  upon  demonstrated  c o u l d be o b t a i n e d by a  draining  t h e b e d f o l l o w i n g backwash t o ^ g i v e n h e i g h t o f w a t e r  above t h e r e s i n ,  usually  was t h e n d e t e r m i n e d  from  c h o s e n a s one i n c h .  T h e b e d volume  t h e column c a l i b r a t i o n  as p r e v i o u s l y  explained. The  r e s i n was a l l o w e d  to settle  by g r a v i t y  before  d r a i n i n g was b e g u n a n d a l l b e d v o l u m e s r e f e r r e d t o w i l l this  b a c k w a s h e d and d r a i n e d b e d v o l u m e .  which t h i s  The f l o w r a t e a t  d r a i n i n g was c a r r i e d o u t i s r e l a t i v e l y  b e c a u s e t h e w a t e r must n o t r u n o u t f a s t  14  be  critical  enough t o c a u s e e x -  cessive  settling The  and  bed  hence pack t h e  was  never a l l o w e d  would cause a i r pockets faulty the  contact  resin  and  resin  of the  to d r a i n dry  t o appear i n the bed  exhausting  limiting  bed.  incoming stream during the  vent  the  bed  from being  The  exhaustion  c o l u m n was  operated  s o l u t i o n through the  The  to which the  the  composition  s e c o n d a r i l y upon t h e volume o f e x c h a n g e r . effluent  i s the  total  r e s i n to the  resin  of the  exhausting The  quality  f o r any  solutions of  s o l u t i o n was  given  solution,  The  and unit  l e n g t h of time  regeneration value.  necessary  ions  optimun c a p a c i t y . various  The  are  to regenerate  .1 e q u i v a l e n t s  small experimental  run through the  r e g e n e r a t i o n and  bottom.  d e s i r e d i n the t r e a t e d  various concentrations  run through the  pre-  the  s o l u t i o n flow rate per  v a r i a t i o n of capacity with  l i t e r with  running  from top to  exhausting  l e v e l w h i c h gave t h e  concentrations,  thus  quantity of regeneration material  t h e r e f o r e i t was  determine t h e  per  downflow by  exchange o f d i v a l e n t o r h i g h e r v a l e n c e  d e s i r a b l e and  cushion  c y c l e and  f a c t o r which determines the  between r e g e n e r a t i o n s  desirable  m a t e r i a l b e i n g e x c h a n g e d i s removed  d e p e n d s p r i m a r i l y upon t h e u s e d and  with  disturbed excessively.  exhausting extent  to  subsequent  solution  M o r e o v e r , i t was  t o have a s m a l l amount o f w a t e r above t h e b e d the  this  causing  or regenerating  exchange.  as  our To  sodium  i n copper  ion  ions  o f s o d i u m c h l o r i d e were  column j u s t  column a f t e r t h e  described. usual  steps  backwash e t c .  e x c h a n g e r e f f l u e n t was 15  sampled from time  to  Each of  time with Na2S to detect the f i r s t leakage of copper ions and the volume of the exhausted leakage was detected.  solution was noted when the f i r s t  This procedure was repeated f o r three  samples of the same solution and i n each case the r e s u l t s were i n perfect agreement.  The capacity was found to decrease  rapidly with increasing concentrations of sodium ions i n the exhaust solutions as expected. experiment  The data obtained i n t h i s  i s given i n table 3 and a plot of t h i s i s shown  i n figure 2.  From such a plot, and knowing the desired t o t a l  bed capacity f o r our subsequent determination of uranium i n sea water, the volume of r e s i n to be employed may therefore be e a s i l y found.  The following table (Table 2) gives the  operating conditions of our small column as s p e c i f i e d by the producers of Amberlite 120, (10) Table 2. Operating Specifications f o r - Amberlite 120 Volume of Resin Regenerant concentration Regenerant flow rate Regenerant l e v e l Rinse flow rate Rinse water requirement Service flow rate Capacity  120cc 10$ 15.9cc/min. 13,7Meq./cc resin,.or S66cc(10^sdn. 15.9cc/min. 800cc 31.8cc/min. .197 equiv.  16  Figure THE CAPACITY OF AMBERLITE  2.  IR-120 v s SODIUM CONCENTRATION.  (Meq./cc v s $ Na  by w e i g h t )  Variation Cone, o f Cu equiv./liter +  Table of Capacity with Cone, o f Na % by w e i g h t  3. Sodium I o n C o n c e n t r a t i o n Max. V o l . o f exhaust s o l n .  +  Capacity Meq,/cc r e s i n  .1  0.0  1990cc  1.66  .1  0.39  1000cc  0.833  .1  0.50  900cc  0.750  .1  1.0  325cc  0.541  A n a l y s i s o f S e a W a t e r Sample In order t o determine as a c c u r a t e l y as p o s s i b l e t h e maximum volume o f s e a w a t e r s u f f i c i e n t analysis  o f the sea water  to just  exhaust t h e r e s i n ,  sample must be p e r f o r m e d .  Of t h e  m a j o r c a t i o n c o n s t i t u e n t s o f s e a w a t e r , magnesium and c a l c i u m comprise t h e g r e a t e s t p o r t i o n o f t h e d i - v a l e n t and h i g h e r ions and  (11).  valence  As h a s a l r e a d y b e e n s t a t e d , i t i s t h e d i - v a l e n t  higher valence  i o n s which a r e exchanged i n t h e sodium c y c l e .  Consequently, the exhaustion  o f o u r column i s t o t a l l y  dependent  u p o n t h e c o n c e n t r a t i o n o f c a l c i u m a n d magnesium i o n s a n d a l s o t h e s o d i u m and p o t a s s i u m i o n c o n c e n t r a t i o n s w h i c h d e t e r m i n e t h e c a p a c i t y o f t h e column. potassium,  once t h e c h l o r i n i t y  by t h e V o l h a r d  c h l o r i n i t y was f o u n d  to hold.  t i t r a t i o n with  t o be 16.383.  17  may be  i s known and t h e f o l l o w i n g  as given i n t a b l e 4 a r e found  was f o u n d  t h a t t h e sodium,  c a l c i u m and magnesium i o n c o n c e n t r a t i o n s  e a s i l y found ratios  I t has been found  silver  Table  The  chlorinity  nitrate  and t h e  4 g i v e s the v a r i o u s  major c o n s t i t u e n t s i n our sample of sea water.  Table  4.  Ma.jor C o n s t i t u e n t s i n Sea Water Sample  Ion Na  Ratio to  +  Chlorinity  Weight i n gms./l  Equiv./l  .5509  9.27  .0200  0.334  Mg *  .06695  1.12  0.0922  Ca  .02106  0.352  0.01755  K  +  +  ++  The  above d a t a a l s o s u p p l i e d enough i n f o r m a t i o n f o r  us t o make up a r t i f i c i a l  sea water f o r our c o n t r o l  w i t h c o n d i t i o n s very s i m i l a r t o those sample.  The  C.P.  determinations  found i n the a c t u a l  s a l t s o f sodium, potassium, magnesium and  c a l c i u m were used and t h e amounts used per l i t e r of s o l u t i o n were as f o l l o w s : Table  5.  Salt  Weight gms./l  NaCl  23.6  MgCl H 0 2  9.38  2  Ca(N0 ) 4H 0  2.07  KC1  0.638  3  2  2  For the s e p a r a t i o n of uranium from sea water a column was  c o n s t r u c t e d c o n s i s t i n g mainly of t h r e e pyrex g l a s s  tubes each 6cm. for  new  i n diameter and  a g l a s s wool p l u g and  124  cm.  i n length.  To  sand t o cushion the r e s i n bed 18  allow and  and t o a l l o w f o r s u f f i c i e n t  e x p a n s i o n o f t h e r e s i n bed  t h e backwash o p e r a t i o n , t h e a c t u a l r e s i n b e d was in  height.  was  The t o t a l  t h e r e f o r e 6,360  in figure  volume o f t h e r e s i n  cc.  A diagram  i n the three  of t h i s  capacity per cc. of r e s i n  c o n c e n t r a t i o n o f 0.924$  a t t h e sodium  i s 0.560 m i l l i e q u i v a l e n t  e q u i v a l e n t s o f magnesium and 4 i s 0.110.  The  calcium per l i t e r  following table  specifications  o f o u r new Table  The  Cone, o f Na  i n exhaust  Total  capacity  resin  v o l . o f exhaust  Exhaust  service flow  Regenerant  cone.  Regenerant  flow  Regenerant  level  The  6.  soln.  equiv.  soln.  32.4  liters  rate  80  cc/min.  20$ rate  80  requirement  I n a c t u a l run(5) A  r e g e n e r a t i o n and w a s h i n g s  o f Uranium  IR-120  0.924$ 3.57  Separation  opera-  column.  requirement  Backwash t i m e  total  from t a b l e  6) g i v e s t h e  (Table  ion  per c c .  O p e r a t i o n a l S p e c i f i c a t i o n s f o r 6 , 3 6 0 cc A m b e r l i t e  Rinse  columns  column i s g i v e n  r e s i n a s d e t e r m i n e d f r o m t h e g r a p h and t a b l e 4 .  Max.  75cm.  only  3. The  ting  in  (approx.) cc/min.  11.25  lb.  85.5  liters  10  min.  From Sea W a t e r  a f t e r the usual preparations of t h e r e s i n  bed,  pumped t h r o u g h t h e c o l u m n f r o m a 40 l i t e r  19  of  the samples  c a r b o y / by  were  compressed  Figure  1.  EXCHANGE COLUMN.  Compressed] Air  A  O Exhaust or Regene l i i n t S o l u t i c us  Sand G l a s s Wool  a i r regulated by a safety valve, A.  The actual route of the  samples through the column was as indicated i n diagram 3. After 30 l i t e r s had been run through the column, instead of 32.4 l i t r e s allowing f o r a safety margin, the column was backwashed with pure water f o r f i v e minutes and then drained u n t i l the surface of the l i q u i d i n column 1 was just that of the r e s i n bed.  This was done by regulating valvesB, B  1  and B".  The eluting agent, 100 cc of 25% sodium cyanide solution, was""" allowed to run through the column at the rate of 50 cc per minute.  The r e s i n bed was always submerged i n water by ad-  mitting water on top of the cyanide solution at 50 cc per minute.  In t h i s way the cyanide solution was i n between two  water layers i n going through the column.  The f i r s t eluent  was collected when cyanide was detected by f e r r i c chloride and c o l l e c t i n g was continued u n t i l no cyanide could be detected by f e r r i c chloride a f t e r which another 100 cc was c o l l e c t e d . In t h i s way, approximately 1600 cc was collected each ruru t o t a l of four runs were made  A  two controls and two sea water  samples. Treatment of the Eluent. The solutions were then evaporated to 150 cc and cooled.  Then 250 cc of concentrated s u l f u r i c acid was added  to each of the solutions and evaporated to dryness to decompose the cyanide complexes (14).  The treatment i n concentrated  s u l f u r i c acid was accomplished i n porcelain casseroles placed i n an, i n c l i n e d position over the flame, and the flame directed against the upper part of the c r u c i h l e .  The heating was caan-  tinued until fumes of s u l f u r i c acid ceased to come o f f . The A  21  residue  consisted  metal sulfates  of the a l k a l i  and u r a n y l  sulfate  sulfate.  g e n t l y w i t h 10 c c o f c o n c e n t r a t e d added l i t t l e sulfates the  by l i t t l e  were r e a d i l y  following  until  took  K ( U 0 ( C N ) ) -t 6H2S04+ 6 H 0 4  2  6  2  i f  This  solutions fully  into  solution.  ->2K2S0  4 +  (U02)S04 3(NH ) S04+6C0  precipitate  any uranium.  chloric  chloride  precipitation  2  and 2 c c o f one  This  complete  and t h e s o l u t i o n technique.  22.  acid  care-  and f i n a l l y t o  co-precipitation  finally  and t h e  hydroxides which would c o p r o c e d u r e was  removal o f uranium.  was washed w i t h a d i l u t e  acid  4  +  the s u l f u r i c  t h e aluminum and f e r r i c  and t h e p r e c i p i t a t e  I t i s presumed  Ammonium h y d r o x i d e was  precipitate  ide  a n d w a t e r was  were a d d e d t o e a c h s o l u t i o n  added t o n e u t r a l i z e  precipitate  acid  place;  h e a t e d up t o b o i l i n g .  repeated t w i c e t o ensure  r e s i d u e was h e a t e d  sulfuric  2 c c o f one n o r m a l f e r r i c normal aluminum c h l o r i d e  heavy  25 t o 30 c c was a d d e d a n d t h e  brought  reaction  and anhydrous  solution  dissolved  treated  This  o f ammonium  i n purified  by t h e f o l l o w i n g  chlor-  hydroco-  Analytical The schematically  Procedure.  c h e m i c a l s e p a r a t i o n o f u r a n i u m , w h i c h i s shown i n table  7 i s adapted  from t h e procedure  given  by U r r y i n h i s p r o c e d u r e ^ f o r t h e a n a l y s i s of, r o c k s a m p l e s ( 1 5 ) .  T a b l e 7. P r e p a r a t i o n o f Uranium F r e e  from Other  O x i d i z e Fe i n t h e f i l t r a t e Evaporate t o dryness. Dissove i n H C l .  Radio-elements. with  HNO3.  P r e c i p i t a t e f r o m t h e b o i l i n g s o l n . w i t h NRYOH i n s l i g h t e x c e s s , F e , Ja, U, R a r e E a r t h s , T h , Z r , T l , some Mn e t c . Dissove ppt. i n H C l . Add 20 mg. Ce a s C e ( N 0 , - ) , E v a p o r a t e i n H C l a n d HNOoJ D i s s o l v e i n s m a l l e s t amount o f H C l a n a make up t h e v o l . t o 1 5 0 c c . Precipitate with a saturated soln. of Oxalic acid, s t i r v i g o r o u s l y and a l l o w t o s t a n d o v e r n i g h t . F i l t e r a n d d i s c a r d p p t . o f Ce, T h , I o , A c . With t h e f i l t r a t e t w i c e r e p e a t t h e t r e a t m e n t w i t h Ce. Evaporate  t h e f i n a l f i l t r a t e w i t h HNOo t o remove o x a l a t e s , Remove HN0-> by e v a p o r a t i o n w i t h H C l . D i s s o l v e i n h$ H C l . Add 10 mg. e a c h o f B i , Pb, a n d Ba a s c h l o r i d e s .  P r e c i p i t a t e t h e Ba ( w i t h some Pb) w i t h a f e w d r o p s o f a S a t d . solution of K^SOi. A l l o w t o stand sxx hours w i t h f r e q u e n t s t i r r i n g and p r e c i p i t a t e B i a n d Pb w i t h H S . F i l t e r a n d d i s c a r d p p t . o f B i , Pb, B a . W i t h t h e f i l t r a t e , t w i c e r e p e a t t h e t r e a t m e n t w i t h B i , Pb, and Ba, r e m o v i n g t h e HgS b e t w e e n t r e a t m e n t s . 2  To e x p e l t h e H~S a n d o x i d i z e t h e F e i n t h e f i n a l filtrate w i t h HN0 . Evaporate t o dryness. D i s s o l v e i n H C l a n d p r e c i p i t a t e w i t h NH^OH i n s l i g h t e x c e s s f r o m t h e b o i l i n g s o l u t i o n ; F e , A l , U, e t e . F i l t e r a n d d r y t h e p p t . o f F e , A l , U. e t c . c  3  23.  The  sequence i n which t h e c o - p r e c i p i t a t o r s  portant.  F o r example, were t h e b i s m u t h  p r i o r t o the cerium p r e c i p i t a t i o n , cerium and l a t e r t h e barium  and  I n a l l c a s e s i t was  important  each  exactly  tests  volumes o f s t a n d a r d s o l u t i o n s each  may  ic  and n i t r i c  mixtures  acids  then  acid.  lead,  and t h e r e s u l t i n g  times.  Barium c h l o r i d e  was  24  puriffei  The p r e c i p i t a t e acid  and  was  evaporated  with oxalic  acid  was  times.  t h r e e times as  sul-  t h e y must n o t c o n t a i n T h , The s u l f i d e s were  acid  dissolved  and a f t e r f i l t e r i n g o f f  a c i d was b o i l e d  chloride  Hydrochlor-  r e c r y s t a l l i z e d three  to uranium.  s u l f u r , the n i t r i c  still.  w a t e r and p r e c i p i t a t -  nitric  t o remove t h e i r o n g r o u p s i n c e  the free  burrette.  n i t r a t e was  and i r o n w e r e p r e c i p i t a t e d  by b o i l i n g w i t h p u r i f i e d n i t r i c  were  constant-boiling  The p r e c i p i t a t i o n p r o c e d u r e  Io a n d Ac i n a d d i t i o n  acid  from  t h e CP s a l t s i n d i s t i l l e d  r e p e a t e d t w i c e and c r y s t a l s  Bismuth; fide  were d i s t i l l e d  i n concentrated d i s t i l l e d  „ to dryness.  Exact  ( s e e p . 33. f o r d e t a i l s )  the laboratory  the hot s o l u t i o n with o x a l i c  dissolved  correction  of the co-precipitators  o f t h e "Reagent" a c i d s C e r i u m  by d i s s o l v i n g ing  from  our  quantof  be a p p l i c a b l e .  one w i t h i t s i n d i v i d u a l  w a t e r was  radio-ele-  and t h e treatment  P r e p a r a t i o n s o f t h e Reagents, The  the  t o u s e t h e same  i d e n t i c a l so t h a t  by o u r c o n t r o l  by a d d i n g  that  lead.  as f a r as p o s s i b l e  used  t o be a d d e d  i t i s possible  i t i e s o f reagents  as determined  and l e a d  would r e - i n t o d u c e the  ments removed by t h e b i s m u t h  s o l u t i o n was  a r e added i s i m -  off in  hydrochloric  s a l t s r e c r y s t a l l i z e d three  r e c r y s t a l l i z e d three times  by s o l -  ution i n distilled allized  four  water.  The  potassium  s u l p h a t e was  times.  R a d i o a c t i v e Measurement w i t h N u c l e a r The  nuclear emulsion  p a r t i c l e s that enter the residual of  necessary  records tracks of a l l alpha  e n e r g y e x c e e d s a minimum v a l u e .  s e n s i t i v i t y , and  vary with the  the m i c r o s c o p i c  to consider the  Although emulsion  and  the  chamber w h i c h a r e i m p o r t a n t  counting  instuments.  factors  t r a c k count  tegration rate,  as each t r a c k i r r e s p e c t i v e  responds to the  emission of  processed  an a l p h a  particle  From p u r e l y g e o m e t r i c  emulsion.  e n t e r i n g the emulsion  dimensionless. a very t h i n The  electronic of  disincor-  by t h e  line  source.  of i n c i d e n c e  l a y e r and  visibility  the  a t right angles  vertical  of these  into  considerations should appear  However, a f t e r f i x a t i o n t h e g e l a t i n  enhanced under d a r k - f i e l d f r o m the  in  p l a t e c a r r i e s a r e c o r d of t h e number o f t r a c k s  the o r i g i n a l  torted.  un-  oftthe  of length  approximate  to  i t is  ionizing  into a  and a l s o e x h i b i t s t h e i r  particles  tracks  T h i s s i m p l i f i e s the t r a n s l a t i o n  the m i c r o s c o p i c a l l y determined  their  composi-  effective area  counting  the  resolution,  complex v a r i a t i o n i n  power a l o n g t h e t r a j e c t o r y  The  Emulsions.  r e c o r d i n g medium p r o v i d e d t h a t  minimum d i s c e r n i b i l i t y  tion,  recryst-  t r a c k s become  dries dis-  erect tracks i s f u r t h e r  i l l u m i n a t i o n by  c o m p r e s s e d column o f s i l v e r  the/light  grains.  With  scattered thin  2 sources weighing  l e s s than  the p a r t i c l e s enter the  1 mg.  emulsion  per  cm  ., o v e r  90%  w i t h e n e r g i e s and  of orienta-  (18)  t i o n f a v o r i n g optimum t r a c k v i s i b i l i t y .  25  A  Tracks  of  alpha  particles  that  spent the  greater  t r a v e r s i n g the  source are  cause o f t h e i r  short  the  part  most d i f f i c u l t  recorded  in  energy i n  to  i s considered  effective  t h i c k n e s s , which  i s the  equivalent  air-centimeters,  i s l e s s than the  mean r a n g e o f a l p h a  particle  mechanical thickness permeability  of the  thickness  system i n dry  or weight carrier  discernbe-  length.  A r a d i o a c t i v e source its  of t h e i r  per  of the  source  effective  a i r at  u n i t area  but w i l l  t h i n when  15°C.  The  varies with  i n general  reside  the  below  2 2 mg.  per  cm.  In our  determination  l i e s w e l l below t h i s v a l u e  and  "thin"  considerations,  source.  which are alpha  Geometric  discussed  pulse  by  counter,  Evans  may  the  (16,  sample  therefore  17)  be  the  thickness  considered details  i n conjunction  a  of  with  show t h a t : 2n  r  d =  , . » n k T -2L ' 2(R-p) where: i s t h e number o f d i s i n t e g r a t i o n s i n t h e s o u r c e d u r i n g exposure. i s t h e t o t a l number o f t r a c k s r e c o r d e d d u r i n g e x p o s u r e . i s the t h i c k n e s s o f the source i n e q u i v a l e n t a i r - c e n t i m e t e r s . i s t h e d i s t a n c e between s o u r c e and e m u l s i o n i n a i r - c e n t i m e t e r s , i s t h e t r a c k l e n g t h i n a i r - c e n t i m e t e r s o f minimum d i s c e r n i bility. i s t h e e f f e c t i v e mean r a n g e o f a l p h a p a r t i c l e s y s t e m i n d r y a i r a t 15°C. r  w  I _  d n T L p R  r  important  I t i s e v i d e n t f r o m t h i s e q u a t i o n t h a t L i s an f a c t o r i n governing the p r o p o r t i o n of alpha-r-particle  tracks  recorded  by  the  values  of k f o r v a r i o u s  emulsion.  Yagoda has  r a d i o a c t i v e compounds  26  computed (18).  several, The  tracks are distributed at random, and, when L i s about 0.05 air-cm., 98$ of the tracks are confined to an area of the same dimensions as the source,  n was therefore determined i n r  d i r e c t l y by a r e s t r i c t e d count on representative areas of the emulsion.  The actual recording of the a c t i v i t y i n our  samples were made with Eastman NTB plates with emulsion t h i c k ness of 100 microns.  The hydroxides were ignited to form the  oxides and were ground to a powder i n t h e i r respective crucibles.  Each sample was sprinkled onto an adhesive sur-  face bordered by an aluminum frame 0.05 cm. thick and leaving 2  an exposed adhesive area of 10.0 cm. . The sample was sprinkled i n excess onto the adhesive surface t o cover the entire surface after which the excess was removed by gentle tapping with the surface inverted.  The nuclear track plate was then  placed over the sample and clamped to commence the exposure. In t h i s way the sample was "thin" and kept at a known distance from the track plate. figure 4.  This arrangement i s i l l u s t r a t e d i n FIGURE 4.  —Clamp Nuclear emulsion Sample on adhesive surface rFrame  27  B e c a u s e t h e samples were e x p e c t e d t o be veryweak, t h e e x p o s u r e was f o r 2^2 h o u r s . p l a t e s were done a c c o r d i n g  The development o f t h e  t o i n s t r u c t i o n s from t h e Eastman  Kodak p u b l i c a t i o n ( 1 9 ) . The lumination  using  t r a c k s were c o u n t e d u n d e r d a r k - f i e l d i l -  a 45X d r y o b j e c t i v e whose a p e r t u r e  duced by s u i t a b l e d a r k - f i e l d s t o p s . aperture ing.  i s o f paramount i m p o r t a n c e  I t increases  pective  one f o c a l  an e x t e r n a l  i n quantitive track  depth so t h a t  area  setting.  source the tracks  surface, o f the g e l a t i n . tricted  of the  a l l tracks,  count-  irres-  o f t h e i r p o s i t i o n i n t h e g e l a t i n l a y e r , a r e brought  i n t o view w i t h with  focal  The r e d u c t i o n  was r e -  When t h e e x p o s u r e i s made reside  c l o s e t o the upper  The t r a c k s were c o u n t e d i n a r e s -  o f the microscope f i e l d with t h e a i d o f a  graduated o c u l a r diaphragm.  With t h e use o f such a d i a -  phragm a l l t h e t r a c k s were c o u n t e d a l o n g t e n d e d f r o m one s i d e o f t h e t r a c k  28  a s t r i p which ex-  plate to the other.  RESULTS. The T a b l e 8.  r e s u l t s o f o u r experiments a r e as enumerated i n  The t r a c k s  were c o u n t e d a s p r e v i o u s l y  d e s c r i b e d and  the  uncertainty  i n t h e c o u n t i s 2.3% a s s u g g e s t e d by Yagoda (20)  The  c o r r e c t i o n f a c t o r was d e t e r m i n e d f r o m t h e r e s u l t s o f t h e  control tests. 3.71*10  6  The a c t i v i t y  ±.085*10  6  o f t h e 15 c c o f s o l u t i o n was  but the control  ±.0476'10° a n d 2 . 0 2 1 0 ± . 0 4 6 5 * 1 0 . ,  varied  6  6  f r o m t h e t o t a l added  respectively  r e s u l t s were 2.07*10  6  The r e s u l t s o f t h e c o n t r o l s  amount by f a c t o r s  o f 1.78" a n d 1.83  a n d y i e l d i n g a n a v e r a g e f a c t o r o f 1.81. T a b l e 8.  THE DETERMINATION OF THE URANIUM CONTENT FROM THE RADIOACTIVE MEASUREMENTS. Sample volume (liters)  Sample  T o t a l weight of oxides.  Weight o f oxide examined.  ^  Alpha p a r t i c l e s counted f o r 2Li h r s . (10*)  Sea w a t e r A  30  .7246  .0280  1.29 ±.0196  Sea w a t e r B  30  .2868  .0310  1.71 +.039  Control A  30  .2393  .0174  6.93 +.140  C o n t r o l B,  30  .2550  .0195-  7.11 +.164  Sample  T o t a l counts for_24i hrs. (105).  Uranium Correction g . ger g . f a c t o r . (10 )sea water. 5  Uranium g./g. (10 ) s e a water c o r r e c t e d  S e a w a t e r A 7.21 ±.166  2.19  1.81  3.93  Sea w a t e r B 3.44 ± . 0 7 ^  1.05  1.81  1.90  Control  A  20.7 +.476  6.32  1.81  11.45  Control  B  20.2 ±.465  6.17  1.81  11.10  The  k v a l u e u s e d was 2.17 ( 1 8 ) . w 29 A  CONCLUSIONS  o f uranium can of  control  tests  be  subjected  to  indicate  the  separation without appreciable  tests the by  The  the  indicate  co-precipitation  alpha-particles e x c h a n g e and  open t o be  a  loss  of  any  results  eluting  precipitations  ceivably  complex c h e m i c a l loss.  so w e l l water of  In  may  of uranium.  both  quantities processes  control  i n greater a c t i v i t y .  lead  to  low  results. loss  compensated by  e f f i c i e n c y o f the  established 3.98'10  although  removal  But,  emit  incomplete  processes along with i n e f f i c i e n t  c r i t i c i s m because a exactly  Incomplete  other radio-elements that  seems t o  Our  grams p e r  con-  removal of be  co-precipitations  1.9*10  results  of uranium might  in radio-chemistry. and  co-  However, t h e  incomplete  other radio-elements although there doubt t h e  small  r e s u l t s were i n v e r y s a t i s f a c t o r y a g r e e m e n t  results  are  that  no  the  reason  which have results for  gram o f  sea  to been sea  water -9  is  higher than that The  w a t e r c a n n o t be great  c a r e and  f o u n d by difference  fully  between the  e x p l a i n e d but  identically.  This  t e s t s w h i c h r e s u l t s were w i t h i n as  s h i p p e d from the  Pacific  the  3.0$  run  c o l u m n were f r o m two  that  the  posed of  stated,  solid  solutions  agreement.  samples o f the  f i l t e r i n g was  r e s i d u e or  sea  and  sea  were h a n d l e d control  The  sea in  drums.  i t was  water two  As  was  noticed  t h u s s e p a r a t e d were  b l a c k s o l i d s a n d / " r e d d i s h brown s o l i d B  .  w a t e r w h i c h were  different  required  impurities  29  results for  Oceanographic Labs  the  already  two  i s shown i n t h e  s t e e l drums and through the  two  1.3*10  K a r l i k whose v a l u e was  matter,  the  com-  with  l a t t e r taken f o r rust.  T h i s r e s i d u e was  f o u n d t o be  i n t h e s a m p l e s e v e n t h o u g h t h e y were w i t h d r a w n w i t h i n two d a y s upon If t h e u r a n i u m may by t h e r u s t .  A l t h o u g h t h e two o f 2.1,  present  p o s s i b l y have  u r a n i u m by f e r r i c  i n the sea water  been o c c l u d e d o r  samples,  co-precipitated  i s u n c e r t a i n but the c o - p r e c i p i t a t i o n of  hydroxide strongly  suggests t h i s  possiblity.  s e a w a t e r d e t e r m i n a t i o n s d i f f e r by a  t h e r e s u l t s were c o n s i d e r e d  the magnitude  f r o m t h e drums  arrival.  r u s t was  This  present  of the  satisfactory  factor  i n view o f  concentration.  SUGGESTIONS FOR  FUTURE WORK  Our s e p a r a t i o n o f t h e m i c r o - a m o u n t s  of uranium  f r o m s e a w a t e r h a s p r o v i d e d a n o t h e r method f o r t h e d e t e r m i n a t i o n of other micro-elements i n the sea.  Since the  tracing  o f t h e v a r i o u s members o f t h e r a d i o - e l e m e n t s i n t h e u r a n i u m family  i n t h e s e a has n o t b e e n d e t e r m i n e d c o n c l u s i v e l y ,  i n v e s t i g a t i o n s would chemist  present very  and g e o - p h y s i c i s t .  radium content made b y E v a n s  o f marine  sea and  life  and b o t t o m s e d i m e n t s have  (21) f r o m P a c i f i c  surroundings.  the radium content  problems t o the  A l t h o u g h many d e t e r m i n a t i o n s o n t h e  e s t a b l i s h e d where t h e v a r i o u s the  intriguing  such  been  ocean samples, i t has not  quantities are d i s t r i b u t e d i n  F o y n , e t a l . (22) h a d f o u n d t h a t  o f s e a w a t e r was  ., -16 .86'10 grams o f r a d i u m -12  p e r c c o f w a t e r a s compared  to  .46*10  gram o f p l a n k t o n a s f o u n d b y E v a n s . evidence r e l a t i v e t o the p o s s i b l e 30  grams o f r a d i u m p e r  However, t h e r e i s some  chemical e x t r a c t i o n of  c a l c i u m by m a r i n e o r g a n i s m s . From K a r l i k ' s  (5) d e t e r m i n a t i o n o f u r a n i u m  -9 in  1.3*10  s e a w a t e r an a v e r a g e o f  w a t e r was  grams p e r gram o f s e a  f o u n d but t h e radium content  a s f o u n d by F o y n  was  -6 o n l y 0.8*10  grams p e r granr o f w a t e r .  amount i s c o r r e c t t h e n water could five  amount.  I n s t e a d , however, we  bottom  content.  On t h e o t h e r h a n d i t was  f o u n d by U r r y  samples o f h i g h radium c o n t e n t had about  The  i t s radium  n o t be i n e q u i l i b r i u m b u t w h a t e v e r t h e s e d i m e n t a -  samples c o n t a i n  since high  concentra-  tens o f thousands of times as  much r a d i u m p e r u n i t w e i g h t as does t h e o c e a n w a t e r . be remembered t h a t  the p r e c i p i t a t i o n  a method f o r p r e c i p i t a t i n g solutions  of f e r r i c  and s u c h a p r o c e s s m i g h t  conceivably  centration of f e r r i c i f all  that  I t must  hydroxide i s  i o n i u m and u r a n i u m f r o m  h a s b e e n o b s e r v e d by Thompson, e t a l . . (23)  s h o u l d be  one  y e a r s and t h e r e f o r e t h e u r a n i u m  t i o n p r o c e s s i s , i t must be e f f i c i e n t , bottom  (9)  r a t e o f d e p o s i t i o n i n t h e deep o c e a n i s a b o u t  c e n t i m e t e r p e r 1,000  and r a d i u m may  tion  have  t i m e s a s much u r a n i u m as n e c e s s a r y t o m a i n t a i n t h e  q u a r t e r a s much u r a n i u m a s n e c e s s a r y t o s u p p o r t  one  latter  .24*10"^ grams o f u r a n i u m p e r gram o f  support t h i s  radium content. that  If this  dilute  occur.  It  the con-  i r o n i n ocean water i s l e s s t h a n i t  the i r o n  r e c e i v e d were h e l d  i n solution  b u t t h e p r e c i p i t a t i o n o f u r a n i u m w o u l d be i n h i b i t e d by t h e presence o f carbonate ions. This could contribute to the means by w h i c h t h e i o n i u m - u r a n i u m u n b a l a n o o - i n t h e s e a w a t e r  31  \  and s e d i m e n t s dcffi unbal&ncejcl. In the p r e c e d i n g d i s c u s s i o n t h e sea water, marine l i f e  and b o t t o m s e d i m e n t s a n d r o c k s were n o t f r o m t h e  same l o c a l i t y these  a n d t o o much emphasis  c a n n o t be p l a c e d u p o n  r e s u l t s a s i t i s w e l l e s t a b l i s h e d b y Sanderman a n d  Utterback  (240 t h a t t h e r a d i u m c o n t e n t  o f ocean  bottom  s e d i m e n t s may v a r y a p p r e c i a b l y w i t h t h e l o c a t i o n . it  s h o u l d be a v e r y i n t e r e s t i n g  t r i b u t i o n and balance  project  Therefore,  t o determine the d i s -  of the radio-elements  o f uranium f a m i l y  i n t h e o c e a n s e d i m e n t s a n d r o c k s and t h e s e a w a t e r  directly  above i t b y means o f a n a l y s e s o n c o r e d s a m p l e s a n d w a t e r samples.  32  APPENDIX. The  HCL and HNO^  were d i l u t e d w i t h d i s t i l l e d  to t h e approximate?.constant distilled.  The f i r s t  b o i l i n g compositions  and l a s t  quarter of the  were d i s c a r d e d and t h e m i d d l e h a l f was sition  of the constant  20.2%. for  HNO,  The c o n s t a n t  b o i l i n g HNO^  was  water  before  being  distillate  collected.  The  compo-  68f. and f o r t h e H C l  b o i l i n g p o i n t s were 120.5°C a n d 110°C  and H C l r e s p e c t i v e l y .  3 3 «A  REFERENCES  1.  Joly,  J . ; P h i l Mag.,  2.  Walker,  3.  d . C a r v a l h o , H;  4.  H e r n e g g e r , F.; A n z e i g . d . W i e n . A k a d .  P.H.;  J . Am.  19,1, 5.  16,  196,  1905.  Chem. S o c ,  20,  Compt. r e n d . , 191,  513,  95,  1898.  1930. d. Wissensch.  1933.  H e r n e g g e r , F., & K a r l i k , B.,  Goteborgs Kungl. Vetenskaps-  ock V i t t e r h e t s - S a m h a l l e s H a n d l i n g a r , Femte S e r b . B, Band 4, 6.  U r r y , Wm.  D.  7.  K e r r , H.W.  8.  Hevesy,  J . Am.  G.,  1935.  J . Sc. 239,  Am.  191,  1941.  Soc. Agron. 20,  309,  U r r y Wm.  (1928).  P a n e t h , F., A m a n u a l o f R a d i o a c t i v i t y ,  O x f o r d U n i v . P r e s s . 1926. 9.  J . S c . .239,  D. Am  10.  Rohm. & Haas Co.  11.  S v e r d r u p , H.,  194,  P.  119.  1941.  Amberlite B u l l e t i n  J o h n s o n , M.  IR-120.  F l e m i n g , R.  "The  Oceans  Physics, Chemistry & General Biology," H a l l I n c . N.Y. 12.  1946.  p.  no. 85,  Thompson, I.G. & C.C.  1932.  their  Prentice  173.  Thompson, I.G. & R o b i n s o n , R . J . " N a t . R e s e a r c h Bull.,  13  Foljden,  Wash.  Council",  D.C.  W r i g h t . "Amer. Chem. S o c . " 3ourn.  52, 915-21, (1930). 14  T r e a d w e l l , H a l l . V o l . 1, Q u a l i t a t i v e &  15  U r r y Wm.  S o n s . N. Y. p . 217 D.  16. E v a n s , R.D.  Am.  J . Sc. 239,  John W i l e y  (1946.) 195,  & Goodman C. P h y s . Rev.  33 B  Analysis,  1941. 65,  216-227,  (1944.)  "17.  E v a n s , R.D. & Goodman C. P h y s . Rev. 6 5 , 2 1 6 - 2 2 7 ,  (1944.)  18.  Y a g o d a , H. R a d i o a c t i v e M e a s u r e m e n t s w i t h N u c l e a r  Emulsions,  J o h n W i l e y & S o n s , Y.Y. p . 118 19.  "Photographic Plates  forScientific  (1949.)  & T e c h n i c a l Use,"  Eastman Kodak Co., R o c h e s t e r 4 , N. Y. 6 t h E d i t i o n s p. 33. 20.  Y a g o d a , H. R a d i o a c t i v e M e a s u r e m e n t s w i t h  Nuclear  E m u l s i o n s J o h n W i l e y & S o n s , N.Y. p . 119 21.  E v a n s , R.D. K i p , A . F . & M o b e r g , E.G. Am. J . S c i . 241-259,  22.  Foyn. E., K a r l i k ,  23.  Thompson,  B. P e t t e r s s o n , H., & Rona.E.,  1-44  'Foljden,  Goteborg.  ( B ) , 6,  (1939.)  T.G., Bremner, R.W., Chem., A n a l . E d . , 4 ,  24.  36,  (193$.)  V e t e n s k - s a m h . H a n d l . Femte (12):  (1949.)  & J a m i e s o n , I.M. I n d . E n g . (1):  288-290,  (1932.)  Sanderman, L.A., U t t e r b a c k , C . L . J.M.R. I V , ( 2 ) , 1 3 2 , (1941.)  34  ACKNOWLEDGEMENT  S i n c e r e s t thanks and a p p r e c i a t i o n t o D r . J . G . H o o l e y u n d e r whose guidance and s u p e r v i s i o n t h i s r e s e a r c h was u n d e r t a k e n . Tjhanks a l s o t o t h e P a c i f i c Oceanographic L a b o r a t o r i e s f o r t h e sea water samples.  35.  

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