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Vanadium in an interlava sediment, Quadra Island, British Columbia Carlisle, Donald 1944

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6  YANADIUH I I AN INTERLAVA SEDIMENT, QUADRA ISLAND, BRITISH COLUMBIA.  Submitted as T h e s i s f o r t h e Degree o f Master o f A p p l i e d S c i e n c e at t h e U n i v e r s i t y o f B r i t i s h Columbia.  April  , 1944.  Donald C a r l i s l e .  ACKNOWLEDGMENTS. The author i s indebted t o Dr. H.C.Gunning f o r d i r e c t i o n i n f i e l d and l a b o r a t o r y work and f o r h e l p i n r e v i e w i n g t h e l i t e r a t u r e , . a n d t o Dr. H.V.Yferren f o r p r o v i d i n g for  facilities  the s p e c t r o s c o p i c a n a l y s e s , a group o f which was made i n  p a r t i a l f u l f i l m e n t of work f o r t h e B r i t a n n i a M i n i n g and S m e l t i n g Company L i m i t e d S c h o l a r s h i p , under h i s d i r e c t i o n . The vanadium d e p o s i t s were examined i n t h e s p r i n g o f 1943 w i t h a s s i s t a n c e ' of a grant from t h e Department o f Geology. The a u t h o r a l s o wishes t o thank Mr.G.A.Dirom f o r assays and other, data on t h e Menzies Bay D e p o s i t s , and D r . V i c t o r Dolmage and other members o f t h e G e o l o g i c a l D i s c u s s i o n Glub* as w e l l as t h e members o f t h e Department of Geology f o r a d v i c e throughout t h e work. - The author has drawn f r e e l y on s e v e r a l standard works i n c l u d i n g ,  Ore D e p o s i t s , Lin,dgr;en; A T r e a t i s e o f  Inorganic Chemistry, M e l l o r ; States,  reference  Ore Deposits  and P r i n c i p l e s of Sedimentation,  of t h e Western Twenhofel.  CONCEITS *  The Problem  Page 1  .  Chapter I  Vanadium:  I t s H i s t o r y , P r o d u c t i o n , Uses and C h e m i s t r y .  History Production "Us ©S  «. ,^  4 5 V  •••••••• a  Chemistry II  8  The;Natural Occurrence o f Vanadium. In In aigneous s s o c i a t Rocks i o n w i t h M a g n e t i t e and T i t a n i f e r o u s I r o n D e p o s i t s ........... I n M i n e r a l s o f Hydrothermal 0 3? i. x n •••••••••••••••••• I n Contact Metamorphic S i l i c a t e s . . . In t h e O x i d i z e d Zone o f S u l p h i d e D e p o s i t s . Broken H i l l , N o r t h e r n Rhodesia ... O t a v i Mountain Region, South-West A f r i c a . . . . Vanadlnite Deposits of United S t a t e s and Mexico ••• Other D e p o s i t s • In  Sediments: (a) O r i g i n P r o b a b l y Syngenetic (b) O r i g i n P r o b a b l y E p i g e n e t i c  13 15 16 18 19 20 23 24 25 28 32  A s s o c i a t e d w i t h Hydrocarbons, W i t h C o a l , Petroleum and A s p h a l t i t e 36 Minasragra, Peru 39 I n Ground Waters. Summary and Theory. III  41 -  4  3  The Occurrence o f Vanadium i n some Rocks and M i n e r a l s from B r i t i s h Columbia. ...... 47 R e s u l t s o f S p e c t r o c h e m i c a l Survey of some Rocks and M i n e r a l s .  50  Page  Chapter IV.  The Deposits on Quadra I s l a n d and a t Menzies Bay  55  G e o l o g i c a l S e t t i n g o f the D e p o s i t s The Quadra I s l a n d D e p o s i t . ........ The Menzies Bay D e p o s i t . .„ The Genesis o f the C h a l c o c i t e . ........ The V a n a d i f e r o u s Sediment. S p e c t r o c h e m i c a l Assays. V.  Theories of O r i g i n f o r the Vanadiferous Sediment.  77  Sources f o r t h e S i l i c a The P r e c i p i t a t i o n o f C o l l o i d a l S i l ica • The C o n c e n t r a t i o n of Vanadium i n "fcti3 3©s,ni• ••••• •••••••••••••••••••••  ILIUSTRATIOCTS.  Flow c o n t a c t o f columnar and p i l l o w l a v a , Quadra I s l a n d , B r i t i s h Columbia.  78 80 82  Opposite page.  F i g u r e I . S k e t c h o f V e r t i c a l W a l l of Open Cut o f Main Showing, Quadra I s l a n d , B r i t i s h Columbia..... Plate I .  55 58 60 65 65 73  59  55  Plate I I  (a) P i l l o w l a v a , H y a c i n t h Bay, Quadra I s l a n d , (b) Folded v a n a d i f e r o u s sediment between l a v a f l o w s , Menzies Bay, B r i t i s h 0 o lumlD iq. ••••• •••••• •••••••••••••• 60  Plate I I I  (a) C h a l c o c i t e r e p l a c i n g b o r n i t e i n an amygdule. (b) S l e n d e r l e n s e s o f c o v e l l i t e i n c h a l c o c i t e i n an amygdule f i l l i n g 63  P l a t e IV.  f a ) The v a n a d i f e r o u s TI II (b) It I! (o.) (a) " "  sediment. II II  66  •THE PROBLEM. A small deposit  of very f i n e - g r a i n e d , t h i n l y beaded d a r k  s i l i c e o u s m a t e r i a l c o n t a i n i n g vanadium, and a s s o c i a t e d e x t e n s i v e l a v a f l o w s , was  found on Quadra I s l a n d i n  The d i s c o v e r y i s d e s c r i b e d "by E l l s w o r t h and  with  1932.  Gunning,  L a s t September, 1932, one of the w r i t e r s (Mr.Gunning) made a b r i e f examination of a p r o p e r t y s i t u a t e d at the n o r t h end of Gowland Harbour, Huadra I s l a n d , where Mr. R. Crowe-Swords had p r e v i o u s l y found and e x t r a c t e d some s m a l l p o c k e t s of a carnot i t e - l i k e m i n e r a l o c c u r r i n g i n c r e v i c e s of the v o l c a n i c r o c k s . Ko more than t r a c e s of these c a r n o t i t e pockets remained, but specimens of the r o c k s were taken and .were subsequently t e s t e d f o r r a d i o a c t i v i t y by means of the a l p h a ray e l e c t r o s c o p e . None of these specimens shov/ed a p p r e c i a b l e r a d i o a c t i v i t y , but one l o t of samples a t t r a c t e d a t t e n t i o n because of t h e i r p e c u l i a r character.. These c o n s i s t e d of a f i n e l y banded, s i l i c e o u s , carbonaceous m a t e r i a l I to 4 inches t h i c k embedded between two l a v a f l o w s ana c a r r y i n g some t n i n g r e e n i s h copper s t a i n s . I t was suspected t h a t t h i s carbonaceous s t r e a k mignt c a r r y vanadium and chemical t e s t s showed that i n f a c t i t d i d , Geo!.  Surv. Canada, Ec. Geol. S e r i e s Ho.11, p.139 .  These a u t h o r s s t a t e t h a t one per cent V 0 . 2  5  The  SiOg content i s about 75 per cent most  of which i s present as q u a r t z . ture i s suggestive  sample y i e l d e d over. 3  In t h i n s e c t i o n the s t r u c -  of a c o l l o f o r m p r e c i p i t a t e , the q u a r t z o s e  bands being composed l a r g e l y of t i n y , i r r e g u l a r l y s p h e r i c a l b o d i e s , between . o n e - f i f t h and meter i n d i a m e t e r .  one  s e v e n t y - f i f t h of a m i l l i -  An assay shows 5 per  cent carbon by  calculation. They f u r t h e r suggest that s i n c e the r o c k does not  appear  to have been o r i g i n a l l y a sandstone or normal c l a s t i c sediment, i t may have been formed o f the remains o f vanadiumb e a r i n g p l a n t s or a n i m a l s , or both, h a v i n g s i l i c e o u s skeletons,, which were g r a d u a l l y d e p o s i t e d on the submerged lower l a v a . When the upper f l o w o c c u r r e d , c o v e r i n g and h e a t i n g t h i s t h i n bedded m i x t u r e of s i l i c a and organic m a t t e r , the s i l i c a may have been more or l e s s r e e r y s t a l l i z e d and the v o l a t i l e o r g a n i c matter d r i v e n o f f , . l e a v i n g f i x e d carbon b e h i n d . There i s a l s o the p o s s i b i l i t y t h a t some o f the mate r i a l may have been o r i g i n a l l y a chemical p r e c i p i t a t e . The f r e s h l a v a s were, found a l s o to c o n t a i n vanadium. The d e p o s i t c o n t a i n s , i n a d d i t i o n , up to 3 per cent copper mainly as c h a l c o c i t e which v e i n s and r e p l a c e s the f i n e grained m a t e r i a l . W i t h the onset of Y/orld War s t r a t e g i c m e t a l and  I I , vanadium a g a i n became a  i n t e r e s t i n the d e p o s i t was  revived.  In  the meantime, p r o s p e c t i n g i n the a r e a had r e v e a l e d s i m i l a r volcanic-sediment  occurrences  a t t h e Copper C l i f f Group near  Gowland Harbour and near Menzies Bay on the mainland o f Vancouver I s l a n d , some t e n m i l e s west o f t h e o r i g i n a l d i s covery. to  1.10  These were found t o c o n t a i n vanadium i n amounts up per cent V 0 g . g  T h e r e f o r e i n t h e s p r i n g of  1943,  the o r i g i n a l d e p o s i t s and those near Menzies Bay were examined i n c o n n e c t i o n w i t h a f i e l d course g i v e n by the Department o f Geology and Geography, a t the U n i v e r s i t y o f B r i t i s h Columbia. The d e p o s i t near Menzies Bay  i s s i m i l a r t o the one  oh  Quadra I s l a n d except t h a t a t Menzies Bay s m a l l l e n s e s of fine-grained, partly reerystallized fossiliferous  dark,  limestone  o v e r l i e the f i n e - g r a i n e d , dark sediments between the l a v a  flows.  I n no p l a c e does t h e t o t a l w i d t h o f the sediments  exceed 8 i n c h e s , and i t i s u s u a l l y much l e s s than t h i s .  The  d e p o s i t s i n t h e two p l a c e s a r e n o t n e c e s s a r i l y a t t h e same h o r i z o n , and, i n f a c t , do n o t l i e a l o n g t h e p r o j e c t e d d i p o f the l a v a s from one a n o t h e r .  The s t r u c t u r e o f t h e i n t e r v e n -  i n g a r e a i s not known. The l a v a s a r e m a i n l y b a s a l t i c i n c o m p o s i t i o n and a r e s i m i l a r over a l l t h e area-and f o r some d i s t a n c e north-westward a l o n g t h e c o a s t o f Vancouver I s l a n d .  They a r e m o s t l y  amygdaloidal and many have p i l l o w s t r u c t u r e p o o r l y to v e r y w e l l developed.  The f l o w s a r e from l e s s than 2 f e e t t o more  than 15 f e e t t h i c k and they d i p from h o r i z o n t a l t o 20° t o t h e south-east i n t h e area near t h e d e p o s i t s .  A l l samples o f  these l a v a s taken from many p a r t s o f t h e a r e a c o n t a i n vanadium i n amounts as l a r g e as.0.5 per c e n t . These d e p o s i t s a r e t o o s m a l l t o be c o n s i d e r e d vanadium ore.  I t i s q u i t e p o s s i b l e , however, t h a t o t h e r l a r g e r and  perhaps commercial  d e p o s i t s o f t h i s type may o c c u r in. t h i s  o r some o t h e r s e r i e s o f l a v a s , and may have a l r e a d y been passed over and not r e c o g n i z e d .  Furthermore, no o t h e r  occurrence o f t h i s t y p e has been d e s c r i b e d i n t h e l i t e r a t u r e . I t i s t h e o b j e c t o f t h i s t h e s i s , t h e r e f o r e , t o review t h e c h e m i s t r y and g e n e r a l occurrence o f vanadium and then t o d e s c r i b e t h e d e p o s i t s and suggest a p o s s i b l e - o r i g i n f o r t h e vanadium i n them.  CHAPTER I . VAKADIUM't  ITS HISTORY, PRODUCTION, USES, AED HISTORY.  The d i s c o v e r y of a new metal "by A.M.  CHEMISTRY.  D e l Rio i n a plumb -  i f e r o u s m i n e r a l (probably v a n a d i n i t e ) from Zimp an, Mexico, announced by A.von Humbolt i n 1801.  wa  D e l R i o named the metal  erytnronium from the Greek e r y t i i r o s m r e d , because i t formed red s a l t s when t r e a t e d with' a c i d .  l o u r y e a r s l a t e r the  supposed new metal was d e c l a r e d to be an impure chromium s a l t and erytnronium was abandoned.. Sefstrom d e s c r i b e d a new  In 1830, however, Is.G.  element w h i c h he found i n the i r o n  ores of Taberg, Sweden, and immediately F.Wb'hler e s t a b l i s h e d the i d e n t i t y of the new  element w i t h D e l R i o ' s ery tnronium,.  Because of i t s b e a u t i f u l and v a r i o u s - c o l o u r e d compounds, Sef.strom named tlie element "vanadium" i n honour of vanaciis, the b e a u t i f u l goddess of y o u t h and l o v e , who  i s none other  than F r e i a of R i c h a r d Wagner•s "Das R h e i n g o l d " and  "Die  Gotterdaromerung"* E l e m e n t a l vanadium does not occur i n n a t u r e , but i t i s one of the more abundant of the minor c o n s t i t u e n t s of. tne e a r t h ' s c r u s t , f o r a c c o r d i n g to C l a r k e and Washington, i t i s more abundantly d i s t r i b u t e d i n the c r u s t than i s n i c k i e , copper, z i n c , or. l e a d .  I t occurs i n the sun and i n meteor-  i t e s and. i s w i d e l y d i s t r i b u t e d i n the bodies of  organisms.  The p r i n c i p a l vanadium m i n e r a l s are the mixed s u l p h i d e s  o c c u r r i n g together as " P a t r o n i t e  33  ( a p p r o x i m a t e l y YS^)  f  s e v e r a l vanadates of which t h e most important i s v a n a d i n i t e . Phg(V0 ) Ql 4  3  s  isomorphous  w i t h a p a t i t e and pyromorphite,  car not i t e Kg0.2UQ^.Yo0g.3HgQ- and other r a d i o a c t i v e s a l t s , ana a vanaaiurn-hearing hydrous mica c l a y m i n e r a l , f o r m e r l y thought to be the same as r o s c o e l i t e . In 18 73, the p i I c e of impure vanadium was over 500 pounds s t e r l i n g per pound, and vanadium o x i d e s o l d f o r about 63 s h i l l i n g s an ounce.  But even a t that time i t s use as an  o x i d i z i n g c a t a l y s t i n d y e i n g a n i l i n e b l a c k was found economic a l owing to the extremely s m a l l amount r e q u i r e d .  Widespread  commercial development of vanadium began w i t h the d i s c o v e r y of the vanaaium ores a t M i n a s r a g r a , P e r u , i n 1905.  PRODUCTION. Peru has been the c o n s i s t e n t l e a d i n g producer of vanadium s i n c e 1907, except f o r those y e a r s f o l l o w i n g 1930 when a heavy export duty e n f o r c e d by the P e r u v i a n Government caused the mines to become i d l e f o r s e v e r a l y e a r s .  The export duty  was g r e a t l y reduced i n 1935 and m i n i n g was resumed.  Peru  and the U n i t e d S t a t e s a r e now the most important p r o d u c e r s , w i t h South-West A f r i c a and N o r t h e r n R h o d e s i a i n t h i r d and fourth place respectively.  •• v/ORIlJ PRODUCTION "OS VANADIUM IN ORES AMD  GOB"GEE'IRATES •  1930-1940, IN METRIC TONS. t  r  t  19,3.0. o i , ^g,, *35-. 54. 5-& >'36. '37» ^58. 'o9» <  Mexico.  _  -  Borth,Ehodesia.  -  61 216 307  Peru  528  »  -  v  1  245  K  36  '  133,  18 2  -  v  =  45 180  3 173 204 235 374  -  S.'tf. A f r i c a . , - 503 445.305 united States.  -  v  1  57 1  384  67 161 583 826 1,016.1,254  34 176 547 591 557 1  148  '40.  61 493 732  514  900  428  948  (1) Shipments; (2) Shipments from s t o c k (5) Bureau of Mines not at l i b e r t y to p u b l i s h V4). Data not a v a i l a b l e . Compiled from the M i n e r a l s Yearbook, U n i t e d S t a t e s Department of the I n t e r i o r , Bureau of Mines. (1931 - 1940). The p u i e l y nominal p r i c e has been 27-g- cents per pound of contained. V 0p- since o  1935.  . The output from P e r u now comes mainly from secondary vanadates a t the Mlnasxagra Mine owned by t h e Vanadium C o r p o r a t i o n of America..  A r i c h e r product c o n t a i n i n g about  11 per cent V Q5 i s s o r t e d out and t h e low grade ore i s g  crushed and burned to e l i m i n a t e the carbonaceous m a t t e r , l e a v i n g an ash w i t h about 22 per cent V^O^.  This ash i s  sacked and shipped to B r i d g c v i l l e , Pa., f o r r e d u c t i o n to f e n o v a n a d i u m i n the e l e c t r i c f u r n a c e . Most of the vanadium from south-western U n i t e d S t a t e s i s recovered from the v a n a d i f e r o u s c l a y mica by r o a s t i n g the ore w i t h s a l t , l e a c h i n g the sodium vanadate w i t h water and p r e c i p i t a t i n g VgO w i t h a c i d . &  The p r e c i p i t a t e i s sintered, to  a product c o n t a i n i n g about 88 per cent VgO^.. In n o r t h e r n Rhodesia the -vanadium i s r e g u l a r l y a n < i  b o t h as tiie oxide w i t h over 90 per' cent V2O5  produced  as f e r r o -  vanadium w i t h about 34 per cent vanadium, In 1939 a l l the ore from South-West A f r i c a a v e r a g i n g about 20 per cent V 0  and coming m a i n l y from three mines was  shipped to England and Europe.  USES. Vanadium i s one o f the most u s e f u l o f the r a r e metals. A s m a l l amount i s used i n manufacturing. i i g S 0  4  where i t i s  s u p e r i o r t o p l a t i n u m because the I n i t i a l cost i s lower and i t i s u n a f f e c t e d by most .of the p l a t i n u m p o i s o n s , More vanadium i s used i n s p e c i a l a l l o y s , m a i n l y f e r r o u s a l l o y s , than anywhere e l s e .  I t i s added d i r e c t l y as f e r r o -  vanadium or t o t h e s l a g as fused V 0p. and s i n c e i t has a very o  s t r o n g a f f i n i t y f o r n i t r o g e n , oxygen, and carbon, i t a c t s as a scavenger and as a c a r b i d e former. a b l e , i m p a r t i n g a toughness  I t s e f f e c t i s very n o t i c e  to the a l l o y and i n c r e a s i n g the  r e s i s t a n c e t o repeated shocks or v a r y i n g s t r e s s e s .  I n amount  not over 25 per cent, i t g r e a t l y i n c r e a s e s the h a r d e n e a b i i i t y of s t e e l s , t h a t i s , the ease w i t h which they can be hardened by heat treatment.  S p r i n g s t e e l s a r e improved m a t e r i a l l y by  i t s presence, and h i g h speed s t e e l s may c o n t a i n as much as 1.3 per cent vanadium, or more.  Before the war, the a u t o -  mobile i n d u s t r y was the great consumer of vanadium.  Chromium-  •vanadium s t e e l s are used i n some armour p l a t e . Minor amounts of vanadium are a l s o used i n Pharmacy and T h e r a p e u t i c s , i n making p a i n t d r i e r s , as i n s e c t i c i d e , f u n g i cide,, and f e r t i l i z e r ,  i n photography,'and i n the ceramic and  g l a s s i n d u s t r y where i t s h i g h e f f i c i e n c y f o r f i l t e r i n g  out  u l t r a - v i o l e t rays i s u s e f u l .  CHEMISTRY. Vanadium w i l l combine w i t h almost a n y t h i n g i t meets, and t h e r e f o r e i t s c h e m i s t r y i s v e r y complex. Vanadium, along w i t h n i o b i u m (» coiumbium) and tantalum belongs to the even s e r i e s of the f i f t h group i n the p e r i o d i c table, N  I n many ways, then, i t i s c h e m i c a l l y s i m i l a r to  I  P  n i t r o g e n and phosphorous w h i c h belong to the odd  / \ "V \ I As Fb | I Sb  s e r i e s of the f i f t h group, a l o n g w i t n a r s e n i c , antimony, and bismuth.  There a r e , however,  Ta :|  important, p h y s i c a l and chemical d i f f e r e n c e s be-  Pa  tween the sub groups? the  i n p a r t i c u l a r , members of  even s e r i e s (V,Mb,Ta) do not form organo-  m e t a i l i c compounds w i t h hydrocarbon r a d i c a l s , whereas the elements of the odd s e r i e s form s t a b l e compounds of the  t h i s type,  -Vanadium i s a l s o a member o f the s e r i e s across  p e r i o d i c t a b l e , T i,V,Cr,Mn,Pe,Co,Hi. The atomic number of vanadium i s 23 and the atomic  weight i s 51.06.  The  pure element i s a d u c t i l e s i l v e r y m e t a l w i t h a  s p e c i f i c g r a v i t y of 5.8 and m e l t i n g a t 1710°C. nitrogen  Unlike  or phosphorous, vanadium i s undoubtedly a m e t a l .  i s i n s o l u b l e In d i l u t e HOT or HgS0 i s soluble  4  It  or aqueous a l k a l i e s ; i t  i n HF and HNOg and i s r e a d i l y decomposed by f u s e d  alkalies. Vanadium forma compounds p o s s e s s i n g the p o s i t i v e v a l e n c e numbers 1,2,3,4,and 5, the two lower v a l e n c e s being basic and the two h i g h e r amphoteric,  ++  Vanadous i o n , V ~ i s a s t r o n g  r e d u c i n g agent and v a n a d i c I o n i s f a i r l y  strong.  The metal  i s o x i d i z e d by moderate o x i d i z i n g agents i n a c i d  s o l u t i o n to  the t e t r a v a l e n t  s t a t e and by p o w e r f u l agents to vanadate. I t  forms a complete s e r i e s of o x i d e s , the s a l t s of which a r e c o l o u r e d as below? s a l t s of YgO Colour  -  VgO or VO g  Lavender or V i o l e t  2°3  V 0  green  blue  V  remarks  2  4  or VQg  o 2 5 orange or yellow  vanadyl: salts  vanadates, most Important .  Vanadium p e n t o x i d e , when i t a c t s as an a c i d i c o x i d e , forms a s e r i e s o f s a l t s c a l l e d vanadates.  These have been regarded  as d e r i v a t i v e s of a s e r i e s of h y p o t h e t i c a l Or the v a n a d i c Pyro vanadic Metavanadic Tetravanadic iiexavanadic  acid acid acid acid acid  vanadic  N.3VG4 H4 VgO'? HVO.3 -^2^4^11 HV3OQ-  acidst  10  In s o l u t i o n or tno-vanadate i s r e a d i l y h y d r o i i z e d . 2V0  4  + H0 g  — T  2  0 g ~  -p 2 0 H "  At n i g h temperature, however, tne o r t n o - s a l t s a r e s t a b l e c o n s t i t u t e ; many o f the vanadium m i n e r a l s .  and  See above.  The a l k a l i pyrovanadates a r e s o l u b l e and the a l k a l i n e e a r t h pyrovanadates a r e s l i g h t l y s o l u b l e .  Metavanadatea of  sodium, potassium, ammonium, barium, and l e a d are but s l i g h t l y s o l u b l e i n c o l d water,  but s a l t s o f other p o s i t i v e ions a r e  s o l u b l e , and t h e i r c o l o u r i s g e n e r a l l y y e l l o w .  Many vana-  dates of the i r o n and aluminum f a m i l y a r e but s l i g h t l y  soluble.  Ammonium metayanadate, M^VGg i s probably the most important  compound c o m m e r c i a l l y S o m e  vanadium e x t r a c t e d  from  i t s ore by l e a c h i n g w i t h s t r o n g h y d r o c h l o r i c a c i d , i s p r e c i p i t a t e d from t h i s s o l u t i o n as ammo n i urn v an ad a t e by  evaporation  of. the s o l u t i o n w i t h excess of ammonium c h l o r i d e .  Ammonium  metava.nad.ate  i s s o l u b l e i n hot water.  In g e n e r a l  the a l k a l i vanadates a r e more or l e s s s o l u b l e  i n water and a l l vanadates of the ''heavy metal3 a r e n e a r l y i n s o l u b l e i n water, but a r e r e a d i l y s o l u b l e i n s t r o n g Many c h l o r i d e s and sulphates  acids.  of vanadium are s o l u b l e i n c o l d  water. Some o f " t h e more abundant vanadium m i n e r a l s ares urthovanadat.es. Vanadinite,  Pb (PbOl}(V0 )3  -Uescloizite  (Fb$ Zn)g(HH}¥0^  4  4  i n s o l u b l e i n water  G u p r o d e s c I o i z i t e ( P b j Z n j O u ) g ( O H ) YQ%  II  Carnotite  K 0 . 2 I I 0 . Y g 0 „ 3HgO  Tyuyamunite  CaO.U0 .Y 0 .nH G  g  3  5  3  2  hydrous  . Volborthitn  5  2  Cu,Ba,Ca,vanadate  B1V0.  Puclierite . Mottramite  2  ) )  (Pb,Cu} (0H)TQ 2  ?  4  Psittacinite) SQuG.Y O -bHgO g  &  tfsbekite 5CuO.TgO.- .2H Q 5  a  Turanite GaO ,2U0 . 6Y 0 . 20HgO 3  2  g  Rauvite (Pb,Mn,Pe) V 0 .HgO ? 3  2  8  Brackebuschit e Pyrovanaaate S Pintaaoit e  2CaO.Y 0 .9H 0 2  5  2  Me t. avan ada t e a i Dechenite Rossite Metarossite Hexavanadates i  Pb VgOg  - sparingly soluble i n water. CaO„V Q .4H 0 2  5  2  CaG„V 0 2H 0 2  5e  2  vary i n s o l u b i l i t y ,  Hewettite CaO^3:V 0 .9H 0 2  5  2  Me t ahewe 11 i t e) Pascoite  2CaO.3Vg0 .IlHg0 g  Vanadovanadat eat Melanoyanaciat e Pernandinite  2CaO«,3V 0,-.2V2O4 - r e a d i l y s o l u b l e in acids. CaO..V 0 „ 5V 0 .14H 0. 2  2  4  " P a t r o n i t e " i s s t a t e d by L i n g r e n  2  2  to be an i n t i m a t e mix-  ture o f t h r e e sulphides,,• VgSg.VgSg»VgS ^ t h e t o t a l 5  being  e q u i v a l e n t to VS. or VpS,-. b u l v a n i t e i s a cuprous orthosulphavanadate Cu„VS . M i n a s r a g r i t e i s a b l u e hydrous sulpliate vg0 .3S0~„16HgQ. 4  S i n c o s i t e i s a hypovana.datopiiospliate CaO.VgO^.PgG^. 5HgO. K o s c o e l i t e i s a vanadium mica " e s s e n t i a l l y a. muscovite. The v a n a d i f e r o u s m i n e r a l o c c u r r i n g i n sandstone i n Colorado, f o r m e r l y thought to be r o s c o e l i t e belongs to the hydrous mica group .of the c l a y m i n e r a l s w i t h the g e n e r a l formula p r o b a b l y 2Kg0.-j5R0.8E 0 .24SIQ -12H 0, where E g 0 2  3  2  2  incliid.es alumina (Al^O^) and f e r r i c i r o n (PegOg).  3  Presumably,  vanadium oxide ( V g 0 ) .replaces ALpOg and PegO^, 3  H l l l e b r a n d and L u n d e l l s t a t e t The c o n n e c t i o n of vanadium w i t h f e r r i c aluminous s i l i c a t e s of r o c k s , taken i n c o n n e c t i o n w i t h the e x i s t e n c e of the m i n e r a l r o s c o e l i t e , c l a s s e d as a vanadium mica, i n d i c a t e s that the vanadium corresponds i n c o n d i t i o n to alumium and f e n : i c i r o n , ana that i t ' i s to be r e garded as r e p l a c i n g one or .both of these elements. Hence i n these cases i t should be r e p o r t e d as V O-,, and not Vg0 . (p., 352.) p  5  I t s c o n d i t i o n i n matter of secondary o r i g i n such as c l a y s , l i m e s t o n e s , sandstones, c o a l s , and ores of i r o n , i s yet  open to d i s c u s s i o n .  CHAPTER I I . THE .STATURAL OCCURRENCE- OP VANADIUM,* we have noted, the widespread occurrence of vanadium and some of the important m i n e r a l s .  In t h i s chapter the types  of occurrence w i l l he i n v e s t i g a t e d more f u l l y and some i n f e r ences w i l l be drawn about the c y c l e of vanadium i n nature and how the element may be c o n c e n t r a t e d . IN IGNEOUS ROCKS. 9  In 1898 H i l l e b r a n d a n a l y z e d 5? igneous r o c k s from a l l over U n i t e d S t a t e s and found n e a r l y a l l to c o n t a i n vanadium i n amounts from l e s s than 0,004 per cent to 0.100 per cent V2O5.  P i v e s y e n i t e s and g r a n i t e s c o n t a i n e d no vanadium.  He concluded that vanadium predominated  i n "Less s i l i c e o u s  igneous r o c k s and i s a b s e n t , or n e a r l y so, i n those of h i g h silica."  H i s s u s p i c i o n that the h e a v i e r s i l i c a t e s or  ferromagnesians c o n t a i n e d most o f the vanadium was j u s t i f i e d by the f o l l o w i n g r e s u l t s : Rock - V 0, Amphibole Gabbro .038 " .020 P y r o x e n i c Gneiss .083 Diorite ,031 Quartz-mica, D i o r i t e .011 Quartz Monzonite .012 S y e n i t e Lamprophyre .033 o  ,f  A  7v  Mineral contained V 0 Amphiboles T062 " .03 7 Motile .127 Amphibole .066 Biotite .=048 Biotite .066 Pyroxene .036 ?  S  H i l l e b r a n d noted that t h e s e m i n e r a l s d i d not c o n t a i n e n o ucrh v a. n ad i urnto account f o r a l l that I s present i n the  14  r o c k s , and suggested r o s c o e l j t e may  t h a t another m i n e r a l perhaps l i k e  he p r e s e n t .  R o s c o e l i t e . i s a g r e e n i s h "brown vanadium mica r e p o r t e d w i t h goId-quartz v e i n s i n C a l i f o r n i a , -Colorado, A t l i n i n B r i t i s h Columbia, and at E a l g o o r l i e , \?estern A u s t r a l i a , Larsen rex>orts two v a n a d i f e r o u s a e g i i i t e s from L i h h y , Montana, c o n t a i n i n g almost respectively.  3 per cent and 4 per cent V 0., 2 b  These are i n h i g h temperature,  deep s e a t e d ,  almost p e g m a t i t i c v e i n s i n an a p a t i t e p y r o x e n i t e c a r r y i n g 0.12  per cent VgOg.  Other i n v e s t i g a t o r s have found  vanadium i n many r o c k s and r o c k m i n e r a l s . 4-  f+ +  C l a r k e and Washington s t a t e t h a t V  i s widely d i f f u s e d  i n igneous r o c k s but i s p r i n c i p a l l y i n the more femic k i n d s . They g i v e the average vanadium content of igneous r o c k as .026 per cent VgO^  or .017 per cent vanadium.  .Tost."estimates that the average vanadium content  of  e r u p t i v e r o c k s i s .018 per cent vanadium. These authors a l s o show t h a t metamorphic r o c k s and  the  very f i n e - g r a i n e d sediments c a r r y <Vanadium i n amounts s i m i l a r to the average igneous r o c k , but t h a t l i m e s t o n e , l i m e y s e d i ment, a r k o s e , conglomerate,  and m a r l , are g e n e r a l l y lower i n  the m e t a l . Vanadium reaches  i t s g r e a t e s t c o n c e n t r a t i o n i n igneous  products i n the u l t r a m a f i c r o c k s and t h e i r a s s o c i a t e d magnetite  and i l m e n i t e d e p o s i t s .  15  1IT ASSOC I ATI01 mm  MAGllETITE MD  IITAUIEEE0US IEOIT DEPOSITS*.  Sefstrom f i r s t separated vanadium from the p i g i r o n maae from t i t a n i f erous i r o n ores of Tab erg, Sweden,. •20  Robinson found s e v e r a l Canadian  t i t a n i f e r o u s i r o n ores  to c o n t a i n -vanadium from a t r a c e t o 0,63 per cent VgO^,  The  vanadium content d i d not bear any constant r a t i o to tiie t i t a n i u m content but a l l tiie t i t a n i f erous i r o n ores were found to be v a n a d i f e r o u s , a ay leyj  from h i s study of t i t a n i f e r o u s i r o n ores i n  C a r o l i n a and Tennessee concludes  that "presence or absence of  vanadium i n i r o n ores i s more c h a r a c t e r i s t i c of the p r o v i n c e i n whicii the ores occur than o f the v a r i e t y o f ore o c c u r r i n g in i t , " The vanadium b e a r i n g t i t a n i f e r o u s i r o n - o r e s of Singhbhum and Mayur.bh.anj,  I n d i a , have been s t u d i e d by Dunn*  The ores  are r e l a t e d to Arcnean gabbro, q u a r t s - a a o r t h o s i t e and u l t r a mafic r o c k .  'They c o n t a i n from 0.59 to 8.80 per cent TgQ^,  p a r t l y o r e n t i r e l y p r e s e n t as a new m i n e r a l ^coulsoiaite"' w h i c i i i s e i t h e r a v a n a d i f e r o u s magnetite or v a n a d i f e r o u s magheraite. Vanadium can be r e c o v e r e d from these v a n a d i f e r o u s magnetites d u r i n g tne s m e l t i n g of the iron, ore.,  I n 1935.  i t was r e p o r t e d from R u s s i a t h a t pure vanadium and n i g n grade forrovanadiurn p i g were b e i n g made from t h e t i t a n i f e r o u s  iron  ores of the U r a l s , and t h a t f e r r o v a n a d i urn had been removed from the l i s t of needed i m p o r t s .  ( M i n e r a l s Yearbbokl^j. 1936.)  16  In 1938, a p l a n t f o r " t h e r e c o v e r y of vanadium presumably I r o n sand was completed  from  i n Japan by the Japan I r o n Sana.  I n d u s t r i a l Company. ( M i n e r a l s Yearbook 1939).  Many "other  occurrences of v a n a d i f e r o u s magnetite have been r e p o r t e d .  IN MINERALS OF HYDROTHERMAL ORIGIN. Here a r e Included occurrences i n which the vanadium i s g e n e r a l l y b e l i e v e d to be of hydro thermal o r i g i n . R o s c o e l i t e , t h e vanadium b e a r i n g mica i n the g o l d - q u a r t s v e i n s of Colorado and C a l i f o r n i a , and the E n g i n e e r Mine a t A t l i n , B.C.. and at K a l g o o r l i e , Western A u s t r a l i a , a p p a r e n t l y f a i l s into t h i s class. At J o a c n i n s t h a i , Bohemia, vanadium i s a s s o c i a t e d w i t h u r a n i n l t e and p i t c h b l e n d e i n me sothermal s i l v e r - b e a r i n g i cobalt-nickel veins. Vanadium o c c u r s i n . t h e r u t i l e o f p n e u m a t o i i t i c a p a t i t e lodes. A c c o r d i n g to Hermanf vanadium i s r a r e l y found i n magma t i c s u l p h i d e s , but i t i s widespread hydrothermal and replacement are v e r y s m a l l .  i n primary s u l p h i d e s of  o r i g i n , a l t h o u g h the amounts  Newhouse found from O.On to G.QOn per cent  i n 13 out of 16-samples o f p y r i t e , s p h a l e r i t e , and galena from w i d e l y separated l o c a l i t i e s  i n U n i t e d S t a t e s and Europe.  He concluded that a l t h o u g h s e v e r a l sources probably  contri-  bute vanadium to the o x i d i z i n g . h e a v y metal d e p o s i t s " i n most  of the lower grade and probably  some of the higher  grade  d e p o s i t s of vanadium . .«, in the o x i d i z e d zones of l e a d leao.-zinc-copper  and  d e p o s i t s , the vanadium ... i s . X a r g t l y d e r i v e d  from s m a l l amounts present  i n the o r i g i n a l 26  suiphidea."  Mewhouse adds t h a t H. M e r i t g r e p o r t e d vanadium i n gulpJaid© ore from Tsuraeb, South « est A f r i c a .  Here term ant i t e ,  e n a r g i t e , s p h a l e r i t e , and other s u l p h i d e s , as w e l l as and d o l o m i t e , p y r i t e may  c o n t a i n around 0.001  calcite  per cent vanadium, and  c o n t a i n as much as 0.01  per cent vanadium.  Galena  from t h i s l o c a l i t y c o n t a i n s very small i n c l u s i o n s of p a t r o n i t e , the aggregate running Moritz.  Newhouse was  0.01  to 0'i005 per cent vanadium s t a t e s  unable to f i n d any p a t r o n i t e i n trie  s u l p h i d e s he examined, and b e l i e v e d t h a t a l l the vanadium present  in solid solution.  A . S t a h l s t a t e d that "almost pure"  galena from Tsumeh c o n t a i n e d vanadium from 0.034 to per. cent VgO^,  was  and Wagner r e p o r t s  + 0.1  0.041  per cent vanadium i n  n i c k e l i f e r o u s p y r i t e from the Merensky h o r i z o n i n the Bushveldt Complex.  - .Note that t h i s i s an e x c e p t i o n  ment.  *  Sulphide  to Herman's s t a t e •  '  samples from exposures of s m a l l s u l p h i d e bodies  i n the San A n t o n i o D i s t r i c t were assayed f o r vanadium. m a j o r i t y snowed a t r a c e or n o t h i n g , but  samples from  s e c t i o n d i d show the f o l l o w i n g vanadium percentages? 0.32,  0.27,  and  one 0.32,  0.27.  Spectroscopic Columbia and  The  a n a l y s i s , b o t h at the U n i v e r s i t y of B r i t i s h  i n the l a b o r a t o r i e s of the P r o v i n c i a l Department  of Mines at V i c t o r i a , have i n d i c a t e d small amounts of  vanadium i n many s u l p h i d e s *  R.M. Thompson found s p e c t r o -  s c o p i c a l i y t h a t of 164 s p h a l e r i t e s from as many l o c a l i t i e s 135 contained no. vanadium and the remaining 29 contained l e s s than 0.01 per cent vanadium.  The p r o p o r t i o n of s p h a l e r i t e s  c o n t a i n i n g vanadium was g r e a t e r i n "low teraperatur e" d e p o s i t s than i n "high temperature" d e p o s i t s . I t should be p o i n t e d out t h a t i n none of the above examples has i t been p o s s i b l e t o prove t h a t the vanadium i s of hydro thermal or :i g i n .  I I COM'ACT METAMORPHIC SILICATES. Vanadium-hearing c o n t a c t s i l i c a t e s a r e thought source f o r t h e vanadium i n secondary  to be a  o r e a t the San Antonio  Mine, i n the Santa E u l a l i a . D i s t r i c t , Mexico. t i n . occur i n l i m e s t o n e - a s replacement  Here l e a d ana  d e p o s i t s of t h e contact  metamorphic t y p e , and vanadium ores have been formed by secondary  concentration.  some replacement  The primary  ore bodies, except f o r  veins', c o n s i s t of / skarn m i n e r a l s ana ore  which have formed on r h y o I i t e - I i m e s t o n e c o n t a c t s and i n l i m e stone i s o l a t e d from igneous r o c k -  The common skarn m i n e r a l s  are g a r n e t , e p i d o t e , and the f i b r o u s s i l i c a t e s . , t r e m o l i t e , a c t i n o l i t e , and p o s s i b l y h e d e n b e r g i t e .  Vanadium was found  i n a i l but a few of u n o x i d i a e d samples of the contact cates.  A l t h o u g h many r a n but a t r a c e or- b e t t e r , a s m a l l  percentage per cent.  sili-  snowed 0.23 per cent or h i g h e r , w h i l e one r a n 0.50 Pour assays, not c o n f i n e d t o any one s e c t i o n of  19  the mine, snow tne I'ol lowing J 0.23, cent.  0„27, 0,27,  ana 0.50  per  G a r n e t - r i c h samples were the lowest i n -vanadium, and  samples w i t h f i n e - t o - m e d i u m - t e x t u r e d , l i g h t c o l o u r e d f i b r o u s s i l i c a t e s were h i g n e s t . .  ,i.P. Hewitt • c o n c l u d e s :  •whether vanadium r e p l a c e s i r o n molecules i n otherwise normal l i m e - i r o n s i l i c a t e s , or occurs as a s p e c i f i c vanadium s i l i c a t e , i s not known. However, the l i g h t - c o l o u r e d f i n e - t o • medium-textured f i b r o u s s i l i c a t e s are regarded as the vanadium c a r r i e r , a.lthough other s i l i c a t e m i n e r a l s may c o n t a i n some vanadium. '  IN THE OXIDIZED ZONE  SULPHIDE DEPOSITS.  The most abundant type of c o m m e r c i a l l y important vanadium d e p o s i t i s t h a t i n which the vanadium occurs i n a s s o c i a t i o n w i t h o x i d i z e d ores or l e a d , z i n c and  copper.  Most of the vanadii:im m i n e r a l s belong to the vanadate and the most important ares  class  vanadinite, descioizite,  dechenite, c u p r o d e s c l o i z i t e , e n d i i c h i t e , c h i l e i t e , moftramite, and p s i t t a c i n i t e .  Commonly a s s o c i a t e d v/itn these m i n e r a l s  are pyromorphite, c e r u s s i t e , w u l f e n i t e , m i m e t i t e ,  aemimorphite,  s m i t h s o n i t e , and l e s s commonly s t o l z i t e and h o p e i t e . vanadium m i n e r a l s a r e c o n f i n e d to the o x i d i z e d zone. combination of m i n e r a l s i n any one d e p o s i t may  The The  be very complex  and c o n s i d e r a b l y . d i f f e r e n t from t h a t i n another d e p o s i t n e a r by.  The d e p o s i t s a r e u s u a l l y s m a l l but i n c l u d e two of tne  l a r g e r vanadium producers of the w o r l d , Broken H i l l , Rhodesia, and Abenab, South west A f r i c a .  Northern  Broken H i l l , Northern Rhodesia: Vanadium i s a s s o c i a t e d w i t h o x i d i z e d l e a d and z i n c ores a t Broken H i l l , about t h r e e hundred m i l e s n o r t h - e a s t o f t h e Victoria Falls.  Here a s e r i e s o f metamorphosed sediments  c o n s i s t i n g m a i n l y o f d o l o m i t e , p h y l l i t e , and a l i t t l e  quartz  s c h i s t and conglomerate have been eroded t o a p e n e p l a i n .  The  ore bodies a r e replacements o f s u s c e p t i b l e beds i n a N.W.band and have t h e form o f s u c c e s s i v e  lenses  S.E.  dipping t o the  n o r t h conformably w i t h t h e e n c l o s i n g d o l o m i t e and h a v i n g a p i t c h t o t h e E.-N.E.  Some o f these o r e bodies c o n s i s t i n g  m a i n l y of l e a d and z i n c m i n e r a l s w i t h s u r r o u n d i n g dolomite r i s e as s m a l l h i l l s o r "Kop.jes" from 75 t o 90 f e e t above t h e general  l e v e l of the peneplain.  Weathered dolomite and c l a y  w i t h o x i d i z e d ore o f l e a d and z i n c and t h e vanadium m i n e r a l s predominate t o a depth o f 150 f e e t .  No. 1 ilopje was t h e  source o f many b e a t i f u l m i n e r a l o g i c a l specimens o f pyrom o r p h i t e , c e r u s s i t e , d e s c i o i z i t e , v a n a d i n i t e , and t h e r a r e z i n c phosphates, t a r b u t i t e , hopeite*, and p a r a h o p e i t e . 35"  A c c o r d i n g t o P e l l e t i e r , t h e more important o r e bodies always c o n s i s t o f fa) a c e n t r a l p o r t i o n o r core o f massive s p h a l e r i t e and g a l e n a , enclosed w i t h i n (b) an envelope o r s h e l l o f o x i d i z e d ore u s u a l l y about 15 f e e t t h i c k , but t h i c k e r w i t h i n 100 f e e t o f t h e s u r f a c e . of quartz,  This o x i d i z e d ore c o n s i s t s  i r o n o x i d e s , and hemimorphite w i t h l e s s e r amounts  of z i n c c a r b o n a t e s , l e a d carbonate, and vanadium m i n e r a l s . It  i s v e r y r i c h i n l e a d and z i n c , and has a j a s p e r o i d appear-  21  ance*  The r i c h vanadium ores are developed on the margins  of  tiie o x i d i z e d ore ana l a r g e l y i n tne broken ground between tiie massive o x i d i z e d ores and tiie d o l o m i t e , as w e l l as i n open f i s s u r e s and c a v i t i e s .  The whole of tne o x i d i z e d ore a v e r -  ages about 0.5 per cent vanadium.  D e s c l o i z i t e , the main  vanadium m i n e r a l , o c c u r s i n f a i r l y l a r g e q u a n t i t i e s i n pockets up to an i n c h i n w i d t h , and as massive seams and mixed w i t h i i m o n i t e .  incrustations  V a n a d i n i t e i s much l e s s abundant than  descloizite. In p a r t s of the d o l o m i t e kopjes are caves, the f l o o r s of which are covered w i t h t r a v i n t i n e and bone b r e c c i a s ?  metall-  i f e r o u s s o l u t i o n s have p e r c o l a t e d through these b r e c c i a s and r e a c t e d w i t h the phosphorous of the bones to produce p y r o morphite and the r a r e phosphates.  Vanadinite in botryoidai  masses accompanies the pyromorphite. - i n 1931, Walker r e p o r t e d the r e s e r v e s at Broken M i l l as 955,000 tons of o x i d e s a v e r a g i n g 0.9 per cent VgOg, and 38,000 tons a v e r a g i n g 3.5 per cent  V^O^.  No doubt the vanadium was d e p o s i t e d by  circulating  ground w a t e r s , but the primary source of the vanadium i s not apparent.  S k e r l found none or l e s s than .005 per cent van-  adium i n three samples of p r i m a r y s u l p h i d e s , one each of galena, s p h a l e r i t e , and p y r i t e .  He p o i n t s out t h a t to account f o r  the average content of 0.5 per cent vanadium or more i n the o x i d i z e d ores from the primary s u l p h i d e s as source, would r e q u i r e a c o n c e n t r a t i o n of a t l e a s t one hundred t i m e s . There a r e , however, not enough c a v i t i e s i n the o x i d i z e d  p o r t i o n of tne ore bodies to account f o r another 99. per cent of primary ore, and S k e r l does not t h i n k i t reasonable t h a t 99 tons of p r i m a r y ore should have been removed by o x i d a t i o n for  every ton of o x i d i z e d ore.  He suggests that i f h i s three  samples ar.e . r e p r e s e n t a t i v e and i f no o t h e r primary vanadium u  m i n e r a l i s segregated somewhere i n the s u l p h i d e body t h e vanadium was o r i g i n a l l y c o n t a i n e d In the s u r r o u n d i n g of  sediments  the Broken H i l l S e r i e s and has m i g r a t e d by s o l u t i o n i n the  s u r f a c e ground waters to the o x i d i z i n g s u l p h i d e b o d i e s which by e l e c t r o c h e m i c a l a c t i o n , p r e c i p i t a t e the vanadium i n the M  form of vanadates. '  . Vanadium i n d i l u t e s o l u t i o n as s o l u b l e  vanadates or vanadic a c i d would be p r e c i p i t a t e d as i n s o l u b l e vanadates of lead and z i n c on c o n t a c t w i t h o x i d i z i n g l e a d and z i n c ores or the s t r o n g s o l u t i o n s near these o r e s . S k e r l ' s h y p o t h e s i s i s p l a u s i b l e , but on the b a s i s of only three a n a l y s e s of -the primary s u l p h i d e s and of no a n a l y ses of the s u r r o u n d i n g Broken H i l l S e r i e s sediments, and i n the f a c e of evidence f o r vanadium from hydrothermal i n p a r t i c u l a r the p a t r o n i t e i n g a l e n a  sources  from Tsurneb i n South-  West A f r i c a , i t h a r d l y seems c o n c l u s i v e .  S k e r l mentions  the  long p e r i o d of p e n e p l a n a t i o n which must have f o l l o w e d the f o r m a t i o n of. the p r i m a r y s u l p h i d e o r e s .  Is i t not p o s s i b l e  that i n the d e s t r u c t i o n of some of these ore b o d i e s by o x i d a t i o n and e r o s i o n , vanadiferous. s o l u t i o n s from the s l i g h t l y v a n a d i f e r o u s decomposing ores might have found t h e i r way the ore bodies t h a t are now mined and have p r e c i p i t a t e d vanadium on the margins of these b o d i e s ?  to  23  ,30.  /  u t a v i Mountain Regions"  South-l/est A f r i c a .  Vanadium d e p o s i t s occur {1) i n o x i d i z e d zones of s u l p h i d e ore bodies and (2) as f r e e vanadium ores without s u l p h i d e s . The  s u l p h i d e ore d e p o s i t s of the O t a v i Mountains a r e  hydro thermal replacements  i n a s e r i e s of f o l d e d l i m e s t o n e s  and d o l o m i t e s of P a l e o z o i c or Pre-Cambrian age.  The main  primary ore m i n e r a l s a r e p y r i t e , g a l e n a , and s p h a l e r i t e , c a r r y i n g copper, s i l v e r , and cadmium*  Tsuraeb, the o n l y l a r g e  s u l p h i d e body, i s a very r i c h replacement  deposit  an a p l i t e s t o c k i n t r u d e d i n t o the d o l o m i t e .  surrounding  The ore m i n e r a l s  i n parageneti c order a r e , p y r i t e , "bornite, s p h a l e r i t e , e n a r g i t e , t e t r a n e d r i t e , g a l e n a , and hypogene c h a l c o c i t e .  To a depth  of about 350 f e e t , however, the c h a l c o c i t e i s e n t i r e l y  super-  gene , and o x i d a t i o n has extended to 60Q f e e t . - By o x i d a t i o n o f these many s u l p h i d e bodies and the forma t i o n of vanadates of l e a d and z i n c , numerous d e p o s i t s of vanadium ores have "been formed a l o n g t h e i r  margins.  D e s c l o i z i t e i s by f a r the most abundant vanadium m i n e r a l and c u p r o d e s c i o i z i t e , v a n a d i n i t e , p s i t t a c i n i t e , and mottramite occur i n s m a l l amounts.  iio r a d i o a c t i v e m i n e r a l s a r e found  w i t h the vanadium. The second and more v a l u a b l e type of vanadium d e p o s i t s i n t h i s r e g i o n a r e the "sand-sacks" sink-holes,  and o r e - b e a r i n g p i p e s or  Band-sacks a r e lumps o f vanadium m i n e r a l s mainly  d e s c l o i z i t e i n r e d sand f i l l i n g numerous p o t - h o l e s and c a v i t i e s i n the d o l o m i t e .  Some of these a r e p u r e l y s u r f a c e d e p o s i t s  but others extend, down i n t o the o r e - b e a r i n g p i p e s or s i n k h o l e s i n which d e s c l o i z i t e and minor amounts of other m i n e r a l s f i l l vugs  and i n t e r s t i c e s i n cave l i m e s t o n e b r e c c i a or en-  c r u s t the d o l o m i t e .  The ore i s almost e n t i r e l y f r e e of  sulphides. • Abenab and U r i s are the two l a r g e s t p i p e - d e p o s i t s . Abenab i s about 200 f e e t l o n g and 120 f e e t wide a t the s u r f a c e and has been one of the l a r g e s t world producers s i n c e the middle t w e n t i e s . f r a c t u r e zone.  I t i s a s o l u t i o n c a v i t y formed w i t h i n a The ore m i n e r a l s , mainly d e s c l o i z i t e occur i n  a r e d cave l i m e s t o n e a l o n g w i t h c o n s i d e r a b l e c a i c i t e . d i n i t e .becomes important i n the lower l e v e l s .  Vana-  Several small  s o l u t i o n c a v i t i e s nearby c o n t a i n vanadium m i n e r a l s and f i l m s of d e s c l o i z i t e have formed along some bedding p l a n e s i n the dolomite. In a l l these d e p o s i t s , a s at Broken H i l l , the o r i g i n o f the vanadium i s i n doubt. i n primary  Both S t a h l and M o r i t z found vanadium  s u l p h i d e s and S t a h l b e l i e v e s t h a t the ores are a 30  c o n c e n t r a t e from o x i d i z i n g primary S u l p h i d e s .  C l a r k e doubts  i f d e p o s i t s of any s i z e c o u l d be formed i n it h i s way and. sugg e s t s a l e a c h i n g of s u r r o u n d i n g sediments by meteoric  waters  and p r e c i p i t a t i o n a t the outcrops of l e a d - b e a r i n g d e p o s i t s .  V a n a d i n i t e D e p o s i t s of U n i t e d S t a t e s and Mexicot D e p o s i t s of t h i s type a l s o occur i n Jforth America, p a r t i c u l a r l y i n the southern r e g i o n o f the Rocky Mountain  25  Chain, i n A r i z o n a , Hew n o r t h and  Mexico, Nevada, C a l i f o r n i a , and i n  c e n t r a l Mexico.  s i l v e r , molybdenum, and contain wulfenite. per cent V-0  .  The d e p o s i t s may  tungsten,  also contain  i n f a c t , n e a r l y a l l of them  They almost i n v a r i a b l y c a r r y 0.1  to  0,6  Hess suggests t h a t vanadium, a r s e n i c , and  phosphorous w i t h l e a d , z i n c , and rnorphous mixtures  copper, are present  i n varying proportions.  as i s o -  Most of these  d e p o s i t s , l i k e those o f South-West A f r i c a , are s m a l l . group of them occurs near C u t t e r , Hew  Mexico.  At  A  the  . S h a t t u c k Mine, B i s b e e , Arizona,3,000 tons of o x i d i z e d ore c a r r i e d 10 per cent v"p0^, and a l a r g e r tonnage c a r r i e d 1.0 1.5  to  per cent V-gOg* A l a r g e d e p o s i t c o n t r i b u t i n g to the present  vanadium  p r o d u c t i o n and t y p i c a l i n i t s mineralogy i s the complex.dep o s i t of the Mamraoth-St.Anthony i n P i n a l County, A r i z o n a . S i l v e r , l e a d , molybdenum, vanadium, and g o l d are Galena, s p h a l e r i t e , and  recovered.  some molybdenite occur as hypogene  v e i n m i n e r a l s i n b r e c c i a t e d shear zones i n g r a n i t e rhyolite.  The  and  g o l d i s s e c o n d a r i l y ' ' e n r i c h e d and m i n e r a l s  the o x i d i z e d zone i n c l u d e l i m o n i t e , h e m a t i t e ,  in  angles!te,  c e r u s s i t e , l i n a r i t e , Vbra.ehiantite, m a l a c h i t e , a z u r i t - e , calamine, wulf en i t e , v a n a d i n i t e , d e s c i o i z i t e , c u p r o d e s o l . o i z i t e , and pyrolusite.  O x i d a t i o n extends down to about 800 f e e t .  Other D e p o s i t s t S i m i l a r d e p o s i t s occur i n A r g e n t i n a , B o l i v i a , and  Peru,  and almost every o x i d i z e d ore tested i n A r g e n t i n a by one i n v e s t i g a t o r , contained was u s u a l l y s m a l l .  and B o l i v i a  vanadium a l t h o u g h the amount  (Mewhouse p.210).  D e p o s i t s a t Talcuna,  C h i l e , a r e a s s o c i a t e d w i t h copper v e i n s .  The Spanish  d e p o s i t s at Santa M a r t a , which s u p p l i e d much of the e a r l y vanadium o r e , were a l s o of the v a n a d i n i t e type.  here c l a y s  cut by the v e i n s are r i c h i n vanadium.. Vanadinite  and d e s c l o i z i t e w i t h s m i t h s o n i t e , hydro-  z i n c i t e , and l i m o n i t e , a r e a s s o c i a t e d w i t h the l e a d - s i . no 37  d e p o s i t of Djebba i n T u n i s i a .  I t i s suggested t h a t the  vanadium could be d e r i v e d from p h o s p h a t i c l i m e s t o n e the m i n e r a l i z e d f a u l t  which  traverses,  vVuifenite and d e s c l o i z i t e occur s p o r a d i c a l l y as probably l a t e a r r i v a l s i n the wel1-known l e a d mine of B l e i b e r g , 31  Austria,  At t h e l e a d d e p o s i t s of Suleiman S a i , i n Kazakstan  U.S.8.K., vanadinite., and wulf e n i t e w i t h c e r u s s i t e and c a l a mine occur i n t h e o x i d i z e d zone of v e i n - l i k e l e n s e s i n Devonian and C a r b o n i f e r o u s  limestones  and sandstones,  Wulfeni t e was formed e a r l i e r than v a n a d i n i t e , and b o t h minera l s encrust  the o x i d a t i o n products of galena.  I t i s suggest  ea that the p r i m a r y source of the molybdenum and vanadium was p r o b a b l y .the country rock or e l s e the p r o t o r e d e p o s i t s , the t r a n s f e r being  e f f e c t e d by s u r f a c e w a t e r s .  J o s t advances the h y p o t h e s i s vanadinite deposits residual soils. centrated  zone o f the  t h a t the vanadium i n t h e  i s d e r i v e d from l a t e r i t i c and other  ITewhouse p o i n t s out that vanaaium. has con-  i n these s o i l s because the compounds formed a r e  l i k e those of i r o n and. aluminum, i n s o l u b l e ana n o n f u g i t i v e ana f u r t h e r m o r e , the b u l k of o x i d i z e d l e a d d e p o s i t s c o n t a i n i n g v a n a d i n i t e are formed i n l i m e s t o n e , d o l o m i t e , snd g r a n i t i c r o c k s , the lowest i n vanadium of a l l r o c k s . however, the. vanadium may  In these r o c k s ,  be i n a more r e a d i l y s o l u b l e form,  and vanadium i s known t o migrate i n m e t e o r i c w a t e r s . The vanadium ores at the San Antonio Mine mentioned •. gn; 'page - 18, were formed by,secondary c o n c e n t r a t i o n i n the zone of o x i d a t i o n .  "They range from y e l l o w i s h c o a t i n g s  surrounding a l l types of r o c k fragments to s t r a t i f i e d manganese muds i n which y e l l o w i s h vanadium-bearing i n t e r c a l a t e d between l a y e r s of wad  s t r e a k s are  or zones of gypsum."'  Minor amounts of vanadium a l s o occur i n s t r a t i f i e d beds of d a r k i s h - y e l l o w sandy m i n e r a l s , and i n c a l c i t e coated v an ad i n ite stalactites.  A l l these ores have been p r e c i p i t a t e d , i n  " l i m e s t o n e caves, caves developed w i t h i n o x i d i z e d ore bodies and the porous and o x i d i z e d mass of the ore body i t self.« The ore m i n e r a l s are v a n a d i n i t e w i t h some d e s c i o i z i t e and rnimetite.  Hewitt observed that some of the primary s u l p h i d e s  and most of the s i l i c a t e s , e s p e c i a l l y the f i n e - t o medium-text u r e d l i g h t - c o l o u r e d f i b r o u s s i l i c a t e s , c a r r i e d vanadium, (see above).  F i e l d evidence suggests that the secondary vanadium  ores were formed from the r e o r g a n i z a t i o n of these vanadiumb e a r i n g s i l i c a t e s as w e l l as vanadium-bearing s u l p h i d e s .  I l l SEDIME1-TTS". (a)  Origin  .Probably S y n g e n e t l c .  Vanadium i s found i n c l a s t i c and chemical sediments terrigenous*, .organic, and v o l c a n i c  of  origin,  il  J o s t s t a t e s that, on the average, l i m e s t o n e s and d o l o m i t e s c o n t a i n l e s s than ,001 per cent vanadium;  c l a y s and s h a l e s  c o n t a i n about .01 per c e n t ; ...bauxites and l a t e r i tes c o n t a i n about .03 to .05 per cent; and r e s i d u a l i r o n and manganese ores c o n t a i n from .04 to 0,10  per cent ,  coals,and bituminous phosphates w i t h as much as 0.70  Bituminous s h a l e s ,  and a s p h a l t i t e are h i g h e s t  per cent vanadium.  The m i n e t t e i r o n o r e s of L o r r a i n e and Luxembourg are a p o s s i b l e , or a c t u a l , commercial  source of vanadium.  a r e p o r t i n tne M e t a l B u l l e t i n (Londonj Dec.  6, 1935,  s t a t e d t h a t the H o c h l i n g I r o n and S t e e l Works a f t e r menting have now ores.  In  1935  p.15)  experi-  i n the. e x t r a c t i o n of vanadium from -Prench minette ores succeeded  i n o b t a i n i n g i t from South Baden o o l i t i c  The presence of vanadium i n the Kerchensk  ores i n the Crimea was noted i n 1928.  oolitic  iron  These ores c o n t a i n  1,00  to 1,25 per cent PgO^;  0.05  0.03  to U 26 per cent V. u . 2 5  In 1933, vanadium was b e i n g saved  0  to 0.12  per cent As 0.y and g  from the s l a g o b t a i n e d i n r e f i n i n g these o r e s , Prench b a u x i t e s and l a t e r i t e s are v a n a d i f e r o u s and i n 1939 enough vanadium to supply o n e - t h i r d of I t a l y ' s annual requirements was b e i n g r e c o v e r e d from the c a u s t i c soda s o l u t i o n employed i n the Bayer p r o c e s s of r e f i n i n g b a u x i t e . ( M i n e r a l s Yearbook 1935)  Tiie very f i n e - g r a i n e d sediments, e s p e c i a l l y txie s i l t s ana muds w i t h tiaeir l a r g e p r o p o r t i o n of c o l l o i d a l m a t e r i a l are most l i k e l y to contain vanadium. contain titanium.  They n e a r l y always  vanadium i s r e p o r t e d  i n c l a y s from Japan '-hi  ana. a great many other p l a c e s .  ( M e l l o r , p.. 717).  3osa za z  s t a t e s that the vanadium content of o l a y s i s from a chemical t r a c e to about 14 per cent vanadium. d i f f e r e n t l i g h t - f i r i n g c l a y s and shales  Palmer s t u d i e d  eight  (ceramics) c o n t a i n i n g  small amounts of i n s o l u b l e vanadium and molybdenum compounds. I t was found that d u r i n g f i r i n g , s o l u b l e s a l t s of these elements were formed -which l a t e r appeared as a g r e e n - y e l l o w e f f l o r e s c e n c e on the f i r e d c l a y .  The e f f l o r e s c e n c e i s  thought to be c h i e f l y due to a l k a l i vanadates. and  Australian  South A f r i c a n c l a y s g e n e r a l l y c o n t a i n l e s s than 1.0 per  cent vanadium, and t h i s i s not water s o l u b l e u n t i l weathered considerably  or heated to 1,000° 0. or more.  e x t r a c t e d w i t h hot water. a l e s s e r extent.  I t can then be  Molybdenum o c c u r s l i k e w i s e but to  The same e f f l o r e s c e n c e was noted i n r e -  f r a c t o r y goods made from c l a y s from 'parts of England and from Mew South v/alea.  Highly vanadiferous  clay i s associated  w i t h t h e o x i d i z e d l e a d ores of Santa M a r t a ,  Spain.  61  S c h r e i t e r f i n d s t h a t bleached spots i n red s h a l e s i n Germany c o n t a i n as much as 14.93 per cent VgOa ana 1.4 0 per cent VgOg. i n t h e i r , dark c e n t r e .  He suggests that the lower  oxides of vanadium reduced the FepO- to PeQ, ana that  this  p r o c e s s may e f f e c t much larger- p a r t s of a g i v e n rock s e r i e s . The  bleached r o c k contained  from O.i to 0 . 2 per cent Y O . p  H  30  f3  Garter d e s c r i b e s s i m i l a r v a n a d i f e r o u s modules In tiie permian red m a r l beds of South Devon,  The nodules, appearing  as d a r k cores surrounded by a u r e o l e s of g r e e n i s h c l a y , are as much as e i g h t inches i n diameter.  They are composed of  coarse c o n c e n t r i c white and dark bands w i t h , i n a d d i t i o n , some r a d i a t i n g d a r k bands, and a r e not r e l a t e d to f o s s i l s . They a r e e s s e n t i a l l y s i l i c e o u s c l a y e y m a t e r i a l w i t h the b l a c k bands r u n n i n g 13.96  per c e n t V 0 v  o  p r o b a b l y present as o x i d e ,  and the white bands w i t h 1,91 per cent VgO^.  They are  radioactive. Sediments r i c h i n o r g a n i c matter p a r t i c u l a r l y  marine  bituminous d e p o s i t s and s l i m e s are noted f o r t h e i r h i g h ' vanadium c o n t e n t .  A carbonaceous  s h a l e bed more than 30  f e e t t h i c k i n the p r o v i n c e of J a u j a , P e r u , c o n t a i n s about 1,0 per cent Vr>0g m a i n l y i n p h o s p h a t i c nodules. 40  Bade 1 i n d i s c u s s i n g the cause of enrichment  of vanadium  i n o r g a n i c sediments suggests that the vanadium i s d e r i v e d from the weathering and l e a c h i n g of the parent r o c k and i s p r o b a b l y used by p l a n t s r a t h e r than 'animals, (Annot •Bib., S'.A.  he  states  G e o l . , 446. 193?,) that i n a l l o r g a n i c  sediments, the d e r i v a t i v e s of c h l o r o p h y l l are thus m a i n l y formed by p l a n t remains.  predominateThey There are a s e r i e s  of complex o r g a n i c compounds of vanadium w i t h the a l k a l o i d porphyrine.  The vanadium i s d e r i v e d from w e a t h e r i n g r o c k s  which, under a r i d c o n d i t i o n s , are always v a n a d i f e r o u s . A s e a r c h of the l i t e r a t u r e on minor elements and p l a n t n u t r i t i o n r e v e a l s t h a t vanadium may  be s t o r e d by some p l a n t s ;  that- i t H e l p s some p l a n t s s l i g h t l y and over c e r t a i n concentrations i s injuriousj  but t h a t on the whole i t seems to  have l i t t l e e f f e c t on p l a n t growth.  On t h e other hand,  P h i l l i p s d i s c o v e r e d marine animals c o n t a i n i n g vanadium,,  He  found that f o r a s p e c i e s of h o l o t h u r i a n from the Tortugas 0.123  per cent of the weight of t h e e n t i r e a n i m a l d r i e d a t  110°G was vanadium.  He r e p o r t s a l s o that M, Henze  (zPhys.  Chem. 79, 223) found an asc.idian i n the Bay of E a p l e s  which  63  c a r r i e d vanadium i n t h e blood. Systematic  Vinogradov r e v i e w s  some  i n v e s t i g a t i o n s " showing t h a t about ,00001 per cent  vanadium i s u s u a l l y found i n v a r i o u s t e r r e s t r i a l and marine animals and p l a n t s .  He b e l i e v e s that the v a n a d i f e r o u s  s p e c i e s of A s c i d i a and H o l o f h u r i a o b t a i n t h e i r vanadium from marine muds, which c o n t a i n  ,03 per cent and more vanadium.  He s t a t e s * On t n e other hand, A s c i d i a , w h i c h forms very s p e c i f i c biocenoses on t h e bottom of many g u l f s and c o n t i n e n t a l seas, a f t e r t h e i r a e a t h set. up c o n d i t i o n s f o r the l o c a l enrichment i n V o f the surrounding sediments. Therefore i t may be supposed t h a t o i l s and bitumen o r i g i n a t i n g from o i l c o n t a i n i n g vanadium a r e connected w i t h s i m i l a r sediments o f the s e a , w i t h c e r t a i n f a d e s of the bottom, f o r m e r l y populated w i t h biocenoses of organisms p a r t i c i p a t i n g i n t h i s or any other c o n c e n t r a t i o n of vanadium. Phosphorous may be p a r t l y r e p l a c e d by vanadium i n the metabolism of some a n i m a l s but i t should be remembered i n considering t h i s hypothesis  that a l t h o u g h vanadium i s c l o s e l y  r e l a t e d to phosphorous, i t does not b e l o n g t o the same subgroup of elements c o n t a i n i n g phosphorous and that many of. i t s  p h y s i c a l and chemical p r o p e r t i e s are e n t i r e l y d i f f e r e n t .  In  p a r t i c u l a r , vanadium does not form o r g a n o m e t a l l i c compounds w i t h hydrocarbon r a d i c a l s , whereas phosphorous does.  This  does not mean that a c i d r a d i c a l s c o n t a i n i n g vanadium could not r e a c t w i t h Organic- compounols which a r e not hydrocarbons. ( c f . Baderfe h y p o t h e s i s . ) (b)  O r i g i n Probably iiipigenetio The most v a l u a b l e type of vanadium d e p o s i t s i n sedimentary  i ocxs, a p a r t from the- unusual d e p o s i t at M i n a s r a g r a , are those i n Mesozoic Sandstones, i n South-Western l a r d e p o s i t s elsewhere i n the w o r l d . c h i e f l y i n a vanadium-bearing  United S t a t e s and  simi-  The vanadium i s found  hydrous mica f o r m e r l y thought to  be r o s c o e l i t e and i n c a r n o t i t e , a y e l l o w potassium-uranium vanadate.  V a n o x i t e , tyuyamunite, u v a n i t e , v o l b o r t n i t e ,  h e w e t t i t e , and m e t t a h e w e t t i t e a l s o o c c u r , and i n a d d i t i o n vanadium has been s e l e c t i v e l y absorbed by s h a l e y m a t e r i a l s . *?Z, f^/4-7, <?#,<?-?,-5-0,-51, S3,  inj.,sy,  In U n i t e d S t a t e s these sedimentary d e p o s i t s are of two mineralogical types: (1) (2)  • The " r o s c o e l i t e " =  vanadium c l a y mica deposits.  The c a r n o t i t e d e p o s i t s .  b o t h these types are found In Colorado, U t a h , and A r i z o n a . i n n e a r l y h o r i z o n t a l sedimentary beds and a r e c o n f i n e d to t h r e e d i s t i n c t s t r a t i g r a p h i c u n i t s , the Shinarump  conglomerate  ( T r i a s s i c ) , the E n t r a d a sandstone ( J u r a s s i c ) , and the M o r r i s o n formation (Jurassic).  The  ore b o d i e s are very s p o t t y and  form i r r e g u l a r t a b u l a r masses about p a r a l l e l to the  sandstone  33  beds but not n e c e s s a r i l y c o n f i n e d t o one bed.  They c o n t a i n  from'a few tons to many t no usand  Commercial ore  tons of ore.  c o n t a i n s from 1 to 5 per cent VgOg and u s u a l l y l e s s than 1 per cent 'DgOg •  '"^'rie  Shinarump conglomerate a l s o c o n t a i n s some  sandstone that i s p a r t l y formed of g r a i n s of a s p h a l t i t e . T h i s a s p h a l t i t e c o n t a i n s vanadium and uranium which i s thought to have been absorbed.  (Hess)  The m i n e r a l i z a t i o n i n the  En trad, a sandstone i s the vanadium c l a y mica type w i t h only minor amounts of c a r n o t i t e .  At P l a c e r v i l i e , the vanadium ore  i s i n the upper 10 to 15 f e e t o f the E n t r a d a sandstone and i s u s u a l l y accompanied above or below, or b o t h above and below, by a l a y e r of l i g h t - g r e e n sandstone c o l o u r e d by a f i n e l y d i s seminated chromium "mineral, ( m a r i p o s i t e - H e s s ) .  The M o r r i s o n  f o r m a t i o n , made up of sandstone, conglomerate, and s h a l e , cont a i n s many more d e p o s i t s than the other two f o r m a t i o n s .  These  are the famous c a r n o t i t e d e p o s i t s a l t h o u g h a c t u a l l y they cont a i n s e v e r a l times as much vanadium as uranium and radium. The vanadium i s a p p a r e n t l y mainly present as the hydrous  clay  mica, but v e r y r i c h l o c a l c o n c e n t r a t i o n s of c a r n o t i t e s u p p l i e d ft-early a l l o f the e a r l y vanadium p r o d u c t i o n .  The ore bodies  i n the M o r r i s o n f o r m a t i o n a r e i n l a r g e sandstone'lenses i n a s i n g l e s t r a t i g r a p h i c zone about 60 f e e t t h i c k i n the lower h a l f of the f o r m a t i o n . The sandstone i n these f o r m a t i o n s i s e x t e n s i v e l y  cross-  bedded, c o n s i s t i n g of a complex assemblage of l e n s e s and channel f i l l s .  E o s s i l l o g s , leaves,- and reeds are s c a t t e r e d  throughout as i f d r i f t e d i n t o p l a c e .  •  Ore' -minerals a r e found impregnating t h e sandstone and  r e p l a c i n g t h e f o s s i l p l a n t s i n and a d j a c e n t t o t h e ore b o d i e s . I n a d d i t i o n , some vanadium has beeh absorbed and c l a y e y m a t e r i a l .  by s h a l e pebbles  The vanadium-bearing hydrous mica i s  both u n i f o r m l y d i s s e m i n a t e d and c o n c e n t r a t e d i n sheets a l o n g bedding planes o r i n r o l l i n g zones up t o s e v e r a l inches t h i c k c u t t i n g a c r o s s t h e bedding.  Where m i n e r a l i z a t i o n was s t r o n g ,  some quartz g r a i n s were p a r t l y o r e n t i r e l y d i s s o l v e d l e a v i n g r e s i d u a l v a n a d i f e r o u s s h a l e - l i k e seams.  The margins.of an  ore body may be sharp o r may b l e n d g r a d u a l l y i n t o b a r r e n sandstone.  5  Where they a r e sharp, a c u r v i n g s h e l l of - highly?.vana-  d i f e r o u s sandstone u s u a l l y has formed around much o f t h e ore body.  The boundaries a r e sometimes so sharp t h a t they c u t  a c r o s s lenses: of. s h a l e pebble conglomerate l e a v i n g some-shale pebbles m i n e r a l i z e d on-one s i d e and u n m i n e r a l i z e d on t h e o t h e r . Although t h e o r e bodies .are r e s t r i c t e d t o c e r t a i n s t r a t i g r a p h i c zones, they a r e a p p a r e n t l y n o t r e l a t e d t o f o l d s o r f r a c t u r e s i n t h e sediments except  i n four places.  Pisher states:  The o r i g i n o f t h e o r e and the f a c t o r s t h a t c o n t r o l l e d i t s l o c a l i z a t i o n cannot be s a t i s f a c t o r i l y explained. The o r e m i n e r a l s impregnate sandstone and i n t h e i r present form were d e p o s i t e d from s o l u t i o n s a f t e r the sands were d e p o s i t e d , but t h e n a t u r e o f the s o l u t i o n s i s not understood, nor i s t h e immediate source o f t h e m e t a l s apparent." and  further-: The p r i m a r y o r e m i n e r a l s a r e thought t o have been Introduced i n t o t h e i r p r e s e n t p o s i t i o n not l o n g a f t e r t h e sands were deposited. I f t h i s i s t r u e , t h e metals were p r o b a b l y t r a n s p o r t e d and d e p o s i t e d  35  by ground waters, and the ores were proba b l y l o c a l i z e d by d e l i c a t e chemical and p h y s i c a l c o n d i t i o n s t h a t now cannot be d e f i n i t e l y recognized. This hypothesis p r o b a b l y r e q u i r e s at l e a s t t h r e e separate p e r i o d s of ore d e p o s i t i o n , to account f o r t h e ore i n the Shiharump, E n t r a d a , and Morrison formations."  . C a r n o t i t e a l s o occurs a t Mauch Chunk, P e n n s y l v a n i a , i n a 40 f o o t l a y e r of c o u r s e - g r a i n e d conglomerate.  The  conglomer-  a t e i s cemented w i t h s i l i c a and c a l c i t e , and t h e c a r n o t i t e i s t h o r o u g h l y but unevenly  d i s t r i b u t e d t h r o u g h t o u t , f i l l i n g open-  ings and c r a c k s and r e p l a c i n g t h e c a l c a r e o u s cement.  It is  d o u b t l e s s a p r e c i p i t a t e from c i r c u l a t i n g ground waters " i n f a c t i t can be seen i n the course o f ' d e p o s i t i o n where streams t r i c k l e out of c r a c k s a t the p r e s e n t time -  i t p r o b a b l y does  not extend below the ground water l e v e l and may  be  restricted  to a v e r y s h a l l o w zone." "  Wherry suggests t h a t primary  v a n a d i f e r o u s ferromagnesian  m i n e r a l s concentrated as r e s i d u a l s  d u r i n g t h e decomposition  of c r y s t a l l i n e r o c k s i n the  i n g r e g i o n under a r i d c o n d i t i o n s may now to the ground w a t e r s .  surround-  be s u p p l y i n g vanadium  A c c o r d i n g to Hess (Ore D e p o s i t s o f the  Western Stat.es, p.474iR e c e n t l y t h o r i a n i t e has been d i s c o v e r e d a t E a s t o n , 30 m i l e s away, and i t seems p r o b a b l e t h a t the Mauch Chunk c a r n o t i t e may be a weathering m i n e r a l from unranium b e a r i n g v e i n l e t s . *'"  C a r n o t i t e occurs as an a l t e r a t i o n product from r a d i o a c t i v e  m i n e r a l s , i n c l u d i n g d a v i d i t e , f e r g u s o n i t e , and monazite, o c c u r r i n g with, f e r r u g i n o u s lodes a t Radium H i l l and Mount P a i n t e r i n South A u s t r a l i a .  i t has been observed i n j o i n t s  i n q u a r t z i t e i n Northerm Utah, and i n a c o a l bed c u t by quartz v e i n s near Denver. C a r n o t i t e has been r e p o r t e d as a t h i n dusty c o a t i n g on c r a c k s i n a n d e s i t e n o r t h o f P i o c h e , Nevada; i n j o i n t s i n T e r t i a r y r h y o l i t e two m i l e s south o f S l o a n , Nevada; i n c r a c k s i n t u f f a t the west end o f t h e V u l t u r e Mountains, A r i z o n a , and Tyuyamunite i n t i n y v e i n l e t s i n sandstone a t B i s b e e , A r i z o n a . (Hess, Ore Deposits o f t h e Western S t a t e s , p. 474.)  Vanadium has been detected  i n the Jiupferschiefer of  M a n s f i e l d , Germany, where i t i s thought t o be e p i g e n e t i c .  ASSOCIATED WITH HYDROCARBONS. With C o a l , Petroleum, and A s p h a l t i t e . We have seen t h a t o r g a n i c sediments a r e v e r y l i k e l y t o c o n t a i n vanadium.  Even l a r g e r amounts a r e found i n c o a l s  and t h e ashes o f c o a l s . De Goyler's  Sason, i n h i s d i s c u s s i o n o f  paper r e p o r t e d a c o a l bed i n Nueva Leon which  c a r r i e d - 5 p e r cent ash, o f which 25 p e r cent was VgOg.  He  found other c o a l s from C o l o r a d o , V i r g i n i a , and C e n t r a l , E a s t e r n , and Southern S t a t e s t o c a r r y from 0.05 p e r cent t o 0.10  p e r cent vanadium. R u s s i a n workers have i n v e s t i g a t e d t h e i r c o a l s r a t h e r  t h o r o u g h l y f o r vanadium'. vanadium content  Z i l b e r m i n t z found a v e r y  low  i n most c o a l s he i n v e s t i g a t e d , but a number  of J u r a s s i c coals-, c h i e f l y - f r o m t h e e a s t e r n s l o p e of the U r a l s , c o n t a i n e d from an a p p r e c i a b l e amount up. to 5 p e r cent of the ash i n some* oases,.; probably  Z i l b e r m i n t z b e l i e v e s the vanadium  i n t r o d u c e d a f t e r the c o a l was  ( c f . Bader's h y p o t h e s i s , p.  was  d e p o s i t e d , however,  SO)  79  V o r o b i e v found seven Upper S i l u r e a n c o a l s from the A l a i and Turkestan Mountains t o have ash contents from 9.25 27.77 per cent, of w h i c h from 0.01  t o 1.30  M . i r o p l o s k y ^ i s c u s s e s t h e occurrence K a u s t o b i o l i t h s (cf«  Grabau:  by d i r e c t a c c u m u l a t i o n  to  per c e n t was  VgOg.  of vanadium i n t h e  c a u s t o b i o l i t h = sediment formed  of-carbonaceous p l a n t m a t e r i a l  e.g.  peat and c o a l ) of T a r t a r i a , and O r l o v d i s c u s s e s i t s occurrence in anthraxolith coals. ( M e l l o r p. E.S.  Many o t h e r occurrences  are reported.  718.) P o r t e r b e l i e v e s t h a t t h e vanadium i n peat,  lignite,  and c o a l , , was a c o n s t i t u e n t o f t h e p l a n t l i f e from w h i c h t h e s e deposits o r i g i n a t e d . The a s s o c i a t i o n of vanadium w i t h petroleum and 68  was  d i s c u s s e d by B i r d i n 1914,  r e p o r t e d i n 1937  asphalt  66,67,6?,7a.7',75~.  and by many o t h e r s , and i t was  t h a t some 50,000 pounds o f VgOg were b e i n g  recovered a n n u a l l y from b o i l e r and s t a c k soot of s h i p s  burning  Venezuela and Mexican o i l f o r f u e l .  recov-  ered b y ' v a r i o u s S t a t e s who  Much o f t h i s was  c o n t r a c t o r s on t h e east coast of the U n i t e d  cleaned t h e b o i l e r s of these s h i p s d u r i n g t h e i r  c a l l s there.  The  soot runs from 2 t o 34 p e r cent VgOg, the  38.  r i c h e r r e c o v e r i e s being, made by t a n k e r s o p e r a t i n g i n and n e a r maracaibo Lake, Venezuela. ages around 6 p e r cent ^gOg*  Soot from Mexican o i l aver( M i n e r a l s Yearbook, 1937.)  Even b e f o r e petroleum was known t o c a r r y vanadium, t h e metal was found i n a s p h a l t I t e s , in. many p a r t s o f t h e w o r l d , n o t a b l y i n U n i t e d S t a t e s , P e r u , Cuba, A r g e n t i n a , and Sweden. The v e i n a s p h a l t i t es o f Peru have been c a l l e d " c o a l Veins"* They a r e c o n f i n e d t o sedimentary and a r e found as continuous  r o c k s , p r i n c i p a l l y limestones,  l e n t i c u l a r f i s s i v e veins cutting  a c r o s s t h e bedding and as f l a t s , o r mantos.  The asphalt-it es  a r e both a n t h r a e i t i e and bituminous, and-the a s h content i s from 1 t o 47 p e r c e n t , o f which- 0.9 t o 15 p e r cent i s vanadium. Baragwanath c o n s i d e r s t h a t t h e a s p h a l t i t e s formed from underl y i n g p o o l s o f petroleum  which, c o n t a i n e d t h e vanadium.  The a s p h a l t i t BS-:-^ o f U n i t e d S t a t e s , p r i n c i p a l l y i n Oklahoma, Nevada, and Arkansas-, a r e i n v e i n s i n - h i g h l y f o l d e d s t r a t a and c a r r y about 0.1 p e r cent ^gOg* 'Secondary c o a l v e i n s i n Southern A l p s c o n t a i n 1.31 p e r cent vanadium.  Hummel suggests t h a t t h e c o a l , was- leached  from o v e r l y i n g c h a l k beds, t h e vanadium b e i n g o r i g i n a l l y c o n c e n t r a t e d by organisms.  A: J u r a s s i c c o a l somewhat resem-  b l i n g a s p h a l t i t e i s r e p o r t e d from t h e Eukul P r e f e c t u r e , Japan. Both t h e c o a l and"' thie sediments above and below c o n t a i n from 0.01  t o 0.03 p e r cent V_0_. An a n t h r a c i t e from Hei'jo, Japan, , 2 3 c o n t a i n s 0.091 p e r cent V 0 . 23 I t i s suggested t h a t t h e vanadium i n a s p h a l t i t e s i s  present,as a s u l p h i d e .  M m a s r a g r a , Peru: -  ,  The ^most important vanadium d e p o s i t i n the world i s at H i h a s r a g r a , near Quisque, P e r u . s u l p h i d e p a t r o n i t e was of a s p h a l t i t e *  There'the mixed, vanadium  discovered i n a s s o c i a t i o n with a k i n d '  M i n a s r a g r a sis on the e a s t e r n s l o p e of the  main Andes, between two ranges t r e n d i n g 1.1.!• and formed of Mesozoic l i m e s t o n e .  The d e p o s i t i s i n red g y p s i f e r o u s s h a l e s  i n the upper p a r t of a s e r i e s of s h a l e and. l i m e s t o n e which dips 45° S.W. porphyry  lumerous d i k e s and  to diabase i n c o m p o s i t i o n  igneous masses from quartz i n t r u d e the sediments and  the ore body occurs at the p o i n t of g r e a t e s t c o n c e n t r a t i o n of dikes.  The o r i g i n a l d e p o s i t was  a l e n t i c u l a r v e i n about  f e e t by 50 t o 100 f e e t , c o n s i s t i n g of t h r e e  400  vanadiferous  m a t e r i a l s i n l a y e r s and t h e i r a l t e r a t i o n p r o d u c t s .  The  first  of these m a t e r i a l s i s Q u i s q u e i t e , a b l a c k l u s t r o u s a s p h a l t i t e 1 i k e substance  c o n t a i n i n g 43 per cent carbon, 45 per cent  s u l p h u r , and about .OS p e r cent V 0 g . g  T h i s grades i n t o a  d u l l b l a c k v e s c i c u l a r c o k e - l i k e substance which a p p a r e n t l y i s coked q u i s q u e i t e . s u l p h u r , and  I t c o n t a i n s 86 p e r cent carbon, 6. per  i t s ash i s h i g h l y v a n a d i f e r o u s .  cent  The vanadium  1  o r e , termed " p a t r o n i t e ' o c c u r r e d as two s e p a r a t e l a y e r s separated by a l a y e r o f coke c o n t a i n i n g an i r r e g u l a r c l a y vein.  P a t r o n i t e c o n t a i n s from about 19 p e r cent t o 30  cent vanadium.  per  According to Lingren, i t i s a f i n e - g r a i n e d  m i x t u r e , o f t h r e e s u l p h i d e s and i s "probably of c o l l o i d a l origin."  -•• Minute, amounts of B r a v o i t e ( P e ^ i l S g and an un-  i d e n t i f i e d s i l i c a t e a r e mixed w i t h the p a t r o n i t e . Vanadium s u l p h i d e can be prepared by t h e a c t i o n o f carbon d i s u l p h i d e vapour on an o x i d e o f vanadium, and i t i s s o l u b l e in asphaltite.  On t h i s b a s i s and t h e g e n e r a l l y accepted view  t h a t a s p h a l t i t e s a r e t h e r e s i d u a r y m a t e r i a l from t h e seepage of petroleum d e p o s i t s , Hewett suggests t h a t t h e n e c e s s a r y c o n d i t i o n s f o r t h e f o r m a t i o n of v a n a d i f e r o u s a s p h a l t i t e ores are: (1) Vanadium as o x i d e , d i s s e m i n a t e d through a . r o c k of a f a i r degree o f p o r o s i t y . (2) Impregnation w i t h a hydrocarbon to a g r e a t e r o r l e s s e r degree. (3)  A source of s u l p h u r o r s u l p h u r e t t e d vapours.  T h e r e f o r e , t h e s e d e p o s i t s w i l l occur i n breaks i n sedimentary r o c k s i n r e g i o n s where petroleum d e p o s i t s have e x i s t e d i n the neighbourhood  of v o l c a n o e s .  These c o n d i t i o n s  a r e thought t o have been s a t i s f i e d i n Peru and Oklahoma. Hewett c o n s i d e r s then t h a t t h e d e p o s i t a t M i n a s r a g r a r e p r e s e n t s "an extreme phase o f d i f f e r e n t i a t i o n from asphaltite." I n 1909 when Hewett developed t h i s h y p o t h e s i s i t was g e n e r a l l y known t h a t petroleum may  c o n t a i n vanadium, or t h a t  vanadium may be c o n c e n t r a t e d by some marine a n i m a l s . A p p a r e n t l y a l l t h e p a t r o n i t e a t M i n a s r a g r a has been mined now,  not  and t h e r e m a i n i n g ore i s a m i x t u r e of m i n e r a l s  r e s u l t i n g from o x i d a t i o n . o f t h e o r i g i n a l d e p o s i t and redeposi t i o n a f t e r very l i t t l e t r a n s p o r t a t i o n .  Some o f these  m i n e r a l s r e p l a c e t h e s h a l e country rock almost e n t i r e l y o r f i l l c r a c k s i n t h e crushed  zone.  They i n c l u d e the hydrous  c a l c i u m hexav'anadates, h e w e t t i t e (red) and p a s c o i t e  (orange);  t h e vanadovanadates, f e r n a n d i n i t e ( d u l l g r e e n ) , and melanov a n a d i t e ( b l a c k ) and t h e b l u e hydrous s u l p h a t e , m i n a s r a g r i t e .  IN GROUND WATERS. I n most o f t h e commercial vanadium d e p o s i t s mentioned above, s o l u t i o n and secondary c o n c e n t r a t i o n o f vanadium by c i r c u l a t i n g ground waters has been s i g n i f i c a n t .  This s t a t e -  ment does n o t a p p l y , o f course, t o t h e d e p o s i t s o f t i t a n i f e r ous m a g n e t i t e o r the r e s i d u a l ores o f i r o n , manganese, and aluminum, c o n t a i n i n g vanadium, and i t may not a p p l y t o those d e p o s i t s a s s o c i a t e d w i t h o r g a n i c m a t e r i a l s , such as phosphatic l i m e s t o n e , c o a l , p e t r o l e u m , a s p h a l t i t e , and t h e o r i g i n a l sulphide deposit at Minasragra.  I t c e r t a i n l y does a p p l y t o  the d e p o s i t now mined a t M i n a s r a g r a ,  which i s a p p a r e n t l y  composed o f f a i r l y s o l u b l e secondary m i n e r a l s .  The vanadate  d e p o s i t s a s s o c i a t e d w i t h o x i d i z e d l e a d , z i n c , and copper m i n e r a l s and t h e c a r n o t i t e d e p o s i t s t i l l f o r m i n g a t Mauch Chunk are good p r o o f o f t h e s o l u b i l i t y o f vanadium i n ground waters.  M e l l o r s t a t e s t h a t vanadium would be d i s s o l v e d i n  n a t u r a l waters c o n t a i n i n g atmospheric gases.  Many s a l t s o f  42  vanadium are s o l u b l e  i n eold water and  s l i g h t l y acid solution.  others are s o l u b l e  in  Vanadium has been detected i n f r e s h  water from B r o o k l y n . 14-  U o t e s t e l n t r i e d to determine the importance of and  solution  p r e c i p i t a t i o n of vanadium i n ground water i n the genesis  of t h e sedimentary uranium-vanadium ores of t h e  South-Western  S t a t e s , by measuring the s o l u b i l i t y of c a r n o t i t e i n s o l u t i o n s r e s e m b l i n g n a t u r a l ground w a t e r s .  he found t h a t :  G a r n o t i t e i s r e a d i l y s o l u b l e i n ground waters c a r r y i n g f r e e s u l p h u r i c a c i d and a l k a l i - s u l p h a t e s and b i s u l p h a t e s . It is v e r y s l i g h t l y s o l u b l e i n weak solution's of a l k a l i b i c a r b o n a t e s but i s i n s o l u b l e i n most s o l u t i o n s of normal a l k a l i b i c a r b o n a t e , c h l o r i d e s , normal a l k a l i s u l p h a t e s , and hydrogen s u l p h i d e . Gale i t e r e a d i l y p r e c i p i t a t e s vanadium and uranium from v a n a d y l and u r a n y l s u l p h a t e solutions. The p r e c i p i t a t e thus formed i s r e a d i l y d i s s o l v e d by s o l u t i o n s of a l k a l i carbonates and b i c a r b o n a t e s and by a s o l u t i o n of c a l c i u m b i c a r b o n a t e . In the l a t t e r s o l u t i o n the l o s s of carbon d i o x i d e r e s u l t s i n the p r e c i p i t a t i o n of both l i m e and the metals. • • , R o t t e n wood and c o a l have so f a r f a i l e d to p r e c i p i t a t e e i t h e r m e t a l . This point should be t e s t e d f u r t h e r . Vanadium p e n t o x i d e a c t i n g as an o x i d i z i n g agent, p r e c i p i t a t e s uranium from a s o l u t i o n of u r a n y l s u l p h a t e . " Vanadium must be p r e s e n t i n sea water, but the amounts are g e n e r a l l y too  s m a l l to be  detected.  I '  I  - 43  '  II If  .  -  :  -  '  SUMMARY AID THEORY. We have seen t h a t vanadium o c c u r s ,  j  ( l ) I n igneous r o c k s , e s p e c i a l l y i n t h e u l t r a m a f i c v a r i e t i e s and t h e i r a s s o c i a t e d t i t a n i f e r o u s d e p o s i t s ("recovered (£•)•  iron  as a b i - p r o d u c t )  i n s u l p h i d e s and i n igneous and c o n t a c t metamorphic s i l i c a t e s (and s p o r a d i c a l l y , i n a great v a r i e t y o f  f  minerals).  The evidence f o r hydrothermal  vanadium  i s n o t good. (3)  i n t h e o x i d i z e d zones o f d e p o s i t s o f l e a d , z i n c , and copper, (recovered  (4)  directly)  i n b a u x i t e and l a t e r i t e s , and o t h e r r e s i d u a l  iron  and manganese d e p o s i t s , i n which i t i s concentrated a p p a r e n t l y because i t i s i n an i n s o l u b l e form. A l s o i n m i n e t t e o r e s , ( r e c o v e r e d as a b i - p r o d u c t ) . (5)  i n sediments o f n e a r l y a l l types but e s p e c i a l l y  (6)  i n t h e s i l t s and muds where i t may be i n a c o l l o i d a l form,  (7)  and even more n o t a b l y  i n sediments w i t h o r g a n i c remains and i n a s s o c i a t i o n w i t h hydrocarbons.  Here i t i s n o t a t a l l c e r t a i n  whether t h e vanadium was o r i g i n a l l y c o n c e n t r a t e d by organisms o r whether t h e o r g a n i c substances  have  p r e c i p i t a t e d o r absorbed t h e vanadium from s o l u t i o n i n ground waters o r t h e sea. product and d i r e c t l y . )  (recovered as a b i -  (8)  as e p i g e n e t i c . c o n c e n t r a t i o n s i n sediments.  The  source of t h e vanadium i s not known i n most of these d e p o s i t s .  ( r e c o v e r e d d i r e c t l y and as a b i -  product.) (9)  in'ground w a t e r s .  Except f o r the o r i g i n a l s u l p h i d e d e p o s i t at M i n a s r a g r a and the magmatic t i t a n i f e r o u s i r o n ores c o n t a i n i n g vanadium a l l the p r e s e n t l e a d i n g producers o f vanadium a r e d e p o s i t s t h a t have been formed p a r t l y ; , o r e n t i r e l y by secondary concentration.  Such a c o n c e n t r a t i o n may  be accomplished by:  A. .Sedimentary P r o c e s s e s w i t h o u t S o l u t i o n : The vanadium i s i n (1)  an i n s o l u b l e , o r non f u g i t i v e form, .e.g. i n b a u x i t e , l a t e r i t e , e t c .  (2) ' a r e s i s t e n t , heavy m i n e r a l , e.g. i r o n sand d e p o s i t s . B. C o l l o i d a l P r o c e s s e s (?) The vanadium may be  e.g. i n f i n e sediments. ,  f  (1)  i n a c o l l o i d a l form, and i s p r e c i p i t a t e d as a r e o t h e r c o l l o i d s .  (2)  p r o t e c t e d o r absorbed by o t h e r c o l l o i d s and c a r r i e d a l o n g w i t h them.  (Note: The vanadium i n c l a y s becomes water s o l u b l e a f t e r prolonged w e a t h e r i n g a c c o r d i n g t o Bosazza. This suggests t h a t i t i s i n a. non-decomposed or o n l y p a r t l y decomposed form i n c l a y s . )  45  0.  S o l u t i o n i n Ground Water (and'the sea) ana P r e c i p i t a t i o n or Fixation:  D.  (1  by o v e r - s a t u r a t i o n o r l o s s o f water, e.g. t h e s o l u b l e secondary m i n e r a l s a t M i n a s r a g r a and elsewhere.  (2  from v a n a d i c s o l u t i o n s by metals f o r m i n g i n s o l u b l e vanadates. These a r e almost always o r t h o v a n a d a t e s . e.g. t h e v a n a d i n i t e and d e s c l o i z i t e d e p o s i t s .  (3  from v a n a d y l s u l p h a t e s o l u t i o n s by CaCO 3' see N o t e s t e i n .  (4  from a l k a l i carbonate and b i c a r b o n a t e and c a l c i u m b i c a r b o n a t e s o l u t i o n by l o s s o f COg; see H o t e s t e i n .  (5  as c a l c i u m ( a l k a l i n e e a r t h ) vanadium s a l t s which a r e a l l p r a c t i c a l l y i n s o l u b l e i n s l i g h t l y a l k a l i n e s o l u t i o n s such as sea water.  (6  as s u l p h i d e s . p r e c i p i t a t e d by ELS i n slightly alkaline solutions.  (7  as i n s o l u b l e double s a l t s o f copper and calcium.  (8  by t h e r e d u c i n g a c t i o n o f l i v i n g organisms or decaying o r g a n i c m a t e r i a l ( ? )  (9  by some p r e c i p i t a t i n g a c t i o n o f o r g a n i c substances,not r e l a t e d t o decay ( ? ) c f i Bader's h y p o t h e s i s .  (10  by organisms u s i n g vanadium i n t h e i r " l i f e processes.  (11  by a b s o r p t i o n i n v e r y f i n e g r a i n e d m a t e r i a l or i n a s p h a l t i t e . e.g. i n s h a l e y m a t e r i a l i n the' sedimentary d e p o s i t s o f t h e Southwestern'States'.  By o t h e r Processes r e l a t e d o r u n r e l a t e d t o t h e above. Hydrothermal p r o c e s s e s c o n t r i b u t e l i t t l e t o t h e  c o n c e n t r a t i o n o f vanadium. The a s s o c i a t i o n o f vanadium w i t h c e r t a i n elements i s striking;  w i t h t i t a n i u m i n magnetites and i n c l a y s ;  with  molybdenum i n c l a y s and i n v a n a d i n i t e , d e s c l o i z i t e ores; w i t h uranium and radium i n v e i n s and i n sedimentary ores; w i t h carbon;  and w i t h l e a d , z i n c , copper, and s i l v e r i n  v a n a d i n i t e , d e s c l o i z i t e ores and sedimentary o r e s .  CHAPTER I I I . v  THE OCGIfRRElCE OS YAffADIUM I I SOME ROCKS A¥D MINERALS FROM BRITISH COLUMBIA. During t h e u n i v e r s i t y s e s s i o n 1943-44, a l a b o r a t o r y  survey o f t h e occurrence o f vanadium i n 80 specimens o f rocks and m i n e r a l s from B r i t i s h Columbia was made by t h e author as a p a r t i a l f u l f i l m e n t o f work f o r t h e B r i t a n n i a M i n i n g and S m e l t i n g Company l i m i t e d S c h o l a r s h i p .  The specimens were  o b t a i n e d from t h e c o l l e c t i o n s a t t h e u n i v e r s i t y and from i n t e r e s t e d people from time t o time, and, i n a d d i t i o n , a s u i t e of c o a l and a s s o c i a t e d r o c k samples was s u p p l i e d by t h e e n g i n e e r i n g s t a f f o f t h e Dunsmuir C o l l i e r i e s a t Cumberland, B r i t i s h Columbia. The survey was based on s p e c t r o chemical a n a l y s i s o f t h e m i n e r a l s and r o c k s , made on a H i l g e r medium quartz s p e c t r o graph a t t h e U n i v e r s i t y o f B r i t i s h Columbia.  A motor  g e n e r a t o r s e t s u p p l i e d D.C. v o l t a g e a t 110 v o l t s . i n g c o n d i t i o n s were adopted as s t a n d a r d .  The f o l l o w  The a r c w i t h s e r i e s  inductance was operated a t 6 amperes w i t h a 2 m i l l i m e t e r gap, t h e lower e l e c t r o d e b e i n g made p o s i t i v e .  Carbon e l e c t r o d e s  *Vl6 i n c h diameter w i t h square ends, made by n a t i o n a l Carbon Company, were p l a c e d 61 c e n t i m e t e r s from t h e s l i t , and t h e l i g h t was foeussed by means o f a q u a r t z condensing  l e n s on a  p o i n t beyond t h e p r i s m so t h a t t h e p r i s m a p e r t u r e was completely f i l l e d with l i g h t .  The r e s u l t i n g l i n e s on t h e  spectrogram were o f u n i f o r m i n t e n s i t y from top t o bottom. s l i t w i d t h was  .01 m i l l i m e t e r s , and the Hartman diaphram  The was  p l a c e d over the s l i t to produce l i n e s 2 m i l l i m e t e r s l o n g on the p l a t e . Twenty m i l l i g r a m s o f t h e sample were packed i n a s m a l l h o l e bored i n the lower e l e c t r o d e ( p o s i t i v e ) of the a r c . Each sample was a r c e d f o r 30 seconds, and a spectrum of  ^  vanadium and of i r o n from H i l g e r i r o n rods was made w i t h the sample f o r comparison and l i n e  interpolation.  The spectrograms were t a k e n on Eastman S p e c t r o s c o p i c p l a t e s , t y p e I I J , w i t h wavelength range of 2200-6800 Angstroms.  The p l a t e s were developed i n D . l l f o r 3-J- minutes  r i n s e d , f i x e d i n P.5 f o r 20 minutes, washed f o r one hour, d r i e d , and examined on an o p a l g l a s s v i e w i n g s c r e e n w i t h an eyepiece. R e l a t i v e q u a n t i t a t i v e e s t i m a t i o n s a r e based on v i s u a l comparison o f t h e s p e c t r a , and a r e s u b j e c t t o c o r r e c t i o n s r e q u i r e d by t h e v a r y i n g compos i t ion,-of the base m a t e r i a l i n t h e samples,.. and o t h e r f a c t o r s which may change t h e I n t e n s i t y of l i n e produced by a g i v e n amount o f an element i n a sample. The vanadium l i n e s used f o r i d e n t i f i c a t i o n a r e : 3183, 3184, 3185, 4379, 4408, 3095, 3102, .3118, 312-5.-v A Y  3111,  ;  The r e l a t i v e Q u a n t i t a t i v e e s t i m a t e s a r e r e p o r t e d as a  s e r i e s , o f numbers from .1 t o 10, t o i n d i c a t e l i n e from v e r y weak t o v e r y s t r o n g .  intensities:  They cannot be c o n s i d e r e d  a c c u r a t e r e p r e s e n t a t i o n s . o f the,amounts o f vanadium present f o r t h e reasons g i v e n above, and= f u r t h e r m o r e , t h e standards s e t up f o r one type o f m a t e r i a l c e r t a i n l y do n o t a p p l y t o another t y p e , except i n a v e r y approximate way.  The f i g u r e  1 i n d i c a t e s t h a t t h e p r i n e i p a l vanadium l i n e s a r e b a r e l y visible;  10 was t h e l i n e , i n t e n s i t y g i v e n by a sample of  impure secondary  vanadates from M i n a s r a g r a , Peru.  The  f o l l o w i n g c o r r e l a t i o n s were o b t a i n e d between chemical  assays  o f samples and t h e i n t e n s i t y o f t h e p r i n c i p a l s p e c t r o s c o p i c lines: Sample:.  per cent 2°5 c h e m i c a l assay.  B l a c k sediment Quadra I s l a n d  1.96. and 2.16  6 or 8  B l a c k sediment. Menzies Bay  0.75 and 1.14  8 or 9  Basaltic lava Quadra I s l a n d  0.50 and 0.21  6  V  Many o t h e r l a v a s i n same s e r i e s  .Intensity of spectros c o p i c l i n e based on arbitrary scale.  0 t o 7 average 5.  C o a l Ash Princeton  0.26  C o a l Ash Hat Creek  0.27  5 - 6  RESTJITS OF SPEG TRQGHMlIGAJt SURVEY OF SOME ROCKS ATSTD. MI1ERALS  Volcanic  Ro.cks.:  B a s a l t , Texada F o r m a t i o n .  ,..  ...  2  Andesite,  ...  ...  6  Basale, C h i l c o t i n .  ...  ...  5-g-  P u r c e l l l a v a , (Cranbrook)  ...  ...  Yifhitehorse, Y.T.  T e r t i a r y v o l c a n i c ( a n d e s i t i e ) Whitehorse, Y.T. 5 Greenstone, v o l c a n i c , Q u a t s i n o . .  ...  5  B a s a l t , Shulaps v o l c a n i c s  ...  ...  5  basalt volcanics..  ...  0  V e s c i c u l a r b a s a l t , C h i l c o t i n . ..  ...  5-g-  Serpentinized  B a s a l t o r diabase i n t r u s i v e i n "Cache Creek", Quesnel. Y o l c a n i c f l o w , Cache Creek ... ...  6  Serpentine,  Hope.  6  ...  ...  1  "Porphyrite S e r i e s " flow rock...  ...  4-§-  Magnet i t e : V .••-:.--^aml>©ops  . •»  ...  ...  ....  0  Whalis Mountain, o p p o s i t e N o r t h Bend, C.P.R.  S  Tulameen  _.,.;-AssoQiateci:;pink:rock  Associated  :  2,0-  ...  ...  2  ferromagnesian...  ...  0  Head Bay, Uootka Sound  ...  ...  0  E l k R i v e r , Kennedy l a k e  ...  ...  0  Oxidized  Quatsino, Morning G l o r y T r a i l  ...  ... 1  B l a c k Sand, B a r k e r v i l l e  ...  ... 3  B l a c k Sand, Spanish Banks  ...  ... 3  I l l m e n i t e , S t . U r b a i n , Quebec.  ...  ... 3  Sulphides: Oxidized s i l v e r  lead ore, B l u e b e l l , Ainsworth.  Oxidized s i l v e r  lead ore, Slocan..  Oxidized s i l v e r  l e a d o r e , Ferguson, Lardeau... 1-|-  O x i d i z e d galena and manganite, Mayo, Y.T.  1  ... 1  ... 1  Secondary C h a l c o c i t e and y e l l o w  stain,Kennecott, Alaska... 1 Y e l l o w s t a i n on s u r f a c e o r e . No.1.mine, Ainsworth.. 1 2 secondary z i n c m i n e r a l s , P a r a d i s e Mine ... 0 Note:  f o r vanadium i n primary s u l p h i d e s see page 17 o f t h i thesis.  Sediments: A l d r i d g e Formation,  Granbrook a r e a .  Oreston  "  "  Kitchener  "  "•  Siyeh  "  Gateway Phillips  • •* vs» ... 4  H  e • •  t5  "  •  %5  "  "  • « » £3  "  "  •  "  »• * 5  Rooseville. "  .  Cambrian B a s a l Conglomerate  e «  0 0  e » a  3  2  Diatomaceous e a r t h , Okanagan  «•• 1  Diatomaceous e a r t h , Quesnel  «a• 0  Kaolin,  « « e  Soda Creek,  2  52  B e n t o n i t e , Princeton.  ....  ...  0  Gypsum, Windemere.,  ...  ...  0  Hydromagnesite, A t l i n .  ...  ...  1  F e t i d l i m e s t o n e , Rancheria  R i v e r , A l a s k a Highway  ii  l i m e s t o n e from B i g Bend Area, l i g h t - c o l o u r e d bands. Limestone from B i g Bend Area,  Coal  dark-coloured bands  Si-  Ash: Brown l i g n i t e , C o a l R i v e r .  ...  ...  1  Rocky Mountain, Peace R i v e r  ...  ...  G  Hat Creek  ...  P r i n c e t o n cOal ash  ...  ...  5  P r i n c e t o n c o a l soot  ...  ...  8*  P o r t Haney Nicola  5 * 6.  ...  1  '  2  I n T e r t i a r y sandstone, Sooke Harbour Telqua  ...  ...  5 1,0  Quatsino  ...  ...  2ir  Camp Robertson, Graham I s l a n d  ...  ...  lir  Queen C h a r l o t t e  ...  ...  Coke ?  ...  ...  A l e x a n d r i a Mine, South W e l l i n g t o n . . .  ...  South Workings No.  ...  Queen C h a r l o t t e Sound  N o r t h Workings  8 Mine, Cumberland "  "  "  From u n i v e r s i t y power p l a n t (Vancouver I s l a n d . . . coal) Domestic c o a l , m i x t u r e of MacLeod R i v e r and ' Wellington.  4i  Si  1 4i  53  A s u i t e o f 18 samples o f c o a l and a s s o c i a t e d bone o r rock m a t e r i a l from t h e Cumberland Mines, s u p p l i e d by the e n g i n e e r i n g s t a f f o f t h e Dunsmuir C o l l i e r i e s a t Cumberland, B r i t i s h Columbia, produced l i n e from 0 t o 3-g-, but a v e r a g i n g about 1.  intensities  Two samples o f  bone were h i g h e s t i n vanadium, b u t o t h e r bone samples c o n t a i n e d no vanadium. •  Miscellaneous: A p a t i t e green and brown, Quebec A p a t i t e v a r i pebble phosphate, F l o r i d a  « • e  A p a t i t e v a r . p h o s p h o r i t e , Wyoming  • • '•  Rhodonite, K a s l o  ...  0  ...  «•«  1  to  0  .. Wad,  .£aslo  -Rhodonite, M i d d l e R i v e r ( f a k l a Lake):  •  B  2  0  * e  SUMMARY Many b a s i c l a v a s i n B r i t i s h Columbia c o n t a i n a p p r e c i a b l e amounts o f vanadium, perhaps as much as ,0.20 p e r cent YgOg, and some o f them may c o n t a i n as much as t h e l a v a s o f t h e Yaldes  Group on Quadra and Yancouver I s l a n d s .  Several  magmatie d e p o s i t s o f B r i t i s h Columbia and t h e b l a c k sands o f the I r a s e r R i v e r Y a l l e y c o n t a i n vanadium, but t h e c o n t a c t metamo.rphic m a g n e t i t e s o f Yancouver I s l a n d c o n t a i n v e r y  little  or no vanadium. lone o f the oxidized surface portions of lead , zinc,  54  o r copper s u l p h i d e ores t h a t have been t e s t e d  contained  a p p r e c i a b l e vanadium, and i t seems l i k e l y t h a t e i t h e r cond i t i o n s have been u n s u i t a b l e f o r t h e development -of secondary vanadate d e p o s i t s i n a s s o c i a t i o n w i t h these o r e s , or e l s e these d e p o s i t s have been removed by g l a c i a t i o n .  Most  sediments c o n t a i n v a r i a b l e s m a l l amount of vanadium. On t h e b a s i s of s p e c t r o c h e m i c a l a n a l y s i s here and i n the l a b o r a t o r i e s o f the Department o f Mines i n V i c t o r i a , i t would appear t h a t no w e l l known B r i t i s h Columbia c o a l . c o n t a i n s more t h a n 0.30 p e r cent T 0r i n i t s ashed r e s i d u e . p  CHAPTER I T . THE DEPOSITS ON QUADRA ISLAND. M B  AT MENZIES BAY.  We r e t u r n now t o the o r i g i n a l problem, t h e c h a r a c t e r and o r i g i n o f the f i n e l y banded dark v a n a d i f e r o u s seams on Quadra I s l a n d , and near Menzies Bay on Vancouver  Island.  GEOLOGICAL SETTING OF THE DEPOSITS* As mentioned  i n t h e statement o f the problem, both  d e p o s i t s a r e t h i n , i r r e g u l a r seams o f a v e r y f i n e - g r a i n e d sediment between b a s a l t i c l a v a f l o w s . the  The l a v a s b e l o n g t o  V a l d e s Group w h i c h B a n c r o f t d e s c r i b e s as  "massive f l o w s  of a n d e s i t e , v o l c a n i c b r e c c i a s , t u f f s " o f p r o b a b l e T r i a s s i c age. the  I n t h e neighboxirhood o f Quadra I s l a n d and Menzies Bay, l a v a s d i p g e n t l y t o t h e south and south-east a t angles not  o f t e n exceeding 20 degrees.  They a r e u n d e r l a i n conformably  at Open Bay, on t h e n o r t h - e a s t , by a group o f c h e r t y  argillites,  q u a r t z i t e , and impure l i m e s t o n e , w h i c h B a n c r o f t has s u b d i v i d e d i n t o t h e Open Bay Group (Upper P a l e o z o i c ) and t h e Marble Bay F o r m a t i o n ( o l d e r t h a n Open B a y ) .  The c o n t a c t o f t h e Coast  Range B a t h o l i t h i s from one t o two m i l e s f u r t h e r n o r t h - e a s t of t h e vanadium  showing.  The sediments a r e i n t e n s e l y f o l d e d  but t h i s f o l d i n g d i e s out t o the south-west between one and two m i l e s from t h e b a t h o l i t h . s i x m i l e s s o u t h o f the vanadium  On fancouver I s l a n d , about d e p o s i t s , l a v a s o f t h i s same  s e r i e s a r e o v e r l a i n by Upper Cretaceous sandstone and conglome r a t e w i t h some s h a l e and c o a l .  PLATE I .  Plow c o n t a c t of columnar and p i l l o w l a v a , Quadra I s l a n d , B r i t i s h Columbia.  56  The l a v a s are dark, green t o grey and o c c a s i o n a l l y p u r p l i s h on the f r e s h s u r f a c e s , becoming brownish on weathered s u r f a c e s . I n many of them p i l l o w s t r u c t u r e i s p o o r l y to w e l l developed, and  i n some a crude columnar j o i n t i n g has formed.  The  p i l l o w s are e s p e c i a l l y w e l l developed near H y a c i n t h Bay the east c o a s t of Quadra I s l a n d .  on  Some o f t h e f l o w s are very  f i n e - g r a i n e d o r a p h a n i t i c w h i l e i n o t h e r s the g r a i n s are up t o two m i l l i m e t e r s l o n g .  Most of t h e l a v a s are  amygdaloidal.  H a l f a dozen t h i n s e c t i o n s show t h a t t h e o r i g i n a l rock conts i s t e d m a i n l y of p l a g i o c l a s e f e l d s p a r and a u g i t e i n about equal p r o p o r t i o n s .  These m i n e r a l s are now  to c h l o r i t e and e p i d o t e .  largely altered  The p l a g i o c l a s e i s remarkably s o d i e ,  r a n g i n g from a l b i t e - o l i g o c l a s e to o l i g o c l a s e - andesine, and t h e r e f o r e the l a v a s a r e more p r o p e r l y c a l l e d s p i l i t e s , i n the terminology  of the E n g l i s h p e t r o g r a p h e r s .  T y r r e l l states  t h a t " a p i l i t i c l a v a s a r e v e r y commonly p i l l o w - f o r m , and f r e q u e n t l y a s s o c i a t e d w i t h r a d i o l a r i a n c h e r t s and marine sediments. <' origin.  are  other  They are thought to be of submarine  The l a v a s o f Quadra I s l a n d and Menzies Bay a r e more  o r l e s s p i l l o w - f o r m and t h e y c e r t a i n l y have i n t e r f l o w marine sediments. Amygdule f i l l i n g s , which i n a few of the f l o w s form up to one h a l f of the r o c k , c o n s i s t of q u a r t z , chalcedony, c a l c i t e , c h l o r i t e , e p i d o t e , z e o l i t e s , and a f i b r o u s green amphibole. I n some of t h e l a v a s , i n c l u d i n g those near the  vanadiferous  seams, a few of t h e amygdules a r e p a r t l y or e n t i r e l y f i l l e d  57  w i t h copper m i n e r a l s , m a i n l y c h a l c o c i t e , w i t h some b o r n i t e , c o v e l l i t e , n a t i v e copper, and t h e v/eathered p r o d u c t s , a z u r i t e and m a l a c h i t e . Gopper m i n e r a l s a l s o occur i n i n t e r f l o w m a t e r i a l , i n shear zones i n t h e l a v a s as s m a l l i r r e g u l a r f i l l i n g s and replacements,  and to a v e r y minor extent i n s m a l l v e i n f i l l -  i n g s , u s u a l l y w i t h quartz or quartz and  calcite.  • The f l o w s are from l e s s - t h a n two f e e t to more than 15 f e e t t h i c k and have a r e g i o n a l d i p of from 0 t o SO degrees to t h e s o u t h - e a s t .  They a r e f a i r l y u n i f o r m i n c o l o u r and  g r a i n , so t h a t f l o w bedding  i s not always easy to see u n l e s s  t h e r e i s some i n t e r f l o w m a t e r i a l or a marked d i f f e r e n c e i n s t r u c t u r e ' o r t e x t u r e such as c o n t r a s t of p i l l o w s t r u c t u r e o r columnar j o i n t i n g , b r e c c i a t e d t o p s , amygdaloidal t o p s , p i p e amygdules on f l o w bottoms.  From a d i s t a n c e the l a r g e r  s t r u c t u r a l d i f f e r e n c e s between f l o w s and the s t e p l i k e topography of the area produced by f r a c t u r i n g p e r p e n d i c u l a r to the flows, and e r o s i o n , may  be  observed.  I n t e r f l o w m a t e r i a l i s not abundant, but where observed i t has c o n s i s t e d m a i n l y of t h i n seams o f f a i r l y u n i f o r m , g r e e n i s h grey t u f f a c e o u s or c a l c a r e o u s m a t e r i a l u s u a l l y siliclfied.  The dark v a n a d i f e r o u s seams a r e unique i n t h a t  they a r e n o t i c e a b l y l a m i n a t e d and a r e composed of v e r y f i n e g r a i n e d q u a r t z w i t h a minor amount o f carbonaceous m a t e r i a l . Flow b r e c c i a s a l o n g t h e tops o f l a v a s a r e not p a r t i c u l a r l y common.  Some o f t h e c a l c a r e o u s i n t e r f l o w sediments c o n t a i n  indeterminate  brachiopods.  Ho dykes have been observed t o cut t h e l a v a s near e i t h e r o f the p r o p e r t i e s , and t h e r e i s v e r y l i t t l e f a u l t i n g o r f o l d ing.  The few s m a l l v e i n s and  i r r e g u l a r masses of white  quartz are almost or e n t i r e l y b a r r e n .  -  • :  THE QUADRA I S i A l D DEPOSIT,.  The o r i g i n a l d i s c o v e r y o f vanadium was made on Quadra I s l a n d about 1-g- m i l e s n o r t h o f the head of Gowland Harbour and about 600 f e e t above sea l e v e l . undoubtedly  The amygdaloidal  lavas  u n d e r l i e the d e p o s i t f o r s e v e r a l hundred f e e t  and the n e a r e s t n o n - v o l c a n i c r o c k s on t h e s u r f a c e a r e the Open Bay sediments.  The c o n t a c t of the Coast Range B a t h o l i t h  i s about 4 m i l e s t o t h e n o r t h - e a s t .  The l a v a s d i p t o the  south-east at a n g l e s between 10 and 15 degrees, and are f a i r ly well fractured.  I t i s from one of the f r a c t u r e s o r  c r e v i c e s t h a t Crowe-Swords e x t r a c t e d the  "carnotite-like  mineral". S e v e r a l copper showings o f the types mentioned above o c c u r i n the g e n e r a l a r e a and t h e ground staked by CroweSwords comprises a group of t h e s e .  About 600 f e e t n o r t h -  west o f t h i s group of copper showings, and h i g h e r i n the l a v a series,  i s t h e open cut exposing t h e vanadium - b e a r i n g seams.  The open cut ( P i g . 1". ) i s about 60 f e e t l o n g i n a n o r t h - s o u t h d i r e c t i o n and about 6 f e e t deep.  The east w a l l exposes  t h r e e l a v a f l o w s d i p p i n g about 10 degrees south-east  with  v e r y p o o r l y developed p i l l o w s t r u c t u r e , the upper and the 1 lower f l o w c o n t i n u i n g from end to end of the c u t . middle flow i s represented  o n l y i n the southern  The  (right in  t h e . f i g u r e ) two t h i r d s o f the c u t , t e r m i n a t i n g i n a p i l l o w l i k e shape.about 18 f e e t from the n o r t h end.  The middle  and upper f l o w s a r e n o r m a l amygdaloids, f a i r l y dense and g r e e n i s h grey i n c o l o u r , but t h e lower f l o w i s h i g h l y b r e c c i a t e d where observed and The v a n a d i f e r o u s  i s more i n t e n s e l y c h l o . r i t i z e d .  sediment i s an i r r e g u l a r , , f i n e l y  l a m i n a t e d , b l a c k or dark grey seam between the upper and m i d d l e , ana middle and lower f l o w s , v a r y i n g i n w i d t h from paper t h i n up t o s i x i n c h e s .  I n the t h i c k e r p a r t s  and  p a r t i c u l a r l y near t h e end o f the m i d d l e f l o w , the seam i s c r e h u l a t e d and appears,to pillows.  have been f o r c e d between i n c i p i e n t  Quite e v i d e n t l y t h e seam was  l a i d down as a t h i n  bed on the, rough s u r f a c e of the u n d e r l y i n g l a v a , ' and s t i l l p l a s t i c was flow.  while  deformed and p a r t l y removed by the next  The s t r u c t u r e of t h e seam around t h e end o f the  m i d d l e f l o w (see f i g . 1 ) would most l i k e l y be -formed by the upper l a v a floviring i n t o p l a c e from a n o r t h e r l y d i r e c t i o n . F o u r shear zones, one o f them about 4 f e e t wide, cut a c r o s s the l a v a s  jsrith a s t r o n g d i p .  Copper m i n e r a l s a r e present  i n the amygdules i n the  shear zones, i n the seam, and n o t a b l y i n the b r e c c i a t e d top of the l o w e r l a v a .  ;  "  FIGURE-"1>  SKETCH. 03? YERTICAIi WALI.; Of OPEN CUT 03? MAIN VANADIUM SHOWIIG QUADRA .ISLAHI), BRITISH COHJMBIA. looking east.  ••/  Scale 1 inch = 8 feet  Blank a r e a equals amygdaloidal b a s a l t , w i t h minor copper, c h a l c o c i t e , and b o r n i t e i n t h e amygdules, and rude p i l l o w s a t t h e base o f t h e f l o w . V p a t t e r n equals b r e c c i a t e d top o f b a s a l t f l o w w i t h more copper than o v e r l y i n g f l o w s . Heavy b l a c k l i n e equals b l a c k v a n a d i f e r o u s layer. Wavey l i n e s equal f r a c t u r e and shear zones. (115°) equal t r u e s t r i k e o f f r a c t u r e s .  The weathered s u r f a c e o f t h e b l a c k seam u s u a l l y has a c h a r a c t e r i s t i c y e l l o w s t a i n which i s thought t o be a •vanadium s a l t , and two a n a l y s e s . o f t h e seam showed 2.16 per cent and 1.96 p e r cent Y 0 g  g  respectively.  The lower l a v a assayed  0.30 p e r oent.;.f^0g.- ana', .the' middle.; l a v a O.'Sl .per cent Y 0 . g  f o r more d e t a i l e d assays/see t h e l a s t s e c t i o n o f t h i s  5  chapter.  THEME1ZIES BAY DEPOSIT. The d e p o s i t near Menzies Bay i s a b l a c k  vanadiferous  I n t e r l a v a sediment almost i d e n t i c a l i n appearance w i t h the d e p o s i t on Quadra I s l a n d *  I t i s on t h e Conglomerate Copper  Group, two m i l e s west o f t h e head o f Menzies Bay and between 400 and 600 f e e t above sea l e v e l .  Outcrops, open c u t s , and  t r e n c h e s a l o n g a n o r t h - w e s t e r l y d i r e c t i o n f o r about 2,000 f e e t show two or: more o f t h e v a n a d i f e r o u s  l a y e r s u s u a l l y separated  by only, one l a v a flow,, and sometimes accompanied by a f i n e grained," g r e y i s h green calcareous; sediment c o n t a i n i n g p o o r l y p r e s e r v e d f o s s i l brachiopods.  The amygdaloidal  basaltic  l a v a s from two t o a t l e a s t 15 f e e t t h i c k d i p about 10° E. and S.E.  T h e i r surfaces, a r e h i g h l y i r r e g u l a r and  p i l l o w s t r u c t u r e i s . common.  rudimentary  Copper m i n e r a l s a r e not as  abundant i n t h e l a v a s here as t h e y a r e i n t h e l a v a s on Quadra I s l a n d , but t h e v a n a d i f e r o u s  seam c o n t a i n s much more c h a l c o -  c i t e than t h e seam on Quadra I s l a n d does, i n f a c t , t h e y e l l o w  PLATE I I .  F o l d e d v a n a d i f e r o u s sediment between l a v a f l o w s , Menzies Bay D e p o s i t , B r i t i s h Columbia.  s t a i n thought to be i n d i c a t i v e o f vanadium was  found  e s p e c i a l l y where t h e copper m i n e r a l i z a t i o n was  strong.  Most o f t h e i n t e r f l o w m a t e r i a l , however, i s a p p a r e n t l y t u f f a e ceous and c o n t a i n s l i t t l e o r no copper m i n e r a l i z a t i o n .  At  l e a s t one s h o r t l e n t i c u l a r body of h i g h grade c h a l c o c i t e has been d e p o s i t e d a l o n g some f i s s u r e s i n the l a v a , but i t i s some few f e e t below the v a n a d i f e r o u s seam and a p p a r e n t l y i s not r e l a t e d to i t .  At t h e most n o r t h e r l y end o f the show-  ings n a t i v e copper occurs i n some of the amygdules.  The  d i s c o n t i n u i t y o f t h e exposures ,and the i r r e g u l a r i t y of the l a v a f l o w s make i t d i f f i c u l t t o say whether a l l the exposures of the v a n a d i f e r o u s seam a r e at the same h o r i z o n i n the f l o w s but they a r e n e a r l y so, a t l e a s t . The best exposures of the v a n a d i f e r o u s sediment a r e at t h e southernmost workings where two o f the l a y e r s ,  separated  by a l a v a f l o w , occur i n a s i x t o twenty f o o t b l u f f , a l o n g w i t h some g r e e n i s h - g r e y s i l i c i f i e d c a l c a r e o u s and tuffaceous material..  probably  l y i n g a l o n g ; t h e f l o w c o n t a c t s , they  r e v e a l t h a t t h e l a v a s a r e not v e r y u n i f o r m i n t h i c k n e s s . At the narrowest  p a r t of the i n t e r v e n i n g l a v a the seams are  about 2-g- f e e t a p a r t .  The dark v a n a d i f e r o u s l a y e r s have a  maximum t h i c k n e s s of about f i v e inches a l t h o u g h the average i s o n l y about one  i n c h , and the combined t h i c k n e s s o f the  dark l a y e r and t h e c a l c a r e o u s l a y e r which, when p r e s e n t , o v e r l i e s the dark l a y e r , i s never more t h a n t e n i n c h e s . At t h e open cut shown i n the p h o t o g r a p h , ( p l a t e I I b )  ?  62  about f i v e inches of the b l a c k sediment o v e r l a i n by a s i m i l a r t h i c k n e s s of v e r y f i n e - g r a i n e d , brownish-grey been f o l d e d i n t o a t i g h t s y n c l i n e .  l i m e s t o n e , has  Irregular continuations  o f the seam can be t r a c e d around a b o u l d e r - l i k e mass o f l a v a , and a f t e r a s h o r t break, a l o n g the o r i g i n a l h o r i z o n . f a c t t h a t the l i m e s t o n e c o n t a i n s a few uncrushed s u g g e s t s ' t h a t the sediment was theupheaval  The  brachiopods  folded while s t i l l p l a s t i c  by  and r o l l i n g over o f the b o u l d e r - l i k e mass d u r i n g  the next f l o w o f l a v a . The l i m e s t o n e i s p a r t l y r e e r y s t a l l i z e d and i n t h i n sect i o n shows no d i s t i n c t i v e t e x t u r e , o t h e r than i t s extreme fineness of g r a i n .  I t c o n t a i n s a few c l a s t i c g r a i n s of  quartz. The o t h e r showings a r e s i m i l a r to t h i s southernmost but l e s s s t r i k i n g .  one,  The o v e r l y i n g f o s s i l i f e r o u s sediment i s  o f t e n found, a l t h o u g h i t i s a p p a r e n t l y more t u f f a e e o u s than t h a t d e s c r i b e d above* and the seam i s n e a r l y always h i g h l y cupriferous.  *  On the whole, the vanadium content of the seam< .material near Menzies Bay i s somewhat l e s s than i n the seams on Quadra Island.  The h i g h e s t vanadium assays were o b t a i n e d from  l a m i n a t e d f o s s i l i f e r o u s sediment about 1,100 of the southernmost showings, and showed 0.75 1.14  per cent VgOg.  feet  north-west  per cent  and  These and o t h e r assays were s u p p l i e d by  Mr. G. A. Dirom o f Premier Gold M i n i n g Company l i m i t e d . lower vanadium content may  The  be due to i n c l u s i o n of t h e over-  l y i n g f o s s i l i f e r o u s sediment w i t h t h e b l a c k l a y e r i n t h e samples, o r t o t h e e x c e s s i v e amount o f copper present  since  t h e c h a l c o c i t e a p p a r e n t l y c a r r i e s l i t t l e o r no vanadium.  ,;THE;3IE^ The a s s o c i a t i o n o f copper m i n e r a l s , m a i n l y c h a l c o c i t e , w i t h the vanadiferous  seams suggests a p o s s i b l e g e n e t i c  r e l a t i o n s h i p between t h e copper and the vanadium, and t h e r e f o r e a more d e t a i l e d d e s c r i p t i o n o f t h e c h a l c o c i t e i s i n o r d e r . C h a l c o c i t e occurs  i n t h e amygdules, i n shears and f r a c ~ n  t u r e s i n t h e v o l c a n i c r o c k , and i n t h e seams as minute r e placements and v e i n l e t s .  I t s o c c u r r e n c e as amygdule f i l l i n g s  i s i l l u s t r a t e d i n P l a t e I I I a.  The c h a l c o c i t e , i n t h e  form o f a r i n g i n s i d e t h e v e s c i c u l e , i s f a i r l y d e f i n i t e l y c a!*epia<&emejito6toth^rfefirud-tsito«.  The s m a l l remnant i s l a n d s  m  o f b o r n i t e w i t h deeply cremulated borders a r e surrounded by c h a l c o c i t e i n every case.  Under h i g h m a g n i f i c a t i o n t h e  c h a l c o c i t e i s seen t o c o n t a i n t i n y patches o f c o v e l l i t e , mostly  i n i r r e g u l a r zones o f a l t e r a t i o n .  Some of t h e  c o v e l l i t e , however, i s arranged i n l o n g p a r a l l e l resembling  lenses  t e n s i o n c r a c k s l y i n g d i a g o n a l l y i n the r i n g o f  c h a l c o c i t e . ( P l a t e I I I ,b) .  The c o v e l l i t e may s i m p l y be  r e p l a c i n g t h e c h a l c o c i t e but i t i s not i m p o s s i b l e t h a t these l e n s e s c o u l d have been formed by e x s D l u t i o n o f c o v e l l i t e from c h a l c o c i t e , w h i c h takes p l a c e a t 75°G. o r l e s s , as they  PIATE I I I .  S l e n d e r l e n s e s of c o v e l l i t e i n c h a l c o c i t e (white) i n an amygdule f i l l i n g . X 480  appear t o conform w i t h some e r y s t a l l o g r a p h i c d i r e c t i o n i n t h e c h a l c o c i t e or o r i g i n a l bornite.  This c o v e l l i t e and t h e  c h a l c o c i t e may*he contemporaneous i n o r i g i n .  Lindgren  states: The a c t i o n between b o r n i t e and c u p r i c s u l p h a t e at t h e same temperature (4-0°C?) i s expressed by t h e equations ,  5 C u F e S t l l C u S 0 f 8 H 0 — } 18Cu Sv5I eS0 4r8H S0 6  4  4  2  2  4  0u FeS +GuS0 -~4 2Cu S+2CuS+FeS0 5  4  4  2  2  4  4  S 0  B o r n i t e i s a t t a c k e d by H £ 4 r e s u l t i n g i n OuS and CugS and FeSO^., hydrogen s u l p h i d e developing a t t h e same t i m e . These products w i l l r e a c t and form secondary c h a l c o p y r i t e . No c h a l c o p y r i t e was observed  i n these d e p o s i t s .  The h i g h grade c h a l c o c i t e i n t h e l e n s i n t h e v o l c a n i c f l o w s a t the Menzies Bay d e p o s i t i s c r y s t a l l i n e w i t h medium g r a i n s i z e and shows t y p i c a l orthorhombic  cleavage  w i t h abundant t r i a n g u l a r p i t s i n some p a r t s . w i t h FeCl-g o r KCN t h e orthrhombic  cracks,  On e t c h i n g  e t c h p a t t e r n i s formed w i t h  v a r y i n g i n t e n s i t y o f e t c h from c r y s t a l t o c r y s t a l . :  a d d i t i o n , i t i s very weaklyanlsotropic. t h e r e f o r e undoubtedly orthorhombic.  In  The c h a l c o c i t e i s  G o v e l l i t e i s present  as an a l t e r a t i o n product from t h e c h a l c o c i t e , and a few t i n y specks o f n a t i v e copper were seen. The c h a l c o c i t e i n the v a n a d i f e r o u s seams a t t h e Menzies Bay d e p o s i t occurs i n two g e n e r a t i o n s .  The f i r s t  generation  i s f i n e l y disseminated through t h e seam m a t e r i a l and t h e second f i l l s m i c r o s c o p i c v e i n l e t s c u t t i n g across t h e dissemi n a t e d c h a l c o c i t e and t h e l a m i n a t i o n s o f t h e seam.  This  65  c h a l c o c i t e i s a p p a r e n t l y orthorhombic  also.  Very minor  amounts o f n a t i v e copper occur as groups of t i n y specks, but no b o r n i t e has been observed  i n t h e v a n a d i f e r o u s seams from  Quadra I s l a n d and Menzies Bay* There i s no good evidence - whether,  the chalcocite i n  the f i s s u r e s o r t h e seam i s e i t h e r hypogene o r supergene. The occurrence o f copper w i t h b a s i c l a v a s i s world-wide and i s v e r y common on t h e coast o f B r i t i s h Columbia.  It is  thought t h a t t h e primary copper m i n e r a l s i n some o f these occurrences may have been d e p o s i t e d by hot waters  shortly  a f t e r t h e e r u p t i o n and c o n s o l i d a t i o n o f t h e l a v a s .  This  h y p o t h e s i s may apply to t h e copper m i n e r a l s i n t h e amygdules, but i t does not n e c e s s a r i l y a p p l y t o t h e c h a l c o c i t e i n t h e f i s s u r e s and i n the v a n a d i f e r o u s seams.  THE VANADIFERGUS SEDIMENT . The v a n a d i f e r o u s sediment i s almost b l a c k on f r e s h s u r f a c e s and i t weathers a dark grey, showing v e r y t h i n wavey laminations.  Near t h e bottom o f t h e seams these l a m i n a t i o n s  conform w i t h minor I r r e g u l a r i t i e s i n t h e s u r f a c e o f f t h e underl y i n g lava flow*  Subsequent t o d e p o s i t i o n and w h i l e  still  p l a s t i c , t h e sediment was deformed by t h e next f l o w o f l a v a , so t h a t i t now v a r i e s g r e a t l y In t h i c k n e s s and the l a m i n a t i o n s are c o n t o r t e d .  A y e l l o w s t a i n , i n some p l a c e s v e r y f i n e l y  c r y s t a l l i n e , i s o f t e n found on weathered s u r f a c e s o f t h e  sediment, though on many s u r f a c e s exposed f u l l y t o t h e abundant r a i n f a l l o f t h e r e g i o n , t h e r e i s no s t a i n . In t h i n s e c t i o n t h e vanadiferous  sediment i s seen t o  c o n s i s t m a i n l y o f l i g h t and dark wavey l a m i n a t i o n s 'from .01 m i l l i m e t e r s t o .35 m i l l i m e t e r s t h i c k , but a v e r a g i n g about .02 millimeters thick.  ( P l a t e IV. )  The l i g h t and dark  l a m i n a t i o n s do n o t have v e r y sharp c o n t a c t s , but blend  into  each o t h e r through a narrow c o n t a c t zone, and both types p r o b a b l y c o n s i s t : o f masses o f extremely  fine particles with a  few l a r g e r p a r t i c l e s . The  dark l a m i n a t i o n s forming up t o 60 p e r cent o f t h e  rock a r e most commonly j e t black, o r n e a r l y s o , i n s e c t i o n s o f normal t h i c k n e s s , g r a d i n g i n t o grey on t h i n edges o f t h e s e c t i o n o r by admixture o f t i n y g r a i n s o f q u a r t z . c o l o u r e d l a m i n a t i o n s a r e predominantly  The l i g h t  q u a r t z , but always  c o n t a i n a t l e a s t 20 p e r cent o f j e t b l a c k m a t e r i a l , h i g h l y disseminated  as i r r e g u l a r a n g u l a r g r a i n s from l e s s t h a n .003  m i l l i m e t e r s t o .03 m i l l i m e t e r s a c r o s s .  A v e r y few o f t h e  dark g r a i n s a r e as much as 0.10 m i l l i m e t e r s a c r o s s .  Most o f  these dark g r a i n s a r e elongated p a r a l l e l t o the-.laminat ions i n t h e rock, but a l l a r e h i g h l y i r r e g u l a r and they a r e g e n e r a l l y i s o l a t e d from o t h e r s i m i l a r g r a i n s by t h e q u a r t z i n which t h e y occur.  The dark bands may be merely a g r e a t e r  c o n c e n t r a t i o n o f extremely f i n e dark p a r t i c l e s i n v e r y f i n e grained  quartz.  The q u a r t z i n t h e l i g h t c o l o u r e d l a m i n a t i o n s i s i n t i n y  PLATE IT.  (a  (b) a) [b) (e) (d)  i  The The The The  vanadiferous vanaaiferous vanaaiferous vanadiferous  seaiment (White - Q u a r t z ) . O r a i n a r y l i g h t X 15 sediment. O r a i n a r y l i g h t X 38 sediment, s p e r i c a l quartz g r a i n s , O r a i n a r y l i g h t X sediment. P a r a l l e l l i g h t K 300.  300  spherules •with, diameters as l a r g e as 0.2 m i l l i m e t e r s , but u s u a l l y much l e s s .  A l l t h e l a r g e r quartz spherules  contain  one o r more of the dark p a r t i c l e s near the c e n t r e of the s p h e r u l e , and  i n p o l a r i z e d l i g h t most of them are seen to  c o n s i s t o f many g r a i n s o f q u a r t z r a d i a t i n g out from one more o f the b l a c k p a r t i c l e s .  or  As shown i n - t h e photography  t a k e n under h i g h m a g n i f i c a t i o n , some of the s p h e r u l e s have dark p a r t i c l e s arranged  i n a crude c o n c e n t r i c p a t t e r n .  o u t e r c o n t a c t of the quartz s p h e r u l e s  The  i s u s u a l l y f u z z y owing  to minute h a i r s o f dark m a t e r i a l p e n e t r a t i n g between the radiating grains.  The darker l a m i n a t i o n s are c r e n u l a t e d to  conform w i t h the boundaries o f t h e s p h e r u l e s , on both the upper and lower boundaries of the l i g h t c o l o u r e d l a m i n a t i o n s . I n some o f the t h i c k e r l i g h t - c o l o u r e d l a m i n a t i o n s the  quartz  s p h e r u l e s are i n two rows, a c t u a l l y l a y e r s , i n t h r e e dimens i o n s , w i t h v e r y p o o r l y d e f i n e d darker bands and  smaller  quartz g r a i n s s e p a r a t i n g the rows and the g r a i n s i n each  row.  Many of t h e l i g h t - c o l o u r e d l a m i n a t i o n s i n some s e c t i o n s have a smoky or tawny shade. I n a d d i t i o n t o t h e l a t e r copper m i n e r a l s t h e sediment i s cut by t i n y v e i n l e t s of q u a r t z which c a r r y a few specks of chalcocite. The v a n a d i f e r o u s sediment.  l a y e r i s o b v i o u s l y not a normal c l a s t i c  Aqueous sands do not show much rounding  of p a r t i -  c l e s , w i t h diameters below about 0.1 m i l l i m e t e r s , a n d wind blown sands a r e seldom rounded below about .03 m i l l i m e t e r s .  68  The borders o f t h e s p h e r u l e s i n t h i s sediment a r e n o t d i s t i n c t and t h e c r y p t o c r y s t a l l i n e r a d i a l s t r u c t u r e i n d i c a t e s t h a t t h e g r a i n s have e i t h e r formed from a core outward o r have r e e r y s t a l l i z e d from another form o f s i l i c a .  The f a c t  t h a t the dark l a m i n a t i o n s , both above and below t h e l i g h t c o l o u r e d l a m i n a t i o n s , curve around t h e q u a r t z s p h e r u l e s suggests t h a t t h e s i l i c a was d e p o s i t e d as a s t i f f j e l l y which soon a f t e r w a r d was c r y s t a l l i z e d i n t o c r y p t o c r y s t a l l i n e q u a r t z . F i b r o u s s t r u c t u r e i s thought, by some, t o develop w i t h r e c r y s t a l l i z a t i o n under c o n f i n e d c o n d i t i o n s and some o o l i t e s and p i s o l i t e s have r a d i a l s t r u c t u r e i n t h e i r laminae which may have formed i n , t h i s way.  I f almost any dark l a m i n a t i o n s  i n t h e v a n a d i f e r o u s sediment were s t r i p p e d away, the s u r f a c e of t h e r e m a i n i n g l i g h t - c o l o u r e d layer' would have a b o t r y o i d a l appearance. to  A l l t h i s , and t h e l a m i n a t i o n s themselves p o i n t  a rhythmic p r e c i p i t a t i o n o f t h e s i l i c a and dark m a t e r i a l  In. a.-.•polioidal medium f o l l o w e d by c r y s t a l l i z a t i o n . Boydell states:  /  '  The commonest m i c r o s c o p i c evidence o f presumably c o l l o i d a l o r i g i n f o r a m i n e r a l (or r o c k ) i s : (1) The presence o f more-or l e s s ( u s u a l l y the l a t t e r ) p e r f e c t concent r i c o u t l i n e s o r markings on the body of t h e m i n e r a l (2) The o c c u r r e n c e o f c o l l o f o r m boundaries o r banding ( u s i n g " c o l l o f o r m ' i n t h e sense In which Rogers proposed i t i . e . .... f o r t h e rounded more o r l e s s s p h e r i c a l forms assumed by c o l l o i d a l and m e t a c o l l o i d a l substances i n open spaces) 1  4  Together w i t h these, though not o f the same d iagno s t i c v a l u e i s : , (3) The presence o f t h a t m o d i f i c a t i o n of columnar and f i b r o u s s t r u c t u r e known as " r a d i a t e d i v e r g e n t " . " The rough c o n c e n t r i c  arrangement o f some o f the dark  p a r t i c l e s i n t h e l a r g e r s p h e r u l e s has been mentioned and i s I l l u s t r a t e d i n P l a t e IV b. • T y r r e l l p o i n t s out t h a t c e r t a i n banded s t r u c t u r e s i n m i n e r a l s and rocks a r e p r o b a b l y due t o rhythmic p r e c i p i t a t i o n i n g e l s and f u r t h e r :  The  b l a c k p a r t i c l e s i n t h e s p h e r u l e s may have served as  n u c l e i o r aided The  i n the p r e c i p i t a t i o n ' o f the s i l i c a .  thought a l s o a r i s e s , e s p e c i a l l y i n view o f t h e  carbon c o n t e n t o f t h e sediment, t h a t t h e r a d i a l : s p h e r u l i t i c s t r u c t u r e may have been produced by organisms. . R a d i o l a r i a n c h e r t s a r e commonly a s s o c i a t e d w i t h marine p i l l o w l a v a s . R a d i o l a r i a n organisms t h r i v e d wherever t h e r e was an abundant s u p p l y o f s o l u b l e ' s i l i c a i n sea water, whether s u p p l i e d by submarine v o l c a n i c a c t i o n o r some o t h e r means.  They may be  w e l l p r e s e r v e d o r may appear as minute rounded bodies o f crytocrystalline s i l i c a .  When w e l l preserved they would of  course have a d i s t i n c t i v e s t r u c t u r e . R a d i o l a r i a n s , however, a r e m o s t l y p l a n k t o n and one would expect t o f i n d t h e i r s h e l l s d i s t r i b u t e d through a sediment i n a haphazard manner and perhaps accompanied by o t h e r f o s s i l remains, r a t h e r than segregated i n t o d i s t i n c t l a m i n a t i o n s . The f o l l o w i n g assays a r e r e p o r t e d by E l l s w o r t h and Gunning:  i Si0  ...  2  PeO  Al 0 g  3  II  P e r c e n t P e r cent 75.31*. ' Gu . . 2 . 2 8 1  ...  2.29  ...  3.70  TiOg  -  V 0 .1.60 2 5 S0 ..0.48 o  5  0.15  MnO  ...  0.10  GaO  ...  4.08  MgO  ...  0.53  On  •••  2»88  'V'-.O 2 5 S  •••  2 * IL S  P 0 2 5  ...  U,Cr  ...  Not detected  H 0  ...  2.61  ...  2  C,CO ... ' 2 o  0.72 Trace  Present  K  ( 4 )  i n  iv  P e r cent Ou . . 0 . 0 6  P e r cent Gu 4.99  VpOpr.0.29 2 5 SOg..0.03  Y 0 . 0.30 g 5  I.  Average sample of s i l i c e o u s - c a r b o n a c e o u s zone. (•!•) M i c r o s c o p i c examination and chemical t e s t s i n d i c a t e t h a t most of the s i l i c a i s present i n the rock as q u a r t z . (2) Copper i s p r e s e n t as c h a l c o c i t e (CugS), a l s o , as basic carbonate ( m a l a c h i t e ) and probably a l s o i n s m a l l amount as s u l p h a t e and s i l i c a t e . (3) Some of the srilphur i s a p p a r e n t l y present as SG g  (4) Carbon about 5 per cent by c a l c u l a t i o n . hydrocarbons'detected.  No  I I . Shows t h e amounts of Cu, V2O5, and SO* t h a t passed i n t o s o l u t i o n when 1 gramme of the m a t e r i a l of I was d i g e s t e d f o r an hour on t h e hot water bath ' w i t h 100 c c . 1 per cent h y d r o c h l o r i c a c i d s o l u t i o n . III.  Shows t h e amounts of Cu, V2O5, and SOg recovered from the i n s o l u b l e of I I by a r e p e t i t i o n of the treatment w i t h 100 c c . o f 1 per cent h y d r o c h l o r i c a c i d .  IV. Copper and VgOg d e t e r m i n a t i o n s on a sample of the lower l a v a , c o m p r i s i n g m a t e r i a l about 2 inches below the c o n t a c t w i t h t h e v a n a d i f e r o u s zone. I t may  be noted t h a t as the g r e a t e r p a r t of t h e s i l i c a  of  a n a l y s i s I r e p r e s e n t s q u a r t z i n the r o c k , vanadium must be p r e s e n t t o t h e extent o f about 6 per cent i n , say, the t h i r d o f t h e m a t e r i a l t h a t i s not q u a r t z , and most o f i t c o u l d be v e r y e a s i l y and e c o n o m i c a l l y e x t r a c t e d , t o g e t h e r w i t h the g r e a t e r p a r t o f t h e copper, by simple l e a c h i n g w i t h m i n e r a l a c i d , as no a c i d would be consumed by the q u a r t z . " The f o l l o w i n g a n a l y s e s f o r vanadium were made by the Department of Mines at V i c t o r i a , B r i t i s h Columbia, on samples c o l l e c t e d a t the Quadra I s l a n d d e p o s i t i n 1943. 1.  Chip sample of 12 inches of b l a c k sediment 1.96^  V2O5  2.  Mixed sediment and amygdaloid, south end of c u t  0.28% V 0 CD  3. 4.  Same from 20 f e e t west o f n o r t h end o f cut Chip sample o f t h e m i d d l e f l o w of f i g u r e 1.  0.34$ V g 0  5  0.21% V^O,, CD  5.  Dense b l a c k amygdaloid q u a r t e r o f a m i l e north of cut.  0.18$ V 0 g  5  The f o l l o w i n g assays o n , m a t e r i a l from t h e Menzies Bay d e p o s i t were s u p p l i e d by Mr. G*A. Dirom o f t h e P r e m i e r Gold M i n i n g Company L i m i t e d , i n t h e s p r i n g o f 1943.  The open cuts  on t h e Menzies Bay d e p o s i t were numbered from 1 t o 9 s t a r t i n g a t t h e southernmost exposure by Mr. Dirom. $ VgOg  $ Ou.  0.36  14-16  L o c a t i o n and Remarks E. end 1 0.0. 0.2' t h i c k n e s s o f I n t e r f l o w sediments, c o n s i s t i n g o f 0.1'. h e a v i l y impregnated w i t h CuS; remainder f . g . s i l i e i f i e d , f o s s i l i f e r o u s , s l i g h t l y mineralized w i t h OuS. W e l l - d e f i n e d secondary canary y e l l o w " c a r n o t i t e " as t h i n c o a t i n g . . Above r e s u l t s by s p e c t r o g r a p h — a l s o 25-30$ SiOg, 18-20$ CaO, 14-16$ AlgOg, 1.2$ MgO, COg p r e s e n t , no Uranium d e t e c t e d .  Tr.  Thin c h a l k y y e l l o w (as weathered) f o s s i l i f e r o u s sed» smears on s u r f a c e o f v o l c a n i c between 2 and 3 O.C.'s.  0.124  West s i d e draw a t 1 and 2 O.C.'s. Dark g r e y i s h f . g . sediment i n c u r v i n g c r e v i c e s . Trace CuS o n l y .  0.75  0.05  ' 6 & 7 O.C.'s 0.1* o f laminated f o s s i l s e d . h e a v i l y impregnated w i t h CuS and showing well-defined "Carnotite" coating. 0.4  About l / 2 m i l e w e s t e r l y of main showings and around 1,000': e l e v . i n rock c u t on new u n l a i d r a i l w a y grade about l / 2 m i l e beyond end o f s t e e l and a t summit o f r i d g e . Thin  n  fo VgOg ^ ® - -•• 0.26  4.00  sheared and d i s c o n t i n u o u s a r g i l l a c e o u s sed. i n amyg. -flows. Minor OuS and c u p r i t e . 1A O.C. 0.4' f l a t s e d . seam i n f l o w s . Impregnated w i t h f . g . CuS. D i s t i n c t "Carnotite" staining.  0.19 , 7.75  Dark quartzose m a t e r i a l c o n t a i n i n g s m a l l q u a r t z and c a l e i t e "amygdules". CuS, Mn staining.  0.13  1.75  T y p i c a l d u l l c h a l k y y e l l o w weathering s u r f a c e o f v o l c a n i c from a l l a l o n g main w o r k i n g s , but p r i n c i p a l l y between 1 and 3 O.C.'s. H i g h l y a m y g d a l o i d a l , quartz and carbonate amyg. P r o b a b l y minor absorbed sed. m a t e r i a l , l o vanadium weathering. -  0.7  Between 2 and 3 O.C's. f . g . c h l o r i t i c m a t e r i a l , probably c h i l l e d v o l c a n i c . I n c l u d e s some c h e r t y m a t e r i a l . Some n a t i v e Cu. Occurs i n s m a l l quartz n e s t s and h a i r seams.  Tr.  0.40  9 O.C. Grey b l a c k c h e r t y sed. impregnated l i g h t l y w i t h f . g . CuS and n a t i v e Cu. a l s o cuprite. Trace o f c a r n o t i t e weathering.  There I s no d i r e c t r e l a t i o n apparent  between t h e amount  of vanadium and t h e amount o f copper contained i n samples o f t h e b l a c k sediment.  SPECTROCHEMICAI ASSAYS. To supplement t h e above assays and i n an attempt t o l o c a t e t h e vanadium, s e v e r a l s p e c t r o c h e m i c a l assays were made by t h e a u t h o r on the same b a s i s as those r e p o r t e d i n Chapter I I I . The f o l l o w i n g i s a summary o f t h e r e s u l t s , w i t h f i g u r e s  i n d i c a t i n g t h e I n t e n s i t y .of t h e '-vanadium l i n e s on t h e a r b i t r a r y s c a l e of 1 to 10. The 'yellow s t a i n : A l l samples contained vanadium ( i n t e n s i t y 8) and more than a t r a c e o f copper* Mn^En U4': aiie a W e h t . r  s  Zn,Sb,As,Pb,Ti,  The m i n e r a l was not  identified. •The b l a c k sediment: A l l samples c o n t a i n e d vanadium ( i n t e n s i t y 6 to 9 ) . The C h a l c o c i t e : Samples from the c h a l c o c i t e l e n s a t t h e Menzies Bay d e p o s i t and the amygdules no vanadium.  ..  contained .  The Lavas: A l l samples of t h e l a v a , except one, c o n t a i n e d vanadium ( i n t e n s i t y 2 t o 7) even though some o f them were f a r away from.the d e p o s i t s .  A sample  from near t h e Moose F a l l s on Campbell R i v e r c o n t a i n e d vanadium, and samples from a s e r i e s of f l o w s above and below t h e open cut on Quadra I s l a n d and as much as a q u a r t e r of a m i l e away a l l contained  vanadium.  The l i m e s t o n e : The l i m e s t o n e o c c u r r i n g w i t h the b l a c k sediment hear Menzies Bay c o n t a i n e d o n l y a t r a c e of  vanadium ( i n t e n s i t y Z) F e t i d l i m e s t o n e from t h e Open Bay Group contained no vanadium. The Amygdules: None o f t h e amygdules c o n t a i n e d vanadium. Quartz: Samples o f t h e q u a r t z i n v e i n s and i r r e g u l a r l e n s e s c o n t a i n e d no vanadium. I n an attempt t o l o c a t e t h e vanadium i n t h e b l a c k ment, a sample o f b l a c k , sediment w i t h v e r y l i t t l e  sedi-  chalcocite  was ground t o minus 325 mesh (.042 mm.) and separated i n a h i g h speed c e n t r i f u g e w i t h a bromoform a l o o h o l m i x t u r e o f s p e c i f i c g r a v i t y 2.45 as t h e s e p a r a t i n g medium.  Although t h e  s e p a r a t i o n was repeated s e v e r a l times on t h e products o f t h e f i r s t s e p a r a t i o n , and a l t h o u g h t h e m a t e r i a l o f s p e c i f i c  grav-  i t y l e s s than 2.45 was n o t i c e a b l y darker than t h e h e a v i e r m a t e r i a l , t h e s p e c t r o g r a p h f a i l e d t o show any d i f f e r e n c e i n vanadium content o f t h e two p r o d u c t s . E q u a l l y u n s u c c e s s f u l r e s u l t s were o b t a i n e d w i t h samples o f the l a v a where t h e s e p a r a t i o n s were made w i t h bromoform o f s p e c i f i c g r a v i t y 2.9 i n t h e c e n t r i f u g e , and by a l a r g e e l e c t r o magnet.  A p p a r e n t l y t h e r e i s too l a r g e a p r o p o r t i o n o f  a p h a n i t i c m a t e r i a l i n b o t h t h e sediment and t h e l a v a s t o make any s a t i s f a c t o r y p h y s i c a l s e p a r a t i o n . I n o r d e r to t e s t t h e p o s s i b i l i t y o f h a v i n g vanadium l e a c h e d from the c o n s o l i d a t e d l a v a s by ground waters, t e n ,  76  t e n gramme samples o f t h e l a v a were crushed, and each s u b j e c t e d to l e a c h i n g by 50 c c s . o f s o l u t i o n s s i m u l a t i n g n a t u r a l ground waters.  A f t e r 15 days, 10 c c s . o f each s o l u t i o n was evapora-  t e d and t h e r e s i d u e assayed s p e c t r o s c o p i e a l l y  f o r vanadium.  The r e s u l t s a r e as f o l l o w s : leaching  solution  Amount o f vanadium leached as shown by spectrograph.  1. Water, a t about 80^0. 2. 7/ater - 0 0  © • •  doubtful  • % e  trace  2  3. l a t e r - HgS  ......  4. S a t u r a t e d s o l u t i o n o f HaCI  trace  5.  doubtful  /10 H. s o l u t i o n o f H S 0 g  4  trace  1  6. / l 0 II. s o l u t i o n o f HOI 7. / B . H. s o l u t i o n o f fegCOg p l u s 0 0 1  ;  8. ^/lO H. s o l u t i o n o f H S 0 p  /5 1  g  1  /5  10.  /5  4  •  g  « e «  trace  plus  H. s o l u t i o n o f FeSO, H. s o l u t i o n o f H a S 0  contained most vanadium.  plus...  4  H. s o l u t i o n o f CaSO  9. / l 0 N. s o l u t i o n o f H S 0  2  4  e• « • « ......  b e t t e r than trace better than trace.  CHIPPER J . THEORIES OP ORIGIN FOR THE YAHADIPEROUS SEDIMENT. I t was - suggested i n the p r e v i o u s c h a p t e r t h a t the s i l i c a i n t h e l a m i n a t e d v a n a d i f e r o u s sediment was p r o b a b l y a c o l l o i d a l p r e c i p i t a t e which had been c r y s t a l l i z e d i n t o i t s present form a f t e r deposition, (that i s a metacolloid).  Questions now  a r i s e as t o the s o u r c e of the s i l i c a and t h e cause of i t s p r e c i p i t a t i o n , and the p r o c e s s e s by which vanadium was t r a t e d i n t h e sediment. mind; per  concen-  The f o l l o w i n g data s h o u l d be kept i n  t h e vanadium content o f the l a v a s ranges -from 0 t o  c e n t VgOg, and o f t h e b l a c k sediment, from about 0.75  cent t o 2.16 per cent v" 0g; g  0.30 per  the f o s s i l i f e r o u s limestone  c o n t a i n s o n l y a t r a c e o f vanadium, and the amygdules, c h a l c o c i t e and n a t i v e copper, c o n t a i n no vanadium;  including  the  c h a l c o c i t e i n t h e f i s s u r e f i l l i n g s a t t h e Menzies Bay deposit a l s o c o n t a i n s no vanadium*  The seam c o n t a i n s about 75 per  cent s i l i c a , most o f which a p p a r e n t l y i s p r e s e n t as q u a r t z . • In view o f t h e e x c e p t i o n a l l y h i g h vanadium content of the l a v a s i t appears s a f e t o assume t h a t t h e vanadium  In the b l a e k  sediment was d e r i v e d e i t h e r from t h e l a v a s themselves o r from some phase o f igneous a c t i v i t y a s s o c i a t e d w i t h t h e l a v a s . the  If  vanadium were d e r i v e d from t h e l a v a s themselves, the amount  i n t h e b l a c k sediment would r e p r e s e n t a c o n c e n t r a t i o n from the l a v a s of o n l y t e n t i m e s .  Sources f o r t h e S i l i c a : Moore and Maynard, succeeding o t h e r i n v e s t i g a t o r s found t h a t s e v e r a l n a t u r a l s o l v e n t s w i l l d i s s o l v e s i l i c a (and i r o n ) from nor i t e .and d i a b a s e .  T h e i r r e s u l t s , i n condensed form,  are: (l).  Carbonated water i s the most e f f e c t i v e s o l v e n t of i r o n and s i l i c a from n o r i t e and diabase.  '.{•£).  Peat s o l u t i o n i s t h e next most e f f e c t i v e s o l v e n t of i r o n and s i l i c a .  (3) . D i s t i l l e d water i s a v e r y poor s o l v e n t of i r o n • • • • and s i l i c a . (4) .  Oxygenated water i s a v e r y poor s o l v e n t of i r o n and o n l y a f a i r s o l v e n t of s i l i c a .  (5) .  I n g e n e r a l , f i n e g r i n d i n g i n c r e a s e s the s o l v e n t a c t i o n of the various reagents.  (6)  Time i s an important f a c t o r i n the s o l u t i o n of i r o n and s i l i c a from n o r i t e and diabase by d i s t i l l e d water, oxygenated water, and carbonated water, f o r i n v a r i a b l y more i r o n and s i l i c a are d i s s o l v e d by t h e s e reagents i n 287 days than i n 70 days.  (7)  The g e n e r a l c o n c l u s i o n i s t h a t carbonated water i s a b l e t o d i s s o l v e s u f f i c i e n t i r o n and s i l i c a from a b a s i c t e r r a i n t o form a l a r g e sedimentary deposit. Organic m a t t e r , i f p r e s e n t , a s s i s t s a l s o i n d i s s o l v i n g much i r o n and s i l i c a . I n o r g a n i c a c i d s , under e x c e p t i o n a l circumstances cause much i r o n and s i l i c a t o go i n t o s o l u t i o n .  They a l s o concluded t h a t most s i l i c a s i l i c a hydrosol.  i s t r a n s p o r t e d as a  1  Note t h a t time i s an important f a c t o r i n t h e s o l u t i o n o f s i l i c a and i r o n .  The time between l a v a f l o w s can not have  been v e r y l o n g , and even i f i t were l o n g enough t o a l l o w  s u f f i c i e n t weathering o f a g i v e n f l o w s u r f a c e , and s o l u t i o n of s i l i c a t o produce a s i l i c e o u s i n t e r l a v a sediment, one would expect t o f i n d some c l a s t i c m a t e r i a l d e p o s i t e d a l o n g w i t h t h e sediment, e s p e c i a l l y s i n c e t h e source would presumably be so near. Sea water and many streams c a r r y s m a l l amounts o f dis^s s o l v e d and c o l l o i d a l s i l i c a and might be proposed as a source of  the s i l i c a ,  independent o f t h e l a v a s .  Here a g a i n i t must  be remembered t h a t t h e b l a c k l a m i n a t e d sediment r e s t s d i r e c t l y on t h e u n d e r l y i n g f l o w w i t h o u t any a s s o c i a t e d c l a s t i c m a t e r i a l of  sedimentary o r i g i n .  Furthermore, c h e r t and j a s p e r a r e  f r e q u e n t l y a s s o c i a t e d w i t h b a s i c l a v a f l o w s , e s p e c i a l l y marine p i l l o w l a v a s , and i t h a r d l y seems necessary t o seek a source independent o f t h e l a v a s or the v o l c a n i c a c t i v i t y a s s o c i a t e d w i t h . them. Hot s p r i n g s r e l a t e d t o v u l c a n i s m f r e q u e n t l y c a r r y abundant s i l i c a  i n s o l u t i o n , e s p e c i a l l y i f they a r e a l k a l i n e ,  and they a r e a p o s s i b l e , s o u r c e , but an even s i m p l e r and more d i r e c t source can be suggested.  The c o n t a c t of hot l a v a  f l o w s w i t h sea water must r e s u l t i n v i o l e n t r e a c t i o n and qo  s o l u t i o n o f some s u b s t a n c e s .  V a n H i s e and L e i t h  experimented  w i t h the process i n c o n n e c t i o n w i t h t h e i r s t u d y o f t h e Lake S u p e r i o r sedimentary i r o n f o r m a t i o n s ; f r e s h b a s a l t s were heated i n a m u f f l e f u r n a c e to a temperature s u f f i c i e n t t o f u s e t h e e x t e r i o r and t h e n plunged i n t o s a l t water of t h e c o m p o s i t i o n o f sea water, t h e r e s u l t b e i n g a v i o l e n t r e a c t i o n , producing p r i n c i p a l l y sodium s i l i c a t e but a l s o b r i n g i n g a s m a l l  80  amount of i r o n i n t o s o l u t i o n ........ t h e r e was a l s o d u r i n g t h i s r e a c t i o n a tendency toward d i s i n t e g r a t i o n . There i s no doubt t h a t a r e a c t i o n s i m i l a r to t h i s one took p l a c e ' w h i l e some o f t h e l a v a f l o w s o f t h e Valdes Group were formed, f o r they c o n t a i n marine sediments and some o f them, a t l e a s t , must have flowed i n t o o r under sea water.  The P r e c i p i t a t i o n o f C o l l o i d a l  Silica:  S i l i c a i s l a r g e l y t r a n s p o r t e d i n t h e form o f a hydrop h y l l i c c o l l o i d t h a t i s not v e r y s e n s i t i v e t o e l e c t r o l y t e s . It  i s u s u a l l y n e g a t i v e , and t h e r e f o r e i s p r e c i p i t a t e d by  e l e c t r o l y t e s o r c o l l o i d s o f o p p o s i t e s i g n , but c e r t a i n n a t u r a l o r g a n i c c o l l o i d s tend t o s t a b i l i z e i t s c o l l o i d a l form, T a r r , L o v e r i n g , and Moore and Maynard experimented w i t h t h e p r e c i p i t a t i o n o f c o l l o i d a l s i l i c a from sodium s i l i c a t e solutions.  T a r r and L b v e r i n g obtained c o n t r a d i c t o r y r e s u l t s 1  but Moore and Maynard s work i s v e r y i n s t r u c t i v e .  Moore and  Maynard found t h a t sodium s i l i c a t e s o l u t i o n s hyd-rolyse t o c o l l o i d a l s i l i c a and sodium h y d r o x i d e , and t h a t t h e percentage hydrolysing increases with the d i l u t i o n of the s o l u t i o n . found t h a t f o r d i l u t e s o l u t i o n s o f sodium s i l i c a t e , which would c o n t a i n much c o l l o i d a l s i l i c a , c a l c i u m carbonate and sea s a l t s were t h e best p r e c i p i t a t e s o f s i l i c a , c h l o r i d e and potassium  sodium  s u l p h a t e b e i n g not so good.  They  81  i'or d i a l y z e d s o l u t i o n s o f sodium s i l i c a t e , t h a t i n which a l l t h e s i l i c a  i s solutions  i s i n t h e form o f a h y d r o s o l ,  sodium  c h l o r i d e at t h e c o n c e n t r a t i o n o f sea water, and sea water i t * s e l f were t h e most e f f e c t i v e p r e c i p i t a n t s , and both magnesium s u l p h a t e and c a l c i u m b i c a r b o n a t e were n e a r l y i n e f f e c t i v e . Time was found t o be an important f a c t o r , and i n no experiment was  a l l the s i l i c a p r e c i p i t a t e d .  These authors concluded  t h a t -a v a r i e t y o f types o f c o l l o i d a l s i l i c a can e x i s t i n nature and w i t h t i m e , a l l these types can be p r e c i p i t a t e d by e l e c t r o l y t e s o f t h e sea.  They a l s o concluded t h a t p r e c i p i t a t i o n o f  i r o n and s i l i c a from c o l l o i d a l s o l u t i o n by sea s a l t s  could  r e s u l t i n a banded f e r r u g i n o u s and s i l i c e o u s d e p o s i t i f t h e s u p p l y were i n t e r m i t t e n t . Davis found t h a t "when a s o l u t i o n  o f ammonium carbonate  i s c a r e f u l l y i n t r o d u c e d i n t o an aqueous suspension o f f i n e l y divided clay containing  a moderately s t r o n g content o f sodium  s i l i c a t e t h e r e i s a downward d i f f u s i o n o f t h e ammonium carbonate, l e a d i n g t o f l o c c u l a t - i o n o f t h e s i l i c i c a c i d and p r o d u c t i o n of a l t e r n a t e laminae o f f i n e c l a y and c l e a r g e l a t i n o u s  silica.  S u b s t i t u t i o n / : o f powered r e d s h a l e o r powdered c r y s t a l l i n e q u a r t z f o r t h e c l a y produced s i m i l a r laminae." (from Twenhofel) I t seems f e a s i b l e t h a t some o f t h e reagents used by Moore and Maynard, i n c l u d i n g s e a water i t s e l f , might r e p l a c e t h e ammonium carbonate i n D a v i s ' experiment, and t h a t a sediment made up o f l a m i n a t i o n s o f c o l l o i d a l s i l i c a and clayey c o u l d be formed i n the sea by t h e i n t e r m i n g l i n g  material  o f sea water  8S  and s o l u t i o n s o f sodium . s i l i c a t e c a r r y i n g f i n e l y clayey material.  suspended  I n p a r t i c u l a r , i t seems f e a s i b l e t h a t some  of t h e -volcanic f l o w s o f t h e Valdes Group c o u l d have r e a c t e d w i t h sea water, as d e s c r i b e d i n t h e p r e v i o u s s e c t i o n , t o produce sodium s i l i c a t e i n s o l u t i o n and f i n e l y d i v i d e d c l a y e y m a t e r i a l i n s u s p e n s i o n , and t h a t t h i s m i x t u r e r e a c t i n g w i t h f r e s h s u p p l i e s of sea water c o u l d have produced a f i n e l y l a m i n a t e d sediment which on c r y s t a l l i z a t i o n , perhaps under t h e i n f l u e n c e o f t h e s u c c e e d i n g l a v a f l o w , would form t h e f i n e l y l a m i n a t e d sediment as found on Quadra I s l a n d and near Menzies Bay.  The s m a l l amount o f carbonaceous m a t t e r (5 p e r cent)  may have been p r e s e n t i n t h e o r i g i n a l sea water, o r l y i n g on the l a v a s u r f a c e , o r i t may have been brought i n by t h e f r e s h s u p p l y of sea water which caused t h e p r e c i p i t a t i o n o f t h e sediment.  The C o n c e n t r a t i o n o f Vanadium i n t h e Seam: I t was p o i n t e d out t h a t d e r i v a t i o n of t h e vanadium  i n the  sediment from t h e l a v a would r e q u i r e a c o n c e n t r a t i o n of only ten times.  I t i s p o s s i b l e t h a t the vanadium was n o t o b t a i n e d  from t h e l a v a , but t h e l a v a i t s e l f o r magmatic s o l u t i o n s connected w i t h t h e v o l c a n i c a c t i v i t y seem t o be a s i m p l e and d i r e c t source.  I n any ease, the processes by which t h e  vanadium was c o n c e n t r a t e d i n t h e sediment a r e not o b v i o u s , e s p e c i a l l y s i n c e t h e form o f the vanadium  i s n o t known.  The  83  f o l l o w i n g processes a r e a l l t h a t have been considered by t h e author. A.  Syngenetic 1.  Concentration:  Physical  processes:  vanadium i n an i n s o l u b l e form, c o n t r i b u t e d d i r e c t l y from the l a v a s by weathering without e x c e s s i v e decomposition. 2.  C o l l o i d a l processes: (a) vanadium i n a c o l l o i d a l form and p r e c i p i t a t e d as were t h e o t h e r c o l l o i d ( s ) ; (b) vanadium p r o t e c t e d o r absorbed by t h e o t h e r c o l l o i d ( a ) ) and c a r r i e d down w i t h them.  3.  Organic  processes:  (a) by organisms u s i n g vanadium i n t h e i r l i f e processes. (b) by t h e r e d u c i n g a c t i o n o f l i v i n g organisms o r decaying o r g a n i c m a t e r i a l . 4* i . P r e c i p i t a t i o n from s o l u t i o n : (a)  from vanadyl s u l p h a t e s o l u t i o n s by CaCOg  (b) from a l k a l i carbonate and b i c a r b o n a t e and c a l c i u m b i c a r b o n a t e s o l u t i o n by l o s s of co . ; 2  (e) as c a l c i u m ( a l k a l i n e earth) vanadium salt(-s) which a r e a l l p r a c t i c a l l y i n s o l u b l e i n s l i g h t l y a l k a l i n e s o l u t i o n s such as sea wat e r . (d) as s u l p h i d e ^ s ) p r e c i p i t a t e d by H S i n s l i g h t l y alkaline solutions. g  Le) and B.  as i n s o l u b l e double s a l t ( s ) o f copper calcium.  Epigenetic Concentration: P r e c i p i t a t e d i n t h e seam from magmatic o r ground waters,  1.  from vana'die s o l u t i o n s by metals i n s o l u b l e vanadates.  2.  from vanadyl s u l p h a t e s o l u t i o n s by CaOO  3.  forming  from s l i g h t l y a l k a l i n e s o l u t i o n s as c a l c i u m ( a l k a l i n e ) earth) vanadium s a l t ( s )  4.  as i n s o l u b l e double s a l t s of copper and calcium.  5.  by p l a n t o r organic remains,  6.  c f . Bade'r's hypothesis p.  30.  by a b s o r p t i o n i n v e r y f i n e - g r a i n e d m a t e r i a l .  E p i g e n e t i c c o n c e n t r a t i o n i s v e r y u n l i k e l y because, a p a r t from t h e l a v a i t s e l f , vanadium i n a p p r e c i a b l e amounts i s r e s t r i c t e d t o t h e black laminated sediment. present  I t i s not  i n the copper amygdules n o r i n the h i g h grade c h a l c o -  c i t e l e n s , and t h e r e f o r e i t seems h a r d l y p o s s i b l e t h a t i t c o u l d have been i n t r o d u c e d a l o n g "with t h e copper. quartz v e i n s c o n t a i n no vanadium.  I t i s not present  The in  o t h e r amygdules i n the l a v a , n o r i n t h e l i m e s t o n e o v e r l y i n g t h e b l a c k seam.  As f o r l e a c h i n g from the s u r r o u n d i n g rock  by ground waters and p r e c i p i t a t i o n on c o n t a c t w i t h copper s a l t s i n the seam, t h i s process  i s always c o n f i n e d to zones  of o x i d a t i o n , and t h e r e i s very l i t t l e o x i d a t i o n i n the seam itself.  There are no obvious channels by which v a n a d i f e r o u s  s o l u t i o n s c o u l d have reached t h e seam, and i t w i l l be remembered t h a t t h e evidence f o r l a r g e amounts of vanadium i n hydrothermal  s o l u t i o n s i s not good.  I t i s very d o u b t f u l i f  5 jxer cent o f organic m a t e r i a l , even i f i t were not c a r b o n i z e d ,  85  c o u l d p r e c i p i t a t e 0.75  per cent to 2.16  per cent Y 0 . 2 5  The p o s s i b i l i t y of s e l e c t i v e a b s o r p t i o n of vanadium by the seam, accompanied perhaps by a slow m i g r a t i o n of s o l u b l e vanadium s a l t s through a c o n c e n t r a t i o n g r a d i e n t , has  not  been e l i m i n a t e d , but the r a d i c a l d i f f e r e n c e i n vanadium content between the b l a c k seam and t h e o v e r l y i n g l i m e s t o n e  i s too  great to be e x p l a i n e d on the b a s i s of s e l e c t i v e a b s o r p t i o n . The case f o r a syngenetic  o r i g i n i s good.  Physical  p r o c e s s e s , w i t h o u t chemical change, have to be r e j e c t e d however because t h e vanadium i n the seam i s r e a d i l y s o l u b l e i n d i l u t e a c i d s , whereas vanadium i n the l a v a i s s o l u b l e w i t h difficulty.  Vanadium i s not i n the q u a r t z , ( E l l s w o r t h and  Gunning) and t h e r e i s no c l a s t i c m a t e r i a l w i t h t h e v a n a d i f e r ous sediment.  The analyses g i v e n by E l l s w o r t h and  Gunning  show t h a t t h e vanadium cannot be p r e s e n t as a s u l p h i d e , because i f 98 per cent of t h e copper i s present as CugS t h e r e i s j u s t enough s u l p h u r (0.72 per cent) to be combined w i t h the copper (2.88 p e r c e n t ) .  A c t u a l l y about 5 t o 10 per  of the copper i s present as c o v e i l i t e and m a l a c h i t e ,  cent  and  p o s s i b l y as s u l p h a t e and s i l i c a t e , and some of t h e s u l p h u r i s a p p a r e n t l y present copper p r e s e n t  as SOg.  A l s o u n l e s s t h e r e was  enough  i n the s o l u t i o n s from which the vanadium was  p r e c i p i t a t e d , i n s o l u b l e double s a l t s o f copper and  calcium  w i t h vanadium c o u l d not have formed, s i n c e t h e l a r g e r p a r t o f t h e copper m i n e r a l i z a t i o n i n the seam i s o b v i o u s l y e p i g e n e t i c . P r e c i p i t a t i o n by c a l c i u m carbonate i s not l i k e l y because the  a s s o c i a t e d l i m e s t o n e c o n t a i n s v e r y l i t t l e vanadium.  Under  s y n g e n e t i c c o n c e n t r a t i o n then, processes 2 (a) and ( b ) , 3 (a) and  ( b ) , and 4 ( b ) , or some other process under 4 are  l e f t as p o s s i b l e methods o f c o n c e n t r a t i n g the vanadium i n the sediment.  Process 3 (b) o r d i n a r i l y produces s u l p h i d e s  which have, been e l i m i n a t e d because of t h e s h o r t a g e Of s u l p h u r . Organic processes cannot be e l i m i n a t e d , but t h e r e are o n l y a v e r y few s p e c i e s o f marine animals which are' known t o f i x l a r g e amounts o f vanadium i n t h e i r b o d i e s .  The  vanadiferous  sediment i t s e l f c o n t a i n s no r e c o g n i z a b l e f o s s i l s and o n l y about f i v e p e r cent of carbon and a t r a c e of phosphorous. C o l l o i d a l p r o c e s s e s , on t h e o t h e r hand, f i t i n very n i c e l y w i t h t h e proposed t h e o r y f o r the f o r m a t i o n o f the v a n a d i f e r o u s sediment.  Although the evidence f o r concentra-  t i o n of vanadium by c o l l o i d a l processes as d i s c u s s e d i n Chapter I I i s i n d i r e c t , many vanadium compounds a r e known t o assume t h e c o l l o i d a l s t a t e .  In f a c t the c o l l o i d a l s t a t e i s  "one capable o f a d o p t i o n by any s p a r i n g l y s o l u b l e substance." (Glasstone-Textbook  o f P h y s i c a l Chemistry.)  It i s highly  prob&ble t h a t the c o n t a c t of hot vanadium-bearing l a v a s w i t h sea water would p l a c e a p p r e c i a b l e q u a n t i t i e s of vanadium compounds i n t o c o l l o i d a l s o l u t i o n or t r u e s o l u t i o n , or both. C o l l o i d a l vanadium compounds might t h e n be p r e c i p i t a t e d by sea water o r o t h e r s a l t s i n s o l u t i o n , o r they might be c a r r i e d down w i t h c o l l o i d a l s i l i c a o r o t h e r p r e c i p i t a t i n g c o l l o i d s . Some vanadium compounds m a y b e absorbed  by other c o l l o i d s  and p r e c i p i t a t e d w i t h them, or they may he p r e c i p i t a t e d h-~ by o r d i n a r y c h e m i c a l p r o c e s s e s . The author r e g r e t s h a v i n g t o l e a v e t h e problem without v e r i f y i n g the h y p o t h e s i s w i t h f u r t h e r l a b o r a t o r y work. Samples o f t h e f r e s h l a v a of known vanadium content could be heated t o 1200° or 150O°C. i n a m u f f l e f u r n a c e and plunged i n t o s a l t water a p p r o x i m a t i n g t h e c o m p o s i t i o n of sea water, t h e m i x t u r e f i l t e r e d , and the f i l t r a t e for  s i l i c a and vanadium.  and r e s i d u e assayed  Methods of p r e c i p i t a t i n g the  s i l i c a and vanadium might be t r i e d .  F u r t h e r chemical  i n v e s t i g a t i o n and a n a l y s i s would p r o b a b l y r e v e a l t h e form i n which t h e vanadium i s p r e s e n t i n the sediment. Assuming t h a t t h i s c h e m i c a l - c o l l o i d a l h y p o t h e s i s f o r t h e f o r m a t i o n o f t h e sediment and t h e c o n c e n t r a t i o n of t h e vanadium i n i t were c o r r e c t , the t h i c k n e s s o f a g i v e n v a n a d i f e r o u s seam would depend on the amount o f m a t e r i a l put i n t o s o l u t i o n , o r s u s p e n s i o n by t h e r e a c t i o n o f l a v a w i t h sea water, and t h e amount o f t h i s m a t e r i a l which c o u l d be p r e c i p i t a t e d i n one p l a c e b e f o r e the s u c c e e d i n g f l o w of l a v a . It  i s not l i k e l y t h a t t h i s process would form d e p o s i t s l a r g e  enough to be commercial vanadium o r e , but a f t e r a l l most ore d e p o s i t s were formed by an u n u s u a l p e r s i s t e n c e of a s i n g l e p r o c e s s o r group o f p r o c e s s e s .  C o n d i t i o n s o f the s o r t  r e q u i r e d t o produce sedimentary magnesite  deposits, f o r  example, must have p e r s i s t e d f o r an u n u s u a l l y l o n g time t o cause t h e p r e c i p i t a t i o n o f t h e l a r g e magnesite  d e p o s i t at  88  Marysville, British Perhaps  Columbia.  i n a s h a l l o w b a s i n , p a r t l y surrounded by l a v a s  and p r e s e r v e d through many flov/s of l a v a , a commercial sedimentary v a n a d i f e r o u s d e p o s i t o f the^Quadra I s l a n d " might have formed*.  type  BIBLIOGRAPHY. ^  .01 THE OCCURRENCE OP VANADIUM.  General; 1.  Anon.:, Vanadium Ores Monograph, I m p e r i a l I n s t i t u t e , (LondJ 1924.  2.  A l l e n , M.A. and B u t l e r , G.M. Vanadium, A r i z o n a Bur.Mines, B u l l * No.115. 23 pp. S e p t . l , 1921.  3. " C l a r k e , F.W., L a t a o f Geochemistry, U.S.Geol. B u l l . 7 7 0 , pp. 722,723. 1924.  Surv.  4.  C l a r k e , F.W., and Washington, H.S. 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