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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 Thesis f o r the Degree of Master of Applied Science at the U n i v e r s i t y of B r i t i s h Columbia. A p r i l , 1944. Donald C a r l i s l e . ACKNOWLEDGMENTS. The author i s indebted to Dr. H.C.Gunning f o r d i r e c t i o n i n f i e l d and laboratory work and f o r help i n reviewing the l i t e r a t u r e , . a n d to Dr. H.V.Yferren f o r p r o v i d i n g f a c i l i t i e s f o r the spectroscopic analyses, a group of 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 the B r i t a n n i a Mining and Smelting Company Limited Scholarship, under h i s d i r e c t i o n . -The vanadium deposits were examined i n the spri n g of 1943 with assistance' of a grant from the Department of Geology. The author a l s o wishes to thank Mr.G.A.Dirom f o r assays and other, data on the Menzies Bay Deposits, and Dr . V i c t o r Dolmage and other members of the Geol o g i c a l Discussion Glub* as w e l l as the members of the Department of Geology f o r advice throughout the work. - The author has drawn f r e e l y on several standard reference works i n c l u d i n g , Ore Deposits, Lin,dgr;en; A T r e a t i s e of Inorganic Chemistry, M e l l o r ; Ore Deposits of the Western States, and P r i n c i p l e s of Sedimentation, Twenhofel. CONCEITS * Page The Problem . 1 Chapter I Vanadium: I t s H i s t o r y , Production, Uses and Chemistry. H i s t o r y «. ,^ 4 Production 5 "Us ©S •••••••• a V Chemistry 8 I I The;Natural Occurrence of Vanadium. In igneous Rocks 13 In a s s o c i a t i o n with Magnetite and Ti t a n i f e r o u s Iron Deposits ........... 15 In Minerals of Hydrothermal 0 3? i. x n •••••••••••••••••• 16 In Contact Metamorphic S i l i c a t e s . . . 18 In the Oxidized Zone of Sulphide Deposits. 19 Broken H i l l , Northern Rhodesia ... 20 Otavi Mountain Region, South-West A f r i c a . . . . 23 Vanadlnite Deposits of United States and Mexico ••• 24 Other Deposits • 25 In Sediments: (a) O r i g i n Probably Syngenetic 28 (b) O r i g i n Probably Epigenetic 32 Associated with Hydrocarbons, With Coal, Petroleum and Asphalt i t e 36 Minasragra, Peru 39 In Ground Waters. 41 Summary and Theory. - 4 3 I I I The Occurrence of Vanadium i n some Rocks and Minerals from B r i t i s h Columbia. ...... 47 Results of Spectrochemical Survey of some Rocks and Mi n e r a l s . 50 Chapter Page IV. The Deposits on Quadra Is l a n d and at Menzies Bay 55 Geological S e t t i n g of the Deposits 55 The Quadra Island Deposit. ........ 58 The Menzies Bay Deposit. . „ 60 The Genesis of the Ch a l c o c i t e . ........ 65 The Vanadiferous Sediment. 65 Spectrochemical Assays. 73 V. Theories of O r i g i n f o r the Vanadiferous Sediment. 77 Sources f o r the S i l i c a 78 The P r e c i p i t a t i o n of C o l l o i d a l S i l i c a • 80 The Concentration of Vanadium i n "fcti3 3©s,ni• ••••• ••••••••••••••••••••• 82 ILIUSTRATIOCTS. Opposite page. Figure I . Sketch of V e r t i c a l Wall of Open Cut of Main Showing, Quadra I s l a n d , B r i t i s h Columbia..... 59 P l a t e I . Flow contact 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. 55 P l a t e I I (a) P i l l o w l a v a , Hyacinth Bay, Quadra I s l a n d , (b) Folded vanadiferous sediment between la v a flows, Menzies Bay, B r i t i s h 0 o lumlD iq. ••••• •••••• •••••••••••••• 60 P l a t e 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) Slender lenses of 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. fa) The vanadiferous sediment. (b) (o.) (a) " " 66 TI II II It I! II •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 dark s i l i c e o u s m a t e r i a l containing vanadium, and associated w i t h extensive l a v a flows, was found on Quadra Island i n 1932. The discovery i s described "by E l l s w o r t h and Gunning, Last September, 1932, one of the w r i t e r s (Mr.Gunning) made a b r i e f examination of a property s i t u a t e d at the north 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 extracted some small pockets of a carnot i t e - l i k e mineral occurring i n crevices of the v o l c a n i c rocks. Ko more than traces of these c a r n o t i t e pockets remained, but specimens of the rocks were taken and .were subsequently tested f o r r a d i o a c t i v i t y by means of the alpha ray electroscope. None of these specimens shov/ed appreciable 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 consisted 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 lava flows ana c a r r y i n g some t n i n greenish copper s t a i n s . I t was suspected that t h i s carbonaceous streak mignt carry 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. Series Ho.11, p.139 . These authors state that one sample y i e l d e d over. 3 per cent V 2 0 5 . The SiOg content i s about 75 per cent most of which i s present as quartz. In t h i n s e c t i o n the s t r u c -ture i s suggestive of a c o l l o f o r m p r e c i p i t a t e , the quartzose 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 bodies, between .one-fifth and one s e v e n t y - f i f t h of a m i l l i -meter i n diameter. An assay shows 5 per cent carbon by c a l c u l a t i o n . They f u r t h e r suggest that since the rock 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 of the remains of vanadium-bearing plants or animals, or both, having s i l i c e o u s skeletons,, which were gradually deposited on the sub-merged lower l a v a . When the upper flow occurred, covering and heating t h i s t h i n bedded mixture of s i l i c a and organic matter, 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 organic matter driven o f f , . l e a v i n g f i x e d carbon behind. There i s also the p o s s i b i l i t y that some of the mat-e 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 lavas were, found also to contain vanadium. The deposit contains, 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 veins and replaces the f i n e -grained m a t e r i a l . With the onset of Y/orld War I I , vanadium again became a s t r a t e g i c metal and i n t e r e s t i n the deposit was r e v i v e d . In the meantime, prospecting i n the area had revealed s i m i l a r volcanic-sediment occurrences at the Copper C l i f f Group near Gowland Harbour and near Menzies Bay on the mainland of Vancouver I s l a n d , some ten miles west of the o r i g i n a l d i s -covery. These were found to c o n t a i n vanadium i n amounts up to 1.10 per cent V g0g. Therefore i n the s p r i n g of 1943, the o r i g i n a l deposits and those near Menzies Bay were exam-ined i n connection w i t h a f i e l d course given by the Department of Geology and Geography, at the U n i v e r s i t y of B r i t i s h Columbia. The deposit near Menzies Bay i s s i m i l a r to the one oh Quadra Island except that at Menzies Bay small lenses of dark, f i n e - g r a i n e d , p a r t l y r e e r y s t a l l i z e d f o s s i l i f e r o u s 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. In no place does the t o t a l width of the sediments exceed 8 inches, and i t i s u s u a l l y much l e s s than t h i s . The deposits i n the two places are not n e c e s s a r i l y at the same horizon, and, i n f a c t , do not l i e along the projected dip of the lavas from one another. The s t r u c t u r e of the interven-ing area i s not known. The lavas are mainly b a s a l t i c i n composition and are s i m i l a r over a l l the area-and f o r some distance north-west-ward along the coast of Vancouver I s l a n d . They are mostly amygdaloidal and many have p i l l o w s t r u c t u r e p oorly to very w e l l developed. The flows are from l e s s than 2 fe e t to more than 15 feet t h i c k and they dip from h o r i z o n t a l to 20° to the south-east i n the area near the deposits. A l l samples of these lavas taken from many parts of the area contain vanadium i n amounts as la r g e as.0.5 per cent. These deposits are too small to be considered vanadium ore. I t i s quite p o s s i b l e , however, that other l a r g e r and perhaps commercial deposits of t h i s type may occur in. t h i s or some other s e r i e s of l a v a s , and may have already been passed over and not recognized. Furthermore, no other occurrence of t h i s type has been described i n the l i t e r a t u r e . I t i s the object of t h i s t h e s i s , t h e r e f o r e , to review the chemistry and general occurrence of vanadium and then to describe the deposits and suggest a p o s s i b l e - o r i g i n f o r the vanadium i n them. CHAPTER I . VAKADIUM't ITS HISTORY, PRODUCTION, USES, AED CHEMISTRY. HISTORY. The discovery of a new metal "by A.M. Del Rio i n a plumb -if e r o u s mineral (probably vanadinite) from Zimp an, Mexico, wa announced by A.von Humbolt i n 1801. Del Rio named the metal erytnronium from the Greek erytiiros m red, because i t formed red s a l t s when treated with' a c i d . l o u r years l a t e r the supposed new metal was declared to be an impure chromium s a l t and erytnronium was abandoned.. In 1830, however, Is.G. Sefstrom described a new element which he found i n the i r o n ores of Taberg, Sweden, and immediately F.Wb'hler es 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 Del Rio' s ery tnronium,. Because of i t s b e a u t i f u l and various-coloured compounds, Sef.strom named tlie element "vanadium" i n honour of vanaciis, the b e a u t i f u l goddess of youth and love, who i s none other than F r e i a of Richard Wagner•s "Das Rheingold" and "Die Gotterdaromerung"* Elemental vanadium does not occur i n nature, but i t i s one of the more abundant of the minor constituents of. tne earth's c r u s t , f o r according to Clarke and Washington, i t i s more abundantly d i s t r i b u t e d i n the crust than i s n i c k i e , copper, z i n c , or. lead. I t occurs i n the sun and i n meteor-i t e s and. i s widely 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 minerals are the mixed sulphides occurring together as "Patronite 3 3 (approximately YS^) f several vanadates of which the most important i s vanadinite. P h g ( V 0 4 ) 3 Q l 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 mineral, formerly thought to be the same as r o s c o e l i t e . In 18 73, the pi Ice of impure vanadium was over 500 pounds s t e r l i n g per pound, and vanadium oxide sold f o r about 63 s h i l l i n g s an ounce. But even at 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 dyeing a n i l i n e black was found economi-c a l owing to the extremely small amount required. Widespread commercial development of vanadium began w i t h the discovery of the vanaaium ores at Minasragra, Peru, i n 1905. PRODUCTION. Peru has been the consistent leading producer of vanadium since 1907, except f o r those years f o l l o w i n g 1930 when a heavy export duty enforced by the Peruvian Government caused the mines to become i d l e f o r seve r a l years. The export duty was grea t l y reduced i n 1935 and mining was resumed. Peru and the United States are now the most important producers, w i t h South-West A f r i c a and Northern Rhodesia i n t h i r d and f o u r t h place r e s p e c t i v e l y . • v/ORIlJ PRODUCTION "OS VANADIUM IN ORES AMD GOB"GEE'IRATES • 1930-1940, IN METRIC TONS. 19,3.0. t o i , ^ g,, *35-. r54.t5-&<>'36. '37» ^58. 'o9» '40. Mexico. _ - - - - = 45 180 148 57 Borth,Ehodesia. 61 216 307 36 3 173 204 235 374 384 1 Peru 528 » - - 133, 67 161 583 826 1,016.1,254 S.'tf. A f r i c a . , - 503 445.305 18 34 176 547 591 557 514 428 united States. v 1 245 K ' 2 v 1 v 1 61 493 732 900 948 (1) Shipments; (2) Shipments from stock (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 Minerals Yearbook, United States 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. Vo0p- since 1935. . The output from Peru now comes mainly from secondary vanadates at the Mlnasxagra Mine owned by the Vanadium Corporation of America.. A r i c h e r product containing about 11 per cent V gQ5 i s sorted out and the low grade ore i s crushed and burned to eliminate the carbonaceous matter, 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., for reduction to fenovanadium i n the e l e c t r i c furnace. Most of the vanadium from south-western United States i s recovered from the vanadiferous clay mica by r o a s t i n g the ore wi t h s a l t , leaching the sodium vanadate w i t h water and pre-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 containing about 88 per cent VgO^ .. In northern Rhodesia the -vanadium i s r e g u l a r l y produced both as tiie oxide with over 90 per' cent V2O5 a n < i 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 averaging about 20 per cent V 0 and coming mainly from three mines was shipped to England and Europe. USES. Vanadium i s one of the most u s e f u l of the rare metals. A small amount i s used i n manufacturing. iigS0 4 where i t i s superior to platinum because the I n i t i a l cost i s lower and i t i s unaffected by most .of the platinum poisons, More vanadium i s used i n s p e c i a l a l l o y s , mainly ferrous 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 to the s l a g as fused Vo0p. and since i t has a very strong a f f i n i t y for n i t r o g e n , oxygen, and carbon, i t acts as a scavenger and as a carbide former. I t s e f f e c t i s very n o t i c e able, imparting a toughness to the a l l o y and i n c r e a s i n g the resi s t a n c e to repeated shocks or varying st r e s s e s . In amount not over 25 per cent, i t g r e a t l y increases the h a r d e n e a b i i i t y of s t e e l s , that i s , the ease w i t h which they can be hardened by heat treatment. Spring s t e e l s are improved m a t e r i a l l y by i t s presence, and high speed s t e e l s may contain as much as 1.3 per cent vanadium, or more. Before the war, the auto-mobile industry 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 also used i n Pharmacy and Therapeutics, i n making paint 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 glass i n d u s t r y where i t s high 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 is u s e f u l . CHEMISTRY. Vanadium w i l l combine w i t h almost anything i t meets, and therefore i t s chemistry i s very complex. Vanadium, along with niobium (» 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 t a b l e , N In many ways, then, i t i s chemically s i m i l a r to I P nitrogen and phosphorous which belong to the odd / \ "V \ s e r i e s of the f i f t h group, along w i t n a r s e n i c , I As Fb | antimony, and bismuth. There are, however, I Sb 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? i n p a r t i c u l a r , members of the 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 radi c a l s , whereas the elements of the odd s e r i e s form stable compounds of t h i s type, -Vanadium i s also a member of the s e r i e s across the 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 metal w i t h a s p e c i f i c g r a v i t y of 5.8 and melting at 1710°C. Unlike nitrogen or phosphorous, vanadium i s undoubtedly a metal. I t i s i n s o l u b l e In d i l u t e HOT or HgS0 4 or aqueous a l k a l i e s ; i t i s soluble i n HF and HNOg and i s r e a d i l y decomposed by fused a l k a l i e s . Vanadium forma compounds possessing the p o s i t i v e valence numbers 1,2,3,4,and 5, the two lower valences being basic and the two higher amphoteric, Vanadous i o n , V + +~ i s a strong reducing agent and vanadic Ion 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 ac i d s o l u t i o n to the t e t r a v a l e n t state and by powerful agents to vanadate. I t forms a complete series of oxides, the sa l t s of which are coloured as below? s a l t s of YgO VgO gor VO V2°3 V 2 0 4 or VQg o 2 5 Colour - Lavender or V i o l e t green blue orange or yellow remarks vanadyl: s a l t s vanadates, most Import-ant . Vanadium pentoxide, when i t acts as an a c i d i c oxide, forms a s e r i e s of 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 vanadic acids t Or the vanadic aci d N.3VG4 Pyro vanadic a c i d H4 VgO'? Metavanadic a c i d HVO.3 Tetravanadic acid -^2^4^11 iiexavanadic acid HV3OQ-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 + H g0 — T 2 0 g ~ -p 20H" At nigh temperature, however, tne o r t n o - s a l t s are stable and constitute; many of the vanadium minerals. See above. The a l k a l i pyrovanadates are soluble and the a l k a l i n e earth pyrovanadates are s l i g h t l y s o l u b l e . Metavanadatea of sodium, potassium, ammonium, barium, and lead are but s l i g h t l y soluble i n c o l d water, but s a l t s of other p o s i t i v e ions are solu b l e , and t h e i r colour i s generally yellow. Many vana-dates of the i r o n and aluminum family are but s l i g h t l y s o l u b l e . Ammonium metayanadate, M^VGg i s probably the most im-portant compound c o m m e r c i a l l y S o m e vanadium extracted from i t s ore by leaching w i t h strong hydrochloric a c i d , i s p r e c i p i -tated 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 solution w i t h excess of ammonium c h l o r i d e . Ammonium metava.nad.ate i s soluble i n hot water. In general the a l k a l i vanadates are more or l e s s soluble in water and a l l vanadates of the ''heavy metal3 are nearly i n s o l u b l e in water, but are r e a d i l y soluble i n strong a c i d s . Many c h l o r i d e s and sulphates of vanadium are soluble i n cold water. Some of"the more abundant vanadium minerals ares urthovanadat.es. Vanadinite, Pb 4(PbOl}(V0 4)3 i n s o l u b l e i n water -Uescloizite (Fb$ Zn)g(HH}¥0^ GuprodescIoizite(PbjZnjOu)g(OH) YQ% I I Carnotite Tyuyamunite . V o l b o r t h i t n Puclierite . Mottramite ) ) P s i t t a c i n i t e ) tfsbekite Turanite Rauvite Brackebuschit e Pyrovanaaate S P i n t a a o i t e Me t. avan ada t e a i Dechenite Rossite Metarossite Hexavanadates i Hewettite Me t ahewe 11 i t e) Pascoite Vanadovanadat eat Melanoyanaciat e Pernandinite K g0. 2II 20 3. Yg0 5 „ 3HgO CaO.U0 3.Y 20 5.nH 2G hydrous Cu,Ba,Ca,vanadate B1V0. (Pb,Cu} 2(0H)TQ 4 ? SQuG.YgO& -bHgO 5CuO.TgO.-5.2HaQ GaO ,2U0 3. 6Y 20 g. 20HgO (Pb,Mn,Pe) 3V 20 8.HgO ? 2CaO.Y 20 5.9H 20 Pb VgOg - sparin g l y soluble i n water. CaO„V 2Q 5.4H 20 CaG„V 20 5 e2H 20 vary i n s o l u b i l i t y , CaO^3:V205.9H20 2CaO.3Vg0 g.IlHg0 2CaO«,3V20,-.2V2O4 - r e a d i l y soluble i n a c i d s . CaO..V204 „ 5V 20 .14H20. " P a t r o n i t e " i s stated by Lingren to be an intimate mix-ture of three sulphides,,• VgSg.VgSg»VgS5^ the t o t a l being equivalent to VS. or VpS,-. bulvanite i s a cuprous orthosulphavanadate Cu„VS . Minasragrite i s a blue hydrous sulpliate vg04.3S0~„16HgQ. S i n c o s i t e i s a hypovana.datopiiospliate CaO.VgO^.PgG^. 5HgO. Ko 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 vanadiferous mineral occurring i n sandstone i n Colorado, formerly thought to be r o s c o e l i t e belongs to the hydrous mica group .of the clay minerals w i t h the general formula probably 2Kg0.-j5R0.8E203.24SIQ2-12H20, where Eg0 3 incliid.es alumina (Al^O^) and f e r r i c i r o n (PegOg). Presumably, vanadium oxide (Vg0 3) .replaces ALpOg and PegO^, Hll l e b r a n d and L u n d e l l state t The connection of vanadium w i t h f e r r i c aluminous s i l i c a t e s of rocks, taken i n connection w i t h the existence of the mineral r o s c o e l i t e , classed as a vanad-ium 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 fen: 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 reported as VpO-,, and not Vg0 5. (p., 352.) I t s condition i n matter of secondary o r i g i n such as c l a y s , limestones, 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 minerals. 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 cyc l e of vanadium i n nature and how the element may be concentrated. IN IGNEOUS ROCKS. 9 In 1898 Hi l l e b r a n d analyzed 5? igneous rocks from a l l over United States and found nearly a l l to contain vanadium i n amounts from l e s s than 0,004 per cent to 0.100 per cent V 2 O 5 . Pive syenites and granites contained no vanadium. He concluded that vanadium predominated i n "Less s i l i c e o u s igneous rocks and i s absent, or nearly so, i n those of high s i l i c a . " His suspicion that the heavier s i l i c a t e s or ferromagnesians contained most of 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 - Vo0,7v Mineral contained V ? 0 S Amphibole Gabbro .038 Amphiboles T062 " ,f .020 " .03 7 Pyroxenic Gneiss .083 M o t i l e .127 D i o r i t e A ,031 Amphibole .066 Quartz-mica, D i o r i t e .011 B i o t i t e .=048 Quartz Monzonite .012 B i o t i t e .066 Syenite Lamprophyre .033 Pyroxene .036 Hi l l e b r a n d e n o ucrh v a. n ad i urn noted that to account these minerals d i d not contain for a l l that Is present i n the 14 rocks, and suggested that another mineral perhaps l i k e r o s c o e l j t e may he present. Roscoelite. i s a greenish "brown vanadium mica reported w i t h goId-quartz veins in 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 vanadiferous a e g i i i t e s from Lihhy, Montana, containing almost 3 per cent and 4 per cent V 0., 2 b r e s p e c t i v e l y . These are i n high temperature, deep seated, almost pegmatitic veins i n an apatite pyroxenite 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 rocks and rock minerals. 4- f + + Clarke and Washington state that V i s widely d i f f u s e d i n igneous rocks but i s p r i n c i p a l l y i n the more femic kinds. They give the average vanadium content of igneous rock as .026 per cent VgO^ or .017 per cent vanadium. .Tost."estimates that the average vanadium content of eruptive rocks i s .018 per cent vanadium. These authors a l s o show that metamorphic rocks and the very f i n e - g r a i n e d sediments carry <Vanadium i n amounts s i m i l a r to the average igneous rock, but that limestone, limey s e d i -ment, arkose, conglomerate, and marl, are generally lower i n the metal. Vanadium reaches i t s greatest concentration in igneous products i n the u l t r a m a f i c rocks and t h e i r associated magnetite and i l m e n i t e deposits. 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 several Canadian t i t a n i f e r o u s i r o n ores to contain -vanadium from a trace to 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 iron ores were found to be vanadiferous, 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 Carol i n a and Tennessee concludes that "presence or absence of vanadium i n iron ores i s more c h a r a c t e r i s t i c of the province i n whicii the ores occur than of the v a r i e t y of ore occu r r i n g in i t , " The vanadium bearing t i t a n i f e r o u s iron-ores of Singhbhum and Mayur.bh.anj, I n d i a , have been studied by Dunn* The ores are r e l a t e d to Arcnean gabbro, quarts-aaorthosite and u l t r a -mafic rock. 'They contain from 0.59 to 8.80 per cent TgQ^, p a r t l y or e n t i r e l y present as a new mineral ^coulsoiaite"' whicii i s e i t h e r a vanadiferous magnetite or vanadiferous magheraite. Vanadium can be recovered from these vanadiferous magnetites during tne smelting of the iron, ore., In 1935. i t was reported from Russia that pure vanadium and nign grade forrovanadiurn p i g were being made from the t i t a n i f e r o u s i r o n ores of the U r a l s , and that ferrovanadi urn had been removed from the l i s t of needed imports. (Minerals Yearbbokl^j. 1936.) 16 In 1938, a plant fo r " t h e recovery of vanadium presumably from Iron sand was completed i n Japan by the Japan Iron Sana. I n d u s t r i a l Company. (Minerals Yearbook 1939). Many "other occurrences of vanadiferous magnetite have been reported. IN MINERALS OF HYDROTHERMAL ORIGIN. Here are Included occurrences i n which the vanadium i s generally believed to be of hydro thermal o r i g i n . R o s c o e l i t e , the vanadium bearing mica i n the gold-quarts veins of Colorado and C a l i f o r n i a , and the Engineer Mine at 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 , apparently f a i l s into t h i s c l a s s . At Jo a c n i n s t h a i , Bohemia, vanadium i s associated with u r a n i n l t e and pitchblende i n me sothermal s i l v e r - b e a r i n g i c o b a l t - n i c k e l veins. Vanadium occurs in.the r u t i l e of pneumatoiiti c a p a t i t e lodes. According to Hermanf vanadium i s r a r e l y found i n magma t i c sulphides, but i t i s widespread i n primary sulphides of hydrothermal and replacement o r i g i n , although the amounts are very small. Newhouse found from O.On to G.QOn per cent i n 13 out of 16-samples of p y r i t e , s p h a l e r i t e , and galena from widely separated l o c a l i t i e s i n United States and Europe. He concluded that although several sources probably c o n t r i -bute vanadium to the oxidizing.heavy metal deposits " i n most of the lower grade and probably some of the higher grade deposits of vanadium . .«, in the o x i d i z e d zones of lead and leao.-zinc-copper d e p o s i t s , the vanadium ... i s . Xargtly derived from small amounts present i n the o r i g i n a l suiphidea." 26 Mewhouse adds that H. Meritg reported vanadium i n gulpJaid© ore from Tsuraeb, South « est A f r i c a . Here term ant i t e , e nargite, s p h a l e r i t e , and other sulphides, as w e l l as c a l c i t e and dolomite, contain around 0.001 per cent vanadium, and p y r i t e may contain as much as 0.01 per cent vanadium. Galena from t h i s l o c a l i t y contains 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 0.01 to 0'i005 per cent vanadium states M o r i t z . Newhouse was unable to f i n d any p a t r o n i t e i n trie sulphides he examined, and believed that a l l the vanadium was present i n s o l i d s o l u t i o n . A.Stahl stated that "almost pure" galena from Tsumeh contained vanadium from 0.034 to 0.041 per. cent VgO^, and Wagner reports + 0.1 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 horizon i n the Bushveldt Complex. - .Note that t h i s i s an exception to Herman's s t a t e -ment. * • ' Sulphide samples from exposures of small sulphide bodies in the San Antonio Di s t r i c t were assayed f o r vanadium. The majority snowed a trace or nothing, but samples from one section d i d show the f o l l o w i n g vanadium percentages? 0.32, 0.32, 0.27, and 0.27. Spectroscopic a n a l y s i s , both at the U n i v e r s i t y of B r i t i s h Columbia and 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 in d i c a t e d small amounts of vanadium i n many sulphides* R.M. Thompson found spectro-s c o p i c a l i y that 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 proportion of s p h a l e r i t e s containing vanadium was greater i n "low teraperatur e" deposits than i n "high temperature" d e p o s i t s . I t should be pointed out that i n none of the above examples has i t been p o s s i b l e to prove that the vanadium i s of hydro thermal or :i g i n . I I COM'ACT METAMORPHIC SILICATES. Vanadium-hearing contact s i l i c a t e s are thought to be a source f o r the vanadium i n secondary ore at the San Antonio Mine, i n the Santa E u l a l i a . D i s t r i c t , Mexico. Here lead ana t i n . occur i n limestone-as replacement deposits of the contact metamorphic type, and vanadium ores have been formed by secondary concentration. The primary ore bodies, except f o r some replacement veins', consist of / skarn minerals ana ore which have formed on rhyoIite-Iimestone contacts and i n lime-stone i s o l a t e d from igneous rock- The common skarn minerals are garnet, epidote, 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 pos s i b l y hedenbergite. Vanadium was found in a i l but a few of unoxidiaed samples of the contact s i l i -cates. Although many ran but a trace or- b e t t e r , a small percentage snowed 0.23 per cent or higher, while one ran 0.50 per cent. Pour assays, not confined to any one secti o n of 19 the mine, snow tne I'ol lowing J 0.23, 0„27, 0,27, ana 0.50 per cent. Garnet-rich samples were the lowest i n -vanadium, and samples with fine-to-medium-textured, l i g h t coloured f i b r o u s s i l i c a t e s were hignest. . ,i.P. Hewitt • concludes: •whether vanadium replaces i r o n molecules in otherwise normal lime-iron 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 minerals may contain some vanadium. ' IN THE OXIDIZED ZONE SULPHIDE DEPOSITS. The most abundant type of commercially important vanadium deposit i s that 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 minerals belong to the vanadate c l a s s and the most important ares v a n a d i n i t e , d e s c i o i z i t e , 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 associated v/itn these minerals are pyromorphite, c e r u s s i t e , w u l f e n i t e , mimetite, aemimorphite, smithsonite, and l e s s commonly s t o l z i t e and hopeite. The vanadium minerals are confined to the o x i d i z e d zone. The combination of minerals i n any one deposit may be very complex and considerably . d i f f e r e n t from that i n another deposit n e a r -by. The deposits are usua l l y small but include two of tne larger vanadium producers of the world, Broken H i l l , Northern Rhodesia, and Abenab, South west A f r i c a . Broken H i l l , Northern Rhodesia: Vanadium i s associated with oxidized lead and zinc ores at Broken H i l l , about three hundred miles north-east of the V i c t o r i a F a l l s . Here a s e r i e s of metamorphosed sediments c o n s i s t i n g mainly of dolomite, 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 to a peneplain. The ore bodies are replacements of su s c e p t i b l e beds i n a N.W.- S.E. band and have the form of successive lenses dipping to the north conformably with the enclosing dolomite and having a p i t c h to the E.-N.E. Some of these ore bodies c o n s i s t i n g mainly of lead and zinc minerals with surrounding dolomite r i s e as small h i l l s or "Kop.jes" from 75 to 90 fee t above the general l e v e l of the peneplain. Weathered dolomite and c l a y with o x i d i z e d ore of lead and zinc and the vanadium minerals predominate to a depth of 150 f e e t . No. 1 ilopje was the source of many b e a t i f u l m i n e r a l o g i c a l specimens of pyro-morphite, 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 the ra r e zinc phosphates, t a r b u t i t e , hopeite*, and parahopeite. 35" According to P e l l e t i e r , the more important ore bodies always c o n s i s t of fa) a c e n t r a l p o r t i o n or core of massive s p h a l e r i t e and galena, enclosed w i t h i n (b) an envelope or s h e l l of ox i d i z e d ore u s u a l l y about 15 feet t h i c k , but t h i c k e r w i t h i n 100 f e e t of the surface. This o x i d i z e d ore c o n s i s t s of quartz, i r o n oxides, and hemimorphite w i t h l e s s e r amounts of zinc carbonates, lead carbonate, and vanadium minerals. I t i s very r i c h i n lead and z i n c , and has a jasperoid appear-21 ance* The r i c h vanadium ores are developed on the margins of tiie o xidized 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 dolomite, 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 oxidized ore aver-ages about 0.5 per cent vanadium. D e s c l o i z i t e , the main vanadium mineral,occurs i n f a i r l y large q u a n t i t i e s i n pockets up to an i n c h i n width, and as massive seams and i n c r u s t a t i o n s mixed w i t h i i m o n i t e . Vanadinite i s much l e s s abundant than d e s c l o i z i t e . In parts of the dolomite 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 breccias? m e t a l l -i f e r o u s s o l u t i o n s have percolated through these breccias and reacted w i t h the phosphorous of the bones to produce pyro-morphite and the rare phosphates. Vanadinite i n b o t r y o i d a i masses accompanies the pyromorphite. - i n 1931, Walker reported the reserves at Broken M i l l as 955,000 tons of oxides averaging 0.9 per cent VgOg, and 38,000 tons averaging 3.5 per cent V^O^. No doubt the vanadium was deposited by c i r c u l a t i n g ground waters, 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 primary sulphides, 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 that to account f o r the average content of 0.5 per cent vanadium or more i n the ox i d i z e d ores from the primary sulphides as source, would re q u i r e a concentration of at l e a s t one hundred times. There are, 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 think i t reasonable that 99 tons of primary ore should have been removed by oxidation f o r every ton of o x i d i z e d ore. He suggests that i f h i s three samples ar.e .representative and i f no other primary vanadium mineral i s segregated somewhere i n the sulphide body u t h e vanadium was o r i g i n a l l y contained In the surrounding sediments of the Broken H i l l S eries and has migrated by s o l u t i o n i n the surface ground waters to the o x i d i z i n g sulphide bodies which by electrochemical a c t i o n , p r e c i p i t a t e the vanadium i n the form of vanadates. M' . Vanadium i n d i l u t e s o l u t i o n as soluble vanadates or vanadic acid 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 zinc on contact w i t h o x i d i z i n g lead and zinc ores or the strong s o l u t i o n s near these ores. Skerl's hypothesis i s p l a u s i b l e , but on the basis of only three analyses of -the primary sulphides and of no analy-ses of the surrounding Broken H i l l Series sediments, and i n the face of evidence f o r vanadium from hydrothermal sources i n p a r t i c u l a r the p a t r o n i t e i n galena from Tsurneb i n South-West A f r i c a , i t hardly seems con c l u s i v e . S k e r l mentions the long period of peneplanation which must have followed the formation of. the primary sulphide ores. 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 bodies by oxida-t i o n and erosion, vanadiferous. s o l u t i o n s from the s l i g h t l y vanadiferous decomposing ores might have found t h e i r way to the ore bodies that are now mined and have p r e c i p i t a t e d vanadium on the margins of these bodies? 23 / ,30. u t a v i Mountain Regions" South-l/est A f r i c a . Vanadium deposits occur {1) i n oxidized zones of sulphide ore bodies and (2) as fre e vanadium ores without sulphides. The sulphide ore deposits of the Otavi Mountains are hydro thermal replacements i n a s e r i e s of folded limestones and dolomites of Paleozoic or Pre-Cambrian age. The main primary ore minerals are p y r i t e , galena, 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 only large sulphide body, i s a very r i c h replacement deposit surrounding an a p l i t e stock intruded into the dolomite. The ore minerals i n parageneti c order are, p y r i t e , "bornite, s p h a l e r i t e , enargite, t e t r a n e d r i t e , galena, and hypogene c h a l c o c i t e . To a depth of about 350 f e e t , however, the ch a l c o c i t e i s e n t i r e l y super-gene , and oxidation has extended to 60Q f e e t . - By oxidation of these many sulphide bodies and the form-a t i o n of vanadates of lead and z i n c , numerous deposits of vanadium ores have "been formed along 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 mineral 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 small amounts. iio r a d i o a c t i v e minerals are found w i t h the vanadium. The second and more valuable type of vanadium d e p o s i t s i n t h i s region are the "sand-sacks" and ore-bearing pipes or sink-holes, Band-sacks are lumps of vanadium minerals mainly d e s c l o i z i t e i n red sand f i l l i n g numerous pot-holes and c a v i t i e s i n the dolomite. Some of these are purely surface deposits but others extend, down in t o the ore-bearing pipes or sink-holes i n which d e s c l o i z i t e and minor amounts of other minerals f i l l vugs and i n t e r s t i c e s i n cave limestone b r e c c i a or en-crust the dolomite. The ore i s almost e n t i r e l y free of sulphides. • Abenab and U r i s are the two la r g e s t pipe-deposits. Abenab i s about 200 feet long and 120 feet wide at the surface and has been one of the l a r g e s t world producers since the middle twenties. 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 f r a c t u r e zone. The ore minerals, mainly d e s c l o i z i t e occur i n a red cave limestone along w i t h considerable c a i c i t e . Vana-d i n i t e .becomes important i n the lower l e v e l s . Several small s o l u t i o n c a v i t i e s nearby contain vanadium minerals and f i l m s of d e s c l o i z i t e have formed along some bedding planes i n the dolomite. In a l l these deposits,as at Broken H i l l , the o r i g i n of the vanadium i s i n doubt. Both S t a h l and Mo r i t z found vanadium i n primary sulphides and S t a h l believes that the ores are a 30 concentrate from o x i d i z i n g primary Sulphides. Clarke doubts i f deposits of any s i z e could be formed i n it h i s way and. sug-gests a leaching of surrounding sediments by meteoric waters and p r e c i p i t a t i o n at the outcrops of lead-bearing d e p o s i t s . Vanadinite Deposits of United States and Mexicot Deposits of t h i s type also occur i n Jforth America, p a r t i c u l a r l y i n the southern region of the Rocky Mountain 25 Chain, i n Arizona, Hew Mexico, Nevada, C a l i f o r n i a , and i n north and c e n t r a l Mexico. The deposits may also contain s i l v e r , molybdenum, and tungsten, i n f a c t , nearly a l l of them contain w u l f e n i t e . They almost i n v a r i a b l y carry 0.1 to 0,6 per cent V-0 . Hess suggests that vanadium, ar s e n i c , and phosphorous with l e a d , z i n c , and copper, are present as i s o -rnorphous mixtures i n varying proportions. Most of these d e p o s i t s , l i k e those of South-West A f r i c a , are small. A group of them occurs near Cutter, Hew Mexico. At the . Shattuck Mine, Bisbee, 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 to 1.5 per cent V-gOg* A large deposit c o n t r i b u t i n g to the present vanadium production and t y p i c a l i n i t s mineralogy i s the complex.de-p o s i t of the Mamraoth-St.Anthony i n P i n a l County, Arizona. S i l v e r , l e a d , molybdenum, vanadium, and gold are recovered. Galena, s p h a l e r i t e , and some molybdenite occur as hypogene vein minerals i n brecciated shear zones i n g r a n i t e and r h y o l i t e . The gold i s secondarily''enriched and minerals i n the o x i d i z e d zone include l i m o n i t e , hematite, angles!te, c e r u s s i t e , l i n a r i t e , Vbra.ehiantite, malachite, azurit-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 , cuprodesol.oizite, and p y r o l u s i t e . Oxidation extends down to about 800 f e e t . Other Depositst S i m i l a r deposits occur i n Argentina, B o l i v i a , and Peru, and almost every oxidized ore tested i n Argentina and B o l i v i a by one i n v e s t i g a t o r , contained vanadium although the amount was usually small. (Mewhouse p.210). Deposits at Talcuna, C h i l e , are associated with copper veins. The Spanish deposits at Santa Marta, which supplied much of the ea r l y vanadium ore, were also of the vanadinite type. here clays cut by the veins 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 smithsonite, hydro-z i n c i t e , and l i m o n i t e , are associated with the lead-si. no 37 deposit of Djebba i n T u n i s i a . I t i s suggested that the vanadium could be derived from phosphatic limestone which the mineralized f a u l t 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 lead mine of B l e i b e r g , 31 A u s t r i a , At the lead deposits of Suleiman S a i , i n Kazakstan U.S.8.K., vanadinite., and wulf enite with c e r u s s i t e and c a l a -mine occur i n the oxidized zone of v e i n - l i k e lenses i n Devonian and Carboniferous limestones and sandstones, Wulfeni te was formed e a r l i e r than v a n a d i n i t e , and both miner-a l s encrust the o x i d a t i o n products of galena. I t i s suggest ea that the primary source of the molybdenum and vanadium was probably .the country rock or else the protore zone of the dep o s i t s , the transfer being effected by surface waters. Jost advances the hypothesis that the vanadium i n the vanadinite deposits i s derived from l a t e r i t i c and other r e s i d u a l s o i l s . ITewhouse points out that vanaaium. has con-centrated i n these s o i l s because the compounds formed are l i k e those of i r o n and. aluminum, i n s o l u b l e ana nonfugitive ana furthermore, the bulk of oxidized lead deposits contain-ing vanadinite are formed i n limestone, dolomite, snd g r a n i t i c rocks, the lowest in vanadium of a l l rocks. In these rocks, however, the. vanadium may be i n a more r e a d i l y soluble form, and vanadium i s known to migrate i n meteoric waters. The vanadium ores at the San Antonio Mine mentioned •. gn; 'page - 18, were formed by,secondary concentration 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 coatings surrounding a l l types of rock fragments to s t r a t i f i e d man-ganese muds i n which y e l l o w i s h vanadium-bearing streaks are i n t e r c a l a t e d between l a y e r s of wad or zones of gypsum."' Minor amounts of vanadium also occur i n s t r a t i f i e d beds of darkish-yellow sandy minerals, and in c a l c i t e coated v an ad i n -i t e s t a l a c t i t e s . A l l these ores have been p r e c i p i t a t e d , i n "limestone 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 minerals are vanadinite 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 sulphides 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-tex-tured 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 reorganization of these vanadium-bearing s i l i c a t e s as w e l l as vanadium-bearing sulphides. I l l SEDIME1-TTS". (a) O r i g i n .Probably Syngenetlc. Vanadium i s found i n c l a s t i c and chemical sediments of terrigenous*, .organic, and v o l c a n i c o r i g i n , il Jost states that, on the average, limestones and dolomites contain l e s s than ,001 per cent vanadium; clays and shales contain about .01 per cent; ...bauxites and l a t e r i tes contain about .03 to .05 per cent; and r e s i d u a l i r o n and manganese ores contain from .04 to 0,10 per cent , Bituminous shales, coals,and bituminous phosphates and a s p h a l t i t e are highest w i t h as much as 0.70 per cent vanadium. The minette i r o n ores of Lorraine and Luxembourg are a p o s s i b l e , or a c t u a l , commercial source of vanadium. In 1935 a report i n tne Metal B u l l e t i n (Londonj Dec. 6, 1935, p.15) stated that the Hochling Iron and S t e e l Works a f t e r experi-menting i n the. e x t r a c t i o n of vanadium from -Prench minette ores have now succeeded i n obtaining i t from South Baden o o l i t i c ores. The presence of vanadium i n the Kerchensk o o l i t i c i r o n ores i n the Crimea was noted i n 1928. These ores contain 1,00 to 1,25 per cent PgO^; 0.05 to 0.12 per cent As g0.y and 0.03 to U026 per cent V. u . In 1933, vanadium was being saved 2 5 from the slag obtained i n r e f i n i n g these ores, Prench bauxites and l a t e r i t e s are vanadiferous and i n 1939 enough vanadium to supply one-third of I t a l y ' s annual requirements was being recovered from the c a u s t i c soda sol u -t i o n employed i n the Bayer process of r e f i n i n g bauxite. (Minerals 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 large proportion 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. They nearly always contain titanium. vanadium i s reported i n clays from Japan '-hi ana. a great many other places. (Mellor, p.. 717). 3osa zza states that the vanadium content of olays i s from a chemical trace to about 14 per cent vanadium. Palmer studied eight 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 (ceramics) containing small amounts of i n s o l u b l e vanadium and molybdenum compounds. I t was found that during f i r i n g , soluble s a l t s of these elements were formed -which l a t e r appeared as a green-yellow efflorescence on the f i r e d c l a y . The efflorescence i s thought to be c h i e f l y due to a l k a l i vanadates. A u s t r a l i a n and South A f r i c a n clays generally contain l e s s than 1.0 per cent vanadium, and t h i s i s not water soluble u n t i l weathered considerably or heated to 1,000° 0. or more. I t can then be extracted with hot water. Molybdenum occurs l i k e w i s e but to a l e s s e r extent. The same efflorescence was noted i n r e -f r a c t o r y goods made from clays from 'parts of England and from Mew South v/alea. Highly vanadiferous clay i s associated w i t h the oxidized lead ores of Santa Marta, Spain. 61 S c h r e i t e r f i n d s that bleached spots i n red shales i n Germany contain as much as 14.93 per cent VgOa ana 1.4 0 per cent VgOg. i n their, dark centre. He suggests that the lower oxides of vanadium reduced the FepO- to PeQ, ana that t h i s process may e f f e c t much larger- parts of a given rock s e r i e s . The bleached rock contained from O.i to 0 . 2 per cent Y pO H. 30 f3 Garter describes s i m i l a r vanadiferous modules In tiie permian red marl beds of South Devon, The nodules, appearing as dark cores surrounded by aureoles of greenish c l a y , are as much as eight inches i n diameter. They are composed of coarse concentric 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 dark bands, and are not r e l a t e d to f o s s i l s . They are e s s e n t i a l l y s i l i c e o u s clayey m a t e r i a l with the black bands running 13.96 per cent vV o0 probably present as oxide, and the white bands w i t h 1,91 per cent VgO^. They are r a d i o a c t i v e . Sediments r i c h i n organic matter p a r t i c u l a r l y marine bituminous deposits and slimes are noted f o r t h e i r high' vanadium content. A carbonaceous shale bed more than 30 fe e t t h i c k i n the province of J a u j a , Peru, contains about 1,0 per cent Vr>0g mainly i n phosphatic nodules. 40 Bade 1 i n d i s c u s s i n g the cause of enrichment of vanadium i n organic sediments suggests that the vanadium i s derived from the weathering and leaching of the parent rock and i s probably used by p l a n t s rather than 'animals, he states (Annot •Bib., S'.A. Geol., 446. 193?,) that i n a l l organic 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 p r e d o m i n a t e T h e y are thus mainly formed by plant remains. There are a series of complex organic compounds of vanadium with the a l k a l o i d porphyrine. The vanadium i s derived from weathering rocks which, under a r i d c o n d i t i o n s , are always vanadiferous. A search of the l i t e r a t u r e on minor elements and plant n u t r i t i o n reveals that vanadium may be stored by some p l a n t s ; that- i t Helps some plant s s l i g h t l y and over c e r t a i n concen-t r a t i o n s i s i n j u r i o u s j but that on the whole i t seems to have l i t t l e e f f e c t on plant growth. On the other hand, P h i l l i p s discovered marine animals containing vanadium,, He found that f o r a species of holothurian from the Tortugas 0.123 per cent of the weight of the e n t i r e animal d r i e d at 110°G was vanadium. He reports also that M, Henze (zPhys. Chem. 79, 223) found an asc.idian i n the Bay of Eaples w h i c h 63 c a r r i e d vanadium i n the blood. Vinogradov reviews some Systematic i n v e s t i g a t i o n s " showing that about ,00001 per cent vanadium i s usual l y found i n various t e r r e s t r i a l and marine animals and p l a n t s . He believes that the vanadiferous species of A s c i d i a and Holofhuria obtain t h e i r vanadium from marine muds, which contain ,03 per cent and more vanadium. He states* On tne other hand, A s c i d i a , which forms very s p e c i f i c biocenoses on the bottom of many g u l f s and con t i n e n t a l seas, a f t e r t h e i r aeath set. up conditions f o r the l o c a l enrichment i n V of the surrounding sediments. Therefore i t may be supposed that o i l s and bitumen o r i g i n a t i n g from o i l containing vanadium are connected w i t h s i m i l a r sediments of the sea, wi t h c e r t a i n f a d e s of the bottom, formerly 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 concentration of vanadium. Phosphorous may be p a r t l y replaced by vanadium i n the metabolism of some animals but i t should be remembered i n considering t h i s hypothesis that although vanadium i s c l o s e l y r e l a t e d to phosphorous, i t does not belong to the same sub-group of elements cont a i n i n g phosphorous and that many of. i t s p h y s i c a l and chemical properties 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 organometallic compounds wi t h hydrocarbon r a d i c a l s , whereas phosphorous does. This does not mean that acid r a d i c a l s containing vanadium could not react w i t h Organic- compounols which are not hydrocarbons. ( c f . Baderfe hypothesis.) (b) O r i g i n Probably iiipigenetio The most valuable type of vanadium deposits i n sedimentary i ocxs, apart from the- unusual deposit at Minasragra, are those in Mesozoic Sandstones, i n South-Western United States and s i m i -la r deposits elsewhere i n the world. The vanadium i s found c h i e f l y i n a vanadium-bearing hydrous mica formerly 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 yellow potassium-uranium vanadate. Vanoxite, tyuyamunite, uvanite, v o l b o r t n i t e , h e wettite, and mettahewettite also occur, 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 shaley m a t e r i a l s . *?Z, f^/4-7, <?#,<?-?,-5-0,-51, S3, inj.,sy, In United States these sedimentary deposits are of two m i n e r a l o g i c a l types: • (1) The "r o s c o e l i t e " = vanadium clay mica d e p o s i t s . (2) The c a r n o t i t e d e p o s i t s . both these types are found In Colorado, Utah, and A r i z o n a . i n nearly h o r i z o n t a l sedimentary beds and are confined to three 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 Entrada sandstone ( J u r a s s i c ) , and the Morrison formation ( J u r a s s i c ) . The ore bodies are very spotty and form i r r e g u l a r tabular 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 confined to one bed. They contain from'a few tons to many t no usand tons of ore. Commercial ore contains from 1 to 5 per cent VgOg and us u a l l y l e s s than 1 per cent 'DgOg • '"^'rie Shinarump conglomerate also contains some sandstone that i s p a r t l y formed of grains of a s p h a l t i t e . This a s p h a l t i t e contains 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 clay mica type with 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 in the upper 10 to 15 f e e t of the Entrada sandstone and i s usually accompanied above or below, or both above and below, by a layer of li g h t - g r e e n sandstone coloured by a f i n e l y d i s -seminated chromium "mineral, (mariposite - Hess). The Morrison formation, made up of sandstone, conglomerate, and shale, con-tain s many more deposits than the other two formations. These are the famous c a r n o t i t e deposits although a c t u a l l y they con-t a i n s e v e r a l times as much vanadium as uranium and radium. The vanadium i s apparently mainly present as the hydrous clay mica, but very r i c h l o c a l concentrations of c a r n o t i t e supplied ft-early a l l of the early vanadium production. The ore bodies i n the Morrison formation are i n large sandstone'lenses i n a single s t r a t i g r a p h i c zone about 60 feet t h i c k i n the lower h a l f of the formation. The sandstone i n these formations i s extensively cross-bedded, c o n s i s t i n g of a complex assemblage of lenses and channel f i l l s . E o s s i l l o g s , leaves,- and reeds are scattered throughout as i f d r i f t e d i nto place. • Ore' -minerals are found impregnating the sandstone and re p l a c i n g the f o s s i l p l a n t s i n and adjacent to the ore bodies. In a d d i t i o n , some vanadium has beeh absorbed by shale pebbles and clayey m a t e r i a l . The vanadium-bearing hydrous mica i s both u n i f o r m l y disseminated and concentrated i n sheets along bedding planes or i n r o l l i n g zones up to several inches t h i c k c u t t i n g across the bedding. Where m i n e r a l i z a t i o n was strong, some quartz grains were p a r t l y or e n t i r e l y dissolved l e a v i n g r e s i d u a l vanadiferous s h a l e - l i k e seams. The margins.of an ore body may be sharp o r may blend g r a d u a l l y into barren sand-stone. Where they are sharp, a 5 curving s h e l l of - highly?.vana-di f e r o u s sandstone u s u a l l y has formed around much of the ore -body. The boundaries are sometimes so sharp that they cut across lenses: of. shale 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 side and unmineralized on the other. Although the ore bodies .are r e s t r i c t e d to c e r t a i n s t r a t i g r a p h i c zones, they are apparently not r e l a t e d to f o l d s or f r a c t u r e s i n the sediments except i n four places. P i s h e r s t a t e s : The o r i g i n of the ore and the f a c t o r s that 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 ore minerals impregnate sandstone and i n t h e i r present form were deposited from s o l u t i o n s a f t e r the sands were deposited, but the nature of the s o l u t i o n s i s not understood, nor i s the immediate source of the metals apparent." and further-: The primary ore minerals are thought to have been Introduced into t h e i r present p o s i t i o n not long a f t e r the sands were deposited. I f t h i s i s t r u e , the metals were probably transported and deposited 35 by ground waters, and the ores were prob-ably 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 conditions that now cannot be d e f i n i t e l y recognized. This hypothesis probably requires at l e a s t three separate periods of ore deposition, to account f o r the ore i n the Shiharump, Entrada, and Morrison formations." .Carnotite also occurs at Mauch Chunk, Pennsylvania, i n a 40 foot l a y e r of course-grained conglomerate. The conglomer-ate i s cemented with s i l i c a and c a l c i t e , and the c a r n o t i t e i s thoroughly but unevenly d i s t r i b u t e d throughtout, f i l l i n g open-ings and cracks and r e p l a c i n g the calcareous cement. I t i s doubtless 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 of'deposit ion where streams t r i c k l e out of cracks at the present time - i t probably does not extend below the ground water l e v e l and may be r e s t r i c t e d to a very shallow zone." " Wherry suggests that primary vanadiferous ferromagnesian minerals concentrated as r e s i d u a l s during the decomposition of c r y s t a l l i n e rocks i n the surround-ing region under a r i d conditions may now be supplying vanadium to the ground waters. According to Hess (Ore Deposits of the Western Stat.es, p.474i-Recently t h o r i a n i t e has been discovered at Easton, 30 miles away, and i t seems probable that the Mauch Chunk c a r n o t i t e may be a weathering mineral from unranium bearing v e i n l e t s . *'" Ca 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 minerals, i n c l u d i n g d a v i d i t e , fergusonite, and monazite, occurring with, ferruginous lodes at Radium H i l l and Mount Pa 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 coal bed cut by quartz veins near Denver. C a r n o t i t e has been reported as a t h i n dusty coating on cracks i n andesite north of Pioche, 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 miles south of Sloan, Nevada; i n cracks i n t u f f at the west end of the Vulture Mountains, Arizona, and Tyuyamunite i n t i n y v e i n l e t s i n sandstone at Bisbee, Arizona. (Hess, Ore Deposits of the Western States, p. 474.) Vanadium has been detected i n the Jiupferschiefer of Mansfield, Germany, where i t i s thought to be epigenetic. ASSOCIATED WITH HYDROCARBONS. With Coal, Petroleum, and A s p h a l t i t e . We have seen that organic sediments are very l i k e l y to contain vanadium. Even l a r g e r amounts are found i n coals and the ashes of c o a l s . Sason, i n h i s d i s c u s s i o n of De Goyler's paper reported a c o a l bed i n Nueva Leon which ca r r i e d - 5 per cent ash, of which 25 per cent was VgOg. He found other coals from Colorado, V i r g i n i a , and C e n t r a l , Eastern, and Southern States to carry from 0.05 per cent to 0.10 per cent vanadium. Russian workers have i n v e s t i g a t e d t h e i r coals rather thoroughly f o r vanadium'. Zilbermintz found a very low vanadium content i n most coals 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 the eastern slope of the U r a l s , contained from an appreciable amount up. to 5 per cent of the ash i n some* oases,.; Zilbermintz believes the vanadium was probably introduced a f t e r the c o a l was deposited, however, ( c f . Bader's hypothesis, p. SO) 79 Vorobiev found seven Upper S i l u r e a n coals from the A l a i and Turkestan Mountains to have ash contents from 9.25 to 27.77 per cent, of which from 0.01 to 1.30 per cent was VgOg. M.iroplosky^iscusses the occurrence of vanadium i n the K a u s t o b i o l i t h s (cf« Grabau: c a u s t o b i o l i t h = sediment formed by d i r e c t accumulation of-carbonaceous plant m a t e r i a l e.g. peat and coal) of T a r t a r i a , and Orlov discusses i t s occurrence i n a n t h r a x o l i t h c o a l s . Many other occurrences are reported. ( M e l l o r p. 718.) E.S. P o r t e r believes that the vanadium i n peat, l i g n i t e , and coal,, was a constituent of the plant l i f e from which these 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 asphalt 68 66,67,6?,7a.7',75~. was discussed by B i r d i n 1914, and by many others, and i t was reported i n 1937 that some 50,000 pounds of VgOg were being recovered annually from b o i l e r and stack soot of ships burning Venezuela and Mexican o i l f o r f u e l . Much of t h i s was recov-ered by'various contractors on the east coast of the United States who cleaned the b o i l e r s of these ships during t h e i r c a l l s there. The soot runs from 2 to 34 per cent VgOg, the 38. r i c h e r recoveries being, made by tankers operating i n and near maracaibo Lake, Venezuela. Soot from Mexican o i l aver-ages around 6 per cent ^gOg* (Minerals Yearbook, 1937.) Even before petroleum was known to c a r r y vanadium, the metal was found i n asphalt Ites, in. many parts of the world, notably i n United States, Peru, Cuba, Argentina, and Sweden. The v e i n asphalt i t es of Peru have been c a l l e d " coal Veins"* They are confined to sedimentary rocks, p r i n c i p a l l y limestones, and are found as continuous l e n t i c u l a r f i s s i v e veins c u t t i n g across the bedding and as f l a t s , or mantos. The asphalt-it es are both a n t h r a e i t i e and bituminous, and-the ash content i s from 1 to 47 per cent, of which- 0.9 to 15 per cent i s vanadium. Baragwanath considers that the asphalt i t e s formed from under-l y i n g pools of petroleum which, contained the vanadium. The asphalt i t BS-:-^  of United S t a t e s , p r i n c i p a l l y i n Oklahoma, Nevada, and Arkansas-, are i n veins i n - h ighly folded s t r a t a and ca r r y about 0.1 per cent ^gOg* 'Secondary c o a l veins i n Southern Alps contain 1.31 per cent vanadium. Hummel suggests that the coal, was- leached from o v e r l y i n g chalk beds, the vanadium being o r i g i n a l l y concentrated 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 reported from the Eukul Prefecture, Japan. Both the c o a l and"' thie sediments above and below contain from 0.01 to 0.03 per cent V_0_. An a n t h r a c i t e from Hei'jo, Japan, , 2 3 contains 0.091 per cent V 0 . 2 3 I t i s suggested that the vanadium i n asphalt i t e s i s present,as a sulphide. Mmasragra, Peru: - , The ^most important vanadium deposit i n the world i s at Hihasragra, near Quisque, Peru. There'the mixed, vanadium sulphide p a t r o n i t e was discovered i n a s s o c i a t i o n with a k i n d ' of a s p h a l t i t e * Minasragra sis on the eastern slope of the main Andes, between two ranges trending 1.1.!• and formed of Mesozoic limestone. The deposit i s i n red gypsiferous shales i n the upper part of a s e r i e s of shale and. limestone which dips 45° S.W. lumerous dikes and igneous masses from quartz porphyry to diabase i n composition intrude the sediments and the ore body occurs at the point of greatest concentration of dikes. The o r i g i n a l deposit was a l e n t i c u l a r v e i n about 400 f e e t by 50 to 100 f e e t , c o n s i s t i n g of three 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 products. The f i r s t of these m a t e r i a l s i s Quisqueite, a black l u s t r o u s a s p h a l t i t e -1 ike substance containing 43 per cent carbon, 45 per cent sulphur, and about .OS per cent V g0g. This grades into a d u l l black v e s c i c u l a r c o k e - l i k e substance which apparently i s coked qu i s q u e i t e . I t contains 86 per cent carbon, 6. per cent sulphur, and i t s ash i s h i g h l y vanadiferous. The vanadium ore, termed "patronite' 1 occurred as two separate l a y e r s separated by a l a y e r o f coke containing an i r r e g u l a r c l a y v e i n . P a t r o n i t e contains from about 19 per cent to 30 per cent vanadium. According to Lingren, i t i s a f i n e - g r a i n e d mixture,of three sulphides and i s "probably of c o l l o i d a l o r i g i n . " -• Minute, amounts of Bravoite ( 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 are mixed with the p a t r o n i t e . Vanadium sulphide can be prepared by the a c t i o n of carbon disulphide vapour on an oxide of vanadium, and i t i s soluble i n a s p h a l t i t e . On t h i s basis and the generally accepted view that asphalt i t e s are the residuary m a t e r i a l from the seepage of petroleum deposits, Hewett suggests that the necessary conditions f o r the formation of vanadiferous a s p h a l t i t e ores are: (1) Vanadium as oxide, disseminated through a . rock of a f a i r degree of p o r o s i t y . (2) Impregnation with a hydrocarbon to a greater or l e s s e r degree. (3) A source of sulphur or sulphuretted vapours. Therefore, these deposits w i l l occur i n breaks i n sedimentary rocks i n regions where petroleum deposits have ex i s t e d i n the neighbourhood of volcanoes. These conditions are thought to have been s a t i s f i e d i n Peru and Oklahoma. Hewett considers then that the deposit at Minasragra represents "an extreme phase of d i f f e r e n t i a t i o n from a s p h a l t i t e . " I n 1909 when Hewett developed t h i s hypothesis i t was not g e n e r a l l y known that petroleum may contain vanadium, or that vanadium may be concentrated by some marine animals. Apparently a l l the p a t r o n i t e at Minasragra has been mined now, and the remaining ore i s a mixture of minerals r e s u l t i n g from oxi d a t i o n . o f the o r i g i n a l deposit and redepos-i 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 of these minerals replace the shale country rock almost e n t i r e l y or f i l l cracks i n the crushed zone. They include the hydrous calcium hexav'anadates, hewettite (red) and pascoite (orange); the vanadovanadates, f e r n a n d i n i t e ( d u l l green), and melano-vanadite (black) and the blue hydrous sulphate, minasragrite. IN GROUND WATERS. In most of the commercial vanadium deposits mentioned above, s o l u t i o n and secondary concentration of 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 not apply, of course, to the deposits of t i t a n i f e r -ous magnetite or the r e s i d u a l ores of i r o n , manganese, and aluminum, co n t a i n i n g vanadium, and i t may not apply to those deposits associated with organic m a t e r i a l s , such as phosphatic limestone, c o a l , petroleum, a s p h a l t i t e , and the o r i g i n a l sulphide deposit at Minasragra. I t c e r t a i n l y does apply to the deposit now mined at Minasragra, which i s apparently composed of f a i r l y s o l u b l e secondary minerals. The vanadate deposits associated with o x i d i z e d l e a d , z i n c , and copper minerals and the c a r n o t i t e deposit s t i l l forming at Mauch Chunk are good proof of the s o l u b i l i t y of vanadium i n ground waters. M e l l o r states that vanadium would be dissolved i n na t u r a l waters containing atmospheric gases. Many s a l t s of 42 vanadium are s o l u b l e i n eold water and others are soluble i n s l i g h t l y a c i d s o l u t i o n . Vanadium has been detected i n f r e s h water from Brooklyn. 14-Uotesteln t r i e d to determine the importance of s o l u t i o n and p r e c i p i t a t i o n of vanadium i n ground water i n the genesis of the sedimentary uranium-vanadium ores of the South-Western States, 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 resembling n a t u r a l ground waters. he found that: Garnotite 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 sulphuric acid 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 . I t i s very 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 bicarbonates 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 bicarbonate, c h l o r i d e s , normal a l k a l i sulphates, and hydrogen sulphide. 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 vanadyl and u r a n y l sulphate s o l u t i o n s . 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 bicarbonates and by a s o l u -t i o n of calcium bicarbonate. In the l a t t e r s o l u t i o n the l o s s of carbon dioxide 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 lime and the metals. • • , Rotten 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 metal. This point should be t e s t e d f u r t h e r . Vanadium pentoxide 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 sulphate." Vanadium must be present i n sea water, but the amounts are g e n e r a l l y too small to be detected. I ' ' - 43 II If . - - ' I : SUMMARY AID THEORY. We have seen that vanadium occurs, j ( l ) In igneous rocks, e s p e c i a l l y i n the 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 associated t i t a n i f e r o u s i r o n deposits ("recovered as a bi-product) (£•)• i n sulphides and i n igneous and contact metamorphic s i l i c a t e s (and sp o r a d i c a l l y , i n a great v a r i e t y of f m i n e r a l s ) . The evidence f o r hydrothermal vanadium i s not good. (3) i n the ox i d i z e d zones of deposits of lead, z i n c , and copper, (recovered d i r e c t l y ) (4) i n bauxite and l a t e r i t e s , and other r e s i d u a l i r o n and manganese deposits, i n which i t i s concentrated apparently because i t i s i n an i n s o l u b l e form. Also i n minette ores, (recovered as a bi-pr o d u c t ) . (5) i n sediments of n e a r l y a l l types but e s p e c i a l l y (6) i n the 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, and even more notably (7) i n sediments w i t h organic 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 not at a l l c e r t a i n whether the vanadium was o r i g i n a l l y concentrated by organisms or whether the organic substances have p r e c i p i t a t e d or absorbed the vanadium from s o l u t i o n i n ground waters or the sea. (recovered as a b i -product and d i r e c t l y . ) (8) as epigenetic .concentrations i n sediments. The source of the vanadium i s not known i n most of these deposits. (recovered d i r e c t l y and as a b i -product.) (9) in'ground waters. Except f o r the o r i g i n a l sulphide deposit at Minasragra and the magmatic t i t a n i f e r o u s i r o n ores containing vanadium a l l the present leading producers of vanadium are deposits that have been formed partly;,or e n t i r e l y by secondary con-c e n t r a t i o n . Such a concentration may be accomplished by: A. .Sedimentary Processes without 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 , or non f u g i t i v e form, .e.g. i n bauxite, l a t e r i t e , etc. (2) ' a r e s i s t e n t , heavy mineral, e.g. i r o n sand deposits. B. C o l l o i d a l Processes (?) e.g. i n f i n e sediments. The vanadium may be 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 are other c o l l o i d s . (2) protected or absorbed by other c o l l o i d s and c a r r i e d along 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 weathering according to Bosazza. This suggests that i t i s i n a. non-decomposed or only p a r t l y decomposed form i n clays.) 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 F i x a t i o n : (1 (2 (3 (4 (5 (6 (7 (8 (9 (10 (11 by over-s a t u r a t i o n or l o s s of water, e.g. the so l u b l e secondary minerals at Minasragra and elsewhere. from vanadic s o l u t i o n s by metals forming i n s o l u b l e vanadates. These are almost always orthovanadates. e.g. the vanadinite and d e s c l o i z i t e deposits. from vanadyl sulphate s o l u t i o n s by CaCO see Notestein. 3' from a l k a l i carbonate and bicarbonate and calcium bicarbonate s o l u t i o n by l o s s of COg; see Hotestein. as calcium ( a l k a l i n e earth) vanadium s a l t s which are 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. 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 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 i n s o l u b l e double s a l t s of copper and calcium. by the reducing a c t i o n of l i v i n g organisms or decaying organic m a t e r i a l (?) by some p r e c i p i t a t i n g a c t i o n of organic substances,not r e l a t e d to decay (?) c f i Bader's hypothesis. by organisms u s i n g vanadium i n t h e i r " l i f e processes. by absorption i n very f i n e grained 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 shaley m a t e r i a l i n the' sedimentary deposits of the South-western'States'. D. By other Processes r e l a t e d or unrelated to the above. Hydrothermal processes c o n t r i b u t e l i t t l e to the concentration o f vanadium. The a s s o c i a t i o n of vanadium with c e r t a i n elements i s s t r i k i n g ; w i t h t i t a n i u m i n magnetites and i n c l a y s ; w i t h molybdenum i n clays and i n vanadinite, d e s c l o i z i t e ores; with uranium and radium i n veins 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 va n a d i n i t e , d e s c l o i z i t e ores and sedimentary ores. CHAPTER I I I . v THE OCGIfRRElCE OS YAffADIUM I I SOME ROCKS A¥D MINERALS FROM BRITISH COLUMBIA. During the u n i v e r s i t y session 1943-44, a la b o r a t o r y survey of the occurrence of vanadium i n 80 specimens of rocks and minerals from B r i t i s h Columbia was made by the author as a p a r t i a l f u l f i l m e n t of work f o r the B r i t a n n i a Mining and Smelting Company l i m i t e d Scholarship. The specimens were obtained from the c o l l e c t i o n s at the 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 to time, and, i n a d d i t i o n , a s u i t e of c o a l and associated rock samples was supplied by the engineering s t a f f of the Dunsmuir C o l l i e r i e s at Cumberland, B r i t i s h Columbia. The survey was based on spectro chemical a n a l y s i s of the minerals and rocks, made on a H i l g e r medium quartz spectro-graph at the U n i v e r s i t y of B r i t i s h Columbia. A motor generator set supplie d D.C. voltage at 110 v o l t s . The f o l l o w ing conditions were adopted as standard. The arc with s e r i e s inductance was operated at 6 amperes with a 2 m i l l i m e t e r gap, the lower electrode being made p o s i t i v e . Carbon electrodes *Vl6 inch diameter with square ends, made by n a t i o n a l Carbon Company, were placed 61 centimeters from the s l i t , and the l i g h t was foeussed by means of a quartz condensing lens on a point beyond the prism so that the prism aperture was com-p l e t e l y f i l l e d w ith l i g h t . The r e s u l t i n g l i n e s on the spectrogram were of uniform i n t e n s i t y from top to bottom. The s l i t width was .01 m i l l i m e t e r s , and the Hartman diaphram was placed 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 long on the p l a t e . Twenty milligrams of the sample were packed i n a small hole bored i n the lower electrode ( p o s i t i v e ) of the a r c . Each sample was arced 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 with the sample f o r comparison and l i n e i n t e r p o l a t i o n . The spectrograms were taken on Eastman Spectroscopic p l a t e s , type I I J , w i t h wavelength range of 2200-6800 Angstroms. The pla 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 opal glass viewing screen 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 estimations are based on v i s u a l comparison of the spectra, and are subject to co r r e c t i o n s required by the varying compos i t ion,-of the base m a t e r i a l i n the samples,.. and other f a c t o r s which may change the I n t e n s i t y of l i n e produced by a given amount of 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 are: 3183, 3184, 3185, 4379, 4408, 3095, 3102, 3111, .3118, 312-5.-v A ; Y The r e l a t i v e Q u a n t i t a t i v e estimates are reported as a series, of numbers from .1 to 10, to i n d i c a t e l i n e i n t e n s i t i e s : from very weak to very strong. They cannot be considered accurate representations.of the,amounts of vanadium present f o r the reasons given above, and= furthermore, the standards set up f o r one type of m a t e r i a l c e r t a i n l y do not apply to another type, except i n a very approximate way. The f i g u r e 1 i n d i c a t e s that the p r i n e i p a l vanadium l i n e s are barely v i s i b l e ; 10 was the l i n e , i n t e n s i t y given by a sample of impure secondary vanadates from Minasragra, Peru. The f o l l o w i n g c o r r e l a t i o n s were obtained between chemical assays of samples and the i n t e n s i t y of the p r i n c i p a l spectroscopic l i n e s : Sample:. per cent chemical V2°5 assay. .Intensity of spectro-scopic l i n e based on a r b i t r a r y s c a l e . Black sediment -Quadra Is l a n d 1.96. and 2.16 6 or 8 Black sediment. -Menzies Bay 0.75 and 1.14 8 or 9 B a s a l t i c l a v a -Quadra Island 0.50 and 0.21 6 Many other lavas i n same s e r i e s 0 to 7 average 5. Coal Ash -Pri n c e t o n 0.26 Coal 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 Formation. ,.. ... 2 Andesite, Yifhitehorse, Y.T. ... ... 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) ... ... T e r t i a r y volcanic ( a n d e s i t i e ) Whitehorse, Y.T. 5 Greenstone, v o l c a n i c , Quatsino.. ... 5 B a s a l t , Shulaps v o l c a n i c s ... ... 5 Serpentinized b a s a l t v o l c a n i c s . . ... 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-Basalt or diabase i n t r u s i v e i n "Cache Creek", 6 Quesnel. Yolcanic flow, Cache Creek ... ... 6 Serpentine, Hope. ... ... 1 "Porphyrite S e r i e s " flow rock... ... 4-§-Magnet i t e : V .••-:.--^ aml>©ops . •» ... 2,0-_.,.;-AssoQiateci:;pink:rock: ... .... 0 Whalis Mountain, opposite North Bend, C.P.R. S Tulameen ... ... 2 Associated ferromagnesian... ... 0 Head Bay, Uootka Sound ... ... 0 El k R i v e r , Kennedy lake ... ... 0 Quatsino, Morning Glory T r a i l ... ... 1 Black Sand, B a r k e r v i l l e ... ... 3 Black Sand, Spanish Banks ... ... 3 I l l m e n i t e , S t. Urbain, Quebec. ... ... 3 Oxidized Sulphides: Oxidized s i l v e r lead ore, B l u e b e l l , Ainsworth. 1 Oxidized s i l v e r lead ore, Slocan.. ... 1 Oxidized s i l v e r lead ore, Ferguson, Lardeau... 1-|-Oxidized galena and manganite, Mayo, Y.T. ... 1 Secondary C h a l c o c i t e and yellow stain,Kennecott, Alaska... 1 Yellow s t a i n on surface ore. No.1.mine, Ainsworth.. 1 2 secondary zinc minerals, Paradise Mine ... 0 Note: f o r vanadium i n primary sulphides see page 17 of t h i t h e s i s . Sediments: Ald r i d g e Formation, Granbrook Oreston " " Kitchener " "• Siyeh " " Gateway " " P h i l l i p s " " R o o s e v i l l e . " . " Cambrian Basal Conglomerate Diatomaceous earth, Okanagan Diatomaceous earth, Quesnel K a o l i n , Soda Creek, area. H • •* vs» ... 4 e • • t5 • e « %5 • « » £3 • 0 0 3 »• * 5 e » a 2 « • • 1 « a • 0 « « e 2 52 Bentonite, Princeton. .... ... Gypsum, Windemere., ... ... Hydromagnesite, A t l i n . ... ... F e t i d limestone, Rancheria R i v e r , Alaska Highway limestone from B i g Bend Area, l i g h t - c o l o u r e d bands. Limestone from Big Bend Area, dark-coloured bands 0 0 1 i i Si-Coal Ash: Brown l i g n i t e , Coal R i v e r . ... ... Rocky Mountain, Peace R i v e r ... ... Hat Creek ... Princeton cOal ash ... ... Princeton c o a l soot ... ... Port Haney ... N i c o l a ' In T e r t i a r y sandstone, Sooke Harbour ... Telqua ... Quatsino ... ... Camp Robertson, Graham Is l a n d ... ... Queen C h a r l o t t e ... ... Coke ? Queen C h a r l o t t e Sound ... ... Alexandria Mine, South Wellington... ... South Workings No. 8 Mine, Cumberland ... North Workings " " " From u n i v e r s i t y power plant (Vancouver Island... coal) Domestic c o a l , mixture of MacLeod Ri v e r and ' Wellington. 1 G 5 * 6. 5 8* 1 2 5 1,0 2ir lir 4 i Si 1 4 i 53 A s u i t e of 18 samples of c o a l and associated bone or rock m a t e r i a l from the Cumberland Mines, supplied by the engineering s t a f f of the Dunsmuir C o l l i e r i e s at Cumberland, B r i t i s h Columbia, produced l i n e i n t e n s i t i e s from 0 to 3-g-, but averaging about 1. Two samples of bone were highest i n vanadium, but other bone samples contained 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 A p a t i t e var. phosphorite, Wyoming Rhodonite, Kaslo ... .. Wad, .£aslo ... -Rhodonite, Middle R i v e r ( f a k l a Lake): SUMMARY Many basic lavas i n B r i t i s h Columbia contain appreciable amounts of vanadium, perhaps as much as ,0.20 per cent YgOg, and some of them may contain as much as the lavas of the Yaldes Group on Quadra and Yancouver Isl a n d s . Several magmatie deposits of B r i t i s h Columbia and the black sands of the I r a s e r R i v e r Y a l l e y contain vanadium, but the contact metamo.rphic magnetites of Yancouver I s l a n d contain very l i t t l e or no vanadium. lone o f the o x i d i z e d surface portions of lead , z i n c , « • e 2 • • '• 0 • B 0 « • « 1 to * e 0 54 or copper sulphide ores that have been tested contained appreciable vanadium, and i t seems l i k e l y that e i t h e r con-d i t i o n s have been unsu i t a b l e f o r the development -of secondary vanadate deposits i n a s s o c i a t i o n with these ores, or else these deposits have been removed by g l a c i a t i o n . Most sediments contain v a r i a b l e small amount of vanadium. On the basis of spectrochemical 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 of the Department of Mines i n V i c t o r i a , i t would appear that no w e l l known B r i t i s h Columbia coal.contains more than 0.30 per cent T p0r i n i t s ashed residue. CHAPTER IT. THE DEPOSITS ON QUADRA ISLAND. M B AT MENZIES BAY. We r e t u r n now to the o r i g i n a l problem, the character and o r i g i n of the f i n e l y banded dark vanadiferous seams on Quadra I s l a n d , and near Menzies Bay on Vancouver I s l a n d . GEOLOGICAL SETTING OF THE DEPOSITS* As mentioned i n the statement of the problem, both deposits are t h i n , i r r e g u l a r seams of a very 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 flows. The lavas belong to the Valdes Group which Bancroft describes as "massive flows of andesite, v o l c a n i c b r e c c i a s , t u f f s " of probable T r i a s s i c age. In the neighboxirhood of Quadra Island and Menzies Bay, the lavas dip gently to the south and south-east at angles not often exceeding 20 degrees. They are u n d e r l a i n conformably at Open Bay, on the north-east, by a group of cherty a r g i l l i t e s , q u a r t z i t e , and impure limestone, which Bancroft has subdivided into the Open Bay Group (Upper Paleozoic) and the Marble Bay Formation ( o l d e r than Open Bay). The contact of the Coast Range B a t h o l i t h i s from one to two miles f u r t h e r north-east of the vanadium showing. The sediments are i n t e n s e l y folded but t h i s f o l d i n g dies out to the south-west between one and two miles from the b a t h o l i t h . On fancouver I s l a n d , about s i x miles south of the vanadium deposits, lavas of t h i s same s e r i e s are o v e r l a i n by Upper Cretaceous sandstone and conglom-erate with some shale and c o a l . PLATE I . Plow contact 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 lavas are dark, green to 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 surfaces, becoming brownish on weathered surfaces. In many of them p i l l o w s t r u c t u r e i s poorly 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 Hyacinth Bay on the east coast of Quadra I s l a n d . Some of the flows are very f i n e - g r a i n e d or a p h a n i t i c while i n others the grains are up to two m i l l i m e t e r s long. Most of the lavas are amygdaloidal. H a l f a dozen t h i n sections show that the o r i g i n a l rock cont-s i s t e d mainly of p l a g i o c l a s e f e l d s p a r and augite i n about equal proportions. These minerals are now l a r g e l y a l t e r e d to c h l o r i t e and epidote. The p l a g i o c l a s e i s remarkably sodie, ranging 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 therefore the lavas are more properly 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 petrographers. T y r r e l l states that " a p i l i t i c lavas are very commonly pillow-form, and are f r e q u e n t l y associated with r a d i o l a r i a n cherts and other marine sediments. <' They are thought to be of submarine o r i g i n . The lavas of Quadra Is l a n d and Menzies Bay are more or l e s s p i l l o w - f o r m and they 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 flows form up to one h a l f of the rock, c o n s i s t of quartz, chalcedony, c a l c i t e , c h l o r i t e , epidote, z e o l i t e s , and a f i b r o u s green amphibole. In some of the l a v a s , i n c l u d i n g those near the vanadiferous seams, a few of the amygdules are p a r t l y or e n t i r e l y f i l l e d 57 with copper minerals, mainly c h a l c o c i t e , with 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 the v/eathered products, a z u r i t e and malachite. Gopper minerals 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 the lavas as small i r r e g u l a r f i l l i n g s and replacements, and to a very minor extent i n small vein f i l l -i ngs, u s u a l l y w i t h quartz or quartz and c a l c i t e . • The flows 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 dip of from 0 to SO degrees to the south-east. They are f a i r l y uniform i n colour and g r a i n , so that flow bedding i s not always easy to see unless there 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 structure' or t e x t u r e such as contrast of p i l l o w s t r u c t u r e or columnar j o i n t i n g , brecciated tops, amygdaloidal tops, pipe amygdules on flow bottoms. From a distance 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 flows and the s t e p l i k e topo-graphy of the area produced by f r a c t u r i n g perpendicular to the flows, and erosion, 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 consisted mainly of t h i n seams of f a i r l y uniform, greenish grey tuffaceous or calcareous m a t e r i a l u s u a l l y s i l i c l f i e d . The dark vanadiferous seams are unique i n that they are n o t i c e a b l y laminated and are composed of very f i n e -grained quartz w i t h a minor amount of carbonaceous m a t e r i a l . Flow breccias along the tops of lavas are not p a r t i c u l a r l y common. Some of the calcareous i n t e r f l o w sediments contain indeterminate brachiopods. Ho dykes have been observed to cut the lavas near e i t h e r of the p r o p e r t i e s , and there i s very l i t t l e f a u l t i n g or f o l d -i n g . The few small veins 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 barren. - • : THE QUADRA I S i A l D DEPOSIT,. The o r i g i n a l discovery of vanadium was made on Quadra Is l a n d about 1-g- miles north of the head of Gowland Harbour and about 600 feet above sea l e v e l . The amygdaloidal lavas undoubtedly u n d e r l i e the deposit f o r s e v e r a l hundred feet and the nearest non-volcanic rocks on the surface are the Open Bay sediments. The contact of the Coast Range B a t h o l i t h i s about 4 miles to the north-east. The lavas dip to the south-east at angles between 10 and 15 degrees, and are f a i r -l y w e l l f r a c t u r e d . I t i s from one of the f r a c t u r e s or crev i c e s that Crowe-Swords extracted the " c a r n o t i t e - l i k e mineral". Several copper showings of the types mentioned above occur i n the general area and the ground staked by Crowe-Swords comprises a group of these. About 600 feet north-west of t h i s group of copper showings, and higher i n the l a v a s e r i e s , i s the open cut exposing the vanadium -bearing seams. The open cut ( P i g . 1". ) i s about 60 f e e t long i n a north-south d i r e c t i o n and about 6 f e e t deep. The east w a l l exposes three l a v a flows dipping about 10 degrees south-east w i t h very poorly developed p i l l o w s t r u c t u r e , the upper and the 1 lower flow continuing from end to end of the cut. The middle flow i s represented only i n the southern ( r i g h t i n t h e . f i g u r e ) two t h i r d s of the cut, terminating i n a p i l l o w -l i k e shape.about 18 feet from the north end. The middle and upper flows a r e n o r m a l amygdaloids, f a i r l y dense and greenish grey i n colour, but the lower flow i s h i g h l y b r e c c i a t e d where observed and i s more i n t e n s e l y chlo.rit i z e d . The vanadiferous sediment i s an irregular,, f i n e l y laminated, black or dark grey seam between the upper and middle, ana middle and lower flows, varying i n width from paper t h i n up to s i x inches. In the t h i c k e r parts and p a r t i c u l a r l y near the end of the middle f l o w , the seam i s crehulated and appears,to have been forced between i n c i p i e n t p i l l o w s . Quite e v i d e n t l y the seam was l a i d down as a t h i n bed on the, rough surface of the underlying lava,' and while s t i l l p l a s t i c was deformed and p a r t l y removed by the next flow. The s t r u c t u r e of the seam around the end of the middle flow (see f i g . 1 ) would most l i k e l y be -formed by the upper l a v a floviring into place from a n o r t h e r l y d i r e c t i o n . Four shear zones, one of them about 4 f e e t wide, cut across the lavas jsrith a strong d i p . Copper minerals are present i n the amygdules i n the shear zones, i n the seam, and notably i n the brecciated top of the lower 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 area equals amygdaloidal b a s a l t , with minor copper, c h a l c o c i t e , and bor n i t e i n the amygdules, and rude p i l l o w s at the base of the flow. V p a t t e r n equals b r e c c i a t e d top of bas a l t flow with more copper than o v e r l y i n g flows. Heavy black l i n e equals black vanadiferous l a y e r . Wavey l i n e s equal f r a c t u r e and shear zones. (115°) equal true s t r i k e of f r a c t u r e s . The weathered surface of the black seam u s u a l l y has a c h a r a c t e r i s t i c yellow s t a i n which i s thought to be a •vanadium s a l t , and two analyses.of the seam showed 2.16 per cent and 1.96 per cent Y g 0 g r e s p e c t i v e l y . The lower l a v a assayed 0.30 per oent.;.f^0g.- ana', .the' middle.; l a v a O.'Sl .per cent Y g 0 5 . f o r more d e t a i l e d assays/see the l a s t s e c t i o n of t h i s chapter. THEME1ZIES BAY DEPOSIT. The deposit near Menzies Bay i s a black vanadiferous I n t e r l a v a sediment almost i d e n t i c a l i n appearance with the deposit on Quadra Is l a n d * I t i s on the Conglomerate Copper Group, two miles west of the head of Menzies Bay and between 400 and 600 f e e t above sea l e v e l . Outcrops, open cuts, and trenches along a north-westerly d i r e c t i o n f o r about 2,000 feet show two or: more of the vanadiferous 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 containing poorly preserved f o s s i l brachiopods. The amygdaloidal b a s a l t i c lavas from two to at l e a s t 15 fe e t t h i c k dip about 10° E. and S.E. Their surfaces, are h i g h l y i r r e g u l a r and rudimentary p i l l o w s t r u c t u r e i s . common. Copper minerals are not as abundant i n the lavas here as they are i n the lavas on Quadra I s l a n d , but the vanadiferous seam contains much more chalco-c i t e than the seam on Quadra Island does, i n f a c t , the yellow PLATE I I . Folded vanadiferous sediment between lava flows, Menzies Bay Deposit, 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 of vanadium was found e s p e c i a l l y where the copper m i n e r a l i z a t i o n was strong. Most of the i n t e r f l o w m a t e r i a l , however, i s apparently t u f f a e ceous and contains l i t t l e or no copper m i n e r a l i z a t i o n . At l e a s t one short l e n t i c u l a r body of high grade c h a l c o c i t e has been deposited along 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 vanadiferous seam and apparently i s not r e l a t e d to i t . At the most n o r t h e r l y end of 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 of the exposures ,and the i r r e g u l a r i t y of the l a v a flows make i t d i f f i c u l t to say whether a l l the exposures of the vanadiferous seam are at the same horizon i n the flows but they are nearly so, at l e a s t . The best exposures of the vanadiferous sediment are at the southernmost workings where two of the l a y e r s , separated by a l a v a flow, occur i n a s i x to twenty foot b l u f f , along with some greenish-grey s i l i c i f i e d calcareous and probably tuffaceous m a t e r i a l . . l y i n g along;the flow contacts, they r e v e a l that the lavas are not very uniform i n thickness. At the narrowest part of the intervening l a v a the seams are about 2-g- f e e t apart. The dark vanadiferous l a y e r s have a maximum thickness of about f i v e inches although the average i s only about one inch, and the combined thickness of the dark l a y e r and the calcareous l a y e r which, when present, o v e r l i e s the dark l a y e r , i s never more than ten inches. At the open cut shown i n the photograph,(plate I I b ) ? 62 about f i v e inches of the black sediment o v e r l a i n by a s i m i l a r thickness of very f i n e - g r a i n e d , brownish-grey limestone, has been folded into a t i g h t s y n c l i n e . I r r e g u l a r continuations of the seam can be traced around a b o u l d e r - l i k e mass of l a v a , and a f t e r a short break, along the o r i g i n a l horizon. The f a c t that the limestone contains a few uncrushed brachiopods suggests'that the sediment was folded while s t i l l p l a s t i c by t h eupheaval and r o l l i n g over of the b o u l d e r - l i k e mass during the next flow of l a v a . The limestone 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 sec-t i o n shows no d i s t i n c t i v e t e x t u r e , other than i t s extreme fineness of g r a i n . I t contains a few c l a s t i c grains of quartz. The other showings are s i m i l a r to t h i s southernmost one, but l e s s s t r i k i n g . 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 often found, although i t i s apparently more tuffaeeous than that described above* and the seam i s n e a r l y always h i g h l y c u p r i f e r o u s . * 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 I s l a n d . The highest vanadium assays were obtained from laminated f o s s i l i f e r o u s sediment about 1,100 feet north-west of the southernmost showings, and showed 0.75 per cent and 1.14 per cent VgOg. These and other assays were supplied by Mr. G. A. Dirom of Premier Gold Mining Company l i m i t e d . The lower vanadium content may be due to i n c l u s i o n of the over-l y i n g f o s s i l iferous sediment with the black l a y e r i n the samples, or to the excessive amount of copper present since the c h a l c o c i t e apparently c a r r i e s l i t t l e or no vanadium. ,;THE;3IE^ The a s s o c i a t i o n of copper minerals, mainly 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 genetic r e l a t i o n s h i p between the copper and the vanadium, and there-fore a more d e t a i l e d d e s c r i p t i o n of the c h a l c o c i t e i s i n order. C h a l c o c i t e occurs i n the amygdules, i n shears and frac~n tures i n the vol c a n i c rock, and i n the seams as minute r e -placements and v e i n l e t s . I t s occurrence 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 the form of a r i n g i n s i d e the 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 small remnant i s l a n d s m of b o r n i t e with deeply cremulated borders are surrounded by c h a l c o c i t e i n every case. Under high m a g n i f i c a t i o n the c h a l c o c i t e i s seen t o contain t i n y patches of c o v e l l i t e , mostly i n i r r e g u l a r zones of a l t e r a t i o n . Some of the c o v e l l i t e , however, i s arranged i n long p a r a l l e l lenses resembling tension cracks l y i n g d i a g o n a l l y i n the r i n g of 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 simply be r e p l a c i n g the c h a l c o c i t e but i t i s not impossible that these lenses could have been formed by exsDlution of c o v e l l i t e from c h a l c o c i t e , which takes place at 75°G. or l e s s , as they PIATE I I I . Slender lenses 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 to conform with 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 the c h a l c o c i t e or o r i g i n a l b o r n i t e . This c o v e l l i t e and the c h a l c o c i t e may*he contemporaneous i n o r i g i n . Lindgren st a t e s : The a c t i o n between born i t e and cupric sulphate at the same temperature (4-0°C?) i s expressed by the equations 5 Cu 6FeS 4tllCuS0 4f8H 20 — } 18Cu 2Sv5I ,eS0 44r8H 2S0 4 0u 5FeS 4+GuS0 4-~4 2Cu2S+2CuS+FeS04 Bornite i s attacked by H£ S 04 r e s u l t i n g i n OuS and CugS and FeSO^., hydrogen sulphide develop-ing at the same time. These products w i l l react 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 deposits. The high grade c h a l c o c i t e i n the lens i n the volcanic flows at the Menzies Bay deposit i s c r y s t a l l i n e with medium g r a i n s i z e and shows t y p i c a l orthorhombic cleavage cracks, with abundant t r i a n g u l a r p i t s i n some p a r t s . On etching with FeCl-g or KCN the orthrhombic etch pattern i s formed with varying i n t e n s i t y of etch from c r y s t a l to c r y s t a l . In a d d i t i o n , i t i s : very weaklyanlsotropic. The c h a l c o c i t e i s therefore undoubtedly orthorhombic. 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 the c h a l c o c i t e , and a few t i n y specks of na t i v e copper were seen. The c h a l c o c i t e i n the vanadiferous seams at the Menzies Bay deposit occurs i n two generations. The f i r s t generation i s f i n e l y disseminated through the seam m a t e r i a l and the second f i l l s microscopic v e i n l e t s c u t t i n g across the dissem-inated c h a l c o c i t e and the laminations of the seam. This 65 c h a l c o c i t e i s apparently orthorhombic a l s o . Very minor amounts of 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 the vanadiferous seams from Quadra I s l a n d and Menzies Bay* There i s no good evidence - whether, the c h a l c o c i t e i n the f i s s u r e s or the seam i s e i t h e r hypogene or supergene. The occurrence of copper w i t h basic lavas i s world-wide and i s very common on the coast of B r i t i s h Columbia. I t i s thought that the primary copper minerals i n some of these occurrences may have been deposited by hot waters s h o r t l y a f t e r the eruption and c o n s o l i d a t i o n of the l a v a s . This hypothesis may apply to the copper minerals i n the amygdules, but i t does not n e c e s s a r i l y apply to the c h a l c o c i t e i n the f i s s u r e s and i n the vanadiferous seams. THE VANADIFERGUS SEDIMENT . The vanadiferous sediment i s almost black on f r e s h surfaces and i t weathers a dark grey, showing very t h i n wavey laminations. Near the bottom of the seams these laminations conform with minor I r r e g u l a r i t i e s i n the surface o f f t h e under-l y i n g l a v a flow* Subsequent to deposition and while s t i l l p l a s t i c , the sediment was deformed by the next flow of l a v a , so that i t now v a r i e s g r e a t l y In thickness and the laminations are contorted. A yellow s t a i n , i n some places very f i n e l y c r y s t a l l i n e , i s often found on weathered surfaces of the sediment, though on many surfaces exposed f u l l y to the abundant r a i n f a l l of the r e g i o n , there i s no s t a i n . In t h i n s e c t i o n the vanadiferous sediment i s seen to consis t mainly of l i g h t and dark wavey laminations 'from .01 m i l l i m e t e r s to .35 m i l l i m e t e r s t h i c k , but averaging about .02 m i l l i m e t e r s t h i c k . (Plate IV. ) The l i g h t and dark laminations do not have very sharp contacts, but blend into each other through a narrow contact zone, and both types probably consist: of masses of extremely f i n e p a r t i c l e s w i t h a few l a r g e r p a r t i c l e s . The dark laminations forming up to 60 per cent of the rock are most commonly j e t black, or n e a r l y so, i n sections of normal t h i c k n e s s , grading into grey on t h i n edges of the s e c t i o n or by admixture of t i n y grains of quartz. The l i g h t coloured laminations are predominantly quartz, but always contain at l e a s t 20 per cent of j e t black 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 angular grains from l e s s than .003 m i l l i m e t e r s to .03 m i l l i m e t e r s across. A very few of the dark grains are as much as 0.10 m i l l i m e t e r s across. Most of these dark grains are elongated p a r a l l e l to the-.laminat ions i n the rock, but a l l are h i g h l y i r r e g u l a r and they are ge n e r a l l y i s o l a t e d from other s i m i l a r grains by the quartz i n which they occur. The dark bands may be merely a greater concentration of extremely f i n e dark p a r t i c l e s i n very f i n e -grained quartz. The quartz i n the l i g h t coloured laminations i s i n t i n y PLATE IT. (b) ( a l i g h t X 15 a) The vanadiferous seaiment (White - Quartz). Orainary [b) The vanaaiferous sediment. Orainary l i g h t X 38 (e) The vanaaiferous sediment, s p e r i c a l quartz grains,Orainary l i g h t X 300 (d) The vanadiferous sediment. P a r a l l e l l i g h t K 300. i 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 the l a r g e r quartz spherules contain one or more of the dark p a r t i c l e s near the centre of the spherule, and i n p o l a r i z e d l i g h t most of them are seen to con s i s t of many grains of quartz r a d i a t i n g out from one or more of the black p a r t i c l e s . As shown in-the photography taken under high magnification, some of the spherules have dark p a r t i c l e s arranged i n a crude concentric p a t t e r n . The outer contact of the quartz spherules i s u s u a l l y fuzzy owing to minute h a i r s of dark m a t e r i a l penetrating between the r a d i a t i n g g r a i n s . The darker laminations are crenulated to conform w i t h the boundaries of the spherules, on both the upper and lower boundaries of the l i g h t coloured laminations. In some of the t h i c k e r l i g h t - c o l o u r e d laminations the quartz spherules are i n two rows, a c t u a l l y l a y e r s , i n three dimen-si o n s , w i t h very poorly defined darker bands and smaller quartz grains separating the rows and the grains i n each row. Many of the l i g h t - c o l o u r e d laminations i n some sections have a smoky or tawny shade. In a d d i t i o n to the l a t e r copper minerals the sediment i s cut by t i n y v e i n l e t s of quartz which carry a few specks of c h a l c o c i t e . The vanadiferous l a y e r i s obviously not a normal c l a s t i c sediment. Aqueous sands do not show much rounding of p a r t i -c l e s , with diameters below about 0.1 millimeters,and wind blown sands are seldom rounded below about .03 m i l l i m e t e r s . 68 The borders of the spherules i n t h i s sediment are not d i s -t i n c t and the 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 indicates that the grains have e i t h e r formed from a core outward or have r e e r y s t a l l i z e d from another form of s i l i c a . The f a c t that the dark laminations, both above and below the l i g h t -coloured laminations, curve around the quartz spherules suggests that the s i l i c a was deposited as a s t i f f j e l l y which soon afterward was c r y s t a l l i z e d i n to c r y p t o c r y s t a l l i n e quartz. Fibrous s t r u c t u r e i s thought, by some, to develop w i t h re-c r y s t a l l i z a t i o n under confined conditions 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 laminations 4 i n the vanadiferous sediment were st r i p p e d away, the surface of the remaining 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. A l l t h i s , and the laminations themselves point to a rhythmic p r e c i p i t a t i o n of the s i l i c a and dark ma t e r i a l In. a.-.•polioidal medium followed by c r y s t a l l i z a t i o n . B o ydell s t a t e s : / ' The commonest microscopic evidence of presumably c o l l o i d a l o r i g i n f o r a mineral (or rock) i s : (1) The presence of more-or l e s s ( u s u a l l y the l a t t e r ) perfect concen-t r i c o u t l i n e s or markings on the body of the mineral (2) The occurrence of colloform boundaries or banding (using "colloform' 1 i n the sense In which Rogers proposed i t i . e . .... f o r the rounded more or 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) Together w i t h these, though not of the same d iagno s t i c value is:, (3) The presence of that 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 "radiate divergent". " The rough concentric arrangement of some of the dark p a r t i c l e s in the l a r g e r spherules 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 points out that c e r t a i n banded struc t u r e s i n minerals and rocks are probably due to rhythmic p r e c i p i t a t i o n i n gels and f u r t h e r : n u c l e i or aided 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 . The thought also a r i s e s , e s p e c i a l l y i n view of the carbon content of the sediment, that the 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 cherts are commonly associated with 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 there was an abundant supply of s o l u b l e ' s i l i c a i n sea water, whether supplied by submarine v o l c a n i c a c t i o n or some other means. They may be w e l l preserved or may appear as minute rounded bodies of c r y t o c r y s t a l l i n e s i l i c a . When w e l l preserved they would of The black p a r t i c l e s i n the spherules may have served as 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, are mostly plankton and one would expect to 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 other f o s s i l remains, r a t h e r than segregated into d i s t i n c t laminations. The f o l l o w i n g assays are reported by E l l s w o r t h and Gunning: i - II i n iv P e r c e n t Per cent Per cent Per cent S i 0 2 ... 75.31*.1' Gu . . 2 . 2 8 Ou . . 0 . 0 6 Gu 4.99 PeO ... 2 .29 V o 0 K . 1 . 6 0 VpOpr.0.29 Y 0 . 0 .30 2 5 2 5 g 5 A l g 0 3 ... 3.70 S05..0.48 SOg..0.03 TiOg 0.15 MnO ... 0.10 GaO ... 4.08 MgO ... 0.53 On • • • 2»88 'V'-.O • • • 2 * IL S 2 5 S ... 0.72 P 0 ... Trace 2 5 Not U,Cr ... detected H 20 ... 2.61 C,COo ... P r e s e n t ( 4 ) ' 2 I . Average sample of siliceous-carbonaceous zone. (•!•) Microscopic examination and chemical t e s t s i n d i c a t e that most of the s i l i c a i s present in the rock as quartz. (2) Copper i s present as c h a l c o c i t e (CugS), also , as basic carbonate (malachite) and probably a l s o i n small amount as sulphate and s i l i c a t e . (3) Some of the srilphur i s apparently present as SG g (4) Carbon about 5 per cent by c a l c u l a t i o n . No hydrocarbons'detected. I I . Shows the amounts of Cu, V2O5, and SO* that passed into s o l u t i o n when 1 gramme of the m a t e r i a l of I was digested f o r an hour on the hot water bath 'with 100 cc. 1 per cent hydrochloric a c i d s o l u t i o n . I I I . Shows the 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 with 100 cc. of 1 per cent hydrochloric a c i d . IV. Copper and VgOg determinations on a sample of the lower l a v a , comprising m a t e r i a l about 2 inches below the contact with the vanadiferous zone. I t may be noted that as the greater part of the s i l i c a of a n a l y s i s I represents quartz i n the rock, vanadium must be present to the extent of about 6 per cent i n , say, the t h i r d of the m a t e r i a l that i s not quartz, and most of i t could be very e a s i l y and economically extracted, together w i t h the greater part of the copper, by simple leaching w i t h mineral a c i d , as no a c i d would be consumed by the quartz." The f o l l o w i n g analyses 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 at the Quadra I s l a n d deposit i n 1943. 1. Chip sample of 12 inches of black sediment 1.96^ V2O5 2. Mixed sediment and amygdaloid, south end of cut 0.28% V 0 CD 3. Same from 20 fe e t west of north end of cut 0.34$ Vg0 5 4. Chip sample of the middle flow of f i g u r e 1. 0.21% V^ O,, CD 5. Dense black amygdaloid quarter of a mile north of cut. 0.18$ V g 0 5 The f o l l o w i n g assays on,material from the Menzies Bay deposit were supplied by Mr. G*A. Dirom of the Premier Gold Mining Company Lim i t e d , i n the spring of 1943. The open cuts on the Menzies Bay deposit were numbered from 1 to 9 s t a r t i n g at the southernmost exposure by Mr. Dirom. $ VgOg $ Ou. Location and Remarks 0.36 14-16 E. end 1 0.0. 0.2' thickness of Interflow sediments, c o n s i s t i n g of 0.1'. h e a v i l y im-pregnated with 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 m ineralized w i t h OuS. Well-defined secondary canary yellow " c a r n o t i t e " as t h i n coating. . Above r e s u l t s by spectrograph—also 25-30$ SiOg, 18-20$ CaO, 14-16$ AlgOg, 1.2$ MgO, COg present, no Uranium detected. Tr. Thin chalky yellow (as weathered) f o s s i l -i f e r o u s sed» smears on surface of volcanic between 2 and 3 O.C.'s. 0.124 West side draw at 1 and 2 O.C.'s. Dark gre y i s h f.g. sediment i n curving c r e v i c e s . Trace CuS only. 0.75 ' 6 & 7 O.C.'s 0.1* of laminated f o s s i l sed. h e a v i l y impregnated w i t h CuS and showing well - d e f i n e d "Carnotite" coating. 0.05 0.4 About l / 2 mile westerly of main showings and around 1,000': elev. i n rock cut on new u n l a i d railway grade about l/2 mile beyond end of s t e e l and at summit of ri d g e . Thin fo VgOg ^ ®n sheared and discontinuous 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 . 0.26 4.00 1A O.C. 0.4' f l a t sed. seam i n flows. Im-pregnated with f . g . CuS. D i s t i n c t " C a r n o t i t e " s t a i n i n g . 0.19 , 7.75 Dark quartzose m a t e r i a l containing small quartz and c a l e i t e "amygdules". CuS, Mn s t a i n i n g . 0.13 1.75 Ty p i c a l d u l l chalky yellow weathering surface of v o l c a n i c from a l l along main workings, but p r i n c i p a l l y between 1 and 3 O.C.'s. Highly amygdaloidal, quartz and carbonate amyg. Probably minor absorbed sed. m a t e r i a l , l o vanadium weathering. -Tr. 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 . In-cludes some cherty m a t e r i a l . Some nat i v e Cu. Occurs i n small quartz nests and h a i r seams. 0.40 9 O.C. Grey black cherty sed. impregnated l i g h t l y w ith f . g . CuS and nati v e Cu. also c u p r i t e . Trace of c a r n o t i t e weathering. There Is no d i r e c t r e l a t i o n apparent between the amount of vanadium and the amount of copper contained i n samples of the black sediment. SPECTROCHEMICAI ASSAYS. To supplement the above assays and i n an attempt to locate the vanadium, s e v e r a l spectrochemical assays were made by the author on the same basis as those reported i n Chapter I I I . The f o l l o w i n g i s a summary of the r e s u l t s , with f i g u r e s i n d i c a t i n g the I n t e n s i t y .of the '-vanadium l i n e s on the 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 trace of copper* Zn,Sb,As,Pb,Ti, Mn^EnrU4':saiie aWeht. The mineral was not i d e n t i f i e d . •The black sediment: A l l samples contained 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 lens at the Menzies Bay deposit and the amygdules contained no vanadium. . . . The Lavas: A l l samples of the l a v a , except one, contained vanadium ( i n t e n s i t y 2 to 7) even though some of them were f a r away from.the deposits. A sample from near the Moose F a l l s on Campbell River contained vanadium, and samples from a s e r i e s of flows above and below the open cut on Quadra I s l a n d and as much as a quarter of a mile away a l l contained vanadium. The limestone: The limestone occurring w i t h the black sediment hear Menzies Bay contained only a t r a c e of vanadium ( i n t e n s i t y Z) F e t i d limestone from the Open Bay Group contained no vanadium. The Amygdules: None of the amygdules contained vanadium. Quartz: Samples of the quartz i n veins and i r r e g u l a r lenses contained no vanadium. In an attempt to l o c a t e the vanadium i n the black s e d i -ment, a sample of black, sediment with very l i t t l e c h a l c o c i t e was ground to minus 325 mesh (.042 mm.) and separated i n a high speed c e n t r i f u g e w i t h a bromoform aloohol mixture of s p e c i f i c g r a v i t y 2.45 as the separating medium. Although the separation was repeated several times on the products of the f i r s t separation, and although the m a t e r i a l of 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 the heavier m a t e r i a l , the spectrograph f a i l e d to show any di f f e r e n c e i n vanadium content of the two products. E q u a l l y unsuccessful r e s u l t s were obtained with samples of the l a v a where the separations were made with bromoform of s p e c i f i c g r a v i t y 2.9 i n the c e n t r i f u g e , and by a lar g e e l e c t r o -magnet. Apparently there i s too large a proportion of aph a n i t i c m a t e r i a l i n both the sediment and the lavas to make any s a t i s f a c t o r y p h y s i c a l separation. In order to t e s t the p o s s i b i l i t y of having vanadium leached from the consolidated lavas by ground waters, ten, 76 ten gramme samples of the la v a were crushed, and each subjected to leaching by 50 ccs. of so l u t i o n s simulating n a t u r a l ground waters. A f t e r 15 days, 10 ccs. of each s o l u t i o n was evapora-ted and the residue 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 are as f o l l o w s : l e a c h i n g s o l u t i o n Amount of vanadium leached as shown by spectrograph. © • • • % e 1. Water, at about 80^0. 2. 7/ater - 0 0 2 3. l a t e r - HgS ...... 4. Saturated s o l u t i o n of HaCI 5. /10 H. s o l u t i o n of H gS0 4 6. 1 / l 0 II. s o l u t i o n of HOI 7. 1 / B . H. s o l u t i o n of fegCOg plus ;00 2 8. ^/lO H. s o l u t i o n of H pS0 4 p l u s . . . /5 H. s o l u t i o n of CaSO • « e « 9. 1 / l 0 N. s o l u t i o n of H gS0 4 plus 1/5 H. s o l u t i o n of FeSO, e • « • « 10. /5 H. s o l u t i o n of Ha gS0 4 ...... doubtful trace t r a c e doubtful trace contained most vanadium. tra c e b e t t e r than tr a c e b e t t e r than trace. CHIPPER J . THEORIES OP ORIGIN FOR THE YAHADIPEROUS SEDIMENT. I t was - suggested i n the previous chapter that the s i l i c a i n the laminated vanadiferous sediment was probably 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 into i t s present form a f t e r d e p o s i t i o n , (that i s a m e t a c o l l o i d ) . Questions now a r i s e as to the source of the s i l i c a and the cause of i t s p r e c i p i t a t i o n , and the processes by which vanadium was concen-t r a t e d i n the sediment. The f o l l o w i n g data should be kept i n mind; the vanadium content of the lavas ranges -from 0 to 0.30 per cent VgOg, and of the black sediment, from about 0.75 per cent to 2.16 per cent v"g0g; the f o s s i l i f e r o u s limestone contains only a t r a c e of vanadium, and the amygdules, i n c l u d i n g c h a l c o c i t e and n a t i v e copper, contain no vanadium; the c h a l c o c i t e i n the f i s s u r e f i l l i n g s at the Menzies Bay deposit a l s o contains no vanadium* The seam contains about 75 per cent s i l i c a , most of which apparently i s present as quartz. • In view of the e x c e p t i o n a l l y high vanadium content of the lavas i t appears safe to assume that the vanadium In the blaek sediment was derived e i t h e r from the lavas themselves or from some phase of igneous a c t i v i t y associated with the l a v a s . I f the vanadium were derived from the lavas themselves, the amount i n the black sediment would represent a concentration from the lavas of only ten times. Sources f o r the S i l i c a : Moore and Maynard, succeeding other i n v e s t i g a t o r s found that s e v e r a l n a t u r a l solvents w i l l d i s s o l v e s i l i c a (and iron) from nor i t e .and diabase. Their 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 solvent 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 the next most e f f e c t i v e solvent 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 very poor solvent of i r o n • • • • and s i l i c a . (4) . Oxygenated water i s a very poor solvent of i r o n and only a f a i r solvent of s i l i c a . (5) . In general, f i n e g r i n d i n g increases the solvent 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 dis s o l v e d by these reagents i n 287 days than i n 70 days. (7) The general conclusion i s that carbonated water i s able to 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 basic t e r r a i n to form a la r g e sedimentary deposit. Organic matter, i f present, a s s i s t s a lso i n d i s s o l v i n g much i r o n and s i l i c a . Inorganic a c i d s , under exceptional circumstances cause much i r o n and s i l i c a to go into s o l u t i o n . They also concluded that most s i l i c a i s transported as a s i l i c a h y d r osol. 1 Note that time i s an important f a c t o r i n the s o l u t i o n of s i l i c a and i r o n . The time between lava flows can not have been very long, and even i f i t were long enough to allow s u f f i c i e n t weathering of a given flow surface, and s o l u t i o n of s i l i c a to produce a s i l i c e o u s i n t e r l a v a sediment, one would expect to f i n d some c l a s t i c m a t e r i a l deposited along with the sediment, e s p e c i a l l y since the source would presumably be so near. Sea water and many streams carry small amounts of dis^s solved 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 of the l a v a s . Here again i t must be remembered that the black laminated sediment r e s t s d i r e c t l y on the underlying flow without any associated c l a s t i c m a t e r i a l of sedimentary o r i g i n . Furthermore, chert and jasper are fre q u e n t l y associated w i t h basic l a v a flows, 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 hardly seems necessary to seek a source independent of the lavas or the volcanic a c t i v i t y associated with. them. Hot springs r e l a t e d to vulcanism frequently carry 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 are a l k a l i n e , and they are a possible, source, but an even simpler and more d i r e c t source can be suggested. The contact of hot lava flows with 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 of some substances. Van Hise and L e i t h experimented w i t h the process i n connection w i t h t h e i r study of the Lake Superior sedimentary i r o n formations; f r e s h b a s a l t s were heated i n a muffle furnace to a temperature s u f f i c i e n t to fuse the e x t e r i o r and then plunged into s a l t water of the composition of sea water, the r e s u l t being 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 also b r i n g i n g a small 80 amount of i r o n into s o l u t i o n ........ there was also during 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 that a r e a c t i o n s i m i l a r to t h i s one took place'while some of the l a v a flows of the Valdes Group were formed, f o r they contain marine sediments and some of them, at l e a s t , must have flowed into or under sea water. The P r e c i p i t a t i o n of C o l l o i d a l S i l i c a : S i l i c a i s l a r g e l y transported i n the form of a hydro-p h y l l i c c o l l o i d that i s not very s e n s i t i v e to e l e c t r o l y t e s . I t i s u s u a l l y negative, and therefore 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 or c o l l o i d s of opposite s i g n , but c e r t a i n n a t u r a l organic c o l l o i d s tend to s t a b i l i z e i t s c o l l o i d a l form, Tarr, Lovering, and Moore and Maynard experimented with the p r e c i p i t a t i o n of 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 s o l u t i o n s . Tarr and Lbvering obtained c o n t r a d i c t o r y r e s u l t s but Moore and Maynard1 s work i s very i n s t r u c t i v e . Moore and Maynard found that sodium s i l i c a t e s o l u t i o n s hyd-rolyse to c o l l o i d a l s i l i c a and sodium hydroxide, and that the percentage hydrolysing increases with the d i l u t i o n of the s o l u t i o n . They found that f o r d i l u t e s o l u t i o n s of sodium s i l i c a t e , which would contain much c o l l o i d a l s i l i c a , calcium carbonate and sea s a l t s were the best p r e c i p i t a t e s of s i l i c a , sodium c h l o r i d e and potassium sulphate being not so good. 81 i'or d ialyzed s o l u t i o n s of sodium s i l i c a t e , that i s solutions i n which a l l the s i l i c a i s i n the form of a hydrosol, sodium c h l o r i d e at the concentration of sea water, and sea water i t * s e l f were the 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 sulphate and calcium bicarbonate were n e a r l y i n e f f e c t i v e . Time was found to 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 that -a v a r i e t y of types of 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 time, 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 of the sea. They also concluded that p r e c i p i t a t i o n of ir 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 ferruginous and s i l i c e o u s deposit i f the supply were i n t e r m i t t e n t . Davis found that "when a s o l u t i o n of ammonium carbonate i s c a r e f u l l y introduced into an aqueous suspension of f i n e l y divided c l a y c o n t a i n i n g a moderately strong content of sodium s i l i c a t e there i s a downward d i f f u s i o n of the ammonium carbon-ate, l e a d i n g to flo c c u l a t - i o n of the s i l i c i c a c i d and production of a l t e r n a t e laminae of f i n e c l a y and c l e a r gelatinous s i l i c a . Substitution/: of powered red shale or powdered c r y s t a l l i n e quartz f o r the 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 that some of the reagents used by Moore and Maynard, i n c l u d i n g sea water i t s e l f , might replace the ammonium carbonate i n Davis' experiment, and that a sediment made up of laminations of c o l l o i d a l s i l i c a and clayey m a t e r i a l could be formed i n the sea by the inte r m i n g l i n g of sea water 8S and s o l u t i o n s of sodium . s i l i c a t e c a r r y i n g f i n e l y suspended c l a y e y m a t e r i a l . In p a r t i c u l a r , i t seems f e a s i b l e that some of the -volcanic flows of the Valdes Group could have reacted with sea water, as described i n the previous s e c t i o n , to pro-duce 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 divided clayey m a t e r i a l i n suspension, and that t h i s mixture r e a c t i n g w i t h f r e s h supplies of sea water could have produced a f i n e l y laminated sediment which on c r y s t a l l i z a t i o n , perhaps under the influence of the succeeding l a v a flow, would form the f i n e l y laminated sediment as found on Quadra Island and near Menzies Bay. The small amount of carbonaceous matter (5 per cent) may have been present i n the o r i g i n a l sea water, or l y i n g on the l a v a surface, or i t may have been brought i n by the f r e s h supply of sea water which caused the p r e c i p i t a t i o n of the sediment. The Concentration o f Vanadium i n the Seam: I t was pointed out that d e r i v a t i o n of the vanadium i n the sediment from the lava would re q u i r e a concentration of only t e n times. I t i s p o s s i b l e that the vanadium was not obtained from the l a v a , but the l a v a i t s e l f or magmatic s o l u t i o n s connected with t h e vo l c a n i c a c t i v i t y seem t o be a simple and d i r e c t source. In any ease, the processes by which the vanadium was concentrated i n the sediment are not obvious, e s p e c i a l l y since the form of the vanadium i s not known. The 83 f o l l o w i n g processes are a l l that have been considered by the author. A. Syngenetic Concentration: 1. P h y s i c a l processes: vanadium i n an in s o l u b l e form, contributed d i r e c t l y from the lavas by weathering without excessive 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 the other c o l l o i d ( s ) ; (b) vanadium protected or absorbed by the other c o l l o i d ( a ) ) and c a r r i e d down with them. 3 . Organic processes: (a) by organisms using vanadium i n t h e i r l i f e processes. (b) by the reducing a c t i o n of l i v i n g organisms or decaying organic 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 sulphate so l u t i o n s by CaCOg (b) from a l k a l i carbonate and bicarbonate and calcium bicarbonate s o l u t i o n by loss of c o 2 . ; (e) as calcium ( a l k a l i n e earth) vanadium salt(-s) which are 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 er. (d) as sulphide^s) p r e c i p i t a t e d by HgS 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 . Le) as i n s o l u b l e double s a l t ( s ) of copper and calcium. B. Epigenetic Concentration: P r e c i p i t a t e d i n the seam from magmatic or ground waters, 1. from vana'die s o l u t i o n s by metals forming i n s o l u b l e vanadates. 2. from vanadyl sulphate s o l u t i o n s by CaOO 3. 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 calcium (alkaline) 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 plant or organic remains, c f . Bade'r's hypothesis p. 30. 6. by absorption i n very fine-grained m a t e r i a l . Epigenetic concentration i s very u n l i k e l y because, apart from the l a v a i t s e l f , vanadium i n appreciable amounts i s r e s t r i c t e d to the black laminated sediment. I t i s not present i n the copper amygdules nor i n the high grade chalco-c i t e l e n s , and t h e r e f o r e i t seems hardly p o s s i b l e that i t could have been introduced along "with the copper. The quartz veins contain no vanadium. I t i s not present i n other amygdules i n the l a v a , nor i n the limestone o v e r l y i n g the black seam. As f o r leaching from the surrounding rock by ground waters and p r e c i p i t a t i o n on contact w i t h copper s a l t s i n the seam, t h i s process i s always confined to zones of o x i d a t i o n , and there i s very l i t t l e o x i d a t i o n i n the seam i t s e l f . There are no obvious channels by which vanadiferous s o l u t i o n s could have reached the seam, and i t w i l l be remem-bered that the 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 doubtful i f 5 jxer cent of organic mat e r i a l , even i f i t were not carbonized, 85 could 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 absorption of vanadium by the seam, accompanied perhaps by a slow migration of s o l u b l e vanadium s a l t s through a concentration gradient, has not been eliminated, but the r a d i c a l d ifference i n vanadium content between the black seam and the o v e r l y i n g limestone i s too great to be explained on the basis of s e l e c t i v e absorption. The case f o r a syngenetic o r i g i n i s good. P h y s i c a l processes, without chemical change, have to be r e j e c t e d however because the vanadium i n the seam i s r e a d i l y soluble i n d i l u t e a c i d s , whereas vanadium i n the l a v a i s soluble with d i f f i c u l t y . Vanadium i s not i n the quartz, ( E l l s w o r t h and Gunning) and there is no c l a s t i c m aterial with the vanadifer-ous sediment. The analyses given by E l l s w o r t h and Gunning show that the vanadium cannot be present as a sulphide, because i f 98 per cent of the copper i s present as CugS there i s j u s t enough sulphur (0.72 per cent) to be combined wi t h the copper (2.88 per cent). A c t u a l l y about 5 to 10 per cent of the copper is present as c o v e i l i t e and malachite, and p o s s i b l y as sulphate and s i l i c a t e , and some of the sulphur i s apparently present as SOg. Also unless there was enough copper present 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 of copper and calcium w i t h vanadium could not have formed, since the l a r g e r part of the copper m i n e r a l i z a t i o n i n the seam i s obviously epigenetic. P r e c i p i t a t i o n by calcium carbonate i s not l i k e l y because the associated limestone contains very l i t t l e vanadium. Under syngenetic concentration 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 of concentrating the vanadium i n the sediment. Process 3 (b) o r d i n a r i l y produces sulphides which have, been eliminated because of the shortage Of sulphur. Organic processes cannot be eliminated, but there are only a very few species o f marine animals which are' known to f i x l a r g e amounts of vanadium i n t h e i r bodies. The vanadiferous sediment i t s e l f contains no recognizable f o s s i l s and only about f i v e per cent of carbon and a t r a c e of phosphorous. C o l l o i d a l processes, on the other hand, f i t i n very n i c e l y w i t h the proposed theory f o r the formation of the vanadiferous 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 discussed i n Chapter I I i s i n d i r e c t , many vanadium compounds are known to assume the 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 of adoption by any s p a r i n g l y s o l u b l e substance." (Glasstone-Textbook of P h y s i c a l Chemistry.) I t i s h i g h l y prob&ble that the contact of hot vanadium-bearing lavas w i t h sea water would place appreciable q u a n t i t i e s of vanadium compounds into 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 then be p r e c i p i t a t e d by sea water or other s a l t s i n s o l u t i o n , or 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 or other p r e c i p i t a t i n g c o l l o i d s . Some vanadium compounds maybe absorbed by other c o l l o i d s and p r e c i p i t a t e d with them, or they may he p r e c i p i t a t e d h-~ by ordinary chemical processes. The author regrets having to leave the problem without v e r i f y i n g the hypothesis with f u r t h e r laboratory work. Samples of the f r e s h l a v a of known vanadium content could be heated to 1200° or 150O°C. i n a muffle furnace and plunged into s a l t water approximating the composition of sea water, the mixture f i l t e r e d , and the f i l t r a t e and residue assayed f o r s i l i c a and vanadium. 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 . Further chemical i n v e s t i g a t i o n and a n a l y s i s would probably reveal the form i n which the vanadium i s present i n the sediment. Assuming that t h i s c h e m i c a l - c o l l o i d a l hypothesis f o r the formation of the sediment and the concentration of the vanadium i n i t were c o r r e c t , the thickness of a given vanadiferous seam would depend on the amount of material put into s o l u t i o n , or suspension by the r e a c t i o n of lava w i t h sea water, and the amount of t h i s m a t e r i a l which could be p r e c i p i t a t e d i n one place before the succeeding flow of l a v a . I t i s not l i k e l y that t h i s process would form deposits large enough to be commercial vanadium ore, but a f t e r a l l most ore deposits were formed by an unusual persistence of a s i n g l e process or group of processes. Conditions of the s o r t required to produce sedimentary magnesite deposits, f o r example, must have p e r s i s t e d f o r an unusually long time to cause the p r e c i p i t a t i o n of the large magnesite deposit at 88 M a r y s v i l l e , B r i t i s h Columbia. Perhaps i n a shallow basin, p a r t l y surrounded by lavas and preserved through many flov/s of l a v a , a commercial sedimentary vanadiferous deposit of the^Quadra I s l a n d " type might have formed*. BIBLIOGRAPHY. ^ .01 THE OCCURRENCE OP VANADIUM. General; 1. Anon.:, Vanadium Ores Monograph, Imperial 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, Arizona Bur.Mines, B u l l * No.115. 23 pp. S e p t . l , 1921. 3. " Clarke, F.W., Lata of Geochemistry, U.S.Geol. Surv. Bull.770, pp. 722,723. 1924. 4. Clarke, F.W., and Washington, H.S. The Composition of the Earth's Crust. U.S. Geol. Surv. Prof.Paper 127, pp. 20, 40, 1924. 5. Curran T.F.V., Vanadium ores and uses: Eng. & Min. Jour. 1 v o l . 93. 1912. 6. Hermann, F e l i x , (The n a t u r a l occurrence of Va.) M e t a l l ? / i r t -s c h aft, 15 (43): 1007-1015, Oct. 23, 1936. 7. Hentze, Ernst. (World supply of Molybdenum, Vanadium, and Tungsten) Z. 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