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Economic Geology

Vol. 57, 1962, pp. 226-237

DIFFUSION FEATURES OF URANIUM-VANADIUM DEPOSITS


IN MONTEZUMA CANYON, UTAH

LYMAN C. HUFF AND FRANK G. LESURE

CONTENTS
PAGE

Abstract .............................................................. 226


Introduction .......................................................... 227
MontezumaCanyonore deposits......................................... 228
Bleached red beds ..................................................... 231
Diffusion ............................................................. 232
Diffusionhypothesis
of ore deposition.................................... 232
Distribution of diffusion features ........................................ 234
Oxidation of zoned ore bodies .......................................... 235
Guidesfor prospecting ................................................. 235
Suggestionsfor furtherstudy........................................... 235
References ............................................................ 236

ABSTRACT

Uranium-vanadium depositsin the Salt Wash Memberof the Morrison


Formationin MontezumaCanyon,San Juan County,Utah, exhibit zoning
that is interpretedas a result of metal transportby diffusion. The con-
centric zonesconsistof a brown nonmineralizedcore, an olive-gray min-
eralizedshell,and a gray nonmineralized outerzone. The brown zoneis
iron-stained,poroussandstonecommonlycontainingabundantcarbona-
ceousmaterial. The curved mineralizedlayer completelyenclosesthe
brownzone,and is composed of oxidizeduranium-vanadium mineralsthat
impregnatesandstone.The gray zone is light-gray sandstonetightly
cementedwith calciteand commonlyfreckledwith limonitic specks.
Formationof the depositsmostlikely took placeduring Late Creta-
ceousor early Tertiary time when the ore-bearingsandstones were deeply
buried and saturated with conhate waters. The concentration of organic
material in the brown zonesuggeststhat this zonewas oncesaturatedwith
a reducingsolutioncontainingsolubleorganiccompounds like alcoholsand
aldehydesderivedfrom the organicmaterial. The gray zone,on the other
hand, was probably saturated with an oxidizing solution containing
uranium and vanadium. Where these two solutions were in contact,
oxidation-reductionreactionstook place that causedthe precipitationof
low-valent uranium and vanadium minerals.
The ellipsoidalshapeof the ore layer and the lack of any exit or en-
trance for flowing solutionsindicatesthat the dissolvedmetals moved
throughthe gray zoneby diffusionand were precipitatedat the periphery
of the reducingzone. Recentweatheringand oxidationhave alteredthe
primary low-valentminerals to high-valentforms without noticeable
leaching of the ore metals.
Publication authorized by the Director, U.S. Geological Survey.

226
URANIUM-VANADIUM DEPOSITS IN UTAH 227

INTRODUCTION

Tar. ColoradoPlateau of southwesternColoradoand the adjacentparts of


Utah, Arizona, and New Mexico contains numerous uranium-vanadium de-
posits that have been subjectedto intensivegeologicstudy in the last 2
decades. Many of thesedepositsare in the Salt Wash Memberof the Morri-
son Formationof Late Jurassicage, and in any one mining district the ore
is generallyfoundin a singlestratigraphiczonein the Salt Wash (6, p. 3).
The sandstone bedsrangefrom lessthan 20 to more than 80 feet in thickness

UTAH

M onticell'o "

Montezuma Canyon

Area

SAN
JUAN COUNTY :.

o 20 40
Miles

FIG. 1. Index mapof Montezuma


Canyonarea,San JuanCounty,Utah.

and extendfor severalhundredto severalthousand feet (14, p. 269). The


ore, averaging0.25 percentUaO8and 2 percentV20,, impregnates the sand-
stoneand replacesfossilplant material (24, p. 17). The irregular tabular
ore bodiesgenerallylie parallelto the sandstone
bedding,but locallycrosscut
the beddingsharply. The depositshavea spottydistributionand tend to be
grouped in small widely separatedareas. In southwesternColorado and
adjacentUtah someof the larger depositsform groupsthat lie in a narrow
arcuatepathcalledthe Uravanmineralbelt (6, p. 3). The uranium-vanadium
depositsof the MontezumaCanyonarea (Fig. 1) are near the southwestern
end of this belt and exceptfor their small size and low grade are similar to
someof the depositsin the belt to the northeast.
228 L. C. HUFF AND F. G. LESURE

Manytheorieshavebeenadvanced
to explainthe originof theseandother
uranfin-vanadium
d'posits
oftheColorado
Plateau.Deposition
fromhydro-
thermal(juvenile)fluids,connatesolutions,
or groundwaterhavebeenpro-
posedand examinedin terms of geologicfeatures. The chemistryof the
depositsand the chemicalcausesof precipitationhavebeenstudiedin detail.
Lessattention,however,has beenpaid to the mannerof transportof the ore
metalsin solutionor to the relationshipbetweentransportand ore deposition.
During the geologicmappingof the MontezumaCanyonarea the consistent
pattern of mineralized and nonmineralizedsandstonein some of the smaller
uranium-vanadium depositssuggestedan hypothesisinvolvingsolutediffusion
as an explanationfor ore transport.

TABLE 1

GENERALIZED STRATIGRAPHIC SECTION OF THE MESOZOIC ROCKS OF THE


MONTEZUMA CANYON AREA

Thickness
Age Group Formation and member
in feet
Character
__

Mancos Shale 0-380 Dark-gray fissile shale.


Late
Dakota Sandstone 80-150 Sandstone, interbedded carbonace-
Cretaceous
ous shale and coal; thin con-
glomerate at base locally.
Unconformity
Early Burro Canyon Formation 50-180 Conglomeratic sandstone and inter-
Cretaceous bedded green mudstone.
Unconformity
220-440 Varicolored bentonitic mudstone.

Morri-
son
fBrushy
Basin
Member
JWest-wter
Cnyo 0-180 Lenticular sandstone and mud-
stone.
Forma-
1 Member
tion(SaltWash
Member 300-520 Lenticular sandstone and mudstone
Jurassic Unconformity
Summerville Formation 80-130 Even-bedded red mudstone, and
sandstone.

San
Rafael
Group Entrada Sandstone
Carmel Formation
150-165

40-45
Fine-grained white sandstone.
Silty red sandstone.

Triassic
(?)'
Unconformity
Navajo Sandstone 26 Fine-grained white sandstone.

This report is a by-productof geologicmapping and mineral resource


studyof the MontezumaCanyonarea by the U.S. GeologicalSurvey from
1955 to 1957 on behalf of the Division of Raw Materials, U.S. Atomic
Energy Commission.

MONTEZUMA CANYON ORE DEPOSITS

Geologicformationsexposedin the MontezumaCanyonarea range from


the Navajo Sandstoneof Triassic (?) and Jurassicage to the Mancos Shale
of Late Cretaceousage (Table 1). Of theseonly the Salt Wash Member of
the Morrison Formation contains uranium-vanadiumdeposits. The Salt
Wash Member is composedof lenticular beds of white, yellowish-grayor
light pinkish-graysandstone
separatedby.layersof thin-bedded,grayish-red
mudstone. The sandstonebeds form a seriesof steep cliffs separatedby
URANIUM-VANADIUM DEPOSITS IN UTAH 229

debris-coveredmudstoneslopesand benchesalong the sidesof Montezuma


Canyonand its tributaries. The bedsare nearlyhorizontaland in generalare
structurallyundisturbed.

Fee
t

FIG. 2. Generalizedblockdiagramof the Moaburaniumdepositin Montezuma


Canyon, San Juan County, Utah (SW1/4NW1/4 sec.22,T.34S., R.24E.; for
location see Huff and Lesure, 1958).

Only a smallfractionof the Salt Wash Member is mineralized. Most of


the uranium-vanadium depositsare in prominentsandstonelensesnear the
middle of the member. These lensesrange from 20 to 100 feet in thickness
and containmany crossbedded channeland scourfillings. The ore deposits
occurat variousplaceswithin the sandstonelensesand generallycut across
adjacentchannelor scourfillings. None of the known depositsis restricted
230 L. C. HUFF .4ND F. G. LESURE

to one "channel." Many of the ore depositsare near local concentrations


of
carbonaceous plant materials.
Most of the ore depositshave a systematiczonal pattern of mineralized
and nonmineralized rock,bestdeveloped in smalldepositslike the Moab and
Blue Jay No. 3 (Figs. 2, 3). Three concentriczonesare recognized:the
brown zone, the mineralizedor ore zone, and the gray zone. The brown

FIG. 3. Generalizedblock diagram of the Blue Jay No. 3 deposit,Monument


Canyon,San Juan County,Utah (NWlNE4 sec.20, T.37S., R.25E.; for location
seeLesure and Stugard, 1958).

zone,a porousiron-stainedsandstonecommonlycontainingabundantcarbo-
naceous material, forms the center or core. The mineralized zone is an
olive-graysandstoneimpregnatedwith roscoelite,carnotite,metatyuyamunite,
simplotite,metarossite,and other uranium-vanadiumminerals. It forms a
layer or shell that completelysurroundsthe brown zone. The gray zone is
a light-graysandstone, tightly cementedwith calciteand freckledwith limonite
specks,that encloses the mineralizedzone. Assaysindicatelittle or no ore
metals in the brown and gray zones.
URANIUM-VANADIUM DEPOSITS IN UTAH 231

The brown zone and the surroundinglayer of the mineralizedzone com-


monlyform an irregular,flattenedellipsoid20 to 40 feet long, 10 to 20 feet
wide, and 4 to 10 feet thick. The mineralizedlayer may range from to
4 feet in thickness. Generallythis layer followsthe beddingor crossbedding
of the sandstone,but locallyit cutsacrossbeddingandcrossbedding and curves
around to form the ends or the sides of the shell. Most of these "rolls" are
in lensesof clean,well-sortedsandstone. No controlof the location,shape,or
sizeof the ore bodiesby jointing,or by attitudeof the rockswas observed,
and little of the ore directly replacescarbonaceous materials. Commonly
the mineralizedzoneis a singlelayer, but locallyit is a seriesof subparallel
layers resemblingLiesegangrings, or similar to the bandsin depositsob-
servedby Fischer (5, Plate 56A).
Similar zonesare presentin larger uraniumdepositsin the area, but are
not as clearly differentiated. The zonal pattern is more complicated,and
there may have beenseveralstagesof zonal development in someof these
larger deposits.
Someof the depositshavebeenminedrecently,and prospectingwithin the
area has beenactive. The aggregateproduction,however,is small. Few of
the minesextendbackfarther than 50 feet from the outcrop,and only 5
mineshad producedmore than 1,000 tons of ore up to 1957.

BLEACt-IED RED BEDS

Bleachedred bedsare commonin the MontezumaCanyonarea, and the


useof bleachingas a guide for uraniumprospecting(14, 24) has lessvalue
here than in other areasof the ColoradoPlateau. Shortly after deposition,
all the mudstoneand fine-grained sandstonebeds of the Salt Wash Member
were probablyred or reddishbrown (19, p. 516), and the coarse-grained
sandstonelenseswere probablypinkishgray or pale reddishbrown. Much
of the coarse-grained
sandstone
has beenbleachedto white or yellow gray,
and ! to 2 feet of the mudstone, where it is in contact with sandstone, is
bleachedto a light greenishgray. Thin isolatedlensesof fine-grainedsand-
stonecompletelyenclosedin thick layers of mudstone,however,still retain
their original red color. The red of both mudstoneand sandstoneis caused
by a ferric oxide coatingof the clay particlesand sandgrains,and bleaching
is the resultof reductionandremovalof thisiron coating(11, p. 117-118; 16,
p. 136; 22). At least someof the iron removedduring bleachingplus iron
from detrital magnetiteand ilmenitegrains was convertedto pyrite (17, p.
217; 19, p. 517).
To studythe bleachingof the sediments,we took samplesof red mudstone
and pinkish-gray sandstonefrom the Salt Wash Member in Montezuma
Canyonand crushedand sievedeach. Using test tubeswith a layer of mud
or sandaboutan inchdeep,we addedpeatto someand carbonizedwoodfrom
the Salt Wash to others. The test tubeswere filled with water, either tap
or distilled,and allowedto standfor severalweeks. The pinkish-graysand
in contactwith peat becamelighter coloredafter 1 to 2 weeks; the red mud
had a similar reactionbut took severalweekslonger. Neither sandnor clay
232 L. C. HUFF .4ND F. G. LESURE

in contactwith carbonized
woodlost color. The type of water usedmade
no difference in the reactions. Microchemical tests showed that the dis-
colorationwasdueto a lossof iron, presumably from solutionof someof the
ferric oxidegrain coating. Theseresultsare somewhatsimilarto the bleach-
ing of red bedsby hydrogensulfide (10), and to field observationsof the
bleachingof red beds near organicmaterial (21). An importantfactor
involved,however,is that no flow of solutionstook placein our experiments;
the only movementwasthe slowdiffusionof reducingsolutionfrom the peat
into the sedimentsand the migrationof iron away from the sediments. A
slightdeposit'of hydrousiron oxidesgenerallyformedat the surfaceof the
water in the test tubes.

DIFFUSION

The movementof dissolvedsubstances through an undisturbedsolution


in directionstendingto equalizeconcentration in all parts of the solution
is calleddiffusion. A classicexperimentillustratingdiffusionis to placea
blue coppersulfatesolutionbeneatha layer of clear water in a test tube.
If carefullyprepared,the interfacebetweenthe two layersis sharplydefined
at first, but in a few hours the blue color spreadsinto the water layer,
showingthat the blue copperions are moving upward. Such movementis
taking place under a concentrationgradient--that is, the coppersulfate is
moving from an area of high concentrationto an area of low concentration.
When the solutionsare completelymixed, the net movementor diffusion
ceases,althoughthe kinetic or Brownian motion continues. The diffusion
of copperalso can be demonstratedwhere copperis being removedfrom
solution. If iron filings are placedat the bottom of a test tube containing
a coppersulfatesolution,the copperions diffusedownwardto replacethose
beingdepositedon the iron sothat the net effect,as shownby the blue copper
ions,is to decreasecopperconcentration throughthe entire solution.
A classicalstudy of diffusionas relatedto geologicprocesses was made
by Liesegang(13). In his experimentalprecipitationof rings, Liesegang
permittedsolutionsthat reactedto form a precipitateto diffusetoward each
other in gelatine. BesidesLiesegangrings,he explainsmany other rounded
geologicalfeaturessuchas concretions, geodes,nodules,and someore deposits
as the result of diffusion.

DIFFUSION HYPOTHESIS OF ORE DEPOSITION

The ellipsoidalmineralizedshellin the zonedore bodiesshowscontinuous


depositionof ore mineralsat the peripheryof the brown zone. Deposition
of mineralsfrom simplesolutionflow might produceasymmetricore bodies
with depositionof mineralson the "upstream"sideor possiblythe formation
of tubular bodieswith an entranceand an exit for the flowing solution. The
shapeof thesezonedore bodies,however,is analogous to the shapeof
Liesegangrings,concretions,and geodesof probablediffusionorigin. The
bleachingof the red mudstonesin contactwith large sandstone
lensesalso
suggeststhe diffusionof reducingsolutions.The impermeable mudstones
URANIUM-VANADIUM DEPOSITS IN UTAH 233

wouldnot permitmuchsolutionflow throughthem,but a reducingsolution


couldpermeatemudstone by diffusionand thuscausethe bleaching.
In orderto evaluate
the significance
of theseobservations
andthe applica-
bilityof the diffusion
hypothesis,
we musttry to visualize
as nearlyas pos-
siblethe physicaland chemicalconditions at the time of ore formation. Age
determinations of what are believedto be primaryuraniummineralsfrom
depositsin otherpartsof the ColoradoPlateauindicatedeposition of these
mineralsduringLate Cretaceous or early Tertiary time (20). During that
time,the Salt Wash Memberin the MontezumaCanyonarea was buriedby
5,000to 8,000feetofyounger
formations
thathavesincebeenpartlyremoved.
Temperatures at that depthwouldprobablyhavebeenabout100 to 120 C
and the hydrostaticpressureabout200 atmospheres (4; 15, p. 506). The
porosityof the mudstoneunitswouldhavebeenreducedto lessthan 5 per-
centby compaction and the originalwater contentof the mud reducedby 80
to 90 percent(1, p. 32; 2, p. 13).
Accordingto our diffusionhypothesis
the organicmatterdeposited in the
sandstonebedsof the Salt Wash wouldbe decomposing and liberatingwater
solublereducingagentslike alcohols,
aldehydes,
humicacids,and hydrogen
sulfide. As thesereducingagentsdiffusedslowlyoutward,reductionof the
ferric oxide grain coatingsof the sandgrains in the sandstoneand of the
clay particlesin layers of mudstoneadjacentto the sandstonewould take
place. Much of the iron wouldbe reprecipitated as scatteredpyrite grains.
In areas lacking organicmaterialsthe connatewaters would accumulate
oxidizingmaterialslike ferric sulfatethat were in equilibriumwith the ferric
oxidegrain coatings.Locallythe oxidizingsolutions
also containedsome
dissolveduranium and vanadium. Where these oxidizing solutionsen-
counteredthe more concentratedreducingsolutionsnear accumulations of
organicmaterialoxidation-reduction
reactionsprecipitated
ore mineralsalong
the interface between the two solutions. As more uranium and vanadium
diffusedtowards the site of precipitationa completeshell of sandstone
cemented by ore mineralsformedarounda coreof reducingsolutions.
The chemical
reactionsinvolvedin ore deposition
wouldbe: 1) oxidation
of carbonandhydrogenin theorganicmaterialto solubleorganiccompounds,
carbonateand water, 2) reductionof iron, uranium,and vanadiumto their
low-valent states,and3) precipitation
of pyrite,uraninite,coffinite,
montrose-
ite, and roscoelite.All thesematerialsexceptpossibly the ore metalscould
havebeenderivedfrom the enclosing sediments.Only a smallamountof
carbonaceous materialis requiredto reduceand precipitate uraniumfrom
solution(8, p. 157). The amountof carbonaceous materialneededto bleach
the red bedshasnot beencalculated. Plant remains,however,are socommon
in the sandstone
bedsof the Salt Wash that enoughsolubleorganiccom-
pounds wereprobably
present
to bleach
thesedimentsaswellasto precipitate
the ore minerals.
Recentstudyshowsthaturaniumandvanadium are soluble
in mildly
reducing,neutralto alkaline
waterrichin CO2. The metalsareprobably
in solution
as tetravalent
vanadiumionsandcomplexionscontaining
hexa-
valenturaniumand carbonate(I--Iostetlerand Garrels,written coremunica-
234 L. C. HUFF .4ND F. G. LESURE

tion). The source of the uranium and vanadium is uncertain and direct
evidence
of a sourceis notpresent. The generallackof ore mineralsin the
brown zone, however,suggeststhat distributionof uranium and vanadium
in theconnate
waterswasnotuniformat thetimethatreducing environments
beganto develop.It is possible
that the solution
of uraniumtookplacein
theperipheralareasof bleaching
wherea highcarbonate
concentration
resulted
from the oxidationof organiccompounds.
The thickness
of themineralized
layerin thediffusion-type
deposit
would
be relatedto its positionin the enclosing
sandstone.In general,the mineral-
ized layer is thickestand richeston the side facingthe greatestmassof
sandstone. It is thinnest and leanest where the mineralized zone is close
to an impermeable mudstone.This difference probablyreflectsthe principal
directionof transportof thediffusingmetalions. Quantitative studiesshow
thatthe amountof materialtransferred in diffusiondepends on the porosity
in the directionof diffusion(7, p. 1809-1810).
Locallyin the zoneddeposits carbonaceousmaterialis replaced
by ore
minerals,but mostof the ore is in clean,well-sorted
sandstone containing
no traceof organicmaterial. Commonly, carbonizedplantfragmentswith a
negligibleuranium contentcan be found within 10 to 20 feet of ore. The lack
of replacement
of carbonaceousmaterialby ore couldbe interpreted
as indi-
catingno chemicalrelationshipbetweenthem. If the plant matter is the
sourceof water solublereducingcompounds that migratedaway from their
source, this lack of direct correlation between ore and carbonized wood is
explained.

DISTRIBUTION OF DIFFUSION FEATURES

Ore rolls in uranium depositshave beenfound in the Morrison formation


in manypartsof the ColoradoPlateau(5, p. 383-387; 18). In general,these
are openformsthat in crosssectionare C. S, or socketshaped(18) in con-
trast with the closedore bodiesof MontezumaCanyon. The curved form
and bandednature of open rolls are somewhatsimilar to Liesegangrings
and may indicatediffusionto and precipitationalong the interfacebetween
two solutions. The open ends, however, suggestthat solution flow was
alsoimportant (19).
Deposits similar to those describedfor Montezuma Canyon also are
presentin the Thompsonsdistrict and at various placesalong the Uravan
mineral belt (Fischer, written communication). It is possiblethat these
closed ore bodies indicate less solution flow than in other areas of the Colo-
rado Plateau. In all the areas in which closed forms are found the rocks are
flat-lying and structurally undisturbed. The flow of fluids through these
rocksmay have beenlimited largelyto the water expelledduring compaction,
which probablystartedshortlyafter burial and was nearly completedby Late
Cretaceous. This flow would be slow and would not interfere with formation
of diffusion-typeore bodies. The small flow may evenhave helpedto bring
uranium and vandiumfrom a more extensivearea than possiblewithout any
fluid flow. Simple diffusion-typeore depositswould be small if the amount
URANIUM-VAN.51DIUMDEPOSITS IN UTAH 235

of ore metalswas limited entirely to what was originallypresentnear the


growing ore body.

OXIDATION OF THE ZONED ORE BODIES

The primaryore mineralsof the zonedore bodieswere probablyroscoelite,


uraninite,montroseite,and coffinite;elsewhereon the ColoradoPlateau (23)
theseare found today belowthe zone of oxidation. Following the deposition
of the ore bodiesat MontezumaCanyon,the area was uplifted and deeply
eroded. During the cuttingof MontezumaCanyon,the water tablewas low-
ered belowthe level of the ore bodiesand oxidationof the primary minerals
began. Today the ore bodiesare completelyoxidizedexceptfor the vanadium
silicate,roscoelite,
whichis generallyunaffectedby oxidation(3, p. 216; 23,
p. 73). Pyrite in the brownzonehasbeenalteredto goethite,whichgivesthe
zone its characteristic
color. The ore minerals(except roscoelite)have oxi-
dized to carnotite,metatyuyamunite,simplotite,metarossite,and the other
uranium-vanadium
mineralswith little leachingof uraniumor vanadium. The
scatteredgrainsof pyrite in the gray zone have oxidizedto goethite,pro-
ducing the commonbrown freckles.

GUIDES FOR PROSPECTING

The identificationand mappingof the zonesin a zonedore depositpro-


videsa systematic methodof testingwhetherthe ore layerhasbeensatisfac-
torily explored. Severalof the minesand prospects of MontezumaCanyon
containore deposits in whichonesideof the ore bodyhasbeenexploredbut
where explorationhas stoppedwithin the brown zone beforereachingthe
othersideof the ore body. It is particularlyadvisableto explorethe ore layer
betweenthe brown zoneand the main massof sandstonebecausethis may be
the thickestand richestpart of the ore zone.
In the MontezumaCanyonarea the ore bodiesare associated with thick
sandstone lensesthat are the sandyfill of ancientmeanderingstreamchannels.
The ore bodiestend to be elongate,parallelto the axesof thesechannelsas in
other areasof the ColoradoPlateau (5, p. 384) and are likely to be associated
with accumulationsof logs and organic trash. Some depositsin middle
MontezumaCanyonare on the slip-offslopeof meandersthat are comparable
to gentle banks where driftwood accumulatesalong modern rivers. Such
environmentsare consideredfavorablefor prospecting.

SUGGESTIONS FOR FURTHER STUDY

The hypothesisthattheoredepositsof MontezumaCanyonweredeposited


by a diffusionprocess
in a stagnantsolutionhasseveralcorollaries
that may
merit further study. Inasmuchas diffusion is a slow process,practical
limits are placeduponthe distanceof migrationof the ore metalsprir to
deposition.Quantitativegeochemical studiesperhapscouldbe madeto find
the maximumsizeof purely diffusiontype ore bodies. Useful criteriamight
alsobe developed for distinctionbetweendepositsmadeby stagnantsolutions
236 L. C. HUFF .4ND F. G. LESURE

and thoseby flowingsolutions. If thesecriteriawere usedin regionalstudy


they might lead to a betterunderstanding of the migrationof the ore metals
prior to depositionand the origin of the large as well as the small uranium
deposits.
LYMAN C. HUFF,
U.S. GEOLOGICAL SURVEY,
DENVER,COLORAm)
FRANK G. LESURE,
U.S. GEOLOGICAL SURVEY,
WASHINGTON,D.C.,
Oct. 11, 1961

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URANIUM-VANADIUM DEPOSITS IN UTAH 237

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