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Uranium in Granitic Magmas Part 1. Experimental Determination of Uranium Solubility and Fluid-melt Partition Coefficients in the Uranium Oxide-haplogranite-H2O-Na2CO3 system at 720-770°C, 2 kbar, Chantal Peiffert, Michel Cuney, and Chinh Nguyen-Trung

Uranium in Granitic Magmas Part 1. Experimental Determination of Uranium Solubility and Fluid-melt Partition Coefficients in the Uranium Oxide-haplogranite-H2O-Na2CO3 system at 720-770°C, 2 kbar, Chantal Peiffert, Michel Cuney, and Chinh Nguyen-Trung

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Published by Meisam Rasouly
Uranium in granitic magmas: Part 1. Experimental determination of uranium solubility and fluid-melt partition coefficients in the uranium oxide-haplogranite-H2O-Na2CO3 system at 720-770°C, 2 kbar
Chantal Peiffert, Michel Cuney, and Chinh Nguyen-Trung
Geochimica et Cosmochimica Acta , Volume 58 , No. 11 , pp. 2495-2507 , 1994
Elsevier Scince Ltd, 1994 , Pergamon, 0016-7037(94)00052-2

The solubility of uranium was investigated in both carbonated aqueous fluid and granitic melt in equilibrium in the system haplogranite-uranium oxide-H2O-Na2CO3 (0.5–1 molal) at 720–770°C, 2 kbar, andƒo2 fixed by Ni-NiO, Fe3O4-Fe2O3, and Cu2O-CuO buffers. As complete solid solution exists between UO2.00 and UO2.25 (i.e., 75 mol% UO2 + 25 mol% UO3), three distinct uranium oxides: UO(2.01 ± 0.01), UO(2.1.0 ± 0.02), and UO(2.25 ± 0.02) were, respectively, obtained at equilibrium, under the three ƒo2 conditions cited above. Thus, the percentage of U (VI) in uranium oxide increased with increasing log ƒo2. The thermal decomposition of Na2CO3 to CO2 and Na2O led to the decrease of the sodium carbonate concentration from 0.5–1 molal to ~10−2 molal in all aqueous fluids and to the dissolution of Na in the silicate melts. Crystal-free silicate glasses with four agpaitic coefficients, View the MathML source were obtained.

The uranium solubility in 10−2 m aqueous carbonated fluid ((8.1 ± 0.1) ≤ quench pH ≤ (8.9 ± 0.1)) was in the range 1–17 ppm and increased linearly with increasing ƒo2 according to the expression: View the MathML source. This equation is valid for the temperature range 720–770°C and 2 kbar.

U(IV) carbonate possibly were major species in aqueous solutions under reducing conditions (Ni-NiO buffer) whereas U(VI) carbonate complexes dominated under higher oxidation conditions (Fe3O4-Fe2O3, Cu2O-CuO buffers).

The uranium content in silicate glasses varied in a large range (102–2 × 105 ppm) and log (U) (ppm) increases linearly with both ƒo2, and α in the range 1.1–1.5 according to the equation View the MathML source. This equation is valid for (1)ƒ o2 ranging from Ni-NiO to Cu2O-CuO, and (2) the temperature range 720–770°C at 2 kbar. The effect of ƒo2 on the uranium solubility in silicate melt slightly decreased with increasing α from 1.1 to 1.5.

For α in the range 1.5–1.7, the effect of both ƒo2 and agpaicity index on the uranium solubility was considerably reduced.

The temperature variation in the range 720–770°C had no significant effect on the uranium solubility in either aqueous fluid or silicate melt.

The partition coefficient (Dfluid/melt) of uranium was in the range 10−4.0−10−1.5 and depended on both ƒo2 and α according to the equation View the MathML source. The validity conditions of this equation are similar to those of the preceding one.

Results obtained in the present study could be used to predict the geochemical behaviour of uranium during magma fractionation and to further understanding of the formation of uranium ore deposits related to partial melting or fractional crystallization of felsic magmas. The genesis of the Kvanefjeld (Ilimaussaq, Greenland) uranium deposit is discussed.
Uranium in granitic magmas: Part 1. Experimental determination of uranium solubility and fluid-melt partition coefficients in the uranium oxide-haplogranite-H2O-Na2CO3 system at 720-770°C, 2 kbar
Chantal Peiffert, Michel Cuney, and Chinh Nguyen-Trung
Geochimica et Cosmochimica Acta , Volume 58 , No. 11 , pp. 2495-2507 , 1994
Elsevier Scince Ltd, 1994 , Pergamon, 0016-7037(94)00052-2

The solubility of uranium was investigated in both carbonated aqueous fluid and granitic melt in equilibrium in the system haplogranite-uranium oxide-H2O-Na2CO3 (0.5–1 molal) at 720–770°C, 2 kbar, andƒo2 fixed by Ni-NiO, Fe3O4-Fe2O3, and Cu2O-CuO buffers. As complete solid solution exists between UO2.00 and UO2.25 (i.e., 75 mol% UO2 + 25 mol% UO3), three distinct uranium oxides: UO(2.01 ± 0.01), UO(2.1.0 ± 0.02), and UO(2.25 ± 0.02) were, respectively, obtained at equilibrium, under the three ƒo2 conditions cited above. Thus, the percentage of U (VI) in uranium oxide increased with increasing log ƒo2. The thermal decomposition of Na2CO3 to CO2 and Na2O led to the decrease of the sodium carbonate concentration from 0.5–1 molal to ~10−2 molal in all aqueous fluids and to the dissolution of Na in the silicate melts. Crystal-free silicate glasses with four agpaitic coefficients, View the MathML source were obtained.

The uranium solubility in 10−2 m aqueous carbonated fluid ((8.1 ± 0.1) ≤ quench pH ≤ (8.9 ± 0.1)) was in the range 1–17 ppm and increased linearly with increasing ƒo2 according to the expression: View the MathML source. This equation is valid for the temperature range 720–770°C and 2 kbar.

U(IV) carbonate possibly were major species in aqueous solutions under reducing conditions (Ni-NiO buffer) whereas U(VI) carbonate complexes dominated under higher oxidation conditions (Fe3O4-Fe2O3, Cu2O-CuO buffers).

The uranium content in silicate glasses varied in a large range (102–2 × 105 ppm) and log (U) (ppm) increases linearly with both ƒo2, and α in the range 1.1–1.5 according to the equation View the MathML source. This equation is valid for (1)ƒ o2 ranging from Ni-NiO to Cu2O-CuO, and (2) the temperature range 720–770°C at 2 kbar. The effect of ƒo2 on the uranium solubility in silicate melt slightly decreased with increasing α from 1.1 to 1.5.

For α in the range 1.5–1.7, the effect of both ƒo2 and agpaicity index on the uranium solubility was considerably reduced.

The temperature variation in the range 720–770°C had no significant effect on the uranium solubility in either aqueous fluid or silicate melt.

The partition coefficient (Dfluid/melt) of uranium was in the range 10−4.0−10−1.5 and depended on both ƒo2 and α according to the equation View the MathML source. The validity conditions of this equation are similar to those of the preceding one.

Results obtained in the present study could be used to predict the geochemical behaviour of uranium during magma fractionation and to further understanding of the formation of uranium ore deposits related to partial melting or fractional crystallization of felsic magmas. The genesis of the Kvanefjeld (Ilimaussaq, Greenland) uranium deposit is discussed.

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Pergamon
GeochimicnctCosrnochirnicaActa,Vel.58,No.!
i,
op.249.5~2.507,J994Copyright
(f:)
1994,ElsevierScienceLtdPrintedintheU3/\._·;_AIJightsreserved
0016·7037/94%.00
+
.00
0016-7037(9-4)00052-2
Uraniumingraniticmagmas:Part
1.
Experimentaldeterminationofuraniumsolubilityandfluid-meltpartitioncoefficientsintheuraniumoxide-haplogranite-H20-Na2C03systemat
720-77C,2
kbar
CHANTALPEIFFERT,MICHELCUNEY,andCHINHNGUYEN-TRUNGCentredeRecherchesur
la
GeologiedesMatieresPremieresMineralesetEnergetiquesandGdRCNRS-CREGU0077,BP23,54501VandoeuvrelesNancy,Cedex,France
(ReceivedMarch
17,1993;
acceptedinrevisedformJanuarv
18,1994)
Abstract-Thesolubilityofuraniumwasinvestigatedinbothcarbonatedaqueousfluidandgraniticmeltinequilibriuminthesystemhaplogranite-uraniumoxide-H20-Na2C03(0.5-1molal)at
720-nO°C,
2
kbar,and
fo,
fixedbyNi-NiO,Fe304-Fe203,andCu20-CuObuffers.AscompletesolidsolutionexistsbetweenU02.00and·U02.25(i.e.,75mol%UOz
+
25mol%U03),threedistincturaniumoxides:UO(2c01±O.OI),
U0(2.W±0.02J,
andUO(2.Z5±002)were,respectively,obtainedatequilibrium,underthethree
fo,
conditionscitedabove.Thus,thepercentageofU(VI)inuraniumoxideincreasedwithincreasinglog
fo,.
ThethermaldecompositionofNa2C03toCO
2
andNa-Oledtothedecreaseofthesodiumcarbonateconcentrationfrom0.5-1molalto~10
-2
molalinallaqueousfluidsandtothedissolutionofNainthesilicatemelts.Crystal-freesilicateglasseswithfouragpaiticcoefficients,
ex
=
((Na
+
K)/
AI)
=
1.1,1.3,1.5,andL7wereobtained.Theuraniumsolubilityin10-2maqueouscarbonatedfluid((8.1
±
0.1)
:s:
quenchpH
:s:
(8.9
±
0.1»wasintherange1-[7ppmandincreasedlinearlywithincreasing
/0,
accordingtotheexpression:log(U)(ppm)
=
0.09.log
fo,
(bar)
+
1.47.Thisequationisvalidforthetemperaturerange
720-nO°C
and
2
kbar.U(IV)carbonatepossiblyweremajorspeciesinaqueoussolutionsunderreducingconditions(Ni-NiObuffer)whereasU(VI)carbonatecomplexesdominatedunderhigheroxidationconditions(Fe304-Fe203,CUzO-CuObuffers).
=-=
Theuraniumcontentinsilicateglassesvariedinalargerange(10
2
:"2';><
10
5
ppm)andlog(U)(ppm)increaseslinearlywithboth
fo,
and
ex
intherange1.1-1.5accordingtotheequationlog(U)(ppm)
=
0.04log
fo,
(bar)
+
3.80ex-
1.34.Thisequationisvalidfor(I)
fo
z
rangingfromNi-NiOtoCU20-CUO,and(2)thetemperaturerange
720-nO°C
at2kbar..Theeffectof
fo,
ontheuraniumsolubilityinsilicatemeltslightlydecreasedwithincreasing
a
from1.1to1.5.For
a
intherange1.5-1.7,theeffectofboth
fo,
andagpaicityindexontheuraniumsolubilitywasconsiderablyreduced.Thetemperaturevariationintherange
72o-noDe
hadnosignificanteffectontheuraniumsolubilityineitheraqueousliuidorsilicatemelt.Thepartitioncoefficient
(Dfluid/melt)
ofuraniumwasintherange10-40_10-
15
anddependedonboth
fo,
and
ex
accordingtotheequationlog
Dfluid/melt
=
0.05log
f02
(bar)-
3.78a
+
2.84.Thevalidityconditionsofthisequationaresimilartothoseoftheprecedingone.Resultsobtained.inthepresentstudycouldbeusedtopredictthegeochemicalbehaviourofuraniumduringmagmafra-ctionationandtofurtherunderstandingoftheformationofuraniumoredepositsrelatedtopartialmeltingorfractionalcrystallizationoffelsicmagmas.ThegenesisoftheKvanefjeld(Ilimaussaq,Greenland)uraniumdepositisdiscussed.INTRODucnONanothorite(CUNEYandFRIEDRICH,1987),themostfelsicmembersofgraniticassociationsaregenerallyenrichedinuranium.Thus,measuringuraniumsolubilityasafunctionofcompositionofsilicatemeltmayallowustopredictura-niumconcentrationtrendsinmagmasastheydifferentiate.Thedeterminationoffluid-meltpartitioncoefficientsofura-niumisfundamentalforthepredictionofuraniumconcen-trationinfluidscoexistingwithgraniticmagmas.Theknowl-edgeofuraniumsolubilityandfluid-meltpartitioncoefficientsisofmajorimportancefortheunderstandingofthedistri-PARTIALMELTINGANDcrystalfractionationrepresentthemostpowerfulprocessesleadingtoasteadyenrichmentoflithophileelementssuchasuraniumintheEarth'slithosphereandmoreparticularlyintheupperpartofthecontinentalcrust(ROGERSandADAMS,19:69;TAYLORandMcLENNAN,1985).Althoughuraniumcanbestronglypartitionedinalargevarietyofearlycrystallizingmineralsingraniticmagmassuchaszircon,apatite,monazite,titanite,uraninite,andur-
2495
 
I)normalexperimentsusingU(IV)oxideasstartingmaterials2)reversalexperimentsusingdissolvedorsolidU(VI)specie;asstartingmaterials,and
3)
experimentsusingasystemundersaturatedwithuranium.2496e.
Peiffert,M.
Cuney,ande.Nguyen-Trungbutionofthemajorheatproducingelementsinthe-Earthandthegenesisofuraniumdepositsresultingfrommagmaticprocesses.Severalauthorshavecarriedoutexperimentalstudiesusingtwoapproaches.Inthefirstapproach,experimentswereconductedinwater-freesystemstostudythemechanismsofuraniumdissolutioninsyntheticsilicatemeltsatveryhightemperature(1150-1600°C)andatmosphericpressure(CALAS,1979;FARGESet
al.,
1992;SCHREIBER,1980,1983;SCHREIBERandAN-DREWS,1980;SCHRElBERandBALAZS,1982;SCHREIBERetaI.,1981,1982;DOMINEandVELDE,1985).Resultsobtainedfromtheseworksindicatedthaturaniumdissolvedinthemeltunderthreevalencestates-IV,V,andVI-andthattheproportionsdependontheimposed
f02.
Theeffectoftheagpaiticcoefficient
0:
=
(Na
+
K)/Alofaluminosilicatemeltand
fa,
ontheuraniumsolubilityin
alurninosilicate
meltwasdeterminedbyDOMINEandVELDE(1985).Theseau-thorshaveshownthattheuraniumsolubility(41.8-67.5wt%
U
30S>in
aluminosilicate
increasedwithincreasing
0'
and
fo,
at1400°C,Ibar.Inthesecondapproach,fluid-melt
partition
coefficients
(Dflu;d/melt)
ofuraniumweredeterminedbetweensyntheticor-ruituralsilicatemeltandaqueoussolutionsat750°C,2kbar,underaNi-NiObuffer,closetogeologicalconditions.Inmostcases,startingmaterialsusedweresyntheticsilicatemeltandaqueoussolutionswithvariableamountsofHel(KEPPLERandWYLLIE,1990,1991),H20
+
CO
2,
HF(ZHARIKOVet
al.,
1987;KEpPLERandWYLLIE,1990,1991),(Na,K)CI,(Na,K)F,Ag
2
C
2
0
4
(ZHARIKOVetaI.,1987;
Yu-
DINTSEV,1990).Otherexperimentsweredoneusingnaturaltopaz-rhyolitemeltandNaCI(WEBSTEReta!.,1989).ResultsobtainedbyWEBSTEReta!.(1989)aredifficulttoconsiderbecausefinalglassescontainzirconwhichincorporatessig-nificantamountsofuraniuminitsstructure.Theeffectoftemperatureintherange750-1000°Candpressurefrom2to4kbarontheuraniumsolubilityin
haplogranite
(0.78
s;
0:
=
(Na
+
K)/
Al
s;
1.08)containingH20wasmeasuredbyZHARIKOVeta!.(1987).However,
D
fluidZmelt
valuesofuraniumreportedfromabove-mentionedstudiesmustbeusedwithcautionbecauseoflackofdataontheequilibriumstateofthesystemand,insomecases,onthemodificationofthecomposition
of
meltandaqueousfluidafterarun,duetofluid-meltinteractions.Thispaperisthefirstofaseriesofcontributionsdealingwiththesystematicdeterminationoftheurani
urn
solubilityandthefluid-meltpartitioncoefficient
(Dflu;d/melt)
of
uraniumbetweenhaplograniteandaqueoussolutionasafunctionofligandsinaqueoussolution,silicatemeltcomposition,tem-perature,and
fo,
atequilibrium.Preliminaryresultshavebeenreported(PEIFFERTet
al.,
1992),andthepresentstudyreportscomprehensivedataconcerningthesystemuranium
oxide-haplogranite(1.1
s;
0'
s;
1.7)-H20-Na
2
C0
3
inthetemperaturerange720-770°C,2kbar,under
fo,
conditionsfixedbythreebuffers:Ni-NiO,Fe304-Fe203,andCu
2
0-CuO.EXPERIMENTALStartingMaterialsandPreparationofSamplesEarlierworkshavereportedthatthesolubilityofU(VI)'inaqueousfluid(RED'KINetal.,1989)andsilicatemelt(DOMINEandVELDE,1985)ismuchhigherthanthatofU(IV).Inthepresentstudy,the·equilibriumwasattainedusingthreeapproaches:Atequilibrium,allthethreeabove-mentionedtypesofexperimentshavingthesamefluid-meltcomposition,underidentical
P,T,
fo
conditions,shouldprovidesimilarpartitioncoefficient
(Dflmd/melt)
ofuranium.Moreover,bothnormalandreversalexperimentsshouldgivethesameresultsregarding(I)theuraniumoxidecompositionand(2)theuraniumsolubilityinaqueousfluidandsilicatemelt.'Startingmaterialsusedinnormalexperimentswere(
I)
toichio-metricsinteredspheresofU0
2.000
(~IOO
J.lm
indiameter).U02000wereobtainedbyreductionofnaturalU0
2.I'O
byaTi-Zrmixtureinvacuumat900°Cduring36h.U)OSandU02(OHh·H
2
0werealsousedinreversalexperiments;(2)Na,C03solutions(0.5,0.8,and1.0molal)(AnalyticalReagent);
(3)
dehydratedsyntheticgelswithfourcompositions,indicatedinTable1.weremadeusingthemethodofHAMILToNandHENDERSON(1968).ChemicalsusedwerecertifiedNa2C03,
K
2
C0
3,
AI(NO))·9H
2
0,and(C,Hs)4Si04(AnalyticalReagents).Forseveralreversalexperiments,threedifferentstartingmaterialswereused:(I)Na,CO)solutionoversaturatedwithuranyl(VI)andgel,(2)Na,CO)solutionandgeldopedwithuraniumasU)Og(0.5-2wto/c),and
(3)
Na,CO)solution,gel,andschoepiteUO,(OH),·H,O.Fornormalexperiments,sampleswerepreparedusingaquadruplecapsuletechnique.About
SO
rngofstoichiometricU02.
000
andabout200mgofgelwereloadedintoseparateplatinumcapsules(3.6mmID,4.0mmOD,8.0mrnlongforUO"and25.0mrnlongforgel).Thesetwoplatinumcapsuleswereonlycrimped.About100mgofoneofthethreeassemblages(Ni-NiO,Fe)04-Fe,O),orCu,O-CuO)and100mgofH,Owereloadedinthethirdplatinumcapsule(3.6mmID,4.0
mrn
OD,25.0mmlong).Thiscapsulewasweldedshut.ThethreeplatinumcapsulescontainingU02,gel,andoxygenbufferalongwithabout200mgofNa2CO)solutionwereloadedintoagoldcapsule(5.0mmID,5.8mmOD,65.0mmlong).Thegoldcapsuleassemblywasweldedshutandloadedinacold-sealpressurevessel.TheendcontainingtheUO,capsulewasplacedinthebottom,i.e.,thewarmestpartofthevessel.ThecapsulewiththegelwasplacedadjacenttotheUO,capsule(Fig.
I).
Thistechniquehastwomajoradvantages:(I)UO"loadedinexcess,representsaninexhaustiblesourceofuraniumandthussaturatesthesystemwiththiselement;and(2)theseparationofUO,andgelbeforetheexperimentspreventsUO,particlesfromenteringthesilicatemeltandaqueoussolution,thuspreservingpuresolidandaqueousphasesaftertherun.ChemicalreactionsbetweenUO,andsilicatemeltonlyoccurthroughaqueouscarbonatedsolutions.Forreversalexperiments,thetriplecapsuletechniquewasusedtopreparesamples.TwoplatinumcapsulescontaininggeldopedornotwithU(VI)andoxygenbufferalongwithabout200mgofNa,CO)solutionfreeoroversaturatedwithuraniumwereloadedintoagoldcapsule.Thedimensionsofplatinumandgoldcapsulesaresimilartothosecitedabove.Pre-runrupturetestsofplatinumandgoldweldedcapsulesweresystematicallydonebyplacingthemovernightinanovenatl20°e.Subsequentweighingcheckedforpossibleleaks.ExperimentalProcedureMostexperiments(80%)wereconductedwitharapid-quenchcold-sealpressurevesselsimilarindesigntothatusedbyFRANTZand
Por=
(1979).Allotherrunsweredoneinconventionalcold-sealpressurevessels.Thereactionvesselwasexternallyheatedinahor-izontalelectricalfurnace.Experimentsweredoneat2.00
±
0.0Ikbarandtwotemperatures:720
±
15and770
±
15"C.Amixtureofwaterandsolubleoilwasusedasapressuremedium.TotalpressurewasmeasuredusingaHeisegaugeandtemperaturewithcalibratedchro-mel-alumelthermocouple.Thetemperaturegradientinthevesselat2kbarintbetemperaturerange
nO-770°C
wasdeterminedusingtwointernalchromel-alumel
 
Au
Capsul
e
U02
_W---
Na2C03SOLUTION
GEL
Pt
Capsules
FIG.
I.
Thequadruplecapsule(1Au,3Pt)usedforthefluid-meltpartitioningexperiments.thermocoupleswiththeirendslocated
2S
mrnfromeachother.Inordertoduplicatetheactual
run
conditionsascloselyaspossible,thecouplewassuccessivelyinsertedin(
I)
aNifillerrod(80
mm
long)whichwas~dalongitsaxistoallowthethermocoupletopassthroughand
(2)
adummychargegoldcapsule(30
mrn
long).Thelatterwasplacedatthetipofthethermocouple.Resultsobtainedindicatedagradient
~f
2
e
Cforeach10mm.Thetelr~aturegradientforagoldcapsule6)
rnrn
longwasestimatedtobe14°Cacrossthecharge.Rundurationswereintherange2-4weeks.Attheendofeachrun,therapid-quenchcold-sealpressurevesselwastippedandbrought
to
averticalpositionsothatthecapsuleslidfromthehotendtothecoldendofthevesselunderconstantpressure(2kbar).Estimatedquenchingtimewas5sec.Thisvaluewasclosetothequenchingtime(4sec)ofasimilargoldcapsule(70
mrn
long)containingthreeemptysmallplatinumcapsules
UD
mrn
long)heatedto
no°c,
I
bar,andplungedintoH
2
0
at
ambientconditions.Theconventionalcold-sealpressurizedvesselwasdisconnectedfromthepressurelineandwaswithdrawn
from
thefurnace.Pressurizedairandwaterwereusedtoquenchthevessel.3minuteswerenecessarytobringbackthevesseltoroomtemperature
and
approximately50bar.Analysisofrunproductsyieldedsimilarresultsforbothtypesofvessel.Analysisof
Run
ProductsandUncertaintiesEvaluationAfterremovalfromthevessel,thegoldcapsulewasopened.Aqueoussolutionwasremovedusingpolyethylenetransferpipets.Uraniumoxide,silicateglass,andbufferassemblagewereextractedfromthe
three
platinumcapsules.
Analysisofaqueousfluids
QuenchpHwasrapidlymeasured(uncertainty±0.1pHunit)atroomtemperatureusingamicrocombinationglasspHprobe(Mi..croelcctrodesMI-410).Theaqueoussamplewasthenrapidlyandcarefullyfilteredusinganultrafiltrationmembrane(MilliporePTGC,diameter!3mm).Thefilteredsolidconsistsofsilicateglassesandtraceamountsofuraniumandaluminium.ThefiltrationofaqueoussolutionwasnecessarytopreventallrisksofaccidentalpresenceofuraniumoxideparticlesfromU-bearingcapsule.2497TraceamountsofdissolveduraniumweredeterminedbvvisibleabsorptionspectrophotometryusingBromo-PADAPaschromogenicreagent
with
arelativeuncertaintywithin10%.Thedetectionlimitis20ngofuranium.Severalrunsweremadetodeterminewhetherdissolveduraniumprecipitatedduringthequenching.Twotechniqueswereused.The
first
techniqueemployedThesamestartingmaterialsandtheloadingsystemasinnormalexperiments.Aftereachrun,thegoldcapsulewaspunctured,theaqueousfluidwasextractedandtheplat-inumcapsulecontaininguraniumoxidewascarefullvremovedThenthetwoplatinumcapsulescontainingsilicate
glasses
;ndoxyge~bufle;andthegoldcapsulewereboiledinI
m
HCltodissolvepossibleuraniumprecipitates.Thetotaluraniumcontentdeterminedinthefilteredsolidandin1mHCIobtainedafterboilingthecapsuleswasalwaysbelow10%oftheuraniumcontentmeasuredinthefilteredsolution.Insomeexperiments,totaluraniumwasalsoanalysedinnonfilteredaqueousfluidmixedwiththeabovecited1mHCIsolvent.Resultsofthismeasurementagreefairlywellwiththoseobtainedfromfilteredaqueousfluids.The
difference
betweenthetwosetsofresultswasbelow10%.Inthesecondtechnique,anadditionalplatinumcapsule(3.6
rnrn
ID,4.0
rnrn
OD,20.0
mrn
long)perforatedwithmanyholeslessthan0.2mrndiameterandloadedwithpurifiedquartzgrainsap-proximately10}1msizewasplacedin
a
goldcapsulewiththreeotherreducedsizeplatinumcapsulescontainingU02,silicateglass,andbuffer.Onquenching,theaqueousfluidwastrappedinintersticesofquartzgrainsinsidetheperforatedplatinumcapsule.Theperforated,platinumcapsulewasextractedffflrrfthegoldcapsuleandwasrapidlyweighed.Thecapsulewasthendriedinanovenat110°Covernight.Thisdryingconditionwasadoptedsinceexperimentsattemperatureupto200°Cindicatedthatwaterextractionfromquartzgrainswastotalafter
2
hat
110°C.
Afterdrying,thecapsulewasreweighed.The
difference
istheweightoftheaqueousfluid.Theplatinumcapsulewasthencarefullyopened.Bothquartzgrainsandtheplatinumcap-sulewerehoiledin
I
mHNO]andtheanalysisorthisacidsolutionprovidesthetotaluraniumintheaqueousfluid.Inthelasttechnique,theamountofuraniumisupto
!
0%higherthanthatdeterminedinfilteredsolutions(Table
3).
Theuraniumexcessdeterminedinthiscase
is
inthesameorderofmagnitudeasthemeasurementuncer-tainties.Forthisreason,theprecipitationofuraniumduringquench:ingisconsiderednegligible,andtheamountofuraniummeasuredatambientconditionsrepresentseffectivelytheuraniumsolubilityinaqueousfluidathigh
P,T
conditions.ThemolalitiesofNa,
K,
andSiweredeterminedbyatomicab-sorptionspectrometry(relativeuncertainty
=
5%).Traceamountsofaluminiumwerebelowthedetectionlimit(30
ppb)
ofatomicabsorptionspectrometry.Totalaqueouscarbonatewasdeterminedbyionchromatography(detectionlimit:0.1ppm).
Analysisofoxygenbuffers,uraniumoxides,andsilicateglasses
The
buffers
werecheckedbyX-raydiflractometrytodeterminewhetheranyofthephaseshadbeenexhaustedduringtherun.
It
iswellknownthatacompletesolidsolutionexistsbetweenU0200andU0
225
(i.e.,75mol%UO,+25mol%(0
3).
ThecompositionofthesolidsolutionUO(2+X)aftereachnormalexperimentwasde-terminedasfollows:X-raydiffractometrywasfirstemployedtode-terminethe
u
nitcellparameter
a.,
(A)
fromthepositionofthe(620)bandofcubic
UO(2+x)(0
50
X
50
0.25).Valuesof
a.;
(A)
obtainedwerethenusedtocalculatethefraction
x
ofUO,inthesolidsolutionUO(2+x)basedonthelinearcorrelationbetween
a.,
(A)
and
x
(0.00
50
X
s:
0.25)(CATHELINEAUet
al.,
1982)accordingtotheEqn.I:
ao(A)
=
-0.116x+5.471.
(I)
Forreversalexperiments,theamountofuraniumoxideprecipitationobtainedaftereachrunwasnotsufficienttobeanalysedwithaccuracy.Carefulobservationsofrunproductsusingpolarizingmicroscope,electronmicroprobe,andscanningelectronmicroscopediclnotrevealthepresenceofanyadditionalsolidcompoundcontaininguraniumandsilicateglassconstituents(AI,Si,Na,K)aftertherun.Fiveelements,Si,AI,Na,K,andUofsilicateglasseswereanalysedbyelectronmicroprobe(CamecaSX
SO).
Lowuraniumconcentra-

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