Economic Geology

Vol. 58, 1963, pp. 353-374

STUDIES OF FLUID INCLUSIONS III' EXTRACTION AND

QUANTITATIVE ANALYSIS OF INCLUSIONS IN
THE MILLIGRAM RANGE •

EDWIN ROEDDER, BLANCHE INGRAM, AND WAYNE E. HALL

CONTENTS

PAGE

Abstract .............................................................. 352

Introduction .......................................................... 353
Descriptionof the technique............................................ 354
Sampleselectionand preparation..................................... 354
Crushing,andcollection andanalysisof gases.......................... 356
Leaching .......................................................... 359
Microanalysis...................................................... 361
Results obtained ....................................................... 364
Preliminarybulk crushingruns ...................................... 364
Vacuum-crushing runs .............................................. 367
Sampledescriptions .............................................. 367
Interpretation
of results.......................................... 370
Future studies ......................................................... 372
Conclusions........................................................... 373
References ............................................................ 373

ABSTRACT

A methodhas been developedfor the extractionand chemicalmicro-

analysisof individualfluid inclusions,
or groupsof inclusions, in the milli-
gram range. Usablequantitativeanalysesfor Na, K, Ca, Mg, C1,B, and
SO4have been obtainedof mineral samplescontainingseveralmilligrams
of inclusionfluid, and with increasedexperimentalerrors, on fractional
milligrams.amples.The stepsinvolvedare: 1) concentration of inclusions
by sampleselection and cutting;2) electrolyticcleaning;3) crushingin
soft coppersampletubein vacuo;4) conversion of emittedwater to hy-
drogenanddetermination of its volume;5) massspectrometric determina-
tion of the D/H ratio if desired: 6) leachingof the crushedmineral to
dissolvesolublesaltsremaining:7) microanalysis of the tiltrate by sensi-
tive colorimetricand flame photometricmethods.
The methodhas been appliedto determinethe composition of fluid
inclusionsin mineralsamples from severaltypesof deposits,
with special
attentionto a seriesof samplesfrom Mississippi
Valley-typeore deposits.

INTRODUCTION

MANY studieshave been madeof the compositionof the saltsin solutionin

fluid inclusionsin minerals (21, 26), and of the compositionof the gases
• Publication authorized by the Director, U.S. Geological Survey.
353
354 ROEDDER,INGR.,4M,.,4NDH.,4LL

givenoff by crushing
mineralscontaining
fluidinclusions
(5, p. 39; 8, 28), or
upon heating to decrepitation(30). Seldom,however,have these studies
beencombinedon the samesample,to obtaininformationon the concentration
of saltsin fluid inclusions.The first two papersin this series(23, 24) were
basedon a methodof obtainingan indirect estimateof the concentrationof
saltsin inclusions
from the depression
of the freezingpointof the fluids,as-
suminga knowledge of the approximate
composition of the salts. It wouldbe
highlydesirableto havea directmethodof extractionand analysisof fluid in-
clusionswhichwouldyield boththe composition and concentration
of the salts
in solution. For large fluid inclusionsthis determinationis not difficult,and
oneof the very earlypublications on fluid inclusions(8) describes
work of this
kind, involvingdrilling into a large fluid inclusionin quartz.
Another method,basedon analysisof the amountof water obtainedduring
decrepitationof a samplein a gasabsorptiontrain, followedby leachingof the
evaporatedresidueof solublesaltsfrom the decrepitatedsample,was reported
in this journal (21, p. 265-266). As the authorpointedout, however,this
methodhas somerather serioussourcesof ambiguity,suchas possiblelossof
ionsby diffusioninto the mineral surfacesfollowingdecrepitation.
The smaller the inclusionsthat can be studied,the wider the variety of
samplesthat canbe used,as smallinclusionsare far more abundantthan large
ones. This paperreportson a procedureinvolvingcrushingin a high vacuum,
follo•vedby carefulleachingand microanalysis; the resultsare usablein terms
of both concentrationof the salts and their composition,for single fluid in-
clusionslessthan 1 millimeterin diameter. It is bestsuitedfor samplescon-
tainingoneor a groupof reasonably largefluidinclusionshavinga total volume
of about 10 cubicmillimeters (10 mg or 0.01 ml), but also has beenusedsuc-
cessfullyon samplescontainingonly the normal small, but abundant,inclu-
sionsin about this sametotal volume. Although the methodis essentially
simple,it requiresconsiderable care in its execution.

DESCRIPTION OF THE TECHNIQUE

SampleSelectionaud Preparation
As it is desirablewith thisprocedureto havethe fluidinclusionsin as small
a sampleof mineralas is possible,it is generallynecessaryto isolatefrom the
bulk of the specimensmall portionsof the mineral containingthe desired
inclusions.Althoughnormaldiamondsawsand rubber-bonded carborundum
cutoff wheels can be used for much of this work, the nature of some museum
material requires the use of thinner wheelsand more gentle cutting. This is
best obtainedthrough the use of continuousrim diamondcutoff wheels,made
by powdermetallurgyproceduresfor lapidaryuse. A very usefulsize is 4
inchesin diameterand only 0.015 inch thick. On delicatecrystalsor crystal
groups,it is sometimespreferableto usea commercially availablemicro sand-
blast unit. Although this is not designedfor deep cuts through hard min-
erals,it doesgive exceedinglygentleabrasiveaction,and with it very small
piecescan be cut out of the crystalswithout fracturing. Dark minerals of
 STUDIES OF FLUID INCLUSIONS III 355

coursemustbe cut into transparentor translucentslabs(thereby ruining most

of the reallylargeinclusions)beforepolishingandfurther examination.
An additionalrequirementof the vacuumcrushingprocedureis that the
material should contain neither too little nor too much fluid. Too little fluid
(< 1-2 mg) causesa sharp rise in the experimentalerrors, and too large
samples(> 30 mg) causedifficultyin pumpingall the sampleinto the sample
tube in the vacuum extraction train. To determine a) the size of the inclu-
sion and of the gas bubble,and b) the relationshipof the inclusionto such
featuresas crystal growth zones,fractures,cleavage,and other inclusions,it
is necessaryto make a detailedopticalexaminationof each sample. With
mineralsof low index of refractionsuchas quartz or fluorite, it is possible
to view the sampleplate or fragmentfrom variousangleswhile immersedin
a liquid of approximatelythe sameindex of refraction? With mineralsof high
index of refractionsuchas sphalerite,a little help may be obtainedby im-
mersingthe piecesin methyleneiodide,but the opticalstudyof suchhigh-index
materialsis very difficult without highly polishedsurfacesor very smooth
cleavages.Most of the samplesof sphaleritewith whichwe have workedhave
had to be polishedon at leasttwo sides,and someon all six sides,of the little
cubesof sphaleriteas sawn from the polishedplates. In many casesit was
found that the angle of a flattenedinclusionrelative to thesefacesresultedin
total reflection,and additionalfacesat someobliqueangle had to be cut and
polishedin order to obtain adequateopticalconditionsfor examinationand
measurement of the inclusionvolumeand the size of the bubble. Most large
usableinclusionsin sphaleriteappearcompletelyopaqueunlesstreatedin such
a manner. By carefulmeasurement with an ocularmicrometer,it is possible
to calculatethe volumeof someinclusionsthroughassumptions of similarity to
regular geometricshapes. The most difficultmeasurement,the thickness,ap-
parentlyis the major causefor error in the volumescalculated. Not infre-
quently,upon extractionof the inclusions,the calculatedvolumewas found
to be in error by 50 percentor more. With stronglybirefringentminerals,the
differencein birefringencethroughand besidethe inclusioncan be usedas a
thicknessmeasure(4, p. 35), or one can focuson the top and bottomsur-
facessuccessively
and calculatethe thickness.If the bubbleis spherical,and
the inclusionirregular, a crude but still useful estimateof inclusionvolume
can be madeby calculationusingthe bubblevolumeand the degreeof filling
obtainedthroughfilling temperaturedeterminations.Some samplespermit
a goodmeasureof inclusionliquid volumefrom opticalmeasurementof the
gasbubbleand a carefullydeterminedbulk densityfor the sampleplus inclu-
sion (e.g., sampleI--I-1 beyond). On material containingmany small in-
clusions,it is necessary,of course,to make an estimate of the total volume
through the use of countsmade with an ocular grid on visually representative
areas. Opaquemineralsmust be run on a trial and error basis.
The final sample,or sampleswhere severalfragmentsare to be run as a
composite,must then be cleaned,to make them free of all possibleextraneous
2 For fluorite, kerosene of n= 1.45; for quartz, "HB 40 oil," made by the Monsanto
Chemical Co., Wilmington, Delaware, was used, after adjusting to n = 1.55 with kerosene.
$$6 ROEDDER,INGR.4M,.4ND H.4LL

ions. Theyarefirstwashed withsolvents to removeanypolishing compounds,

andarethenplacedin PyrexU-tubeswithdeionized waterandplatinumelec-
trodes,and subjected to electrolysis
for at leastseveraldays,usingestablished
procedures (21, p. 242).3 With thesesmallsamples, thepathlengthandtube
diametercanbe considerably smallerthanis described(21). After cleaning,
theyare driedat 110ø C, andare readyfor crushing.

Crushing,and Collectionand .4nalysisof Gases

The methoddeveloped for recoveryof the water from fluid inclusionsin-
volvescrushingin vacuoin a soft-drawncoppersampletube, convertingthe
releasedwater to hydrogen,and measuringthe volumeof hydrogen. Much of
the creditfor the development of thistechniquebelongsto Irving Friedmanof
the U.S. GeologicalSurveyin whoselaboratorythis part of the work was
done.
The vacuumline used(Fig. 1) is a modificationof oneFriedmanuses•or
deuteriumanalyses of water samples(10). The cleandry sampleis placed
in a sampletube madefrom an 8-inchlengthof soft-drawncoppertubing•
inchin diameter,squeezedtogetherand weldedat oneend.4 The sampletube
(F in Fig. 1) is connectedto the vacuumline (througha copperloop for
flexibility) by a Swagelockunionwith Teflon front ferrules (E), and the line
is evacuatedto 10-5 mm of mercury. Larger samplesare run in 7•-inch bore
tubing,connected to the vacuumline xvitha greasedO-ring seal,adaptedfrom
that of Heinrich (14). After evacuationand checkingfor leakage,the stop-
cockto the high vacuumline is closed,and the sampletube crushedwith a
hydraulicpress(D). The flattenedportionof coppertubingis thensqueezed
open from the sidesto permit easier flow of gases,warmed with a torch to
about 80ø C to ensurecompleteevaporationof the releasedfluid inclusions
from the crushedmineral, and the water and carbon dioxide are condensedin a
liquid-nitrogen-cooledtrap (A).'• At the endof a 20-minutecollectingperiod,
the line is openedto the high vacuumto pump off any noncondensable gases
that may be present,suchas methane,and to checkthe systemfor air leakage.
The high vacuum line is again closedand the liquid nitrogen moved from
aroundtrap A to trap B. The water condensed in trap A is allowedto warm
to room temperatureand hencemovesthrough the hot uranium metal (about
700ø C) in the Vycor trap betweenA and B. The water reactswith the hot
uranium to form hydrogenby the equation:
21-I,,O+ U--• COo_+ 21-I_o.
3 If the sample has deep reentrants likely to trap gas bubbles which would preclude cleaning,
these are filled with water prior to electrolysis by repeated "boiling" the sample in water by
applying a vacuum, alternated with normal atmospheric pressure.
4 Todd (28) reported on a technique for the mass-spectrometric analysis of low-pressure
gas inclusions in glass as small as 0.5 mm diameter by breaking a thinned inclusion wall
in a vacuum system xvith a magnetically dropped tool. Dr. R. K. Smith of the Corning Glass
Works has modified this technique, using crushing in a copper tube, and reports that analysis
of 0.1 /xg of mixed gasesfor nine constituentsto ñ1% is possible(personalcmnmunication,
1961). Although this technique has considerable potential for the study of the volatile com-
ponents in fluid inclusions, much larger samples were used in the present study to obtain
sufficient nonvolatile salts for microanalysis.
5 An intermediate trap between F and A later proved useful.
 STUDIES OF FLUID INCLUSIONS III 357

Any carbondioxidethat may be presentpassesoverthe uraniumand re-

condenses in trapB. The hydrogenis pumpedby an automatic Toeplerpump
into a calibratedmanometer whereits pressureis measuredin centimeters
of
mercury(1 cm -- 0.490mg H20 ). If morethan 20 mg of water is present,
additionalpassesover the uraniummay be made. As the volumeof the
manometersystemand the pressureare known, the milligramsof water re-
leasedfromthefluidinclusions
canbecalculated.After readingthehydrogen
pressure,
it is pumpedintoan evacuated
sampletube (C), andis removedfrom
the samplepreparationline. This sampletube is then connected
to the inlet

Vacuum
Gauge To High Vacuum--

--

Electric Furnace

yrex

Manometer

Copper

Copperff
sample ff
To Toepier
Backing Pump

tube
// D
FIG. 1. Vacuum line for recovery of gasesfrom fluid inclusions.

systemof a Nier-type 60-degreemassspectrometerfor the determinationof

the relative deuterium concentration.
The amountof carbondioxidein the samplecanbe determinedin a similar
manner,after the hydrogenis collected,by allowingtrap B to warm to room
temperature.The carbondioxideis pumpedby the Toeplerpumpinto the
manometer,and the weight of carbon dioxide can then be calculatedfrom its
pressure(1 cm = 1.22 mg CO2). The coppersampletube is then removed
from the Swagelock
fitting and immediately
sealed,pendingthe leaching
operation.
3.58 R'OEDDEI•, L\•Gt•.4M, .4ND HALL

Samplescontainingbetween5 and 15 mg of fluid inclusionsare handled

most easilyon the vacuumline; difficultiesand experimentalerrors become
moreseriouswith < 2 or > 30 mg. Ten milligramsof H20 can be measured
with this techniqueto -----1-2%.
A seriesof samplesof fluorite,barite,and calcitefrom severalore deposits
of the Mississippi
Valley-type,containing largenumbersof minuteinclusions,
wererun. Opticalestimates of the numberof inclusionsindicated4 x 104to
4 x 105inclusions
per cm3. On crushing,the water recovered
from these
samplesrangedfrom 0.01 to 0.22 weightpercent. Galenasampleswith an un-
kno•vndistributionof inclusions
yieldedsimilaramounts. Material containing
largesingleinclusions
canbe concentrated
muchmoreby selective
cutting;
sometransparent sphalerite
samples
preparedthusyieldedmorethan3.5•o
H20 on crushing.
The relativedeuteriumconcentration
was determinedby Irving Friedman
for eachsample.This is determinedas percentvariationin deuteriumrela-
tive to a laboratory
standard,
Lake Michiganwater,andis expressed by the
following equation:
Relative deuterium concentration (in %)

-I( D/H standard

- D/H sample
Lake Mich. water)-1]X100
whereD = deuteriumconcentration;
H = hydrogenconcentration,
in atomic
percent.Thus"+ 1%" meansthe sample hasonepercent moredeuterium
thanLake Michiganwater. Thesevaluescanbe relatedto NationalBureau
of Standards
isotopic
reference
samplesNo. 1 and No. 1A by meansof the
determination
that NBS-1 is -0.73% and NBS-1A is -16.45%, relativeto
Lake Michiganwater (11, p. 222).
TABLE 1

DEUTERIUM CONTENT OF FLUIt, INCLUSIONS IN SOME MISCELLANEOUSSAMPLES

Relative deuterium
concentration in
Sample No. Run No. Mineral Location percent (variation
from Lake Michigan
water)

Ice Cave, Vailes --9.6

15• -6 Quartz phenocrysts in rhyolite
(probably secondary inclu- Mountains, New
sions) Mexico

Garfield --9.8
H60-43 15/-3 Quartz crystals from miarolitic
cavities in granite of the An- quadrangle,
tero Formation of Stark and Colorado
others (26a)

Holy Cross --1.5

15• -3 Quartz phenocrysts from Lin-
coln Porphyry (probably quadrangle,
secondary inclusions) Colorado

H-Pa-1 15, -4 Vein quartz Catasauqua, Pa. --1.2

 STUDIES OF FLUID INCLUSIONS III 359

The samplesin Table 1 are miscellaneous mineralsrun while developing

the extractiontechnique;where samplenumbersare given, the samplesare
describedin greater detail in the secondpaper of this series (24). Little
significancecan be drawnfrom thesenumberswithoutconsidering the chem-
istry of the solublesaltspresent,but it is interestingto note that the first
two sampleshaveparticularlyloxvdeuteriumconcentrations, i.e., their water
is light,ashasbeenpostulated
for magmaticwatersin general(11, p. 226).
A test was made to seeif the solublesalts in the fluid inclusionsmight re-
tain some of the fluid and cause a fractionation between the water sample
collected
andthe waterretainedby the salts. Four samples of standardocean
water,rangingfrom 3 to 10 mg, in capillarytubes,wereplacedin sequencein
coppersampletubescontainingpreviouslycrushedbut unleachedfluorite. The
capillary tubes were broken and the samplerun in a similar manner to a
crushedmineral. The relative deuterium content of all four sampleswas
within experimentalerror (ñ0.1) of the deuteriumcontentof the standard
water. Thus no error is evident either from the size of samplerecoveredor
from fractionationby selectiveretainingof deuteriumby the solublesalts.

Leachi•g
The object of the leachingprocedureis to dissolveout for analysisthose
water-solublesaltsthat were left behindby the evaporationof the water solu-
tion on crushingin the vacuumtrain. Obviouslyit is desirableto dissolveas
muchas possibleof thesesaltswith as little as possibleof the mineral. As the
total amountof saltsinvolved,per sample,may vary from 0.1 to a maximumof
only about3 mg, contaminationis a very seriousproblem.
Ordinarydemineralized water is completelyinadequate for the leachingand
filter preparation,and so must be passedthrough a speciallaboratory de-
mineralizerwhich yields water of one million ohms-cm -a resistivity (manu-
facturedby Betz LaboratoriesInc., Gillinghamand Worth Streets,Phila. 25,
Pa.). Although suchdemineralizedwater probablycontainsmore organic
matter than water redistilledin a fusedsilicastill (13), this doesnot affectthe
analysis,and the high electricalresistivity permits better control of the
leachingand analysisstepsas describedbelow.
High-gradeanalyticalfilter paperswere foundto havefar too muchsoluble
chlorideto be used for filtering the leach solutionfrom the crushedmineral.
Asbestosfilters were used instead,preparedas follows: High-grade acid-
washedchemicalfilter asbestos is first preparedby extendedboilingwith de-
ionizedwater, filtering,and repeatedwashingwith deionizedwater. A slurry
of this asbestoswith deionizedwater in a polyethylenebeakeris usedto make
a thin filter pad approximately20 mm in diameterin a porcelainGooch
crucible. The pad is washedwith large volumesof deionizedwater and then
checked for the presence
of solubleionizablematerialsby testingthe electrical
conductivity of high-qualitydeionizedwater beforeand after passingthrough
the filter, usinga high-sensitivityconductivitybridge. Any appreciable in-
creasein conductivitythroughcontactwith the filter indicateseither that the
360 ROEDDER, IA'GR./IM, ./IND H,4LL

filter needs more •vashingor must be discarded. A polyethylene"Gooch

adaptor"was constructed with a polyethylenedeliverytube to avoidall contact
with Pyrex. Filtering is donedirectly into polyethylenesamplebottlesin a
Witt filtering apparatus.
When the filter is provensatisfactory,a dry, weighedsamplebottleis put
underthe deliverytube,and the crushedsamplefrom the coppertube is placed
in a smalldry polyethylene beaker. The coppersampletube is cut lengthwise
as well as crosswiseto permit openingup for inspectionand rinsing of the
innerwalls. A quantityof water,chosento be as smallas possibleto permit
mixing with the sample(• 10 ml), is then addedto the samplein the beaker
by rinsingoff the insideof the coppertube with a polyethylene
washbottle.
The sampleand water are swirledin the beakerfor approximatelyoneminute,
and then decantedonto the filter, with the vacuum on. A small additional
quantityof water is addedto the sampleas a washand drawn off. The sample
bottle is replacedwith a clean bottle and additionalleachesare made. De-
pendinguponexperience, 2, 3, or even6 leachesare thusmade,eachcollected
in a separatebottle. The conductivityof each of these leachesis then de-
termined,in turn, usinga differentconductivitycell than usedin testingthe
filter, as the 1.0 ml pipette-typeconductivitycells used cannotreadily be
rinsedsufficiently cleanfor a changefrom a "concentrated" solution(> 10
ppm) to a very dilute solution,even with bare platinumelectrodes,stripped
of platinumblack. The conductivityof the leachesis usuallyfound to drop
drasticallyfrom the first to the second,xvhichin turn usuallyhas very little
more conductivitythan the succeeding leaches. Where an appreciableamount
of saltsis presentin the secondor even third leach,theseare combinedwith
the first leach,so that > 90• of the saltsare obtainedin • 20 ml of solution.
The final samplesize is determinedby re-weighingthe polyethylenesample
bottlexvithsample. The conductivityceil determinationsof the concentration
of the leachesare of use not only as a control on the leachingprocedureitself,
and for samplecompositing,but also as a rough measureof the concentration
of salts in the original inclusion,sincethe amount of dilution of the inclusion
fluids is now known (i.e., leachvolumeused/H20 obtainedon crushing).
The conductivitiesalso give SOlneguidancein sampleallquotingand in the
selectionof chemicalanalyticalprocedures.
The entire leachingprocessis done as rapidly as possibleonce water is
put in contact with the sample,to avoid unnecessarycontaminationof the
leachatewith dissolvedhost mineral, as well as possiblereactionsupon dilu-
tion. In spite of this, it has been found that the amount of calcium, and of
fluorine, from repeatedrinsesof fluorite samples,was maintainedat a level
corresponding to approximatelytwo-thirdsof saturationwith respectto CaEn,
yet the sodiumcontent of the solutionsdroppeddrasticallyafter the first
leach,as illustratedin Table 2. Presumablythe small amountsof Na found
in the later leaches(after correctionfor blank) comefrom the slow escapeof
inclusionsalts through cracks, but the analysisobtainedfor calciumon a
leachatefrom such a mineral can be consideredonly as a maximum. With
carefullystandardizedsamplesand procedures,the amountof host mineral
 STUDIES OF FLUID INCLUSIONS III 361

dissolvedmay becomesufficientlypredictablethat appropriatecorrections

may be madein the analysesobtained. If, however,there is any calciumbi-
carbonatepresentin the inclusionfluids,it will presumablydecompose to form
solid CaCO3 when exposedto the vacuum; suchcalciumcarbonateshouldbe
dissolvedin the leachingprocedureandincludedin the analysisof the inclusion
fluids. The existenceof solid daughtermineral grains in the fluid of the in-
clusionsbeforeopeningpresentssimilar problemsin the selectionof a leaching
technique,and similarambiguityin the interpretationof the results. Sulfide
minerals oxidize during leaching, so leached sphalerite samplescontinue to
yield rinsewater with appreciableconductivity,which showedon analysisan
amountof zinc (1 ppm) adequateto explainthe conductivities
found. Analy-
TABLE 2

ANALYSES OF SUCCESSIVE LEACH SOLUTIONS FROM FLUORITE SAMPLE ER59-10a

Analysis, ppm
Leach solution M1 ppm by conductivity
Na Ca

1 21.0 36.7 7.3 5.6

2 +3 28.5 17.2 0.32 4.5
4+5+6 37.5 14.2 0.23 n.d.*

,rn.d. = not determined.

sesfor chloride or sodium on serial leachesverified, however, that the bulk of

the inclusion salts are extracted on the first leach.

Microa•mlysis
The major problemin the analysisof the fluid inclusionleachsolutionsis
the combination of very smallsamplesizewith very low concentration.Con-
centrationbeforeanalysisis practicallyalwaysruled out becausethe volumeof
the solutionis usuallytoo smallto gain any advantage. Methodswere chosen,
therefore,that couldbe usedto determineone tenth of a part per million of
eachion if a total of 20 ml of solutionwere availablefor analysis.
The following determinationswere made: sodium,potassium,calcium,
magnesium,boron, chloride, and sulfate, and lithium if the concentrationand
amountof solutionavailablefor analysispermitted. Sodium,potassium,lith-
ium, and calciumwere determinedflamephotometrically at the wavelengths
specified. The BeckmanDU spectrophotometer with flame attachmentwas
usedwith an oxygen-hydrogen burner of mediumbore. Magnesium,boron,
chloride,and sulfatewere determinedcolorimetrically
usinga BeckmanDU
spectrophotometer
for absorbancemeasurements.
Separatealiquots of the solution were taken for each determination. If
only 20 millilitersof solutionwere availablefor analysis,the aliquotstaken
would be approximatelyas follows: for magnesium,5; for chloride, 3; for
sulfate,2; for boron,2; andfor the flamedeterminations,
8. A description
of
the methodand other pertinentinformationfor eachelementfollows:
362 ROEDDER,I•\;GI?./tM,
,4ND H,4LL

oCodium.--Measurement
wasmadeat 589.3m•. Standards wereprepared
from reagentgradeNaC1,dried at 110ø C. The solutions
presented
no
problemfor this determination.
Potassiu•.•.--Measurement
wasmadeat 766.5m•. Standards
werepre-
paredfrom reagentgradeKC1, dried at 110ø C.
The sodiumcontentmaybe highenoughin somesamples(> 30 ppm) to
causeinterference
in the potassiumdetermination.This canbe checkedafter
thepreliminarydeterminationby preparinga standardcontaining
theapproxi-
mateconcentrationsfoundfor both potassium and sodiumand comparingit
with a potassiumstandard.If thereis a difference,
the potassium
shouldbe
determinedagain using mixed standards.
The potassium shouldbe at least0.1 ppmfor directmeasurement.
Lithium.--Measurement was madeat 670.8 m/•, usingthe blue sensitive
photomultiplier
tubeto gain extra sensitivity. Li2COa,acidifiedwith HC1,
was usedfor the standardlithium solution. The limit of determination,with
reasonablyaccuracy,is about0.01 ppm.
Calcium.•Measurement wasmadeat 422.7m•. Calciumcarbonate, acidi-
fied with HC1, was used for the standard calcium solution. It was standard-
izedby precipitating
calciumoxalate,ignitingit and weighingthe calciumas
calcium oxide.
The solutions
obtainedon leachingfluorideand sulfidemineralsmaypre-
sent a problem, as both fluoride and sulfate depresscalcium in the flame.
Testsshowedthat asmuchas 7 ppmof fluoridecouldbe toleratedbut that 10
ppmdefinitelyinterfered. Leachares from the fluoritesthat havebeenanalyzed
containedabout5 ppm of fluoride. If the calciumis 5 to 10 ppm, as muchas
30 ppm of sulfate can be tolerated, and most of the sulfide leachatesare
within theselimits. A_checkon interferencecanbe madeby comparinga cal-
cium standardwith a standardcontainingboth calciumand sulfateor calcium
and fluoride of the approximate concentrationin the leachate. If there is
interference,the calciumshouldbe determinedusingstandards that alsocontain
the interferingion.
The concentrationof calcium should be at least 0.05 ppm for direct
determination.
Ma•lnesium.--A colorimetricmethod involving 1-azo-2-hydroxy-3-(2,4-
dimethylcarboxanilido)-naphthalene-l'-(2-hydroxybenzene)
as the color rea-
gent was used (19). The reagent and a borax solution for buffering were
addedto an aliquotthat was just acid to phenolphthalein,
and dilutedto 25 ml
with ethyl alcohol. A'bsorbance was measuredat 505 m•. The methodcan be
used to measure0.5 to 10 •g of magnesium.
Even as little as one ppm of iron, copper,or aluminumcausessubstantial
interference,and suchsolutionscannotbe used directly. The interfering ions
were extractedwith 8-quinolinolin chloroform (18); the color can be de-
velopedusingthe extractedsolutionwithout additionaltreatment.
The extractionprocedurewas modifiedas follows: The entire extracted
solutionwas usedfor color developmentinsteadof an aliquotof this solution;
an extractionpH of 5 insteadof 7 was necessary;and a 1 to 1 ratio of aqueous
solutionto chloroformsolutionwas neededfor completerecovery.
 STUDIES OF FLUID INCLUSIONS III 363

The extractionwas conveniently

doneby extracting5 ml of the aqueous
solutionin a 60-ml separatoryfunnelwith 5-ml portionsof 8-quinolinol-chloro-
form solution. If the aliquotof leachate
for analysiswassmallerthan 5 ml, it
was diluted to 5 ml with water before extraction. The maximum aqueous
volume that could be extracted was 10 ml. When this volume was used, the
volume of the chloroform solution was increased to 10 mi.
The colorreagentwaspurchased froln La Motte ChemicalProductsCo.,
Chestertown,Maryland and was labeled"La Motte Magon." Apparently
it is not as sensitiveas the compound preparedby Mann and Yoe (19). It
givessatisfactory results,however,if the aliquotof the reagentpreparedwith
it is increased from 5 to 10 ml.
Two-centimeter cells were used for absorbance measurements instead of
one-centimeter
cellsand a reagentblankwas usedas the referencesolution.
Boron.--Boronwas determinedcolorimetrically using 1,1'-dianthrimide.
Conditions
considered
optimumfor the reactionby Danielsson(7) were
followed.
The leachate
wasevaporated
to drynesswith saturatedcalciumhydroxide
in a silicaglassbeaker. Ten ml of dianthrimidereagent (0.2 mg per ml of
concentrated H_•SO,)wereaddedandthe colordeveloped by heatingat 100ø C
for 1.5 hours. Opticaldensitywas measuredat 620 m/• usingone-centimeter
cells. A blankcarriedthroughthe procedurewas usedas the referencesolu-
tion. The methodcanbe usedin the range of 0.05 to 3 /•g of boron.
Leachsolutionsfrom fluoritegive only maximumvaluesby this procedure,
as tests showed that fluoride enhanced the boron color. Sodium fluoride alone
carriedthroughthe procedure doesnot reactwith the reagentbut whenboron
is alsopresentthere is definiteenhancement of the color. Five micrograms
of fluoride can be tolerated in the method but if the solution was from a fluorite
sample,the aliquot usuallyneededwould containat least 25 /•g of fluoride.
At present,no satisfactorymethodhas been worked out for boron in such
fluorite leachates.
Chloride.--A colorimetricmethodusingferric ammoniumsulfateand mer-
curic thiocyanate(3, 27) was found to presentno problems. The method
dependsupon the displacement of thiocyanateion from mercuricthiocyanate
by chlorideion, and the formation of the highly coloredferric thiocyanate
complex.
An aliquot of the leachatewas treated with ferric ammonium sulfate and
mercuricthiocyanateand diluted to 25 ml. After 10 minutes,the absorbance
was measuredat 460 m/•, using water as the referencesolution. If chloride
wasbetween0 and 50/•g, five-centimeter cellswereusedfor the measurement;
if between50 and 200/•g, two-centimetercellswere used. As chlorideis the
major anionin mostinclusionfluids,the amountof chloridein the samplesolu-
tions is roughly one half of the total salt concentration,expressedas ppm
NaC1, obtainedby the conductivitymeasurements.
Sulfate.--The method involves the reduction of sulfate to sulfide and a
spectrophotometric measurement of the methyleneblueformedfroin the sulfide
after additionof aminodimethylaniline and ferric ammoniumsulfate. The re-
sults should be considered to be determinations of total sulfur as sulfate unless
364 ROEDDER, I.\'GR:t3,i, .lIND H./ILL

the samplepreparationstepsused would causeloss of any H2S originally

presentin the sample. In view of the rarity of free H.,S in inclusionsin
amountsthat canbe smelleduponcrushingsamples(approximately 0.15 •g),
and the known contaminationof leach solutionsfrom sulfide minerals 1)y oxi-
dationduringleaching,the sulfatedeterminations
shouldhe considered
to be
maximum values both for sulfate and for sulfide sulfur.
The procedureof Johnsonand Nishita (15) was nsed. A one- or two-
milliliter aliquotof the leachatewas digestedwith a redricingmixtnre of red
phosphorous, hydriodicand formic acids. With the aid of nitrogengas as a
sweepingagent,the hydrogensulfideformed was distilledand absorbedin a
zinc acetate-sodiumacetate solution. Aminodimethylanilineand ferric am-
monium sulfate solutionswere added to form methyleneblue. Absorbance
was read at 670 m•.
To increasethe sensitivityof the method, the volumesof the absorbing
solution,aminodimethylaniline and ferric ammoniumsulfatesolutions,and the
final volumeof dilutionwere reducedto onefourthof thosespecified
by John-
sonand Nishita. Readingswere madewith five-centimetercells. With these
modifications,0.2 to 10 •g of sulfateion couldbe measured.
A 25-ml glassstopperedgraduatedcylinderinsteadof a volumetricflask
was used for absorptionand color development. This gave a longer travel
path for the nitrogen through the absorbingsolution. Frequent blank and
standarddeterminationswere necessary.

RESULTS OBTAINED

Prelimi•mryBulk Crushing7
Ru•s
During the developmentperiod a seriesof samplesrepresentinga variety
of geologicalenvironmentswere run to explore the potentialitiesand limita-
tions of the method. As it was desirableto try out the leachingprocedure
first, and to obtainan estimateof the ionic ratios to be expected,severallarge
sampleswere run by simplecrushingin air, followedby water leaching. The
sampleswere carefully picked and electrolyticallycleanedand the leaching
operationwas madeas similar to that describedaboveas the larger sample
sizewouldpermit. The larger leachsamplesizemadeit possibleto take opti-
mumaliquotsfor eachanalysisas well. The samplesusedin thesepreliminary
runs were as follows:

Fluorite (ER59-13).--White to brownish, massive,pure granular (1 cm)

to coarselycleavable (10 cm) fluorite ore with no visible impurities. Moderately
strong petroleum odor on crushing, and a trace of carbonate grains found in
crushedsample. From center of a sheared,nearly vertical vein of nearly pure
fluorite, 1,950 feet south of shaft, 800-level south, Fairview mine, Rosiclare District,
Hardin County,II1., a MississippiValley-typedeposit;37025' N, 88020' W. This
is the samevein as sampleER59-14 belowand sampleER59-15 in the next series.
Fluorite (ER59-14).--Massive, white, strongly-shearedpure fluorite ore,
450 feet north of shaft, 800-level north (125 feet southof number 11 raise), Fair-
view mine, from samevein as above. Also containsa trace of carbonategrains.
Galena (ER59-62a,b,c& d).--From Platteville, Grant County, Wisc., a
Mississippi
Valley-typedeposit;collected
by D. E. White; 42044' N, 90029' W. A
 STUDIES OF FLUID INCLUSIONS III 365

large rough but euhedralcube, 10 cm squareand 5 cm high, formerly attachedby

one face. The cleavedbase showedabundant semiradially arranged lineage blocks
indicating growth from the physicalcenter outward. Small marcasitecrystalsare
embeddedin the surface,which is coveredxvith small cubo-octahedralbumps. The
sample was first split into equal weights of rim and core, by sawing slabsapproxi-
mately 1 cm thick off of all five external crystal faces. These two portions then
were sawn into quarters (relative to the original crystal) parallel to the cleavage
directionsand diagonallyoppositequarterscombinedto yield a matchedpair of rim
samples(a & b) and a matchedpair of core samples(c & d).
Quartz (ER61-3 & 4).--A series of inclusion-richportions cut from a num-
ber of Brazilian quartz crystal rejects from the electronicoscillatorindustry. Lo-
calities (?) unknown but presumablypegmmtiteor quasipegrnatiticveins (16).
Most of the inclusionsoccur in healed curving planes and are presumablypseudo-
secondaryin the usage of Yermakov (34), but some may be primary. Two
samplesfrom this group were examinedfor freezing behavior (24, Sec. E, Table
1); their freezingtemperatures
rangedbetween--3.4 and --8.5ø C.
The analyticalresultsare shownin Table 3. None of thesesampleshad
any odorof H2S on crushing.As thereis no possible
controlon the amount
Table 5.--Analytical results on preliminary bulk crushing runs

½ •e Leachate
analysis •o
ø Atomic
ratios
• • (ppm) • • ••
S•=p•e
No.* • Na • C• • C• • SO• • • •/N• C•/N••/N• m/N••/N• SO•/• C•/•
•59-k3 k078 388 •0.0 0.77 9.5 0.38 2•.k .... 0.39 •.44 54 0.0450.5•6 0.056k.59 --- 0.009 •5
ER59-1h 7• 106 6.8 0.548.8 0.2914.5 .... 0.26 31.19 •6 0.0470.743O.OhO
1.38 --- 0.009 18
•fRtm•
• 538185
6• 25322.91.23.8
16.70.• 4.60.97
1.044.9
35.50.01
O.O115.•
7.2 90.01
63.0491
61 0.031
O.115
0.030 O.Ohl
0.131 1.27
1.300.•
0.055 O.001O.161
0.103 2.8
2.4
501 251 18.6 0.98 4.9 0.92 39.8 0.O1 •.2 69.hl 70 0.0310.15 0.0471.59 0.001 0.054 3.2
•61-3&4 600 550 5.5 1.2 1.6 0.22 ll.6 0.06 0.Th 20.92 2& 0.15 0.1660.0381.370.023 0.032
Bl•k --- 138h0.02 0.02 0.05 0.02 0.Oh •.005 0.04 0.19 0.3• 0.6 1.h 0.9 1.3 ( 0.5 0.5 1.5
*Thetop six ar•lyses are all of samplesfromMississippiValley-type deposits.

of inclusionfluid releasedon crushing such samples,and the ratio of total

sampleweightto leachvolumevaries,the only valid comparisonof suchanaly-
sesis by their atomicratios,also shownin the table. These ratios,however,
are usefulin understandingcertaingeologicprocesses.It would be desirable
to be ableto make truly duplicateruns,but this is essentiallyimpossible.From
independentevidence,it can be calculatedthat only about 70 mg of inclusion
fluid was leachedin sampleER59-13, althoughthe sampleweigheda kilo-
gram. The presenceof a single large inclusion--as has been seen in Illinois
fluoritesamples--couldstronglyinfluencethe grosscomposition of the leachate
from sucha sample.
Althoughfluoritesamples
ER59-13and59-14camefromnearlyhalfa mile
apart in the mine, they are from the same level in the samevein, and the
atomic ratios are very closefor the two samples. The largest deviation,in
Ca/Na ratio, is probablythe result of variableamountsof leachingof the
crushedhostfluorite,as well as the tracesof carbonatepresent. The discrep-
ancybetweenthe totalppmfrom the sumof the analysisand the conductivity
of the leachateis due in largepart to the F- ion, representingsolutionof fluo-
366 ROEDDER,INGR.4M, •IND HALL

rite. The amount of fluorine found in severalsuch samplesdid not vary

greatly from the first to the last leaches,and as this representsa very high
and somewhatvariable"background,"fluoridewould have to be presentin
rather large amountsin the inclusionfluidsto be recognizedas such. The con-
ductivity of the leacharesstayedat about 25 ppm equivalentafter the first
leach. The sulfateanalysis(total sulfuras sulfate) may be considered only a
maximumvalue for inclusionsin thesesamples,as the oxidationof only 0.1
mg of sulfideminerals (i.e., 0.1 ppm) would accountfor it.
SamplesER59-62a through d, from the WisconsinPb-Zn deposits,were
run in part to act as nearly duplicatesamplepairs (a rs. b, c rs. d), and in
part to detectpossiblechangesin the compositionof the fluids trapped in
inclusionsat different times during the growth of sucha crystal (a & b rs.
c & d). Although the amount of salts obtained on analysis of these four
samplesshowsa two-fold variation,the atomicratios are rather uniform. The
variationswithin paired samplesare largest for the ions presentin smallest
amount,but it is not possibleto tell whether these variationsare partly real
or only experimental. The large differencebetweencore and rim for the
ratio Ca/Na is probablyreal; assumingthis to be true, the variationsfound
in this sameratio for the two coresamples,and for the two rim samples,may
well be due to samplingproblems. The still larger differencein the ratio
SO4/Na may not be real, as the physicalnatureof the galenasample--and
henceits rate of surfaceoxidation--couldbe the controllingfactor.
In view of the extensiveearly dolomitizationin the vicinity of many of the
MississippiValley-typedeposits,the ratio Ca/Mg is particularlyimportant.
The valuesfor this ratio obtainedfrom the two fluorite samplesabove are
high by at least a factor of two from the solution of fluorite during the leach-
ing. The galenasamplesshouldgive more valid data, however,as only traces
of carbonatewould be availablefor solution,occurringas solid particlesin-
cludedin the crystaland exposedon crushing. The Ca/Mg ratiosfor these
four samplesdo show a very appreciabledecreasefrom core to rim; those
from the coreare higherthanthe Ca/Mg ratiosfor mostoil field brines(32).
Such data, obtainedon samplesthat can be spatiallyand temporallyrelated
to dolomitization,may eventuallyhelp to delineatethe conditionsunder which
dolomitization can occur in nature.
Sample Et•61-3 •' 4 was run particularly to determinethe general range
of theK/Na ratio in suchinclusionfluids.in view of the recentwork of Orville
(20) on the equilibrationof feldsparswith alkali halide fluids. The quartz in
the pegmatitedepositsis associatedwith albite (cleavelandite)and microcline
feldspars,and the closegradationaland geneticrelationshipof the quartz
veinsto the pegmatites(16) would indicatethat the fluid of theseinclusions
may have been in equilibrium with respectto these two feldspars. At the
probabletemperatureof formationof theseveinsandpegmatites, it thusshould
havea K/K + Na ratio somewhat
lessthan0.16 (20). The ratio K/K + Na
for the analysisshown is 0.11. This is a compositesample,however. and
should be checkedwith careful studies of single localities of known mineral-
ogy. There is evidencethat someof thesedepositsformed from fluids that
were saturatedwith respectto CaCO• as well (16, p. 615).
 STUDIES OF FLUID INCLUSIONS III 367

The amountof boronis ratherhighand reflectsthe probablesignificance

of boronin pegmatitic
fluids. Many of the Brazilianquartzcrystaldeposits
of the pegmatite
typeshowtourmaline(16) andthe presence of actualborax
crystalsin fluid inclusions
from pegmatitemineralshas beenrecordedin the
extensiveRussianliteratureon inclusionresearch(29, 33). Further work on
suchmaterialsis in progress.
The high sulfatefound is also interesting. Various sulfidesoccurwith
thesedeposits(16), andoneof us (ER) hasseena Brazilianquartzsample
withlargefluidinclusions
eachof whichcontained a singleloosepyritecrystal,
presumablya daughtermineral,deposited
aftertrapping(22). Carefuloptical
measurements indicatedthat thesepyrite crystalsamountedto only 0.0003
percentof the enclosed fluid (3 ppm).
The Blankwasrunby followingthenormalleaching procedure,but without
a sample. The water usedfor leachinghad a conductivityof 0.5 t•mho,cor-
responding to 0.25ppmsalts;the "leachate"(after passing throughthe filter)
had a conductivity of 0.72 t•mho,corresponding to the value of 0.36 ppm
givenin the table. From the analysis,it is evidentthat the blankdoesnot
constitutea very significantportionof the saltsfoundon mostanalyses of the
leachatesfrom actual samples,althoughit does amount to as much as 20
percentof the totalfor certainelements in a few of the very smallsamples.
As it probably variessomewhat in itself,no attempthasbeenmadeto correct
theresultsfor it. The ratiosfoundfor it are significant
onlyin indicating
the
general nature of the contaminationfrom such sourcesas the filter asbestos.

Yacuum-crushi;•g
The vacuum-crushingprocedureitselfwastestedby runninga seriesof 14
samples,selected
mainlyon the basisof suitability
andavailability.The first
sevenwere from Mississippi
Valley-typedeposits.The natureand sourceof
thesesamplesaregivenbelow,andtheanalytical resultsobtained
are givenin
Table 4. All but one of thesesamplenumbersare referredto in the second
paperin this series(24). Althoughthe samesamplematerialwas usedfor
bothinvestigations,
differingsamplerequirements generallyprecluded the
application
of bothprocedures in sequence to the sameinclusions.The ap-
proximateoriginalconcentrations
of salts(NaC1equivalent) in thesesamples,
as estimated
from the freezingtemperatnres (24) for similarinclusions
from
thesamesamples,arealsogivenin thetableforcomparison withtheanalytical
determination.

Sample Description.--Fluorite (ER59-10M-N).--Acomposite sample of many

cubicnegativecrystalprimaryinclusions 0.1-1.0min. frmn 5-10 cm purple
cubesfrom vugsin southwest endof Hill mine,Cave-in-Rock district,Hardin
County,III. 37028 ' N, 88o11' W. Inclusions arrangedin planesparallelto cubic
growthandcolorpattern. Severalshoxved fillingtemperatures
(uncorrected) of
142-145øC. Sample prepared to exclude
all possiblepseudosecondary
or secondary
inclusions;of thetotalfluidspresent,probably % 1% byvolumeis fromnonprimary
inclusions.
Fluorite (ER59-10P).--Same samplematerial as above, but cut as thin
plates,sothateachcontains
a planeof small,complexly
faceted,
negative
crystal
 368 ROEDDER,IA•GR_/1M,
•IN'D H_/1LL
TABLE 4.--11%% OF VAGlf•i CRUSHIDi /d.nO1ECROAiU•LYSiS07 FLUID INCLUSIONS

I288ISSIPP! VALIiIY-itPE DEPLsI_S

EP59-10•ZI ER59-10P E-R59-10a ER59-15 EPS)-15a .•61-1 C-437

Mineral Flaor. Fluor. Pluer. Fluor. Y~uor. Sphal. Sphal. Calc. Qzz. Sphal. Spbal. Sph•l. Sphal. Sphal.
H20 visual est. • ng !0 10 4 i 1 ? 1.• 7 75 23.2 3 fv•O 2-3 5 5
Ha0
vacuum
anal.•mg
• 6.9 lost 2.6 O.L4 los5
I•' 18.5 1.4 i18
i-/ 2hl J.0 4.26 3.• 1.7 5.Z
D/H rel. to Lake ]!ich. •0.1 -- +2.1 +0.9 -- +3.5 +1.4 -- -5.2 +0. i +2.6 - .s -2.3 +0.5
Leach vol.• P• 105.8 •2.1 21.0 7.2 •L.1 69.0 %5.7 32.9 ll.1 31.1 49.0 119 hl.2 55.4
Leachate analysis• ppm
?Is 3.• 16.5 7.5 4.4 2.7 19.3 1.8 O.kl 2.8i C.'} 5.2 C.20 0 .ES 2.7
K 0.79 0.8• 0.54 0.3,• C .28 0.•2 0.09 C.1! 0.10 C .3• 0.27 0.18 0.1• 0.L 9
Ca 5.2 13.0 5.6 !,1 6.1 C. '•9 ) .0 0.12 2.1 1.% 0.29 0.25 1.6
Mg 0.46 1.62 0.58 <0.2 0.21 0.82 <0.05 !.O <0.2 C.35 0.25 0.i0 0.07 0.22
C1 7.! 12.8 1 •.a 8.0 6.0 2.• 3.• <0.5 1.2 _!.l 2.• 0. '9 0.82 6.•
$ <0.01 <0.0• <0,037 <0.55 r.z. 0.Ol C .02 <0.Ol n.d. <0.Dl <c.01 <o.01 <c.c1 O.C1

s0• ½.1 <0.1 0.2S .__!_0

• 0.65 0.7 2.'- 1.œ 02- C.a7 0.50 C. 5 0.68
stum 16.16 64.6f• 28.74 18.67 7c.35 6.55 8.a3 5.•i 2•.2,17. 9 1.77 2.07 12.50
c d t' '•?-/
on nc •v• 25 77 31.8 15 28.5 65 •.! 16 • .• 25 18 •.8 5.7 14
Atomic
ratlos•
K/Ns O.05• 0.030 O.O•
4 0.052 0.061 o.c28 0.029 0.16 C.I• 0.025 0.05C 0.55 0.29 0.11
Ca/Ns <0.91 <0.45 <0.44 <0.14 • .7 6._8 0.156 <5.6 0.07• 0.135 0.15L 0.83 0.51 0.3-
•/Xa 0.13 0.093 0.075 <0.04 0.07• 3.31 0
<O.026 •.3 <C.a 0.037 0.046 0.47 0.'-7 0.077
C1/Na 1. •0 1.29 1.28 1.18 1.4 !. 41 1.22 <0.8 0.•7 1.17 1.22 1.59 1.89 1.64
B/NS <O.006 <0.00• •O .011 <0.28 -- c .OCl
0.02• <0.05 -- <0.002 <0.00• <0.1 <O.07 0.008
<o .el •
S04/Ha 0.007 <0.001 0.009 0.2i• 0 .$58 <C.ON3 1.to 0.323 <0.011 <0.022 <0.599<O.'•O
5 <0.062
Ca/Mg <6. q <•.9 <5.9 • 37 <23 •.5 >6 <2.L >0.4 3.6 32+ 1.8 z.1 • •
Totalcharge
unbalance
c-• +2LD +575 +236 -!98 -7 +235 +7 +65 +35 +9 -2 +18

Original consentration• d/
weight • of solution -•
N• 4.0• •,8 5.5 5.(- 9.012 0,C 7 7,16 5.0 0.72 C,65 2.5
C .27 C .003 0.011 O.3! 0.ø-6 0.65 C.32 0.46
K
Ca 0.35
0.862/ 3.35./
0.72
• 0
•.38 1.8 <0.11 0.CC'6 1.7 1.3'• hO v C.5B i .50
I•g 0.56 o .38 <c .25 6.24 <0.13 0.Oi• <0.613 C.2• C.2• 0.36 0.16 0.21
C1 8.7 9.'•6 10.05 12. • <0.0!'• 0.063 12.26 9. • 1.76 1.9 •'.56
B <0.01 <0.024 <0,75 0 .CO5 C .05 <0.0003 n.a. <0,GO8 <0.01 <0.036 <0.02 0.O!
S0• 0.12 0.18 5 .C <c .53 •- .2
0.067 0.063 0.3 0.45 1.80 1.15_ 0.6•
Total by anal. 14.6 15.9 23. 20.8 17.5 0.23 0.28 22.7 16.7 62• h.8 11.7
Total
byfreezin•
e-/ 19.9- 20.1- 19.4- -- •6.6- 0.0 0.7 13.0- 13.0- 4.2- • .2- 12.0
20.7 21.5 19.6 !T .o -5. • 13.4 5.O 5.0

a_/All sampleswere checkedfor noncondensablegasesand for COsmnz,,e '.'aca•. tzaih. All wezeat o•' belowthe sensitzvzzythresholmsfo• the me,ohods
i.e.• < x•g noncondensablegasesand < 0.1 mgCO•.
•_/ This is expressedin ppnNaC1equivalent; it includesprobablysignificant •-r',ounts
of ions novanalyzedfor• suchas Y-• Si03=, C03=•andHCOa•and
possiblyminoramounts
of Fe+++, AI++• etc.
•_• Theratios a•e indicatedas beingmaxima
whereversolubility of th• host•lnera! or analytzcallimit of sensitivity in•erferel,
c_/This is givenin unitsof millimicroequivalents
per ml of leachate,•.•. 10-• eq./m2,as the analyses
are irostconve-i•n
ßly converted
•o :ill.micro
per ml. Its sign is pos•tzve where an excess of cat ions was found, and v.

d• Obtainedby correcting the water dilution factor (ragleach solution/ragHaCin insiuszons)for tae concenvrationof salts found.
e_•(Yotained
fromsimilar inclusionsin the sameoriginal stumplos
(ref. 24); ass,•.inga pureNaC1-Hm0
system.
f_• Includes0.02 Li.
•/ Includes 0.01 Li.
h_/Calculationsfrom.comparison
of the analysiswith that of •R59-15wo4ldindicate about2.6 m• Ha0.
i_/ Weightloss determination--seetext.
• t•sed on •n •sslun•i correction of 4.5 ppm. Ca in the leachate,from solution of

pseudosecondary inclusions essentiallyparallelto cleavage.One planeshowed

fillingtemperatures
(uncorrected) of 139ø C. Manyshowthreephases, gas,liquid,
anda tinycrystal(seefig. 1 V in ref. 24); approximately
40 cm2 of suchplanesin
sample(i.e., about10s inclusions),andonlya very few smallprimaryinclusions.
probably% 1% by volumeof total fluid present.
 STUDIES OF FLUID INCLUSIONS III 369

Fluorite (ER59-10a).--Duplicateof ER59-10Pabove.

Fluorite (ER59-15).--A compositesampleof many cubic negative crystal
primary inclusions0.1-1.0 ram, from 1-3 cm colorlessglassycubes,occurringin
vug with crystalsof galenaand sphalerite,500 level south,near 22 raise, Fairview
mine, Rosiclaredistrict, Hardin County, II1., 37o25' N, 88ø21' W. Inclusionsar-
ranged in groups parallel to crystal surfaces,and contain occasionaldroplets of
yellow oil alongwith the water solutionand gasbubble. The oneprimary inclusion
measuredshoweda filling temperatureof 153ø; scarcetiny secondary(?) inclusions
gave 149.5ø C.
Fluorite (ER59-15•).--Duplicate of ER59-15 above.
Sphalerite (ER61-1).--Velie Lion mine, Tri-State district, Ottawa County,
Oklahoma, NE1/4 of SW1/4 of Sec. 19, T 29 N, R 22 E, 36o59' N, 94o59'
W. Collectedby E. T. McKnight, his numberVL-F1. A roundedmass8 X 8 X 3
cm, consistingof a single crystal with many minute crystal terminationsin mossy
subparallelarray over the rounded top; internally a single, cleavablezoned crystal
with few thin twin bands. A band of chalcopyritecrystalsoccurs3-4 mm beneath
surface. As the very dark yellow brown color precludedfinding visible inclusions,
a 36.4 gram samplefor crushingwas taken at randomfrom the portion insidethe
chalcopyritezone.
SphaIerite (USNM C437).--Santander, Spain; 43o28' N, 3o48' W. Yellow
transparent3 X 3 cm cleavage; from a replacementzinc depositin Carboniferous
limestone,connectedwith fracturing and consideredby Behre (1) to be Missis-
sippi Valley-type. Deposit contains somecinnabar, and the light-yellow sphalerite
has 0.4% or more Cd (17, p. 633). Although the estimatedvolumeof the single
large primary inclusionwas 9 mm3 (from crude optical measurements),measure-
ment of the ellipsoidalbut movablegas bubble (0.134 mm3) and an estimateof the
volume percentof gas from other inclusions(8%), correctly indicatedthe volume
of liquid to be 1.47 mm•.
Calcite (F-1).--La Aurora mine, Chihuahua, Mexico; about 26o40' N,
107o15
' W. Euhedraltapering2 X 10 cm prismsof opticalgradewith somepri-
mary inclusionsup to 2 cm long arranged along c axis. Samplefrom Carl Fries,
from a near-surfacebarren hydrothermalcalcitevein in latite, possiblyrepresenting
channelwayto former hot spring (12). Single inclusionusedwas 4 X 13 ram; the
volumeof the gas bubble(from diameter) and the volumeof water (by analysis)
show the gas to occupy0.9 volume percent.
Quartz (H-1).--From vein in rhyolite, near Oatman, Mohave County, Ari-
zona,from Mr. H. F. Heather; 35o02' N, 114ø25' W. Euhedralclear crystal 2 X 8
cm, with large (1 cm) primary inclusions,flattened parallel to rhombohedron.
Sampleusedcontainsa single4 X 5 mm primary inclusion. A piece of quartz
weighing 0.6 gram and containing this inclusionwas cut out with the micro sand-
blast unit; its apparentdensitywas only 2.479. From this densityand the gas
bubblevolume,measuredoptically, the volume of liquid •vas calculatedas 23.2 mm'•.
Sphalerite (USNM 18309c-d).--Cartagena. Spain; 37o36' N, 0o59' W.
Yellow transparenteuhedral 7 X 15 cm crystal riddled •vith large tubular and
planar primary inclusions,somewith precipitatedopaquespecks(Fig. 4 in ref. 22).
Deposit is a Pb-Zn-Ag vein filling, with Mn and some Sn, in andesiteand contact
metasomaticmaterial; gangueis siderite,ankerite,and rhodochrosite(2, p. 404).
Sphalerite (USNM 18309cs).--From same sampleas above. Containsap-
parently hundredsof overlappingthick planar primary inclusions,with 30 mma as
a very rough estimateof the volume of liquid; apparentlythe thicknessor the
numberwas greatly overestimated.
Sphalerite (USNM R552a).--Enterprise nfine, Rico, Dolores County, Colo-
rado; 37ø41' N, 108o03 ' W. Dark green, transparenteuhedral4 X 6 cm crystal
associatedwith etchedgalena and enclosingchalcopyritecrystals which causedthe
trapping of the large primary fluid inclusionswhere they gre•v on the surfacesof
the sphalerite crystal. Epithermal Pb-Zn-Ag deposit with gangue of quartz,
rhodochrosite,calcite, and fluorite, in volcanic rocks and sedimentsintruded by
370 ROEDDER,IArGR•tM,.,4NDH.,4LL

monozonite(17). Samplecontainsone large and severalsmall primary fluid

inclusions,
andonelargeamoeboid
emptyinclusion,7 X 7 ram,opento the surface.
Sphalerite(USNM R552b).--Same sampleas above,with one 3-mm amoeboid
inclusion.
Sphalerite (USNM 18557 Ba).--"Ani Ugo, Japan" Euhedral brownishto
orangezoned5 cmcrystal,originallylabelled"Aui Ugo." Probablya misspelling
of "Ani Ugo," an old namefor area now containingthe Ani (or "Ani-Kozan")
mine, in Akita prefecture,northernHonshu; 39059' N, 140o26
' E. It is a Miocene
Au-Ag-Cu depositin volcanics,
in a Au-Ag-Cu-Pb-Znprovince(25). Sample
usedcontained
largeramblingprimaryinclusions asmuchas 5 mmlong. A very
largeemptyinclusion,
opento surfacethrougha tiny tube,•vasopenedup with the
micro sandblastunit prior to electrolyticcleaning. A slight odor of H_o xvas
obtainedon crushingparts of this specimen.
I•terpretationof Results.--Althoughmuchsmalleramountsof saltswere
availablefor analysisin this series(only about 100 •g in one), the ratios
foundfor thevariousionsin the sevensamples from MississippiValley-type
depositsare generallyvery similarto eachother and to thosefound using
largersamples.The majordifferences between the samplesare probablyreal.
The closest approachto a true duplicate
in thisgroupof sevenis the pair
ER59-10PandER59-10a,bothfromplanesof pseudosecondary inclusions
in
fluorite,equivalentto sampleER59-10B & C in reference 24. The paired
valuesfor all fourmajorratios(K/Na, Ca/Na, Mg/Na, andCI/Na) arenot
onlyvery close,but all are well underthe equivalent ratiosfor the primary
inclusionsextractedfromthe samespecimens (sampleER59-10M-N). This
corroborates
the freezingdata which indicatethat smallbut real differences
existbetween thefluidsin theprimaryandthe pseudosecondary inclusions
in
thesesamples.The low valueof +0.1 for the D/H ratio of sampleER59-
10M-N is probablyin error,as furthermeasurements on similarsamples are
higher. The boronvaluesare probablyonly valid as maximadue to inter-
ferencefrom fluorine. The variationin the SO4 analysesis inexplicable
at
present. All thesesampleswere carefullypickedwhile immersedin oil of
similarindex (kerosene),whichpermittedthe recognitionand discarding of
any fragmentcontainingvisiblesulfideminerals. The amountsof sulfatefound
in samplesER59-10M-N and -10a indicatethat the original inclusionswere
nearsaturationwith respectto CaSO4. This wasdetermined by makingnp
synthetic
fluidsof similarcomposition;
sulfatein excessof 1-2 gm/1precipi-
tated from such solutions as calcium sulfate.
The two analyses ER59-15 and ER59-152,althoughof app-xrently similar
material,differ very greatly. ER59-15 wasa very smallsample(0.44 mg of
I-I20), but the concentration of saltsfoundand partsof the analysisseem
valid. The Ca/Na ratio is muchhigherin 15., probablybecause it contained
morethan 10 gramsof fluorite,whereassample15 contained only0.53 gin,
permitting little contactof the leachatewith the broken fluorite surface. The
sampleswere closelyassociated with sulfidesin the vug, and as the leachvol-
ume was very small for salnple15, very tiny amountsof sulfideminerals
(0.05 mg) couldcausethe high sulfate. The causesfor the variation in the
C1/Na ratio and the excessartionsin samplesER59-15 and 15._,, and for the
differences
betweentotalconcentration
by analysisandby freezingfor samples
ER59-10M-N, -10P, and -10a are not known.
 STUDIES OF FLUID INCLUSIONS III 371

Althoughthe dark colorprecludedseeingany inclusions in sphaleritesam-

ple ER61-1fromthe Tri-Statedistrict,a very adequate amountof fluid was
extractedon vacuumcrushing,amountingto about0.05 percentof the total
sample.This sampleis particularlyinterestingin that its valuefor Ca and
hencefor the ratio Ca/Mg (4.5) shouldbe morenearlyvalid for the included
fluids than the ratios obtainedfrom the fluorite sampleswhere leachingof
fluoriteoccurs.Severalsphaleritesamples
showed on leachinga continuous
contribution
of severalppmto theconductivity
of theleachsolutions.This was
from the oxidationof ZnS, asthe bulk of the cationspresentby analysiswere
Zn++ (presumably as sulfate). Thus the SO• analysisfor sampleER61-1,
even thoughvery low, still representsa maximum possiblevalue for total
sulfuras sulfatein the originalinclusionfluid. This leachatehad the highest
totalppmof all the samples, andyet hada low positivechargeunbalance,indi-
catingthat very little F-, SiOf, CO3:or HCOg- waspresent. The analysisof
sphaleritesampleUSNM C437, from the MississippiValley-typedepositat
Santander, Spain,is verysimilarto ER61-1,exceptfor lowermagnesium and
chlorinerelativeto sodium. It mightalsobe pointedout that all sevenMissis-
sippiValley-typesamples run by this method,plusall six shownin Table3,
showK/Na ratios (by weight) higher than the highestvalue in the range
givenfor oil field waters (32, p. 1666).
The large inclusionin opticalcalcitesample:F-1 was intersectedby a very
thin cleavagecrackthat formedduring samplepreparation. After this crack
formed,the sample•vasweighedquickly,and the water contentdeterminedby
weight lossto constantweight at 60ø for 25 days. The leachingof calcite
causesthe dominanceof calciumin the analysis--a rather uniform conductiv-
ity of about16 ppm wasfoundfor all leachesfrom this sample. Other ratios,
suchas K/Na, Mg/Na and SO4/Na, are probablyvalid, and differ drastically
from the ratiosfor all the MississippiValley-typesamples. The original con-
centrationas determinedby analysisis only half of that determinedby con-
ductivity; this is probably due to comparativelylarge but undetermined
amountsof carbonateor bicarbonateion. The discrepancybetweenoriginal
concentration by freezingandby analysismay representdifferencesin samples.
Ironically,the inclusionsin thesesamplesxverepracticallyall too large to per-
mit freezingwithout breaking,as they had smallbubbles;only one inclusion
was found that did not break on freezing.
SampleI-I-l, a large primary inclusionin a quartz crystal from "a vein in
rhyolite,"wasinteresting
in severalrespects.The volumeof I-I20 estimated
from densitymeasurements was verifiedon analysis. The differencesbetween
originalconcentration by freezingand by analysis(and conductivity)may well
be a samplingproblem,as the inclusionsfrozen were much smaller,and from
a different part of the crystal; the large inclusionanalyzedcouldnot safely
be frozenas it had only about 10 percentof gasphase. The analysisobtained
is quite unusualin severalrespects,being very low in calciumand chlorine,
and high in sulfate. As the samplethat was crushedand leachedcontainedno
visiblesulfideminerals,the sulfatevalue is probablyreal.
The pair of samplesof sphaleritefrom Cartagena,Spain (18309) and the
pair from Rico, Colorado(R522) illustratethe variabilityto be expectedin
372 ROEDDER,INGRAM, AND HALL

the analysisof "duplicate"samples. There are considerabledifferencesin

ratiosthat shouldbe identicalif the sampleswere true duplicates.The bulk
of thesedifferences betweenpairedsamplesprobablyare not real, and are the
resultof experimentalerrors inherentin treatingvery smallsampleswith the
methodsused. (For example,later work on similar pairedsampleshas given
much more concordantD/H ratios.) The differencesbet•veenvalues for the
two sample localities,however, are very striking and definitive in all ratios,
even though the two localitieshave much in commongeologically. The dif-
ference in samples 18309 bet•veen the original concentrationby freezing
(13.0-13.4%) and by analysis(16.7-22.7%) may well be a result of the
natureof the samplescrushed. They containedsomelarge apparentlyempty
inclusions,as well as large numbers of normal two-phaseinclusionswith
small (7-8%) gas bubbles. Any inclusionthat is cut by a cleavagecrack
extendingto the surfacewill eventuallylose all of its water by evaporation,
leavingthe saltsbehindeither in the inclusionor in the cleavagecrack. These
salts•vouldbe very difficultto removeduring the electrolyticcleaningoper-
ation as diffusionthroughsuchsmall crackswould not only be slow, but the
air in the inclusionand crack might prevent the •vater from contactingthe
salts, precluding any electrolyticcleaning. On vacuum crushing, however.
thesesalts would be exposedfor leachingalong with the rest of the sample.
Where possible,suchdried-outinclusions were openedup by useof the micro
sandblastunit prior to electrolyticcleaning.
Sphaleritesample18557,from a Japanesedepositalso associatedwith vol-
canicrocks,showeda very concordantanalysis,with atomic ratios differing'
from all other samplesrun.
The analysesof the Cartagenasarnplesare very similar to thosefrom the
MississippiValley-type deposits,but the concentrations found by freezing
were appreciablyless. Some of the ratios found for the samplesfrom Rico
and Ani Ugo are quite different frorn thosefor the MississippiValley-type
samples. In particular,they show-nmchlower total concentrations, and much
higherratiosfor K/Na, Ca/Na, and C1/Na, than all MississippiValley-type
samplesrun. Considerably more analyticalwork is neededbeforethe signifi-
canceof suchdifferencescan be fully understood.

FUTURE STUDIES

The reconnaissance work with this methodreportedhere has beenadequate

to reveal its limitationsand applicability,as well as to provide informationon
the compositionof inclusionsin certain types of samples. More detailed
studiesnow in progresson largenumbersof samples,carefullyrelatedto their
geologicoccurrence,should yield even more useful data. Several refinements
in the techniques usedare obviouslydesirable,and underinvestigation.These
includeparticularlythe determinationof the varioussulfur speciessuchas S:,
I-IS- and SO4=,as well as CO:•--and HCOa-. In orderto be of greatestutility
in recognizingpossiblerelationshipsbetween these inclusionfluids and the
varioustypesof thermalwatersit would be desirableto have analysesfor the
rarer alkaliesand halogens(9, 31, 32) but the quantitiesprobablypresentare
 STUDIES OF FLUII) I.VCLUSIOA•3
' III 373

too low for presentmethods;neutron-activation

methodsare beinginvesti-
gated for theseand other constituents.

CONCLUSIONS

1. Nearly completequantitativechemicalmicroanalyses
of the saltsin
solution,as well as their concentration
in the fluid of fluid inclusionsin the
milligramrange,can be obtainedby the methodsdescribed.
2. The technique
permitsanalyses
of smallsamples,
andhenceof individual
zonesor inclusiontypesthat cannotbe obtainedin larger amounts,as well as
specimens with very few or small inclusions.
3. For many purposes,the eliminationof ambiguityof inclusionorigin
throughthe use of small samplesoutweighsthe lossesin analyticalprecision,
accuracyand completeness.
4. A numberof samplesyieldeddata on concentrationas determinedby
analysisthat are very similar to thosebasedon freezing data on similar ma-
terial; othersamplesgavevaluesthat are discordant, in part inexplicably.
$. The compositionsof fluid inclusions
in severalMississippiValley-type
deposits,althoughrather similar to eachother, differ considerably from the
compositions
of inclusions
in ore and ganguemineralsfrom all othertypes
of depositsstudied.
6. Suchdatacanbe usefulin understandingthe environmentof deposition
of ores and in delineatingthe conditionsunder which such processesas
dolomitization have occurred.

U.S. GEOLOG•C^LSURW¾.
W^SnI•GT0• 25, D.C.,
September 18, 1,o62
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