Economic Geology

Vol. 61, 1966, pp. 1390-1398

STUDIES IN THE PROVIDENCIA AREA, MEXICO; III

NEUTRON ACTIVATION ANALYSES OF FLUID
INCLUSIONS FROM NOCHE BUENA

HERBERT F. PUCHNER AND HEINRICH D. HOLLAND

ABSTRACT

Fluid in inclusionsin four samplesof quartz from the Noche Buena

mine, Zacatecas,Mexico, has beenanalyzedby meansof a neutron activa-
tion technique. The sampleswere irradiated prior to extractionof the
fluid from the inclusions in order to minimize contamination. The con-
centrationof sodiumin the inclusionfluids rangedfrom 0.8 to 1.8 percent,
and their manganese contentrangedfrom 50 to 170 ppm. Neither copper
nor zinc was detected. Studiesof the detectionlimits of our analytical
techniques indicatedthat the concentration of copperwas lessthan 12 to
24 ppm and that of zinc lessthan 260 to 580 ppm in all of the inclusion
fluids. The inclusionfluidsanalyzedwere almostcertainly saturatedwith
respectto chalcopyriteand sphaleriteat the time of entrapment. There-
fore, at least some hydrothermal solutions in equilibrium with these
mineralscontainonly small concentrations of copperand zinc.

INTRODUCTION

THE concentrationof the ore metals in ore forming fluids is a matter of

long-standing debate. A summaryby Roedder (6) setslimits of about 1 to
1,000ppm on the concentration rangeof heavymetalsthat may be precipi-
tated as a resultof temperaturedecreasefrom fluids that have formed many
base-metaldeposits. This is a very large range indeed,and a resolutionof
the presentcontroversies regardingthe natureof the ionic and/or molecular
heavymetalcomplexes in ore formingfluids (seefor instance(8), pp. 1385-
1387) depends criticallyon the portionof this rangewithin whichthe .con-
centrationof the heavymetalsnormallyfalls.
There are few satisfactorymethodsfor determiningthe concentrationof
heavymetalsin ore formingfluids. Direct measurement of their concentra-
tion in hot brines such as those encountered in the Salton Sea drill holes
still leavesessentiallyunanswered
the questionof their concentration
in the
fluidsthat haveactuallybeenresponsiblefor the formationof ore deposits.
Analysesfor heavy metalsin ganguemineralssuchas calciteassociatedwith
ore, can yield data on the ratio of the activity of heavy metalsto that of other
ionsin ore formingfluids,but not on the concentrations themselves(see for
instance(3) and (12)). The most directly applicableanalysesare of fluid
inclusionsin hydrothermalminerals. The internal consistency of measure-
mentsof the filling temperature,salinity,and isotopiccomposition of contem-
poraneous fluid inclusions(seeRye (10) and Sawkins(11 ) ) indicatesthat at
least some fluid inclusionshave retained their chemicalidentity since they
1390
 NEUTRON ACTIVATION ANALYSES 1391

wereformed,andgeometric criteriaareoftensufficient
to differentiate
primary
frompseudosecondary andsecondary inclusions.
Small samplesize makesanalysisfor heavymetalsin fluid inclusions
ratherdifficultexceptby atomicabsorption spectrometryand neutronactiva-
tion analysis.The lattertechnique is particularly
suitablefor sodium,man-
ganese,
zinc,andcopper,andhasbeenappliedby Czamanske, Roedder,and
Burns(2) to inclusions
in a sample
of quartzfromCreede,Colorado,
andin
a sampleof fluoritefrom southernIllinois.
Quartzcrystals fromthedumpof the Chivoorebodyof the NocheBuena
mine,20 km westof Providencia, Zacatecas,Mexico,were foundto contain
ratherlargefluidinclusions particularly
suitablefor singleinclusion
neutron
activationanalysis. We irradiatedthesein their quartzmatrixbeforeextrac-
tion of the fluids in order to avoid contamination of the fluids between ex-
traction and irradiation.

GEOLOGIC SETTING

The Noche Buena mine is located near the western end of the Sierra de la
Caja, closeto the contactbetweengranodiorite,probablyof upper Eocene
age, and the Upper JurassicLa Caja formation. The generalgeologyof
the areahasbeendescribedby Rogerset al. (9). The ore depositshave not
beendescribed in any detail,but are obviouslysimilar to thoseat Provi-
dencia(11). The ore occursin pipeswithinlimestone andcalcareous shale,
and consists largelyof sphalerite, galena,and pyritewith subsidiary sulfo-
salts. The ganguemineralsin the lower levelsare predominantly calc-
silicates. At higherlevelscalcitepredominates.Quartz is apparentlya late
mineral,and is distributedrather irregularly,but, as at Providencia,seemsto
increasein abundance towardthe top of the ore bodies.
The orepipesare all heavilyoxidizedto a depthof severalhundredmeters
belowtheir outcrop. On the dumparoundthe Chivo ore body partly clear,
euhedralquartzcrystalsup to 6 incheslongand2 inchesin widthwerefound
togetherwith oxidizedore. Accordingto Sr. Luis Gutierrezmost of this
quartzhad comefrom rugs on the 140 m level of the Chivoore body.

PREPARATION AND DESCRIPTION OF TI-IE QUARTZ SAMPLES

The crystalswerecutwith a diamondsawto isolatesmallpiecescontaining

inclusionslarge enoughfor analysis. Groupsof inclusions{n clear quartz,
orientedparallelto crystalgrowth planes,at somedistancefrom healedor
unhealedfractureswere sought. The final size reductionwas done by
grindingand polishingon a lap.
The final fragment shapewas dictatedby the requirementof minimum
size consistentwith a sufficientwall thicknessfor the inclusion(s) and good
visibility under the microscope.Foreign bodiesnear the surfacewere re-
movedwith a vibratingdiamondpoint.
The volume of the fluid in the inclusions was estimated under a micro-
scopefitted with a micrometerocular. This procedurewas less accurate
than the directdetermination
of water volumeby crushingthe samplefollowed
1392 H. F. PUCHNER AND H. D. HOLLAND

by reductionof water over uraniumand volumetricdetermination of the

hydrogen.It hadtheadvantage of avoidingthecomplexitiesintroduced into
the interpretations
of the analyticaldataby the precipitation
of a varietyof
compounds duringthecrushing in vacuum.The directmeasurement of fluid
inclusionvolumes by measuring the dimensions of inclusions
in a numberof
orientations
is probablytheleastaccurate of severalpossible
strategies.Un-
certaintiesof 40% in the inclusionvolumedeterminedin this mannerare not
unusualandvary with the natureof the material. However,the volumeof
thegasbubblein inclusionscanoftenbe measured with considerably
greater

Fxc. 1. (Left) Photographof SpecimenNo. 4; the distancebetweenmarks

on the scale is 1 min.
Fxc. 2. (Right) Photographof SpecimenNo. 2; the distancebetweenmarks
on the scale is 1 min.

accuracy;and, as the thermalexpansionof aqueoussolutionsis not a par-

ticularlysensitivefunctionof their ionicstrength,the filling temperature
of
a fluid inclusiontogetherwith a measurement of the size of the gas bubble
at roomtemperature cangive a figurefor the volumeof liquid at roomtem-
perature. Additionaldataon the internaldimensions of fluid inclusions
can
oftenbe obtainedby determiningthe sizeof the gasbubbleat elevatedtem-
peraturesat whichthe bubbleis just ableto movefreelyin the variousparts
of an inclusioncavity.
Inclusionsin four specimens
of quartzwere selected
for analysis:
SpecimenNo. I containedthree large inclusions,
eachwith a gas/liquid
ratioca. 1/10. The threeinclusions
wereisolatedfromeachother,but lines
of tiny inclusionsindicated
an earlierconnection betweentwo of them. No
signof a connection withthesurface of thequartzspecimenwasfound.
SpecimenNo. 2 (Fig. 1) containedone inclusioncloseto the centerof
the specimen, at a distanceof ca. 1 canfrom the surface. A planeof sec-
 NEUTRON ACTIVATION ANALYSES 1393

ondaryor pseudosecondary inclusionspassedwithin 0.4 mm of the major

inclusion,but no sign of a former connectionbetweenthe two was found.
The gasto liquid ratio was approximately1/6.
SpecimenNo. 3 was an entirely clear piece of quartz containingthree
inclusionsof comparablesize, which were evidentlyconnectedat one time.
One wascompletelyfilledwith liquid,the secondconsistedof about90 percent
liquid and 10 percentgas, the third was almostdevoidof liquid. The gas
to liquid ratio for the groupas a wholewas estimatedto be about 1/4.
SpecimenNo. 4 (Fig. 2) containedone large, easilymeasurable,isolated
inclusion,whosefilling temperaturewas found to be 220-----2øCon a cali-
brated heating stage. This correspondsto a gas:liquid ratio at room
temperaturenear 1/5.
ANALYTICAL PROCEDURES

After the inclusionshad beendescribed,the specimenswere washedseveral

timeswith acetoneunder reducedpressureto removetracesof oil and polish-
ing material. Inorganic impuritieswere then removedby cleaningwith aqua
regiaand with nitric acid,and by boilingin doubledistilledwater. The size
of the gas bubble(s) was then remeasured,and the few samplesin which
changesof bubblesizehad taken placewere discarded? The specimens were
finally cleanedfor about2 daysin an electrolyticcleaningcell at 90 volts as
recommended by Roedder(5), and were then oven-driedat 102ø C.
Comparisonstandardswere irradiatedwith eachquartz specimen. Silica
glasscapillarytubing (ca. 1.1 mm O.D. and 0.7 mm I.D.) was drawn over
a hot micro-flame. Pieces approximately6 cm in length were thoroughly
cleanedwith nitric acid and doubledistilledwater, dried, and weighedto the
nearest0.01 mg. The cleanedpiecesof tubing were filled by dippingthem
into a standardsolutionfor a fractionof a second. The capillarywas then
reweighedin a horizontalposition. In this positionthe liquid was brought
to the middle of the capillary. The end through which the solutionentered
the capillarywas closedby holdingit in a very small,hot flamefor approxi-
mately 1 second. During cooling,the liquid movedtowardsthe closedend.
The otherend of the capillarywas thenlengthened by meansof a silicaglass
rod, andwassealedoff by drawingout overa hot flame. The weightof solu-
tion in the sealedcapillarieswasknownto -*-2 percentof the amountpresent.
Each quartz specimentogetherwith A1-Cowire as a monitorand capil-
laries containingknown quantitiesof sodium,copper,manganese,and zinc
were packedin a polyvial and were irradiated in the "pool" type reactor of
the Industrial ReactorLaboratories,Inc., Plainsboro,N.J. In the volume
occupiedby our samples,the reactorproduceda neutronflux of ca. 1.3 x 10•a
neutronsper cm• per second. Specimens1, 2, and 3 were irradiated for 5
hours,specimen
4 for 25 hours. After irradiationthe sampleswere allowed
to cool for a minimum of 1 hour.
The contentsof the polyvialwerewashedwith 6 molarhydrochloric acid
and with distilledwater, and the quartzspecimen
was placedin a tefloncon-
x The bubblesize of the four specimensdescribedabovedid not changeon boiling.
1394 H. F. PUCHNER AND H. D. HOLLAND

tainertogetherwith 2 ml of slightlyacidified(pH 3 to 4) carriersolution

containing0.5 mg eachof Na+, Mn+", Co+", Cu+2,and Zn+" as the chloride.
The quartzspecimenwasbrokenunderthissolution with a goldplatedchisel
into pieceswhichwere sufficiently
smallto ensurethe openingof the large
inclusions.After three minutesof contact,the solutionwas decantedinto
a smallBuchnerfunnelandfilteredinto a pear-shaped distillingflask. The
quartz fragmentswere washedwith two 1-2 ml portionsof hot, distilled
water, and thesesolutionswere addedto the flitrate throughthe Buchner
funnel. This combined flitrate was our "water leach."

Table I

Elution of sodium. manganese!cob,

alt I copper! and zinc
from Dow•x 1 cola

Ali•uot. No. Vo,1

.umeo,f Molarit[ of HCl Percentage o.f cation
aliquot in, ali%uot in ali%u$t
1 10 ml 10 M 85 • 3% of Na

2 h 10 15 + 3% of Na

3 2.5 6

2.5 6

5 12 6 88 * 5% of Mn

6 3 4

7 12 4 95 • 5% of Co

8 4 2.5

9 12 2.5 92 • 5% of Cu

lO 4 o. oo5

11 20 0.005 96 ß 4% of Zn

The quartz fragmentswere then washedwith 2 ml of 6 N HC1 contain-

ing 0.5 mg eachof Na*, Mn+•',Co% Cu+2,and Zn+•'as the chloride. The acid
leachsolutionwas kept in contactwith the quartz fragmentsfor 2 minutes,and
was then filtered into a secondflask. The quartz was washedwith two 1-2
ml portionsof hot distilledwater, which were filtered and added to the acid
tiltrate. This combined flitrate was our "acid leach."
In someinstancesthe quartz fragmentswere crushedmore extensivelyat
this pointand were subjectedto a further acid leach. No significantadditional
quantitiesof the elementssoughtwere releasedduring this process. The
fragmentswere dried, storedfor 1 week to allow essentiallyall of the Siax
 NEUTRON ACTIVATION ANALYSES 1395

to decay,and were then examinedto verify that the large inclusion(s)had

beenopened.
After 1 ml 6 N HC1 had been added to each water leach flitrate, the volume
was reducedto «--• ml, and 2 ml of concentrated HC1 were added.
The separationprocedurefollowedwas that of Kraus and Moore (4),
usinga 15 cm columnof Dowex 1 stronglybasicanion exchanger(100-200
mesh). The cationswere separatedby passingaliquotsof successively more
diluteHC1 throughthe column. Table I showsthe volumeand concentration
of HC1 in the aliquotsof eluant and the percentageof sodium,manganese,
cobalt, copper,and zinc which were found in these aliquots after passage
througha columninitially chargedwith theseelements. The total quantity
of eachelementin the varioussampleswas obtainedeither by combiningthe
activity of that elementin all of the pertinentaliquotsor by multiplyingthe
activity found in the aliquot containingthe bulk of an elementby the appro-
priate factor. The separationwas monitored with a scintillation counter,
and the chemicalyieldsof Mn, Co, Cu, and Zn were checkedby complexo-
metric titrations with EDTA. The completeness of the sodium separation
was confirmedby flame emissionanalysis. The eluateswere transferredto
7 dram glassvials and the volumebroughtup to a commonvalue. The
capillariescontainingthe standardsolutionswere brokeninto smallfragments
with a gold plated chisel in a beaker containingacidified carrier solution,
•'
were filtered into similar 7 dram vials, and were treated in the same man-
ner as the aliquotsfrom the ion exchangecolumns. Diluted portionsof
thesesolutionswere usedto determinethe detectionlimits of the counting
system.
The 7 dramvialswereplacedin glassbeakerson top of a 3-in. X 5-in. NaI
(T1) scintillationcrystal connectedto an RIDL transistorized400 channel
pulseheightanalyzer. Na24 (15h) and Mn '6 (2.58h) decayswere counted
in the 0 to 3 Mev energyrange; Cu64 (12.8h), Zn•9 (14h), W x87(24h),8 and
Sb•2• (2.8d) 8 were countedin the 0-1.5 Mev range. The instrumentwas
calibratedwith Na • and CuOt Countingtimesrangedfrom 1 to 60 minutes,
depending.on the activity of the sample. Uncertaintiesintroducedinto the
countingmeasurementsdue to variations in the thicknessof the beaker
bottomsand the dimensions of the countingvials were negligible.
RESULTS

Our results are summarized in Table II. In the calculation of concentra-

tionsfrom the countingdata a value of 5 percentper mm of quartz was taken
for the neutron flux diminution; this resultedin correctionsof 23, 10, 19
and 10 percent,respectively,for the 4 specimens.
The sodiumcontentin all four specimens was easily measurable;as
expected,well over 90 percentof it was in the water leach. Inclusionsfrom
the nearbyProvidenciadepositsshowhighly variable,but generallyhigher
• Astorbit acid was also added to manganese standard solutions.
a Minor amounts of these two isotopes were detected in Specimens I and 3. W •s7 was
present in the water and acid leaches of both specimens. Sbx•' was detected in the acid leach
of sample I and in the water leach of sample 3.
 1396 H. F. PUCHNER AND H. D. HOLLAND

TABLE II

/
ResUlts of neutron activation analysis of fluids in fluid inclusions

Sodiu• •ngasese Copper Zinc

Wei •ht • of
Specimen solution
No. aaa3.vzed Water Acid Water Acid Water Acid Water Acid
•h •ach •ach Leach •ach •ach •ach •ach

770* 250•g 5.68•g O.•O•g 0.039•g 0.0023•g<0.00073•g<O.001h6•g

<0.0083•g<0.0166•g•t fo•
1 0.7•% 520ppm 51ppm 3 ppm <1ppm <2ppm <11ppm •22ppm %or ppm
In flui•
inclusion
ll•ul•

3• * hug 0.2•5•gO.018gg0.0056•gO.000h3pg
<0.00022•g<O.000153ug
<O.0102gg
<0.0102½g
•t fo•(
2 0.73% 515ppm 160ppm 12ppm <6ppm <hppm •290ppm <290ppm %or ppm
in fluid
incl•lon
liquid
.,

51 * 10gg O.•9gg O.OhOgg0.002hug0.00028½g

<0.00054½g
<0.00062pg
<O.0113gg
<O.0113ug
•o•t fo•
3 1.•% 790ppm h7ppm 6 ppm <11ppm <12ppm <220ppm <•0 ppm %or ppm
in fluid
inclusion
liquid
.

6.3 * 0.6•g O.lO0•g

O.0008•g0.00038•g
O.00002Ug
<0.000035•g
<0.000035•gl .0.00163•g •t fo•d
• 1.59%133ppm60•m hppm <6ppm <6•m <260
p• %orppm
in flui•
inclusion

..

Productof measured
volume
andestimateddensity(1.03 for 1 + 2, 1.05 for 3 + h), basedon an
assumedNaCi:CaC12ratio of 1.

salt concentrations(11). Most of the manganesewas also removed during

the water leach,suggesting that little manganese
is presentin water-insoluble
phaseswhich might have precipitatedon the walls of the indusionsduring
their cooling. Czamanske,Roedder,and Burns (2) observeda similar be-
havior for manganese, but at concentrationsapproximatelyan order of magni-
tudehigher.
We were unableto detectcopperor zinc in any of the inclusionfluids.
The concentration of copperin the analyzedfluidsmust be < 12 ppm. The
analyticallimits for zinc were, unfortunately,a good deal higher, exceptfor
the solutionsfrom SpecimenNo. 1. However, even the upper limits for
Specimens 2, 3, and 4 indicatethat the solutionsin thesefluids containcon-
siderablyless copper and zinc than reported by Czamanske,Roedder, and
Burns(2) for inclusions in quartzfrom Creede(Cu: 140ppm,Zn: 1330ppm).
INTERPRETATION OF THE RESULTS

The positionof our quartz samplesin the mineral paragenesis at Bloche

Buenaandhencethe relationship of thesefluidsto the ore fluidsare not known.
At Providenciaquartz is a late mineral (11). The habit of the quartz at
Noche Buena indicatesthat it grew as free standingcrystalsin rugs. The
temperatureof filling of the inclusionin SpecimenNo. 4 would placeit near
the end of the period of mineralizationat Providencia. These shredsof
evidencetogethersuggestthat quartz at Noche Buena was late, and that the
fluidsthat we analyzedpostdatethosethat were responsible for ore deposition.
 NEUTRON ACTIVATION ANALYSES 1397

Whetherthesefluidspassed up throughtheoldorechannels or whetherthey

representrecirculated,
heatedgroundwaters,theyalmostcertainlywerein
contactwith orepriorto entrapment.It is therefore likelythat thesesolu-
tionswere saturated with respectto sphalerite
and probablywith respectto
chalcopyrite
at thetimeof entrapment.Thus,theverylow copperandzinc
contentof ourfluidsimpliesthatthe"solubility"
of sphalerite
andchalcopyrite
in thesefluidswasvery smallindeed,and that ionscapableof stronglycom-
plexingcopperand zincwerepresentin correspondingly low concentrations.
The difference between our data and those of Czamanske,Roedder and
Burns(2) for the copperand zinccontentof fluidsin the inclusions within
quartzis striking;it maybe significantthat their quartzcrystalsappearto
havegrownat leastin part contemporaneously with sphalerite.What seems
quitedear is that theseneutronactivationanalysesmustbe joinedby many
othersbeforethe problemof the concentration of the heavymetalsin ore
forming fluidswill be solved.

ACKNOWLEDGMENTS

We wouldlike to expressour sincerethanksto Sr. Luis Gutierrezand to

Sr. GustavoGutierrezfor their permissionto work at NocheBuenaand for
theirverywarmhospitality duringour visit. Sr. M. Camachoof Metalurgica
Mexicana
Petioles
andMr.H. Ohmoto
weremost
helpfulfluting
thecollection
of the quartz samples.
We wish to thank Mrs. M. Borcsikand Mr. J. I. Drever for their assist-
ancein theanalyticalworkandDr. D. Greenberg of U.S. IndustrialChemicals
Co. for securingpermissionfor us to usethe Plainsboro Reactor,as well as
for hisadvicein planningandevaluatingthe irradiationexperiments.
Prof. R. Naumannkindly put at our disposalhis 400 channelanalyzer,
without which these measurements could not have been made.
Financialsupportfor this work camefrom ContractNo. AT(30-1)-2266
betweenPrincetonUniversity and the U.S. Atomic Energy Commission.
Dr. E. Roedrier,Dr. G. K. Czamanske,Dr. D. Greenberg,and Dr. R. O.
Rye kindly read and commented on the paper.
DEPT. OFGEOLOGY,
PRINCETON,N.J.,
September14,1966

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