Economic Geology

Vol. 64, 1969, pp. 629-643

ChemicalCompositionof the HydrothermalFluids

Responsible
for the Lead-ZincDepositsat
Providencia, Zacatecas, Mexico
ROBERTO. RYE AND JOSEPHHAFFTY

Abstract

The chemicalcompositionof 22 samplesof primary fluid inclusionsin quartz,

calcite,and sphaleritefrom Providencia,Mexico, has beendetermined. Sampleswere
prepared,crushed,and leachedas describedby Roedderet al. (1963). Cationanalyses
of leachatesweremadeby atomicabsorption spectroscopy,and the anionswere analyzed
by a special X-ray fluorescencetechnique.
The Na, K, Ca, and C1 concentrationsshow a considerablerange that reflectsthe
widespreadsalinityvariationsin the hydrothermalfluids observedby Sawkins (1964).
The K/Na atomicratiosof mostsamplesrange from 0.18 to 0.43 and the ratiostend to
increasewith the salinity of the inclusions. The temperaturesindicatedby the K/Na
ratios from the publishedcurves of K/Na ratios rs. temperatureare mostly at least
100ø C greater than correspondingfilling temperatures. The Ca/Na atomic ratios of
inclusionsin sphaleriterangefrom 0.12 to 0.61. The K/Na and Ca/Na data agreewell
with previous•O •8 data (Rye, 1966; Rye and O'Neil. 1968) which indicatethat the
hydrothermalfluidswere derivedfrom the magmarelatedto the Providenciagranodiorite
stockand that the fluids reactedonly slightly with the crystallinestock during the late
phasesof ore deposition. The data also indicatethat the salinity variationsin the hydro-
thermal fluids probablyoccurredat the sourceof the fluids and may have resultedfrom
boiling in the magma chamber.
Mg concentrationsare generally no more than a few hundred parts per million.
Most of the Mg in the hydrothermal fluids was evidently removed during the forma-
tion of calcium-magnesium silicatesin the lower levels of the ore pipes. Mg/Ca atomic
ratios are generally lessthan 0.08 and are consistentwith the paucity of dolomitein the
area.

Zn and Cu concentrationsin water leachesof inclusionsin calcite are generally less

than 50 ppm. Maximum base-metalconcentrationsfrom water leachesof two samples
of inclusionsin quartz are 890 ppm Zn and 530 ppm Cu.
Chloride is the major anion in the fluids, and C1 concentrationsvary with corre-
spondingcation concentrations. With two exceptions,sulfur concentrationsof the in-
clusionsin calcite and quartz, analyzed as SO4, are below the level of detection.

Contents

PAGE PAGE

Introduction .................................. 630 K/Na atomic ratios .......................... 635

Experimental techniques....................... 630 Calcium concentrations ...................... 637
Cleaningof samples......................... 630 Ca/Na atomic ratios ........................ 637
Crushingand leaching........................ 630 Magnesiumconcentrations .................... 638
Microanalysis ............................... 631
Results ....................................... 631
Mg/Ca atomic ratios ........................ 638
Blank contamination ......................... 632 Zinc and copperconcentrations ............... 639
Chloride concentrations ..................... 641
Duplicate samples............................ 634
Comparison of salinity by direct and indirect $ulfate concentrations ....................... 641
methods .................................. 634 History of the Providenciaore fluids--A recapitu-
Cation/anion equivalent ratios ............... 634 lation ...................................... 641
Chemical nature of the Providencia ore fluids .... 635 Acknowledgments............................. 642
Sodium and potassiumconcentrations......... 635 References .................................... 643

Publication authorized by the Director, U.S. GeologicalSurvey.

629
630 R. O. RYE AND J. HAFFTY

Introduction coolercrystallineportionsof the stockand eventu-

Tar. lead-zincdepositsat Providencia,Mexico, are ally entered the limestoneformations that contain
the ore. If this model is correct it should be re-
pipelike ore bodies that occur in steeply dipping
Mesozoiclimestonesadjacent to a Tertiary grano- flectedin the chemistryof the ore fluids.
diorite stock. These depositshave been the object Experimental Techniques
of severaldetailedgeochemicalstudies,and consider-
able progress has been made in understandingthe The chemicalcompositionof the hydrothermalore
processes of ore deposition(Sawkins, 1964; Ohmoto fluids was determinedby analyzing primary fluid
et al., 1966; Rye, 1966; Rye and O'Neil, 1968). inclusionsin calcite, quartz, and sphalerite. Pri-
K-Ar and Rb-Sr age dating of ore mineralsand mary fluid inclusionscan usuallybe shownto con-
the associated granodioriteby Ohmotoet al. (1966) tain a sampleof the fluid from whichthe hostcrystal
showedthat the ore depositsmost probablyformed precipitated(Roedder, 1967). Therefore an analy-
sis of the inclusions is sufficient to determine the
1-3 m.y. after the emplacementof the granodiorite.
chemicalcompositionof the parent fluid. Most of
Filling temperaturestudiesof fluid inclusionsin
the data reportedin this paper are from the same
calcite,quartz, and sphaleriteand paragenesisstud-
inclusionsusedin previouslypublished•O •8 and 8D
ies of mineralsin vugsby Sawkins (1964) indicated
studies(Rye, 1966; Rye and O'Neil, 1968). A few
that the temperaturesof the hydrothermal fluids
additional samples were prepared especiallyfor
dropped rather continuouslyduring ore deposition.
chemicalanalysesonly. The nature of the Provi-
The bulk of the sulfideswas depositedat tempera- dencia fluid inclusions and the methods that were
tures above350ø C, but depositionof late sphalerite
used to select primary inclusionshave been dis-
continuedto 200ø C. Quartz was depositednear
cussedin an earlier paper (Rye, 1966).
300ø C and calcite in various forms, was precipi-
tated at 350 ø C to 200 ø C. Sawkins also made Cleaning of Samples.--The average Providencia
sample used in this study containedonly a few
freezing measurementson fluid inclusions which
hundred t•gof saltsin the inclusio'n
•fluids. It was
indicatedthat the salinity of the hydrothermalfluids
thereforenecessarythat each samplebe completely
ranged from 5 to 40 equivalentweight percent of free of surface contamination. The methods used
NaC1 without any noticeablerelationship to the
in cleaning the samplesare essentiallythose de-
mineralogy.
Studies of the •D of fluid inclusions
scribed by Roedder (1958) and Roedder et al.
and the
(1963). The sampleswere washedin an acetone-
•O TMof quartz and calcite (Rye, 1966) suggested ethyl alcohol mixture to remove organic matter.
very stronglythat the ore fluids originatedas a late- Sphaleriteand quartz were soakeda few minutes
stage differentiate of the magma related to the in dilute HC1 to removepossibleCaCOa, and quartz
Providencia stock and that no other fluids were in- was also boiled in concentratedHC1 to remove pos-
volved in ore deposition. •C TMsudies on calcites siblesulfides. All sampleswere washedin distilled
(Rye, 1966) indicatedthat a considerableportion water to remove most of the surface contamination.
of carbonin the calciteprobablycamefrom a deep- In order to force cleaningsolventinto cracksand
seatednonlimestonesource. The stable isotopedata broken inclusions,the first and last stepsmentioned
also indicatedthat the large salinityvariationsnoted above were carried out in a vacuum filtrator which
by Sawkins in his fluid inclusion studies resulted was alternatelyevacuatedand vented.
either from variations at the source of the fluids or To remove ionized material from the surface and
from intermittent incorporationof sedimentarysalt cracks, the sampleswere placed in a U-shaped
by the hydrothermal fluid. Some of these conclu- electrolyticcleaningcell, coveredwith deionizedwa-
sionswere recently strengthenedby analysesof the ter, and subjectedto a potentialof 90 volts direct
•O TMand •C •a of water and CO2 in fluid inclusions current. The sampleswere cleanedfor severaldays
of Providenciaminerals(Rye and O'Neil, 1968). with frequent changesof water until the current
The purposeof the present paper is to present through an ammeter attachedto the cell reacheda
data on the chemicalcompositionof the ore fluids low and constant value. The samples were then
as determinedfrom analysesof solutionsin primary dried in vacuoand sealedin precleanedpolyethylene
fluid inclusionsand to interpret thesedata in terms bagsuntil they were crushed.
of the origin and evolution of the ore fluids. Pre- Crushingand Leaching.--Thetechniques of crush-
vious work by all investigatorsat Providenciais ing and leachingthe fluid inclusions to measurethe
consistentwith a genetic relationshipbetween the amount of water and collect the salts for chemical
ore bodiesand the magmaticactivity responsiblefor analysesare also similar to those describedby
the granodiorite stock. After the fluids left the Roedder et al. (1963). The cleanedfluid inclusion
magmaticsourcethey must have passedthrough the sampleswere crushedin precleanedtype 304 stain-
 CHEMICAL COMPOSITION OF HYDROTHERMAL FLUIDS 631

lesssteeltubesthat were connectedto a high vacuum elementsexcept Ca. Standardsused for Ca con-
system designed to measure the amount of water tained 1% La in 2.5-volume-percentHC1 solutions.
in the fluid inclusions and to convert it into a form The concentration of chloride and sulfate was
suitablefor isotopicanalysis (Rye, 1966; Rye and determinedby an X-ray fluorescencetechnique. To
O'Neil, 1968). a measuredaliquot of sample,10/•g of bromideand
The saltsleft behindupon evaporationof the wa- chromate ions in solution were added to act as car-
ter of the inclusionswere removedfrom the powder riers for chloride and sulfate. The solution was
by successive 25 ml leachesof speciallyprepared acidified with 2N HNOa after dilution to 20 to 30
distilled-demineralizedwater (conductivitylessthan ml. It was then heatedto near boiling after which
1 X 10-6 mhos cm-a). The leach water was added 1 ml of a solutioncontaining10 g Ba(NOa)= and
to the crushedsamplein the stainlesstubes,shaken, 0.35 g AgNOa per liter wasadded.
and allowed to stand in the tubes for 10 minutes. The solutionwas then filtered through a 0.45 t•
The resultingsolutionwas filtered through a special millipore filter 1-inch in diameter. The precipitate
5-micronpyrex glassfilter into a precleanedpoly- was washedtwice with 0.01N HNOa. Finally the
ethylenebottle. The electricalconductivityof the sidesof the glassfilter apparatuswere washeddown
leach was measuredwith a 5-ml pipette-typecon- with denatured alcohol. The millipore filter with
ductivity cell that was connectedto an Industrial precipitate was then mounted on a 1-inch X-ray
InstrumentsRC-16 conductivitybridge. Successive liquid cell and subjectedto X-ray fluorescence analy-
leacheswere made until the conductivityapproached sis for both C1 and SO4.
that of the demineralizedwater for quartz and The standardsused for analysis were made to
sphalerite samplesor a constantvalue for calcite cover a range of 0-100 /•g of anionsby diluting a
samples. Usually this occurred on the fourth or stock solutionof KC1 and K=SO4. The procedure
fifth leach. The leachareswith high conductivities describedfor the unknownsampleswas usedfor the
were combined and if the resulting solution was standards. The sensitivityof the method is about
judged too dilute for analysesit was evaporated 1 /•g for both C1 and SO•.
down to 15-20 ml in a teflon beaker under infrared
Results
lamps. The exact size of the final leachatefor each
sample was recorded, so that the concentrationof The resultsof the chemicalanalysesof the Provi-
dencia fluid inclusionsand significantatomic ratios
salts in the fluid inclusions could be calculated from
the leachateanalysis. are presentedin Table 1. The concentrationof
Microanalysis.--Cationconcentrations were deter- ions in the fluid inclusion solutions in parts per
mined on a Perkin-Elmer model 303 atomic absorp- million of water have been calculatedby multiplying
tion spectrophotometer using an air acetyleneflame. their concentrationin the leachatesof each sample
A 10-ml sample of leachatewas transferred to a by their appropriate dilution factor. Approximate
precleaned 1-oz polyethylenebottle and 0.1 ml of total salt concentrationsand cation/anion equiva-
lent ratios of the inclusion fluids are included. The
concentratedHC1 was added to give a 1-volume-
salt totals and cation/anionequivalentratios of in-
percent hydrochloricacid solution. The concentra-
clusion fluids in sphalerite do not reflect leachate
tion of Na, K, Mg, Cu, and Zn was determinedon concentrations of Zn and SO4 and the totals and
this solution.
ratios of inclusionfluids in all samplesdo not re-
Calciumwas determinedon a solutionconsisting flect the presenceof elementswith concentrations
of 4 parts of leachateand 1 part of a 5% lanthanum below the level of analytical sensitivity. The total
solution in 12.5-volume-percent HC1. The lantha- salt values are given as minimum values when a
hum eliminatespossibleinterferenceby other com- possiblemajor elementof the fluid was not included
ponentsof the leachates. If a sufficientamount of in the total. Publishedfilling and freezing tempera-
sample was available after removal of the 10 ml tures and aO •* and aD values for the same or similar
mentioned above, 4 ml were transferred to a clean inclusionsare also included (Sawkins, 1964; Rye,
1-oz polyethylenebottle, and 1 ml of the lanthanum 1966; Rye and O'Neil, 1968).
solution was added. If no additional leachate was Before discussingthe results as they apply to
available, some of the original 10 ml of solution Providencia,we will evaluatetheir reliability as an
could be used for the calcium determination, with a indicationof the chemicalcompositionof the parent
proportional amount of lanthanum. hydrothermalfluids. Acceptedcriteria for good re-
Standards used for analyses were made from sults include lack of blank contamination,agreement
"specpure"grade CaCOa, CuO, KC1, MgO, NaC1, of analysesof duplicatesamples,agreementof salin-
and ZnO. Single-elementstandardsin a 1-volume- ity as determined from freezing temperatures of
percent hydrochloricacid solutionwere used for all fluid inclusionsand from chemicalanalyses,and a
632 R. O. RYE AND ]. HAFFTY

TABLE1.--CHEMICAL COMPOSITIONS
ANDATOMICRATIOS OF PRIMARYFLUID INCLUSIONSIN QUARTZ,CALCITE, ANDSPHALERITEFROMPROVIDENCIA

[Numberin parentheses indicates presence as element in host mineral. Asterisk (*) indicates probable
contamination during leaching or by solid inclusion. Less than symbol (<) indicates
below level of analytical sensitivity. Leaders (---) indicate not analyzed.]

Size of DiluZiQn
Hostmineral Location Sample sample factor Nappm K ppm Cappm Mgppm Zn ppm Cuppm Cl ppm
(mgs H20)

Early sphalerite-- San Marcos..... 62-S-146 3.5 6,370 11,800 4,800 2,500 120 (6,200) <160 27,400

62-S-145 1.3 9,830 27,000 11,800 ........ 180 (23,800) <250

1.5 13,930 22,300 10,200 10,000 140 (5,000) <350 97,500

Animas 15 ...... 60-H-67 1.2 10,000 6,800 2,500 6,800 220 (25,700) <250 ........

3.3 4,240 7,700 3,000 3,000 420• (4,200) <100 21,200

Animas 20 ...... 60-H-36-57 3.1 4,870 21,500 8,300 12,100 150 (10,800) <120

3.1 4,710 19,800 6,800 23,800 * 940* ( 3,100 ) <120 37,700

3.9 3,820 21,800 9,000 15,400 190 (1,500) <100 42,000

Animas 22 ...... 63-R-22 5.8 3,200 8,100 2,900 4,200 450 (5,400) <80 12,900

2.0 10,250 8,400 3,400 5,200 550 (8,400) <210 16,400

Rucio .......... 62-S-320 3.8 21,240 63,700 46,700 57,400 250 (19,300) <530 212,400

63-R-39 6.8 13,790 80,000 50,500 89,600 380 (15,100) <350 419,000•

Late sphalerite--- Rucio- ......... 63-R-39 23.2 2,980 21,800 7,000 8,700 180 (100) <90 59,000

Early calcite ..... Zinc West 15--- 62-S-169 11.0 6,630 9,400 3,300 (35,800) (350) <60 <170 21.600

10.0 1,360 4,000 1,500 (24,600) (240) <10 <30 13,600

Zinc Wear 21A-- 61-Hu-54 4.0 5,100 6,900 2,300 (67,300) (4,900) <50 <130 40,800

7.3 2,360 4,300 1,400 (59,000) (920) <20 <60 14,200

Animas 18 ...... 61-Hu-305 6.6 2,940 27,900 14,800 (88,200) (850) <30 <80 88.200

Late calcite ...... Animas 18 ...... 61-Hu-319 12.4 940 700 140 (20,300) (350) <10 <20 1,900

Quartz San Eligio 63-E-4 10.8 1,540 3,500 550 1,300 20 890 340 13,900

surface.

63-R-1 1.7 8,940 9,800 3,000 27,200• 730' .... 35,800

Zinc West 63-R-23A 4.6 4,090 800 300 2,000 40 400 530 4,000

surface.

k/Same
o• similarinclusions
in Sawkins
(1964)andRye(1966).
k/Same
o• similarinclusions
in Sawklns
(1964)andEye(1966),exceptsample
61-Hu-319
fromunpublished
data.

cation/anion chargebalancenear unity (Roedder cleaned,crushed,and leached in the same manner

et al., 1963). as the samples.To determinemaximumblankcon-
Blank Contamination.--The amount of water in centrationsthe leach volumes were slightly larger
the inclusionrangedfrom 1.2 to 23.2 mg andin most than those used on the samplesand the blank
instancesit was lessthan 10 mg. The amountof leachates wereevaporated to a slightlysmallervol-
dilutionof the samplesrangedfrom 940 to 21,240 umethanthe sampleleachates.The concentrations
but mostsamples weredilutedby lessthana factor obtainedfor the evaporated blankleachates are given
of 10,000. In somesamplesonly a very smallcon- in Table 2. Blank 3 was analyzed only for Zn and
taminationduring cleaning,crushingor leaching Cu. The contaminationfrom blanks 1 and 2 differs
could lead to erroneous results for the concentration considerably both in absoluteconcentration
of dif-
of one or more ions in the fluid inclusions. To check ferent elements and in elemental ratios.
for the possibility
of generalcontamination,
1-inch Some idea of the maximum possible effect
of blank contamination on the inclusion concen-
portionsof thick-walled
silicaandpyrextubingwere
 CHEMICALCOMPOSITION
OF HYDROTHERMAL
FLUIDS 633;

TABLE 1. (cone'd)

S04ppm K/NaCa/Na Mg/CaNa/ClK/Cl Ca/Cl Cation

equiv./
anion
equiv. Total
salts Equivalent,
(ppm)wt. FillinE
(øC)•/ 6D•OW
%NaCl•-'temp. 6018
ø/oo•-!

(<6,400) 0.24 0.12 0.08 0.66 0.16 -0.09 1.00 46,620 330 .... 6,0

......... >38,980 11.2 330-333 -7.6 ---

(<27,900) .27 .26 .023 .35 .09 0.09 .63 140,140 11.2 330-333 .......

......... .22 .57 .053 >16,320 ........ 350-365 -7,5 ---

(8,480) .23 .22 .23• .56 .13 .12 1.21 35,320 350-365 .... 6,2

......... .23 .32 .020 >42,050 360-370 -7.8 ---

(9,400) .20 .69•m .065' .80 .16 .56* 2.12 • 89,040* 360-370 -6.9 ---

(<7,600) .24 .40 .020 .80 .19 .32 1.66 88,390 ........ 360-370 -6.9 ---

(9,700) .21 .30 .18 .97 .20 .29 1.85 28,550 362-368 -6.8 ---

(14,350) .24 .36 .17 .79 .19 .30 1.87 33,950 ........ 362-368 -7.6 ---

(63,700) .43 .52 .007 .46 .20 .23 380,450 31 365 -?.3 ---

( 30,600) .37 .61 .007 .29* .11 • , .19* 639,480* 35 372 -7.7 -•

(7,000) ,19 .23 .034 .57 .11 .13 .95 96,680 •10.0 290 .... 5.8

6,200 ,20 (2.19) (.016) .67 .14 (1.46) (3.81) >40,500 340-350 -7.7 ---

2,700 .22 (3.53) (.016) .45 .10 (1.59) (3.82) >21,800 340-350 -8.3 .u

<10,200 .20 (5.60) (.12) .26 .05 (1.45) (3.60) >50,000 340-350 -?.8 ---

<4,600 .20 (7.87) (.027) .47 .09 (3.66) (8.12) >19,900 340-350 -7.8 ---

<5,900 .32 (1.81) (.016) .49 .15 (.88) (2.44) >130,900 35 •330-350 -7.1 ---

<1,9.00 .12(16.64) (.028) .57 .07 (9.40) (19.92) >2,740 •210 -8.1 ---

.14 (6.36) (.062) ,42 .06 (2.67) •210 ......

<3,100 .09 .21 .025 .39 .04 .08 .59 20,500 300-315 -7.2 ---

.1• 1.59' .044* .42 .08 .67' 2.12' .76,530' 4.8-13.2 300-315 -8.3

<8,200 .1( 1.43 .033 .31 .07 .44 1.27 8,070 300-315 -8.2

3/Data
onsame
inclusions
in Rye(1966).•
T/'/Data
oneame
inclusions
in'RyeandO'Neil(1968).

trations can be obtainedby multiplying the blank and the very low concentrations in some of the
values by the dilution factors of each sample. If samples themselves (e.g., Mg concentration
of 63-R-
the low values for blanks 1 and 2 are considered, 23A) suggests that blank contamination
is probably
the contamination level of each element involves not a significantfactor for most samples. Even
such a small percentage of the total concentra- thoughgreat care was usedto insurethat all steps,
tion for most samplesthat it can be ignored. If the
high values are considered,the blank contamination Table 2.--Cation
tn•ter
concentrations•
leaches
in parts per aillion•
of crushed silica and pyrex
couldaccountfor considerableamountsof Na, K, and tubt•.

all the Mg in somesamples. The degreeof blank

Na K Ca M• Zn Cu
contaminationprobably varies from sampleto sam-
Blank i (silica) 0.05 O.00 0.25 0.015 ....
ple as it doesfor blanks 1 and 2, and no attempt is
made to apply any correctionto the original data. Blank2 (pyrex) 0.27 0.015 0.10 < 0.005 < 0.010 < 0.025

The general excellentagreementof duplicateresults Blank3 (silica) ........ < 0.010 < 0.02•
634 R. O. RYE AND .t. HAFFTY

were done under ultra clean conditions,significant in this calcite have highly variable liquid-vapor
•:ontamination aboveblankvalueswasalwaysa possi- ratios, and some but not all of the inclusionscontain
bility and each sampleneededto be examinedcare- large daughterminerals. Becausesalinitymeasure-
fully for evidenceof this. Analysesbelievedto have ments were made only on the inclusions with
been contaminatedin amounts greater than blank daughtermineralsthe measurements
are not repre-
values are indicated in Table 1. sentativeof the salinity of fluids in the entire sam-
Duplicate Samples.--If the results are reliable, ple. The freezing salinity measurementson inclu-
analysesof duplicate samplesshould check fairly sionsin quartz were not made on the same part of
well. Although it is difficult to show that two the crystalsason thoseanalyzedfor chemicalcompo-
samples of fluid inclusionsare exact duplicates, sition.
many of the inclusionsamplesfrom the samemineral Cation/anionEquivalentRatios.--Completeand
zone had nearly identical filling, temperaturesand accurate analyses of fluid inclusions should show
$D values,and it was to be anticipatedthat their excellent charge balances. Cation/anion rates of
chemical compositionswould be nearly identical. unity should not necessarilybe expected in this
Samplesfrom the samemineral zone have identical study becauseanion and cation analyseswere not
numbers in Table 1. Most of the fluid inclusion of the sameprecision,and anions,other than those
concentrationsof Na, K, Ca, Mg, and C1 in the analyzed,may have been presentin the inclusions.
possibleduplicate samplesof sphaleritecheck re- As can be seen in Table 1, both dilute inclusions in
markably well (except for obviouslycontaminated sphaleritefrom Animas 15, San Marcos,and Rucio
samples)even where the size of the inclusionand and concentratedinclusionsin sphaleritefrom Rucio
the dilutionfactorsfor eachsampleare quite differ- have cation/anionequivalentratios near unity. All
ent. Zn and SO4 values do not agree well but this inclusionsin calcite have large ratios. This is to
is to be expected,as the concentrationof thesecom- be expectedbecausethe Ca and Mg obtainedfrom
ponentsin solutionsfrom sphaleritedependuponthe dissolutionof the calcite host mineral during leach-
amount of oxidation of the host mineral during ing is balancedin solutionby I-ICOa-, whoseconcen-
leaching. Analysesof possibleduplicatesamplesof tration was not determined. Ca analysesof inclu-
inclusionsin calcite do not agree as well as for sions in calcite have meaning only as very large
sphalerite samplesbut this is not surprising as it maxima. Inclusionsin one of the quartz samples
is virtually impossible
to be certainthat two samples from San Eligio and all complete analysesof in-
of inclusions in calcite were from the same zone in clusionsin sphaleritefrom Animas 20 and 22 have
the crystal. large cation/anionratios. There is a good possi-
Comparisonof Salinity by Direct and Indirect bility that the quartz samplewas contaminateddur-
Methods.--As a crude check on the effectiveness of ing leaching.
the leachingprocedurein removingthe total salts, The reason for excess cations in the Animas
the actualsalinitiesas determinedby chemicalanaly- sphalerite
samplesis not entirelyclear. The Na/C1,
ses can be comparedwith those determinedindi- K/C1, and Ca/C1 ratios of the inclusions in the
rectly from freezingtemperaturesof fluid inclusions. Animas samplestend to be larger than in other
Roedder et al (1963) and Hall and Friedman sphaleritesamplesbut K/Na and Ca/Na ratios are
(1963) found fairly goodagreementbetweenfreez- in the range of those in other sphaleritesamples.
ing and leachatesalinities. Available salinitiesob- This suggeststhere may be somethingunusualabout
tained by Sawkins (1964) and Rye (1966) for the the anion chemistryof the Animas fluid inclusions.
Providencia inclusionsfrom freezing temperature The excesscationsmight be balancedby anionsnot
studies of fluid inclusions or by observationof analyzed,such as HCOa-, F-, SO4= and HS-, but
daughtermineralsduring heatingare given in Table theseartionsare normallynot found in large amounts
1. Exact agreementwith salinitiesfrom chemical in fluid inclusions.
analysesshouldnot be expected. The freezingtem- The large cation/anion ratios could also be a
perature determinationsare of limited accuracybe- result of the solution of undetected solid inclusions
causea pure NaC1 solutionin the inclusionis as- in the host mineral. Most of the sphaleritecrystals
sumed. Furthermore, heating and freezing measure- from the Animas ore deposit containedareas that
mentswere usuallynot made on the inclusionsactu- were full of very fine calcitesolid inclusionswhich
ally crushed,and to someextent the differencesare were probablycarried alongas trash by the hydro-
normal for different samples. For fluid inclusions thermal fluids. One of the Animas 20 samples
in sphaleritethe two determinationsof salinityagree definitelycontainedsomeof this trash, and the high
fairly well. The salinityby analysisfor inclusionsin Ca and Mg concentrationof the inclusionsis at-
calcitesample61-Hu-305 is only abouthalf that of tributed to the solution of these solid inclusions dur-
the publishedsalinity by freezing. The inclusions ing leachingof the sample. Every attemptwas made
 CHEMICAL COMPOSITION OF HYDROTHERMAL FLUIDS 635

to selectmaterial for the other Animas samplesthat o

was free of solid inclusions. The possibilityof un-

detectedsolidinclusions,
however,canprobablynever
be completelyeliminated. If solutionof solid inclu-
sions did contributeto large cation/anion ratios in
the Animas fluid inclusions, the Ca concentrations __.0.25-
reportedfor thesesamplesare usefulonly as maxi- _
mum values. Such contamination would account for
high Ca/C1 ratios of the Animas inclusionbut could
z
0.20 OX J 0Eorly
•ph•lerHe
not accountfor the high Na/C1 and K/C1 ratios.
0'10-- • X 1
The Ca analysesof inclusionsin sphaleritefrom
the Animas ore body and someof the analysesof O.O5-
/ X
ions with very low concentrations
in other samples o.oo
0
I
IOO
I
•OO
I
300
I
400 5OO
I I
•O
I

may be questionable. Also a few other isolated TEMPERATURE {*C}

analysesof different elementsmay have been con- Fro. 1. The variation of K/Na atomic ratios of fluid
taminated as indicated in Table 1. However, at least
inclusionswith correspondingfilling temperatures. Tie lines
to a first approximation,the data on Table 1 for connect duplicate samples. The curve is based on the dia-
gram compiled by White (1968) from data by Orville
most samplesmust reflectthe chemicalcomposition (1963), Hemley (19•), and White (1965), and shows the
of the parent hydrothermalfluids. generalizedtemperaturedependence of K/Na ratios of fluids
in equilibrium with granitic rocks.
Chemical Nature of the Providencia Ore Fluids
Sodium and Potassium Concentrations.--As can
that presumablyare in equilibrium with rhyolitic
be seen in Table 1, the Na and K concentrationsin volcanics at temperatures between about 300 and
inclusionsin each generationof. the Providencia 100ø C (White, 1965). A similar curve has been
minerals show a considerablerange. This range compiledby Ellis and Mahon (1967). It is empha-
reflectsthe variationsof salinity first observedby sized that the curve showsonly a generalizedrela-
Sawkins(1964) in his studyof the freezingbehavior tionshipbetweenK/Na in the fluid phaseand tem-
of the fluid inclusions. Most of the concentrations perature. The precise position of the curve for a
in Table 1 are in the rangeof previouslypublished given systemis dependentupon the total pressure
values for ore fluids and fluid inclusions (e.g., on the systemand upon the compositionof the en-
White, 1968; Roedder,1967). One notableexcep- closingrocks, especiallytheir Ca content (Orville,
tion is that the K and Ca concentrations observed 1963). There is also evidencethat the positionof
in the very salineRucio inclusionsare considerably the curve is sensitiveto the salinity of the fluid
larger than previouslyreportedconcentrations of in- phasein the system(D. E. White, written commun.,
clusions from ore veins. 1968). To be strictlyapplicableto Providenciathe
K/Na Atomic Ratios.--The actual alkali concen- curve in Figure ! would needto be basedon experi-
trationstell little about the genesisand history of mental data which include at least the above vari-
a hydrothermal fluid. The K/Na atomic ratios, able. However, further refinementof the position
however,have considerable importancewith regard of the curve probably would not affect the salient
to the origin and temperaturehistory of hydro- featuresof the following discussion.
thermal fluid. In both experimentaland natural The K/Na ratios of the inclusionshave been
systemsthe K/Na ratiosof hydrothermalfluids that plotted in Figure ! versusthe filling temperatures..
are in contactwith reactive granitic rocks increase All the data exceptthe K/Na ratiosof the inclusions
as the temperatureincreases. A generalizedcurve in quartz sample63-R-4, from San Eligio lie above
showingthis temperaturedependenceis given in the curve. (This samplehas a K/Na ratio greatly
Figure 1. The curve is basedon the diagramcom- differentfrom that of the other San Eligio sample,
piled by White (1968). The upper portionof the and the reported K/Na ratio may be in error.)
curve is determinedby Orville's (1963) experi- All but one of the temperaturesindicatedby the.
mental data for K/Na ratios of fluids in equilibrium K/Na ratios of the inclusionsare at least 100ø C
with two feldsparsbetween500-670ø C and at 2,000 greaterthan the filling temperatureof the inclusions,
bars pressure. The middle portion is based on and some of the K/Na ratios correspondto those
Hemley's(1968) experimental datafor K/Na ratios characteristicof magmatic temperatures, although
of fluids in equilibriumwith alkali feldsparand K filling temperaturesare only 370ø C. These results
mica between300-500øC and 1,000 bars pressure. indicatethat the hydrothermalfluids were probably
The lower portion of the curve is determinedby in contactwith granitic rocks that were at tempera-
K/Na ratiosof deepcirculatingwatersin hot springs tures greater than the temperaturesof ore depo-
636 R. O. RYE AND J'.HAFFTY

is probably
slightlylessthanthatof magmatic
waters
at their source. The •O TMvalues of the inclusions
indicatethat someexchange tookplacebetweenthe
hydrothermal fluidsandthe granodiorite
wallrockat
submagmatic
temperatures,and that the amount of
exchange was roughlyconstantfor variousgenera-
tionsof orefluids.The K/Na datathusagreevery
0 Eorly epholerlto wellwithconclusionsbasedon an independent
study
ß LOIo ephoIorlto
0 Eorly colcite
(Rye, 1966) of the oxygenisotopiccomposition
of
ß Loll COIclfo the hydrothermalfluids. Both sets of data indicate
X Quartz a magmaticsourcefor the hydrothermalfluids and
suggest
thatthe fluidsreactedonlyslightlywith the
20 40
granodioritestock before enteringthe limestone.
60 80 I00 120 140
t•Jo+ K)(ppmX I0-•) The originalmagmatic
characteristics
of the hydro-
Fro. 2. K/Na atomic ratios of fluid inclusions versus
thermalfluidswere probablypreservedso well be-
corresponding Na+K concentrations. Tielines connect causethe ore conduitswere probablynearly in
duplicate samples. equilibriumwith the magmaticfluids in the later
stagesof mineralizationat Providenciathat are rep-
sition. The resultsare in excellentagreementwith resented in our fluidinclusion
samples.
oxygen isotopedata, which indicatethat the fluids It waspreviouslyconcluded(Rye, 1966) that the
were derivedfrom a very high-temperature silicate widespread salinityvariationsin the hydrothermal
source(Rye, 1966). But unlike the temperature fluidsthat were first notedby Sawkins(1964) re-
at the sourceof the fluids,whichisotopedata show sulted either from the events which occurred at the
remainedconstantthroughoutore deposition,the sourceof the fluids or from the incorporationof
temperaturesindicatedby K/Na ratios vary over variousamountsof sedimentary salt by the fluids.
a considerablerange. About 40 km north of Providencia the limestone
In Figure2 the K/Na ratiosof the inclusions
are sectionthat containsthe ore depositsis underlain
plotted versustheir correspondingNa+K concen- by an evaporiteformationconsisting predominantly
trations. This is a convenientway of plotting the of halite with some gypsum. There is no direct
ratios versussalinity. The K/Na ratios definitely evidencefor the evaporitesin the Providenciaarea.
tend to increasewith increasingsalinity. The trend If a salt formation did exist at Providencia and if
cannotbe relatedto temperaturebecausethe K/Na the salinity variations were the result of the in-
ratios of inclusionsin the same generation of corporationof variableamountsof sedimentarysalt
$phaleriteandcalcitevaryovera !argerange. by the hydrothermalfluids,the K/Na ratios would
If hydrothermal fluidsare derivedfrom a granitic almostcertainlydecrease with salinity. Exactly the
magma they will initially have a high K/Na ratio. oppositeis the casein Figure 2. It is possiblebut
The 0.43 ratio of the salineRucioinclusionsis very rather unlikelythat the fluidsdissolvedlarge quan-
reasonablefor the initial K/Na of a fluid derived titiesof sylvite. Also, it wouldseemhighlyfortui-
from a magmahavingthe K/Na ratio of the grano- tous that fluidswith initial high K/Na ratios could
diorite stock at Providencia (Gammon et al., in mix with a salt bed of any composition and retain
press). The initial ratio in the fluids will decrease K/Na ratios so typical of fluids derived from a
if chemicalexchangeoccursbetweenfluids and the magma unlessthe fluids reequilibratedwith high
cooler crystallizedportions of the stock. If equi- temperature silicatesafter incorporatingthe salt.
librium was not always reachedbetweenthe fluids The hydrothermalfluidsprobablydid not get their
and granodioriteand if the amountof exchangeper salt from a sedimentary bed and the salinityvaria-
unit volumeof solutionwas roughlyconstantfrom tionsmostlikely occurredat the sourceof the fluids
one generationof the fluids to the next, the very or in a magma-vaporsystem.
salinefluidswouldtendto retaintheir originalK/Na The salinity variations may merely reflect the
ratios while the more dilute fluids would show more variation in the volume ratio of magmato volatiles
evidenceof exchange. In other words, the trend at the sourcearea or magmaticprocesses may be
shownin Figure 2 can be interpretedas the effect much more complicatedthan is realized and the
of a uniform amountof chemicalexchangebetween salinityvariationsmay be the result of phenomena
granodioritewallrocksand fluidsof variablesalinity. about which little is known.
This modelof exchangeagreeswith previouslypub- A possiblemechanismfor salinity variations at
lished •O TMdata on the fluid inclusions(Rye and the sourceof the fluidshas beensuggested by Hol-
O'Neil, 1968). The O x8 contentof the inclusions land (1967) and is illustratedby a reproduction of
 CHEMIC.4L COMPOSITION OF HYDROTHERM.4L FLUIDS 637
4O0O
ponent. If the 8D of meteoricand magmaticwater•
were virtually the same such a mechanismwould
$ooo
be consistent
with the reportednarrowrangeof $D
values of the hydrothermalfluids at Providencia
(Rye, 1966). The salinityvariationscouldhave
beencontrolled by variablemagmatic/meteoric
ratios
in the fluidsand the •O•s and K/Na valuesof the
fluidscouldhavereceiveda magmaticcharactera•
a result of exchangewith very high-temperature'
silicates. This possibilityis not consideredvery
likely. It doesnot seemlikely that suchmixing of
o
fluids and subsequent equilibrationwith wallrock,
400 5OO •8OO 7OO
TEMPERATURE
800 900 iooo
couldoccurso that the •O•s valuesof hydrotherma!
fluidswerealwaysabout6•, eventhoughthe tem-
Fro. 3. Critical curve in the systemsNaC1-H20 (Sourira- peratureof ore depositionwas continuallydecreas-
jan and Kennedy, t962) and its relationshipto Tuttle and ing (Rye, 1966;Rye and Oneil, 1968).
Bowen's (1958) melting point curve of granites. Diagram
based on that of Holland (1967). Calcium Concentrations.--The concentration of
Ca in fluidinclusions
in sphalerite
andquartzranges
his diagram in Figure 3. The critical curve for the from 1,300to 89,600ppm. The valuesfor the Ca
NaCl-water systemintersectsthe minimum melting concentration
in inclusions
in calciteare usefulonly
temperaturecurve for granitesat a temperatureand as maximum concentrations because most of the
pressure which are reasonablefor the Providencia Ca is derived from the solution of the calcite host
magma during ore deposition. Fluids derived at mineralduringleaching
of the sample.An attempt
conditionsabovethe criticalcurvewill be one phase.was madeto determinethe approximateCa concen--
Thosebelowcouldconsistof two phases--ahighly trationin the fluidinclusions in calciteby subtract-
salinephaseand a lesssalinecounterpart(Sourira- ingenough Ca to makethecation-anion ratiosequal
jan and Kennedy,1962). If the criticalphenomena unity. The corrected concentrationsand corrected
in Providencia hydrothermalfluids were similar to ratiosare presentedin Table 3, and are in the same
thosein simpleNaC1 solutionsand if the pressure rangeof thatobserved for inclusionsin sphalerite.
fluctuated as a result of tectonic events it is reason- Ca/Na •ltomicRatios.--TheCa/Na atomicratios
able that both one and two phasefluids were de- of inclusions in sphaleriterangefrom 0.12 to 0.61.
rived from the Providenciamagma and there would Ratiosof inclusions in quartz are lessreliablebut
have been ample opportunityfor salinity variations the valueof onesamplefallsin this rangeand the
in the hydrothermalfluids. This would really be a corrected ratiosof inclusionsin calcitevary over
caseof boiling at very high temperature. a similarrange from 0.26 to 0.65. Most Ca/CI
The datacannotbe usedto rule out the possibility atomicratiosalso fall in a narrow rangebetween
that the salinityvariationsresultedfrom mixing of 0.08 and 0.32.
variableratiosof dilute meteoricand salinemagmatic After the fluidsleft the magmaticregionthey
•vaters very near the sourceof the magmatic com- probablyacquiredsomeCa and Na from the cooler

Table 3.--Corrected Ca concentrations of inclusions in calcite:

based on cation/anion equivalent ratios of unity.

Size of
sample Dilution Analyzed Analyzed Analyzed Corrected Corrected Corrected
Sample Location (m•s H20) factor Ca (ppm) Ca/Na Ca/el Ca (ppm) Ca/Na Ca/el

62-S-169 Zinc West 15 11.0 6,630 35:800 2.19 1.46 4:300 0 26 0.18

10.0 1:360 24:600 3.53 1.59 3:300 47 .21

61-Hu-54 Zinc West 21A 4.0 5:100 67:300 5.60 1.45 7:800 65 .17

7.3 2•360 59:000 7.87 3.66 2:000 27 .13

61-Hu-305 Animas 18 6.6 2:940 88:200 1.81 0.88 16:600 34 .16

61-Hu-319 Animas 19 12.4 940 20:300 16.64 9.40 ~ 300 ~ 24 ~ .13

638 R. O. RYE AND J. HAFFTY

granodiorite stock in exchangefor I(. Since the silicates. Some Mg may also have been removed
Ca/Na ratio of the feldsparsin the granodioriteat from the fluidsprior to silicationby the formationof
Providenciais greater than 0.6, the initial Ca/Na chloritein smallalterationveinletsin the grano-
ratios of even the dilute fluids may not have been diorite stock (Davidson,1963).
altered significantlyby exchangewith the wallrock. Mg/Ca •ttomic Ratios.--The Mg/Ca ratios in
Precipitationof calcitein the lower levels of the Table 1 are generallyless than 0.08. These low
ore conduitswould changethe Ca/Na ratio of the ratiosare consistent
with the paucityof dolomiteat
fluidsduringsphaleritedepositionbut this seemsun- Providencia. The mineralis found only in small
likely, in view of the fact that mostof the sphalerite amounts at one locality and no dolomitization of
sampleswere depositedbefore calcite precipitation wallrock has been observed.
began. Rosenberget al. (1967) have determinedthe
The Ca/Na ratio of the fluids may have been in- Ca/Mg ratiosof solutionsin equilibriumwith dolo-
creasedby the solutionand/or replacementof lime- mite and calciteat temperaturesbetween275 and
stone. Data on the carbon isotopiccompositionof 425ø C. It is obviousfrom their analyticalcurve,
the fluidsindicatethat possiblyonly a smallpercent- whichis presented in Figure4, in termsof Mg/Ca
age of the total hydrothermal carbon came from the ratiosthat calciteis stablein the presenceof solu-
limestonehost rock (Rye, 1966). H. D. Holland tions only when Mg/Ca ratios of the solutionsare
and M. Borcsik (personal commun., 1968) have quite low.
shown that most of the Mn and Sr in the calcites at If someof theinclusions
in Animassphalerite
con-
Providenciacould not have comefrom the enclosing tain excess Ca from solution of calcite solid inclu-
limestonehostrocksand that they were probablyde- sionsthey probablyalso containexcessMg. It is
rived from a deep-seatedsource. It thus seems notedhoweverthat inclusions in calcitehaveMg/Ca
likely that the limestonedid not contributethe major ratiossimilarto that observedin inclusions
in sphal-
portion of Ca to the hydrothermalfluids. eriteandthe Mg/Ca ratio of the inclusions may not
It is probablethat mostof the Ca in the inclusions be effectedsignificantly
by excessCa and Mg.
in sphaleritewas acquiredfrom the magmaor the The Mg/Ca ratios of most of the inclusionsin
immediately surroundinghigh temperaturegrano- quartz and sphaleriteversustheir filling tempera-
diorite and that most of the Ca/Na ratios reflect tures are plotted in Figure 4. Omitted from the
nearly original values. It remainsto be seen if the figure are obviouslycontaminatedsamplesas indi-
Ca/Na ratios are reasonablefor fluids derived from cated in Table I. The results show a considerable
a magma related to a granodiorite. scatter,but from all the localitiesexceptAnimas22
Magnesium Concentrations.--The concentration at leastoneof the duplicatesamplesis very closeto
ß
of Mg in the fluid inclusionsis much less than the or entirely within the calcite stability field. If ex-
concentrationof Ca. The concentrations of 3/[g forperimentalerror is taken into accountall samples
fluid inclusionsin quartz and sphaleriterangefrom other than thosefrom Animas22 couldbe entirely
20 to 550 ppm and evenlower valueswould be re- within the calcitestabilityfield. The samplesthat
corded if there was appreciable3/[g blank contami- occurentirely within the calcitestabilityfield cover
nation. Even for inclusionsin calcite,which prob-
ably contain some Mg from solution of the host
crystalduring leaching,the Mg concentrationis gen- DOLOMITE + SOLUTION

erally lessthan 1,000 ppm. The inclusionsin sphal-

erite and quartz, which appear to have excessCa,
probablyalso have excessMg. The Mg concentra-
Rosenberg,
Burr,
and
Holland
(1967)
V
350
tion of the hydrothermalfluids was obviouslyquite
low.
The low Mg concentrations of the fluidswere pre-
dicted from the presenceof Ca-3/[g silicates in
300
o-o •x =8
Earlysphaleritl
Late Spholerile
Quartz
o

I
x
o

the lower levels of the ore pipes at Providencia. CALCITE + SOLUTION

These silicatesprobablyformed during ore deposi-

tion as a result of interaction between the hydro- 0.:•0
I
0.15
I
0.10
I
0.0.5 0.00
'thermalfluids and the limestonewallrock (Sawkins, Mg/Ca ATOMIC RATIO

1964). Sincethe originallimestonewasalmostpure Fro. 4. Variations of Mg/Ca ratio of fluid inclusions

,calcite,the Mg for the silicatemust have comefrom with corresponding filling temperatures. The curve shows
the hydrothermalfluids, and a considerableamount the results of Rosenberget al. (1967) for Mg/Ca ratios
of solutionsin equilibrium with dolomite and calcite at tem-
of Mg could have been removedfrom the hydro- peraturesbetween275 and 425ø C. Tie-linesconnectdupli-
thermal fluids during the .formationof the Ca-Mg cate samples.
 CHEMICAL COMPOSITION OF HYDROTHERMAL FLUIDS 639

a large part of the paragenesis,and the host min- Noche Buenadeposits,which are near Providencia
erals for the inclusionsbracketthe major phaseof and which were probablyformed during the same
calcite deposition. At least at times during the ßperiod of mineralization. The resultsalso demon-
various stagesof ore depositionat Providenciathe strate rather strikingly that water leachescan be
Mg/Ca ratio of the solutionswas consistentwith made consistentlywithout significantcontamination
the generalabsenceof dolomitecrystalsin the rugs of Zn and Cu from external sources. If detectable-
and with the lack of dolomitization of wallrock. It is concentrations of Zn and Cu are obtained under
interestingthat the samplesthat lie entirely within similar conditions in the water leaches, the base-
the dolomite field were collected from the level below metals are probablyfrom the inclusionand not a•
that which containsthe only known occurrenceof result of contamination.
dolomite. The resultsof additionalanalysesfor Cu and Zrr
Zinc and Copper Concentrations.--Thezinc and in fluid inclusionsin quartz from Providenciaare
coppercontentof hydrothermalfluids that deposit presentedin Table 4. Also included are new data
sulfides of these elements has been the object of for inclusionsin quartz from Noche Buena which
considerabledebate (Puchner and Holland, 1966; were previouslyanalyzedfor 8D and are presented
Czamanskeet al., 1963). Fluid inclusionsoffer the for comparisonwith Puchner and Holland's data.
most direct method to determine these concentra- The base metal concentration in the inclusions
tions, but it is difficult to determine Zn and Cu con-from water leachesin the two Providenciasamples
centrations in fluid inclusions. A mineral that does are 890 and 400 ppm for Zn and corresponding
not contain Cu or Zn must be used in the analysis valuesof 340 and 530 ppm for Cu. The Zn con-
and, althoughmineralswith suitablefluid inclusions centrationsin the Providenciaquartz are similar to
are easilyfoundin sulfideore bodies,it is very diffi- those obtainedby Czamanskeet al. (1963) from
cult to demonstrate that inclusions suitable for anal- water leaches for inclusions in minerals from differ-
yses have formed simultaneously
with Zn and Cu ent sulfide ore bodies,and the Cu concentrationsare
sulfides. The concentration of Zn and Cu in fluid slightly greater than they observed.
inclusionsis probablynot large, and the possibility The Zn and Cu of inclusionsin quartz from Noche
of significantcontaminationfrom apparatusor the Buena, presentedin Table 4, are from crystalsof
hostmineral is probablymuchgreaterthan for other the samegenerationas thosethat were analyzedby
elementsin fluid inclusions. An additionalproblem Puchner and Holland (1966). The inclusionsare
is that some metal may be present as undetected not identical, however, and therefore identical re-
daughter minerals or will precipitate as insoluble sultsshouldnot necessarilybe expected. The sam-
sulfides when the inclusion is crushed. Thus an acid
ples used in the presentstudy were mainly minute
leach as well as water leach is necessaryto be sure inclusionsin milky zones,in contrastto the large
that all Zn and Cu is removed from the crushed singleinclusionsanalyzedby Puchnerand Holland.
inclusions. Cu concentrations of inclusions in water leaches are
The Zn and Cu concentrations of fluid inclusions belowlevel of detectionin all three samples,just as
presentedin this paper were determinedby atomic Puchner and Holland observed. Zn concentrations
absorptionanalysesof water leachesof inclusionsin are 220-560 ppm or at leasttwice as large as they
sphaleriteand calcite and of water and acid leaches found, but the differencecould easily be the result
of inclusionsin quartz. The results of all Zn and of a differencein samples.
Cu analysesof fluid inclusionsfrom water leaches Acid leacheswere madeat roomtemperaturewith
are presentedin Table 1. 5-volume-percent solutionof HNOa, usingthe same
In sphaleritethe concentration of Cu in inclusions filter previouslyused for water leachesof the sam-
is invariably below the limit of detection,which is ples. Three acid leacheswere made on each of the
rather surprising becausemost of the sphalerite two Providencia samples. During the first and
samplescontainedexsolvedchalcopyrite. The cor- third leaches,the sampleswere in contactwith the
respondingZn concentrations,however, are variable acid for 5 minutes;during the second,the time was
and often quite large, as is to be expectedbecauseof severalhours. With the exceptionof the Zn content
solution of oxidized host mineral during leaching of the third acid leachof the Zinc West sampleall
of the sample. The Zn concentrationsfor inclusions the acid-leach concentrationsare greater than the
in sphaleritethereforehave meaningonly as maxi- water-leach concentrations. It is obvious from the
mum concentrations. results of the second acid leaches that the Zn and Cu
In calcite the base metal concentrations of inclu- concentrationdependsupon the amount of time the
sions are below the level of detection. These values samplesare in contactwith the leach. With the pos-
are consistentwith those found by Puchner and sible exceptionof the Zn concentrationof the Zinc
Holland (1966) for inclusionsin quartz from the West sample the total base metal concentrations
640 R. O. RYE AND ]. HAFFTY

_•J.J Table 4.--Zn and Cu concentrations, in parts per m•llion, from water and
acid leaches of inclusions in quartz from Providencia and Noche Buena.

Water
leach
Acid leaches
Size of

Providencia:

San Eligio 63-R-4 10.8 1540 890 340

1620 1840 3420

1410 3680 17,640

1320 1900 4960

Zinc West 63-R-1 4.6 4090 400 530

4160 700 3840

3330 1400 6250

3330 180 3120

Noche Buena: 62-S-155 2.5 4440 500 < 150

10,720 5450 8000

5.2 2900 560 < 90

7060 4660 5650

62-S-155A 7.5 2370 220 < 70

4490 4080 5850

from the acid leachesis unreasonablyhigh and pre- the water leachesto give the total base metal con-
sumablymoreZn and Cu couldhavebeenrecovered centrationsin the inclusions,but this possibilitycan-
from the samplehad more acid leachesbeenmade. not be evaluatedfrom presentevidence. It is also
For the Noche Buena samplesonly one 5 minute possiblethat both sampleswere somehowcontami-
acid leach was made but base metal concentrations nated, but in view of general absenceof contamina-
range from 4,080 to 8,000 ppm whereasPuchner tion in the crushing and leaching techniquethis is
.andHolland (1966) found no basemetalsin much not likely. The valuesas reportedfor water leaches
strongeracid leachesof similar samplesby a more in Table 4 probablydo reflect the Zn and Cu con-
preciseprocedure and technique that eliminatedthe centrationof the hydrothermalfluids during quartz
major possibilities of contamination. deposition.
In 30-ml acid leacharesof silica tubing crushedin The Zn and Cu concentrations were probablyeach
stainless steel tubes, the Cu concentrationranged less than 50 ppm during depositionof calciteand
from 0.13 to 0.23 ppm for Cu and from < 0.010 to closeto 500 ppm during the depositionof quartz.
0.025 ppmfor Zn (D. M. Pinckney,oral commun., These values do not necessarilyindicate the base-
1968). At least someof the basemetalsfrom the metal concentrationof hydrothermal fluids during
:acid leaches,therefore,could have come from the sulfidedeposition. Sphaleritewith exsolvedchalco-
stainless steel tubes in which the samples were pyrite bracketsquartz in the paragenesisat Provi-
<:rushed. Some could also have come from solution dencia. Quartz also precipitatedas free-standing
.of imperceptible solid inclusions in the milky por- crystalsat temperaturesnear 300ø C and occursas
tion of the quartzcrystals. Regardless of the source solid inclusionsin yellow sphaleritewhich precipi-
of Zn and Cu in the acid leaches,it would appear tated at the sametemperature. It cannot,however,
that the inclusion concentrations from these leaches be demonstratedconclusivelythat the fluid inclu-
have little relevance to the Zn and Cu concentrations sionsin quartz were trappedduring sphaleritedepo-
of the Providenciahydrothermalfluids. A portion sition. It is perhapssignificantthat the Salton Sea
of the Zn and Cu contentof the acid leachespossibly geothermalbrines,which in many respectsare simi-
should be added to the Zn and Cu concentration of lar to the Providenciahydrothermalfluids and which
 CHEMIC,4L COMPOSITION OF HYDROTHERM,4L FLUIDS 641

depositedcopperand silversulfidesin the discharge dencia in this and previouspapers. It is believed

pipeand localsphalerite
andchalcopyrite in the sedi- that the fluids were derived from a magma-vapor
ments, have Zn and Cu concentrations not unlike system that was related to the Providencia stock.
those observed in the Providencia and Noche Buena After the fluids left the magmathey passedthrough
fluid inclusions(Skinner et al., 1967; White, 1968). the coolercrystallineportionof the stockandeventu-
Chloride Concentrations.--The chloride concentra- ally entered the adjacent limestoneformations that
tion of the inclusions
rangesfrom slightlylessthan now contain the ore. All the data that have accumu-
2,000ppmto morethan 200,000ppm. This range lated about Providencia since 1960 are consistent
reflectscorrespondingvariationsof cation concen- with the model.
trations and indicates that most of the cations are The Providenciastock and ore depositsare re-
present as chloridesin the inclusions. lated in time as well as in space (Ohmoto et al.,
Sulfate Concentrc•tions.--H2Shas not been de- 1966). The 80 TMdata indicatethat the temperature
tectedin any of the Providenciainclusions. Any at the source of the fluids remained constant even
sulfur that might have been present as H2S in thoughthe temperaturesof ore depositiondecreased
the inclusions would have been removed when the by at least 150ø C (Rye, 1966). Both 80 •8 and
samplewas crushedin a vacuumsystem. Sinceall K/Na data very stronglyindicatea magmaticsource
remainingsulfurwasoxidizedin the analyticalpro- for the fluids. After the fluids left the magmatic
cedureandanalyzedas SO4thetypeof sulfurspecies environmentthey traveledthrough the coolercrys-
originally presentin the inclusionscannotbe deter- talline granodiorite. The 80 •8 and K/Na data in-
mined with certainty. The SO4 concentrations of dicate that some isotope and chemicalexchange
the inclusions
are of interest,therefore,primarilybe- occurred between the fluids and the wallrock so
causeof their relationshipto the sulfur/base-metal that the fluids have slightly lower 80 TMvaluesand
ratio of the hydrothermalfluids. There is evidence K/Na ratios than the initial magmaticfluids. The
that the sulfides
of someoredeposits are precipitated data suggestthat during late mineral deposition
from sulfur-deficientore fluids, although most equilibrium was not always reachedbetween fluid
authorshave arguedonly for sulfide-deficient ore and fresh wallrock and that the amount of chemical
fluids (Lovering, 1961; White, 1968, Skinner, and isotopeexchangewas roughlyconstantfrom one
1968). generation of the fluids to the next. When the
The sulfateanalysesfor inclusionsin sphalerite fluids entered the limestonewallrock they reacted
are usefulonly as maximumvalues,althoughit may with the limestoneto form the calcium-magnesium
be significantthat the SO• contentof the inclusions silicatesthat are presentin the lower levels of the
in sphaleriteare usuallymorethantwicethat needed ore pipes. The formation of thesesilicatesremoved
to balancethe corresponding Zn concentrations.The considerable amountsof Mg from the hydrothermal
concentration of SO• in inclusions in calcite and fluids and is probablyprimarily responsiblefor low
Mg/Ca ratios of the fluids which account for the
quartz are belowthe level of analyticaldetectionex-
general absenceof dolomite in the area. Silication
cept that in two samplesof calcitefrom Zinc West
15 in which the concentration of SOi is 6,200 and of limestonealso removedmuch silica and is pre-
2,700 ppm, respectively.Sincethe correspondingsumablythe reasonwhy quartzis foundonly in the
base-metal concentrations for these inclusions are upper levels at Providencia (Sawkins, 1964).
The isotopedata for Providenciaindicatethat the
very low, a very high total sulfur/base-metal ratio
hydrothermalfluids did not exchangemuch carbon
for the hydrothermal fluidsduringcalcitedeposition or oxygen with the limestone wallrock in the ore
is suggested. However, it is possiblethat SO•
concentrations are due to solution of solid inclusions conduits(Rye, 1965). Data on hydrothermalcal-
cites (Rye, 1966) and on the •C •a of CO2 in in-
in the hostmineral. Also, the analyticaltechniques
clusionsin sphalerite (Rye and O'Neil, 1968) in-
were not sensitiveenoughto adequatelytest for a
dicate that possiblyonly a small percentageof the
blank contamination of SO4. Additional samples
carbonin the hydrothermalfluidscamefrom the sili-
wouldneedto be analyzedby more sensitivemeth-
odsto establish the propositionthat the total sulfur/ cationof limestonehostrock. The narrow rangeof
base-metal ratios of the Providencia solutions were Ca/Na and Ca/C1 ratios of the fluid inclusionsin
indeed high. sphaleritesuggestthat the limestonealso contributed
only a minor percentageof the total Ca to the hy-
drothermal fluids and that most Ca was derived from
History of the Providencia Ore Fluids--
a deepseated
source.
A Recapitulation
The uniformity,in time and space,of the 8D and
A simplemodelhas beenpresentedfor the origin 80 •s valuesof the hydrothermalfluid indicatesthat
and historyof the hydrothermalore fluidsat Provi- magmatic and meteoric waters did not mix in the
642 R. O. RYE AND J. HAFFTY

area of ore deposition;they may have mixed near higher K/Na ratios and $Ox8 values of the Provi-
the magmaticsource,but this doesnot seemvery denciafluidsindicatederivationfrom a muchhigher
likely. The K/Na ratios of the fluids indicate also temperature source.
that the ore fluids did not incorporatesignificant The $D of the Providenciafluids is in the range
amountsof sedimentarysalt. The very largesalinity of present-daymeteoricwaters in the Providencia
variationsin the fluids were most likely a result of
(Rye, 1965). The proposalcouldbe made on the
events which occurred at the source of the fluids basisof this fact and the preponderallceof meteoric
and the variations may have resulted from boiling water that seemsto be presentin many ore fluids
in a magma-vapor system. studied to date, that the Providencia ore fluids, like
The $S • values of sulfide minerals are in the
the Salton Sea brines,were not involvedin a magma
"magmatic hydrothermal" range and indicate that but were meteoricwaters that obtaineda magmatic
the sulfur derived either from the mantle or from characterby equilibrationwith very high-tempera-
a well-homogenizedcrustal source (Sawkins, 1964). ture silicaterocks. This proposalcan not be dis-
The calculatedcarbon isotopiccompositionof CO2 proved; howeverwe do not considerit very likely.
in hydrothermal fluids indicates that much of the Certainly hydrous magmas such as formed the
hydrothermalcarbonwas most likely from a deep- Providenciastockmust emit hydrothermalfluids at
seatedand nonlimestone source(Rye, 1966; Rye and some stage in their history. At the present time
O'Neil, 1968). there is no reasonto supposethat suchfluids are
The data do not definethe sourceof the magmatic not sufficientin volumeand chemistryto form ore
fluids. Prior to its involvement in the granitic deposits. On the other hand it is difficult to visual-
magma the water could have been juvenile, connate, ize how surficial waters could enter into and leave
or meteoric. Any fluid that passedthrougha mag- a very high or near-melting temperatureenviron-
matic phase would have $O•8 and chemical charac- ment in the Providenciastockthroughoutthe period
teristics similar to those of the Providencia fluids. of ore depositionand always obtain a chemicaland
$Ox8valuesof the fluidswould be large and positive isotopiccharacterthat is typical of fluids from a
as a result of isotopicexchangebetween fluids and single magmatic source. The surficial waters that
the high-temperaturesilicates;the K/Na ratio would producedthe Pb-Zn depositat the BluebellMine, for
be large as a result of chemicalexchange. At the example,have a markedlydifferent oxygenisotopic
presenttime the $D of the fluids cannotbe used to characterthan the Providenciafluids (Ohmoto and
eliminate some of these possiblesources. The $D Rye, 1968). If meteoricwaters were involved in
of juvenile water is not known, but it is probably the Providenciafluids they must have been incorpo-
well within the range of meteoric waters. Recent rated in the magma-vaporsystemduring late stage
evidence indicates that near surface intrusions com- mineralization. The Providencia fluids and the Sal-
monly incorporatemeteoric waters at some stage of ton Sea brines may representend member types in
their history (Taylor and Epstein, 1968). a whole spectrumof ore-bearingfluids that contain
Recent studiesof Pb-Zn and other depositshave variousamountsof magmaticand meteoricwaters.
indicatedthat most ore-bearingfluids were not de-
rived from a simple magma-vapor system as has Acknowledgments
been describedfor Providencia. Sheppard et al.
(1968) have presentedevidencethat the hydrother- ProfessorH. D. Holland of PrincetonUniversity
mal fluidsassociated with mineralizationin porphyry initiated geochemical research at Providencia in
copper depositscontain a significantmeteoric com- 1960, and he introduced the senior author to the
ponent. The mineralizing fluids of the Pb-Zn de- possibilitiesof research in that area. His interest
positsat Kootenay Lake, B.C., were largely heated throughoutthe presentproject has been profitable
meteoric fluids (Ohmoto and Rye, 1968). These and is greatly appreciated.
depositsseem to have formed in a system that is Much of the equipmentfor cleaningand leaching
similar to that which producedthe Salton Sea brines
fluid inclusionswas designedby D. M. Pinckney,
where the bulk of the hydrothermalfluids were not
involved in a magma. U.S. GeologicalSurvey. The procedureused for
analysis of C1 and SO4 was developedby J. S.
The Salton Sea brines, which have the potential
of producingeconomicallyimportant depositsof ore, Wahlberg, U.S. GeologicalSurvey. The anion
are predominantlymeteoric waters that have equili- analyseswere madeby M. W. Solt, U.S. Geological
brated with high-temperature silicates (White, Survey.
1968). The chemistryof thesebrines is similar to Reviews by D. E. White and Edwin Roedder,
that of some of the Providencia fluids, although U.S. GeologicalSurvey, and H. D. Holland con-
 CHEMICAL COMPOSITION OF HYDROTHERMAL FLUIDS 643

tributed substantiallyto the improvementof this partial chemical analysis of fluid-filled inclusions from
minerals: EcoN. Gv.OL., v. 53, no. 3, p. 235-269.
manuscript. , 1967, Fluid inclusionsas samplesof ore fluids, p. 515-
574 in Barnes, H. L., ed., Geochemistryof Hydrothermal
U.S. GEOLOGICAL
SURVEY, Ore Deposits: Holt, Rinehart and Winston, Inc., 670 p.
DENVER,COLORADO, Roedder, Edwin, Ingram, Blanche, and Hall, W. E., 1963,
Nov. 13, 1968; •tpri! 17, 1969 Studiesof fluid inclusions--[Pt.] 3, Extraction and quanti-
tative analysisof inclusionsin the milligram range: EcoN.
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