Economic Geology

Vol. 71, 1976, pp. 1036-1048

TheEffectof CuprousChlorideComplexes
in theOriginof
Red-BedCopperandRelatedDeposits
ARX•UR W. ROSE

Abstract

Geological,mineralogical,and isotopicdata indicatethat red-bedcopperdepositsare

introducedinto their host rocks af.ter sedimentation
by flowing subsurfacewaters ap-
proximately in equilibriumwith hematite,quartz, feldspar,and mica at temperaturesless
than about75øC. Precipitationof copperis causedby encountering
a reducingenviron-
ment. In most normal oxidizing terrestrial ground waters, solubility of copper is less
than 1 ppm at reasonablepH values, so these waters are relatively ineffective in trans-
port of Cu. However, cuprousion (Cu+) forms the complexions CuC12-and CuCla2-
with formation constantsof 105'4and 105.sat 25øC. These complexesallow solubilities
of about 100 ppm Cu in 0.5 m C1- at intermediateEh in the stability field of hematite at
pH 7.0, and solubilitiesof 6 ppm at pH 8.2. Weaker complexesof Cu2+ with OH-,
SO42-,SOag-, and C1-are known but have comparativelylittle effect on coppersolubility
in most natural waters. Most red-bed copper and cupriferoussandstone-typeuranium
depositsare associatedwith evaporiteswhich could have furnished chloride-rich ground
waters. Escape of connate marine waters from underlying marine sedimentsmay have
furnisheda copper-transportingfluid in other cases. Cuprouschloride complexingmay
also have been important in the origin of the Kupferschiefer and Zambian deposits,
which also occur in associationwith red bedsand evaporites.

Introduction (Papenfus, 1931), in Bolivia at Corocoro (Ljung-

gren and Meyer, 1964), in Russia southwestof the
ThE origin of a mineraldepositformedby precipita- Urals and in Siberia at Udokan and elsewhere
tion from solutioncan usefully be consideredfrom
(Bastin, 1933; Narkelyun et al., 1969, 1971; Feokti-
four aspects: (1) the sourceof the valuable con-
soy and Kochin, 1972; Bakun et al., 1966). Cur-
stituents,accessoryconstituents,and solvent, (2)
rently mined depositsinclude those at Creta and
the mechanismfor solubilityof importantconstitu-
Mangum, Oklahoma; Nacimiento, New Mexico; and
ents, (3) .thecontrolsfor movementof solution,and
Corocoro, Bolivia. In addition, the large copper
(4) the mechanismfor precipitationfrom solution.
depositsat Dzhezkazganin Russiaand at White Pine
This paper concentrateson the mechanismsfor
in the United States(Brown, 1971) have.manysimi-
solubilityand precipitationof copperin low tempera-
larities to the red-beddeposits. The Kupferschiefer
ture deposits,especiallyred-bed deposits. Other
of Germany, some Cu-U depositsin the U.S., and
stratiform copper depositsand cupriferoussand-
the Zambiandepositsdiffer in somerespects,but in
stone-typeuranium depositsare also considered.
These low temperaturedepositsof copper pose a view of their low temperatureof depositionand cer-
distinctproblembecause of the very low solubilityof tain similar lithologicand geologicfeatures (sulfides,
copperat the near-neutralto alkalinepH valuesex- organicmatter, occurrencenear evaporitesand red
pectedfor mostsurfaceand groundwaters. In con- beds), the samechemicalrelationshipsmay apply.
trast to higher temperaturedeposits,the chemical Common features of red-bed copper depositsin-
data for low temperaturesare good enough for clude their sedimentaryand tectonicenvironment,
quantitativeevaluationof most hypothesized mecha- the oxidation-reduction 'features of ore and surround-
nismsfor coppersolubility. ings, and the mineralogy of the ores. Red-.bed
A large numberof depositshave beenincludedby copperdepositstypicallyoccurwithin or immediately
variousworkers under the term "red-bed copperde- marginal to thick sequencesof red, brown, purple,
posit," so somediscussion of the group is appropri-
ate. Summaries of the characteristics and distribu- or yellow sandstone, mudstone,and shaledeposited
.tion of red-bedcopperdepositsare given by Lind- in fluvial, del.taic,or other terrestrial or .marginal
marine environments. The color is due to hematite
gren (1933, p. 403-409) and Bastin (1933). Good
examplesof these depositsoccur in Oklahoma, or other ferric oxyhydroxidesoccurringas coatings
Texas, New Mexico, Utah (Bastin, 1933), Pennsyl- on grains,as cement,and as matrix. The sediments
vania (Butler, 1938; McCauley,1961), Nova Scotia are typically arkosic,derived from debris shed by
1036

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by Juan I. Guzman
 ORIGIN OF RED-BED COPPER DEPOSITS 1037

late-tectonicupliftsalongcontinentalmarginsor up-
lifts within the continentalplatform. 25øC
The mineralizedzonesare lenses,pods,and layers,
grossly ,conformablewith the enclosingsediments .8
but usuallycross-cutting in detail, with thicknesses 10-3
of centimeters to a meter and lateral dimensions of a (63
ppm) 10-5(.6
meter to kilometers. In .contrastto the surrounding
red oxidizedsediments, the mineralizedzoneis typi- 10-4 (6ppm)
callygrayto greenishandcontainsironpredominantly Cu 2+ CuO
in the ferrous state, along with reducedsulfur and
carbon. Most if not all of the depositscontainfossil-
ized plant .fragmentsor other evidenceof organic
material which would have provideda reducingen- Eh
vironment. Most mineralized zones are associated
either with large podlike accumulationsof plant
debris in a relatively permeablesandstoneor with CuzO
lower ,concentrations of organic matter in shales
adjacentto sandstone bodies.
Cu2S
The major primary mineralsof the depositsare
"chalcocite,"pyrite, and variableamountsof bornite,
chalcopyrite,native copper,and ,covellite,along with
minor amounts.of many other sulfides. In view of
the recent recognitionof 'digenite,,djurlei.te,anilite
and other new mineralsin the Cu-Fe-S system,and
the problemsin distinguishingthesefrom chalcocite, -.4
3 5 7 9 11
it is likely that much remainsto be learnedas to de-
tails o.f the mineralogyof Cu at red-.beddeposits. pH
Several workers report digenite (McCauley, 1961;
Kidwell and Bower, 1974) or blue chalcociteat red- Fro. 1. Eh-pH diagramfor systemCu-O-H-S, 25øC,
:ZS = 10-4 m.
bed ,deposits. Brett and Yund (1964) and Mc-
Cauley (1961) found that bornitefrom severalred- the characternormallyassociated
with hydrothermal
bed depositsin Utah and Pennsylvaniais sulfur rich veins is lacking.
and exsolveschalcopyriteon heating to 75øC or In many of the red-bed deposits,textures show
above. Yund and Kullerund (1966) were able to that at leastsomeof the coppersulfidesreplaceeither
synthesizesimilar S-rich bornitesat temperaturesup plant material or earlier pyrite. Replacement of
to 140øC. The specimens from red-beddepositsap- pyrite by chalcociteis reported by Rogers (1916),
,pearto be a metastablephaseformed at temperatures Papenfus (1931), Bastin (1933), Butler (1938),
less than about 75øC, althoughthe possibilityof McCauley (1961), Brown (1971), Gann and Hagni
sulfur loss during heatingdoesnot allow firm con- (1974), Kidwell andBower (1974), and W,oodward
clusionson an upper temperaturelimit. McCauley et al. (1974, fig. 4, and ,p. 118). In 'severalinstances
shows pictures of chalcocitewith apparent ortho- the replacedpyrite is inferred to be "syngenetic."
rhombiccleavageand crystalform. If the chalcocite Hoxvever,syngenetic precipitatesare typicallyamor-
was actuallydepositedin orthorhombic•orm, a tem- phousFeS, greigite,or mackinawite,which are con-
peratureof lessthan 103øCis indicated(Roseboom, verted to pyrite only during diagenesis. The woody
1966). Native silver or silver 'sulfideis commonly material appearsto have been at least partly con-
present (Gann and Hagni, 1974; Woodward et al., verted to coal before replacementby sulfides. In
1974; Shockeyet al., 1974; Ljunggren and Meyer, view of this evidence,plus the apparentdifficul,tyof
1964,p. 117). Small amountsof galena,sphalerite, dissolvingand transportingcopper in the stream
waters depositing the red 'sands and muds (see
and minerals of arsenic, antimony, molybdenum,
below), the copperis inferred to .beepigenetic,hav-
gold, cobalt,and nickelare alsoreported. Introduced
ing beenintroducedd.uring diagenesis or later.
ganguemineralsare not common,althoughbarite is On the other hand, little or no evidence exists for
locallyreported(Kidwell and Bower, 1974), and the controlof the depositsby faults or othercross-cutting
sulfidesare accompanied by quartz, feldspar,ohiorite, structures. The sandstonesappear to have furnished
illite, and other mineralsof sedimentaryor diagenetic the permeable zones in which mineralizing fluids
origin. Wall-rock alterationto micasand claysof reachedthe site of deposition. The generallack of

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by Juan I. Guzman
 1038 .4RTHUR 14
z. ROSE

controlby cross-cutting structuressuggeststhat stability field of hematite. For waters with K con-
depositionof copperwas relativelyearly, before tent up to that in sea water, expectedpH from the
structural disturbances.Copper was apparently assemblage K-feldspar-muscovite-quartz is about8.1
broughtin by subsurface watersflowinglargely (Usdowskiand Barnes,1972) at 30øC. Waters of
alongbedding in the sedimentarysequence andwas lower pH wouldbe expectedto react with the rock
depositedat temperaturesbelowabout75øC. Values at a geologically significan,t
rate to destroyfeldspar
of aSa4of sulfidesshowwidevariabili,ty
in therange and precipitatemica,raisingthe pH in the process.
-20 to --5050 (McCauley,1961; Jensen,1971) Calcite similarly .constrainsthe pH to relatively
and are thusconsistent with an originby bacterial alkalinevaluesunlessvery high CO2 pressures are
reductionof sulfate,althought'hisrangecannotbe attained.
considered proof of suchan origin in view of the From this evidenceit appearsthat transport of
possibleeffectsof oxidationpotentialand pH copperby surfacewaters or ,diluteground waters is
(Ohmoto,1972). unlikely. Only in relativelyunusualgeologicen-
The solubilityof Cu in the simplesystemCu-O- vironmentsare watersacid enoughto transportCu,
H-S is illustratedin Figure 1. Data for the con- and the sedimentsshow no sign (alteration of .feld-
struction(Table 1) are basedon valueslistedby sparto clay, lack of calcite) of suchacid waters. In
Wagmanet al. (1968, 1969). The diagramshows addition,the restrictionof the depositsto thick se-
that coppersolubilityis about6.3 ppm at pH 5.67, quencesof arkosicred bedsis not explained.
0.6 ppmat pH 6.17,an,ddecreases rapidlyat higher
pH. Solubilityi's also negligibleunder reducing Complexing of Copper
condition.
s because of precipitation
of Cu20 (cu- The formation of strong complexesbetweencu-
prite), Cu,or Cu2S(chalcocite).This simplesystem prousion (Cu+) and ,chlorideion is clearlyrecorded
approxi,mates,fresh'surface
watersanddiluteground in the chemicalliterature(Sillen and Martell, 1964)
waters. Taking 1 ppm as significantfor ore forma- but has not received much attention from low tem-
tion, transportof significantamountsof copperin perature geochemis.ts.Helgeson (1969) reports
solutionat pH valuesof 6.1 or aboveis notpossible. these complexesalong with many others, and his
Most surfaceand groundwatershavepH values data on cuprouschloride complexeswere used by
in therange6.5 to 8.0. For instance,
42 groundwa- Brown (1971) to explainsolubilityof copperin solu-
ters from ,the arkosic Tertiary sedimentsof ,the tions depositingthe ores at White Pine, Michigan.
ShirleyBasin,Wyoming,havepH between6.2 and In view of the widespreadoccurren.ce of chloride-rich
8.4 (Harshman,1972). Of 17 typicalgroundwa- waters in the form of seawater, evolvedconnatewa-
tersin sandstonereportedby White et al. (1963), 14 ters, and hydro.thermalwaters, these complexesare
havepH valuesbetween6.7 and8.2. Of 158ground of considerable interest.
waters from Cretaceousand Tertiary sedimentsof In Table 1 are compiledthe thermodynamicdata
the Atlan.tic Coastal Plain, 138 have pH values used in this paper. Most of the data are from
greaterthan 6.0 (Back, 1966). The relativelyacid standard sources noted in the table; the derivation
waters reported in the last two studies are either of a few values is discussed below.
very low in dissolvedsolids(25 to 50 ppm) or ap- Free energy of CuC1,.-is calculatedfrom data for
pear to be contaminated,
as indicatedby high nitrate the reaction
values. The waters with low dissolved solids have
evidentlymigratedonly a short distancein the rocks CuCl(s) + CI-= CuC12-(aq) (1)
and interactedonly slightly with rock or soil. If usingthe free energyof CuCl(s) from electrometric
waters of this type contained1 ppm Cu, it would measurements by Nielsenand Brown (1928) and the
amount to several percent of the .total dissolved concentrationratio (CuC12-)/(C1-) of 0.0661 found
solids. Although suchwaters might developlocally by Noyesand Chow (1918) .andHikita et al. (1973)
near a pre-existing concentrati.onof copper, the for CuC1in equilibriumwith 0.1-0.3 M HC1 at 25øC.
leaching by such waters of large amounts of Cu Because both CuC12- and C1- are univalent, .the
from normal or slightly enrichedrocks, followedby activity coefficients
shouldbe approximatelyequal,
depositionin ore grades.andtonnages,doesnot seem as suggested by Nielsenand Brown (1928), and the
possible. concentrationratio can be taken as .anactivity ratio.
The pH of ground waters in the sandstones of the These considerationsgive a value of 10+5'4for the
red beds should be approximatelyin equilibrium equilibrium constantof the reaction
with the mineral assemblages of the sediments,which
contain'hematite(or other Fea+ minerals), quartz, Cu+ + 2C1-= CuC1._,- (2)
feldspars,usually illite, and 'sometimes calcite. The Free energieslisted by Wagman et al. (1969) give
waters must have beenoxidizing enoughto be in the a value of 104'8•for this equilibriumconstant,but no

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by Juan I. Guzman
 ORIGINOF RED-BEDCOPPER
DEPOSITS 1039
TABLE1. Thermodynamic
Data Usedin Calculations
for Cu

Species State zIGør(2•søK) AHøf(298øK) Reference

Cu c 0 0 1
Cu+ aq + 11.95Kcal/mol + 17.13Kcal/mol 1
Cu2+ aq + 15.66 + 15.48 1
CuO(tenorite) c --31.0 --37.6
Cu20(cuprite) c -- 34.9 -- 40.3 1
Cu•S(chalcocite) c -20.45 - 19.0 1, 9
Cul.96•S (djurleite) c - 20.23 9
Cu•.gaS (djurleite) c - 20.04 9
CuL75S (anilite) c - 18.77 9
CuS(covellite) c - 12.88 - 12.7 1, 9
Cu4(OH)11SO4 (brochantite) c -434.5 -525.4 1, 6
CuC1(nantokite) c -28.37 --32.2 1, 2
Cui(OH)•CI•(atacamite) c --320.2 --396.2 1, 6
CuCI•- aq -58.1 --66.3 2, 3, 8
CuClat- aq --90.1 -108.5 4, 5, 8
CuC1+ aq - 16.3 - 15.98 1, 7
C1- aq --31.37 -39.95 1
SO42- aq -- 177.97 - 217.32 1
H2S aq --6.66 -9.5 1
HS- aq +2.88 -4.2 1
H 20 liq - 56.687 -- 68.315 1
Fe2+ aq - 18.85 -21.3 1
Fe2Oa(hematite) c -- 177.7 -- 197.3 10
FeS2(pyrite) c --39.9 -42.6 1

1 Wagman et al., 1968, 1969.

2 Nielsen and Brown, 1928.
3 Noyes and Chow, 1918.
4 Naray-Szabo and Szabo, 1933.
5 Hikita and others, 1973.
6 Barton and Bethke, 1960.
7 Helgeson, 1969.
8 See text.
9 Potter, 1975, and personalcommunication.
10 Robie and Waldbaum, 1968.

sourceof data is given. Helgeson (1969) lists a ion. The stabilityconstant(K•) for CuC1 + ranges
value of 104.9L basedon results quoted•by Chalty- from about 1 to about10 (Ohlson and Vannerberg,
kyan (1948), but the latter referencedoesnot report 1974) according to variousinvestigators usingdif-
detailsof the experiments,which •vereconductedin ferent methods and different media. The values of
concentrated chloridesolutionsby otherworkersand Wagmanet al. (1969) areusedin thispaperandare
involvedlinear extrapolationof activity coefficients equivalentto 2.8 for K1 and 1.4 for K2, whereK•
for moderatelyconcentratedsolutions. In view of and K2 are constantsfor formationof complexesof
these discrepanciesbetween workers, an error of one ,and two chloride ions, respectively,with the
---+0.6in log K is estimated. Enthalpy is computed cupric ion.
from the changein log K for reaction (1) (Noyes The complexCuSO4(aq)is well substantiated by
and Chow, 1918), usingenthalpyfor CuCl(s) from a numberof investigators (SillenandMartell,1964),
Wagman et al. (1969), which is supportedby recent most of whom obtain values of about 10-ø'•for its
data of Bugdenand Shelton (1970). formationconstant. Complexes of cupricion with
For CuCla2-, the experiments of Naray-Szaboand carbonate weremeasured by Sihnan(1958) and are
Szabo(1933), givinga valueof 10+*'sfor the equi- availablein Garrels and Christ (1965).
librium constant of the reaction
Complexing
of Cu2+with OH- is wellestablished.
Cu + d- 3C1- = CuCla2- (3) Mesmerand Baes (1974) summarizeevidencethat
the major cationiccomplexis Cu2(OH)22+. The
seemto be the best values, although other workers
suggestsomewhatlowervalues. An error of ---+0.6 equilibrium constant,acu2•On,•2+'an2+/ac•2+,
is about
10-•ø'•, where a• is the activity of speciesx, so
again seemsappropriate. Enthalpy of CuCI:•
2- is that in dilute solutions,Cu2(0I-I)2 2+iS unstablerela-
derivedfrom the data of Hikita et al. (1973) and is
within 0.6 kcal of the value calculatedby Helgeson tive to CuO and is impor.rantonly in solutionsof
(1969, table5). high ionicstrength
near the stabilityfield of CuO.
of cupricion (Cue+)with C1-are also The species
Complexes CuOH+, for whichthe analogous
con-
known but are much weaker than those of cuprous stant, acton+ 'an d-/acu2d-,iS about 10% pre-

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by Juan I. Guzman
 1040 .4RTIfUR I/F. ROSE

tion, concentrations
have been approximately
con-
25øC vertedto activitiesby the Debye-Huckelexpression
(Garrels and Christ, 1965, ,p. 61). The "effective
diameter"parameterfor CuC12-,CuCla-ø-,and CuC1+
Cu2+
has been approximatedas 6 x 10-s cm, and for Cu+
10'4(6
pprn) as 2.5 x 10-s cm; othervaluesare as givenby Gar-
rels and Christ (1965, p. 62). Activity coefficients
in this solution are approximately0.71(CuC12-),
0.25(CuCla-ø-),0.18(SO(ø-), 0.25(Cu'•+), and 0.71
(CuCI+). Althoughthesevaluesare not precisein a
CuO solutionas concentrated as 0.5 m, .theyare consider-
Eh ably more accuratethan the uncorrectedvalues.
CuCl•3
' The equilibriumbetweenthe two cuprouscom-
-I- plexes can be expressedas
CuCl; CuCIa2- = CuCIe- + CI- (4)
CLCuC
12-' gC1- mcuc 12-' mc 1-
k4 =
C•uC 132- mcucla 2-
Cu•O
'¾CuC13- ' "Yc1-
"YcuC132-
Cu
wherem.•is molarityof species.v, ax is activityof x,
and y.• is the individualion activity coefficient. For
rnct- = 0.5, I: 0.5, the y valuesas noted above,
-.4
3 5 7 9 11 and the equilibriumconstantsat 25øC for the com-
plexespresentedpreviously(K4 = 10-ø'42),rnc,cl_o-/
pH rnc•cl•- is 0.41, althoughthe activity ratio is 1.15.
FIG. 2. Eh-pH diagram for system Cu-O-H-S-C1, 25øC, Both speciesare significant,although CuCI:•- pre-
2;S=10 -4 m, CI-=0.5 m as NaC1. Cov--covellite, an= dominatesin molarity. Figure 3 shows the pre-
anilite, dj = djurleite. dominantspeciesfor other valuesof acl-.

dominatesover Cu2+only at pH > 8.0 in solutions

of very low Cu content.
Complexesof copperwith organicligands,especi-
ally humicandfulviccomplexes,
are known (Steven-
son et al., 1973), but adequate amounts of these -2
ligands are unlikely to be present in circulating
groundwaiersin the oxidizingenvironment
of or-
ganic-poorred beds. -3
In view of all these,complexes,the form of copper
in solutionand the solubilityof ,coppermineralsare
a ,complexfunctionof the other constituentsin solu- log
-4
tion. Figure 2 portrayssolubilityon an Eh-pH dia- m•cu
gram for a chloride-bearingsolutionat 25øC to indi-
cate the generalform of the relations. The diagram
-5
is drawn for a 0.5 m NaC1 solution with :•S -- 10 4
m. The chloridemolality is approximatelythat of
sea water; the sulfur content is much lower than that
of sea water to simplify calculationsand to match
fresh water ,approximately. However, use of :•S --
-6
Cu•+j
10-• m does not significantlychangethe diagram;
I i i i
brochantiteis not quite stable,molarity of CuSO•
-4 -3 -2 -1 0
(aq) is ,barelyequal to molarity of Cuø'+,Cues is
stable at slightly higher Eh, and djurleite, anilite, log mc•-
and covellite'haveslightly larger fields of stability. FIG. 3. Maximum solubility of Cu at pH 7 as a function
Becauseof the high ionic strength (I) ot•this solu- of chloride content in system Cu-O-H-C1.

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by Juan I. Guzman
 ORIGINOF RED-BEDCOPPER
DEPOSITS 1041

For the cupric species,similar calculations indi-

catethatrncuet+/rneu2+is 0.315 (althoughthe activity
ratio is about0.9), and.thatCuC12(aq)is negligible.
For rnso•- of 10-4, as usedon the diagram,the
CuSO4(aq) speciesis negligible,.butat rnso•2-of
10-• and aboveit is significant,
basedon calculations
analogousto those above for cuprouschlorides.
Boundariesbetweensolidsand aqueousspeciesare
drawn at 10-a and 10-4 total Cu, equivalentto 64 and
6.4 ppm. Taking 1 ppm as the minimumfor sig-
nificanttransportof ore metals,thesevalueswould
be significantfor metal transport.
Comparison of Figure 2 with Figure 1 showsa
very large increasein Cu solubilityat the expense
of the Cu20 and Cu fields, extendingsolubilityup b.. X
to pH valuesof 8.5. Atacamiteappearsas a solid
phase,but the solubilityboundaries in the cupric
regionchangelittle from Figure 1. Only minor 0
additionalsolubilityoccursin the sulfidefield.
Figure4 showsthe relationship of thesesolubility
fieldsto stabilityof somespecies
in the systemFe-S- t'u I
O. A largepart of the regionof CuCla 2- solubility
is seento fall within the stabilityfield of hematite
(or otherferricoxyhydroxides).Within this solu-
bility field,sulfuris presentas sulfate,not sulfide. -.4 3, 5
.
7 9
1
Figure 3 showsthe maximumsolubilityof copper
ionsin equilibriumwith Cu20 at pH 7.0 as a func- pH
tion of chlorideconcentration.Significantsolubili-
ties are reached at about 10-2 m C1-. Fro. 4. Eh-pH diagramfor systemCu-O-H-S-CI, 25•C,
ZS = 10-• m, CI- • 0.5 m as NaCI, with boundariesfor some
An Eh-pH diagramfor 75øC (348øK) has also Fe and S-bearingspecies.Boundariesof Cu speciesat 10•-
beenconstructed,
usingthe dataof Ta.ble1 and the m. Stability of coppersulfidesother than chalcociteis no.t
shoxvn.
relations

H 298 1
log K• = log K208 ppm C1 or more are not normal, although deep
258' ground waters and "conhate"brinesusuallycontain
TAG208 muchhighera.mounts.High-chloridewatersin red
298nF
H
nF
2081- •9• beds seemlikely in two geologicalsituations:near
evaporitesand near zoneswhere cormatewaters are
are verysimilarto thoseat 25øC. moving out of marine sediments.
The relationships
The atacamitefieldnearlydisappears,and the solu- As discussed below,many red-bedcopperdeposits
bility at pH 6.5 to 8.0 is somewhatlarger. are nearevaporiteswhichcouldhavefurnishedhigh-
These results demonstrate that chloride solutions C1brinesto the red sandstones.White et al. (1963,
containingmorethan about0.01 m C1- (350 ppm) table27, nos.5 and9) givetwo examples of oxidiz-
can be effectivesolventsfor copper,evenat 25øC if ing high-C1ground wa•tersassociatedwith evapo-
the oxidationpotentialis maintainedat an inter- rites. These waters contain sulfate .but not detectable
mediate level. Without accessto the atmosphere, •-I2S (i.e., they are relatively oxidized) and rela-
few watersare oxidizingenoughto fall in the cupric tivelyhighCu contents of 0.5 and0.6 ppm. One of
field (Baas-Beckinge.t al., 1960), so that deep the watersis a surfaceseepinto a river, indicating
groundwatersare notexpected to be saturated with shallow,circulation,and the other is a seepin a salt
tenorite or atacamite. In red .beds,organic matter mine. Several other shallow waters with high C1
is rare and local. The widespreadhematiteis indi- are listed in this compilation. Similar brine emerg-
cative of conditions•oo oxidizing for survival of ing as seepsand springsin red-bedareasnearcopper
organicmatter. Waters circulatingthrough red deposits
is reportedby EntwistleandGouin(1955)
beds will therefore tend to remain in •he intermediate and Norman (1931).
Eh rangeof high-copper
solubility. Release of brines from marine sediments into ad-
Shallowcirculating 350 jacent red bedsis expectedduring compaction
groundwaterscontaining of

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by Juan I. Guzman
 1042 ARTHUR W. ROSE

limoniteand hematite,in the latticesof major rock

minerals,or in otherforms. Dissolution or recrys-
tallizationof any of theseminerals,for instance,re-
crystallizationof limoniteto hematite,will allow dis-
solutionof the containedcopper. Walker (1967,
1974) demonstrates
that hematitein certainred beds
hasdeveloped diagenetically
from Fe-bearingoxides
and silicates,and Berner (1969) showsthat hema-
tite is an expectedstablephase. A changein the
Ag(s) .: pore solution from fresh water to chloride solution
Eh
should.tendto promoterecrystallization
of goethite
to hematitebecause
of the reducedactivityof water
in the chloride brine. Selective chemical extraction
of Fe oxidesfrompresent-day streamsediments indi-
'•... AgCI;+AgCI,•..., catesthat the iron oxide componentcontains100 ,to
1,000ppm Cu (Rose and Suhr, 1971; Rose,unpub.
data). Accumulationof 'significantcontentsof dis-

0•AgzS
'%......... solvedcopperby a circulatingchloride-richground
water thus seems feasible.
Precipitationof copperfrom this chloridesolution
I -e • [ I 1 I% [ I I I will occurwhen it encountersreducingconditions,
3 5 7 9 11 whichare usuallygenerated
in sedimentary rocksby
pH .thepresenceoœorganicmaterial or other products,
suchas pyrite or H2S, originallyformed within the
Fie. 5. Eh-pH diagram for silver, comparing chloride-
bearing and chloride-free relations. Dashed line is chloride- reduced environment of organic material. The
free, solid lines are for 0.5 m CI- and 10-• m Ag, dotted localizedaccumulations of fossil logs and organic
line is 104 m Cu from Figure 2. trash in a stream channel, as at the Nacimiento
mine, New Mexico, and at the former Dorchester
sedimentsor during tectonic movements. In oil mine, New Brun.swick (Van de Poll, 1972), con-
wallsin Mississippi,Carpenteret al. (1974) report sti,tuteone form of reducing agent encounteredby
evidence for upwardmigrationof brines(reducing, such solutions. It is likely that the reducing en-
in this case) from the Louann salt into overlying vironment extends some distancefrom the original
clasticsedimentaryrocks. Chloridesolutionsmight organicmaterialdue to transportand mixing of H2S,
alsoenter red bedsduring a marine transgressionor CH4, and other dissolvedreducingagentswith sur-
during extremelyarid epochs. White et al. (1963) roundingwaters. Although native Cu would be the
list severalsampleswith 400 to 2,000 ppm C1 and first precipitateat pH >6.0, apparentlyreducedsul-
oxidized sulfur from shallow (400 m) wells in fur is normallyabundantenoughto form chalcocite,
marine sandstone and shale. Movement of Cl-rich bornite,and chalcopyrite.
solutionsinto red bedsfrom overlyingor underlying The reducingenvironmentmay also occur as an
marine sediments must have been common in the extensivelayer overlying,underlying,or interbedded
past. with a red-bed sequence. This situation occurs at
The requiredamountof porefluid (containing100 Creta, Oklahoma, where the reducing Flowerpot
ppm Cu) to producea deposi.t oœ1 percentCu, 1 km=
TABLE 2. Thermodynamic Data for Ag Species
in area and 0.5 m thick, is calculatedto be available
from a prism of sourcesediment1 km= and 400 m State /xGør(20s) Source
thick if the pore spaceis about 30 percent. Leach-
ing of about 15 ppm Cu from a similar volume of Ag c 0 1

sedimentcouldfurnishthe copper. If the hydrologic Ag+ aq + 18.43kcal/mole 1

situation is such that water is channelled from a AgC1 c -26.24 1
Ag2S c -9.72 1
large sourcearea into a 'small ore deposit,the re- AgCI=- aq -51.12 2

quirementsare less.stringent. The sourceand trans- Ag+ q- CI- = AgCl(aq) KI : 10TM 2

port condi.tions
do not seemseriousproNems. Ag+ q- 2Cla- = AgCl=- K2: 10 5-ø1 2
In an intermediate oxidation state, chloride-bear- Ag+ q- 3C1- = AgClaz- Ka: 10 •'ø4 2
Ag+ + 4C1- = AgC14 a- K4: 10 •'aø 2
ing groundwaterswill tend to leach,copperfrom the
rock. Such copper could be present as traces of 1 Wagman et al., 1969.
oxidized copper minerals, as trace constituentsin 2 Berne and Leden, 1953; Ivanenko, 1975.

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by Juan I. Guzman
 ORIGIN OF RED-BED COPPER DEPOSITS 1043

TABLE3. Ratio of Cu to Ag in Red-Bed Copper Deposits

Locality Cu Ag Cu/Ag Material Reference

Nacimiento, N. Mex. 39-66% 5-7 oz/T 2,000 High-grade
ore Woodward et al., 1974,p. 112-113
Paoli,Okla. 0.75 6 oz/T 40 Ore Shockeyet al., 1974
White Pine, Mich. 1. 30 ppm 300 Ore Brown, 1971
NegraHuanshya,Pa. 3.2 2.9 oz/T 350 Ore Petersen,1965
NuggetSandstone, Wyo. -- -- 40-100 High-gradesamples LoveandAntweiler,1973
Corocoro,Bolivia 65-70 40 ppm 20,000 Concentrates Entwistleand Gouin,1955,p. 562
LenaR., Siberia 1. 20 g/T 500 Ore Narkelyunet al., 1971
Creta, Okla. 2. 30 ppm 700 Ore Johnson,1974

(John- tionsin whichCu is very insoluble,

Shaleoccurswithin a thick red-bed.sequence as discussedby
son, 1974) and at White Pine, Michigan,where the Barnes(1975). In a 0.5 m chloridesolutionat Eh
reducingNonesuchShale overlies,the red Copper = 0.02 v and pH = 6.0 (chalcocite and native Cu
Harbor congl.omerateand underlies the red Freda in equilibriumwith 10-4 m dissolved Cu) calcula-
sandstone (White andWright, 1954). The copper- tions show that the sulfides of Pb and Zn are 6 to 9
bearinggroundwater may encounterthe reduced orders.ofmagnitudemoresolublethanchalcocite and
layer either by simpleflow throughadjacentsand- have a solubilitysimilarto ,pyrite,so that solutions
stone,by being forced to flow through the reduced containing Cu, Pb, Zn, andFe in ratiosapproximat-
layer, as postulatedby White (1971) for White ing theircrustalabundance will precipitate
chalcocite
Pine, or by diffusi.oninto the reducedzone, as dis- and pyrite upon encountering reducingconditions
cussedby Brown (1971). but requireconsiderablymorereducingconditions to
precipitatePb and Zn.
Behavior of Silver and Other Metals
Relation of Red-Bed Copper Deposits to
Although many other metalsform chloridecom- Sources of Chloride Solution
plexes, the only chalcophilemetals'showingcom-
plexing as strongas cuprousion are Ag and Hg If chloride.solutions
are responsible
for dissolu-
(Helgeson,1969). Figure 5 compares the behavior tion and transportof the copperformingthe red-
of silver in chloride-freeand chloride-bearingsolu- bed copperdeposits, then thesedepositsshouldbe
tions, using.the data of Table 2. In the Ag-O-H associated with situations in which a source of
system,silver solubilityis 'significant
only in solu- chloride 'solution exists. Examination of the litera-
tions with Eh in the range of surfacewaters, and ture on red-bed deposits.shows,that most are as-
nativesilveris the stablephaseunderevenslightly sociatedwith evaporites,and the remainderare in
reducingconditions. However, in 0.5 m NaC1, silver situationswherecormatebrinesmay have had access
solubilitiesextendinto the regionof cuprouschloride to the red beds. Davidson (1965) documentsa
complexing Although precipitationof AgC1 would generalassociation
of low temperaturecopperde-
maintaina low Ag+ concentration at low molaritiesof positswith evaporites,and cuprouschloridecom-
CI-, at 0.5. m C1-the complexingis strongenough plexingprovidesa mechanism that accounts
for the
so that AgC1 is not geologicallysignificant. association.
Silver is a commonaccessoryin red-bedcopper For instance, the red-bed copper deposits of
deposits. Table 3 lists silver contentsand Cu/Ag Oklahoma, Texas, and New Mexico are associated
ratios of severalred-bed.copperores. In most de- wi.than extensivearea of evaporitesin the Permian,
posits,the Cu/Ag ratio is 40 to 2,000. Considering as illustratedin Figure 6. Halite and gypsumare
.that the ra.tio o.f crustal abundanceof Cu to Ag is present in the subsurfacein many of these areas
500 to 1,000, silver is enriched about as much as (JordanandVosburg,1963). The FlowerpotShale,
copper in forming most of the red-bed deposits, in which the depositsat Creta and Mangurn,Okla-
except at Corocoro. Becauseof the different Eh vs homa, .occur,is a reducing carbonaceousshale en-
pH behavior.of silver and copper .solubilities,and closedin red bedsand interlayeredwith and over-
becauseCu/Ag in the source material may vary lain by evaporites
and,in particular,overliesa rela-
considerably,it is not surprisingthat the ratio in tivelypermeable sandstone(Fig. 7; Ham andJohn-
ores showsconsiderable variability. son, 1964; Johnson,1974). In centralOklahoma,
Other basemetals,suchas Zn, Pb, and Cd, form the Wellingtonevaporitesextendan unknowndis-
weaker chloride complexesand have much more tancefarther east of the limit of the youngerevapo-
solublesulfides,so that their solubilitiesat low tem- ri.tesshownon the .sectionand are a typical faciesof
peraturesare not sostronglyaffectedby the presence the Wellingtonformationin whichthe red-bedcop-
of chlorideand are relatively solubleunder condi- per deposits occur(MacLachlan,1967,p. 88).

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by Juan I. Guzman
 1044 ARTHUR l/V. ROSE

I
COLORADO • : KANSAS

P i OKLAHOMA
.... }
=.½. ß .:! TEXAS

NE MEXIC i . oo
"-x/"-' -_

• 200KM.
•. I

Evaporites-M.Permian
.....

'•i,%f Post
Permian
host_
" Middle
orLatePermian
host_
Early Permian host ........

ß Producing
mine
.........

Ft. 6. Relationof red-bedcopperdeposits

to evaporitesin Oklahoma,Texas,and New
Mexico. Boundaryof evaporites after Ham t1960).

In New Mexico, evaporites,includinghalite, are 'somedepositslie outside the publishedlimit of

commonin the Permian in areasof many of the de- evaporites,subsurface stratigraphicdata are limited,
posits; and in north-centralNew Mexico, where and an extensionof the evaporites is not improbable.
Salt is also presentin the Permianof southwestern
DogCreekShale DogCreekShale Utah, where other red-bed copper depositsare
Yelton
salt•.• known (McKee et al., 1967).
Love and Antweiler (1973) describeCu-Ag-Zn
• Blaineanhydrite•o Blai
• s••un•
ne
(;y-p occurrencesin Wyoming in oil-stainedreducedzones
•• ø•'Glørieta
ss•"•'•• Flowerpot/
l:m.
.•____•h
ickasha at the top of the normally red Nugget Sandsto.he.
The overlyingGypsumSpring memberof the Twin
Flowerpot
salt • Sandstone CreekLimestonecon.tains
gypsumand anhydrite.
In the Corocororegion of Bolivia, gypsum and
•Upper
Cimarron• halite are known in the units containing the de-
•m ' tlennessey
Shale posits(Ljunggren and Meyer, 1964), as summarized
salt in Figure 8. Saline springsoccur in the area, and
11ennesseysha]e presentmine waterscontainup to 7 percentchloride
"RedCave"inTexas• •/Garber (Entwistle and Gouin, 1955).
In the Southern Siberian platform, a number .of
(gray
shale)
Upper
anhyd
• Wichita
ellington red-bedcopperdepositshave beenrecognized. One
group of red-bed .copperdeposits.occursin Upper
•• unit
/ Formatio•
Førmat
[øn
.•'• shaleunit
• • Lower salt-
• • anhydrite
• unit
Cambriansandstones alongthe marginsof .theSiber-
ian platform (Narkelyun et al., 1969). The prov-
ince also includesthe importantUdokan depositin
Proterozoic rocks, which occurs in interbedded ter-
• • Chase
Group Pontotoc
Group restrial red sandstones and tidal marine rocks. Also
in this region,the Yeneseizone of red-beddeposits
Ft. 7. Stratigraphic relations in Permian of western occurs in Cambrian limestones and terrigenous
Oklahoma and Texas, af.ter Jordan and Vosburg (1963), clasticswith intercalatedgypsumand anhydriteand
showingassociationof evaporiteswith the Flowerpot .shale,
which contains the copper. occasionallybeds of halite (Kutyrev, 1969). In

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by Juan I. Guzman
 ORIGIN OF RED-BED COPPER DEPOSITS 1045

Umala group (tuffs)

6000.
Corocoro group
ft.
Crucero fm. (sandstone and tuff)

4000- Vetas congl. (congl. and sandstone)

Ramos fm. (red sandstone and shale with evaporites)

2OOO

Chicarilla sandstone (gray-brown, arkosic)

Coniri conglomerate

Llanquera sandstone (red sandstone with shale)

Chuquichambi group (gypsiferous shales and marls)

Significant deposits in interval

Fro. 8. Stratigraphyat Corocoro,Bolivia,showingassociation

of Cu deposits
with
evaporites (after Ljunggren and Meyer, 1964).

Uzbekistan,Petrov and Chistyakov(1972) report tracesof uranium.The more southeasterly

groupare
cupriferoussandstones
in a red-bedsequenceinter- primarilyuraniumdepositswith only smallamounts
layeredwith evaporites. of copper. Two possiblesourcesof chloride solu-
Most of theseRussiandepositsoccurnear evapo- tions exist in this region. Halite and anhydrite of
rites that may have furnisheda sourceof chloride. Silurian age occurbeneaththe Catskill in the north-
Although gypsumis much more commonthan halite western part of the area. Figure 9 shows 50 feet
at the surface,halite is probablymuchmore com- or more of salt in the Silurian. The eastern limit
monat depth,as is foundin Oklahoma(Jordanand of salt is not well definedbecausevery few wells are
Vosburg, 1963). At Udokan, connatemarine wa- availablein this region. A secondpossiblesourceof
ters may have furnishedthe chloridefor dissolution chloride is connate waters from the marine section at
of copper.
In Peru, red-bedcopperdepositsat Negra Huanu-
shaandDonaBasilia(Kobe,1960;Petersen,1965)
occurin a regionknownto containsmallevaporite
bodiesand .perhapslarger units (Haapala, 1953;
Nagell, 1957).
In Canada,Kirkham (1974) givesexamples
of Cu
in red bedsnear evaporitesin Nova Scotiaand New
Brunswick and in the Redstone area of the northern
Cordillera.
In Pennsylvania,
numeroussmallred-bedcopper Red
Bed
Cu-U
Occurrences
] ,,>
in Devonian
ß

depositsoccur in Devonian sandstones

and shalesof
the Catskill formation (Fig. 9). Many of these
occurrences contain uranium in trace .to moderate Fro. 9. Distribution of red-bed copperprospectsin Devon-
amounts(McCauley, 1961). The more northwest- ian of Pennsylvania in relation to Silurian evaporites.
Dashed line is southeasternlimit of evaporitesfrom Fergu-
erly occurrences
containpredominantlycopperwith son and Prather (1968).

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by Juan I. Guzman
 1046 ARTHUR I/V. ROSE

the base of the Catskill, which ex.tendsbeneath the oxidationstatein large volumesof rock. Silver has
entire region of copper-uraniumoccurrences(Glae- propertiessmiliarto copperand is usuallyconcen-
ser, 1974) and locallyinterfingerswith the red beds. trated in .the red-beddeposits. Similar sourcesof
Considerable amounts of saline cormate fluids must metal and mechanismsto transport shouldbe con-
have escapedfrom the marine sectionduring dia- sideredfor the other low temperaturecopper de-
genesisand.mayhavedissolved copperfrom the red- posi.ts.
bed sequenceand redepositedit in reducingzones.
The very large Cu depositsof the Kupferschiefer Acknowledgments
and Zambia-Zaireappear to differ somewhatfrom The manuscripthas benefitedconsiderably from
the typical red-beddeposits,but both occurin close reviewsby H. L. BarnesandH. Ohmoto. Prepara-
association with evaporitesand red beds. The Kup- tion .of this manuscripthas beensupportedby the
ferschieferhas generallybeenconsideredas syngene- Mineral ConservationSection,Collegeof Earth and
tic, but Rentzsch(1974) givesevidence.thatat least Mineral Sciences, PennsylvaniaStateUniversity.
someof the copperore cuts acrosslithologicunits
and conforms•o the marginsof red ("Rote Faule") DEPARTMENT OF GEOSCIENCESAND MINERAL
areasin .theunderlyingand adjacentsediments.An- CONSERVATION SECTION
neis (1974) describesabundantanhydrite in the THE PENNSYLVANIA STATE UNIVERSITY
Zambiandeposits .andsuggeststhat somedeposition 119 MINERAL SCIENCES BUILDING
was not during sedimentationbut by later replace- UNIVERSITYPARK,PENNSYLVANIA
16802
ment. Thus, deposition of Cu in thesemajor dis- September
2, 1975;March19,1976
tricts may alsoinvolve.transportin Cl-rich brines
REFERENCES
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Bugden,W. G., and Shelton.R. A. J., 1970,Thermodynamic
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cipitatedby sulfatereductionor replacementof py- ments on galvanic cells with a solid electrolyte: Inst.
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usuallyreducingenoughso 'Thatcoppersulfidesare 634.

stableandcopperis insoluble,thuspreventingleach- Carpenter,A. B., Trout, iV[. L., and Pickett, E. E., 1974,
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Chaltykyan, O. A., 1948, On the properties of cupro-com-
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uniquelysuitedto maintenance of the appropriate Russian).

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by Juan I. Guzman
 ORIGIN OF RED-BED COPPER DEPOSITS 1047

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by Juan I. Guzman
 104g ARTHUR W. ROS'E

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by Juan I. Guzman