SECONDARY

ENRICHMENT

IN

ORE-DEPOSITS

OF

COPPER.

JAEsFurmAN
Among the later conceptionswhich have been establishedin
the last five years regardingthe formation of ore-deposits;such
as the shallownessof the meteoric groundwater; the necessarily
correlative importanceof magmatic waters; and the secondary
enrichmentof veins; the last-namedis, in its practical applications, of the greatest importance. The other two are more
largely theoretical, although not for that reason of any less
scientificinterest. Furthermore,it is true that secondaryenrichment hasbeenspeciallyelaboratedin the caseof copper,and the
investigations,
whichhaveprovedreally fruitful havebeenchiefly
basedupon its ore-deposits. Neverthelessthere is little doubt
that severalother metalswill, in time, justify the samestatement
regarding them.
Copper is a peculiarlysolublemetal in nearly all of its compounds. It is almost invariably associatedwith sulphidesof
iron, which are exceptionallyvulnerableto descendingoxidizing
waters. In certain casesof the first magnitudethe coppersulphides,or rather the copper-ironsulphides,are found in association with limestone,so that acid solutionsproducedby their oxidation cannotmigrate far before being subjectedto a powerful
alkaline reagent.
Copperactsboth as monadand dyad in its chemicalrelations,
but its dyad quantivalenceinvolvesgreater stability in the compound. Its solutionsare very susceptible
to reducingagents,and
the efficientprecipitantsof this characterare now recognizedto
embrace,not only the organicor carbonaceous
matter, which was
much trusted by earlier writers and which was supposedto be
derived both from the sedimentarybeds of the wall-rocks and
from the descendingwaters from the surface,but also the excessof sulphur which appearsin certai.nminerals like pyrite,

whereinthere is more than is absolutelyrequiredto satisfythe

Ii

12

JAMES

FURMAN

KEMP

iron. The strong affinity, moreover,of sulphur for oxygen and

its ability to form sulphurouscompoundsas contrastedwith the
more fully oxidized sulphuric,often place this elementin situations favorableto a reductionof coppersalts.
The influence of the wall-rocks must also not be overlooked,

sinceit is of the highestimportance. Where the rocksconsist

of silicates,as 'in the caseof the eruptives,the productsof secondary enrichmentare chieflychalcocite,covellite,and chrysocolla;
but where limestoneformsthe walls the blue and greencarbonates
and the red oxide predominate. The garnet contact zones,
whose importancewe are but beginning to appreciateoften start
with chalcopyriteand yield chrysocollaas the oxidized result, a

very seriousfactor in the metallurgicaltreatment of low-grade

oresin a siliceousgangue.
If these general relations are kept in mind we may pass in
review the chief copper ores with commentsupon them, which
it is hopedmay servein a measureto emphasizethe crucialpoints
and stimulate close study of their successionin formation or
paragenesis. While not always essential,yet microscopicstudy
is often a great aid in such investigationsand enough is now
known to establishthe fact, that the succession
is not always uniform and that for examplechalcopyritemay not only not be the
original mineral with which the reactionsbegin, but may even
be the last memberwith which they close.
Copperhas somethirteendifferentmineralswhich may be consideredores,and someeighty-fiveor ninety others into which it
enters as the only or the most important base. Almost none of
the latter are of more than minor or exceptionalimportancein
secondaryenrichment and they will not be further mentioned.
In the twelve mineralsconsideredof chief importancetetrahedrite
and enargite are used as general names for both arsenicaland
antimonial varieties. With these limitations we may establish
the most important ores as the following:
SULPI-IIDES.
I.
2.
3.
4.

Chalcopyrite,
Bornite,
Covellite,
Chalcocite,

CuFeS=,(Cu2S,Fe2S3).....................
CmFeSs(3CmS,FeS0 ....................
CuS .....................................
Cu=S ....................................

CU.
34.60
55.50
66.48
79.80

ENRICHMENT

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ORE-DEPOSITS

OF COPPER

13

SULPHARSENIDES AND SULPHANTIMONIDES.

5. Enargite,
6. Tetrahedrite,

CuaAsS
(3Cu2S,As2S)...................
CusSb2S7
(4Cu2S,SbSa)...................

48.4o
52.06

7. Melaconite,

CuO ....................................

78.86

8. Cuprite,

CuO ...................................

88.80

OxIDv. S.

CARBONATES.

9. Malachife,
Io. Azurite,

CuCOa,Cu(OH) ..........................
2CuCOa,
Cu(OH) 2 .......................

CuSiOa,2H20 ............................

HY)RATm)

Chrysocolla,

57.27
55.1o

SILICATV..

36.00

OXYCHLORIDE.

2. Atacamite,

CuC1,(OH) a ............................

I3. Native Copper,

Cu ......................................

NATIVE

59.29

METAL.

oo.oo

The chief omissions from the list are the arsenates and related

compounds
which constitutethe secondarymineralsin the Tintic,
Utah, district, where they have probably been derived from
enargite, and where they are presentin great variety. So far as
we know at present,atacamitehas no specialimportancein North
America although an abundant ore in Chili. Twelve minerals
therefore embracenearly all those of the first importance.
While not often succinctlystated,yet it has beenthe belief or
assumptionof nearly all observersuntil recently,that the starting
point of copper-enrichment
hasbeenchalcopyrite;and with much
reason,thosewho have written or reflectedupon the subjecthave
in the past harked back to this mineral as the natural point of departure. In the Sudbury,Ont., type of deposit,where chalcopyrite and pyrrhotite are disseminatedin basic eruptives,this is
true: It also holds good in the pyrrhotite-chalcopyrite
ores of
the eastern Green mountains, and at Ducktown, Tenn.

In the

latter locality there is someevidencethat the chalcopyriteis, in

part at least, of later introductionthan the pyrrhotite. Chalcopyrite as an original mineral so far as we know, accompanies
still
more abundantpyrite at Pelly's Island, Newfoundland; Capelton, Quebec; Arminius, Va., and in some of the Ducktown ore
bodies. It is likewise in many garnet zones,and with it in all

14

JAMES

FURMAN

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these the secondaryreactions appear to have begun. Yet as

already remarked and as will be stated in detail under chalcopyrite itself, it may be the last numberin the secondaryseries.
On the other hand the recent observationsof Weed at Butte;

of Ransomeand Lindgrenin Arizona and in a comparatively

small way, of the writer at the Rambler mine, Vyoming,have
suggestedthat lean copper-bearing
pyrite was probablyin these
casesthe mineral originally depositedand that with it the reactionsbegan. In Dana's "System of Mineralogy,"fifth edition,
the followinganalysisis given:
PYRITE FROM CORNWALL,PA., s J. C. BoorI.

Fe,
q-63.4
56=
Cu, 44.77
2.39 q-- .80
.038 }
S,

53.37 q- 32

= 1.67

.84or Fe=oCu,S42
1.67

In someexceedinglyimportantexperimentsin the production

of chalcocitein the laboratory,H. V. Winchellbeganwith pyrite
containing.5 copperand taken from. the veins at Butte2 If
we assumethat the copperactually replacedthe iron in the above

casesand was not includedchalcopyrite,

a startingpoint is provided for secondaryreactionswithout involving chalcopyrite
and we may at least hold the view in a tentativeway. All
who are familiar with the mines at Butte are aware that chatco-

pyrite is a relatively rare mineral there, and that it is not an im-

'portantcontributor
to theoutputof copper.It is notprominent
in the Arizonamines,the copperin the sulphuretted
oresthere
as at Butte, cominglargely from the little black films of chalcocite upon pyrite.

In a generalway the interestand importance

of the question
lies in this phaseof it. Copper,like all the othermetalsexcept
iron and aluminum,is a very rare elementin the economyof
nature. Its concentration
intoan ore-bodyrich enoughto mine
is an extraordinaryphenomenon,far more so than that of iron

andstillmoresowhendeveloped
Withoutthegreatpreponderanceof iron. If, in the first precipitation
or formation,it is a
H. V. Winchell,"Synthesis
of Chalcocite
andits Genesis
at Butte,Mont.,"
Bulk Geol.Soc.Arner.,XIV., 269-276,9o3. Eng. and Min. Jour.,LXXV.,
728-784, 19o3.

ENRICHMENT

IN

ORE-DEPOSITS

OF COPPER

15

minorcomponent
alongwith iron,and.whenonceplacedin these
favorablerelationships,
if the percentage
in the oresis raised.
by
secondaryenrichment,a less remarkableand exceptional,and
thereforea moreprobableorigin is indicated. Passingthis question with the remark that it deserveswide-spreadconsideration

and the test of applicationin specialcases,wherethe succession

of the mineralscan be worked out, the individual ores may now
.be passedin review.
CHALCOPYRITE.

Chalcopyrite
isa peculiar
coxpound
whose
chemical
formula,
CuFeS2, is open to severalinterpretations. By doublingthis
form, it may be expandedinto Cu2S,FeSa;that is, into a molecule of chalcocitecombinedwith a moleculeof a ferric sulphide

whichisnotknown
byitself.Theformula
alsoimplies
thatthe
copperacts with its lower or monad quantivalenceand the iron
with its higher.or triad. A graphicformulamaybe constructed
as follows:

sFe?S--Cu

FeS2orFe,/ inwhich
Werethereoriginally
present
pyrite,
XS

somedyad copperreplacedthe ferrousiron, then, if by any possible reactionthe quantivalenceof the iron were increasedto the
triad state and that of the copperreducedto the monad,--reactions which are in a way complementary,--twomoleculesof
cupriferouspyrite would just yield chalcopyrite. ProfessorPaul

Groth has suggestedin his "TabellarischeUebersichtder Mineralien," a work, which in its suggestiveand critical character,
has beenin the highestdegreefruitful, that chalcopyritemight
be a salt of a supposed
acid, I-IFeS, in which iron possessed
the
triad quantivalence.
x The changefrom cupriferouspyrite might
also take placewith the probableproductionof by-productsnot
referred to above,and as illustratedin the following equation
' Comparein this connectiona letter signedAgricola, in the Engineering
and Mining Journal, June I5, I9o5, p. xx47.

16

JAMES

FURMAN

KEMP

whichrequirescupriferous
pyriteat onepointto be oxidizedand
yield coppersulphatefor the enrichmentof pyrite elsewhere.
2FeS2q- 2CuSO----Cu2S,Fe2Sa
q- 2SO q- 40

In coppersmelting,underconditions
of reductionand with
oxygenenoughto combine
with the iron,we knowthat at high
temperatures
coppergoesto the sulphurand iron oxideto the
silicaby preference.In dilute solutions,however,and having
regardto ionization,thermodynamic
reactions
donot alwayshold
goodand one may speculate
as to whetherany soundchemical
principleis opposed
to this reaction,whereinwith respectto sulphur iron actsas a reducingagent on the quantivalence
of the
copper,profiting just so much in raising its own combining
power.

At least two instances have now been observed in which chalco-

pyriteappearsasa secondary
mineraland oneof verylate formation in the series. After microscopic
studyof a suiteof bornite
specimenscollectedby the writer at Copper Mountain, near
Princeton,B. C., JulesCatherinet was able to establishthe folIo.wingparagenesis:
. Bornite.

2. Corellite

and limonite.

3. Chalcocite.
4. Chalcopyriteand chalcocite.
Thus the yellow sulphidewas in the last group. Recentlyat
Butte, covellite has been found with thin films of later chalco-

pyrite filling the crevicesbetween its tabular crystals. The

Buttecovellite
isoneof thesecondary
products
fromthechanges
in cupriferouspyrite and it is of great interestto find the chalcopyrite formed so late in the process.

Chalcopyrite
occurssooften in association
with pyrrhotitethat
one cannotbut speculateupon the possibilityof a cupriferous
variety of the latter from which reactionsmight start and yield
the former. A few trial equationswill show,however,that the
changescan only take place with the loss of iron from the
" Copper Mountain, British Columbia," Engineering and Mining Journal,
June I9, 9o5, p. 25.

ENRICHMENT

IN

ORE-DEPOSITS

OF COPPER

17

pyrrhotite,sincethe atomicratio of iron to sulphurin it is 7:8,

whereasin chalcopyriteit is 2:3.
In passingfrom chalcopyriteone may again remark that there
is no doubt of its occurrence,so far as our observationsgo, as
an original mineral in many ore-bodies;but enoughis now known
to prevent us attributing this characterto it in new' instances
without close observationand interpretation.
BORNITE.

Bornite, on accountof its high percentageof copper,has been

generally considered'
a product of secondaryenrichment,so far
as it hasbeenconsideredat all. Its condensed
formula, CusFeSs,
may be doubledand expandedinto 3Cu2S,Fe2Ss,and this may
be written graphically.
Cu--StFe--S--Cu

Cu--S--FeS--Cu
As in chalcopyritethe iron acts as a triad and the copperas
a monad. The possibleacid of which this might be a salt is
HsFeSs. An equationsimilar in all respectsto the one given
above under chalcopyritecan easily be written for bornite as
follows'

2FeS q- 6CuSO -- 3CmS,FeSsq- 4SO q- 160

It has, however,little significance

other than to suggestthat
bornite would requirean excessof coppersulphateand in its
presencewould perhapsform insteadof chalcopyrite.Many
other factorsmight enterinto the combination
and modifythe
mathematicalexactnessof the expression.
Borniteis not, however,necessarily
nor alwaysa secondary
mineral. In the caseof CopperMountain, B.C., abovereferred
to, it occurredas an originalmineralin largeand coarsepeg-matite dikes or veins, in several claims; and in others filled small
a.nd narrow crevicesin the country rock, while closeat hand,

similar crevicescontainedfeldsparsand related peg-matitic

Besidesthe reference
to Mr. Catherinet's
paperjust given,seealsoJ. F.
Kemp, Trans. Amer. Inst. Min. Eng., XXXI., 182, and O. N. Scott,;;ournal
CanadianMining Institute, V., 493, 19o2.

I8

fAMES

FURMAN

KEMP

minerals. The parageneticchangesbeganin this casewith bornite. The peacockore furnishesan interestingcasefor further
study and definiterecordsof its relationsand derivationmight
be much amplified.
COVELLITE.

Covellite,CuS, the normal sulphideof dyad copperis a beautiful blue mineral, which hasbeenesteemeduntil recentlyto be a
rare one in America.

It remains one of the least common of the

sulphur compoundsof copper,even though it is the usual one

which we obtain in the reactionsof the laboratory. It occurs
in amounts of some size at Butte, especiallyin a crushedand
kaolinizedzone in the Grey Rock mine, Wyoming. It is known
at Bingham, Utah, and doubtlessin many other camps in a
small way. Nevertheless,its rarity will be apparentfrom the
fact that a considerablequantity of the Rambler covellite was
sold by the poundto dealersin mineral specimens,
rather than
to the coppersmelters.

Covelliteis, so far as known, a secondarymineral and results

from the reactionsproduceduponthe leaneroriginal sulphides,

by the descendingatmosphericwaters and the subsequentreduction and precipitationof the coppersulphide. T.T. Read has
worked out the paragenesisat the Rambler mine, Wyoming, as
the following:
t. Chalcopyrite.
2. Covellite

and chalcocite.

3. Pyrite.
He suggeststhe following reactionsas perhapsapplicable:
Chalcopyrite.

Corellite.

CuFeS=q- CuSO4= 2CuS q- FeSO4

Chalcopyrite.

Chalcocite. Corellite.

CuFeS2q- 2CuSO, q- SO2q- 2HO -- Cu=Sq- CuS q- FeSO, q- 2H=SO,

Chalcocite.

Corellite.

Cu,S q- H, SO, q- O = CuS q- CuSO, q- H=O

As H. V. Winchell has shown, the presenceof the reducin

agent SO2 leads to the formation of chalcocite,while it would
aT. T. Read, "Platinum and Palladium in Certain Ores," Engineering and
Mining fournal, May 25; I9O5, p. 985.

ENRICHMENT

IN

ORE-DEPOSITS

OF COPPER

I9

appearthat in its absenceor in its presencein small quantity,

corellite may form. The relative rarity of corellite suggests
that SO. is almost always present. The interesting case of
pyrite as later than both the simplecoppersulphides,established
by Mr. Read, is striking and affords another reversal of the
ordinary succession.Starting with bornite Mr. Catharinethas
given the following reaction:
Bormte.

Covellite.

Limonite.

4CusFeSs-3-60 -3-3H20 -- 2CuS -3-2Fe2Os,3H20

This coincideswith the relations shown in the microscopic.

slides,in which, in veinletscrossingbornite, covellite formed a
band next the walls with limonite

in the center.

CHALCOCITE.

Chalcocite(copperglance,redruthite)is the blacksubsdlphide,Cu.S,in whichthe copperexercises

monadquantivalence.
Althoughsometimes
in orthorhombic
crystals,it is almostalways
massiveor in blackcrustsor pulverulentcoats,which, as W. H.
Weed has shown in the caseof Ducktown, have sometimesbeen
taken for melaconite, the black oxide.

So far as observed and

interpreted chalcociteis a secondarymineral and must be

esteemedto-day the most important one of all, since as H. V.

Winchell has remarked,it probablyfurnishesthe gredterpart

of the copper now produced in North America. The latter

writer, in a very interestingand very importantseriesof experimentsin which he endeavoredto reproduceartificiallythe reactions taking placein the veinsat Butte, has shownthat the
chalcocite
moleculewill be precipitated
in the presence
of SO.
as follows. If we recallthat the ordinaryprecipitateof copper
sulphide,formedin the laboratoryby passingH2S throughan
acid solutionof copper,is CuS, it becomesevidentthat, to obtain
Cu.S,somereducingagentmustbe present,yet onenot strong
H. V. Winchell, "Synthesisof Chalcociteand its Genesisat Butte, Mont.,"
Bulletin Geol.Soc.Amer., XIV., 269-276,9o3. Eng. and Min. Your.,LXXV'.,'
782-784, 9o3. In this reference will be found a review of the experiments
for the artificial productionof chalcociteand of the general chemistryof
the precipitation of copper sulphides.

20

JAMES

FURMAN

KEMP

enough to bring down native copper. Reasoningin this way

Mr. Winchell placed in a jar some lean copper-bearingpyrite
(Cu 1.5o) from the Butte veins,in a slightly acid solutioncontaining also SO2. After three monthsthe pyrite was coatedwith
a black crust of chalcocite;whereas in a similar jar and in a
slightly acid solutionwith no SO2, the same pyrite remained
bright and unchangedfor two years. Experiment also showed
that SOg is liberatedby the actionof pyrite and chalcopyriteupon
CuSO4, a salt which beyondquestionis yielded by the action
of oxidizing waters upon the natural sulphides.
Various other reducingagents,which are strongenoughto deprive two moleculesof coppersulphateof six atomsof oxygen,
releaseSOg and leave the two atoms of copperfree to combine
with the remainingatom of sulphur,may be expectedto lead to
chalcocite. Organic matter in one descendingcurrent of surface water, which might meet another current, whoseoxidizing
action had availed elsewhereto yield copper sulphate; ferrous
iron salts; and the ferrous oxide in magnetite, will all occur as
possibilitiesto one who reflectsupon the subject,but no one of
these is so generally presentor so probablea reagent or in such
quantity as pyrite with its excessof sulphur.
Chalcociteis especiallyprone to form in veins in rocksconsisting of quartz and the silicates,as in the granites of Butte, the
mica-schistsof Ducktown and the porphyries of Morenci,
Cananea and Bingham. Where, however, limestonesform the
walls, malachite,azurite and cupriteare in greater quantity and
are the natural resultswheneverthe oxidized solutionsmigrate
beyondthe influenceof the pyrite in the unoxidizedore-body,or
meet waters coming in from the wall-rock itself. One can only
speakin approximatetermssincethe phenomenaare not possessed
of mathematical

exactness.

The importanceof chalcocitehas only beenappreciatedin recent years. In earlier times it was not regardedas a specially
prolific sourceof copper,but now that we understandits enriching influencein bringing lean, original pyrite up to profitable
grade--and now that processesof concentrationhave been so
wonderfully improvedas to treat very low-grade impregnations

ENRICHMENT

IN

ORE-DEPOSITS

OF

COPPER

2I

(forinstance
atBingham,
UtahandEly,Nev),
theblack
copper
glancehas comeinto the very fore-front of the ores.
ENARGITE.

Enargite, 3Cu2S,As2S5and Famatinite 3Cu2S,SbS5suggest

analogiesat oncewith the formula of bornite, 3CuS,FeSa,and
in their relationsto questionsof enrichmentthey are similar.
That is they are not necessarilyof secondaryformation and
probablyare among the original vein-fillers. At the sametime,

the formulasandthe knownfactsof occurrence

in instances
give
ground for the former interpretation. Enargite is much the
most importantmemberof the pair and it alonewill be hereafter
specifically
treated. If, as in the previouscasesof chalcop.yrite
and bornitewe tentativelyconsiderenargiteand famatiniteas
salts of acids,the latter would be respectively,
HaAsS and
HaSbS. Thoughregardedbut a few yearsagoasa ratheruncommonore, yet the abundance
of enargiteat Butte hasservedto
bringit into greatprominence
andthe interesting
and valuable
observations
of W. H. Weed uponthis localityare almostthe

onlyinstances
in whichits truecharacters
havebeenspecifically
treated. In Mr. Weed'spaperthe view is advanced
that long
after the veinsof leancopper-bearing
pyriteshad beenformed
newshattering
occurred
andin connection
withlaterigneous
intrusions
a new,uprising
series
of arsenical,
copper-bearing
waters
entered
andenriched
theolderveinswith laterenargite.In this
senseenargiteis really an originalmineral,althoughof such
late introduction.At Tintic, Utah, wherethe veinshavebeen

described
by TowerandSmith
enargiteappears
to havebeen
theoriginalmineralandfromit camethearsenates,
carbonates,
etc.,whicharethesecondary
results,
nowrepresented
in all the
mineral-cabinets of the world.

Close
paragenetic
observations
onotherdeposits
of enargite

wouldbe of greatinterest. The ore is knownin severalother

xW.H. Weed,"OreDeposition
andVeinEnrichment
byAscending
Hot

Waters,"Trans.Amer.Inst.Min. Eng.,XXXIII., 747,9o3.

Geo.W. TowerandGeo.O. Smith,XIX., Ann.Rept.Div. U.S. Geol.

Sure., Par III., pp. 79 and 720.

22

JAMES

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placesin North America where its depositsare not so large as to

be unduly formidable. The observer may carry in mind as a
working hypothesisthe surmiseas to whether copper solutions
may developit from mispickel,a much more widely distributed
mineral.
TETRAHEDRITE.

Tetrahedrite (gray copper) 4Cu2S,Sb2Saand Tennantite,

4Cu2S,AsgSa,are inverselyrelated much as enargite and lamafinite, but in the present case the antimonial compoundis the
more common.

Considered

as salts of acids the latter would be

respectivelyHsSbgS7and HsAsgS7. Both these minerals are

seldomof the above simple compositionbut have a number of
metals replacingthe copperin greater or lessquantity. Among
these silver is the chief element of value and as a result, gray
copper is more often sought for its silver than for its copper.

Thenatureof theformulas
suggests
secon.
daryenrichment
with,
in the arsenical varieties, mispickel as a possiblenucleus--but
many facts of occurrencelead to the conclusionthat in some
veins it is an originally depositedmineral. Thus in those of
Clear Creek Co., Colorado, the tetrahedrite is associated with

galenaand blende,extendsto considerable

depths,and gives, at
least to the cursoryobserver,the impressionthat it is one of the
"first

settlers."
MELACONITE.

Melaconite, often called also Tenorite, the black protoxide

CuO, is a comparativelyrare mineral. It is doubtlesstrue that
the black pulverulent crusts which have often. been considered
reelaconitewere really chalcocite,and in suchcasesa blow-pipe
test for sulphur is advisablebefore drawing too confidentconclusionsregarding paragenesis. Melaconite and cuprite are re-

lated in muchthe sameway as covelliteand chalcocitealthough

contrasted in that the former are the results of oxidation and the

latter of reduction. Yet it would appear to be true that with

abundant oxygen present, melaconiteresults, whereas, with in-

sufficientoxygen or in the presenceof some reducingagent,

which makes itself felt to this degree, cuprite the sub-oxideis
precipitated. Melaconitewell deservesfurther studyand obser-

ENRICHMENT

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23

vationwith the objectof throwinglight on the circumstances

of
its formation.
CUPRITE.

Cuprite, the sub-oxide, CuuO, is a not uncommon gossan

mineralbut appearsto be most abundantwhere limestones

are
associated
with the originalsulphides
or at leastwherethe alteration and seconda
N- enrichmenthavebeenprolongedand thorough. As remarkedabove,insufficient
oxidationmustbe necessary for its productioninsteadof melaconite,but the probable
courseis the production
of sulphateor still later.carbonate,
which
has then beenreducedto cuprite. Not infrequentlynative copper is associated
with cupriteand this fact emphasizes
the conditions of reductionnecessaryto its formation.
In later phasesand with changedconditionscupritemay pass
into malachite. Pseudomorphsof the latter after the former
are familiar to all studentsof mineralogy. Among American
localitiescuprite has been most extensivelydevelopedin the
southeastern Arizona

mines.

MALACHITE

AND

AZURITE.

Malachite, the green hydrous carbonate, CuCOa,Cu(OI-I)_.

and Azurite/ the blue, 2CuCOa,Cu(OH)2 are with chrysocolla,

the commonest,
products
of the oxidation
of copper
sulphides.
If we assumethat coppersulphate,affordedby the oxidationof
cupriferouspyrite or of chalcopyriteor evenof one of the secondary sulphides,meets calcium carbonatein solution necessarily
These two closely related compoundscan be best understood when written
graphically, viz:

Malachite,

H--O--Cu--ONfi
H__O__Cu'O
CO
It--O--Cu--Oc
O
O/----

Azurite,

CU(o

c----O
H--O--Cu--O
/

24

- JAMES

FURMAN

KEMP

as the bicarbonate,
the followingreactionprobablyexpresses
the
changewith at least an approximationto the truth.
Calcium

bicarbonate.

VIalachite.

2CuSO,-t- 2H2Ca(COa)2-- CuCOa,Cu(OH) q- 2CaSO,q- 3C0 q- HO

This wouldleavethe anhydritemoleculein solution. Whether it

wouldcrystallizeas anhydriteor as gypsumis questionable,
at all
eventsneitherof thesemineralsis a particularlycharacteristic
associateof malachiteand the presumptionis, that the calciumsulphate passesaway in solution. The reactioncastssomelight on
the commonassociationof the coppercarbonatesand limestone.
Carbonatedwatersof themselves
would scarcelysufficeto break
up so stronga compoundas coppersulphate.
The reaction
Calcium

for azurite
bicarbonate.

is similar.

Malachite.

3CuSO, q- 3HCa (COa)2m 2CuCO Cu (OH) q- 3CaSO, q- 4C0, -Jr-2HO

The carbonates
are almostinvariablycloselyassociated
and the
causeof the productionof one rather than the other is not apparent. It must be physicalrather than chemicalor elsecaused
by the presenceof some third componentin the process,.since
the ratio of the coppersulphateto the calciumbicarbonateis the
samein both equations.
CHRYSOCOLLA.

Chrysocolla, the bluish-green, hydrated silicate CuO,SiOg,

2H20 , is especiallydevelopedamid porous or open-textured
siliceousrocks, suchas tuffs or in the garnet contact-zones. It
alsooften appearswith malachiteand azurite,probablyresulting
from the gelatinizing silica which we find in many limestones.
It may be written graphicallyas

H--0--Cu--0
H--0

H--03S

H--0

from which we see that it is a partially satisfiedmoleculeof

orthosilicic acid. Some weak compoundof copper in a relatively dilute solutionwould seemto be necessary
to its formation,
or else it may perhaps form in the presenceof calcium bicarbonate as follows:

ENRICHMENT

IN

ORE-DEPOSITS

Calcium bicarbonate.

OF COPPER

25

Chrysocolla.

CuSOq- H2Ca(CO), q- H, SiO----CuO,HSiO-t- CaSO, q- H,O -t-2C0

Yet, in caseslike the Black Copper mine west of Globe, Arizona, where the chrysocollais the only ore and where it has replaceda dacitetuff the necessary
presenceof calciumbicarbonate
would not be suggestedby the wall rock.x
NATIVE

COPPER.

Native metal is the last possiblestagein the reductionof copper

compounds. It is a not uncommongossanmineral--and it must
be reachedafter sulphideshave beenoxidizedand their secondary
productshave been reduced. The reductionappearsto be occasionedin somecasesby organicmatter, that is, by hydrocarbons
of somesort which are carrieddownwardby the meteoricwaters.
In othersand especiallyin the caseof the Lake Superiordeposits'
the oxidationof ferrouscompoundsto the ferric state has been
suggestedas the most probablereducing agent. And again
electrolysisby earth currents,a most improbablemethodof precipitation,has beenurged. Whether sulphuror sulphurouscompoundsupon which we have chiefly dependedin explaining the
formation of chalcocite and covellite, will suffice to rob oxidized

coppersaltsso completelyof their oxygen as to leave the native

metal may be questioned.At all events,the copperis the last
stage in the process,and one cannot avoid the conclusionthat
eitherthe copperof Keweenawpoint hasresultedfrom an original
depositthat is very old and that hasrun the full gamutof secondary enrichmentor else some factor has entered which is quite
different from the normal courseof changes.
In conclusiona word may be again said regardingthe interest
and importancewhich attach to detailed studiesof paragenesis,
for which this magazinefurnishesa natural avenueof publication. A very great ore-bodyis not essentialto the elucidation
of the processand it may well happenthat a lean or relatively
unimportant ore may furnish a simpler and clearer series than
thosewhosemagnitudecontributescomplexityand obscurity.
F. L. Ransome, professionalpaper No. 12, U.S. Geological Survey, p. 157.