THE HYDROTHERMAL ALTERATION OF FELDSPARS IN

ACID SOLUTIONS BETWEEN 300 ø AND 400 ø C.

JOHN W. GRUNER.

ABSTRACT.

About 30 experiments,largely with feldspars,were made in HC1 solu-

tions at 300ø to-400ø C. (one at 525ø C.). The concentrationsof K and
A1 were varied to some extent. It was found that kaolinite forms only
below 350ø --+10ø C. and muscoviteabove this temperatureto as high as
525ø C. Pyrophyllite may form over the whole range from 300ø to
525ø C. thoughit may be only metastablebelow 350ø C. K feldsparsare
metastable(probably also Na feldspars) at 400ø C. providedthe concen-
trations of the correspondingalkalies are high. Some of these reactions
takeplaceat suchlow pressures
that the presence
of a liquidphasein the
bombsis precluded. The writer has attemptedto explain some of the
reactions.

INTRODUCTION.

FIVE yearsagothe writer described• a numberof experimentswhichshowed

that muscoviteco•d be synthetizedin I-IC1 solutionsat 400ø C. providedan
excessof K ionswerepresentin the solutions. The term "solution"as used
here includesthe gaseousphase. At 300ø C. muscovitewas stableor meta-
stableunder theseconditionsbut couldnot form at this temperaturein HC1
solutions. At 300ø C. kaoliniteformedevenin the presenceof a large excess
of KC1.
In the presentinvestigationthe experimentswere extendedto the altera-
tion of potashand sodafeldspars. Schwarzand Trageser2 had alteredfeld-
sparsto kaolinitein 1.0 and 0.5N HC1 solutionsat about330ø C. and below
this temperature. Later theya altered feldsparto pyrophyllitein the same
kind of solutionat temperaturesfrom 400ø to 530ø C. It is not statedclearly
whetherthey wereableto makepyrophyllitefrom 320ø to 400ø C. or whether
kaoliniteonlywastheir productin this range. Accordingto their description
they usedautoclavebombswith a volumeof 160 c.c. which they filled with
120c.c.of liquid (80 c.c.solution+ 40 c.c.water) whichis a very high degree
of filling and musthaveled to pressuresfar in excessof thoseordinarilypro-
duced. It wasreasoned in the presentinvestigation
that I-IC1solutionsshould
sericitizefeldsparsaround400ø C. providedthe concentration of K ionswere
highenough. It will be shownthat this is the casethoughNoll,4 on the basis
• Gruner, J. W.: Formation and stability of muscovite in acid solutions at elevated tem-
peratures. Am. Min. 24: 624-628, 1939.
• Schwarz, R., and Trageser, G.: Ober die kfinstliche Umwandlung yon Feldspat in Kaolin.
Zeit. anorg. Chem. 215: 190-200, 1933.
a Schwarz, R., and Trageser, G.: t•ber die Synthese des Pyrophyllits. Zeit. anorg. Chem.
225: 142-150, 1935.
4Noll, 'W.: Ober die Bildungsbedingungenyon Kaolin, Montmorillonit, Serlcit, Pyro-
phyllit und Analelm. Mineral. ?etrog. Mitt. 48: 227, 1936.
578
 HYDRO THERM,4 L,.4 L TER,4 TION OF FELDSP,4RS. 579

of experiments,claimedthat muscovite(sericite) doesnot form at 400ø C. in

acid solutions. It had been plannedoriginally to extend the temperature
rangeand the concentrations in the experimentslistedbelow. In 1942, how-
ever, it becameimpossibleto obtain new gold linings for the bombs. The
writer, therefore,decidedto publishthe data,thoughincomplete, sinceit may
be sometime beforethe work can be resumed. He is indebtedto Mr. Lynn
Gardiner for much assistance and to the Graduate School of Minnesota for
financialaid in carryingout the investigation.
EXPERIMENTS.

Gold-linedbombs,which have been describeda number of times,5 were

used. Thesehavea volumeof 51 to 52 c.c. In all experiments they were
filledwith 18 to 25 c.c.of solution,
dependinguponthe temperatureto which
they were to be raised. Taking into consideration the specificvolumeof
waterbelowthe criticaltemperature the bombswere nevercompletely filled
withliquidat thesetemperatures.
On account
of theotherconstituents
pres-
ent the pres.
suresof saturatedwater vapor alonewere not reached,and the
criticaltemperatures weresomewhat higher. The air abovethe liquidwas
replaced by CO2at roomtemperature andatmospheric pressure. The bombs
wereheated in largeelectric
mufflefurnaces
controlledbyLeedsandNorthrop
recordingpotentiometers.The thermo-couples
were as closeto the bombs
as possible. Maximum temperaturefluctuationsamountedto 5ø C.m. The
considerableweightsof the bombsshouldhave minimizedthem inside.
The followingmaterialswereusedin the experiments:
Two analyzed feldspars
fromunknown localities.They are the identical
specimens
that Armstrong6 analyzedand usedin his experiments on the
hydrolysis
of feldspars.Theircomposition
is givenin Table1. Theywere
groundto passthrough 100 mesh.
TABLE 1.

ANALYSES O1' FZLDSPARS.

(L. C. Armstrong, analyst.)
Microcline Albite

% %
SiO• ............................ 65.46 66.01
AlcOa ........................... 19.12 21.40
CaO ............................ nil 1.74
Na•O ........................... 3.51 10.27
K20 ............................ 11.93 .56
Li20 ............................ n.d. n.d.
Ignition ......................... 0.18 .27
Total ....................... 100.20 100.25

Microcline:Localityunknown. Grayishwhitecleavagefragments. Albitepresentin perthitic

intergrowth;calculationof the norm indicatesa composition
of 70.6 per cent ort,hoclasean•l
29.4 per cent albite.
Albite: Locality unknown. Grayishwhite moonstone cleavagefragments;calculationof the
norm indicatesa compositionof 86.8 per cent albite, 8.6 per cent anorthite,and 3.1 per cent
orthodase.

5 Gruner, J. W.: op. cit., p. 624.

6 Armstrong,
L. C.: Decomposition
andalterationof feldspars
and spodumene
by water.
Am. Min. 25: 813, 1940.
580 JOHN W. GRUNER.

Aluminum hydroxide (Merk). This material is a white powder and

givesan X-ray patternof bayerite,AI(OH)a, and contains37 per cent H20.
Theoreticallyit shouldhave 34.6 per cent.
"Silicic acid" (C.P., Mallinckrodt). It is a powder and contains10.36
per cent H•O = approximatelySiO' «H•O. It is amorphousunderX-rays.
In all experiments,in which one of the feldsparswas used,200 mg. was
put into the bombunlessstatedotherwise. After completionof the experi-
ments,the solutionswere testedfor their approximatehydrogenion concen-
trations. In someexperimentsthe SiO• contentof the filtered solutionas
well as the resultingacidity were determined. SiO2 was hydrofluorizedand
the acidity was obtainedby titration with NaOH. The solid material in the
bombswas washedcarefullyand then dried at about 50ø C. The powders
were X-rayed in precisioncameraswith radii of 57.3 mm. UnfilteredFe
radiationwas used. Good,sharppatternswere obtainedin mostexperiments
described. There was no difficultyin recognizingthe productsexceptin two
caseswhereweakpyrophylliteand boehmitepatternswere superimposed.
Sucha c•mbination
of patterns,
if faint,couldbemistaken
formontmoril-
lonite or sericite,as possiblyhappenedin someof Norton's experiments. 7
His X-ray data are confusing,probablybecausethe measurements were made
with a cameraof too small a radius (28.6 mm.). Also, the characteristic
linesof the mineralswhichhavea spacingof 7.0 A or morewere omittedin
his data. The data were recalculatedby the writer and it was found, for
example,that Norton'sconversion productof albite (Table 11, p. 14) which
he callsheidellite,is probablypyrophyllite,if it canbe identifiedat all. It is
not clear to the writer how Norton 8 was able to identify as many as four
mineralsin oneX-ray patternwhen thesemineralswere as closelyrelatedas
dickite and kaolinite.
No boehmite,A10(OH), was reportedin Norton'sexperiments though
Noll 9 and the writer obtainedthis productfrequently. Nortonx0 reported
gibbsiteas end productfrom nephelitein one experiment. His data,how-
ever,agreemuchbetterwith boehmite. The resultingconfusion showshow
importantit is to usethe properX-ray techniquein obtainingdata for the
identificationof silicatesand other mineralsgiving many and often diffuse
lines;
TM Besidesthe 28 experiments whichare tabulatedin Tables2, 3, and
7 Norton, F. H.: Hydrothermal formation of day minerals in the laboratory. Am. Min.
24: 1-17, 1939.
8 Norton, F. H.: Hydrothermal formation of clay minerals in the laboratory, Part II.
Am. Min. 26: 10, 1941.
9 Noll, W.: op. tit., pp. 210-247.
x0 Norton, F. H.: op. tit., 1939, p. 14, Table 12.
xx The reproductions of photographs or diagrams are rarely satisfactory. They do not
show small but 'important differences that are brought out by actual measurements. On the
other hand, tables with all the measurementsare too expensive to print. If they are published,
however, a definite system should be used. The interplanar spacings on the films should be
converted to angstrom units in the tables and should not be given in sines or angles. The
lines nearest the zero beam are very important and absolutely essential in recognizing minerals.
Data without them have little value. If photographs or diagrams are reproduced they should
also contain the interplanar spacings in angstrom units. The diagrams by Norton (op. tit.,
1941, pp. 4 and 6) are not usable because they contain only a part of the necessary information.
Another point needs emphasis. The intensities of the lines of synthetic products and the
corresponding natural minerals, particularly in layer silicates, may be very different due to
HYDROTHERMAL ALTERATION OF FELDSPARS. 581

I I
582 JOHN W. GRUNER.
 HYDROTHERMALALTERATIONOF FELDSPARS. 583
TABLE 4.

HYDROTHERE•ALEXPERIMENT• IN HCI SOLUTIONS BETWEEN 340ø AND 525ø C,

Volume of bomb $0 c.c.

C.C. Of
Re- pH Solution

in Bomb Original
No. MaterialPlaced Acidity sultingafter Tiinme
Acid- Expert- ' Conversion
Product Temp.
in C.
ity ment Days At Recov-
Start ered

170 .058 g AI(OH)• 0.105 N 0.081 About I 9 muscovite 18 18 400ø

.148 SiO2.•H20 and some
1.000 KCI boehmite

181 .090gAI(OH)3 0.105 About

I 10 pyrophyllite
18 1• 400
ø
.153 SiO2.•H20

184 .227 g AI(OH)3 0.105 About 1 10 pyrophyllite 18 18 ,360ø

.201 SiOn.•H20 and
.500 KCI boehmite

186 as in No. 184 but 0.105 About 4 10 muscovite 18 18 360 ø

2.00 g KCI

189 as in No. 184 but 0.105 About 1 12 muscovite 18 17 360ø

1.00 g KCI and some
boehmite
187 as in No. 186 0.105 16 boehmite 18 moist 340 ø

188 as in No. 189 0.105 About 1 10 pyrophyllite 18 18 340ø

and
boehmite

174 .200 g sodafeldspar 0.105 About 1 1 muscovite 25 • 525ø

.100 AI(OH) •
.5OO KCI

4, a numberof otherswere madewhich were only partially successful due to

somefailuresin the apparatus. In two of thesethe gold discson the top of
the bombshad been"eatenthrough"with the resultthat muchiron had been
dissolved,and crystalsof magnetitehad formed. The dissolvingof gold
from the liningsof the bombs,while not a part of the problem,is worth men-
tioning. In experiments159 and 160 muchgold was found in the solutions,
whichwereof a yellowcolor. On standing,thisgoldwas slowlyprecipitated
as a brownishdeposit. Why othervery similarsolutionswere colorlessand
containedno gold is not understood.There was, however,evidencethat
gold recrystallizedin dodecahedrons in someof the other experiments,pre-
sumablyby going into solutionand crystallizingout probablyalmostim-
mediately. In unpublished experimentsin whichMgC12was usedwith tIC1
solutionsthe amountof gold "transfer" in this mannerwas quite remarkable.
ß

some preferred orientation of the larger particles of the natural material though the inter-
planarspacings are exactlythe same. Most conspicuou• examplesof this kind are pyro-
pfiyllite and muscovite.The few lines of montmorillonite
agreewith lines of pyrophyllite
exceptfor (001) near the zero beam. Therefore, great care must be exercisedin comparing
films.
584 JOHN W. GRUNER.

This behaviormay suggesta reasonfor the commonassociation of gold with

the chloriteand mica groups.
In someof the experimentsonly a part of the original solutionwas re-
covered. The leakagemust have occurredearly in the heating. If the top
of the bombwas not screwedon tight enoughthe solutionscouldhave l•ar-
tially escapedbeforethe copperwasherand gold collar of the bombhad ex-
pandedsufficiently to stopthe leak. Thoughpracticallyall the solutionshad
escapedin experiments179, 175, and 177, the resultsare exactly what one
wouldhaveexpectedif the solutionshad beenstill present. They were gone
whenthe bombswere removedfrom the furnaceas couldeasilybe ascertained
by shakingthe bombs,and, therefore,leakagewas not due to cooling. In the
experiments of Table 2, the pressures
wereprobablybetween80 and 87 atm.,
dependinguponthe saltõin solution. In thoseof Table 3 the pressureswere
between250 and 350 atm., exceptin thosecasesin whichthe solutionswere
largelylost.
mscussxos oF I•ESULTS.

Exclusive'
ofboehmite
A10(O.EI), whichis a dimorph
ofdiaspore,
wedeal
with only five mineralsin our experiments. They are:
K feldspar K A1 Si308, K:AI:Si=i:I:3
Nafeldspar Na A1 Si308, K:AI:Si=0:I:3
pyrophyllite (OH)2 A12 Si4Ox0,K:AI: Si = 0:1:2
muscovite (OH) 2K A13 Si30•0, K: A1: Si = 1: 3: 3
kaolinite (OH) s A14 Si•Ox0,K: A1: Si = 0: 1: 1.
They seemto be the only oneswhichcanexist in the solutionstried, and which
form in the temperaturerangebetween300ø and 525ø C. Quartz, of course,
wouldbe stablebut it is formedin noneof the experiments. The writer, so
far, has obtainedquartz only in experimentsin whichtalc was treatedwith
0.175N or strongerEIC1solutions at 300ø C. in whichtalc is completely
soluble. Evidentlysaturationwas reachedin thesesolutionswith respectto
SiO2. Mg ions,evidently,are not capableof combiningwith SiO• groupsto
form new Mg silicatesin acid solutions. A1 and SiO• ions,on the other hand,
can produceinsolubleand stablecompounds.The SiO• ions are, th.erefore,
withdrawnfrom solutionsufficientlyrapidlythat they cannotreachthe satura-
tion pointnecessary for the formationof quartz. This statementis basedon
the beliefthat quartzdoesnot form directlyfrom colloidalsolutionsof SiO•
but that mineralizersare necessarywhich causeSiO• to ionize, the SiO4
groupsthen formingquartzin eitheracid or basicenvironments•
The end productsin acid solutionsshouldbe differentfrom thoseof neutral
or basiconeswheneverthe acid is capableof leachinglarge amountsof a
constituentandholdingthemin solution. This happensto the alkaliesof the
feldsparswhichcanbe takeninto solutionas longasthe acidityis maintained
and their concentration doesnot exceeda certainmaximum. This explains
the formationof pyrophyllitefrom microclinein experiment160, Table 2.
The reactiontakesplaceaccording to equation(1).
2KA1SiaOs
+ 2HC1-->(OH)•AI•Si•O•o+ 2SiO•+ 2KC1 (1)
 HYDROTHERMAL ALTERATION OF FELDSPARS. 585

Evenin experiments 158,162,and 163in the presence of a relativelylargeK

ion concentration,
this reactionproceedsfrom left to right. It demonstrates
that no potassium
silicatecanform at 300ø C. in acid solutionsthoughsome
havebeensynthetized in neutraland basicones,as, for example,muscovite
and leucite.
It wasstatedby Noll x2that pyrophyllite
couldnot form muchbelow400ø
C.,andthewriterhadbeenofthesame
opinion,
basing
it onhisearlierexperi-
mentsx3in which only kaolinitewas obtainedat 300ø. In Table 2, it is seen,
however,that pyrophyllite
formsat 300ø C., if the concentration
of A1 ionsis
low at any given time. If it is considerable,
as in 168 and 169, kaolinitewill
form and any A1 in excesswill becomeboehmite,A10(OH). The reaction
is expressed
by equation(2)
KA1Si308
+ AI(OH)• + HCI-->(OH)4Al•Si205
+ SiO•+ KC1 (2)
in whichfreesilicaappears
onthe rightor by equation(3)
2KA1SiaO8
+ 4AI(OH)a + 2HC1-->3(OH)4Al.•Si205
+ 2KC1+ H20 (3)
in whichall SiO• is neededfor the kaolinite. One tenth of' a gram of
AI(OH)a, whichwas addedin experiments of Table 2 and 3, wouldhave
beenjust aboutenoughto convert0.2 gramsof microcline to muscoviteor
kaoliniteif all theSiO2hadbeenusedup in thereactions.Therefore,equa-
tion (2) is themorelikelyreaction
in our experiments because boehmite
is
a by-product.
In thenaturalalteration of feldsparstheformation of pyrophyllite
seems
to be rare,probably
because thereis usuallymuchA1 available.It hasbeen
reported by Buddingtonx4andClappx5asan alteration productof feldspars.
There existsa possibilitythat it has beenmistakenfor sericitein somein-
stances,asthetwomineralsresemble eachotherunderthe microscope.
Table3 showsclearlyhowthe products of the alteration
dependon the
respectiveconcentrations
of K andAI whenthe experiments are madetrader
the sameconditions
otherwise.
•In experiments
161and 178the feldspars
will alter to pyrophylliteprovidedthe concentrations
of K are not much
greaterthanthe amounts that canbe leached
fromthe feldspars.This had
alsobeendemonstrated earlierby SchwarzandTrageser xofor the sametem-
perature of 400 ø C.
If the K ion concentration is materiallyincreased,withoutadding
AI(OH)a, noalterationseemsto takeplaceasshown in experiments159and
171. Potash feldspar
maybe metastable undertheseconditions thoughit
does notformasshown in experiment
170,Table4, in whichtheproperpro-
portionsof AI(OH)a andSiO•to makefeldsparcombine to muscovite.Ex-
'12 NolI, W.: op. cit.
111Op. cit., p. 627.
x4Buddington,A. F.: Pyrophyllltization,
pinitlzationand silicificatlonoœrocks around
Conception
Bay, Newfoundland.Jour. Geol.24: 130, 1916.
x5Clapp,C. H.: Aluniteandpyrophyllite
in TriassicandJurassic
voleanlcs
at Iiyoquot
Sound,B.C. Eco• G•_or..10: 70, 1915.
x6Zeitsch.anorg. Chem.225: 142, 1935.
586 JOHN PV. GRUNER.

periment 180 indicatesa similar stability for sodafeldsparprovidedthe Na

ion concentration
is high.
Experiment164 is significantbecauseit showsthat no simpleexchangeof
Na for K ions.takesplace though the K ions are quite concentrated. This
statementneedsmodificationfor O'Neill 17workingwith the writer foundthat
potashfeldspar,adularia,will form from sodafeldsparprovidedthe K ion
concentration
is high and the solutionis not more acid than about 0.001N.
This simplebaseexchangeis also reversible.
Theoreticallymuscovitecan form from feldsparsin a numberof ways as
shownby equations(4), (5), (6), and (7).
3KA1Si•O8+ 2HC1• (OH)2KAlaSi•Ox0+ 6SiO2+ 2KCI (4)
3NaA1SiaO8
+ 2HC1 + KC1ms(OH)=KAlaSiaO•0+ 6SiO=+ 3NaC1 (5)
KA1SiaO,+ 2AI(OH)a •=• (OH)=KAI•SiaO•0 + 2H=O (6)
NaA1SiaOs+ 2AI(OH)a + KC1ms(OH2KAlaSiaO•0+ 2H=O + NaC1 (7)
In the experiments166, 165, 175, and 183 muscovitewas produced,but an
excessof A1 and K ions was necessary. Which of the four reactionswere
involvedis difficultto decide. Reactions(4) and (6), or (5) and (7) could
occur more or less simultaneouslydependingupon the concentrationsand
acidities. It shouldbe notedthat the acidityin experiment183 was as high
as 0.35 N. On the other hand, the same results were obtained in ex-
periments177 and 182 in whichthe solutionswere neutral.
It will be observedthat in someexperimentssmallportionsof the feldspar
remainedunaltered. The reasonfor this incompletereaction may be that
equilibriumwas reached. It is more likely, however,that the time was too
short for the coarsergrains to becomealtered. That the unchangedgrains
werecoarse(about100 mesh)couldbe seenin the X-ray powderphoto-
graphs,for the linesof the feldsparpatterncongistedof discontinuous dotsand
dashes. This is alwaysa signof coarseness of grain, especiallyif the powders
are rotatedin the camerasas they were.
Some of the experimentsof Table 4 were made for the purposeof estab-
lishing more closelythe point abovewhich kaolinite is not stableand below
which muscovitewill not form in acid solutions. In experiments184, 186,
189, 187, and 188 the quantitiesof AI(OH)a and SiO-«H20 were propor-
tional to those necessaryto form muscovite. The concentrationsof KC1
varied betweenwide limits. Thesevariationsapparentlyaccountfor pyro-
phyllitein experiment
184andmuscovite
in experiment
189at 360ø C. An
importantfact is that kaolinitexvasnot producedat 360ø C. or above,and
muscovitedid not form at 340ø C. or below. Therefore,the boundarybe-
tween the fields of formation of the two minerals lies somewhere between
340ø and 360ø C. for aciditiesin the neighborhood
of 0.1 N.. As the acidity
decreasesthe field of formationof muscoviteprobablyextendsto lower tem-
peraturesbut doesnot reach300ø C. at 0.05N as shownin the earlierpaper
by the author?
x7 O'Neill, T. F.: Unpublished Ph.D. Thesis.
•80p. cit., p. 627.
 HYDROTHERMAL ALTERATION OF FELDSPARS. 587

In experiment170,AI(OH)a and SiOn.werechosenin the proportionsof

potashfeldsparthoughthis mineralwas not expectedto form. Apparently
the reactionwas that of equation(4) for the productwas muscoviteand a
little boehmite. In experiment181 the proportionschosenwere those of
pyrophyllite,and this was the mineral which resulted.
The two experiments187 and 172 are of interestbecausethe pressures
on accountof leakagemusthavebeenlow. In experiment172 the tempera-
ture 'control had been accidentallyshifted, and the bomb was at a low red
heat. With « c.c. of solutionit wouldbe difficultto calculatethe pressure
under which this muscovite formed at 525 o C. It must have been less than 36
atm. In experiment187the pressureevidentlywasnot highenoughto pro-
ducekaoliniteor pyrophyllite. AI(OH)a was simplyconvertedto the lower
hydrate boehmite.
CONCLUSIONS.

The conceptthat the more volatile constituentsof the magmasas they

leavethe crystallizingmassesare acid in reaction,thoughthey may change
their characteristics
as they moveon, has becomefairly well established in
the last twenty years29 It is not necessaryat this placeto enter into ex-
tendeddiscussioffsas Graton2ohas doneas to the inadequacy of suchacid
solutionsto produceore deposits.It is also probablyimmaterial,at least
in somecases,whethertheacidityis produced by halogens or the SO4radical,
sincethe pH of a solutionis the moreimportantfactor. What mattersin
our investigation
is that suchsolutionsexist and that certainhydrothermal
mineralsmayhavebeenformedby them,or if not,maybe stablein them,as
shouldbe demonstrable in the laboratory. K andNa feldspars wereselected
for the experimentalstudybecause they are not only formedby somehot
solutionsbut evenmorereadilyaltered. The temperature rangewas 300ø
to 400ø C. exceptin one experiment. The acidity of the solutionswas
usually0.1N, though0.35N wastriedwith similarresults. The following
conclusions
may be reached:
1. Kaolinire,pyrophyllite,
muscovite
(sericite),andboehmite
are formed
in acid solutions.
2. The feldspars
themselves
do notformbut maybe metastable.
3. The concentration
of K ionsandtheratioof A1to Si ions(or AL.O•
to SiO2) determinewhichmineralwill formandbe stableat a giventem-
perature.
4. Kaolinite
willformfromfeldspars
andis stable
below
approximately
350ø-----
10øC.,regardless
ofK ionconcentration,
provided
theratioofAI:Si
is about1:1. This meansthat additionaleasilyavailableA1 has to be in
the system.
5. If thisis not presentpyrophyllite
will forminstead,sincethe ratioof
A1: Si in pyrophylliteis 1: 2, and in kaoliniteit is 1: 1.
6. Pyrophyllite
will alsoformfromfeldsparsfrom350ø C. upwardto at
least530ø C. Thelatterfigureis by Schwarz
andTrageser,
whoused0.5N
x9For summariessee papersby N. L. Bowen, C. N. Fenner, and C. S. Ross in "Ore
Depositsof the WesternStates,"Lin.dgrenVolume,A. I. M. E., 1933.
2oGraton,L. C.: Natureof theore-forming
fluid. 'Ecoa.GEox..
35: 197-358,1940.
588 JOHN W. GRUNER.

HC1 solutions. The K ion concentrationmust not be much greater than the
amountthat the acid can removefrom the K feldspar. Boehmitemay form
in such a solution if A1 ions are present in excessof those required for
pyrophyllite.
7. If K and Na ions respectivelyare high but no additionalA1 is available
the feldsparsremainunaltered. This is not a true stabilitythoughno altera-
tion was noticedat 400ø C. in 16 days. It is certain that no K feldsparcan
be synthetizedat this temperaturein acidsolution. Muscoviteor pyrophyllite
will be the resulteventhoughthe proportionschosenare thoseof K feldspar.
8. Muscovitewill form readilyfrom feldsparsbeginningat 350ø q- 10ø C.
to 525ø C., the highesttemperaturetried, providedboth K and A1 are in
sufficient concentrations. This reaction occurs also in 0.35 N. HC1 solution.
We know from the experimentsof Noll 2t and thosein Table 3 that mus-
covite also forms in neutral solutionsat as low a temperatureas 200ø C.
O'Neill 22producedit in basicsolutionswhichhad a normalityof 0.01 KOH.
If the solutionsare more basic,however,minerals like kaliophilite or leucite
will result at 300 ø to 400 ø C. Under neutral or somewhat basic conditions
the feldsparsthemselves
may be stableand it is easyto changeNa feldspar
to adulariaby simplebaseexchangeaccordingto O'Neill. This reactionis
reversible.
In experimentsmadeby Friedel, Doelter,Thugutt, Allen, Baur, K6nigs-
berger,M/filler,Niggli, Morey, Fenner,and others, 2smuscovitewasproduced
very rarely becausethe solutionswere commonlyso high in potashand suf-
ficientlybasicthat kaliophillite,leucite,or orthoclaseformed. Experimental
factspointthento the presence of slightlybasicto acidsolutionsas causesof
sericitization.
The alterationof individual feldsparcrystalsto sericiteis in the nature of
leachingof SiO• and the simultaneous additionof AlcOa and I(.•O. If it
were leachingonly the masswould be reducedto one-halfwhile the volume
remained constant, a condition not observed in the field or under the micro-
scope. It is not easyto accountfor the sourceof the addedAlcOain either
acid or slightlybasicsolutions. It couldcomefrom adjoining regionsnow
completelysilicifiedas has beenadvocatedby somestudentsof the'problem.
In this casewe would have simplya movementof SiO2 out of the feld-
spathicareastowardthe centersof silicification and of AltOs in the opposite
direction. I( ionswould travel in the samedirectionas AI•O,. AlcOacould
be carriedas KA10• which has a basicreaction,or as A1Cla'which is acid.
One finds the statementthat carbonateswhich are frequently found in
sericitizedrocks would have been destroyedif the mica had formed in an
acid environment. This would depend,of course,on the partial pressureof
CO2 in sucha system,as well as the concentrationof the metallicions which
usuallyare found in carbonatesin hydrothermallyaltered rocks. It is con-
ceivablethat the reaction CaCO• + 2HC1 --> CaC12+ H•COa proceedsfrom
right to left if the pressureof CO• is very high.
•x Noll, W.: op. cit.
g2 O'Neill, T. F.: Unpublished thesis, University of Minnesota.
•a For abstractssee: Morey, G. W., and Ingerson, Earl: The pneumatolyticand hydro-
thermal alteration and synthesis of silicates; EcoN. Gzo•.. 32: 607-761, 1937.
 HYDROTHERMAL ALTERATION OF FELDSPARS. 589

Evidentlythevaporpressure of H:O in someexperiments in whichthere

wasleakage wasnot veryhigh. Yet the resultswereessentially similarto
thosein whichthepressurewasthatof saturated H20 vapor. A liquidphase
cannothaveexistedin thebombandit is difficultto imagine by whatprocess
theSiO2,A12Oa, andKC1moved' at 400ø C. Thetransferof SiO2at suchlow
pressuresasa fewatmospheresmustbeextremely slow,if it takesplaceat all.
Theformation of newsilicatesfromothersolidphases likefeldsparsand
AI(OH)8 in thistypeof experiment is littleunderstood. Doesthefeldspar
dissociate
hydrolytically
in the solution with the resulting ionsK+, A1+**,
SiOa•-=,OH- andH+,anddothenewinsoluble compounds formfromthose
ions? The degreeof ionization mustbe extremely smallin sucha system
particularly
withrespect
to SiO4groups.The dissociation
of thefeldspar
wouldnotproceed
anymorerapidlythanthe precipitation
of thenewcom-
poundcouldtakeplace.If it happens thattwocompounds aspyrophyllite
andkaolinite,arestableor metastableat the sametemperature.
of 300ø C.,
andbothareapproximately equally
insoluble,thatonewouldprobably form
for whichat thismoment theratioof A1to Si ionswerejustaboutcorrect.
ßLet usassume
thatit werepyrophyllite.If by a lateraddition
of A1ionsthe
equilibriumwere shiftedin favor of ka01initethe first mineralwoulddissolve
andkaolinitewouldbeprecipitated.
In a similarmannerthemetastability
of microcline
in experiments 159
and171canbeexplained. Theadditionof KC1,ascanbeseenin equation
(4), wouldhavea tendencytodrivethereaction
to theleft,thatis,prevent
thedissociation
of themicrocline.
On theotherhand,in experiment 170,
in whichthe compounds AI(OH)8, SiO2andKC1wereused,the first two
in the proportion
of K feldspar,muscovite
resultedbecausethis mineralis
stableandit wasnot necessary
to dissolve
first anothermetastable
oneas a
sourceof supply.
It is hopedthatthisinvestigation
canbe resumed
afterthe war andthose
pointsattacked whichstill needexplanation.
U•iVE•SITX• ovM•NNESOT^,
MINIq'E^POLIS,MINNESOT.%
• June 24, 1944.