25. METASOMATIC GARNETS IN CALCITE (MICARB) CHALK AT SITE 251,SOUTHWEST INDIAN OCEAN

D. R. C. Kempe and A. J. Easton, Department of Mineralogy, British Museum (Natural History), London, England

ABSTRACTAn occurrence of metasomatic microscopic garnet of the grandite

series in micarb chalk above basalt from the southwest branch of theIndian Ocean Ridge is described. The physical parameters (a =11.92658Å, Sp. G. = 3.54, n 1.764) and chemical analysis aregiven, and the composition of the garnet is discussed. Possiblesources of the constituents and mode of formation (paragenesis) arediscussed; it is considered most probable that hydrothermalemanations from the magma source below the basalt transportedsilica, alumina, and ferric iron oxide into the ooze above it.

INTRODUCTION

The lower Miocene yellowish-brown semilithifiedcalcite (micarb) chalk forming lithologic Unit 5 at Site251, southwest branch of the Indian Ocean Ridge,contains some 20wt.% microscopic garnet grains, 2to3µin diameter. The lithology of the sediments forming Units1 to 4 at Site 251 consists entirely of white, bluish-white,or yellowish nannoplankton ooze and chalk, containingbetween 0.5% and 11% of detrital or clay minerals(Cook, Zemmels and Matti, this volume, Chapter 24).Usually as much as 98%-99% calcium carbonate ispresent. Burrows, mottling, and framboidal and finelydisseminated pyrite are common in the ooze and chalk(Criddle, this volume, Chapter 26).

Unit 5, comprising the base of Core 28 and all of Core29, overlying basement basalt, contains virtually nomineral other than recrystallized calcite and garnet. Thelatter was detected, and, subsequently, repeatedly con-firmed, by X-ray diffractometry and powderphotographs. Under high power the garnets are clearlyvisible in smear slides (Plate 1).

In this paper, the chemistry and physical parametersof the garnets are reported and their paragenesisdiscussed.

Although the garnets are believed to be metasomatic,they must be considered in the context of authigenesis,in which such an occurrence is extremely rare or evenunique. Authigenic garnets may be present in the GreenRiver Formation, the mineralogy of which has been des-cribed (cf. Milton et al., 1960). Kennan (1972) describedsome unusual hollow, ellipsoidal clusters formed ofmanganiferous garnet. The clusters occur in thin layers(<20 mm) within pelitic and semipelitic schists of thegarnetiferous beds forming part of the aureole of theLeinster Granite. The garnets are thought to have beenformed by the reconstitution of original sedimentaryconcretions. Donnelly and Nalli (1973) describe twooccurrences of garnet in sediments from the Caribbeansampled on Leg 15 of the Deep Sea Drilling Project. Oneof these, considered by Donnelly and Nalli to be authi-genic, consists of rectangular plates, 20µ or more across,

of golden brown garnet, apparently spessartine (Site146). The second occurrence, at Site 153, is of brownishdodecahedrally modified octahedral grains, generallyless than lOµ across, in a single smear slide; such crystalsare rare among garnets. This occurrence more closelyresembles the Site 251 garnet, but, unfortunately,further garnets could not be located in the surroundingsediment, and the X-ray data on grains from the smearslide were not conclusive. It is tentatively suggested thatthe mineral is garnet and possibly of volcanic origin.The present authors have failed to find any otherreported occurrences of authigenic or sedimentary meta-somatic garnets. Those in ancient sediments are alwaysof metamorphic origin; contact and regional meta-morphism account for the vast majority of all garnetoccurrences. A few are of igneous origin, including peg-matitic occurrences. Metasomatic garnets, as commonlydefined, include, for example, andradites in skarns andhydrogrossulars in rodingites. It is this latter type ofoccurrence that is considered most nearly comparablewith the Site 251 example; the analogy is discussed in alater section. Further points of comparison derive fromsynthetic garnets, some of which may grow under con-ditions closely resembling those at Site 251.

PHYSICAL PARAMETERSThe garnet crystals are dodecahedral (Plate 2),

possibly with icositetrahedral modifications* and average2 to 3µ across; they may range up to 4.5µ and down to1.5µ. They show considerable intergrowths. Zabinski(1966, p. 32) observes that hydrogarnets are charac-teristically octahedral. Despite their very small size, it ispossible to see opaque inclusions within some of thegarnets: possibly such material acted as minute nuclei.In color, they are pale honey yellow. The X-ray patternshows very well-crystallized material. Their physicalparameters are

α - 11.9265Å ±0.0015 (minor phase with α =11.992Å ±0.002); n = 1.764 ±0.005; Sp. G = 3.54.WinchelPs (1958) chart does not accommodate theseparameters.

The presence of a minor phase with a longer cell edgeis probably due to minor chemical fluctuations in the

593

D. R. C. KEMPE, A. J. EASTON

constituents available at the time of growth; a similarphenomenon has been observed to be common in thespinels of the hornblende mylonitized peridotites fromthe Saint Paul Rocks (unpublished data).

CHEMISTRY

The garnet analysis given in Table 1 (Analysis 1) wasthe third chemical analysis made on material separatedfrom the core, two previous analyses carried out on theacid-insoluble residue having shown an excess of silica(about 8% by weight) which is inconsistent with a garnetformulation. This was thought to be due to contami-nation of the residual garnet grains by colloidal silicareleased during dissolution of the matrix. In view of this,the final separation used for the reported analysis wasmade by dissolving the matrix in AM hydrochloric acidand warming for 30 min in a water bath to ensure disso-lution of all carbonate material. The insoluble residuewas washed free of calcium salts with water and thentreated with portions of hot, 2% (by weight) sodium car-bonate solution to dissolve any adsorbed colloidal silica.After each treatment trie insoluble residue was separatedand the supernatant liquid tested colorimetrically forsilica (by the reduced molybdenum blue complexmethod [Jeffery and Wilson, I960]). The treatment wasrepeated until all silica had been removed.

In order to confirm that the above treatment had noadverse leaching effect on the grains of garnet, a finelyground sample (< 100 mesh) of garnet of known compo-sition was reanalyzed after being treated with the sameacid and sodium carbonate solutions. Ground olivinewas added to the control garnet to simulate the libera-tion of colloidal silica from the core. Comparison of theanalyses before and after treatment showed that theaddition of olivine had no effect on the subsequentanalysis of the garnet. It would appear, therefore, thatthis method is effective in decontaminating such asample. Some 8% (by weight) of crystalline quartzknown to be present as inclusions in the control garnetwas not affected.

The analyses were made on material dried at 110°Cand checked by X-ray powder photograph to be vir-tually pure. Silica was determined spectrophoto-metrically on a sodium hydroxide fusion of 1 mg ofmaterial (Shapiro and Brannock, 1962); the Fe3 +/Fe2 +

ratio was determined by dissolution of a further 1 mg ofmaterial under an atmosphere of nitrogen using thedipyridyl complex (Riley and Williams, 1959). Theremaining major constituents were determined byatomic absorption spectroscopy on a lithium meta-borate fusion of 5 mg of material, fusion being followedby dissolution of the fusion cake in dilute nitric acid(Suhr and Ingammells, 1966), using standards as sug-gested by Abbey (1968). Unfortunately, water (H2θ+)could not be determined because of the very limitedamount of material available.

COMPOSITION OF THE GARNETSCalculation of the garnet formula (Table 1) reveals a

deficiency in the trivalent group (Al, Fe3+, Ti) and anexcess of silicon and calcium. This tendency is morecommon among hydrogrossular garnets than amonggrossular garnets and andradites. In the absence of a

TABLE 1Chemical Analysis of the Garnet from Site 251, with Comparisons

SiO2

TiO2

A 12°3Cr2°3Fe2°3FeO

MnO

MgO

CaO

Na2O

K2°H 2 0 +

H2°

Total

n

Sp. G.

a(Å)

SiOH/4Al

AlCrFe 3

Ti

MgFe 2 +

MnCaNa+K

AlmandineAndraditeGrossularPyropeSpessartineUvarovite

l a

38.18

0.42

11.89

0.01

11.69

0.64

0.26

1.47

34.87

0.10

0.02

n.dd

nü

99.55

1.764

3.54

11.9265

Ab

36.92

0.12

12.47

-

14.14

1.84

0.95

-

33.63

-

-

-

0.57

100.64

1.801

3.71

11.94

Bc

34.01

0.12

8.45

0.20

18.28

1.72

0.12

9.96

21.47

0.30

0.10

5.29

0.18

100.20

12.063

Numbers of Ions on the Basis of 24 Oxygens

6.04—-

2.22-

1.390.05

0.350.090.035.91

6.04

3.66

6.42

0.04 J

1.539.452.16.30.6

-

5.89-

0.11

2.24-

1.700.01

_

0.240.135.75

6.00

3.95

6.12

- •

4.041.952.0

-2.1

—

5.061.31-

1.480.022.050.01

2.21 '0.210.023.42

6.37

3.56

5.96

0.10 >

3.652.6

5.637.60.30.3

^Garnet, Sample 251A-29-2, 130-132 cm. Anal: A. J. Easton.bGrossular, South Africa (Clark 1957). Anal: J. Ito.'llydrougrandite, Hsiaosungshan (Tsao-Yung-Lung, 1964).Not determined.

water determination and in view of the excess silica, it isconsidered that the Site 251 garnet is more likely to bean anhydrous member of the hydrogarnet series than a(possibly slightly hydrous) member of the anhydrousseries. As discussed in the final section of this report, thelatter situation would be more difficult to explain thanthe occurrence of a hydrogarnet. For comparison,

594

METASOMATIC GARNETS IN SOUTHWEST INDIAN OCEAN

therefore, analyses of a grossular (Analysis A) and ahydrougrandite (Analysis B) are given in Table 1.

The calculated end-member composition of the Site251 garnet is approximately (Gros52And4oPyóAlm2), forwhich the theoretical physical parameters are a =11.90A; n = 1.80; and Sp.G. = 3.71 (Deer et al., 1962).

Specific gravity, as determined, is considered lowpossibly because of inclusions and experimental inac-curacy due to the small size of the garnets. For a compo-sition close to the Site 251 garnet (Gros52And42Alm4Sp2)Clark (1957) gives a specific gravity of 3.71.

PARAGENESISAs stated in the Introduction, the Site 251 occurrence

of andraditic grossular garnet may be unique.An explanation of the paragenesis cannot thereforedraw on preexisting theories and must answer two majorquestions: (1) the origin of the components (SiO,AI2O3, and Fe2θ3, with lesser amounts of TiCh, FeO,and MnO), considerable quantities of which must havebeen introduced into a wet carbonate mud (calciumcarbonate with very minor magnesium carbonate),where a high proportion reacted and crystallized to formsome 20 wt.% garnet in the ooze; (2) the physicalconditions, especially pressure and temperature, underwhich the garnets, once nucleated, were able to grow.

The garnets are found in a zone of ooze, recrystal-lized into calcite (micarb) chalk, from 0 to 18.3 metersabove the underlying basement basalt. If they grew as aresult of reaction between wet lime and includedcolloidal Siθ2, AI2O3, and Fe2Ch, this boundary wouldnot be sharp, and the garnets would be spread diffuselyover a considerable depth.. It therefore seems reason-ably certain that the source of the metasomatic materialwas the magma chamber below the basalt, from whichalkaline hydrothermal fluids emanated, traveling to thebasalt surface through cracks, veins, and fissures, and,possibly, intergranular pore spaces. These fluids eithercarried the components (SiCh, AI2O3, Fe2θ3, etc.) orleached them deuterically from the basalt and sub-sequently conveyed them to the basalt surface. Since thestratigraphic limit of garnet growth is the upper limit ofUnit 5 (the recrystallized and semilithified paleyellowish-brown calcite [micarb] chalk), it is consideredthat at the time of the hydrothermal event the upperboundary of Unit 5 probably represented the water-sediment interface or sea floor. As a result, the limitedvolume of ooze behaved as a closed system within whichunlimited diffusion could take place. The age of theupper boundary of Unit 5 could be some 10 or 20 m.y.younger than that of the basalt (estimated from paleon-tological and K/Ar ages). The hydrothermal fluidsrecrystallized the ooze into calcite (micarb) chalk andenriched it somewhat with iron (iron content = 3%),compared with the 468 meters of overlying unalterednannoplankton chalks and oozes (average iron content= 1.1%) (Fleet and Kempe, this volume, Chapter 21). Itis interesting to consider the possibility that, althoughthe iron enrichment is small compared with that in theiron-rich basal sediments from eastern Pacific Ocean(iron content up to 20%) described by Boström andPeterson (1966) and Cronan et al. (1972), and ascribed

to the hydrothermal leaching of newly extruded basalt,formation of the garnets may represent an alternativehydrothermal process to "umber" formation and mustalmost certainly take place in other basal carbonatesediments.

Alternative suggestions, however, proposed by A. J.Horowitz (personal communication), are that themicarb chalk might be authigenic, precipitated directlyfrom the heated sea-water at the time of extrusion of thebasalt. Or, again, that the micarb chalk might representthe sediment present, as ooze, at the time of extrusion ofthe basalt; the latter would then be analogous with anintrusive sill, and could have baked the ooze into itspresent form.

If the metasomatic components derive from thebasalts themselves, they must be extracted eitherby leaching or by deuteric decomposition of the basaltto the extent that the resulting material is able to dis-perse, possibly by convection, through the overlyingooze. The first suggestion would be substantiated if thealtered basalt could be shown to be significantlydepleted in Siθ2, AI2O3, and Fβ2θ3. Such depletioncould not, however, be considered as proof since altera-tion may result in such depletion of the basalt, withother gains and losses, without growth of garnet in theoverlying sediment. In Table 2, three analyses of fresh,intermediate, and, as near as possible, "contact" basaltare given (Kempe, this volume, Chapter 14). It can beseen that, in fact, the intermediate basalt is more highlyaltered than the "near contact" sample. Although itswater content is slightly lower, it shows greater loss inCaO and MgO and gain in K2O, Tiθ2, and total iron(Hart, 1970). It also shows a greater Fe2θ3/FeO ratio.So far as the garnet components are concerned, there isclearly no correlation. Silica is depleted but total iron isenriched; alumina is also enriched, although depleted inthe "near contact" rock.

If the metasomatic material derives directly fromdecomposition, it is worth considering theproposition that an analysis of palagonite from SwallowBank, North Atlantic Ocean (Matthews, 1971, p. 564)will (if the alkalis, phosphorus, water, and othervolatiles are replaced by lime) calculate to a very closeapproximation to the Site 251 garnet (Table 2). Palago-nite represents sideromelanic glass typical of surfacepillows of a ridge basalt altered by hot exotic water.Such glass is known to have been extruded at the base-ment contact at Site 251 (Kempe, Chapter 14, thisvolume). Similar replacement and calculation of theanalyzed basalt Sample 251A-31-1, 39-41 cm, gives amuch less satisfactory result. It is tempting to speculate,therefore, whether decomposition of palagonite formedfrom volcanic glass, rather than decomposition ofcrystalline basalt, could lead to the formation of thegarnets. A further possibility is that decompositioncould come about as a direct result of reaction withseawater upon extrusion (Hart, 1973, p. 77). However, itmust be stressed that total decomposition or activeleaching of the basalt is necessary to obtain the requiredcomponents. Deuteric alteration or reaction withseawater, while producing very considerable changes inthe chemistry of the basalt or basaltic glass, will

595

D. R. C. KEMPE, A. J. EASTON

TABLE 2Basalt and Palagonite Analyses from Site 251 and Swallow Bank, Atlantic Ocean,

with Two Analyses Recast as Garnet Compositions

sio2

TiO2

A12°3Fe2°3FeO

MnO

MgO

CaO

Na2O

K2O

H 2 0 +

H2°P2°5co2

Others

Total

SiAl

Al

Fe3+

Ti

Mg

Fe2+

MnCa

AlmandineAndraditeGrossularPyropeSpessartine

A a

50.37

1.60

14.60

1.70

8.74

0.17

7.13

10.84

2.67

0.12

0.90

0.62

0.15

0.23

0.16

100.00

B b

45.68

1.78

15.65

8.05

5.31

0.18

4.88

10.96

2.58

0.60

1.16

1.95

0.27

1.53

0.02

100.60

C c

45.89

1.47

13.44

6.77

5.14

0.18

7.43

11.48

2.57

0.30

1.47

2.17

0.16

1.60

0.01

100.08

B>d

45.68

1.78

15.65

13.95

-

0.18

4.88

19.07

-

-

-

-

-

-

-

101.19

l e

38.18

0.42

11.89

11.69

0.64

0.26

1.47

34.87

0.10

0.02

n.d.1

nü

-

-

-

99.54

D' f

41.96

1.63

16.06

9.39

nil

0.08

3.69

27.30

-

-

-

-

-

-

-

100.11

Numbers of Ions on the Basis of 24 Oxygens

6.63

2.68

1.530.20

1.06

0.022.97

64.29.1

26.20.5

6.04

2.22

1.390.05

0.35

0.090.035.91

1.539.452.16.30.6

6.29

2.84

1.060.18

0.82

0.014.37

38.051.310.40.2

41.96

1.63

16.06

9.39

nil

0.08

3.69

1.49

1.82

3.48

6.34

13.99

0.01

nil

0.17

100.11

E h

47.44

1.88

15.58

10.52

0.68

0.15

2.89

6.87

2.94

2.96

2.35

4.90

0.28

0.73

0.09

100.26

Fresh basalt, southwest branch, Indian Ocean Ridge, Sample 251A-31-4, 29-31 cm(Kempe, Chapter 14, this volume). Anal: C.J. Elliott and V.K. Din.

Altered intermediate basalt, Sample 251A-31-1, 39-41 cm (Kempe, Chapter 14, this volume).Anal: V. K. Din.cAltered "near contact" basalt, Sample 251A-30-1, 140-145 cm (Kempe, Chapter 14, thisvolume). Anal: V. K. Din.Analysis B, with alkalis, water, P2O5, and others replaced by CaO; total Fe is given as

Fe2°3eGarnet (Table 1, Analysis 1). Anal: A.J. Easton.Analysis D, with alkalis, water, P^^s> an{* others replaced by CaO.

gPalagonite, Swallow Bank (Matthews, 1971, Table 3, p. 564). Anal: W. H. Herdsman.hTypical basalt, Swallow Bank (Matthews, 1971, Table 3, p. 564). Anal: W. H. Herdsman.*Not determined.

596

METASOMATIC GARNETS IN SOUTHWEST INDIAN OCEAN

probably result in net gains to the basalt in iron, eithergains or losses in alumina, and rather limited losses insilica (Hart, 1970).

The answer to the second question — the physicalconditions of formation of the garnets — is far moredifficult to obtain. As stated earlier, no previous com-parable parageneses are known, and the most commongeneral paragenesis for garnets, metamorphism, is pre-cluded for lack of metamorphic temperatures andpressures. Only rodingites and synthetic garnets areavailable for comparison. Rodingites are generallyconsidered to result from metasomatic alteration ofgab-broic rock during the serpentization of the enclosingultramafic country rock. Such hydrothermal attacks ongabbroic rocks release and hold silica and alumina; theywill also release and hold lime, which may or may not besupplemented from an external source (de Waal, 1969).Silica tends to be deficient in such basic to ultrabasicrocks and hydrogrossular garnet, in which (OH)/4replaces silicon, is the main newly crystalline phase,often accompanied by the magnesium silicate, idocrase.Idocrase may also occur as an impurity in the hydro-grossular. Temperatures and pressures are relativelylow, and hydrogarnet is known to be far more commonthan the anhydrous species. Nevertheless, grossular hasbeen reported (Zabinski, 1966) and possibly, as may bethe case with the Site 251 garnets, nearly anhydrousmembers of the hydrogarnet series are fairly common inrodingitic parageneses.

Synthetic garnets have largely been high temperaturespecies, many of them gem varieties (cf. Nassau, 1972).Webster (1970) reviewed the range of rare earths andother trace elements (which include vanadium, zirco-nium, germanium, yttrium, and scandium) used in thesegarnets. Isaacs (1965) synthesized uvarovite in order tostudy its relationship with grossular and andradite.However, garnet syntheses, reviewed by Zabinski (1966,p. 55), include low-temperature examples. Zabinski alsomentions that hydrogrossular is among the resultantproducts of the hydration of Portland cement. Clayreactions with alkali solutions producing hydrogarnetshave been described by Krönert et al. (1964) andIwamoto and Sudo (1965). Krönert et al. found that claymixtures, including kaolinite, montmorillonite, andillite, reacted with calcium hydroxide to give productsthat included hydrogrossular, a process important insoil stabilization. Iwamoto and Sudo heated aluminousclays, some containing magnesium, with calcium car-bonate and ammonium chloride for 1 hr, at atmosphericpressure, at 500-1000°C. Without the aluminumchloride, the temperature of reaction rose higher,suggesting that the hydrogen in the NH•»+ cations mayhelp in the formation of hydrogarnet. Midgley andChopra (1960) found hydrogarnet among the productswhen lime and slag glass aggregate were autoclaved at188°C for between 2 and 48 hr at 11 bars.

Following Yoder's (1950) attempts to synthesizegrossular, Roy and Roy (1960) set out to investigate thepossibility of a complete solid solution series betweengrossular and hydrogrossular, as suggested by Yoder'swork, and the effects of time, temperature and pressureupon the stability of the phases. Roy and Roy's studysnowed a number of experimental facts: for example, it

is usually assumed, when a hydrogrossular forms from atotal grossular starting composition silica has beenleached out. Their hermetically sealed systems gavesimilar products and disproved the suggestion. Theyalso showed that gels yield more nearly anhydrousgarnets than do glasses when used as starting materials.

Using the grossular composition, in runs of (usually)at least one week and pressures of 2000 bars, theyobtained essentially pure grossular, with negligiblewater content, between 860° and 550°C; a solid solutionseries from pure grossular (Ca3AhSi3θi2) toCa3AhSi2.75θii(HO), probably metastable, at in-termediate temperatures (300-600°C); and a stable lowtemperature series from pure "hydrogarnet"(Ca3Al2(HO)i2) to about Ca3Al2Si2θ8(OH)4 at 360° to300°C. Thus it was shown that grossulars containing alittle water are probably metastable, since anhydrousgrossular can form at temperatures at least as low as600°C, needing only water to catalyze its formation; atlower temperatures (550° to 400°C) garnets with slightlyexpanded lattices may form. The earlier confusion, thea u t h o r s conclude, over the formation ofhydrogrossulars from the pure grossular composition isshown to be due to failure to attain equilibrium.

Lastly, and most relevant, Ito and Frondel (1967)produced a series of hydrogarnets from the appropriategels and silicon-deficient aqueous sodium hydroxidesolutions at a pH of 13.5. The mixture, at 1 bar, wasboiled for 10 min at 105°C and subsequently held at85°C for periods of between 1 and 3 days. Nucleationbegan during the initial boiling, with the formation of abulky precipitate which gradually coarsened and settledout. The garnets were centrifuged without washing andair dried at 120°C. They included the speciesCa3Fe2(Siθ4)(OH) and others in the same series, andzirconium- and titanium-bearing species. Finally,Arrhenius (1971) and L. H. Fuchs (in preparation),discussing chemical effects in plasma condensation inthe context of the formation of solar system, suggestthat among the final, low-temperature products of theresidual ionized fraction of a condensing gaseous systemwould be calcium aluminum garnet containing trivalentiron, such as has been observed in some carbonaceousmeteorites.

SUMMARY AND CONCLUSIONSIt is clear from synthesis experiments that garnets can

form at low temperatures (<100°C) and atmosphericpressure. Usually, such garnets are hydrogarnets, butFrankel (1959), and Roy and Roy (1960) quotedevidence that water can act as a catalyst to promotecrystallization of even anhydrous grossular inhydrothermal transformations. An environment such asthe Site 251 ooze where water is abundant but silica isalso probably in excess might be ideal for such growth,in contrast with a rodingite environment where silica ismarkedly deficient. The Site 251 garnets, therefore, areprobably anhydrous garnets containing small amountsof water, or, more likely, nearly anhydrous members ofthe hydrogarnet (grandite) series. The material in-troduced for their formation (Siθ2, AI2O3, Fβ2θ3) wasprobably transported from the magma source below thebasalt in a highly alkaline hydrothermal fluid, in which

597

D. R. C. KEMPE, A. J. EASTON

silica would be in solution and the trivalent oxides formcolloidal gels. Upon introduction into the ooze, agelatinous Ca-Al(Fe) complex may form, which, by achemical exchange process, would lead to widespreadnucleation of the garnets. Such nucleation might well bemetastable, controlled by, in addition to pressure andtemperature, such factors as pH, Eh, composition andconcentration of the components, and other variablesaffecting surface tension (Kirkinskiy, 1970). Thetemperature was probably rather less than 100°C,though presumably sufficient to recrystallize the oozeinto calcite (micarb) chalk, at a hydrostatic pressure ofthe order of 500 bars; the present pressure, in a totalwater plus sediment depth of about 4 km, must be of theorder of 600 bars. Zabinski concludes (1966, p. 56) thatthe most probable temperature range for the formationof natural hydrogarnets is 200 to 400°C, while pressuresare more difficult to assess. He suggests a relatively highpartial pressure of H2O, dependent to some extent onpH and chemical composition and considers thatgeological time, not available for synthetic products,may contribute substantially to natural hydrogarnetcrystallization at low temperatures and pressures.

Donnelly and Nalli (1973) suggest that the spessar-tine in the Leg 15 sediments might be authigenic.Spessartine is indeed one of the first minerals to crystal-lize in low-grade metamorphic facies. The present occur-rence cannot be described as authigenic since it involvesmetasomatism; it is, perhaps, a form of skarn. But thegarnets appear to have formed under normal diageneticconditions of pressure and temperature or, at most,those of the zeolitic facies. Zabinski (1966) sums up hisconsiderable study of the hydrogarnets by concludingthat they form and show maximum stability under con-ditions typical of the zeolitic and greenschist facies ofregional metamorphism and of the albite-epidote-hornfels contact facies; the latter two, in which tempera-tures in excess of 400°C are found, broadly mark thelower limits of stability of anhydrous garnets.

It is suggested, finally, that a search through calcite(micarb) chalks overlying basement basalt from otherDSDP sites would almost certainly reveal other garnetoccurrences and possibly shed more light on their modeof origin.

ACKNOWLEDGMENTSProfessor G. Arrhenius and Dr. M. H. Hey are sincerely

thanked for reviewing the manuscript and making manyhelpful suggestions. The authors are grateful to H. A. Buckleyfor taking the SEM photographs and to Miss Eva Fejer forrepeatedly confirming that the material under investigationand analysis was, in fact, garnet and for determining a.

REFERENCESAbbey, S., 1968. Analysis of rocks and minerals by atomic

absorption spectroscopy. Part 2. Determination of totaliron, magnesium, calcium, sodium and potassium: Geol.Surv. Canada, Paper 68-20.

Arrhenius, G., 1971. Chemical effects in plasma conden-sation: Nobel Symposium 21, from plasma to planet, Proc,Saltajöbaden, p. 117.

Boström, K. and Peterson, M. N. A., 1966. Precipitates fromhydrothermal exhalations on the East Pacific Rise: Econ.Geol., v. 61, p. 1258.

Clark, S. P., Jr., 1957. Absorption spectra of some silicates inthe visible and near infrared: Am. Mineral., v. 42, p. 732.Cronan, D. S., van Andel, T. H., Heath, G. Ross, Dinkelman,

M. G., Bennett, R. H., Bukry, D., Charleston, S., Kaneps,A., Rodolfo, K. S., and Yeats, R. S., 1972. Iron-rich basalsediments from the eastern equatorial Pacific: Leg 16, DeepSea Drilling Project: Science, v. 175, p. 61.

Deer, W. A., Howie, R. A., and Zussman, J., 1962. Rock-forming minerals, vol. 1: London (Longmans).

de Waal, S. A., 1969. On the origin of hydrogrossularite andother calcium silicates in serpentinites: Geol. Soc. S. AfricaTrans., v. 72, p, 23.

Donnelly, T. W. and Nalli, G., 1973. Mineralogy andchemistry of Caribbean sediments. In Edgar, N. T.,Saunders, J. B., et al., Initial Reports of the Deep SeaDrilling Project, Volume 15. Washington (U.S. Govern-ment Printing Office), p. 929.

Frankel, J. J., 1959. Uvarovite garnet and South African jade(hydrogrossular) from the Bushveld complex: Transvaal.Am. Mineral., v. 44, p. 565.

Hart, R. A., 1970. Chemical exchange between sea water anddeep ocean basalts: Earth Planet. Sci. Lett., v. 9, p. 269.

, 1973. Geochemical and geophysical implications ofthe reaction between sea-water and the oceanic crust:Nature, v. 243, p. 76.

Issacs, T., 1965. A study of uvarovite: Mineral. Mag., v. 35, p.38.

Ito, J. and Frondel, C, 1967. New synthetic hydrogarnets:Am. Mineral., v. 52, p. 1105.

Iwamoto, S. and Sudo, T., 1965. Chemical reactions amongclay minerals, calcium carbonate and ammonium chloride:Am. Mineral., v. 50, p. 886.

Jeffery, P. G. and Wilson, A. D., 1960. A combinedgravimetric and photometric procedure for determiningsilica in silicate rocks and minerals: Analyst, v. 85, p. 478.

Kennan, P. S., 1972. Some curious garnet clusters from theGarnetiferous Beds of the Leinster Granite aureole: Geol.Mag., v. 109, p. 165.

Kirkinskiy, V. A., 1970. Mechanism of metastable crystal-lization: Dokl. Akad. Sci. U.S.S.R., Earth Sci. Sect., v.192, p. 119.

Kroiiert, W., Schwiete, H. E., and Wetzel, K., 1964. Reak-tionen von Erdalkalihydroxiden mit Tonmineralieri inwassriger Suspension: Naturw, v. 51, p. 381.

Matthews, D. H., 1971. Altered basalts from Swallow Bank,an abyssal hill in the NE Atlantic and from a nearby sea-mount: Roy. Soc. Lond., Phil. Trans., Series A, v. 268, p.551.

Midgley, H. G. and Chopra, S. K., 1960. Hydrothermal reac-tions between lime and aggregate fines: Mag. ConcreteRes., v. 12, p. 73.

Milton, C, Chao, E. C. T., Fahey, J. J., and Mrose, M. E.,1960. Silicate mineralogy of the Green River formation ofWyoming, Utah and Colorado: Int. Geol. Congr. 21st,Norden, v. 21, p. 171.

Nassau, K., 1972. The state of the art — crystal growth. PartIII: Min. Record, v. 3, p. 103.

Riley, J. P. and Williams, H. P., 1959. The microanalysis ofsilicate and carbonate minerals. 1. Determination offerrous iron: Mikrochim. Acta, v. 4, p. 516.

Roy, D. M. and Roy, R., 1960. Crystalline solubility andzeolitic behavior in garnet phases in the system CaO-Ahθ3-Siθ2-H2O: Paper III-S9, Symp. Chem. Cement, 4th Inter-natl., Proc, Washington, D.C., p. 307.

Shapiro, L. and Brannock, W. W., 1962. Rapid analysis of sili-cate, carbonate and phosphate rocks: U.S. Geol. Surv.Bull. 1144-A.

Suhr, N. H. and Ingamells, C. O., 1966. Solution technique foranalysis of silicates: Anal. Chem., v. 38, p. 730.

598

METASOMATIC GARNETS IN SOUTHWEST INDIAN OCEAN

Tsao-Yung-Lung, 1964. Hydrougrandite, a new variety of Winchell, H., 1958. The composition and physical propertieshydrogarnet from Hsiaosungsha (abstract): Acta Geol. of garnet: Am. Mineral., v. 43, p. 595.Sinica, v. 44, p. 228. Yoder, H. S., 1950. Stability relations of grossularite: J. Geol.,

v. 58, p. 221.Webster, R., 1970. Modern synthetic gemstones: J. Gem- Zabinski, W., 1966. Hydrogarnets: Polska Akad. Nauk, Prace

mology, v. 12, p. 101. Min., v. 3, p. 3.

599

D. R. C. KEMPE, A. J. EASTON

PLATE 1

Photomicrographs (plain light, xlOOO) of the garnet-bearing calcite (micarb) chalk (Sample 251A-29-1-137).

600

METASOMATIC GARNETS IN SOUTHWEST INDIAN OCEAN

PLATE 2

SEM photographs by H. A. Buckley of the garnets, which are mostly 2µ - 3µ across (gold coating).

601