344-355, 1985 AmericanMineralogist,Volume70, pages

of Genesis diamond:a mantle saga

HsNnv O. A. MeYEn Department of Geosciences Purdue Uniuersity West Lafayette, lndiana 47907 Abstract basedon the physical,chemical A model for the genesis natural diamond is presented of that individual and mineralogicalpropertiesand featuresof diamond. Optical studiessuggest diamonds have had complex growth histories in which growth and dissolution may have similar occurred.Growth was not always continuousnor did diamonds grow in necessarily Evidencefor this is provided by variation in the nitrogen and trace chemicalenvironments. elementcontentsin diamondsas well as information from studiesof the mineralsincluded in diamond. Isotopic data suggestthat diamonds formed from carbon whose sourcesvaried isotopically.The possibilityexiststhat somediamondsmay be productsof recycledsubducted carbon, whereasothers have formed from primordial material either through magmatic or metasomaticprocesses. is also likely that most diamonds formed in the Archaean or It Proterozoic.The cognate host rocks for diamond in the mantle were severalbut can be broadly grouped into eclogitic and ultramafic (peridotitic); however, in mineralogic and chemical detail these rocks are quite diverse.Although diamond is commonly found in thesetwo rocks are not geneticallyrelated kimberlite and in lamproite at the earth's surface, in to diamond formation. Insteadthey are the transportingvehicles which diamond ascended rapidly from mantledepthsto the crust. Introduction Although diamond has beena sourceof fascination,the origin of this mineral has for centuriesperplexedman. Greek philosophers and medieval alchemists ziscribed many mystical properties to diamond. When taken as a powder,voluntarily or involuntarily, it could, among other poison ones enemiesor make the things, cure diseases,
honest strong and agile. An unusual belief, especially held in Greece and India was that diamond could procreate itself-a boon to the owner of a diamond mine. In 1772 Lavoisier demonstrated that diamond, like carbon, would burn in air. However, it was only later in 1797 that Smithson Tennant proved that diamond consisted of carbon. This led several gentlemen scientists of the nineteenth century to suggest that diamond was formed through the action of heat and pressure on plant remains (Des Cloizeaux, 1855; Goppert, 1862). The discovery of diamonds in a volcanic rock (kimberlite) at Kimberley, South Africa in 1871 led to more scientific, and less philosophical studies. This did not, however, deter various authors from presenting opposing viewpoints, as summarized by Williams (1932). For example, Lewis (1887) considered that diamond formed in the crust as the kimberlite host rock solidifled-the carbon being derived from coal and other carbonaceous material. In contrast others maintained that diamonds had originally formed in ultrabasic rocks at depths, and were subsequently released as the rocks fractured upon incorporation into the kimberlite melt (Harger, 1905; Holmes, 1936).The 0003-{04xl85/0304-{344$02.00

initial evidencefor this latter idea was the discovery of diamond in an eclogitexenolith from kimberlite (Bonney, Wagner (1914)and Sutton (1928) 1899).Du Toit (1906), that the eclogiteand perimodified this idea and suggested dotite xenoliths were cognate with the kimberlite. Diamond was thus genetically related to the early crystallization of kimberlitemagma. have lasted until the present The above two hypotheses and have developed with some modifications into the phenocrystversusxenocryst schools(Dawson, 1980).For example,Gurney et al. (1979)and Harte et al. (1980)maintain that diamonds are geneticallyrelated to early crystallization products of kimberlite within the upper mantle and are thus phenocrysts.In contrast, Meyer and Tsai (1976a),Robinson (1978),and Meyer (1982 a,b) have arguedthat diamondsare accidentalinclusionsin kimberlite and thus are xenocrysts;the associationof diamond and transporting and kimberlite being one of passenger vehicle. familiar with diamond concedethat diaMost scientists mond has grown stably within the upper mantle (Kennedy and Nordlie, 1968; Meyer and Boyd, 1972;Orlov, L973; of Omitted for purposes Sobolev,1974;Robinson,1978). of this discussionare the polycrystalline aggregates diamond (carbonado,framesite,boart) which have received Trueb study(Trueband DeWys,1969;1971; little scientific and Barrett, 1972; Gurney and Boyd, 1982) and whose origin is even more uncertain than the single crystal diahere. mond considered

344

MEYER: GENES/S OF DIAMOND: A MANTLE SAGA

345

Suggestions to the sourceof carbon from which diaas mond forms have been diverse and range from coal and plant remains as favored in the 1800's, carbon dioxide to and methanetoday. However,whetheror not the carbon is primitive or from recycledcrustal material is a necessary question.Current studieson carbon isotopes(Deines,1980; 1982;Milledge et al., 1983), well as on nitrogen (Becker, as 1982)and rare gases (Ozima and Zashu, 1983)bear on this question. An important factor in understandingthe formation of natural diamond is afforded by detailed examination of minerals included in diamond. Thesestudies,mostly crystallographic and mineralogical,have beenreviewedby Sobolev (1974),Meyer and Tsai (1976a), Harris and Gurney (1979)and Meyer (1982a). Isotopic studies of these small inclusions in diamond are now possibleand future work should provide significantresultsconcerningdiamond and the evolution of the upper mantle. This paper suggests model for the genesis diamond, a of and its subsequent passage the earth's surface.Current to interest in the evolution of the upper mantle and magma generationconsiders diamond to be an unreactive chemical probe from the depths. One aim of the discussionand model presented herein is to place the genesis diamond of within the correct context of mantle processes. is also It hoped that the discussionwill remove various misunderstandingsthat are prevalent with respectto diamond and its relationshipto kimberlite and other rocks. A subsidiary aim of this paper is to bring to the attention of mineralogiststhe large amount of important information contributed by physiciststo diamond research,and equally to exposephysiciststo geologicalprocesses attendenton diamond formation and the subsequent history of diamond. Although the host rocks for diamond at the earth's surface are kimberlite and lamproite, it is believedthat these rocks are not geneticallyrelated to diamond. Accordingly, it is not the aim of this paper to dwell on the nature of the chemical and mineralogical differencsbetween various kimberlites,and betweenkimberlites and lamproites.The interestedreader is referredto Dawson (1980)for kimberlites, Mitchell (1984)for lamproites, and the proceedings volumesof the threeInternational Kimberlite Conferences. Physical features of diamond A considerable amount of detailedstudy into the physics of diamond has been undertaken over the past 35 years (Berman,1965; Field, 1979).Much of this research has significance mineralogy and bears on the formation of to diamond. Figure la is a photographofa typical clear and colorless diamond without any visible flaws. This clarity, shown by many diamonds,suggests the observercrystallizationin to a singleuninterruptedevent.This is not the case. Figure In lb is shown a polished and etched surfaceof a diamond displayinga seriesof geometricallayers-referred to as the stratigraphy of diamond (Harrison and Tolansky, 1964; Seal, 1965). These patterns were interpreted by Frank (1966)as being due to periodic growth on octahedraland

Fig. l. (a) A transparent, and well shaped clear octahedron of diamond.Octahedral edgeI mm. (b) A polished and etched section throughan octahedral (2.4 diamond mm on edge), showing the internalstratigraphy diamond. of Variousgrowthlayersare eitherTypeI or TypeII diamond (Figure Harrison Tol3.1; and ansky, 1964).

cuboid surfaces.More detailed descriptionsof this phenomenon are to be found in Suzuki and Lang (1976)and Lang(1979).The stratigraphyof diamond can also be illustrated by cathodoluminescence polishedsurfaces on ofdiamond (Moore, 1979) and by X-ray topography (Lang, 1979). The growth stratigraphyis observed because various layers consist of either Type I or Type II diamond, and these two types have different chemical and physical properties(Table 1). The presence Type I and II diamond was first demonof strated by Robertsonet al. (1934)basedon differences in UV and IR absorption.Lonsdale(1942)showedthat Type I diamond producesextra X-ray diflraction reflections,or spikes.Thesespikeswereinterpretedto be due to platelets within the diamond structure (Frank, 1956).Kaiser and Bond (1959), and later Lightowlersand Dean (1964)proved

t46

MEYER: GENES/SOF DIAMOND: A MANTLE SAGA Table 1. Somepropertiesof diamond

CI ass i ficat ion Type la - Xosr comnon, appror. 981 of natural dianonds. Contains nitrogen up to 2500 ppn by uc. ss aggregares and platelets Lype Rare in naturc but mosc synthecic diamondE are of lhis < 20 pr fom. Nitrogen by pt in drsperscd Eubstitutional Very ra.e. NitroAen. large gen diamonds are by ur, 20 pF rhis rype. Often the very

of the presence nitrogen in Type I diamondsand showeda correlation betweennitrogen content and optical absorption at 7.8 pm (1282 cm- r). In contrast Type II diamond containsvery little nitrogen and no platelets. The aboveevidence suggests that the stratigraphyof diamond recordsperiodic growth in chemicallydifferent environments,at least with respectto the amount of nitrogen present.Alternatively, the rate of crystallization,or length time after partial growth may also contribute of residence in to differences nitrogencontent. At high pressure is possibleto causemigration of the it substitutional nitrogen in diamond so that the nitrogen (including platelets)found in natural diamonds aggregates Basedon the resultsof are produced(Evansand Qi, 1982). this study Evans and Qi suggestthat Type Ia diamond must haveexistedfor between200 million and 2000million years.This range in time is admittedly large but is due to knowledgeof the activation energyof migration insuffrcient and temof certain aggregates diamond at high pressure in perature. Nevertheless, the data indicate that some diaof monds have had gestationperiods in excess the age of the kimberlite eruption that transportedthem to the crust. In summary, although individual diamonds are grossly similar in physical properties detailed examination shows subtle differencesresulting in four distinct types of diamond (Table 1). Growth of diamonds is crystallographically discontinuous and reflects possible variation in chemistryof the growth environment.Experimentalaggregation of nitrogen to form platelets and other nitrogen very long residence times aggegatesin diamond suggests for diamond within the upper mantle prior to reachingthe earth'ssurface.

Type

lb -

Type lla

Type 1lb

rare 3nd generally blc in color. Semi_conducrins Ext.eoely (B .20 pr by wt.) uosc pure Eype of diadond.

Space croup: unit cell:

Fd3tu - Oil 3.56683 + o.oO00I to 3.56125. O.oOOOrl

D e n si r y : Type I - 1.51537 + 0.00005 go cn-3Type 1I - 3,51506 + 0,00005 go cn-r Ultrsviolet and lnfrared Type I Type II <140 nn and blteen SrronS absorpLion to 225 nm a.d berueen 6 to Trsnspare.r 6 to llxlo3 nm llxlo3 nm

Type ra rype lb type lIa TYpe tIb Therftal ConductrviEy Type la Type lI Resrs t Lvr ly

- various - various

(e.e. (e.s.

colortess, pale yerrov, yerlou, dark brom)

brom)

_ Colorless, - lllue

broen

6OO-1OOO -I m K-l (at 293"K) Z O O O - z t O Om - 1 K - l ( a t 2 9 3 ' K )

- >1016 ohm n Tvpe I Iype lla - ca.lu'" ohn n Typ IIb - tol - to5 "n.

'

Chemical features of diamond The presence of nitrogen as a major impurity in diamond has been noted, as also has the occurrence of boron ( < 20 ppm) which accounts for the semi-conducting properties of Type IIb diamond (Table 1). As a chemical sink for various elements, diamond is fairly poor with regard to concentration levels, although 58 elements have been recognized at the trace impurity level (Sellschop, 1979).Most of the results reported by Sellschop were obtained using instrumental neutron activation analysis, but early studies used emission spectrographic techniques (Chesley, 1942;Raal, 1957). Elements occurring in amounts greater than I ppm are listed in Table 2 (Sellschop, 1979), and most of these elements are typically present in silicate and sulfide magmas. In a significant contribution, Fesq et al. (1975)suggested that in certain instances the trace elements in diamond were contained in sub-microscopic inclusions that represented quenched, or temperature re-equilibrated, melt from which diamond had crystallized; composition of the melt was thought to be picritic. At the time of the study (197273) Fesq and coworkers were able only to examine batches of diamonds, and thus the data represent diamond of different type and origin. Recent developments in analytical

techniques (e.g. nuclear activation and ultra sensitive gamma ray spectroscopy) have enabled trace elements to be studied in a single diamond, and the results should provide significant information regarding the chemical differences between the various types ofdiamond. Various diamonds have diflerent trace element contents (Sellschop, 1979). This variation in trace element content suggests that different diamonds have not always formed under identical chemical conditions even though the diamonds may have been obtained from the same kimberlite pipe. If color is due to variation in trace element content,

presentin diamond (maximumppm by weight) Table 2. Elements

Element H I N o Na Mg AI Elenent Anount EleEnt

I r00 IO 5500 r700 34 370 I00 EO

s90 cl K48 ca Ti8 cr ln5 Fe t40 t000

Ce Hg

2 c
NT Cu

80 40 30 58 t4 t1 5

195

Ag Ba

si

present Elenent6 <lpFbyut:

in

diarcnd

F, Tb,

Sc, V, As, Rb, Sr, Sb, C3, Ih, Eu, Au Dy, Ho, Yb, Lu, Hf, Ta, W, Ir,

present in diabond Elenents values avarlable: but no absolute

Ar, Nd, pers.

zn, Ga, Ge, Br, Zr, Sn, U, Sn, Gd, Er, Pt, Pb,

Data

frm

sellschop

(1979,

and

coom.)

MEYER: GENES/SOF DIAMOND: A MANTLE SAGA then the wide range of colors in different diamonds from the same pipe can also be used, in part, to support the above arguement (Robinson, 1978). Isotopic studies Geochemical information bearing on the genesis of diamond is available from studies on the isotopes of carbon, nitrogen and rare gases. Carbon On the basis of a few measurements, the d13C value for diamond was once considered to be generally in the range -4 to -9o/oo(Craig, 1953; Wickman, 1956).More recently several authors (Galimov et al., 1978; Gurkina et al., 1979: Sobolev et al., 1979; Deines, 1980 and Milledge et al., 19g3) have extended the range from *3 to -34%oo. Nevertheless, the majority of diamonds studied (e.g.,Deines, 19g0) have 613C values in the range -4 to -8oln. In a significant study, Milledge et al. (1983) have examined the d13C content of 18 Type II diamonds and obtained a range of values between 0 and -32y@, although only two values were below - l5y@. It was concluded that Type II diamond is isotopically lighter than Type Ia diamond which presumably comprises the majority of diamonds. as noted above. The existenceof a range of dr3C values for diamond has a bearing on the source of carbon and the chemical reactions that produce diamond. Recent models (Deines, 1980; Mitchell, 1975) as to the role of a vapor phase in diamond formation have proven ambiguous, although the presence of a vapor could help explain the range of d13C. Deines (1980) concluded that this range was most likely inherited from the source carbon, suggesting isotopic heterogeneity in the mantle. Mitchell (1975) in contrast has pointed out that variation in the isotopic composition of diamond may be the result of re-equilibration (isotopic) of the solid phase with changing carbon-bearing gas compositions. Discussed later is the fact that minerals included in diamond can be assigned to either an ultramafic or eclogitic suite. A careful study by Sobolev et al. (1979) involved examination of d13C values of diamonds in terms of whether they contained ultramafic or eclogitic suite inclusions. For diamonds with ultramafic inclusions the majority had a 613C value of -5%oo and a restricted range between -2 and -9'/oo. Conversely, diamonds with eclogitic suite inclusions had 613C values ranging from 0 to -34%o. As pointed out by Milledge et al. (1983), this latter range is similar to that of Type II diamond, whereas the peak at -5Y* for the ultramafic suite diamonds corresponds to that of Type I. A study of the type of diamond in which eclogitic inclusions occur has yet to be undertaken. Nitrogen and rare gases Attempts to determine the origin of diamond and the geochemical nature of the upper mantle have also involved studies of the isotopes of nitrogen as well as those of rare gases,notably helium. Data on nitrogen isotopes are sparse and consequently any conclusions are speculative. Wand et

347

al. (1980)obtained a mean value for 61sN of +L5h, whereas Becker(1982) reporteda mean value of *29oln tor five diamonds,with a rangeof 0 to * Sc/n. Both thesemean valuesat presentresult in diamond being isotopicallylighter in nitrogen than mantle rocks (Becker and Clayton, 1977) whoserangeis +6 to +20o/',. Studies rare gases of in diamond (Ar, He, Ne) have been undertakenby Takaoka and Onma (1978),Oama and Zashu (1983), and Ozima et al. (1983).The latter authors reported 3HelnHevaluesfor three diamondsthat werein excess the primordial value of (1.42+ 2 x l0-a; Reynolds al., 1978), for meteorites et and close to the solar value (-{ x 10-a; Black, 1972).A second group of diamonds have much lower 3He/aHe ratios. Ozima and coworkers propose that the diamonds with high 3He74He ratios trapped primitive helium soon after the formation of the earth. whereasthose with lower valuesmay have formed later and included more evolved helium from the mantle. Most of the variations in isotopic contents of diamond can be explainedby considering that the carbon has passed through a subductioncycle(Frank, 1966). contrast,very In high 404r/36Ar ratios obtained by Takaoka and Ozima (1978)are interpreted as indicating that the carbon from which diamond formed has never reachedthe earth's surface; a similar comment is pertinent for the high 3He/4He valuesof Ozima et al. (1983).Melton and Giardini (1980) obtaineda 4o{rf361ltratio of 190for a diamondfrom the Prairie Creek diatreme,Arkansas,well below that of the atmospherewhich is taken as 296. Interestingly,this diatreme has recentlybeenreclassified a lamproitic kimberas lite (Scott Smith and Skinner, 1984), whereasMitchell and Lewis (1983)regard part of the diatremeto be a madupite. The data of Melton and Giardini (1980)representthe first published results of rare gas contentsin diamond from a non-kimberlitic primary source(seealso Roedder,1984,p. 508-51 1). Geochemicaland isotopic studies show that diamond contains many elementsin trace amounts, but generally those occurringin the largestconcentrations similar to are those presentin silicateand sulfide magmas.This suggests that diamond grew in a similar environment to most silicate-bearing rocks. Isotopic data, particularly the d13C values,show that the carbon from which diamond formed was isotopically variable. Furthermore, the variation in d13CbetweenType I and Type II diamond can be interpreted as diamond having formed in more than one environment, and one possibility is that somediamondsrepresent recycled crustal carbon. It is important that future isotopic studiesbe carried out on well-documented specimens,including geographic sourceand type of diamond. Mineral inclusions Various studiesof mineralsincluded in natural diamond are documented by Sobolev (1974), Meyer and Tsai (1976a),Harris and Gurney (1979)and more recently by Meyer (1982a). The significance mineral inclusionswith of regard to diamond genesis and the upper mantle characterization was appreciatedearly (e.g.,Bauer, 1896),

348

MEYER: GENESISOF DIAMOND: A MANTLE SAGA Table 3. Minerals occurringas inclusionsin diamond

but apart from Sutton (1921)and Williams (1932)little work was done until the 1950's(G0belin, 1952; Mitchell 1956,1958,1960). These and Giardini, 1953;Futergendler, were mostly optical and X-ray diflraction studies,and it was not until 1967that the first electronmicroprobeanalyses were obtained (Meyer, 1968; Meyer and Boyd, 1969, 1972).Since then others have contributed significantly to the study of inclusions(seeMeyer, I982a for references). A number of resultsfrom thesestudiesbear on the genesis of diamond. For example,most inclusionscan be assigned to one of two mineral suites-an ultramafic suite and an eclogitic suite (Table 3). Membersof the two suites that is, mineralsof one suite do not are mutually exclusive; coexist in the same diamond with minerals of the other (Meyer and Boyd, suite.The discoveryof this phenomenon was the first proof that diamonds L972;Prinzet al., 1975) grew in more than one geochemical environment. It should be noted that inclusionscan also be subdivided For purposes into protogenetic, syngenetic, and epigenetic. inclusionsare ofthis discussion only proto- and syngenetic considered.Many syngeneticinclusions, particularly olivine, display a cubo-octahedralmorphology that is imposed by the diamond host. In spite of diligent searchby scientists through severaltensofthousandsofdiamonds no macroscopic or microscopic fluid or gaseousinclusions havebeenfound (Roedder,1982;1984). The majority of mineral inclusionsare small (- 100 pm) and monominerallic,although bi- and polyminerallic inclusionsdo occur. Multiphase inclusionsare important becausethe chemicaland physical information they provide enables estimationof the pressure and temperatureof equilibration of the inclusions, and by inference that of the host during diamond genesis.Estimated conditions of equilibration for co-existingultramafic suite inclusions in diamond are between 900 and 1300'C and 45 to 65 kbar (Prinz et al., 1975; Meyer and Tsai, 1976b; Hervig et al., Thesevalueslie within the 1980;Boyd and Finnerty, 1980). region of diamond stability (Kennedyand Kennedy, 1976) and and are similar to those obtainedfor diamond-bearing diamond-freegarnet lherzolite xenoliths(Sheeet al., 1982). of It is not possibleto determineunequivocallypressures equilibration for eclogitesuite inclusions,but temperatures lie within the rangecalculatedfor the ultramaficsuite. A major unsolvedproblem at presentis the direct determination of the age of diamond from the diamond itself. to Currently, it is necessary obtain the age of syngenetic mineral inclusions and to assumethis approximatesthe diamond age. Kramers (1979) examined batches of inclusion-bearing diamonds from kimberlites in South Africa, and using lead isotopic techniquesdemonstrated that in general the inclusions,and by inferencethe diamonds, were much older than the kimberlite eruption. In the caseof the Finsch and Kimberley kimberlites,the age the of the diamondsis greaterthan 2 b.y.,whereas kimberlites erupted about 90 m.y. ago. More recent work by suggests somediamonds that may have Ozimaet al. (1983) agescomparableto the ageof the earth. Most ultramafic and ecloeitic suite inclusions have

Ultrenefic

Suite

Eclogitic Omphaci ie

suite

Oli vine EnEtatite Diops ide Cr -pyrope PhI ogopi te Cr - s p i n e I Mg-i 1reni te Zi r c o o Sulf ides Dianond

Py rope-alnandine Kyani te coesite Rut i Ie Ruby I lneni te Chrooite su1 fide s Dianond (Qurtz)

EP IGENETIC coethite, Kaolinite Serpentinc, craphite, Henatite, Sellaite, Xnotine

IJNCERTAIN PAMGENESIS Huscovite, Bioti!e, Senidine, Uagnetite, Anphibole

chemistries that differ in detail from similar minerals that occur in kimberlite. This is not to say that one cannot find of in kimberlite rare examples mineralsthat are chemically equivalent to those occurring as inclusions (Gurney and Switzer,1973)but thesemineralsare most probably xenocrystsunrelatedto kimberlite crystallization. Kimberlite and lamproite Kimberlites are widely distributed throughout the continental regionsof the world (Bardet, 1974,1977;Wilson, and Most are not diamond-bearing, comparedto the 1982). diamondiferousones have been little studied. Diamondiferouskimberlites appear to be confined mainly to the interiors of stable cratons. such as Southern Africa and Siberia, although somedo occur closeto continentalmargins 1982). Haggerty, in Liberia and SierraLeone(Bardet,1974; Dawson (1980)has provided a review of kimberlites and their xenoliths,and recentlyClementet al. (1984)haveproposed a redefinition and classificationof kimberlite (see 1979). alsoSkinnerand Clement, dikes and rarely as sills; Kimberlite occursin diatremes, multiple intrusions within a single diatreme are common. Neighboring diatremes,or pipes, may contain similar or very different suitesof xenoliths,or none at all. Somekimberlites contain almost entirely xenoliths of eclogite, for example the Roberts Victor kimberlite, whereas others, such as the Kimberley pipes, are rich in lherzolitic xenoliths. Multiple intrusionsin a singlepipe often contain their and more importantly own suite of xenoliths,or xenocrysts diamond. Type I and II diamonds can occur in the same pipe, and diamondswith ultramafic inclusionscoexistwith ones that contain eclogitic suite minerals.In spite of the economicimportance of diamond, it is a trace mineral in kimberlite and rangesonly up to I part in 2.5 million; a quoted figure is I in 20 million (e.g., Kennedyand Nordlie, 1968). Confusion has arisen due to the discoveryof diamondAustralia that unfortunately bearingrocks in north-western et 1982; were referredto initially as kimberlite (Jacques a1., The so-called"kimberlites" in that McCulloch et al., 1983).

MEYER: GENES/SOF DIAMOND: A MANTLE SAGA

349

A large number of eclogite xenoliths that contain diamond are known (Hatton and Gurney, 1979)but only a Discussion small number of diamondiferousultramafic xenolithshave beenfound. In contrast, the majority of diamondsstudied Relation of diamonil to kimberlite and lamproite contain ultramaflc suite inclusions (Boyd and Finnerty, The presence diamonds in both kimberlite and lam- 1e80). of proite, the presence similar inclusionsin diamondsfrom of Diamonds that contain eclogitic suite inclusions, and kimberlite and lamproite, the chemicaldifferences between diamonds that occur in eclogite are obviously easily astheseinclusionsand cognateminerals in the host kimber- signed to an eclogite source rock. Sobolev et al. (1972) lite and lamproite,plus the largedisparity between ages documentedthis relationship by examining inclusions in the of diamond and kimberlite intrusions lead to the con- diamond that itself was contained in an eclogite.The inclusion that diamond is not geneticallyrelated to either clusionsand the constituentminerals of the eclogite(clinkimberlite or lamproite.The relationshipof thesetwo rock opyroxeneand garnet)werechemicallyequivalent,suggesttypesto diamond is that they are the transportingmedium ing that the diamond is a constituent of the eclogite and by which diamond ascends the earth'ssurface. to Diamond thus formed contemporaneously with the eclogitehost. is best describedas a xenocryst in kimberlite and lamIn contrast,it is lesseasyto determinethe sourcerock in proite. which diamonds with ultramafic suite inclusions formed. One reasonfor this is that few rocks are known that have Transport of iliamond mineral phasesof comparablechemistryto the inclusions, The processof kimberlite ascentthrough the mantle is Furthermore,the ultramafic xenolithsthat do contain diaunknown although severalauthors have suggested various mond are chemically and mineralogically varied and inmodels which include zone refining (Harris and Middle- clude dunites (garnet * olivine-Pokhilenko et al., 1977), most, 1969),diapirism (Green and Guegen, 1974; Wyllie, harzburgites (garnet + olivine + orthopyroxene-

region are tuffaceouslamproites (i.e.,Ellendale,Argyle)---someof which are rich in diamonds(Jacques al., 1984). et Lamproitesare ultrapotassic rocks that may be plutonic, hypabyssal, volcanic.In the latter instanceboth lavas, or tuffs and vent breccias may be present. Generally the various rocks occur in groups,or fields,but worldwide they are relativelyrestricted(e.g.,LeuciteHills, Wyoming; West Kimberley, N.W. Australia).Mineralogicallyleucite(or sanidine) and Ti-rich minerals are almost ubiquitous. Tiamphibole,Ti-phlogopite,priderite,etc. are usually present and dependingupon the abundanceand type of minerals severalrock names are possible(e.g.,orendite, wolgidite, wyomingite,fitzroyite,etc.-Hughes, 197 p. 321; Mitchell, 2, 1984). The significanceof the diamond-bearinglamproites is that kimberlite is now not the only primary crustal source of diamond.It has beenreportedthat somenon-kimberlitic rocks in the Soviet Union contain diamonds (Kaminsky and Gevorkin,1976;Kaminsky, 1980;Dawson,1980). In several instancesre-evaluation of what were once considered"odd" kimberliteshas shownthem to be lamproitic. The diamond-bearingPrairie Creek diatreme in Arkansas is one such example,and is now referredto as lamproite (Scott Smith and Skinner, 1982,1984), and most likely the metakimberlites (Bardet, 1974)of the Ivory Coast (Knopf, 1970) and Gabon are lamproites. The question of whether or not diamonds from lamproiteshave differentinclusionsthan thosefrom kimberlite has been answered part from evidenceat Prairie Creek, in Arkansas.Diamonds from the Prairie Creek "lamproite" contain similar inclusions to those in diamonds from kimberlite-namely, olivine, enstatite,diopside,Cr-pyrope, pyrope-almandine, chromite and sulfides (Newton et al., 1977; Pantaleo et al., 1979).It is anticipated that similar mineral inclusions will be present in diamonds from the lamproitesin N.W. Australia.

1980; Anderson, 1982; Allegre, 1982)and conduit formation (Mercier, 1979\.McGetchin and Ullrich (1973)calculated a speedof ascentfor kimberlite of approximately70 km/hr on the basis of xenolith size and density.A similar value was computedby Mercier (1979)from olivine annealing data. Both theserates of ascentare consistentwith the cooling rates calculated by McCallister et al. (1979) for exsolution phenomenain pyroxenesfrom kimberlite. The evidenceat present thus favors a rapid ascent,possibly hours, for kimberlite (and diamond) from depths in the upper mantle. Although geochemical processes a diapir in may have contributed to the formation of kimberlite, the route through the upper mantle was probably by crack propagation(D. H. Eggler,pers.comm.,1984). It can be argued that the speedof ascenthas servedto preserve diamondsthat would havebeenabsorbedinto the kimberlite magmawith slow ascent. Other factorsaflecting the stability of diamond would be temperature, particularly the length of residence time at high temperatures and pressures outside the diamond stability field, and oxygen fugacity. Preliminary experiments(Meyer, unpub.) on the effect of temperatureandfo, on the oxidation rate of diamond at room pressure haveprovidedinteresting data.At an fo, equivalentto 10-12 atm. and a temperatureof 1000'C, roughly between the FMQ and MW (fayalitemagnetite-quartz, magnetite-wustite) buflers, diamond would disappearin about 2l days.In contrast under the same1[o,but at 800"C diamond would remain for about 110 years. At present the /or-temperature conditions for generationof kimberlitic, or lamproitic, magmasat depth are unknown. Arculus et al. (1982),Haggerty and Tompkins (1983)and Eggler (1983)suggestconditionsin the regionof the FMQ-MW bufers. Mantle rocks and diamond

350

MEYER: GENES/SOF DIAMOND: A MANTLE SAGA

Sobolev, 1974; McCallum and Eggler, 1976), and lherzol(garnet ites olivine clinopyroxene + + + orthopyroxene-Dawson and Smith, 1975; Shee et al., 1982). Diamond-bearing dunites consist of olivine and garnet whose chemistries are somewhat similar to those of the ultramafic suite inclusions from Siberian diamonds (Pokhilenko et al., 1977). Thus some Siberian diamonds may have been derived from the disaggregation of dunitic rocks, but such dunites have not been recognized elsewhere in the world. In contrast Shee et al. (1982), with specific reference to the Finsch kimberlite, South Africa, report no similarity in chemistry between the constituent minerals of a diamond-bearing garnet lherzolite and inclusions in loose diamonds from the same kimberlite. Any model of diamond genesis for the ultramafic suite diamonds also must explain the chemical variation, on a worldwide basis, of some of the mineral inclusion types. For example, clinopyroxene inclusions show a range in Cal(Ca * Mg) values from sub-calcic (<40 Cal(Ca + Mg)) to normal diopsides, while some are Cr-rich (Sobolev et al., 1975).It is unlikely that the sub-calcic diopside inclusions would have formed in the same environment as the Cr-rich ones, and thus it seems probable that diamond forms in more than one rock type of ultramafic character. The aforementioned differences in chemistry and mineralogy of the ultramafic xenoliths and inclusions, as well as the variety of xenolith types (dunite, harzburgite, lherzolite, etc.) that contain diamond are also paralleled by the mineralogical variety of eclogite xenoliths. Diamonds witb coesite inclusions (Milledge, 1961; Sobolev et al., 1976) and coesite eclogite (Smyth and Hatton, 1977)most likely have formed under conditions chemically distinct from those of ruby-bearing diamond (Meyer and Gubelin, 1981) or corundum eclogite. Further evidence in support of diamond having grown in several rock types within the broad classification ofeclogite and ultramafic rock is the variation of dr3C values. noted earlier, for eclogitic and ultramaflc suite diamonds. The view that diamond is a constituent of several mantle rocks has also been expressedby Sobolev (1974).

within the same general range (900 to 1300"C; 45 to 65 inkbar) as those obtained for xenoliths and megacrysts, thosewhich contain diamond.Thus it appearsthat cluding diamonds with inclusionshave equilibrated in the mantle at depths between140 and 200 km; within the bounds of and the asthenosphere roughly coincidingwith the thermal by maximum suggested Anderson (1980)to occur in the profile of the upper mantle. temperature

Cr y stallization of diamond The manner in which diamond grows is a subject of that diamond forms in a It controversy. has beensuggested solid state i.e., metamorphic reaction (Meyer and Boyd, or 1969;Boyd and Finnerty,1980), is the product of some (Sheeet al., 1982)or is of igneous form of metasomatism origin and crystallizedfrom a magma (Meyer and Boyd, 1972;Harte et al., 1980;Meyer, I982a,b). The evidenceis conflicting. The small size of the inclusions plus the fact that most are monominerallic led Meyer and Boyd (1972\to suggestthat diamonds crystallized from a melt. It is possiblethat the chemicaldissimilarity (particularly with regard to the ultramafic suite) of in inclusions diamondsand mineralsfrom the host xenoliths is a result of the inclusionshaving formed early on the liquidus and having been removed from further chemical reactionswith the liquid by the armoring effect of the diaby mond. Similar views have been expressed Fesq et al. (1978). (1975) and Robinson Although Gurney et al. (1979)and Harte et al. (1980) consider diamond to be an igneous phase they relate its genesisdirectly to the kimberlite magma. In view of the disparity betweenkimberlite agesand the age of diamond, growth from a kimberlite magmais untenable. of The presence alternatingstratigraphyof Type I and II discontinuousgrowth and minor chemidiamond suggests cal variation in the environmentin which growth occurred. Clues as to whetherthe growth processwas either igneous or metamorphicmay be found through a detailedstudy of the relationship betweenmineral inclusions and the host diamond strateigraphy. and baromeOn the basis of various geothermometers Boyd ters,particularlythoseof O'Neil and Wood (1979), Pressures and temperatures of diamond growth that the majority of and Finnerty (1980)cautiouslysuggest The proto- and syngenetic inclusions in diamond are all diamonds with ultramafic suite inclusionshave formed in phases that are stable at high pressuresand temperatures, subsolidusevents.The main reason for this conclusionis and are compatible with formation in the stability field for the fact that most inclusions in diamonds have equilibelow1150'C. diamond. Estimates of equilibration conditions for diabrationtemperatures monds are based on the chemistries of the inclusions and Metasomatic processesin the mantle are currently utilize the various geothermometers and barometers that widely discussed(Bailey, 1984; Boettcher et al., 1979; are also used in determining pressure and temperature reWyllie, 1980)although recently Walker (1983)has caugimes for xenoliths (e.g., Boyd, 1973; MacGregor, 1974; tioned, quite correctly, against solving all geochemical problemsof the mantle by invoking the "deusex machina" Lindsley and Dixon, 1975; Wells, 1977; O'Neil and Wood, Metasomatisingagentsrelevant to dia1979). Ideally for thermobarometric calculations three of metasomatism. coexisting and touching inclusions should be present in the mond formation are variouscombinationsof C, H and O. diamond. This is seldom the case and accordingly some Experimental studies of COr-HrO-peridotite systems (Eggler, 1977 1978;Wyllie, 1977 1978;Eggler and Wendassumptions have to be made. In spite of probable errors in , ; the use of these geothermobarometers, the equilibration landt, 1979;Ellis and Wyllie, 1980)have provided signifiand eruption of kimtemperatures and pressures obtained for diamonds are cant data and modelsfor the genesis

MEYER: GENESISOF DIAMOND: A MANTLE SAGA

351

Summary Various partial melting or metasomaticeventsin which dissolved CHo or CO, were present, resulted in crystallization of diamond at depths of approximately 180 km in the upper mantle. Isotopic data, especially that of carbon, are compatiblewith the possibility that diamonds iormed from carbon whosesources wereisotopicallydifferent. Variation in isotopecontentcould havebeenproduced by inhomogeneity primitive mantle material,the presin ence of recycled crustal carbon, or both. The growth of diamond was not unique to a singlerock but took placein any mantle material in which chemical interactions produced elemental carbon. Consequentlyseveral types of rock broadly grouped under eclogiteand ultramafic (peridotite) are the original cognatehostsof diamond.Evidence suggests that this crystallization of diamond occurred in the Archaean or Proterozoic.Subsequent mobilization of physicaland thermal perturmantle diapirs and associated bation of the proximal mantle rocks resultedin the incorSource of mantle carbon poration of diamond and xenoliths. Dependingupon the The source of the carbon that forms diamond is an locationofthe diapirismrelative the lithosphere, to various enigma.Variationsin d13Cvaluesfor diamondsmay reflect magmatic end products could have been produced.Kimeither an isotopically inhomogeneous of mantle or the pres- berlite or lamproite magmas,formed as a consequence enceof recycledcrustal material, or both. A similar com- diapiric processes, conveyeddiamond rapidly to the crust. ment is valid for the 3He/4Heand 404r/364'r values,al- Rapid ascentwas possibly through crack propagation in though more data are obviouslyneeded order to remove the mantle, and through a thick cool lithosphere whose in ambiguities. Meteorites, particularly the carbonaceous thermal regimeresultedin little lossof diamond. variety,havea rangeof 613Cvaluesthat is similarto that for diamond (Robertand Epstein,1982). Acknowledgments In addition to continual degassing the mantle in CHn of T. I. I thankDrs.F. R. Boyd, Eggler, Evans, D. MacGregor, D. and CO2 as suggested Gold (1979),the intriguing and R H. Mitchell, M. Moore, J. P. F. Sellschop and P. J. Wyllie for by

berlite magma (e.g.,Wyllie, 1980).However,the formation of kimberlite with or without CO, has little to do with the much earlier genesis diamond.Furthermore,if most diaof mondsare Archaeanor Proterozoic,it could be questioned as to whetherpresentthermal modelsof the mantle (Sleep, 1979;Anderson,1980)are valid for discussions the genof esisof diamond. Carbon in a melt is unlikely to be in elementalform (Olaffson and Eggler, 1983)but rather as some dissolved speciessuch as CO, or CHo. Whether CO, or CHo is presentin the melt depends the redox conditions.Studon ies of ilmenite (Haggerty and Tompkins, 1983; Arculus et al., 1982)and megacrysts (Eggler,1983)suggest values /., in the mantle to range from fayalite-magnetite-quaftzto magnetite-wustite. Theseconditionspossiblydo not reflect those of the early mantle which may have been more reduced (Haggerty and Tompkins, 1982). Sobolev et al. (1981)have reportedmetallic Fe inclusionsin Siberiandiamonds. In the event of a more reduced mantle, perhaps equivalent to iron-wustite bufer, the predominant dissolvedspecies a magma would be CHo (Woerman and in Rosenhauer, 1982;Egglerand Baker, 1982;Eggleret al., 1980;Ryabchikovet al., 1981). The occurrence CHn in of the mantle and its role in diamond formation has beenthe subjectof modellingby Deines(1980). It has been hypothesized (Gold, 1979; Gold and Soter, 1979)that the deep mantle is being degassed methane. of Melton and coworkers(1973, 1974)reported the presence of CO, and CHn among gasesthat were evolved from diamondsthey crushedbetween steelanvils in a massspectrometer.They found indications that other organic complexesof C and H were present,but their results require independentsubstantiation.As noted earlier, no macroscopic fluid or gaseous inclusions have been observedin diamond, although CO, has been recorded in fluid inclusionsin olivines from xenolithsin kimberlite (Roedder, 1963,1982, 1984). In summarythe evidence generallyfavors the formation of diamond either directly from an igneousmelt or from some type of metasomatisingfluid that has pervaded various types of mantle rock, perhapsat different times.It is not clear whether the carbon was derived from CO, or CHn but the presence CHn in diamond,metallic iron as of inclusions,and Cr2+ in olivinesincluded in diamond indicatereducedconditionswhich would favor CH..

speculative model of Dickey et al. (1983)provides a ready source of carbon. In this model elementalcarbon in the lower mantle is in the form of a metallic liquid. Subsequent perturbations causeupward migration of the carbon resulting in the formation of mantle plumes.Oxidation of the carbon produces CO, which causespartial melting and carbonation of the mantle silicate rocks. Theoretically,if elemental from the lower mantle it should carbon ascended pass through the hexagonaldiamond phase-lonsdaleite (Bundy and Kasper, 1967; Frondel and Marvin, 1967) beforeinverting to cubic diamond at lower pressures. However, the absenceof lower mantle phasesas mineral init clusionssuggests is unlikely that the carbon of Dickey et directlyformsdiamond. al. (1983) Recycledcrustal carbon in the form of carbonatein the mantle may be presentwithin regions of subduction.It is stableto appropriatedepths(Wyllie, L978,1980)and under the correct conditions diamond should be produced.The influence of such carbon is unknown, but generation of some diamondsfrom recycledcarbon (say eclogitic types), and other diamond from primitive carbon (mostly ultramafic types)would accountfor various chemicaland isotopic features.If this is the caseand if eclogitic diamonds are also very old (i.e. Proterozoicor older) then a corollary is that subductionmust have beenoperativeduring the early historyof the earth.

352

MEYER: GENESISOF DIAMOND: A MANTLE SAGA in Chesley,F. G. (1942)Investigationof the minor elements diamond. AmericanMineralogist,27, 20-36. Clement,C. R., Skinner,E. M. W. and Scott-Smith,B. H. (1984) Journal of Geology,92, 22T228. Kimberlite redefined. of Craig, H. (1953)The geochemistry stable carbon isotopes.Geet ochemica CosmochimicaActa,3, 53-92. Dawson, J. B. (1980)Kimberlites and Their Xenoliths. SpringerVerlag,New York. of Dawson,J. B. and Smith, J. V. (1975)Occurrence diamond in a mica-garnetlherzolite xenoliths from kimberlite. Nature, 254, 580-581. Deines, P. (1980)The carbon isotopic composition of diamond: relationship to diamond shape,color, occurrenceand vapor Acta, 44,943-961Geochimicaet Cosmochimica composition. Deines,P. (1982)The relationshipbetweeninclusion composition and carbon isotopic composition of host diamond. (abstr') Terra Cognita,2,2O2. A. DesCloizeaux, (1855)Note sur le diamant noir. Annalles des Mines Memoires,8, 30,t-306. Dickey, J. S., Bassett,W. A., Bird, J. M. and Weathers,M' S. (1983) Liquid carbonin the lower mantle.Geology,ll,2l9-22o. Du Toit, A. L. (1906)Geologicalsurveyof the easternportion of Griqualand West. Eleventh Report Geological Commission CapeColony, 89-176. Eggler,D. H. (1977)The principle of the zone of invariant vapor system the in An example composition: CaO-MgO-SiO2lOz-H2O and implications for the mantle solidus. Yearbook of the CarnegieInstitution of Washington, 't6,428435.

their constructivereviewsof the manuscript.Many of the ideas herein were formulated during the award from NSF of expressed grant EAR76-22698; however,I hastento add that errors in interpretation are mine alone. Note aildeilin press: for After the presentmanuscriptwas written and accepted publication, Richardsonet al. (Science, 310,198-202,1984)have pregarnet inclusions(ulsentedisotopic evidence that chrome-pyrop tramafic suite inclusions)in diamondshave model agesof 3.2 to 3.5 b.y., whereasthe host South Africa kimberlites were intruded roughly90 m.y.B.P.

Reference

an Allegre,C. J. (1982)Diapirism and magma genesis: instability (abstr.)Terra Cognita,2, 239. analysis. Anderson,D. L. (1982)The role of kimberlite in mantle evolution. (abstr.)Terra Cognita,2, 239. Anderson, O. L. (1980) The temperature profile of the upper mantle.Journal of Geophysical Research, 7003-7010. 85, Arculus, R. J., Dawson, J. B., Mitchell, R. H. and Gust, D. A. (1982)The intrinsic oxygen fugacities(/Or's) of megacrystilmenitesfrom southernAfrica kimberlites,Types A and B spinel peridotitesfrom San Carlos, Arizona. (abstr.)Terra Cognita, 2, 228. Bailey,D. K. (1984)Kimberlite: "The Mantle Sample"formed by ultra metasomatism. Kornprobst, Ed., Kimberlites I: KimIn New York. Eggler, D. H. (19?8)The effect of CO2 upon partial melting of berlite and RelatedRocks,p. 323-334. Elsevier, peridotite in the system NarO{aO-Al2O3-MgO-SiO2{O2 Bardet, M. G. (19'14) Geologiedu diamant. vol. II. Memoires du to 35 kb, with an analysisof melting in a peridotite-HzO{.O2 BureauRecherches Geologieet Mineralogie.No.83,Paris. 278,301343. AmericanJournal of Science, system. Bardet,M. G. (1977)Geologiedu diamant. vol. III. Memoiresdu from BureauRecherches Geologieet Mineralogie.No.83,Paris. Eggler,D. H. (1983)Upper mantle oxidation state: evidence Geophysical Re' vols.Reprintoftranslationby olivine-orthopyroxene-ilmeniteassemblages. Precious Stones.2 Bauer,M. (1896) New York, 1968. L. J. Spencer, 1904. Dover Publications, searchLetters,10,365-368. Becker,R. H. (1982)Nitrogen isotopic ratios of individual diaEggler, D. H. and Baker, D. R. (1982)Reducedvolatiles in the C-o-H: implicationsto mantle melting,fluid formation, systern mond samples. (abstr.) Fifth International Conference GeIn and diamond genesis. S. Akimoto and M. Monghnani, Eds., ochronology, Cosmochronology, Isotope Geology. Nikko, p.237-250. Center for in High PressureResearch Geophysics, Japan. Tokyo. AcademicPublications, Becker, R. H. and Clayton, R. H. (1977) Nitrogen isotopes in rocks. (abstr.) Transactions of the American Geophysical Eggler, D. H. and Wendlandt, R. F. (1979)Experimentalstudies on the relationship between kimberlite magmas and partial Union, 58,536. melting of peridotite.In F. R. Boyd and H. O. A. Meyer, Eds., Berman, R. (1965) Physical Properties of Diamond. Clarendon Kimberlites, Diatremes and Diamonds: Their Geology, PetPress, Oxford. rology and Geochemistry,p. 330-338.American Geophysical Black, D. C. (1972)On the origins of trapped heliurn,neon, and D.C. argon isotopic variations in meteorites-I. Gas-rich meteorites, Union, Washington, lunar soil and breccia.Geochemica CosmochimicaActa, 36, Eggler,D. H., Baker, D. R. and Wendlandt, R. F. (1980) et /O, of experigraphite-nstatite-forsterite-magnesite: 347,375. the assemblage Boettcher,A. L., O'Neil, J. R., Windom, K. E., Stewart,D. C. and ment and application to mantle/O2 and diamond formation. (abstr.)GeologicalSocietyof America Program with Abstracts, and the genesis kimberof Wilshire,H. G (1979)Metasomatism In lites and alkali basalts. F. R. Boyd and H. O. A. Meyer, Eds., 12,420. The Mantle Sample:Inclusionsin Kimberlites and Other VolEllis, D. E. and Wyllie, P. J. (1980)Phaserelationsin the system up canics,p. 173 182.American GeophysicalUnion, Washington, MgO-SiOr-HrO-CO2 at pressures to 100 kbar and petDC. rologicalimplications.AmericanMineralogist,65, 5'!0-556. Bonney,T. G. (1899)The parent rock of the diamond in South Evans, T. and Qi, Z. (19E2\The kinetics of the aggregationof ofthe Royal Societyof Africa. Proceedings ofthe Royal Society,65,223-236. nitrogen atomsin diamond.Proceedings Boyd, F. R. (1973)A pyroxenegeotherm.Geochimicaet CosmoLondon,A381,159-178. chimica Acta. 37. 2533-2546. Fesq, H. W., Bibby, D. M., Erasrnus,C. S., Kable, E. J. D. and J. Boyd, F. R. and Finnerty, A. A. (1980)Conditions of origin of Sellschop, P. F. (1975)A comparativetrace elementstudy of mines,South natural diamonds of peridotite affrnity.Journal of Geophysical diamondsfrom Premier,Finsch and Jagersfontein ofthe Earth,9,817-836. and Chemistry Africa.Physics Research. 6911-6918. 85. Field, J. E. (1979\The Propertiesof Diamond. Academic Press, Bundy, F. P. and Kasper,J. S. (1967)Hexagonaldiamond-a new New York. form of carbon.Journal of ChemicalPhysics,46,3437-346.

MEYER:GENESTSOF DIAMOND: A MANTLE SAGA Frank, F. C. (1956)On the X-ray diffraction spikesof diamond. Proceedings the Royal Societyof London, A37,168-174. of Frank, F. C. (1966)Defectsin diamond.Proceedings International Industrial Diamond Conference,p. 119-135. Industrial Diamond Information Bureau,London. Frondel, C. and Marvin, U. B. (1967)Lonsdaleite,a hexagonal polymorph of diamond.Nature, 214,587-589. Futergendler, I. (1956)The study of inclusionsin diamondsby S. the method of x-ray structural analysis.(in Russian)Zapiski Vsesoyznyi MineralogiaObshchestva, 568-656. 85, Futergendler,S. L (1958)X-ray study of solid inclusionsin diamond (in Russian) SovietPhysics-{rysrallography, 3, 49U97. Futergendler,S. L (1960)X-ray study of solid inclusionsin the Ural and Yakutia diamonds.MaterialsVsesoiuznogo NauchnoIssledovatel'skogo Geologicheskogo Instituta, no. zt0, 3_82 (in Russian). Galimov, E. M., Kaminsky, E. V. and Ivanovskaya,I. N. (1928) Study of carbon isotop compositionsof diamonds from the Urals, Timan, Sayany,Ukraine and other regions.(in Russian) Geokhimiy43,3fi-349. Gold, T. J. (1979)Terrestrial sourcesof carbon and earthquake outgassing. Journal of PetroleumGeology,l, 1-19. Gold, T. J. and Soter, S. (1979) Brontides: Natural explosive noises. Science, 2M, 37l-37 5. Goppert,H. R. (1862)Uber Einschluse diamant.Breslau. in Green,H. W. and Guegen Y . (1974)Origin of kimberlite pipesby , diapiric upwelling in the upper mantle. Nature physical Scienes,249,617-620. Giibelin, E. (1952) Inclusions in diamonds. Journal of Gemmology, 3, 174-187. Gurkina, G. A., Ivanovskaja,I. N., Kaminski, F. V. and Galimov, E. M. (1979) Geokhimiy4 1897-1905. Gurney, J. J. and Boyd, F. R. (19E2)Mineral intergrowths with polycrystalline diamonds from the Orapa Mine, Botswana. Yearbook of the CarnegieInstitution of Washington,8l,267273. Gurney, J. J. and Switzer,G. S. (1973)The discoveryof garnets closely related to diamonds in the Finsch pipe, South Africa. Contributionsto Mineralogyand Petrology,39, 103-116. Gurney, J. J., Harris, J. W. and Pickard, R. S. (1979)Silicateand oxide inclusionsin diamonds from the Finsch kimberlite pip. In F. R. Boyd and H. O. A. Meyer,Eds.,Kimberlites,Diatremes and Diamonds: Their Geology,Petrologyand Geochemistry, p. 1-15.AmericanGeophysical Union, Washington,D.C. Haggerty, S. E. (1982)Kimberlites in WesternLiberia: An overview of the geologicalsetting in a plate tectonic framework. Journal of Geophysical Research, l08f f-10826. 87, Haggerty,S. E. and Tompkins, L. A. (1983)Rdox stateof Earth's uppermantle frorn kimberlitic ilmenites. Nature, 3O3,295-ZW. Harger, H. S. (1905)The diamond pipes and fissuresof South Africa. Transactionsof the GeologicalSocietyof South Africa, 8. 110-134. Harris, J. W. and Gurney,l. J. (1979) Inclusionsin diamonds.In J. E. Field, Ed., The Propertiesof Diamond, p. 555-594.Academic Press, New York. Harris, P. G. and Middlemost, E. A. K. (1969)The evolution of kimberlites.Lithos, 3, 77-88. Harrison, E. R. and Tolansky,S. (1964)Growh history of a natural octahedraldiamond. Proceedings Royal Societyof London, 41279,490496. Harte, 8., Gurney, J. J. and Harris, J. W. (1980)The formation of peridotitesuiteinclusionsin diamonds.Contributions to Mineralogy and Petrology,72, l8l-190.

353

Hatton, C. J. and Gurney,J. I. (1979)A diamond-graphite eclogite from the Roberts Victor mine. In F. R. Boyd and H. O. A. Meyer, Eds.,The Mantle Sample Inclusionsin Kimberlites and : Other Volcanics, p. 29-36. American Geophysical Union, Washington, D.C. Hervig R. L., Smith, J. V., Steele, M., Gurney, J. J., Meyer, H. I. O. A. and Harris, J. W. (1980)Diamonds: Minor elementsin silicate inclusions: Pressure-ternperature implications. Journal of Geophysical Research,85, 69194929. Holmes, A. (1936)A contribution to the petrology of kimberlite and its inclusions.Transactionsof the Geological Society of South Africa, 39,379427. Hughes, J. (1982) C, Igreous Petrology.Elsevier, New York. Jacques, L., Gregory,G. P., Lewis,J. D. and Ferguson, (1982) A. J. The ultrapotassic rocks of the West Kimberley region, Western Australia, and a new class of diamondiferouskimberlitc. (Extendedabstr.)Terra Cognit4 2,251152. Jacques, L., Lewis, J. D., Smith, C. B., Gregory, G. P., FergusA. on, I., Chappell, B. W. and McCulloch, M. T. (1984) The diamond-bearing ultrapotassic (lamproitiQ rocks of the West Kimberley region,WesternAustralia.In Kornprobst, Ed., Kimberlite I: Kimberlites and related rocks, 223-254.Elsevier,New York. Kaiser, W. and Bond, W. L. (1959)Nitrogen, a major impurity in cornmontype I diamond.Physics Review,f 15,857-863. Kaminsky, F. V. (1980)Authentic and valid diamond occurrences in alkali-basaltoids and ultramafic (non-kimberlitic)bodies.(in Russian)Zapiski VsesoyrrmyiMineralogia Obshchestva,109, 488-493. Kaminsky, F. V. and Gevorkin, P. G. (1976)Non-kimberlitic pri mary diamonds. (in Russian) Izvestia An. Armenia SSR, 2, 32-q. Kennedy, C. S. and Kennedy, G. C. (1976) The equilibrium boundary betweengraphite and diamond. Journal Geophysical Research, 24'll-247 4. 81, Kennedy,G. C. and Nordlie, B. E. (1968)The genesis diamond of deposits. EconomicGeology,63,495-503. Knopf, D. (1970)Les kimberliteset les rochesapparentees Cote de d'Ivoire. SODEMI, Abidjan. Kramers, J. D. (1979)Pb, U, Sr, K, and Rb in inclusion-bearing diamonds and mantle-derivedxenoliths from southern Africa. Earth and PlanetarySciences Letters,42,58-70. Lang, A. R. (1979) Internal structure. In J. E. Field, Ed., The Propertiesof Diamond, p.425469. AcademicPress, New York. periodotite and thc genesis Lewis, C. (1887)On a diamondiferous 4,22-24. of the diamond.GeologicalMagazine, Lightowlers,E. C. and Dean, P. J. (1964)Measurement nitrogen of concentrationsin diamond by photon activation analysisand optical absorption. Diamond Research1964, p. 21-25. Supplementto Industrial Diamond Review,London. Lindsley, D. and Dixon, S. H. (1975) Coexisting diopside and enstatiteat 20 kbar and 900-1200"C.AmericanJournal of Science,276, 1285-1301. Lonsdale,K. (1942)Extra reflexionsfrom the two types of diamond. Proceedings ofthe Royal Society,4179,315-320. MacGregor, l. D. (1974) The system MgO-A.lrOr-SiOr: Solubility of AlrO, in enstatitefor spineland garnetperidotite cornpositions.AmericanMineralogist,59, I 10-l 19. McCallister,R. H., Meyer, H. O. A. and Aragon, R. (1979)Partial thermal history of two exsolved clinopyroxenes from the Thaba Putsoa kimberlite pipe, Lesotho. In F. R. Boyd and H. O. A. Meyer, Eds.,The Mantle Sample:lnclusionsin Kimberlitesand

354

MEYER: GENESISOF DIAMOND: A MANTLE SAGA A Moore, M. (1979) Optical studiesof diamond and their surfaces: Tolansky'swork. In J. E. Field, Ed., reviewof the late Professor The Propertiesof Diamond, p.243-277. AcademicPress,New York. Newton, M. G., Melton, C. E. and Giardini, A. A. (1977)Mineral inclusionsin an Arkansasdiamond.American Mineralogist,62, 583-586. Olaffson,M. and Eggler,D. H. (1983)Phaserelationsof amphiboperidotite: le, amphibole-carbonate, and phlogopite-carbonate Earth and Planepetrologic constraintson the asthenosphere. Letters,64, 305-315. tary Science study of O'Neil, H.St. C. and Wood, B. J. (1979)An experimental Fe-Mg partitioning betweengarnet and olivine and its calibraContributions to Mineralogy and tion as a geothermometer. Petrology,70, 59-70. Orlov, Yu. L. (1973)The mineralogy of the diamond. Izdatel'stva Nauka. (Transl.,J. Wiley and Sons,New York, 1977). Ozima, M. and Zashu, S. (1983)Primitive helium in diamonds. 219,1067-1068. Science, Ozima, M., Zashu, S. and Nitoh, o. (1983)tHeloHe ratio, noble gas abundanceand K-Ar dating of diamonds-An attempt to searchfor the recordsof early terrestrialhisrory. Geochimicaet -2224. CosmochimicaActa,47, 2217 Pantaleo,N. S., Newton, M. G., Gogineni, S. V., Melton, C. E. and Giardini, A. A. (1979)Mineral inclusionsin four Arkansas diamonds: their nature and significance. American Mineralogist,64,1059-1062. Pokhilenko, N. P., Sobolev,N. V. and Lavrentyev,Yu. G. (1977) Xenoliths of diamantiferousultrarnafic rocks from Yakutian (abstr.)SecondInternational Kimberlite Conference. kirnberlies. AmericanGeophysical Union, Washington,D.C. Prinz, M., Manson, D. V., Hlava, P. F. and Keil, K. (1975)Inclusions in diamonds. Garnet lherzolite and eclogite assemofthe Earth,9,79'l-815. Physics and Chemistry blages. study of the minor element Raal, F. A. (1957)A spectrographic contentof diamond.AmericanMineralogist,42,35+361. Reynolds,J. H., Frick, U., Neil, J. M. and Phinney,D. L. (1978) Rare gas-rich separatesfrom carbonaceouschondrites. Ge5-1797. ochimicaet CosmochimicaActa,42, 177 Robert, F. and Epstein,S. (1982)The concentrationand isotopic compositionof hydrogen,carbon and nitrogen in carbonaceous Acta,46, 81-95. et meteorites. Geochimica Cosmochimica Robertson,R., Fox, J. J. and Martin, A. E. (1934)Two types of diamond. Philosophical Transactions of the Royal Society, A232,463-538. of Robinson, D. N. (1978)The characteristics natural diamond and Engineering,10, and their interpretation.Minerals Science 55-'t2. Roedder,E. (1963)Studiesof fluid inclusionsII: freezingdata and -211. their interpretation.EconomicGeology,58,167 Valuable deRoedder,E. (1982)Fluid inclusions in gemstones: fects. International Gemological Symposium Proceedings,p. 479-502. GemologicalInstitute of Americ4 Los Angeles. Roedder,E. (1984)Fluid Inclusions.Reviewsin Mineralogy, Vol. 12.MineralogicalSocietyof America. I. Ryabchikov, E., Green,D. H., Wall, V. J. and Brey,G. P. (1981) The oxidation state of carbon in the reduced-velocityzone. International,18,221-232. Geochemistry Seal, M. (1965) Structure in diamonds as revealedby etching. AmericanMineralogist,50, 105-123. Sellschop,J. P. F. (1979)Nuclear probes in physical and geochemicalstudiesof natural diamonds.In J. E. Field, Ed., The AcademicPress, New York. Propertiesof Diamond, p. 107-163.

Other Vofcanics, p. 244-248. American Geophysical Union, Washington,D.C. McCallum, M. E. and Eggler,D. H. (1976)Diamondsin an upper mantle periodotite nodule from kimberlite in SouthernWyoming. Science,192,253-256. McCulloch, M. T., Jacques, L, Nelson, D. R. and Lewis, J. D. A. (1983)Nd and Sr isotopesin kimberlites and lamproites from WesternAustralia: an enrichedmantle origin. Nature, 3O2,4W403. McGetchin, T. R. and Ullrich, G. W. (1973)Xenoliths in maars and diatremeswith inferences the Moon. Mars and Venus. for Journalof Geophysical Research, 1833-1853. 78, Mercier, J.-C. C. (1979)Peridotite xenoliths and the dynamicsof kimberlite intrusion. In F. R. Boyd and H. O. A. Meyer, Eds., The Mantle Sample:Inclusionsin Kimberlites and Other Volcanics,p. 197-212.American GeophysicalUnion, Washington, D.C. Melton, C. E. and Giardini, A. A. (1974)The composition and significance gas released of from natural diamondsfrom Africa and Brazil. AmericanMineralogist,59,775-782. Melton, C. E. and Giardini, A. A. (1980)The isotopecomposition of argon includedin an Arkansasdiamond and its significance. Geophysical Research Letters,7, 461464. Melton, C. E., Salotti, C. A. and Giardini, A. A. (1974)The observation of nitrogen,water,carbon dioxide,methaneand argon as impurities in natural diamond. American Mineralogist, 57, 1518-1523. Meyer, H. O. A. (1968)Inclusions in diamond. Yearbook of the Carnegie Institution of Washington,66, 44450. Meyer, H. O. A. (1982a) Mineral inclusions natural diamond. in International GemologicalSymposiumProceedings, 441465. p. GemologicalInstitute of America,Los Angeles. Meyer, H. O. A. (1982b)The genesis diamond. (abstr.)Terra of Cognita,2,199. Meyer, H. O. A. and Boyd, F. R. (1969)Inclusionsin Diamond. Yearbook of the CarnegieInstitution of Washington,68, 315324. Meyer, H. O. A. and Boyd, F. R. (1972)Compositionand origin of crystallineinclusionsin natural diamonds.Geochimicaet CosmochimicaActa. 36. 1255-1273. Meyer,H. O- A. and Giibelin,E. (1981) Ruby in diamond.Gems and Gemology,l7, 153-156. Meyer, H. O. A. and Tsai, H.-M. (1976a)Mineral inclusionsin natural diamond: their nature and significance. Mineral Science g, and Engineerin 8, 242-261. Meyer, H. O. A. and Tsai, H.-M. (1976b)Mineral inclusionsin diamond: Temperatureand pressureof equilibration, Science, 191, 849-851. Milledge, J. (1961) H. Coesite an inclusion C. E. C. synthetic as in diamonds. Nature,190,1181. Milledge, H. J., Mendelssohn, J., Seal,M. Rouse,J. E., Swart, M. P. K. and Pillinger, C. T. (1983)Carbon isotopic variations in spectraltype II diamonds. Nature, 303,791-792. Mitchell, R. H. (1975)Theoreticalaspects gaseous of and isotopic equilibria in the systemC-H-O-S with application to kimberlite. Physicsand Chemistryof the Earth, 9, 903-915. Mitchell, R. H. (1985)A review of the mineralogy of lamproites. Transactions GeologicalSocietyofSouth Africa, in press. Mitchell, R. H. and Lewis,R. D. (1983)Priderite-bearing xenoliths from the Prairie Creek mica peridotite, Arkansas. Canadian Mineralogist,21, 59-64. Mitchell, R. S. and Giardini, A. A. (1953) Oriented olivine inclusionsin diamond.AmericanMineralogist,38, 136-138.

MEYER: GENESISOF DIAMOND: A MANTLE SAGA Scott Smith, B. H. and Skinner,E. M. W. (1984)A new look at Prairie Creek, Arkansas. In Kornprobst, Ed., Kimberlites I: Kimberlitesand relatedrocks,p. 255154. Elsevier, New York. Shee, S. R., Gurney, J. J. and Robinson, D. N. (1982) Two diamond-bearingperidotie xenoliths from the Finsch kimberlite, South Africa. Contributions to Mineralogy and Petrology, 81,79-87. Skinner,E. M. W. and Clement,C. R. (1979)Mineralogicalclassification of southern African kimberlites.In F. R. Boyd and H. O. A. Meyer, Eds., Kimberlites, Diatremes and Diamonds: Their Geology, Petrology and Geochemistry, p. 129-139. AmericanGeophysical Union, Washington, D.C. Sleep,N. H. (1979)Thermal history and degassing the earth: of Somesimplecalculations. Journal of Geology,87,671-686. Smyth,J. R. and Hatton, C. J. (19'17) coesite-sanidine A grospydite from the Roberts Victor kimberlite. Earth and Planetary Sciences Letters,34,28+290. Sobolev,N. V. (1974)Deep-seated inclusionsin kimberlites and the problem of the composition of the upper mantle. (Translation by American Geophysical Union, Washington, D.C., r977). Sobolev, V., Ellimova, E. S. and Pospelova, N. (1981)Native N. L. iron in Yakutian diamonds, its paragenesis. Russian)Ge(in ology and Geophysics, Doklady Akademii Nauk SSR,Siberian Division. 12.25-29. Sobolev,N. V., Efimova, E. S., Koptil, V. I., Lavrent'yev,Yu. G., and Sobolev,V. S. (1976)Inclusionsof coesite, garnet and omphacite in Yakutian diamond: the first discovery of coesite paragenesis. Russian)Doklady Akademii Nauk SSSR,230, (in 1442-1446. Sobolev,N. V., Galimov, E. M., Ivanovskaya, N. and Yefimova, I. E. S. (1979)The carbon isotopecompositionsof diamondscontaining crystallographicinclusions.(in Russian)Doklady AkademiiNauk SSSR,249, 1217-1220. Sobolev,V. S., Sobolev,N. V. and Lavrent'yev, Yu. G. (1972) Inclusions in diamond extractedfrom a diamondiferouseclogite.(in Russian) Doklady AkademiaNauk SSSR, 2O7, l&-167. Sobolev, S., Sobolev, V. and Laurent'yev, V. N. Yu. G. (1975) Chrome-rich clinopyroxenesfrom the kimberlites of Yakutia. NeuesJahrbuchfiir Mineralogie,Abhandlungen, 123,213-218. Sutton, J. R. (1921)Inclusions in diamonds from South Africa. MineralogicalMagazine, 2O8-21O. 9, Sutton, J. R. (1928)Diamond: A descriptivetreatise.T. Murby, London.

355

Suzuki, S. and Lang, A. R. (1976)Internal structuresof natural diamonds revealing mixed growth habit. Diamond Research 1976, p. 39 47. Supplementto Industrial Diamond Review, London. Takaoka, N. and Ozima, M. (1978) Rare gas isotopic compositionsin diamond. Nature,271,4546. Trueb, L. F. and Barrett, C. S. (1972) Microstructural investigation of ballas diamond. American Mineralogist, 57, 16641680Trueb,L. F. and De Wys,E. C. (1969) Carbonado:Naturalpolycrystallinediamond.Science, 165,799-802. Trueb, L. F. and De Wys, E. C. (1971)Carbon from Ubangi-a microstructuralstudy.AmericanMineralogist,56, 1252-1268. Wagner, P. A. (1914)The Diamond Fields of Southern Africa. Reprinted l97l,C. Struik (fty) Ltd, CapeTown. Walker, D. (1983)New developrnents magmaticprocesses. in Reviewsof Geophysics and Space Physics, 21,1372-1384. Wand, U., Nitzsche,H.-M., Muhle, K. and Wetzel,K. (1980)Nitrogen isotope composition in natural diarnond-First results. Chemieder Erde, 39,85-87. Wells, P. R. A. (1977)Pyroxenethermometryin simple and complex systems. Contributions in Mineralogy and Petrology, 62, 129-139. Wickman, F. E. (1956)The cycle of carbon and stable carbon isotopes. Geochimica Cosmochimica et Acta,9, 13G153. Williams, A. F. (1932)The Genesisof Diamond, 2 vols. London: E. Benn. Wilson, A. N. (1982)Diamonds from birth to eternity. Gemological Institute of America,Los Angeles. Woerman,E. and Rosenhauer, (1982)Oxygenfugacity and the M. fluid C-H-O phasein the earth'smantle.(abstr.)Terra Cognita, 2,227. Wyflie, P. J. (1977)Peridotite-Co2-HrO and carbonatiticliquids in the upper asthenosphere. Nature, 266,4547. Wyllie, P. J. (1978) Mantle fluid compositions buffered in peridotite-CO2-HrO by carbonates,amphibole, and phlogopite. Journal of Geology,86,687-713. Wyllie, P. J. (1980)The origin of kimberlite. Journal of Geophysical Research, 6902-6910. 85,

Manuscript receioed, February 9, 1984; acceptedfor publication, Nouember 15, 1984.