Occurrence and petrological significance of graphite in the Upper Critical Zone,western Bushveld Complex,South Africa

Graphite occurs as a major rock-forming constituent in pyroxenitic pegmatites near the platiniferous Merensky Reef in the western Bushveld. It is associated with amphibole, biotite, low-K phyllosilicates, chlorite, sulphides and platinum-group minerals (RhAsS-IrAsS). Locally, rocks with up to 80% graphite occur. Chlorine is a significant constituent in both, hydrous silicates (0.1–0.3% Cl) and graphite (0.2–1.9%). Magnetite and quartz also occur with the above association. This facilitates estimation ofT (500–600°C) andf_O2 (10⁻²¹ to 10⁻²³ bar) during graphite deposition, which took place from COHS fluids at an oxygen fugacity in the vicinity of QMF in equilibrium with maximum H₂O mole fraction. The latter accounts for the widespread association of graphite with hydrous silicates. There is evidence for buffering off_O2 of the melt by fluid phase; this process may be more widespread than hitherto assumed. COHS fluids are considered instrumental not only in the formation of graphite-rich pegmatites and associated mineralization, but also in the genesis of pothole depressions, and in the general development of stratiform pegmatites (such as the Merensky Reef) in layered igneous complexes.     

The effect of initial230Th disequilibrium on young UPb ages: the Makalu case,Himalaya

Comparative UPb dating of zircon, xenotime and monazite from two different samples of the Himalayan “Makalu” granite shows the two U decay series to be in disequilibrium, particularly in monazite. This disequilibrium is due to excess or deficit amounts of radiogenic²⁰⁶Pb which originate from an excess or deficit of²³⁰Th, respectively, occurring initially in the mineral. Such an initial disequilibrium is caused by UTh fractionation between the crystallising mineral and the magma. Therefore, the UPb ages of Th-rich minerals such as monazite (and allanite) have to be corrected for excess²⁰⁶Pb due to excess²³⁰Th, whereas Th-poor minerals such as zircon and xenotime require a correction for a deficit of²⁰⁶Pb due to deficiency of²³⁰Th. The extent of this correction depends on the degree of ThU fractionation and on the age of the rock. For the two monazite populations analysed here, these excess amounts of²⁰⁶Pb were, with reference to the amount of radiogenic²⁰⁶Pb, 8–10% and 15–20% respectively, and less than 1% for zircon and xenotime. The varying degrees of Th enrichment relative to U in monazite show that the ThU partition coefficients for this mineral are not constant within a single granite. Furthermore, for monazite there is evidence for excess amounts of radiogenic²⁰⁷Pb originating from the decay of initial excess²³¹Pa, also enriched during crystal growth.The very low Th/U ratios of 0.196 and 0.167, determined for thetwo whole rocks from which the minerals have been extracted, substantiate the view that granite formation is a fundamental mechanism for ThU fractionation in continental crust.The different ages of 21.9 ± 0.2m.y. and24.0 ± 0.4m.y., obtained by averaging the corrected²³⁸U²⁰⁶Pb ages of the monazites, suggest that the apparently homogeneous Makalu granite was generated over a period of at least 2 m.y.     

Mineral age patterns in ca. 3700 my old rocks from West Greenland

KAr,⁴⁰Ar³⁹Ar and RbSr dates are reported for minerals from the ca. 3700 my-old Amîtsoq and Isua gneisses of the Godthaabsfjord area of West Greenland. KAr dates on biotites and hornblendes range from about 1900 to 3500 my, with hornblendes having a much narrower range (ca. 2250–2750 my) than biotites. One biotite from Isua gives an impossibly high KAr date of 4940 my.⁴⁰Ar³⁹Ar mineral dates are in close agreement with conventional KAr dates over the entire range of apparent age values. The presence of minor amounts of excess argon is observed in the hornblendes, but radiogenic and excess argon in the biotites are completely homogenised and cannot be differentiated.Rb-Sr measurements on biotites are closely concordant and show that all biotites were completely open to diffusion of radiogenic⁸⁷Sr at about 1600–1700 my. This is the first proof of a regional thermal event at this time in the Archaean of West Greenland, although similar dates are well known from the Proterozoic belts to the north and south.The evidence suggests that those KAr biotite dates greater than about 2700–2800 my result from excess radiogenic argon incorporated during a thermal event of about this age or, more probably, during the 1600–1700 my Sr isotope homogenisation event. Scatter of mineral dates below about 2700 my could also be due, at least in part, to overprinting by the 1600–1700 my event.KAr mineral dates and an Rb-Sr mineral isochron from a pegmatite associated with the last major rock-forming event in the Godthaabsfjord area, namely the Qo?rqut granite, indicate an age of emplacement of 2580 ± 30 my.     

U–Th–Pb and Rb–Sr systematics of Apollo 17 boulder 7 from the North Massif of the Taurus-Littrow Valley

Portions of highland breccia boulder 7 collected during the Apollo 17 mission were studied using UThPb and RbSr systematics. A RbSr internal isochron age of3.89 ± 0.08b.y. with an initial⁸⁷Sr/⁸⁶Sr of0.69926 ± 0.00008 was obtained for clast 1 (77135,57) (a troctolitic microbreccia). A troctolitic portion of microbreccia clast 77215,37 yielded a UPb internal isochron of3.8 ± 0.2b.y. and an initial²⁰⁶Pb/²⁰⁷Pb of 0.69. These internal isochron age are interpreted as reflecting metamorphic events, probably related to impacts, which reset RbSr and UPb mineral systems of older rocks.Six portions of boulder 7 were analyzed for U, Th, and Pb as whole rocks. Two chemical groups appear to be defined by the U, Th, and Pb concentration data. Chemical group A is characterized by U, Th, and Pb concentrations and²³⁸U/²⁰⁴Pb values which are higher than those of group B. Group A rocks have typical²³²Th/²³⁸U ratios of ～ 3.85, whereas-group B rocks have unusually high Th/U values of ～ 4.1.Whole-rock UPb and PbPb ages are nearly concordant. Two events appear to be reflected in these data — one at ～ 4.4 b.y. and one at ～ 4.5 b.y. The chemical groupings show no correlation with documented ages. The old ages of ～ 4.4 b.y. and ～ 4.5 b.y. may, like the younger ～ 4.0 b.y. ages, be related to basin excavation events.     

Nd isotopic systematics and chemistry of Central Australian sapphirine granulites: an example of rare earth element mobility

Lower Proterozoic sapphirine-bearing and associated granulites from Central Australia exhibit the greatest range of present-day¹⁴³Nd/¹⁴⁴Nd ratios (∈_Nd(O)= ?26.5 to +112.3) yet reported for rocks believed to be cogenetic. The Nd isotopic data and REE abundances of these rocks demonstrate extreme fractionation of the rare earths during the formation of stratiform CuPbZn sulfide deposits with which they are closely associated. Field relationships, petrography and chemistry of the sapphirine granulites suggest that their protoliths comprised chlorite-rich rocks which were generated by hydrothermal alteration of a range of rock types prior to metamorphism; calculations employing REE abundances of the sapphirine granulites and associated rocks, combined with bulk solid-fluid distribution coefficient data yield high fluid/rock ratios, consistent with a pre-metamorphic hydrothermal origin for the unusual REE patterns. The SmNd data for these rocks define an age of 1760±75Ma, which is significantly younger than the crust formation age of the terrain ( 2070±125Ma) but indistinguishable from the RbSr whole rock age for granulite facies metamorphism (1790±35Ma). These data are interpreted in terms of major hydrothermal fractionation of the rare earths shortly (perhaps tens of millions of years) before granulite facies metamorphism, followed by redistribution of Nd isotopes or small fractionations of the Sm/Nd ratio during the granulite facies event, and possibly also during intense retrogression which reset RbSr whole rock and UPb zircon and monazite systematics at about 1700 Ma.     

The age and emplacement of obducted oceanic crust in the Urals from SmNd and RbSr systematics

The Urals contain a 2000 km belt of mafic-ultramafic bodies. The SmNd and RbSr systematics of two of these bodies, the Kempersai Massif in the South Ural Mountains and the Voykar-Syninsky Ophiolite Complex in the Polar Ural Mountains have been examined. These data confirm the hypothesis that these bodies represent fragments of pre-collision oceanic crust and establish constraints on the nature and timing of events in the Uralian Orogeny. Two Kempersai gabbros define SmNd internal isochrons of397 ± 20My and396 ± 33My withε_Nd(T) = +8.7 ∓ 0.6 and+8.4 ∓ 1.3, respectively. Whole rock samples of pillow basalt, diabase, gabbros, troctolite, and a metasediment give SmNd values which lie on this isochron indicating that these rocks are genetically related and have an igneous crystallization age of 397 My. Whole rock samples of Voykar-Syninsky diabase, gabbros, and clinopyroxenite give SmNd values which lie on or within∼ 1 ε-unit of this isochron indicating an age andε_Nd(T) virtually identical to those of Kempersai.ε_Nd(T) for the Kempersai and Voykar-Syninsky mafic samples range from +7.3 to +9.0 with an average value of +8.4. This indicates that the Urals ophiolites are derived from an ancient depleted mantle source and are most plausibly pieces of the oceanic crust and lithosphere. The fact that a metasediment has the sameε_Nd(397 My) as the other samples indicates derivation from an oceanic source with negligible continental input.ε_Nd(T) for the massifs is∼ 1.5 ε-units lower than the average for modern MORBs. This may be due to the differential evolution of the MORB source over the past 397 My and in conjunction with data for other ophiolites and Mesozoic MORB suggests that over the past 750 My the source for MORB has evolved at a rate less than or equal to its rate of evolution averaged over the age of the earth. Initial⁸⁷Sr⁸⁶Sr ratios are highly variable ranging fromε_Sr(T) = −25.2 for a gabbro to +70.3 for a highly serpentinized harzburgite. This reflects the effects of seawater alteration which is particularly strong on ultrabasic rocks. We conclude that the long belt of mafic-ultramafic rocks in the Urals, which includes the Kempersai and Voykar-Syninsky Massifs, represents segments of Siluro-Devonian oceanic crust. Our igneous age for Kempersai in conjunction with other age constraints suggest that these segments of oceanic crust formed at least 80 My before the collision that produced the Urals.     

Composition of the core,II. Effect of high pressure on solubility of FeO in molten iron

An experimental and theoretical investigation of the effect of pressure on the solubility of FeO in molten iron has been carried out. Analyses of shock-wave compression data on iron oxides combined with measurements of the FeO bond length in “metallic” oxides suggest that the partial molar volume of FeO(V^*) dissolved in molten iron is substantially smaller than that of molten wüstite. Hence the effect of high pressure should be to increase the solubility of FeO in molten iron at a given temperature. This inference is confirmed by an experimental investigation of the effect of pressure on the position of the FeFeO eutectic. Thermodynamic calculations based on these experiments yield an estimate forV^* which is in reasonable agreement with the theoretical estimates. The experimental value ofV^* is used to calculate the effect of high pressure upon the FeFeO phase diagram. Solubility of FeO in molten iron increases sharply with pressure, the liquid immiscibility region contracts and disappears around 20 GPa and it is predicted that the FeFeO phase diagram should resemble a simple eutectic system above about 20 GPa. Analogous calculations predict that the solubility of FeO in molten iron in equilibrium with magnesiowüstite (Mg_0.8Fe_0.2)O at 2500°C increase from 14 mol.%(P = 0) to above 25 mol.% at 20 GPa. If the core formed by segregation of metallic iron originally dispersed throughout the earth, it seems inevitable that it would dissolved large amounts of FeO, thereby accounting for the observation that the density of the outer core is substantially smaller than that of pure iron under correspondingP, T conditions.     

Major-element vapor fractionation on the lunar surface: An unusual lithic fragment from the Luna 20 fines

A 250-μm fragment in the Luna 20 fines has a very fine-grained “igneous” texture and has the composition (wt.%): SiO₂, 41.1; TiO₂, 0.35; Al₂O₃, 27.2; Cr₂O₃, 0.14; FeO, 4.2; MnO, 0.06; MgO, 8.5; CaO, 17.8; Na₂O, 0.05; and K₂O < 0.02. It contains ～ 65% plagioclase An_99–100, ～ 15% olivine Fo₉₀, ～ 2% Mg-Al spinel and the remainder an unusual interstitial phase with composition SiO₂, 34.8; TiO₂, 1.78; Al₂O₃, 18.3; Cr₂O₃, 0.04; FeO, 14.1; MnO, 0.22; MgO, 5.0; CaO, 24.1; Na₂O, 0.34; K₂O < 0.02. This fragment probably represents a portion of a normal highland rock (anorthositic norite) which was heated to a very high temperature by impact, lost volatiles including SiO₂, and then partially crystallized. The observed phases and their inferred crystallization sequence are consistent with experimental results in the system CaOMgOAl₂O₃SiO₂ (Schairer and Yoder, 1969), assuming the unusual phase to be a residual glass. This type of internal fractionation, leading to silica depletion in the residuum, is different from that normally observed in lunar rocks and is attributed to slightly lower bulk SiO₂ resulting from vapor fractionation due to impact (which also results in lower Na₂O and other volatiles). Because differentiation of the type shown by this fragment is rare in lunar materials, we infer that such major-element vapor fractionation is uncommon on the surface of the moon. The experimental CaOMgOAl₂O₃SiO₂ phase relations also have a bearing on the lunar model proposed by D.L. Anderson in 1973: his “refractory” original lunar composition would differentiate to produce silica deficient liquids, like the unusual phase in our fragment, rather than the normal lunar crustal rocks.     

Inherited isotope systems and the source region pre-history of early Caledonian granites in the Dalradian Series of Scotland

RbSr and UPb isotope analyses are reported for two pre-metamorphic Caledonian granites which intrude Dalradian rocks in the Central Highlands of Scotland. These data indicate that the origin of the granitic magmas involved partial fusion of old crustal material.UPb systems of zircon size and magnetic fractions from the Ben Vuirich granite are strongly discordant. However, U/Pb isotopic ratios precisely define a chord which intersects concordia at 514_?7⁺⁶ m.y. and 1316_?25⁺²⁶ m.y. Geological constraints suggest that the lower intersection records the post-F₂, pre-M₃ emplacement age of the granite. The upper intersection reflects the presence of old zircon xenocrysts incorporated into the granite magma without complete isotopic resetting. The ultimate source of these xenocrysts is probably a metamorphic basement complex which formed about 1320 m.y. ago, but the immediate source region of the granites could have been Dalradian sediments derived therefrom.RbSr whole-rock systems of the Ben Vuirich granite are also strongly discordant, although 8 out of 13 data points scatter about an “errorchron” of 564 ± 24 m.y. with an initial⁸⁷Sr/⁸⁶Sr ratio of about 0.716. This is interpreted as a spurious result due to incomplete homogenization of Sr isotopes in the source region during partial fusion. Initial⁸⁷Sr/⁸⁶Sr ratios at the time of emplacement indicated by the zircon data ranged from 0.7173 to 0.7191. Whole-rock samples from the Dunfallandy Hill granite have Rb/Sr ratios 2–3 times higher than those from Ben Vuirich and define a reasonably good isochron age of 491 ± 15 m.y. with an initial⁸⁷Sr/⁸⁶Sr of 0.7185 ± 0.0008. This may date granite emplacement or subsequent resetting of the high Rb/Sr rocks during Caledonian metamorphism. RbSr systematics indicate that the crustal source regions of these and other Caledonian granites separated from the upper mantle at least ca. 800 m.y. ago and probably ca. 1300 m.y. ago, thus confirming the interpretation of the upper intersection age of the zircon UPb data.     

Hydrothermal Mn-deposits of the Franciscan Assemblage,II. Isotope and trace element geochemistry,and implications for hydrothermal convection at spreading centers

Major element, trace element and Sr, Nd, Pb and O isotopic data for a Franciscan Mn-deposit suggest an origin by seafloor hydrothermal circulation. Based onQ-mode factor analysis the cherts and Mn-lenses of the Blue Jay mine formed from a combination of 4 components representing 1 biogenic, 1 hydrothermal, and 2 detrital sources. RbSr, UThPb and O isotopic systematics in the Mn-lenses were affected by input from the hydrothermal circulation of material leached from the underlying basalts. Nd isotopic compositions in both cherts and Mn-lenses are identical and within the range measured for Pacific Ocean water suggesting the REE were not mobilized by hydrothermal activity. Correlation of δ¹⁸O with SiO₂ and MnO₂ in the Mn-lenses implies the lenses formed by simple mixing of hydrothermally derived Mn-oxides with seawater and biogenic silica. δ¹⁸O of the cherts is both uniform and depleted relative to DSDP Jurassic cherts but similar to microquartz-bearing cherts of the Monterey Formation: this suggests that diagenetic activity exerted more control on oxygen isotope compositions then hydrothermal alteration or metamorphism. Finally, a well defined RbSr isochron of158 ± 5Myr was obtained for these cherts and opens the possibility of determining absolute radiometric ages for similar cherts throughout the geologic record.     

Morphology versus UPb systematics in zircon: a high-resolution isotopic study of a zircon population from a Variscan dike in the Central Alps

UPb isotopic measurements on individual zircon crystals combined with morphological analyses permit the identification of three distinct components within the zircon population of the Saedelhorn diorite, a Variscan dike from the western Gotthard (Central Alps, Switzerland): (i) 94% of the grains in the zircon population are elongate crystals with pronounced skeletal morphology indicative of rapid growth from a supercooled melt. (ii) 5% of the population consist of turbid, mostly subhedral zircons frequently showing D-type morphology (classification according to Pupin and Turco [1]) and elevated uranium contents compared to the skeletal variety. Single-crystal and multi-grain UPb isotopic data of group (i) and (ii) zircons define an intrusion age of 293 +5/−4 m.y. for the dike. (iii) Rare, transparent zircon crystals (<1% of the zircon population) yield apparent UPb ages in the range of 370–490 m.y. and display morphological and isotopic characteristics closely resembling those of a Caledonian orthogneiss intruded by the dike. This implies presence of assimilated wall-rock components in the macroscopically homogeneous dike sample.A comparison of the data obtained by conventional analysis of multi-grain zircon fractions and those obtained by grain-by-grain analysis demonstrates that age resolution is considerably improved by single-crystal UPb dating. Furthermore, quantitative identification of zircon components assimilated by the ascending magma along its path to the present level of exposure is feasible by the latter technique. Since it is likely that such zircon grains are common to a broad variety of magma types, valuable information on age and composition of crustal layers not accessible to direct observation may readily become available by application of precise micro-analytical techniques.Low initial¹⁴³Nd/¹⁴⁴Nd(ε_Nd = −2.7) at the time of intrusion of the Saedelhorn dike requires the magma to be derived partially or totally from a crustal source. For this crustal precursor, a model age of 1050 m.y. (T_DM) is obtained, indicating that Proterozoic crust was involved in the petrogenesis of the Variscan intrusives of the Gotthard area.     

RbSr dating of the Yatsushiro granite and gneiss,Kyushu, Japan

RbSr measurements on the Yatsushiro granite and gneiss, which had been considered stratigraphically to be of possible Precambrian age, are reported. The whole rock isochron for the granite gives an age of 352 ± 8 my with a low initial⁸⁷Sr/⁸⁶Sr ratio of 0.7037 ± 0.0006. Data for constituent minerals of the granites are dispersed irregularly around the whole rock isochron (possibly by later tectonic events). For the gneiss, a metamorphic event around 410 my is indicated by the muscovite RbSr ages. The present results do not support the possibility that the Yatsushiro granite and gneiss are Precambrian in age.     

Interpretation of a discordant KAr age pattern (Capo Vaticano,Calabria)

KAr age determination on whole rocks, biotites, quartz-feldspar separates and pegmatitic muscovites from a small quartz dioritic stock give a complex discordant age pattern. KAr dates from whole rocks and mineral separates define a single 116 my isochron with positive intercept, whereas muscovites from pegmatites fit a 180 my isochron with a probable negative intercept.Both ages are younger than the probable crystallization age of the stock (around 300 my), indicating a complex post-crystallization history. The fit of different mineral phases and whole rocks to a single isochron with positive intercept suggests that a thermal event caused rehomogenization of Ar among different mineral phases.