The Ni-S System and Related Minerals

The system Ni-S has been studied systematically from 200^? to1, 030^? C by means of evacuated, sealed silica-glass tube experimentsand differential thermal analyses. Compounds in the system areNi₃S₂ (and a high temperature, non-quenchable Ni_3?S₂ phase),Ni₇S₆, Ni₁–S₄ Ni₃S₄, and NiS₂. The geologic occurrenceof the minerals heazlewoodite (Ni₂S₂), millerite (ßSNi₁-₂S),polydymite (Ni₃S₄), and vaesite (NiS₂) can now be describedin terms of the stability ranges of their synthetic equivalents. Hexagonal heazlewoodite, which is stoichiometric within thelimit of error of the experiments, inverts on heating to a tetragonalor pseudotetragonal phase at 556^? C. This high-temperature phase(Ni₃ has a wide field of stability, from 23.5 to 30.5 wt percent sulfur at 600^? C, and melts incongruently at 806^??3^? C.The ßNi₇S₆ phase inverts to Ni₇₈ at 397^? C6 when inequilibrium with Ni₃S₂, and at 400^? C when in equilibrium withNiS. Crystals of Ni₇S₆ break down to Ni₃-S₂+NiS at 573^??3^?C.The low-temperature form of Ni₁-S₁ corresponding to the mineralmillerite, is rhombohedral, and the high-temperature form hasthe hexagonal NiAs structure. Stoichiometric NiS inverts at379^??3^?C, whereas Ni₁-S with the maximum nickel deficiency invertsat 282^??5OC. The Ni₁-alphS-NiS₂ solvus was determined to 985^??3^?C,the eutectic temperature of these phases. Stoichiometric NiSis stable at 600^?C but breaks down to Ni₂-S₂ and Ni₁-S below797^?C, whereas Ni₁-S with 38.2 wt per cent sulfur melts congruentlyat 992^??3^?C. Vaesite does not vary measurably from stoichiometricNiS₂ composition, and melts congruently at 1.007?5^?C. Polydymitebreaks down to aNi-S? vaesite at 356^??3^?C. Differential thermalanalyses showed the existence of a two-liquid field in the sulfur-richportion of the system above 991^?C and over a wide compositionalrange.     

A Method for Thermodynamical Calculation of Basicity Indicators of Rocks and Minerals

A new method has been suggested for evaluating the overall basicityof minerals and rocks by using ionization reactions involvingone proton: (sum of cations) + H₂O = mineral + H⁺, (sum of cations) + H₂O = (sum of normative minerals of a rock)+ H⁺. The basicity indicators are expressed as standard free energychanges of these reactions (). At standard water pressure (logP_H2O = 0) and chemical activity of the metal ions ( log _Mⁿ⁺= 0), the relationship between and alkalinity of solutions(pH) becomes: = –2.303 RTlog _H⁺ = 2.303 RT pH. The overall basicities of rock-forming oxides, minerals andmajor rocks were calculated from the thermodynamic data on ionsin water solutions and solid compounds.     

Oxygen and Hydrogen Isotope Geochemistry of the Mourne Mountains Tertiary Granites, Northern Ireland

An oxygen and hydrogen isotopic study of minerals and wholerocks from the granites of the Mourne Mountains Tertiary complex,and related rocks, shows that whereas a significant circulationof meteoric water was associated with the complex, it had onlyminor and localized effects on the granites themselves. TheSilurian slate and greywacke country rocks, which would havehad ¹⁸O_(SMOW) values of +10 to +20 before the Tertiary igneousevents, have been depicted ¹⁸O to values of –40 to –05Tertiary acid minor intrusions outside the main granite massesare also ¹⁸O depleted. ^l8O whole-rock data on the granites showa range of +6.0 to +9.5, and include values significantly higherthan most of those obtained for the granites of the Tertiarycentral complexes of Skye, Mull, and Ardnamurchan. Many of thelowest whole-rock ¹⁸O values are found in samples where theminerals are not in isotopic equilibrium. The mineral oxygenisotopic data can be explained in terms of localized interactionwith meteoric water, resulting in preferential ¹⁸O depletionin feldspar(s) and biotite, with quartz being much less affected.The granites all show low values of D_(SMOW) for biotite andamphibole separates (–137 to –104). The lowest valuesoccur close to the margins of the plutons, near internal contactsor near greisen localities, and these probably reflect limitedinteraction with meteoric water. The higher D values are fromsamples which show evidence of chloritization. This processappears to have occurred both during interaction with meteoricwater, and also during autometasomatism by an exsolved magmaticfluid in other parts of the plutons, including central locationswhere there is little or no evidence for the penetration ofmeteoric water. Granite samples which exhibit near-equilibriumoxygen isotope fractionations for constituent minerals are characterizedby magmatic O-isotopic compositions. The G2 granite, the largestpluton of the eastern centre, has a magmatic ¹⁸O_(SMOW) valueof {small tilde}+95; intrusions G3 (eastern centre) and G4(western centre) both have ¹⁸O_(SMOW) values of {small tilde}+90.The other two main intrusive phases have distinctly lower ¹⁸O_(SMOW)values: {small tilde}+75 for Gl (the least fractionated graniteof the Mourne Mountains central complex), and from +75 to +85for G5. The oxygen isotopic data rule out simple partial meltingof the country rocks as the origin of the granites and alsopreclude an origin by closed-system fractional crystallizationof basaltic magma typical of that represented by Tertiary basicigneous rocks of the region. ^* Present address: NERC Isotope Geosciences Laboratory, Keyworth, Nottingham BG12 5GG, UK Present address: School of Engineering Technology, Georgian College, Barrie, Ontario, L4M 3X9, Canada     

Stable Isotopic Evidence for Fluid-Rock Interactions in the Ivrea Zone, Italy

Stable isotope compositions of Ivrea Zone marbles and associatedlithologies are in general heterogeneous. The oxygen isotopecomposition of quartz in pelites ranges from ¹⁸O +9 to + 17(SMOW) and does not vary systematically with metamorphic grade.Peridotites retain oxygen isotope signatures close to mantlevalues. Marble calcites vary in isotopic composition from ¹³C + 2(PDB),¹⁸0 +24(SMOW)to ¹³C –6(PDB), ¹⁸O + 13 (SMOW).Depletions in ¹⁸O and ¹³C may be explained dominantly by interactionwith fluids derived from within the observed metasedimentarysequence during prograde metamorphism. ¹⁸O and ¹³C show gradients of greater than 5/m across marblemargins and within marbles. The preservation of such isotopicgradients is not consistent with the long-term presence of grain-boundary-scaleinterconnected fluid films in and around marbles. There is ageneral lowering of ¹⁸O within individual marble bodies althoughlarge carbon and oxygen isotopic gradients are present. Calcitein marbles may attain oxygen isotope equilibrium, but rarelycarbon isotope equilibrium, with surrounding metapelites. Infiltrationof marbles must involve a component of channelized fluid flow. The general lack of isotopic equilibration within the sequencerequires channelized fluid flow and limited fluid-rock ratios.Large pervasive mantle to crust fluid fluxes are not consistentwith the observations. ^*Present address: Natural Environment Research Council, Polaris House, North Star Avenue, Swindon SN2 1EU, England     

Petrogenesis of the Swaziland and Northern Natal Rhyolites of the Lebombo Rifted Volcanic Margin, South East Africa

The Jozini and Mbuluzi rhyolites and Oribi Beds of the southernLebombo Monocline, southeastern Africa, have geochemical characteristicsthat indicate they were derived by partial melting of a mixtureof high-Ti/Zr and low-Ti/Zr Sabie River Basalt Formation types.Compositional variations within the different rhyolite typescan largely be explained by subsequent fractional crystallization.The Sr- and Nd-isotope composition of the rhyolites is uniqueamongst Gondwana silicic large igneous provinces, having _Ndvalues close to Bulk Earth (–0·94 to 0·35)and low, but more variable, initial ⁸⁷Sr/⁸⁶Sr ratios (0·7034–0·7080).Quartz phenocryst ¹⁸O values indicate that the rhyolite magmashad ¹⁸O values between 5·3 and 6·7, consistentwith derivation from a basaltic protolith with ¹⁸O values between4·8 and 6·2. The low-¹⁸O rhyolites (< 6·0)come from the same stratigraphic horizon and are overlain andunderlain by rhyolites with more ‘normal’ ¹⁸O magmavalues. These low-¹⁸O rhyolites cannot have been produced byfractional crystallization or partial melting of mantle-derivedbasaltic material. The rhyolites have low water contents, makingit unlikely that the low ¹⁸O values are the result of post-emplacementalteration. Modification of the source by fluid–rock interactionat elevated temperatures is the most plausible mechanism forlowering the ¹⁸O magma value. It is proposed that the low-¹⁸Orhyolites were derived by melting of earlier altered rhyolitein calderas situated to the east, which were not preserved afterGondwana break-up. KEY WORDS: rhyolite; Lebombo; stable and radiogenic isotopes; low-¹⁸O magmas; partial melting     

A New Interpretation of Centimetre-scale Variations in the Progress of Infiltration-driven Metamorphic Reactions: Case Study of Carbonated Metaperidotite, Val d'Efra, Central Alps, Switzerland

Progress () of the infiltration-driven reaction, 4olivine +5CO₂ + H₂O = talc + 5magnesite, that occurred during Barrovianregional metamorphism, varies at the cm-scale by a factor of3·5 within an 3 m³ volume of rock. Mineral and stableisotope compositions record that X_CO2, ¹⁸O_fluid, and ¹³C_fluidwere uniform within error of measurement in the same rock volume.The conventional interpretation of small-scale variations in in terms of channelized fluid flow cannot explain the uniformityin fluid composition. Small-scale variations in resulted insteadbecause (a) reactant olivine was a solid solution, (b) initiallythere were small-scale variations in the amount and compositionof olivine, and (c) fluid composition was completely homogenizedover the same scale by diffusion–dispersion during infiltrationand subsequent reaction. Assuming isochemical reaction, spatialvariations in image variations in the (Mg + Fe)/Si of the parentrock rather than the geometry of metamorphic fluid flow. Ifinfiltration-driven reactions involve minerals fixed in composition,on the other hand, spatial variations in do directly imagefluid flow paths. The geometry of fluid flow can never be determinedfrom geochemical tracers over a distance smaller than the oneover which fluid composition is completely homogenized by diffusion–dispersion. KEY WORDS: Alpine Barrovian metamorphism; diffusion; metamorphic fluid composition; metamorphic fluid flow; reaction progress     

Fluid--Rock Interaction during Low-Pressure Polymetamorphism of the Reynolds Range Group, Central Australia

Marbles and metapelites from the Reynolds Range Group (centralAustralia) were regionally metamorphosed at low pressure duringM₂ at 1.6 Ga, M₂ ranged in grade from greenschist to granulitefacies along the length of the Reynolds Range, and overprinted1.78 Ga granites and their contact aureoles in the ReynoldsRange Group metasediments. At all M₂ grades the marbles andmetapelites have highly variable oxygen isotope ratios [marbles:¹⁸O(carb) 14–20%; metapelites: ¹⁸O 6–14%). Similarly, 1.78 Ga granites have highly variable oxygen isotope ratios(¹⁸O 5–13%), with the lowest values occurring at thegranite margins. In all rock types, the lowest oxygen isotopevalues are consistent with the infiltration of channelled magmaticand/or meteoric fluids. The variable lowering of oxygen isotopevalues resulted from pre-M₂ contact metamorphism and fluid—rockinteraction around the 1.78 Ga granites. In contrast, mineralassemblages in the marbles define a trend of increasing X_CO2with increasing grade from <0.05 (greenschist facies) to0.7–1.0 (granulite facies). This, together with the lackof regionally systematic resetting of oxygen isotope ratios,implies that there was little fluid—rock interaction duringprograde regional metamorphism. KEY WORDS: low pressure; polymetamorphism; fluids; stable isotopes; petrology ^*Corresponding author Fax: 61–3–94791272. e-mail: geoisb{at}lure.latrobe.edu.au     

Oxygen Isotope Evidence for Chemical Interaction of Ki lauea Historical Magmas with Basement Rocks

Klauea historical summit lavas have a wide range in matrix ¹⁸O_VSMOWvalues (4·9–5·6) with lower values in rockserupted following a major summit collapse or eruptive hiatus.In contrast, ¹⁸O values for olivines in most of these lavasare nearly constant (5·1 ± 0·1). The disequilibriumbetween matrix and olivine ¹⁸O values in many samples indicatesthat the lower matrix values were acquired by the magma afterolivine growth, probably just before or during eruption. BothMauna Loa and Klauea basement rocks are the likely sources ofthe contamination, based on O, Pb and Sr isotope data. However,the extent of crustal contamination of Klauea historical magmasis probably minor (< 12%, depending on the assumed contaminant)and it is superimposed on a longer-term, cyclic geochemicalvariation that reflects source heterogeneity. Klauea's heterogeneoussource, which is well represented by the historical summit lavas,probably has magma ¹⁸O values within the normal mid-ocean ridgebasalt mantle range (5·4–5·8) based on thenew olivine ¹⁸O values. KEY WORDS: Hawaii; Klauea; basalt; oxygen isotopes; crustal contamination     

Oxygen and Hydrogen Isotope Stratigraphy of the Rustenburg Layered Suite, Bushveld Complex: Constraints on Crustal Contamination

New ¹⁸O values for plagioclase, pyroxene and olivine, and limitedwhole-rock D values are presented for samples from the RustenburgLayered Suite of the Bushveld Complex, South Africa. In combinationwith existing data, these provide a much more complete compositeO-isotope stratigraphy for the intrusion. Throughout the layeredsuite, mineral ¹⁸O values indicate that the magmas from whichthey crystallized had ¹⁸O values that were about 7·1,that is, 1·4 higher than expected for mantle-derivedmagmas, suggesting extensive crustal contamination. More limitedH-isotope data suggest that the OH present within whole rocks,regardless of the degree of alteration, is of magmatic originand not an alteration phenomenon. There appears to be no systematicchange in ¹⁸O value with stratigraphic height and this requiresthe contamination to have taken place in a ‘staging chamber’before emplacement of the magma(s) into the present chamber.Large amounts (30–40%) of contamination by the lower tomiddle crust are needed to explain these ¹⁸O values, which isin general agreement with previous estimates based on Sr- andNd-isotope data. Alternatively, smaller amounts of contamination(20%) by sedimentary rocks, or their partial melts, representedby the country rock can explain the data, but it is not apparenthow such material could have been present at the depth of the‘staging chamber’ in the lower to middle crust. KEY WORDS: Bushveld Complex; Rustenburg Layered Suite; oxygen isotopes; hydrogen isotopes; crustal contamination     

Oxygen Isotope Geochemistry of the Lassen Volcanic Center, California: Resolving Crustal and Mantle Contributions to Continental Arc Magmatism

This study reports oxygen isotope ratios determined by laserfluorination of mineral separates (mainly plagioclase) frombasaltic andesitic to rhyolitic composition volcanic rocks eruptedfrom the Lassen Volcanic Center (LVC), northern California.Plagioclase separates from nearly all rocks have ¹⁸O values(6·1–8·4) higher than expected for productionof the magmas by partial melting of little evolved basalticlavas erupted in the arc front and back-arc regions of the southernmostCascades during the late Cenozoic. Most LVC magmas must thereforecontain high ¹⁸O crustal material. In this regard, the ¹⁸O valuesof the volcanic rocks show strong spatial patterns, particularlyfor young rhyodacitic rocks that best represent unmodified partialmelts of the continental crust. Rhyodacitic magmas erupted fromvents located within 3·5 km of the inferred center ofthe LVC have consistently lower ¹⁸O values (average 6·3± 0·1) at given SiO₂ contents relative to rockserupted from distal vents (>7·0 km; average 7·1± 0.1). Further, magmas erupted from vents situated attransitional distances have intermediate values and span a largerrange (average 6·8 ± 0·2). Basaltic andesiticto andesitic composition rocks show similar spatial variations,although as a group the ¹⁸O values of these rocks are more variableand extend to higher values than the rhyodacitic rocks. Thesefeatures are interpreted to reflect assimilation of heterogeneouslower continental crust by mafic magmas, followed by mixingor mingling with silicic magmas formed by partial melting ofinitially high ¹⁸O continental crust (9·0) increasinglyhybridized by lower ¹⁸O (6·0) mantle-derived basalticmagmas toward the center of the system. Mixing calculationsusing estimated endmember source ¹⁸O values imply that LVC magmascontain on a molar oxygen basis approximately 42 to 4% isotopicallyheavy continental crust, with proportions declining in a broadlyregular fashion toward the center of the LVC. Conversely, the¹⁸O values of the rhyodacitic rocks suggest that the continentalcrust in the melt generation zones beneath the LVC has beensubstantially modified by intrusion of mantle-derived basalticmagmas, with the degree of hybridization ranging on a molaroxygen basis from approximately 60% at distances up to 12 kmfrom the center of the system to 97% directly beneath the focusregion. These results demonstrate on a relatively small scalethe strong influence that intrusion of mantle-derived maficmagmas can have on modifying the composition of pre-existingcontinental crust in regions of melt production. Given thisresult, similar, but larger-scale, regional trends in magmacompositions may reflect an analogous but more extensive processwherein the continental crust becomes progressively hybridizedbeneath frontal arc localities as a result of protracted intrusionof subduction-related basaltic magmas. KEY WORDS: oxygen isotopes; phenocrysts; continental arc magmatism; Cascades; Lassen     

Fluid Flow During Contact Metamorphism at Mary Kathleen, Queensland, Australia

Corella marbles in the Mary Kathleen Fold Belt were infiltratedby fluids during low-pressure (200-MPa) contact metamorphismassociated with the intrusion of the Burstall granite at 1730–1740Ma. Fluids emanating from the granite [whole-rock (WR) ¹⁸O=8.1–8.6%]produced Fe-rich massive and banded garnet—clinopyroxeneskarns [¹⁸O(WR)=9.1–11.9%]. Outside the skarn zones, marblemineralogies define an increase in temperature (500 to >575C) and XCO₂ (0.05 to >0.12) towards the granite, andmost marbles contain isobarically univariant or invariant assemblagesin the end-member CaO–MgO–Al₂O₃–SiO₂–H₂O–CO₂system. Marbles have calcite (Cc) ¹⁸O and ¹³C values of 12.3–24.6%and –1.0 to –3.9%, respectively. A lack of down-temperaturemineral reactions in the marbles suggests that pervasive fluidinfiltration did not continue after the thermal peak of contactmetamorphism. The timing of fluid flow probably correspondsto a period of high fluid production and high intrinsic permeabilitiesduring prograde contact metamorphism. The petrology and stableisotope geochemistry of the marbles suggest that these rockswere infiltrated by water-rich fluids. If fluid flow occurredup to the peak of contact metamorphism, the mineralogical andisotopic resetting is best explained by fluids flowing up-temperaturetoward the Burstall granite. However, if fluid flow ceased beforthe peak of regional metamorphism, the fluid flow directioncannot be unambiguously determined. At individual outcrops,marble ¹⁸O(Cc) values vary by several permil over a few squaremetres, suggesting that fluid fluxes varied by at least an orderof magnitude on the metre to tens-of-metre scale. Fluids werefocused across lithological layering; however, mesoscopic fracturesare not recognized. The focusing of fluids was possibly viamicrofractures, and the variation in the degree of resettingmay reflect variations in microcrack density and fracture permeability.The marble—skarn contacts represent a sharp discontinuityin both major element geochemistry and ¹⁸O values, suggestingthat, at least locally, little fluid flow occurred across thesecontacts.     

Age and Geochemistry of Basement and Alkalic Rocks of Malaita and Santa Isabel, Solomon Islands, Southern Margin of Ontong Java Plateau

Geochemical and ⁴⁰ Ar—³⁹ Ar studies of the Malaita OlderSeries and Sigana Basalts, which form the basement of Malaitaand the northern portion of Santa Isabel, confirm the existenceof Ontong Java Plateau (OJP) crust on these islands. Sr, Nd,and Pb isotopic ratios of Malaita Older Series and Sigana lavasfall within limited ranges [(⁸⁷Sr/⁸⁶Sr)T= 0.70369–0.70423,E_Nd(T)= + 3.7 to +6.0, and ²⁰⁶Pb/²⁰⁴Pb = 18.25–18.64]virtually indistinguishable from those found in the three OJPbasement drill sites as far as 1600 km away, indicating a uniformhotspot-like mantle source with a slight ‘Dupal’signature for the world's largest oceanic plateau. Three chemicaltypes of basalts are recognized, two of which are equivalentto two of the three types drilled on the plateau, and one withno counterpart, as yet, on the plateau; the chemical data indicateslightly different, but all high, degrees of melting and slightvariation in source composition. All but one of the ⁴⁰Ar-³⁹Arplateau ages determined for Malaita Older Series and SiganaBasalt lavas are identical to those found at the distant drillsites: 121.30.9 Ma and 92.01.6 Ma, suggesting that two short-lived,volumetrically important plateau-building episodes took place30 m.y. apart. Aside from OJP lavas, three isotopically distinctsuites of alkalic rocks are present. The Sigana Alkalic Suitein Santa Isabel has an ⁴⁰ Ar-³⁹ Ar age of 91.70.4 Ma, the sameas that of the younger OJP tholeiites, yet it displays a distinct’HIMU‘ -type isotopic signature [²⁰⁶Pb/²⁰⁴Pb 20.20,(⁸⁷Sr/⁸⁶Sr) T 0.7032, _Nd(T) 4.4], possibly representing small-degreemelts of a minor, less refractory component in the OJP mantlesource region. The Younger Series in southern Malaita has an⁴⁰Ar-³⁹Ar age of 44 Ma and isotopic ratios [_Nd(T)=-0.5 to +1.0,(⁸⁷Sr/⁸⁶Sr)_T =0.70404–0.70433, ²⁰⁶Pb/²⁰⁴Pb = 18.57–18.92]partly overlapping those of the ‘PHEM’ end-memberpostulated for Samoa, and those of present-day Rarotonga lavas;one or both of these hotspots may have caused alkalic volcanismon the plateau when it passed over them at 44 Ma. The NorthMalaita Alkalic Suite in northernmost Malaita is probably ofsimilar age, but has isotopic ratios [(⁸⁷Sr/⁸⁶Sr) _T 0.7037,_Nd(T) +4.5, ²⁰⁶pb/²⁰⁴pb 18.8) resembling those of some OJP basementlavas; it may result from a small amount of melting of agedplateau lithosphere during the OJP's passage over these hotspots.Juxtaposed against OJP crust in Santa Isabel is an 62–46-Maophiolitic (sensu lato) assemblage. Isotopic and chemical datareveal Pacific-MORB-like, backarc-basin-like, and arc-like signaturesfor these rocks, and suggest that most formed in an arc—backarcsetting before the Late Tertiary collision of the OJP againstthe old North Solomon Trench. The situation in Santa Isabelappears to provide a modern-day analog for some Precambriangreenstone belts. KEY WORDS: oceanic plateaux; Ontong Java Plateau; Solomon Islands; Sr-Nd-Pb isotopes; age and petrogenesis ^*Corresponding author.     

Hafnium Isotope and Trace Element Constraints on the Nature of Mantle Heterogeneity beneath the Central Southwest Indian Ridge (13{degrees}E to 47{degrees}E)

Hafnium isotope and incompatible trace element data are presentedfor a suite of mid-ocean ridge basalts (MORB) from 13 to 47°Eon the Southwest Indian Ridge (SWIR), one of the slowest spreadingand most isotopically heterogeneous mid-ocean ridges. Variationsin Nd–Hf isotope compositions and Lu/Hf ratios clearlydistinguish an Atlantic–Pacific-type MORB source, presentwest of 26°E, characterized by relatively low _Hf valuesfor a given _Nd relative to the regression line through all Nd–Hfisotope data for oceanic basalts (termed the ‘Nd–Hfmantle array line’; the deviation from this line is termed_Hf) and low Lu/Hf ratios, from an Indian Ocean-type MORB signature,present east of 32°E, characterized by relatively high _Hfvalues and Lu/Hf ratios. Additionally, two localized, isotopicallyanomalous areas, at 13–15°E and 39–41°E,are characterized by distinctly low negative and high positive_Hf values, respectively. The low _Hf MORB from 13 to 15°Eappear to reflect contamination by HIMU-type mantle from thenearby Bouvet mantle plume, whereas the trace element and isotopiccompositions of MORB from 39 to 41°E are most consistentwith contamination by metasomatized Archean continental lithosphericmantle. Relatively small source-melt fractionation of Lu/Hfrelative to Sm/Nd, compared with MORB from faster-spreadingridges, argues against a significant role for garnet pyroxenitein the generation of most central SWIR MORB. Correlations between_Hf and Sr and Pb isotopic and trace element ratios clearly delineatea high-_Hf ‘Indian Ocean mantle component’ that canexplain the isotope composition of most Indian Ocean MORB asmixtures between this component and a heterogeneous Atlantic–Pacific-typeMORB source. The Hf, Nd and Sr isotope compositions of IndianOcean MORB appear to be most consistent with the hypothesisthat this component represents fragments of subduction-modifiedlithospheric mantle beneath Proterozoic orogenic belts thatfoundered into the nascent Indian Ocean upper mantle duringthe Mesozoic breakup of Gondwana. KEY WORDS: mid-ocean ridge basalt; isotopes; incompatible elements; Indian Ocean     

Genesis of Ultramafic Lamprophyres and Carbonatites at Aillik Bay, Labrador: a Consequence of Incipient Lithospheric Thinning beneath the North Atlantic Craton

Numerous dykes of ultramafic lamprophyre (aillikite, mela-aillikite,damtjernite) and subordinate dolomite-bearing carbonatite withU–Pb perovskite emplacement ages of 590–555 Ma occurin the vicinity of Aillik Bay, coastal Labrador. The ultramaficlamprophyres principally consist of olivine and phlogopite phenocrystsin a carbonate- or clinopyroxene-dominated groundmass. Ti-richprimary garnet (kimzeyite and Ti-andradite) typically occursat the aillikite type locality and is considered diagnosticfor ultramafic lamprophyre–carbonatite suites. Titanianaluminous phlogopite and clinopyroxene, as well as comparativelyAl-enriched but Cr–Mg-poor spinel (Cr-number < 0.85),are compositionally distinct from analogous minerals in kimberlites,orangeites and olivine lamproites, indicating different magmageneses. The Aillik Bay ultramafic lamprophyres and carbonatiteshave variable but overlapping ⁸⁷Sr/⁸⁶Sr_i ratios (0·70369–0·70662)and show a narrow range in initial _Nd (+0·1 to +1·9)implying that they are related to a common type of parentalmagma with variable isotopic characteristics. Aillikite is closestto this primary magma composition in terms of MgO (15–20wt %) and Ni (200–574 ppm) content; the abundant groundmasscarbonate has ¹³C_PDB between –5·7 and –5,similar to primary mantle-derived carbonates, and ¹⁸O_SMOW from9·4 to 11·6. Extensive melting of a garnet peridotitesource region containing carbonate- and phlogopite-rich veinsat 4–7 GPa triggered by enhanced lithospheric extensioncan account for the volatile-bearing, potassic, incompatibleelement enriched and MgO-rich nature of the proto-aillikitemagma. It is argued that low-degree potassic silicate to carbonatiticmelts from upwelling asthenosphere infiltrated the cold baseof the stretched lithosphere and solidified as veins, therebycrystallizing calcite and phlogopite that were not in equilibriumwith peridotite. Continued Late Neoproterozoic lithosphericthinning, with progressive upwelling of the asthenosphere beneatha developing rift branch in this part of the North Atlanticcraton, caused further veining and successive remelting of veinsplus volatile-fluxed melting of the host fertile garnet peridotite,giving rise to long-lasting hybrid ultramafic lamprophyre magmaproduction in conjunction with the break-up of the Rodinia supercontinent.Proto-aillikite magma reached the surface only after coatingthe uppermost mantle conduits with glimmeritic material, whichcaused minor alkali loss. At intrusion level, carbonate separationfrom this aillikite magma resulted in fractionated dolomite-bearingcarbonatites (¹³C_PDB –3·7 to –2·7)and carbonate-poor mela-aillikite residues. Damtjernites maybe explained by liquid exsolution from alkali-rich proto-aillikitemagma batches that moved through previously reaction-lined conduitsat uppermost mantle depths. KEY WORDS: liquid immiscibility; mantle-derived magmas; metasomatism, Sr–Nd isotopes; U–Pb geochronology     

The Gronnedal-Ika Carbonatite-Syenite Complex, South Greenland: Carbonatite Formation by Liquid Immiscibility

The Grønnedal-Ika complex is dominated by layered nephelinesyenites which were intruded by a xenolithic syenite and a centralplug of calcite to calcite–siderite carbonatite. Aegirine–augite,alkali feldspar and nepheline are the major mineral phases inthe syenites, along with rare calcite. Temperatures of 680–910°Cand silica activities of 0·28–0·43 weredetermined for the crystallization of the syenites on the basisof mineral equilibria. Oxygen fugacities, estimated using titanomagnetitecompositions, were between 2 and 5 log units above the fayalite–magnetite–quartzbuffer during the magmatic stage. Chondrite-normalized REE patternsof magmatic calcite in both carbonatites and syenites are characterizedby REE enrichment (La_CN–Yb_CN = 10–70). Calcite fromthe carbonatites has higher Ba (5490 ppm) and lower HREE concentrationsthan calcite from the syenites (54–106 ppm Ba). This isconsistent with the behavior of these elements during separationof immiscible silicate–carbonate liquid pairs. _Nd(T =1·30 Ga) values of clinopyroxenes from the syenites varybetween +1·8 and +2·8, and _Nd(T) values of whole-rockcarbonatites range from +2·4 to +2·8. Calcitefrom the carbonatites has ¹⁸O values of 7·8 to 8·6and ¹³C values of –3·9 to –4·6. ¹⁸Ovalues of clinopyroxene separates from the nepheline syenitesrange between 4·2 and 4·9. The average oxygenisotopic composition of the nepheline syenitic melt was calculatedbased on known rock–water and mineral–water isotopefractionation to be 5·7 ± 0·4. Nd and C–Oisotope compositions are typical for mantle-derived rocks anddo not indicate significant crustal assimilation for eithersyenite or carbonatite magmas. The difference in ¹⁸O betweencalculated syenitic melts and carbonatites, and the overlapin _Nd values between carbonatites and syenites, are consistentwith derivation of the carbonatites from the syenites via liquidimmiscibility. KEY WORDS: alkaline magmatism; carbonatite; Gardar Province; liquid immiscibility; nepheline syenite     

Primary Igneous Graphite in Ultramafic Xenoliths: II Isotopic Composition of the Carbonaceous Phases Present in Xenoliths and Host Lava at Tissemt (Egg?r?, Alegerian Sahara)

¹³C/¹²C ratios have been analysed in graphite adcumulate crystalsassociated with the olivine and orthopyroxene of a suite ofultramafic xenoliths in the alkali basalts of Tissemt (Egg?r?,Algerian Sahara). The ¹³C of these graphites varies from –24?6to – 14?4 per milk with internal variations of up to 1?6per mille within a given sample. Carbonates, linked to the volcanicphase and precipitated at medium temperatures have ¹³C valuesfrom –0?8 to + 3?5 and ¹⁸O values from 21?6 to 31?5 Thehost lava has a high carbon content of 675 p.p.m. with a global¹³C of –4?2. It can be separated into three parts: a majorpeak is obtained between 670 and 985 ?C and also liberated byslow acid attack with a ¹³C of up to +7?3 and representing CO₂trapped in the natrolite; a high temperature peak (above 1160?C with 47 p.p.m at –25?8) will represent carbon trappedin silicates and there is an additional carbon not well determinedextracted from 300 ?C to high temperature which represent 215p.p.m. at –23?0 with a possible fraction as low as –68?0.The graphite is interpreted as the result of the precipitationof carbon from an interstitial liquid previously outgassed thensupersaturated by the ongoing crystallization process. The volcanicevent can be considered to a first approximation as remobilizingthe carbon from the xenoliths by oxidation to CO₂, subsequentpartial reduction upon cooling and precipitation of carbonateand trapping of residual CO₂ within zeolite. Only volatilereducedspecies can be significantly outgassed so that the total ¹³Cof –4?2 is probably close to (or a little higher than)the original ¹³C.     

Petrographic, Chemical and B-Isotopic Insights into the Origin of Tourmaline-Rich Rocks and Boron Recycling in the Martinamor Antiform (Central Iberian Zone, Salamanca, Spain)

Tourmaline in the Martinamor antiform occurs in tourmalinites(rocks with >15–20% tourmaline by volume), clasticmetasedimentary rocks of the Upper Proterozoic Monterrubio formation,quartz veins, pre-Variscan orthogneisses and Variscan graniticrocks. Petrographic observations, back-scattered electron (BSE)images, and microprobe data document a multistaged developmentof tourmaline. Overall, variations in the Mg/(Mg + Fe) ratiosdecrease from tourmalinites (0·36–0·75),through veins (0·38–0·66) to granitic rocks(0·23–0·46), whereas Al increases in thesame order from 5·84–6·65 to 6·22–6·88apfu. The incorporation of Al into tourmaline is consistentwith combinations of ^xAl(NaR)_–1 and AlO(R(OH))_–1exchange vectors, where ^x represents X-site vacancy and R is(Mg + Fe²⁺ + Mn). Variations in ^x/(^x + Na) ratios are similarin all the types of tourmaline occurrences, from 0·10to 0·53, with low Ca-contents (mostly <0·10apfu). Based on field and textural criteria, two groups of tourmaline-richrocks are distinguished: (1) pre-Variscan tourmalinites (probablyCadomian), affected by both deformation and regional metamorphismduring the Variscan orogeny; (2) tourmalinites related to thesynkinematic granitic complex of Martinamor. Textural and geochemicaldata are consistent with a psammopelitic parentage for the protolithof the tourmalinites. Boron isotope analyses of tourmaline havea total range of ¹¹B values from –15·6 to 6·8;the lowest corresponding to granitic tourmalines (–15·6to –11·7) and the highest to veins (1·9to 6·8). Tourmalines from tourmalinites have intermediate¹¹B values of –8·0 to +2·0. The observedvariations in ¹¹B support an important crustal recycling ofboron in the Martinamor area, in which pre-Variscan tourmaliniteswere remobilized by a combination of mechanical and chemicalprocesses during Variscan deformation, metamorphism and anatexis,leading to the formation of multiple tourmaline-bearing veinsand a new stage of boron metasomatism. KEY WORDS: tourmalinites; metamorphic and granitic rocks; mineral chemistry; whole-rock chemistry; boron isotopes     

Geochemical Constraints on the Origin of the Late Archean Skjoldungen Alkaline Igneous Province, SE Greenland

The present work reports the first broad geochemical investigationof the recently discovered late Archean (2700 Ma) Skjoldungenalkaline igneous province (SAP) in southeast Greenland. Therocks studied range in composition from ultramafic to felsicand comprise pyroxenites, hornblendites, hornblende noritesand diorites, monzonites, syenites, and nephelinitic rocks andcarbonatites. Various lithologic units from the host Archeangneissic basement are also investigated. The magmatic rocksshow remarkably coherent major element, trace element, rareearth element (REE), and Sr and Nd isotope systematics, suggestinga petrogenetic relationship. The most important geochemicalfeatures are high normative proportions of nepheline, forsteriteand albite, low TiO₂ (<15 wt %) and moderate FeO (total)(<12 wt %) contents, enrichments in large ion lithophileelements (LILE) and light rare earth elements both absoluteand relative to high field strength elements (HFSE) that displaylarge negative anomalies, and generally low to moderate abundancesof compatible elements. Field relations and REE and compatibleelement systematics among Skjoldungen rocks suggest that maficand ultramafic hornblende-rich samples may represent cumulatelithologies of the regional parental magma. On the basis ofmineral data, this is deduced to have had mg-number of 064,shoshonitic affinities (K₂O15 wt %), been close to silica saturationand volatile rich. Major element, trace element and REE systematicsfurther suggest that felsic intrusions are related to the maficregional parental magma through extensive olivine, hyperstheneand hornblende fractionation. Lack of correlation between La/Yband other critical trace and REE ratios indicates that apatite,zircon and titaniferous minerals were not important cumulusphases at advanced stages of evolution. The measured Sm–Ndwhole-rock isochron age is 2716 23 Ma (2 error) [mean squareof weighted deviates (MSWD) = 14], whereas linear regressionof the Sr isotope data yields an age of 26047 Ma (2 error)(MSWD = 22•2). The age obtained by Nd isotopes is corroboratedby U–Pb zircon results (2698 7 Ma), suggesting thatthe Sm–Nd system remained closed since crystallization.By contrast, the 100 Ma younger age obtained by Sr isotopessuggests that the Rb–Sr system has been disturbed. Initial¹⁴³Nd/¹⁴⁴ Nd ratios span a narrow range corresponding to _Nd(27Ga) =+074 to –109, whereas initial _Sr values at 27Ga cover a comparatively larger interval from –10 to +20.Neither initial _Nd nor initial _Sr values conform to previouslysuggested mantle depletion curves and no meaningful correlationexists between Nd and Sr isotopes for the Skjoldungen magmaticrocks as a whole. Although compositionally heterogeneous, theanalyzed suite of samples from the host agmatitic basement isextremely homogeneous with respect to age, with T^CHUR crustalresidence times around 2700–2800 Ma confirming limitedavailable isotopic evidence. Large-scale assimilation of Archeancrust or recycling of sediments derived from the local basementinto the mantle source fails to explain adequately negativeNb anomalies and low ^Nd signatures characteristic of the Skjoldungenintrusions. Rather, the nearchondritic isotopic compositionof Nd in the Skjoldungen samples together with the decoupledLILE and HFSE enrichment and slightly positive _Sr values areconsidered to reflect characteristics of the mantle source ina subduction zone environment. The geodynamic site hosting theSkjoldungen province thus may be an early manifestation of modern-styleplate tectonics. KEY WORDS: Skjoldungen province; Greenland; Archean; alkaline igneous rocks; geochronology; geochemistry ^*Corresponding author. Present address: Ecole Normale Suprieure de Lyon, 46 AlLe d'Italie, 69364 Lyon Cedex 07, France     

Geochemical Constraints on the Petrogenesis of Diamond Facies Pyroxenites from the Beni Bousera Peridotite Massif, North Morocco

The petrogenesis of pyroxenite layers within the Beni Bouseraperidotite massif is investigated by means of elemental andNd-Sr-Pb-O-S isotope analyses. The light rare earth element(LREE) depleted nature of many of the pyroxenites, their widevariation in composition, and lack of correlation between incompatibleelements and fractionation indices preclude them from representingcrystallized melts from a peridotitic source. The physical characteristicsof the pyroxenites and their large (greater than a factor of20) range in Ni rule out partial melting as the cause of theirpetrological and geochemical diversity. Major and compatibletrace element geochemistry is consistent with formation of mostof the pyroxenite suite via high-pressure crystal segregationin magma conduits intruding the peridotites. These magmas crystallizedclinopyroxene, orthopyroxene, and garnet. The pressure of crystallizationis constrained to be above {small tilde}45 kbar from the presenceof graphitized diamonds in pyroxenite layers. Lack of correlationbetween fractionation indices and highly incompatible elementsand the wide variation in incompatible element abundances suggestthat the suite did not form from genetically related magmas.The presence of positive and negative Eu anomalies (Eu/Eu* =0•54–2•0) in pyroxenites which crystallizedat pressures much greater than the plagioclase stability field({small tilde} 45 kbar) suggests that the parental magmas originatedfrom precursors which formed in the crust. Oxygen isotope compositionsof coexisting minerals in the pyroxenites indicate high-temperatureequilibration but ¹⁸O values vary from +4•9 to + 9•3,ruling out their derivation from the host peridotites or othernormal mantle sources. The extreme O-isotope variation, togetherwith ³⁴S values of up to + 13 in sulphides included within CPXstrongly suggests that the melts from which the pyroxenitescrystallized were derived from hydrothermally altered, subductedoceanic lithosphere. Extreme initial radiogenic isotope variationin the pyroxenites (_Nd + 26 to –9 , ⁸⁷Sr/⁸⁶Sr 0•7025–0•7110,²⁰⁶Pb/²⁰⁴Pb 18•21–19•90) support such an originbut also require a component with ancient, high U/Pb and Th/Pbin their source to explain the high 7/4 and 8/4 values of somepyroxenites. This component may be subducted hemi-pelagic sediment.Further evidence for a sediment component in the pyroxenitesis provided by isotopically light carbon in the graphite pyroxenites(¹³C–16 to – 28). Parentdaughter isotopes in thepyroxenites are strongly decoupled, making estimation of formationages speculative. The decoupling occurred recently (<200Ma), probably as a result of partial melting associated withdiapiric upwelling and emplacement of the massif into the crustfrom the diamond stability field. This late partial meltingevent further depleted the pyroxenites in incompatible elements.The variably altered nature of the subducted protolith and complexhistory of trace element fractionation of the pyroxenites haslargely obscured geochemical mixing trends. However, Nd–Pbisotope systematics indicate that incorporation of the componentwith high U/Pb–Th/Pb occurred relatively recently (<200Ma) for some pyroxenites. Other pyroxenites do not show evidencefor incorporation of such a component and may be substantiallyolder. Tectonic, geophysical, and isotopic constraints indicateformation of the pyroxenites in the mantle wedge above a subductingslab during the Cretaceous. Physical and chemical evidence forhigh-pressure fractionation seen in most of the pyroxenitesprecludes them from simply representing ancient subducted oceaniclithosphere, thinned by diffusion. However, the petrologicaland isotopic diversity of the massif support the concept ofa ‘marble cake’ mantle capable of producing theobserved geochemical diversity seen in oceanic magmas. *Present Address: Department of Terrestrial Magnetism, 5241 Broad Branch Road, N.W., Washington, DC 20015 Present address: Department of Geological Sciences, 1066 C.C. Little Building, University of Michigan, Ann Arbor, Michigan 48109     

Properties of Synthetic Triclinic KFeSi3O8, Iron-microcline, with some Observations on the Iron-microcline{rightleftharpoons}Iron-sanidine Transition

Triclinic KFeSi₃O₈, iron-microcline, has been synthesized fromoxide mixes and by complete conversion of monoclinic KFeSi₃O₈,iron-sanidine. Iron-microcline is triclinic, C, a=8?68?0?01?, b=13?10?0?01, c=7?34?0?01, =90? 45'?10', ß=116?03'?10', =86?14'?10'. The optical properties (Na light) are:=1?585?0?002, ß=1?596?0?002, =1?605?0?002, 2V=85?(calc.), Xb, Z c=20??5?. A reversible phase transition betweentriclinic and monoclinic KFeSi₃O₈ occurs at 704??6? C at 2000bars total pressure. Iron-microcline is the low-temperaturepolymorph; no intermediate polymorphs were observed in eitherhydrothermal or dry heating experiments.