Boron isotope geochemistry of Paleozoic brachiopod calcite: Implications for a secular change in the boron isotope geochemistry of seawater over the Phanerozoic

Boron isotope composition of marine carbonates has been proposed as a paleo-pH proxy and potential tool to reconstruct atmospheric pCO₂. The precise knowledge of the boron isotopic composition of ancient seawater represents the fundamental prerequisite for any paleo-pH reconstruction. This contribution presents boron isotope values for Silurian to Permian brachiopod calcite that might be used to reconstruct pH or boron isotope composition of past oceans. All brachiopod shells were screened for diagenetic recrystallization by means of cathodoluminescence microscopy, trace element geochemistry (B, Fe, Mn, Sr) as well as SEM. Only nonluminescent shells revealing well-preserved microstructures, high strontium and boron concentrations as well as low iron and manganese contents were accepted for boron isotope analysis. The boron isotope ratios of Silurian, Devonian, Pennsylvanian and Permian brachiopod calcite range from 6.8 to 11.0‰, 7.3 to 14.9‰, 12.4 to 15.8‰ and 10.1 to 11.7‰, respectively. These δ¹¹B values are significantly lower in comparison to δ¹¹B values of modern biogenic carbonates and indicate that the Paleozoic oceans were depleted in ¹¹B by up to 10‰. Box modeling of the boron geochemical cycle suggests that the significant depletion of ¹¹B in the oceanic reservoir may have been initiated by an enhanced continental boron discharge. Our data support the earlier made conclusion that boron isotopes may not be used in the geological past as reliable paleo-pH proxy unless the boron isotopic composition of ancient oceans can be constrained by further studies.     

The major-ion composition of silurian seawater

One-hundred fluid inclusions in Silurian marine halite were analyzed in order to determine the major-ion composition of Silurian seawater. The samples analyzed were from three formations in the Late Silurian Michigan Basin, the A-1, A-2, and B Evaporites of the Salina Group, and one formation in the Early Silurian Canning Basin (Australia), the Mallowa Salt of the Carribuddy Group. The results indicate that the major-ion composition of Silurian seawater was not the same as present-day seawater. The Silurian ocean had lower concentrations of Mg²⁺, Na⁺, and SO₄²⁻, and much higher concentrations of Ca²⁺ relative to the ocean’s present-day composition. Furthermore, Silurian seawater had Ca²⁺ in excess of SO₄²⁻. Evaporation of Silurian seawater of the composition determined in this study produces KCl-type potash minerals that lack the MgSO₄-type late stage salts formed during the evaporation of present-day seawater. The relatively low Na⁺ concentrations in Silurian seawater support the hypothesis that oscillations in the major-ion composition of the oceans are primarily controlled by changes in the flux of mid-ocean ridge brine and riverine inputs and not global or basin-scale, seawater-driven dolomitization. The Mg²⁺/Ca²⁺ ratio of Silurian seawater was ∼1.4, and the K⁺/Ca²⁺ ratio was ∼0.3, both of which differ from the present-day counterparts of 5 and 1, respectively. Seawaters with Mg²⁺/Ca²⁺ <2 facilitate the precipitation of low-magnesian calcite (mol % Mg < 4) marine ooids and submarine carbonate cements whereas seawaters with Mg²⁺/Ca²⁺ >2 (e.g., modern seawater) facilitate the precipitation of aragonite and high-magnesian calcite. Therefore, the early Paleozoic calcite seas were likely due to the low Mg²⁺/Ca²⁺ ratio of seawater, not the pCO₂ of the Silurian atmosphere.     

The composition and evolution of primordial solutions on Mars, with application to other planetary bodies

We examine a model for Mars involving bulk primordial solutions (oceans and lakes) that were relatively Mg-rich and SO₄/(SO₄ + Cl)-rich. Such solutions could be produced when (1) volatiles leached a planet (or portions of a planet) with an ultramafic-mafic composition in a process called “planetary leaching”; and/or by (2) “impactor leaching” where meteoritic and/or cometary impactor fragments were leached. When Mg-SO₄/(SO₄ + Cl)-rich solutions are concentrated, we predict that the following sequence of salts precipitates: phosphates; carbonates; gypsum; epsomite; bloedite; halite; hexahydrite; and, finally bischofite. This sequence is modified slightly if appreciable Fe-, Mg- or Na-carbonates, Fe-sulfates, Mg-phosphate, or other halide salts crystallized before the Mg-Na-sulfate salts, or if HCO₃+CO₃ concentrations vary due to other effects (e.g., atmosphere CO₂ levels change).On Mars, the initial primordial solutions would have been relatively salt-rich and water-poor; therefore, the surface solutions formed Mg-Na-SO₄-Cl salts (cements, veneers, and dust) and subsurface solutions or ice (solid H₂O). This model is supported by the compositions of cements in the regolith on Mars (high Mg, Na, S, and Cl) and geochemical and petrographic evidence that the salts precipitated in the predicted sequence. We suggest that the partial pressure of oxygen was above the hematite-magnetite buffer where Fe³⁺-(hydrous)-oxides are stable and SO₄^2- or HSO₄^- are solutes in any solution. Such a partial pressure of oxygen may have been attained via H₂-loss.In contrast, on the Galilean satellites (Europa, Ganymede, and Callisto) surface solutions were relatively water-rich and formed ice, Mg-SO₄-rich salts, and solutions, thereby producing surface features dependent on the initial water content and the crystallization path. Unlike the Na-Cl-rich oceans on Earth, the solutions of these planetary bodies likely did not change greatly from their bulk primordial Mg-rich, SO₄/(SO₄ + Cl)-rich compositions; hence they did not attain compositions similar to modern seawater.     

The influence of primary magma composition,H2O and pressure on mid-ocean ridge basalt differentiation

MORB suites display variations in their chemical differentiation trends which are closely related to the incompatible element enrichment of the basalts. We examine suites of primitive to evolved basalts from the Pacific-Nazca Ridge at 28° S (mostly depleted); from the Juan Fernandez microplate region (depleted) and from the Explorer Ridge, northeast Pacific (mostly enriched). Trends for incompatible element enriched MORBs consistently show less depletion of Al₂O₃ and less enrichment of FeO when plotted on MgO variation diagrams.Least squares modeling indicates that enriched basalts have undergone less plagioclase crystallization than depleted basalts especially in the early stages of differentiation. Using thermodynamic modelling, we show that variations between MORB differentiation trends result largely from differences in the major element chemistry and H₂O content of primary magmas. Our chosen enriched and depleted near-primary magmas are similar in major element chemistry but the enriched near-primary magma has higher H₂O and lower Al₂O₃ than the depleted near-primary magma. The MORB crystallization sequence is: olivineolivine+plagioclase olivine+plagioclase+high-Ca pyroxene; and the separate and combined effects of lower Al₂O₃ and higher H₂O are to cause plagioclase to crystallize later (lower temperature), and to make the interval of olivine+plagioclase crystallization shorter. As a result, enriched differentiates have higher Al₂O₃ and lower FeO than depleted MORBs at a given MgO content, even though their parents' Al₂O₃ is lower. Crystallization of enriched basalts at higher pressure than depleted basalts is not able to account for differences between the differentiation trends because the proportion of plagioclase is higher during three-phase crystallization at high pressure.The variations in trends do not depend on geographic location and thus are superimposed on any regional variations in MORB chemistry or mantle source. Nor are they related to spreading rate. Depleted basalts from the fast-spreading 28° S and Juan Fernandez ridges have differentiation trends similar to depleted basalts from the medium-spreading Galapagos Spreading Center, whereas differentiation trends for enriched basalts from the medium-spreading Explorer Ridge are quite different. Fe³⁺/Fe_total is similar (and quite low) for enriched and depleted basalts, indicating that neither oxidation state nor early magnetite crystallization are important.     

Subsolidus and melting phase relations of basaltic composition in the uppermostlower mantle

The phase relations and the element partitioning in a mid-oceanic ridge basalt composition were determined for both above-solidus and subsolidus conditions at 22 to 27.5 GPa by means of a multianvil apparatus. The mineral assemblage at the solidus changes remarkably with pressure; majorite and stishovite at 22 GPa, joined by Ca-perovskite at 23 GPa, further joined by CaAl₄Si₂O₁₁-rich CAS phase at 25.5 GPa, and Mg-perovskite, stishovite, Ca-perovskite, CF phase (approximately on the join NaAlSiO₄-MgAl₂O₄), and NAL phase ([Na,K,Ca]₁[Mg,Fe²⁺]₂[Al,Fe³⁺,Si]_5.5-6.0O₁₂) above 27 GPa. The liquidus phase is Ca-perovskite, and stishovite, a CAS phase, a NAL phase, Mg-perovskite, and a CF phase appear with decreasing temperature at 27.5 GPa. Partial melt at 27 to 27.5 GPa is significantly depleted in SiO₂ and CaO and enriched in FeO and MgO compared with those formed at lower pressures, reflecting the narrow stability of (Fe,Mg)-rich phases (majorite or Mg-perovskite) above solidus temperature. The basaltic composition has a lower melting temperature than the peridotitic composition at high pressures except at 13 to 18 GPa (Yasuda et al., 1994) and therefore can preferentially melt in the Earth’s interior. Recycled basaltic crusts were possibly included in hot Archean plumes, and they might have melted in the uppermost lower mantle. In this case, Ca-perovskite plays a dominant role in the trace element partitioning between melt and solid. This contrasts remarkably with the case of partial melting of a peridotitic composition in which magnesiowüstite is the liquidus phase at this depth.     

Compositional variability of spinel-group minerals from the shergol serpentinized peridotites along indus suture zone,ladakh himalaya (India): constraints on tectonomagmatic history

The Shergol ophiolitic peridotites along ISZ, Ladakh Himalaya are serpentinized to various degrees and are harzburgite in composition. Electron microprobe analyses of spinels from Shergol Serpentinized Peridotites (SSPs) were carried out in order to evaluate their compositional variation with alteration. Chemical discontinuity was observed from core to rim in analyzed spinel grains with Cr-rich cores rimmed by Cr-poor compositions. From unaltered cores to rims it was observed that Cr³⁺# and Fe³⁺# increases while Mg²⁺# decreases due to Mg²⁺ − Fe²⁺ and Al³⁺ (Cr³⁺) − Fe³⁺ exchange with surrounding silicates during alteration. These peridotites contain Al-rich spinels forming subhedral to anhedral grains with lobate and corroded grain boundaries; altered to ferritchromite or magnetite along cracks and boundaries by later metamorphism episode. The unaltered Cr-spinel cores are identified as Al-rich and are characterized by lower values of Cr³⁺# (0.34–0.40), high Al³⁺# (0.58–0.68) and Mg²⁺# (0.52–0.70). Mineral chemistry of these Al-rich Cr-spinels suggest that host peridotites have an affinity to abyssal and alpine-type peridotites. High TiO₂ concentration of magmatic Cr-spinel cores are in agreement with MORB melt-residual peridotite interaction. Presence of unaltered magmatic Cr-spinel cores suggest that they do not have re-equilibrated completely with metamorphic spinel rims and surrounding silicates. Cr-spinel core compositions of SSPs suggest an ophiolitic origin derivation by low degrees of melting of a less-moderate depleted peridotite in a mid-ocean ridge tectonic setting. Based on textural and chemical observations the alteration conditions of studied spinel-group minerals match those of transitional greenschist-amphibolite facies metamorphism consistent with estimated metamorphic equilibration temperature of ∼ 500–600 ^°C.     

Carbonate alteration of ophiolitic rocks in the Arabian–Nubian Shield of Egypt: sources and compositions of the carbonating fluid and implications for the formation of Au deposits

Ultramafic portions of ophiolitic fragments in the Arabian–Nubian Shield (ANS) show pervasive carbonate alteration forming various degrees of carbonated serpentinites and listvenitic rocks. Notwithstanding the extent of the alteration, little is known about the processes that caused it, the source of the CO₂ or the conditions of alteration. This study investigates the mineralogy, stable (O, C) and radiogenic (Sr) isotope composition, and geochemistry of suites of variably carbonate altered ultramafics from the Meatiq area of the Central Eastern Desert (CED) of Egypt. The samples investigated include least-altered lizardite (Lz) serpentinites, antigorite (Atg) serpentinites and listvenitic rocks with associated carbonate and quartz veins. The C, O and Sr isotopes of the vein samples cluster between ?8.1‰ and ?6.8‰ for δ¹³C, +6.4‰ and +10.5‰ for δ¹⁸O, and ⁸⁷Sr/⁸⁶Sr of 0.7028–0.70344, and plot within the depleted mantle compositional field. The serpentinites isotopic compositions plot on a mixing trend between the depleted-mantle and sedimentary carbonate fields. The carbonate veins contain abundant carbonic (CO₂±CH₄±N₂) and aqueous-carbonic (H₂O-NaCl-CO₂±CH₄±N₂) low salinity fluid, with trapping conditions of 270–300°C and 0.7–1.1 kbar. The serpentinites are enriched in Au, As, S and other fluid-mobile elements relative to primitive and depleted mantle. The extensively carbonated Atg-serpentinites contain significantly lower concentrations of these elements than the Lz-serpentinites suggesting that they were depleted during carbonate alteration. Fluid inclusion and stable isotope compositions of Au deposits in the CED are similar to those from the carbonate veins investigated in the study and we suggest that carbonation of ANS ophiolitic rocks due to influx of mantle-derived CO₂-bearing fluids caused break down of Au-bearing minerals such as pentlandite, releasing Au and S to the hydrothermal fluids that later formed the Au-deposits. This is the first time that gold has been observed to be remobilized from rocks during the lizardite–antigorite transition.     

Chemistry of glass inclusions in olivines of the CR chondrites Renazzo, Acfer 182, and El Djouf 001

Glass inclusions in olivines of the Renazzo, El Djouf 001, and Acfer 182 CR-type chondrites are chemically divers and can be classified into Al-rich, Al-poor, and Na-rich types. The chemical properties of the glasses are independent of the occurrence of the olivine (isolated or part of an aggregate or chondrule) and its composition. The glasses are silica-saturated (Al-rich) or oversaturated (Al-poor, 24% normative quartz). All glasses have chondritic CaO/Al₂O₃ ratios, unfractionated CI-normalized abundances of refractory trace elements and are depleted in moderately volatile and volatile elements. Thus the glasses are likely to be of a primitive condensate origin whose chemical composition has been established before chondrule formation and accretion, rather then the product of either crystal fractionation from chondrule melts or part melting of chondrules. Rare Na-rich glasses give evidence for elemental exchange between the glass and a vapor phase. Because they have Al₂O₃ contents and trace element abundances very similar to those of the Al-rich glasses, they likely were derived from the latter by Ca exchange (for Na) with the nebula. Elemental exchange reactions also have affected practically all olivines (e.g., exchange of Mg of olivine for Fe²⁺, Mn²⁺, and Cr³⁺). Glasses formed contemporaneously with the host olivine. As the most likely process for growing nonskeletal olivines from a vapor we consider the VLS (vapor-liquid-solid) growth process, or liquid-phase epitaxy. Glasses are the possible remnants of the liquid interface between growing crystal and the vapor. Such liquids can form stably or metastably in regions with enhanced oxygen fugacity as compared to that of a nebula of solar composition.     

Formation of pyroxenite layers in the Totalp ultramafic massif (Swiss Alps) - Insights from highly siderophile elements and Os isotopes

Pyroxenitic layers are a minor constituent of ultramafic mantle massifs, but are considered important for basalt generation and mantle refertilization. Mafic spinel websterite and garnet-spinel clinopyroxenite layers within Jurassic ocean floor peridotites from the Totalp ultramafic massif (eastern Swiss Alps) were analyzed for their highly siderophile element (HSE) and Os isotope composition.Aluminum-poor pyroxenites (websterites) display chondritic to suprachondritic initial γ_Os (160 Ma) of −2 to +27. Osmium, Ir and Ru abundances are depleted in websterites relative to the associated peridotites and to mantle lherzolites worldwide, but relative abundances (Os/Ir, Ru/Ir) are similar. Conversely, Pt/Ir, Pd/Ir and Re/Ir are elevated.Aluminum-rich pyroxenites (clinopyroxenites) are characterized by highly radiogenic ¹⁸⁷Os/¹⁸⁸Os with initial γ_Os (160 Ma) between +20 and +1700. Their HSE composition is similar to that of basalts, as they are more depleted in Os, Ir and Ru compared to Totalp websterites, along with even higher Pt/Ir, Pd/Ir and Re/Ir. The data are most consistent with multiple episodes of reaction of mafic pyroxenite precursor melts with surrounding peridotites, with the highest degree of interaction recorded in the websterites, which typically occur in direct contact to peridotites. Clinopyroxenites, in contrast, represent melt-dominated systems, which retained the precursor melt characteristics to a large extent. The melts may have been derived from a sublithospheric mantle source with high Pd/Ir, Pt/Ir and Re/Os, coupled with highly radiogenic ¹⁸⁷Os/¹⁸⁸Os compositions. Modeling indicates that partial melting of subducted, old oceanic crust in the asthenosphere could be a possible source for such melts.Pentlandite and godlevskite are identified in both types of pyroxenites as the predominant sulfide minerals and HSE carriers. Heterogeneous HSE abundances within these sulfide grains likely reflect subsolidus processes. In contrast, large grain-to-grain variations, and correlated variations of HSE ratios, indicate chemical disequilibrium under high-temperature conditions. This likely reflects multiple events of melt-rock interaction and sulfide precipitation. Notably, sulfides from the same thick section for the pyroxenites may display both residual-peridotite and melt-like HSE signatures. Because Totalp pyroxenites are enriched in Pt and Re, and depleted in Os, they will develop excess radiogenic ¹⁸⁷Os and ¹⁸⁶Os, compared to ambient mantle. These enrichments, however, do not possess the requisite Pt-Re-Os composition to account for the coupled suprachondritic ¹⁸⁶Os-¹⁸⁷Os signatures observed in some Hawaiian picrites, Gorgona komatiites, or the Siberian plume.     

Polygenetic sources of kimberlites, magma composition, and diamond potential exemplified by the East European and Siberian cratons

The petrological and geochemical characteristics of kimberlites from two Russian provinces of the northern East European craton (EEP) and the Siberian craton (SC) (especially the Yakutian diamondiferous province, YDP), and aphanitic kimberlites from the Jericho pipe (Canada) were compared for the elucidation of some aspects of the genesis of these rocks. The comparison of the EEP and YDP showed that they comprise identical rock associations with some variations in kimberlite composition between particular fields and regions, which are clearly manifested in the TiO₂-K₂O, TiO₂-(Y, Zr, HREE), SiO₂-MgO, SiO₂-Al₂O₃, MgO-Ni, MgO-CO₂, and MgO-H₂O diagrams and in variations in light element ratios (Li/Yb, Be/Nd, and B/Nb). The compositions of YDP kimberlites are confined mainly to quadrant III; i.e., their source was mainly the depleted mantle, whereas the compositions of EEP kimberlites fall within all four quadrants in the fields of both enriched and slightly depleted mantle reservoirs. The initial (¹⁴³Nd/¹⁴⁴Nd) _i ratio of kimberlites from the Yakutian collection is 0.5121–0.5126. The lead isotopic characteristics of the EEP and YDP kimberlites are similar to mantle values: ²⁰⁶Pb/²⁰⁴Pb of 16.19–19.14, ²⁰⁷Pb/²⁰⁴Pb of 15.44–15.61, and ²⁰⁸Pb/²⁰⁴Pb of 34.99–38.55. In the ²⁰⁷Pb/²⁰⁴Pb-²⁰⁶Pb/²⁰⁴Pb diagram, part of the kimberlites, including those from the Botuobiya pipe, fall within the lower part of the field of group I kimberlites from southern Africa near the Pb isotopic composition of the depleted mantle. It was shown that the chemical compositions of the aphanitic kimberlites of the Jericho pipe (supposedly approaching the composition of primary magmas) are similar to those of some individual kimberlite samples from the YDP and EEP. It was supposed that the initial kimberlite melt arrived from the asthenosphere and was enriched in water and other volatile components (especially CO₂). During its ascent to the surface, the melt assimilated mantle components, primarily MgO; as a result, it acquired the compositional characteristics observed in kimberlites. Subsequent compositional modifications were related to diverse factors, including the type of mantle metasomatism, degree of melting, etc. We emphasized the importance of petrological and geochemical criteria (low contents of HREE and Ti in the rocks and a kimberlite source similar to BSE or EMI) for the estimation of the diamond potential of rocks.     

Dissolved Al in sediments and waters of the East China Sea: Implications for authigenic mineral formation

Numerous previous studies indicate that several different authigenic aluminosilicates form in the oceans. In this study we show, using dissolved Al distributions in sediments and waters from the nearshore regions of the East China Sea, that the process of aluminosilicate formation probably begins rapidly upon contact of detrital clays with seawater. Statistical analyses of dissolved Al-Si-H⁺ relations in surface sediments indicate that the minerals forming in East China Sea sediments low in dissolved Fe are dioctahedral chlorites with an average composition EX_0.91Mg_0.77Al_5.0Si_2.7O₁₀(OH)₈ (where EX = exchangeable + 1 cation). This composition is also consistent with dissolved Al and Si measurements as a function of salinity in turbid overlying waters. Results suggest a dissolution—reprecipitation mechanism for clay mineral reconstitution. This mechanism can help to explain why different authigenic clays are found in different areas of the oceans. In the East China Sea the total amount of authigenic clays present must constitute a very minor fraction of the bottom sediments. Thus, the formation of these minerals has a relatively small impact upon dissolved Si distributions. Clay mineral reconstitution in nearshore regions may provide a mechanism for buffering sediments and overlying waters with respect to pH, as the composition of minerals formed should be a direct function of the H⁺ activity in the surrounding environment.     

Structure and physical property relations of Mn ilvaite

Structural and compositional data as well as ⁵⁷Fe Mössbauer parameters were determined on a natural Mn-rich monoclinic ilvaite crystal (ideal composition CaFe ₂ ²⁺ Fe³⁺Si₂O₈(OH)) which was used for electrical conductivity and thermopower measurements (part 2 of this paper). A zonar structure was found by electron microprobe analysis with a strong decrease in Mn concentration from the rim to the centre of the crystal in a plane perpendicular to the [001] direction. X-ray powder diffraction analysis of the most Mn-rich composition was performed. Mn²⁺ cations populate preferentially M2 sites of the ilvaite unit cell (space group P21/a), to a lower extent they reside on M1 and a reduced part is on Ca sites. The monoclinic angle was determined to β=90.178(4)°. The structural results are compared to literature data for other natural Mn-rich as well as low-impurity ilvaites; this concerns in particular the lattice b parameter and the undecided issue of the varying β angle. In the literature, the order parameter σ, which describes the varying degree of ordering of Fe²⁺–Fe³⁺ pairs on M11 and M12 sites in chains running parallel to the [001] direction, and structural defects are thought to be related to β. The interrelationship between β and σ with respect to a possible twin domain structure is discussed. Various ⁵⁷Fe Mössbauer spectra were recorded between 151 K and 327 K. Mössbauer parameters and Fe²⁺/Fe³⁺ concentration ratios were determined from the fits to the spectra. Fitting of subspectra was accomplished with the idea to find assignments of Fe²⁺ and Fe³⁺ doublets in agreement with X-ray results. The fraction of Mn²⁺ substituting Fe²⁺ on M1 sites could be estimated.     

Ultra-depleted, shallow cratonic mantle beneath West Greenland: dunitic xenoliths from Ubekendt Ejland

Dunitic xenoliths from late Palaeogene, alkaline basalt flows on Ubekendt Ejland, West Greenland contain olivine with 100 × Mg/(Mg + Fe), or Mg#, between 92.0 and 93.7. Orthopyroxene has very low Al₂O₃ and CaO contents (0.024–1.639 and 0.062–0.275 wt%, respectively). Spinel has 100 × Cr/(Cr + Al), or Cr#, between 46.98 and 95.67. Clinopyroxene is absent. The osmium isotopic composition of olivine and spinel mineral separates shows a considerable span of ¹⁸⁷Os/¹⁸⁸Os values. The most unradiogenic ¹⁸⁷Os/¹⁸⁸Os value of 0.1046 corresponds to a Re-depletion age of ca. 3.3 Gy, while the most radiogenic value of 0.1336 is higher than present-day chondrite. The Os isotopic composition of the xenoliths is consistent with their origin as restites from a melt extraction event in the Archaean, followed by one or more subsequent metasomatic event(s). The high Cr# in spinel and low modal pyroxene of the Ubekendt Ejland xenoliths are similar to values of some highly depleted mantle peridotites from arc settings. However, highly depleted, arc-related peridotites have higher Cr# in spinel for a given proportion of modal olivine, compared to cratonic xenolith suites from Greenland, which instead form coherent trends with abyssal peridotites, dredged from modern mid-ocean ridges. This suggests that depleted cratonic harzburgites and dunites from shallow lithospheric mantle represent the residue from dry melting in the Archaean.     

Characterization of a La-Ce-Sr-Ca aluminous hydroxy phosphate in nuclear zone 13 in the Oklo uranium deposit (Gabon)

A La-Ce-Sr-Ca aluminous hydroxy phosphate of the goyazite-florencite-crandallite series was observed in the nuclear reactor zone 13 in the Oklo uranium deposit (Gabon). It has a trigonal elementary cell with a?=?6.98 ± 0.03 Å and c?=?16.35?±?0.04?Å (space group P3m). It occurs in a U-rich sample depleted in ²³⁵U (²³⁵U/²³⁸U?=?0.0047). Its chemical composition, measured by ion microprobe analyses, shows that it contains fission products (Zr, LREE) whereas the isotopic composition of Ba and Sr is natural. Ion microprobe imaging indicates that the nearby uraninite crystals are depleted in fissiogenic LREE. This study shows that the migration of some fission products, probably related to a dolerite dike intrusion, is limited by the formation of aluminous hydroxy phosphates.     

Large-scale melt-depletion in granulite terranes: an example from the Archean Ashuanipi Subprovince of Quebec

This study uses field, petrographic and geochemical methods to estimate how much granitic melt was formed and extracted from a granulite facies terrane, and to determine what the grain‐ and outcrop‐scale melt‐flow paths were during the melt segregation process. The Ashuanipi subprovince, located in the north‐eastern Superior Province of Quebec, is a large (90 000 km²) metasedimentary terrane, in which > 85% of the metasediments are of metagreywacke composition, that was metamorphosed at mid‐crustal conditions (820–900 °C and 6–7 kbar) in a late Archean dextral, transpressive orogen. Decrease in modal biotite and quartz as orthopyroxene and plagioclase contents increase, together with preserved former melt textures indicate that anatexis was by the biotite dehydration reaction: biotite + quartz + plagioclase = melt + orthopyroxene + oxides. Using melt/orthopyroxene ratios for this reaction derived from experimental studies, the modal orthopyroxene contents indicate that the metagreywacke rocks underwent an average of 31 vol% partial melting. The metagreywackes are enriched in MgO, CaO and FeO_t and depleted in SiO₂, K₂O, Rb, Cs, and U, have lower Rb/Sr, higher Rb/Cs and Th/U ratios and positive Eu anomalies compared to their likely protolith. These compositions are modelled by the extraction of between 20 and 40 wt %, granitic melt from typical Archean low‐grade metagreywackes. A simple mass balance indicates that about 640 000 km³ of granitic melt was extracted from the depleted granulites. The distribution of relict melt at thin section‐ and outcrop‐scales indicates that in layers without leucosomes melt extraction occurred by a pervasive grain boundary (porous) flow from the site of melting, across the layers and into bedding planes between adjacent layers. In other rocks pervasive grain boundary flow of melt occurred along the layers for a few, to tens of centimetres followed by channelled flow of melt in a network of short interconnected and structurally controlled conduits, visible as the net‐like array of leucosomes in some outcrops. The leucosomes contain very little residual material (< 5% biotite + orthopyroxene) indicating that the melt fraction was well separated from the residuum left in situ as melt‐depleted granulite. Only 1–3 vol percentage melt remained in the melt‐depleted granulites, hence, the extraction of melt generated by biotite dehydration melting in these granulites, was virtually complete under conditions of natural melting and strain rates in a contractional orogen.     

Pumpellyites and coexisting minerals in different low-grade metamorphic facies of Liguria, Italy

Pumpellyite from four-phase assemblages (pumpellyite + epidote + prehnite + chlorite; pumpellyite + epidote + actinolite + chlorite; pumpellyite + epidote + Na-amphibole + chlorite, together with common excess phases), considered to be low variance in a CaO-(MgO + FeO)-Al₂O₃-Fe₂O₃ (+Na₂O + SiO₂+ H₂O) system, have been examined in areas which underwent metamorphism in the prehnite-pumpellyite, pumpellyite-actinolite and low-temperature blueschist facies respectively. The analysed mineral assemblages are compared for nearly constant (basaltic) chemical composition at varying metamorphic grade and for varying chemical composition (basic, intermediate, acidic) at constant metamorphic conditions (low-temperature blueschist facies). In the studied mineral assemblages, coexisting phases approached near chemical equilibrium. At constant (basaltic) bulk rock composition the MgO content of pumpellyite increases, and the X_Fe3+ of both pumpellyite and epidote decreases with increasing metamorphic grade, the Fe³⁺ being preferentially concentrated in epidote. Both pumpellyite and epidote compositions vary with the bulk rock composition at isofacial conditions; pumpellyite becomes progressively enriched in Fe and depleted in Mg from basic to intermediate and acidic bulk rock compositions. The compositional comparison of pumpellyites from high-variance (1–3 phases) assemblages in various bulk rock compositions (basic, intermediate, acidic rocks, greywackes, gabbros) shows that the compositional fields of both pumpellyite and epidote are wide and variable, broadly overlapping the compositional effects observed at varying metamorphic grade in low-variance assemblages. The intrinsic stability of both Fe- and Al-rich pumpellyites extends across the complete range of the considered metamorphic conditions. Element partitioning between coexisting phases is the main control on the mineral composition at different P-T conditions.     

Zinc and sulfur isotope variation in sphalerite from carbonate-hosted zinc deposits,Cantabria, Spain

We studied zinc and sulfur isotopes and the chemical composition of sphalerite samples from Picos de Europa (Aliva mine) and sphalerite and hydrozincite samples from La Florida mine, two carbonate-hosted Mississippi Valley-type (MVT) deposits located in northern Spain; despite being close, they are hosted in carbonatic rocks of different ages, Lower Carboniferous and Lower Cretaceous, respectively. The two generations of sphalerite at Picos de Europa show different δ⁶⁶Zn values (stage 1 sphalerite +0.24 per mil and stage 2 sphalerite from ?0.75 to +0.08 per mil). Both generations also differ in the sulfur isotope composition (stage 1 has δ³⁴S?=?+6.6 and stage 2 has δ³⁴S?=??0.9 to +2.9 per mil) and the chemical composition (stage 1 sphalerite, compared to stage 2 sphalerite, is significantly enriched in Pb, As, Mn, Sb, slightly enriched in Ag, Ni, and Cu and depleted in Co, Ga, Tl, Te, Ge, and Sn). We suggest that Zn isotope fractionation was controlled predominantly by pH and T changes. High Zn isotope values reflect rapid precipitation of sphalerite from higher-temperature acidic fluids that carried Zn mostly as chloride species after interaction with carbonate rocks while lower Zn isotope values most likely resulted from a longer precipitation process from fluid at higher pH and decreasing T that carried dominantly Zn sulfide species. At La Florida, sphalerite samples show light ⁶⁶Zn-depleted signatures with δ⁶⁶Zn values from ?0.80 to ?0.01 per mil (mostly between ?0.80 and ?0.24 per mil) and δ³⁴S values from +10.7 to +15.7 per mil without any relationship between the δ⁶⁶Zn and δ³⁴S values. Here, the variation in Zn isotope values is interpreted as related to mixing of fluids from two reservoirs. The Zn was carried by a single deep-seated and higher T (~250–320 °C) fluid, and precipitation took place after mixing with a connate S-rich fluid in a system with mH₂S?>?mZn²⁺ as a result of change in pH, T, and Zn predominant species. The light δ⁶⁶Zn accompanied by heavy δ³⁴S values resulted from fractionation of Zn aqueous sulfides at near-neutral pH and decreasing T. Hydrozincite samples show much heavier δ⁶⁶Zn values (+0.21 to +0.33 per mil), consistent with fractionation during supergene processes.     

Interpreting the Ca isotope record of marine biogenic carbonates

An 18 million year record of the Ca isotopic composition (δ^44/42Ca) of planktonic foraminiferans from ODP site 925, in the Atlantic, on the Ceara Rise, provides the opportunity for critical analysis of Ca isotope-based reconstructions of the Ca cycle. δ^44/42Ca in this record averages +0.37 ± 0.05 (1σ SD) and ranges from +0.21‰ to +0.52‰. The record is a good match to previously published Neogene Ca isotope records based on foraminiferans, but is not similar to the record based on bulk carbonates, which has values that are as much as 0.25‰ lower. Bulk carbonate and planktonic foraminiferans from core tops differ slightly in their δ^44/42Ca (i.e., by 0.06 ± 0.06‰ (n = 5)), while the difference between bulk carbonate and foraminiferan values further back in time is markedly larger, leaving open the question of the cause of the difference. Modeling the global Ca cycle from downcore variations in δ^44/42Ca by assuming fixed values for the isotopic composition of weathering inputs (δ^44/42Ca_w) and for isotope fractionation associated with the production of carbonate sediments (Δ_sed) results in unrealistically large variations in the total mass of Ca²⁺ in the oceans over the Neogene. Alternatively, variations of ±0.05‰ in the Ca isotope composition of weathering inputs or in the extent of fractionation of Ca isotopes during calcareous sediment formation could entirely account for variations in the Ca isotopic composition of marine carbonates. Ca isotope fractionation during continental weathering, such as has been recently observed, could easily result in variations in δ^44/42Ca_w of a few tenths of permil. Likewise a difference in the fractionation factors associated with aragonite versus calcite formation could drive shifts in Δ_sed of tenths of permil with shifts in the relative output of calcite and aragonite from the ocean. Until better constraints on variations in δ^44/42Ca_w and Δ_sed have been established, modeling the Ca²⁺ content of seawater from Ca isotope curves should be approached cautiously.     

Pb and Nd isotopic study of two archean komatiitic flows from Alexo,Ontario

Isotopic analysis of two Archean komatiitic flows from Alexo, Ontario, gives a Pb-Pb isochron age of 2690 ± 15 Ma and a Sm-Nd isochron age of 2752 ± 87 Ma. These ages agree well with U-Pb zircon ages from underlying and overlying volcanics. The variations in element ratios that define the isochrons were not produced during crystallization of the lavas. The spread in U/Pb was caused by submarine alteration soon after eruption, and the spread in Sm/Nd resulted from (a) differences in the composition of the residue of melting, and (b) contamination of the upper komatiite flow through thermal erosion of the lower flow.The ¹⁴⁷Sm/¹⁴⁴Nd ratio of uncontaminated komatiite is 0.25 which reflects the depleted nature of its mantle source. The Th/U ratio of about 3.4 is probably also representative of depleted mantle. The initial ?_Nd of +2.44 ± 0.51 indicates that the mantle depletion took place long before magma formation.