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M.F. Horan

Publications and source records attributed to M.F. Horan.

12 recordsLinked to original sources

Sources of osmium to the modern oceans: New evidence from the 190Pt-186Os system

High precision Os isotope analysis of young marine manganese nodules indicate that whereas the composition of modern seawater is radiogenic with respect to 187Os/188Os, it has 186Os/188Os that is within uncertainty of the chondritic value. Marine Mn nodule compositions thus indicate that the average continental source of Os to modern seawater had long-term high Re/Os compared to Pt/Os. Analyses of loess and freshwater Mn nodules support existing evidence that average upper continental crust (UCC) has resolvably suprachondritic 186Os/188Os, as well as radiogenic 187Os/188Os. Modeling the composition of seawater as a two-component mixture of oceanic/cosmic Os with chondritic Os compositions and continentally-derived Os demonstrates that, insofar as estimates for the composition of average UCC are accurate, congruently weathered average UCC cannot be the sole continental source of Os to seawater. Our analysis of four Cambrian black shales confirm that organic-rich sediments can have 187Os/188Os ratios that are much higher than average UCC, but 186Os/188Os compositions that are generally between those of chondrites and average-UCC. Preferential weathering of black shales can result in dissolved Os discharged to the ocean basins that has a much lower 186Os/188Os than does average upper crust. Modeling the available data demonstrates that augmentation of estimated average UCC compositions with less than 0.1% additional black shale and 1.4% additional ultramafic rock can produce a continental end-member Os isotopic composition that satisfies the requirements imposed by the marine Mn nodule data. The interplay of these two sources provides a mechanism by which the 187Os/188Os of seawater can change as sources and weathering conditions change, yet seawater 186Os/188Os varies only minimally. ?? 2004 Elsevier Ltd.

Geochimica et Cosmochimica Acta↗

Highly siderophile elements in chondrites

The abundances of the highly siderophile elements (HSE), Re, Os, Ir, Ru, Pt and Pd, were determined by isotope dilution mass spectrometry for bulk samples of 13 carbonaceous chondrites, 13 ordinary chondrites and 9 enstatite chondrites. These data are coupled with corresponding 187Re-187Os isotopic data reported by Walker et al. [Geochim. Cosmochim. Acta, 2002] in order to constrain the nature and timing of chemical fractionation relating to these elements in the early solar system. The suite of chondrites examined displays considerable variations in absolute abundances of the HSE, and in the ratios of certain HSE. Absolute abundances of the HSE vary by nearly a factor of 80 among the chondrite groups, although most vary within a factor of only 2. Variations in concentration largely reflect heterogeneities in the sample aliquants. Different aliquants of the same chondrite may contain variable proportions of metal and/or refractory inclusions that are HSE-rich, and sulfides that are HSE-poor. The relatively low concentrations of the HSE in CI1 chondrites likely reflect dilution by the presence of volatile components. Carbonaceous chondrites have Re/Os ratios that are, on average, approximately 8% lower than ratios for ordinary and enstatite chondrites. This is also reflected in 187Os/188Os ratios that are approximately 3% lower for carbonaceous chondrites than for ordinary and enstatite chondrites. Given the similarly refractory natures of Re and Os, this fractionation may have occurred within a narrow range of high temperatures, during condensation of these elements from the solar nebula. Superimposed on this major fractionation are more modest movements of Re or Os that occurred within the last 0-2 Ga, as indicated by minor open-system behavior of the Re-Os isotope systematics of some chondrites. The relative abundances of other HSE can also be used to discriminate among the major classes of chondrites. For example, in comparison to the enstatite chondrites, carbonaceous and ordinary chondrites have distinctly lower ratios of Pd to the more refractory HSE (Re, Os, Ir, Ru and Pt). Differences are particularly well resolved for the EH chondrites that have Pd/Ir ratios that average more than 40% higher than for carbonaceous and ordinary chondrite classes. This fractionation probably occurred at lower temperatures, and may be associated with fractionation processes that also affected the major refractory lithophile elements. Combined, 187Os/188Os ratios and HSE ratios reflect unique early solar system processing of HSE for each major chondrite class. ?? 2002 Elsevier Science B.V. All rights reserved.

Chemical Geology↗

Comparative 187Re-187Os systematics of chondrites: Implications regarding early solar system processes

A suite of 47 carbonaceous, enstatite, and ordinary chondrites are examined for Re-Os isotopic systematics. There are significant differences in the 187Re/188Os and 187Os/188Os ratios of carbonaceous chondrites compared with ordinary and enstatite chondrites. The average 187Re/188Os for carbonaceous chondrites is 0.392 ?? 0.015 (excluding the CK chondrite, Karoonda), compared with 0.422 ?? 0.025 and 0.421 ?? 0.013 for ordinary and enstatite chondrites (1?? standard deviations). These ratios, recast into elemental Re/Os ratios, are as follows: 0.0814 ?? 0.0031, 0.0876 ?? 0.0052 and 0.0874 ?? 0.0027 respectively. Correspondingly, the 187Os/188Os ratios of carbonaceous chondrites average 0.1262 ?? 0.0006 (excluding Karoonda), and ordinary and enstatite chondrites average 0.1283 ?? 0.0017 and 0.1281 ?? 0.0004, respectively (1?? standard deviations). The new results indicate that the Re/Os ratios of meteorites within each group are, in general, quite uniform. The minimal overlap between the isotopic compositions of ordinary and enstatite chondrites vs. carbonaceous chondrites indicates long-term differences in Re/Os for these materials, most likely reflecting chemical fractionation early in solar system history. A majority of the chondrites do not plot within analytical uncertainties of a 4.56-Ga reference isochron. Most of the deviations from the isochron are consistent with minor, relatively recent redistribution of Re and/or Os on a scale of millimeters to centimeters. Some instances of the redistribution may be attributed to terrestrial weathering; others are most likely the result of aqueous alteration or shock events on the parent body within the past 2 Ga. The 187Os/188Os ratio of Earth's primitive upper mantle has been estimated to be 0.1296 ?? 8. If this composition was set via addition of a late veneer of planetesimals after core formation, the composition suggests the veneer was dominated by materials that had Re/Os ratios most similar to ordinary and enstatite chondrites. ?? 2002 Elsevier Science Ltd.

Geochimica et Cosmochimica Acta↗

Applications of the 190Pt-186Os isotope system to geochemistry and cosmochemistry

Platinum is fractionated from osmium primarily as a consequence of processes involving sulfide and metal crystallization. Consequently, the 190 Pt 186 Os isotope system ( 190 Pt → 186 Os + α) shows promise for dating some types of magmatic sulfide ores and evolved iron meteorites. The first 190 Pt 186 Os isochrons are presented here for ores from the ca. 251 Ma Noril'sk, Siberia plume, and for group IIAB magmatic iron meteorites. Given the known age of the Noril'sk system, a decay constant for 190 Pt is determined to be 1.542 × 10 −12 a −1 , with ±1% uncertainty. The isochron generated for the IIAB irons is consistent with this decay constant and the known age of the group. The 186 Os/ 188 Os ratios of presumably young, mantle-derived osmiridiums and also the carbonaceous chondrite Allende were measured to high-precision to constrain the composition of the modern upper mantle. These compositions overlap, indicating that the upper mantle is chondritic within the level of resolution now available. Our best estimate for this 186 Os/ 188 Os ratio is 0.119834 ± 2 (2σ M ). The 190 Pt/ 186 Os ratios determined for six enstatite chondrites average 0.001659 ± 75, which is very similar to published values for carbonaceous chondrites. Using this ratio and the presumed composition of the modern upper mantle and chondrites, a solar system initial 186 Os/ 188 Os ratio of 0.119820 is calculated. In comparison to the modern upper mantle composition, the 186 Os/ 188 Os ratio of the Noril'sk plume was approximately 0.012% enriched in 186 Os. Possible reasons for this heterogeneity include the recycling of Pt-rich crust into the mantle source of the plume and derivation of the osmium from the outer core. Derivation of the osmium from the outer core is our favored model.

Geochimica et Cosmochimica Acta↗

Rhenium-osmium concentration and isotope systematics in group IIAB iron meteorites

Rhenium and osmium abundances, and osmium isotopic compositions were measured by negative thermal ionization mass spectrometry in thirty samples, including replicates, of five IIA and eight IIB iron meteorites. Concentrations in HA irons range from 4800 ppb Re and 66000 ppb Os (Negrillos) to 160 ppb Re and 800 ppb Os (Lombard). In the IIB subgroup, concentrations vary from 28 ppb Re and 180 ppb Os (Navajo) down to 0.8 ppb Re and 9 ppb Os (São Julião de Moreira and Santa Luzia). Log plots of Os vs. Re abundances for HA and IIB irons describe straight lines that approximately converge on Lombard, which has the lowest Re and Os abundances and highest 187 Re/ 188 Os measured in a IIA iron to date. The linear HA trend may be exactly reproduced by fractional crystallization with constant k Re and k Os , but is not well fitted using variable partition coefficients. The IIB iron trend, however, cannot be entirely explained by simple fractional crystallization. One explanation is that small amounts of Re and Os were added to the asteroid core during the final stages of crystallization. Another possibility is that diffusional enrichment of Os may have occurred in samples most depleted in Re and Os. The combined Re-Os isotopic data for HA irons give the following results: slope = 0.07803 ± 0.00076; intercept = 0.09609 ± 0.00045; age = 4584 ± 43 Ma (neglecting the uncertainty in the decay constant of ±3%). Four IIB iron meteorites (Mount Joy, Central Missouri, DRPA 78009, Santa Luzia) also plot within the analytical uncertainty of the HA isochron. These results are consistent with rapid (probably <50 Ma) core segregation, differentiation, and crystallization in the IIAB parent. Several IIB irons (Navajo, Sandia Mountains, Smithsonian Iron, and perhaps São Julião de Moreira) lie beyond analytical uncertainty above the IIA iron isochron, averaging 8 ± 2% higher in 187 Os/ 188 Os. These irons may have crystallized significantly after the HA irons and Mount Joy, but only if the 187 Re/ 188 Os of the melt was ≥2.2. There is no evidence for a IIA iron crystallizing in equilibrium with a melt having such a high ratio. Alternatively, the osmium isotopic systematics of these irons may have been slightly disturbed long after crystallization at ca. 3.3 Ga ago.

Geochimica et Cosmochimica Acta↗

Osmium and neodymium isotopic constraints on the temporal and spatial evolution of Siberian flood basalt sources

Picrites from the Gudchikhinsky suite, the oldest rocks examined, have ??Os of +5.3 to +6.1 and ??Nd of +3.7 to +4.0. The osmium and neodymium isotopic compositions of these rocks are similar to some modern ocean-island basalts (OIB), consistent with their derivation from an mantle plume. Picrites from the stratigraphically higher Tuklonsky suite have similar ??Os of +3.4 to +6.5, but ??Nd of -0.9 to -2.6. The similar ??Os, but lower ??Nd , suggest that some magmas from the same OIB-type, mantle source were contaminated by lithospheric components. A differentiated ankaramite flow, associated with the top of the stratigraphically higher Morongovsky suite, has ??Os of +9.8 to +10.2 and ??Nd of +1.3 to +1.4. The higher ??Os may indicate that the plume source was heterogeneous with respect to osmium isotopic composition, consistent with osmium isotopic measurements in rocks from other plume sources. Mg-rich, alkaline rocks (meymechites) from the Guli area that erupted much nearer the end of the flood-basalt event have ??Os of -1.2 to -2.6 and ??Nd of +3.7 to +4.9. These rocks were probably produced by low degrees of partial melting of mantle after the main stages of flood-basalt production. -from Authors

Geochimica et Cosmochimica Acta↗

Osmium-187 enrichment in some plumes: Evidence for core-mantle interaction?

Calculations with data for asteroidal cores indicate that Earth's outer core may have a rhenium/osmium ratio at least 20 percent greater than that of the chondritic upper mantle, potentially leading to an outer core with an osmium-187/osmium-188 ratio at least 8 percent greater than that of chondrites. Because of the much greater abundance of osmium in the outer core relative to the mantle, even a small addition of metal to a plume ascending from the D" layer would transfer the enriched isotopic signature to the mixture. Sources of certain plume-derived systems seem to have osmium-187/osmium-188 ratios 5 to 20 percent greater than that for chondrites, consistent with the ascent of a plume from the core-mantle boundary.

Science↗

Re-Os isotopic evidence for an enriched-mantle source for the Noril'sk-type, ore-bearing intrusions, Siberia

Magmatic Cu-Ni sulfide ores and spatially associated ultramafic and mafic rocks from the Noril'sk I, Talnakh, and Kharaelakh intrusions are examined for Re-Os isotopic systematics. Neodymium and lead isotopic data also are reported for the ultramafic and mafic rocks. The Re-Os data for most samples indicate closed-system behavior since the ca. 250 Ma igneous crystallization age of the intrusions. There are small but significant differences in the initial osmium isotopic compositions of samples from the three intrusions. Ores from the Noril'sk I intrusion have γ Os values that vary from +0.4 to +8.8, but average +5.8. Ores from the Talnakh intrusion have γ Os values that range from +6.7 to +8.2, averaging +7.7. Ores from the Kharaelakh intrusion have γ Os values that range from +7.8 to +12.9, with an average value of +10.4. The osmium isotopic compositions of the ore samples from the Main Kharaelakh orebody exhibit minimal overlap with those for the Noril'sk I and Talnakh intrusions, indicating that these Kharaelakh ores were derived from a more radiogenic source of osmium than the other ores. Combined osmium and lead data for major orebodies in the three intrusions plot in three distinct fields, indicating derivation of osmium and lead from at least three isotopically distinct sources. Some of the variation in lead isotopic compositions may be the result of minor lower-crustal contamination. However, in contrast to most other isotopic and trace element data, Os-Pb variations are generally inconsistent with significant crustal contamination or interaction with the subcontinental lithosphere. Thus, the osmium and lead isotopic compositions of these intrusions probably reflect quite closely the compositions of their mantle source, and suggest that these two isotope systems were insensitive to lithospheric interaction. Ultramafic and mafic rocks have osmium and lead isotopic compositions that range only slightly beyond the compositions of the ores. These rocks also have relatively uniform ϵ Nd values that range only from −0.8 to + 1.1. This limited variation in neodymium isotopic composition may reflect the characteristics of the mantle sources of the rocks, or it may indicate that somehow similar proportions of crust contaminated the parental melts. The osmium, lead, and neodymium isotopic data for these rocks most closely resemble the mantle sources of certain ocean island basalts (OIB), such as some Hawaiian basalts. Hence, these data are consistent with derivation of primary melts from a mantle source similar to that of some types of hotspot activity. The long-term Re/Os enrichment of this and similar mantle sources, relative to chondritic upper mantle, may reflect 1. incorporation of recycled oceanic crust into the source more than 1 Ga ago, 2. derivation from a mantle plume that originated at the outer core-lower mantle interface, or 3. persistence of primordial stratification of rhenium and osmium in the mantle.

Siberia↗

Rhenium and osmium isotopes in black shales and Ni-Mo-PGE-rich sulfide layers, Yukon Territory, Canada, and Hunan and Guizhou provinces, China

Rhenium and osmium abundances and osmium isotopic compositions were determined by negative thermal ionization mass spectrometry for samples of Devonian black shale and an associated Ni-enriched sulfide layer from the Yukon Territory, Canada. The same composition information was also obtained for samples of early Cambrian Ni-Mo-rich sulfide layers hosted in black shale in Guizhou and Hunan provinces, China. This study was undertaken to constrain the origin of the PGE enrichment in the sulfide layers. Samples of the Ni sulfide layer from the Yukon Territory are highly enriched in Re, Os, and other PGE, with distinctly higher Re/ 192 Os but similar Pt/Re, compared to the black shale host. Re-Os isotopic data of the black shale and the sulfide layer are approximately isochronous, and the data plot close to reference isochrons which bracket the depositional age of the enclosing shales. Samples of the Chinese sulfide layers are also highly enriched in Re, Os, and the other PGE. Re/ 192 Os are lower than in the Yukon sulfide layer. Re-Os isotopic data for the sulfide layers lie near a reference isochron with an age of 560 Ma, similar to the depositional age of the black shale host. The osmium isotopic data suggest that Re and PGE enrichment of the brecciated sulfide layers in both the Yukon Territory and in southern China may have occurred near the time of sediment deposition or during early diagenesis, during the middle to late Devonian and early Cambrian, respectively.

Guizhou Province, Hunan Province, Yukon Territory↗

Rhenium-osmium isotope constraints on the age of iron meteorites

Rhenium and osmium concentrations and the osmium isotopic compositions of iron meteorites were determined by negative thermal ionization mass spectrometry. Data for the IIA iron meteorites define an isochron with an uncertainty of approximately ±31 million years for meteorites ∼4500 million years old. Although an absolute rheniumosmium closure age for this iron group cannot be as precisely constrained because of uncertainty in the decay constant of 187 Re, an age of 4460 million years ago is the minimum permitted by combined uncertainties. These age constraints imply that the parent body of the IIAB magmatic irons melted and subsequently cooled within 100 million years after the formation of the oldest portions of chondrites. Other iron meteorites plot above the IIA isochron, indicating that the planetary bodies represented by these iron groups may have cooled significantly later than the parent body of the IIA irons.

Science↗

Re - Os isotopic constraints on the origin of volcanic rocks, Gorgona Island, Colombia: Os isotopic evidence for ancient heterogeneities in the mantle

The Re - Os isotopic systematics of komatiites and spatially associated basalts from Gorgona Island, Colombia, indicate that they were produced at 155??43 Ma. Subsequent episodes of volcanism produced basalts at 88.1??3.8 Ma and picritic and basaltic lavas at ca. 58 Ma. The age for the ultramafic rocks is important because it coincides with the late-Jurassic, early-Cretaceous disassembly of Pangea, when the North- and South-American plates began to pull apart. Deep-seated mantle upwelling possibly precipitated the break-up of these continental plates and caused a tear in the subducting slab west of Gorgona, providing a rare, late-Phanerozoic conduit for the komatiitic melts. Mantle sources for the komatiites were heterogeneous with respect to Os and Pb isotopic compositions, but had homogeneous Nd isotopic compositions (??Nd+9??1). Initial 187Os/186Os normalized to carbonaceous chondrites at 155 Ma (??Os) ranged from 0 to +22, and model-initial ?? values ranged from 8.17 to 8.39. The excess radiogenic Os, compared with an assumed bulk-mantle evolution similar to carbonaceous chondrites, was likely produced in portions of the mantle with long-term elevated Re concentrations. The Os, Pb and Nd isotopic compositions, together with major-element constraints, suggest that the sources of the komatiites were enriched more than 1 Ga ago by low (<20%) and variable amounts of a basalt or komatiite component. This component was added as either subducted oceanic crust or melt derived from greater depths in the mantle. These results suggest that the Re - Os isotope system may be a highly sensitive indicator of the presence of ancient subducted oceanic crust in mantle-source regions. ?? 1991 Springer-Verlag.

Contributions to Mineralogy and Petrology↗

Re-Os, Rb-Sr, and O isotopic systematics of the Archean Kolar schist belt, Karnataka, India

The Re-Os, Rb-Sr, and O isotopic compositions of mafic and ultramafic amphibolites, gold ores, and granitic gneisses of the circa 2700 Ma Kolar schist belt reveal at least two episodes of post-magmatic alteration that affected these systems. The Re-Os isotopic systematics of many of the rocks of the belt indicate that Os was introduced to the area via fluids that carried very radiogenic Os ( 187 Os 186 Os 2.4Ga &gt; 39 "> 187 Os 186 Os 2.4Ga > 39 ). The source of the radiogenic Os was likely ancient crust. On an outcrop scale, this alteration is also characterized by relatively minor additions of excess 87 Sr and δ 18 O values higher than magmatic. The Rb-Sr systematics of most of these rocks are consistent with closed-system behavior since a period between 2700 and 2400 Ma ago, indicating that the alteration event likely occurred no later than the early Proterozoic. In contrast to this late Archean or early Proterozoic alteration, samples of several komatiitic amphibolites have very 187 Os-depleted compositions, indicating that open-system behavior also occurred at a much later time. This alteration may have been caused by surficial weathering or the interaction of the rocks with fluids bearing unradiogenic Os. Results suggest that the Re-Os system may have only limited utility for geochronologic applications in regions for which post-crystallization noble metal mineralization is evident (e.g., gold ores). In such regions, however, the system may have an important application in assessing the timing and the ultimate sources of noble metal additions.

Geochimica et Cosmochimica Acta↗