Lead and uranium isotopic behavior in diagenetic and epigenetic manganese nodules, Timna Basin, Israel, determined by MC-ICP-MS

Isotope ratios of U and Pb were measured in two types of Mn nodules from the Cambrian Timna Formation, Israel. Type A nodules are mainly composed of pyrolusite and hollandite, with Mn, Ba, Pb and U concentrations of 30–60%, 0.2–2.5%, 0.2–1.0% and 500–3500 ppm, respectively, whereas type B nodules were formed by alteration of the former, and contain mainly coronadite, with Mn, Ba, Pb and U concentrations of 7–48%, 0.2–7%, 0.6–5% and 10–160 ppm, respectively. The isotopic composition of U and Pb was measured by MC-ICP-MS on Mn-rich solutions (up to 100 mg/L) without and with chromatographic separation. The values for the 207/206 and 208/206 ratios have been determined with precisions of up to 50 ppm and those of 206/204, 207/204 and 208/204 – up to 200 ppm. The values for the 234/238 ratios have been determined with precisions of 0.4–1%. The results of the separated and unseparated solutions were shown to be equal within the error. Thus there is no significant matrix effect while measuring U and Pb in Mn rich solution using the MC-ICP-MS.The isotopic composition of Pb and U support the distinction between the two types of Mn nodules. Type A nodules have a wide range of ²⁰⁶Pb/²⁰⁴Pb ratios (18.278–19.776), and an almost constant ratio of ²⁰⁸Pb/²⁰⁴Pb. In contrast, type B nodules have almost constant ²⁰⁶Pb/²⁰⁴Pb ratios and a wide range of ²⁰⁸Pb/²⁰⁴Pb ratios (37.986–38.079). Type A nodules form a linear array on a ²⁰⁷Pb/²⁰⁴Pb vs ²⁰⁶Pb/²⁰⁴Pb diagram, while type B nodules form a tight group characterized by lower Pb isotope ratios that slightly deviate from the type A array. The ²³⁴U/²³⁸U ratio differs between the two types of nodules; type A nodules exhibit a uniform and close to equilibrium ²³⁴U/²³⁸U ratio while type B nodules show a wide range of ²³⁴U/²³⁸U ratios above and below the equilibrium value. The isotopic composition of Pb in type A nodules might reflect Pb contributions from plutonic rock weathering, exposed at the time of deposition or later, to the Cambrian sea. These nodules have remained unaffected by processes that occurred since the Cambrian. The higher ²⁰⁸Pb/²⁰⁴Pb values of type B indicate that these nodules were formed from a Th-enriched solution probably during epigenetic processes which occurred also during the last 1 Ma.Thus the two isotopic systems of U and Pb can record formation, leaching and redeposition of Mn ores.     

Metallogeny and lead isotopic composition of base metal sulfide deposits in the Rappen area,northern Sweden

Early Proterozoic volcanic and sedimentary rocks of the Rappen district in northern Sweden were deposited at a destructive plate margin to the south of the Archaean craton of the western Baltic Shield. The volcano-sedimentary suite was intruded by two generations of early Proterozoic granites at ca. 1.89–1.85 Ga and ca.1.82–1.78 Ga, respectively, and metamorphosed at upper amphibolite facies conditions. Small stratabound iron, copper, and zinc deposits occur in felsic to mafic tuffs and arkosic sediments. Small deposits of molybdenum, tungsten, and uranium formed during the emplacement of the younger granites. The lead isotopic compositions of sulfide trace lead from the various deposits are highly heterogeneous. In the ²⁰⁶Pb/²⁰⁴Pb–²⁰⁷Pb/²⁰⁴Pb diagram they fall on mixing arrays between little evolved early Proterozoic lead and highly radiogenic Caledonian lead. The least radiogenic lead isotopic compositions from the various deposits have a wide range of ²⁰⁷Pb/²⁰⁴Pb ratios and thus indicate variable involvement of Archaean crustal lead in the Proterozoic deposits. Deposits hosted by siliciclastic rocks have higher ²⁰⁷Pb/²⁰⁴Pb ratios than deposits hosted in mafic to felsic tuffites. The lead isotopic heterogeneity suggests that the lead in the various deposits was locally derived and, furthermore, that the sedimentary rocks in part originated from the Archaean craton to the north. Lead mixing arrays in the ²⁰⁶Pb/²⁰⁴Pb–²⁰⁷Pb/²⁰⁴Pb diagram demonstrate that in Paleozoic time radiogenic lead was mobilized and transported in the basement. Source ages calculated from the mixing arrays (ca.1.9 Ga and ca.1.8 Ga) correspond to the age of the Early Proterozoic volcanism and metamorphism respectively. One group of deposits includes lead from at least three sources and illustrates that radiogenic lead was multiply mobilized and transported in the Proterozoic basement. It occurs in deposits that occur in zones that became permeable during the reactivations of the basement.     

Evaluation of drilling priorities using lead isotopes at the Lady Loretta lead-zinc-silver deposit, Australia

The weathered surface expression of the Lady Loretta lead-zinc-silver deposit outcrops almost continuously over a distance of about 4 km. Lead isotope ratios have been determined for samples, some of which contain > 4000 ppm Pb, from geochemically anomalous areas in order to assign drilling priorities to the anomalies.Twelve of the 43 samples analyzed contain isotopically homogeneous lead with ratios (²⁰⁷Pb/²⁰⁶Pb 0.9532–0.9549) similar to the expected targets for major ore deposits in the Mount Isa-McArthur River metallogenic province (²⁰⁷Pb/²⁰⁶Pb 0.955–0.962). Three main zones of interest can be outlined on the basis of lead isotopic data. The top priority is assigned to a 100-m-long section of the ironstone which coincides with the known outcrop of the ore. Lower priority for drilling is given to the two other zones which outcrop over smaller areas and have more radiogenic lead in their immediate surroundings. Several samples with anomalously high lead contents (> 1000 ppm) contain more radiogenic lead (²⁰⁷Pb/²⁰⁶Pb < 0.950) which was most likely derived from the weathering country rocks by supergene leaching and redeposition. Of the 22 samples containing ≥ 380 ppm Pb, lead isotopic analyses would have reduced the number deserving further attention to 10. Lead isotopic analyses in the early stages of exploration could have assisted in minimizing exploration expenditure at Lady Loretta.     

Ion microprobe U–Pb dating of zircon with a 15 micrometer spatial resolution using NanoSIMS

We developed a ²³⁸U–²⁰⁶Pb and ²⁰⁷Pb–²⁰⁶Pb zircon dating method using a Cameca NanoSIMS NS50 ion microprobe. A 7-to 9-nA O⁻ primary beam was used to sputter a 15-μm crater, and secondary positive ions were extracted for mass analysis using the Mattauch–Herzog geometry. The multicollector system was modified to detect ⁹⁰Zr⁺, ²⁰⁴Pb⁺, ²⁰⁶Pb⁺, ²³⁸U¹⁶O⁺, and ²³⁸U¹⁶O₂⁺ ions simultaneously. A mass resolution of about 4000 at 10% peak height and with a flat peak top was attained, and the sensitivity of Pb was about 4 cps·nA^− 1·ppm^− 1. A multicrystal zircon standard (QGNG) from South Australia with a U–Pb age of 1842 Ma was used as a reference for Pb⁺/UO⁺–UO₂⁺/UO⁺ calibration, and on the basis of the positive correlation between these ratios, we determined the sample ²⁰⁶Pb/²³⁸U ratios. ²⁰⁷Pb/²⁰⁶Pb ratios were measured by magnetic scanning in single-collector mode. The standard zircons 91500, from Canada, and SL13, from Sri Lanka, were analyzed against QGNG. Observed ²³⁸U–²⁰⁶Pb and ²⁰⁷Pb–²⁰⁶Pb ages agreed well with published ages within experimental error. Then, 16 zircon grains in a metamorphic rock from Nagasaki, Japan, were analyzed. Observed ages were compatible with SHRIMP ages, suggesting that the NanoSIMS with a 15-μm probe diameter is suitable for ion microprobe U–Pb zircon dating.     

Pb and Sr systematics of ultrapotassic and basaltic rocks from the central Sierra Nevada,California

This study presents Sr and Pb isotopic ratios and Rb, Sr, U, Th, and Pb concentrations of an ultrapotassic basaltic suite and related rocks from the central Sierra Nevada, California. The ultrapotassic suite yields a narrow range of Sr and Pb isotopic compositions (⁸⁷Sr/⁸⁶Sr=0.70597–0.70653; ²⁰⁶Pb/ ²⁰⁴Pb=18.862–19.018; ²⁰⁷Pb/²⁰⁴Pb=15.640–15.686; ²⁰⁸Pb/ ²⁰⁴Pb=38.833–38.950). Associated basalts containing ultramafic nodules have less radiogenic Sr (⁸⁷Sr/⁸⁶=0.70430–0.70521) and generally higher Rb/Sr ratios than the ultrapotassic suite. Leucitites from Deep Springs Valley, California, contain high ⁸⁷Sr/⁸⁶Sr (71141–0.71240) and low ²⁰⁶Pb/²⁰⁴Pb (17.169–17.234) ratios, reflecting contamination by crustal granulite.The isotopic relationships support an origin of the ultrapotassic basaltic suite by partial melting of an enriched upper mantle source. Dehydration of a gently inclined oceanic slab beneath the Sierra Nevada may have provided Ba, K, Rb, Sr, and H₂O, which migrated into the overlying upper mantle lithosphere. The end of subduction 10 m.y. ago allowed increased asthenospheric heat flow into the upper mantle lithosphere. The increased heat flow enhanced fluid movement in the upper mantle and contributed towards isotopic homogenization of the upper mantle source areas. Continued heating of the enriched upper mantle caused partial melting and subsequent eruption of the ultrapotassic lavas.     

U-Pb garnet chronometry in high-grade rocks—case studies from the central Damara orogen (Namibia) and implications for the interpretation of Sm-Nd garnet ages and the role of high U-Th inclusions

Garnets from different migmatites and granites from the Damara orogen (Namibia) were dated with the U-Pb technique after bulk dissolution of the material. Measured ²⁰⁶Pb/²⁰⁴Pb ratios are highly variable and range from ca. 21 to 613. Variations in isotope (²⁰⁸Pb/²⁰⁴Pb, ²⁰⁶Pb/²⁰⁴Pb) and trace element (Th/U, U/Nd, Sm/Nd) ratios of the different garnets show that some garnets contain significant amounts of monazite and zircon inclusions. Due to their very low ²⁰⁶Pb/²⁰⁴Pb ratios, garnets from pelitic migmatites from the Khan area yield Pb-Pb ages with large errors precluding a detailed evaluation. However, the ²⁰⁷Pb/²⁰⁶Pb ages (ca. 550–500 Ma) appear to be similar to or older than U-Pb monazite ages (530±1–517±1 Ma) and Sm-Nd garnet ages (523±4–512±3 Ma) from the same sample. It is reasonable to assume that the Pb-Pb garnet ages define growth ages because previous studies are consistent with a higher closure temperature for the U-Pb system in garnet relative to the U-Pb system in monazite and the Sm-Nd system in garnet. For igneous migmatites from Oetmoed, Pb-Pb garnet ages (483±15–492±16 Ma) and one Sm-Nd garnet whole rock age (487±8 Ma) are similar whereas the monazite from the same sample is ca. 30–40 Ma older (528±1 Ma). These monazite ages are, however, similar to monazite ages from nearby unmigmatized granite samples and constrain precisely the intrusion of the precursor granite in this area. Although there is a notable difference in closure temperature for the U-Pb and Sm-Nd system in garnet, the similarity of both ages indicate that both garnet ages record garnet growth in a migmatitic environment. Restitic garnet from an unmigmatized granite from Omaruru yields similar U-Pb (493±30–506±30 Ma) and Sm-Nd (493±6–488±7 Ma) garnet ages whereas the monazite from this rock is ca. 15–25 Ma older (516±1–514±1 Ma). Whereas the monazite ages define probably the peak of regional metamorphism in the source of the granite, the garnet ages may indicate the time of melt extraction. For igneous garnets from granites at Oetmoed, the similarity between Pb-Pb (483±34–474±17 Ma) and Sm-Nd (492±5–484±13 Ma) garnet ages is consistent with fast cooling rates of granitic dykes in the lower crust. Differences between garnet and monazite U-Pb ages can be explained by different reactions that produced these minerals at different times and by the empirical observation that monazite seems resistant to later thermal re-equilibration in the temperature range between 750 and 900 °C (e.g. Braun et al. 1998). For garnet analyses that have low ²⁰⁶Pb/²⁰⁴Pb ratios, the influence of high- inclusions is small. However, the relatively large errors preclude a detailed evaluation of the relationship between the different chronometers. For garnet with higher ²⁰⁶Pb/²⁰⁴Pb ratios, the overall similarity between the Pb-Pb and Sm-Nd garnet ages implies that the inclusions are not significantly older than the garnet and therefore do not induce a premetamorphic Pb signature upon the garnet. The results presented here show that garnet with low ²³⁸U/²⁰⁴Pb ratios together with Sm-Nd garnet data and U-Pb monazite ages from the same rock can be used to extract geologically meaningful ages that can help to better understand tectonometamorphic processes in high-grade terranes.Editorial responsibility: J. Hoefs     

Rn-generated206Pb in hydrothermal sulphide minerals and bitumen from the Ventersdorp Contact Reef, South Africa

Summary The auriferous conglomerate horizons (reefs) in the Witwatersrand Basin of South Africa are in many places cut by hydrothermal quartz veins that frequently contain sulphide, bitumen, and, less commonly, free gold. New Pb isotopic results for the Ventersdorp Contact Reef which has experienced particularly intense hydrothermal alteration, reaffirm the radiogenically enriched nature of the Pb in this reef and provide additional insight into its origin. This study focuses on analyses of galena, chalcopyrite, pyrrhotite, and bitumen from quartz veins, which presumably formed during the 2.020 Ga Vredefort meteorite impact event. The radiogenic, mainly uranogenic, component of the Pb appears to have been derived almost entirely from uraninite in the surrounding reef rock. Assigning a 2.02 Ga age of mineralization and constructing secondary isochrons for paragenetically early galena and chalcopyrite, ages of the source uraninite are calculated as 2.6–2.4 Ga. No special significance is ascribed to these source ages, which likely reflect extensive radiogenic Pb loss from originally somewhat older detrital uraninite during transport, sedimentation, and post-burial alteration. Analyses of detrital(?), syngenetic, and epigenetic pyrite from a reef conglomerate define a subsidiary linear array with a considerably shallower slope. Interpreted as a secondary isochron, the array gives an implausibly young mineralization and/or source age indicative of a superimposed isotopic disturbance.Five analyses of paragenetically late chalcopyrite and pyrrhotite plot on a²⁰⁷Pb/²⁰⁴pb versus²⁰⁶Pb/²⁰⁴Pb diagram with nearly constant²⁰⁷Pb/²⁰⁴Pb of 24.1–24.6 despite a huge range in²⁰⁶Pb/²⁰⁴Pb from 60–230. This trend is further revealed by Pb with similar²⁰⁷Pb/²⁰⁴Pb but still higher²⁰⁶Pb/²⁰⁴Pb ratios (up to 949) in bitumen globules deposited on quartz crystals lining cavities in the veins. This nearly horizontal array cannot be interpreted as a secondary isochron, and requires the addition of virtually pure²⁰⁶pb to a more normal, radiogenically-enriched Pb. The most plausible explanation for this decoupling of the²³⁸U and²³⁵U decay schemes is that an intermediate daughter isotope, most likely²²²Rn, diffused from uraninite and was selectively captured by the bitumen where it subsequently decayed to²⁰⁶Pb. Whether the 206 Pb was acquired mainly at the time of hydrothermal activity by fluids at elevated temperatures, or more or less continuously until the present remains unresolved.

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Durch Rn erzeugtes²⁰⁶Pb in hydrothermalen Sulfid-Mineralen und Bittunen vom Ventersdorp Contact Reef, Südafrika

Zusammenfassung Die goldhältigen Konglomeratehorizonte (Reefs) im Witwatersrand Becken von Südafrika werden vielerorts von hydrothermalen Quarzadern durchkreuzt, die verschiedene Sulfide, Bitumen, und Spuren von Gold führen. Neue Pb-Isotopendaten vom Ventersdorp Contact Reef (VCR), welches besonders intensive hydrothermale Veränderung erfahren hat, bestätigen die abnormal radiogene Natur des Pb in diesem speziellen Reef. Darüber hinaus führen sie zu einem neuen Verständnis der Herkunft dieses Pb. Schwerpunkt dieser Studie war die Analyse von Bleiglanz, Kupferkies und Bitumen in Quarzadern, deren Bildung dem 2.020 Ga Vredefort Impaktereignis zugeschrieben wird. Die radiogene, hauptsächlich uranogene Pb-Komponente kann beinahe ausschließlich von Uraninit im umgebenden Reef abgeleitet werden. Von sekundären Isochronen, deren Berechnung auf der Annahme eines Mineralisationsalters von 2.02 Ga beruht, lassen sich Alter von 2.6–2.4 Ga für den Uraninit ableiten. Diesen Altern wird jedoch keine weitere Bedeutung beigemessen, da sie wohl eher erheblichen radiogenen Pb-Verlust eines ursprünglich etwas älteren Uraninit während Transport, Sedimentation und spät- bis post-diagentischer Alteration widerspiegeln. Analysen von detritischem (?), syngenetischem und epigenetischem Pyrit von einem Reef-Horizont folgen einem abweichenden Trend mit erheblich geringerer Neigung in einem²⁰⁶Pb/²⁰⁴Pb versus²⁰⁷Pb/²⁰⁴Pb Diagramm. Als sekundäre Isochrone betrachtet, entspricht dieser Trend entweder einem unwahrscheinlich jungen Alter oder er drückt eine spätere Störung des Isotopensystems aus.Fünf Analysen von paragentisch spätem Kupferkies und Magnetkies haben ein nahezu konstantes²⁰⁷Pb/²⁰⁴Pb Verhältnis von 24.1–24.6 trotz einer enormen Spanne in deren²⁰⁶Pb/²⁰⁴Pb Verhältnissen (60–230). Dieser Trend wird weiters duch Pb mit ähnlichen²⁰⁷Pb/²⁰⁴Pb aber noch höheren²⁰⁶Pb/²⁰⁴Pb Verhältnissen (bis zu 949) in Bitumen-Aggregaten innerhalb von Quarz-Drusen unterstrichen. Diese extrem flache Datenverteilung in einem²⁰⁷Pb/²⁰⁴Pb versus²⁰⁶Pb/²⁰⁴Pb Diagramm kann nicht als sekundäre Isochrone interpretiert werden, sondern verlangt die Zufuhr von praktisch reinem²⁰⁶Pb zu eher normalem, radiogen angereichertem Pb. Diffusion eines intermediären Tochterisotops, höchst wahrscheinlich²²²Rn, und selektiver Einbau desselben in das Bitumen mit anschließendem Zerfall zu²⁰⁶Pb halten wir für die naheliegendste Erklärung dieser Entkoppelung der²³⁸U- und²³⁹U-Zerfallsreihen. Offen bleibt die Frage, ob der Einbau des²⁰⁶Pb hauptsächlich zum Zeitpunkt der hydrothermalen Überprägung oder mehr oder weniger kontinuierlich bis heute stattgefunden hat.

     

Initial Pb–Sr(–Nd) isotopic heterogeneity in a single allanite–epidote crystal: implications of reaction history for the dating of minerals with low parent-to-daughter ratios

We analyzed 17 fragments from a zoned allanite–epidote crystal (ca 2.2 mm × 4.0 mm), which had formed during different prograde and retrograde stages of ultra high pressure (UHP) and amphibolite facies metamorphism (240–230 Ma, Sulu Belt, E China), for the isotopic composition of Pb, Nd, and Sr and contents of Pb, U, and Th, Sr and Rb, and Nd and Sm. Since most fragments had ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb values less than 1, corrections for in situ Pb growth are small and uncertainties in the recalculation of the Pb isotopic compositions to 240 Ma are insignificant. The recalculated Pb falls on a linear trend in the ²⁰⁶Pb/²⁰⁴Pb vs ²⁰⁷Pb/²⁰⁴Pb diagram with the allanite defining the low–²⁰⁶Pb/²⁰⁴Pb end (17.07) of this trend and the epidote defining its high–²⁰⁶Pb/²⁰⁴Pb end (17.56). The recalculated data scatter in the ²⁰⁶Pb/²⁰⁴Pb vs ²⁰⁸Pb/²⁰⁴Pb diagram, which implies that the initial Pb isotopic variation reflects the involvement of at least three different Pb sources. The low ⁸⁷Rb/⁸⁶Sr values account for a change in ⁸⁷Sr/⁸⁶Sr by in situ ⁸⁷Sr growth of less than 0.0007, which implies that the isotopic heterogeneity of ⁸⁷Sr/⁸⁶Sr (0.70601–0.7200) is a primary feature. The Pb and Sr isotope data unequivocally demonstrate that contributions from different precursor minerals result in initial isotopic heterogeneity in the metamorphic reaction product. It is likely that such an initial isotopic heterogeneity also exists for Nd, but it could not be resolved in the present study. Initially heterogeneous Pb and Sr isotope compositions imply that age differences between core and rim of large crystals may result in the determination of highly arbitrary geological rates, especially for minerals with relatively low parent-to-daughter ratios.     

Lead in prehistoric,historic and contemporary Japanese: stable isotopic study by ICP mass spectrometry

Lead concentration and isotopic composition of prehistoric (middle and latest Jomon era, 2000–4500 BP, n=6), historic (Edo era, 130–400 BP, n=10), and contemporary (died in 1987–88, n=15) Japanese bones, and deciduous teeth from contemporary Japanese children born during 1985–88 (n=17) were analyzed by inductively coupled plasma mass spectrometry. Lead concentration was lowest in Jomon bones and was higher in rural Edo, contemporary, and urban Edo, in that order. Elevated Pb concentration in historic Edo people, as reported previously, was reconfirmed. The average isotopic ratios (²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb) in excavated (prehistoric and historic) bones, contemporary bones, and deciduous teeth were different from each other. The contemporary bones had the least radiogenic composition (mean ²⁰⁷Pb/²⁰⁶Pb: 0.879; mean ²⁰⁸Pb/²⁰⁶Pb: 2.126) while the excavated bones the most (0.848; 2.098), and teeth intermediate (0.866; 2.111). The comparison with the literature data of isotopic compositions of environmental samples showed that the isotopic composition of the excavated bones was within the range of Japanese ores, rocks and soils, indicating the absence of foreign Pb sources in preindustrialized Japan. That of the contemporary bones was closer to the average gasoline Pb, the use of which had been banned in the late 1970s, than to the Pb in airborne particulate matter or refuse incineration ash of 1980s. The average Pb isotopic ratios in the deciduous teeth was close to the isotopic ratios of Pb in airborne particulate matter and refuse incineration ash. These data indicated that the contemporary Japanese population was exposed to foreign Pb which had different isotopic composition from domestic Pb. Exposure to Pb of foreign origin was particularly evidently recorded in people born before the leaded gasoline ban. The history of human Pb contamination in Japan is discussed based on the present results and other previously published data.     

Pb isotope evidence for contaminant-metal dispersal in an international river system: The lower Danube catchment,Eastern Europe

Lead isotope signatures (²⁰⁷Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁴Pb, ²⁰⁶Pb/²⁰⁴Pb), determined by magnetic sector ICP-MS in river channel sediment, metal ores and mine waste, have been used as geochemical tracers to quantify the delivery and dispersal of sediment-associated metals in the lower Danube River catchment. Due to a diverse geology and range of ore-body ages, Pb isotope signatures in ore-bodies within the lower Danube River catchment show considerable variation, even within individual metallogenic zones. It is also possible to discriminate between the Pb isotopic signatures in mine waste and river sediment within river systems draining individual ore bodies. Lead isotopic data, along with multi-element data; were used to establish the provenance of river sediments and quantify sedimentary contributions to mining-affected tributaries and to the Danube River. Data indicate that mining-affected tributaries in Serbia and Bulgaria contribute up to 30% of the river channel sediment load of the lower Danube River. Quantifying relative sediment contributions from mining-affected tributaries enables spatial patterns in sediment-associated metal and As concentrations to be interpreted in terms of key contaminant sources. Combining geochemical survey data with that regarding the provenance of contaminated sediments can therefore be used to identify foci for remediation and environmental management strategies.     

A Correction Approach to the Common Pb Contribution to ^207Pb／^206Pb Ratios Obtained by the Zircon Evaporation Technique

An approach is recommended for the correction of common Pb contribution to ^207Pb/^206Pb ages obtained by the zircon evaporation technique.A comparison with that by Cocherie et al.(1992)shows that two approaches yield similar results in the ^207Pb*/^206Pb* ratios.But when using the new approach,only two errors of the measured ^204Pb/^206Pb and ^207Pb/^207Pb ratios are introduced to the calculated ^207Pb^*/^206Pb^* ratios.     

Isotopic and elemental analysis of uraninite concentrates using inductively coupled plasma-mass spectrometry (ICP-MS)

Inductively coupled plasma-mass spectrometry (ICP-MS) is capable of measuring isotopic and elemental abundances in geologic materials easily and rapidly. Although the precision of isotope ratio data obtained by ICP-MS is inferior to that by thermal ionization mass spectrometry, it is adequate for application to a number of geochemical exploration problems.National Institute of Standards and Technology (NIST) Pb metal standard reference material 981 (NBS981), was used as the isotopic standard to correct the measured isotope intensities for mass discrimination. The mean relative standard deviation (RSD) of the determinations of the abundances of ²⁰⁶Pb, ²⁰⁷Pb, and ²⁰⁸Pb in the two other NIST Pb isotope reference materials, NBS981 and NBS982, was better than 0.3%, whereas the RSD for the determination of the less abundant ²⁰⁴Pb was 0.4%. Accuracy was demonstrated by repeated analysis of NBS981, NBS982, and NBS983. The Student t-statistic ranged between −1.75 and 2.04 for the abundances of the 4 Pb isotopes in the three NIST materials.Data from a suite of 13 uraninite-rich samples from Labrador demonstrate the ability of ICP-MS to determine age and geochemical information sufficient for regional interpretations. The determined radiogenic ²⁰⁷Pb/²⁰⁶Pb ratios of 12 of the samples give ages between 1697 and 1805 Ma with average uncertainties (one standard deviation) of 4 Ma, whereas one of the samples has an age of 495 ± 4 Ma. The average age of the 12 samples was 1752 ± 27 Ma. Along with the Pb isotope intensities, ²³²Th and ²³⁸U were measured and the U-Pb age determined from a fit of the ²⁰⁶Pb/²³⁸U vs. ²⁰⁷Pb/²³⁵U for 9 of the samples. The concordia intercept age of 1740 Ma for the best-fit line is in good agreement with the mean ²⁰⁷Pb/²⁰⁶Pb age of 1752 Ma.     

Lead isotopes of the carbonate-hosted Kabwe, Tsumeb, and Kipushi Pb-Zn-Cu sulphide deposits in relation to Pan African orogenesis in the Damaran-Lufilian Fold Belt of Central Africa

Lead isotope ratios of galena from the carbonate-hosted massive sulphide deposits of Kabwe (Pb-Zn) and Tsumeb (Pb-Zn-Cu) in Zambia and Namibia, respectively, have been measured and found to be homogeneous and characteristic of upper crustal source rocks. Kabwe galena has average isotope ratios of ^206/204Pb = 17.997 ± 0.007, ^207/204Pb = 15.713 ± 0.010 and ^208/204Pb = 38.410 ± 0.033. Tsumeb galena has slightly higher ^206/204Pb (18.112 ± 0.035) and slightly lower ^207/204Pb (15.674 ± 0.016) and ^208/204Pb (38.276 ± 0.073) ratios than Kabwe galena. The isotopic differences are attributed to local differences in the age and composition of the respective source rocks for Kabwe and Tsumeb. The homogeneity of the ore lead in the two epigenetic deposits suggests lead sources of uniform isotopic composition or, alternatively, thorough mixing of lead derived from sources with relatively similar isotopic compositions. Both deposits have relatively high ²³⁸U/²⁰⁴Pb ratios of 10.31 and 10.09 for Kabwe and Tsumeb galenas, respectively. These isotope ratios are considered to be typical of the upper continental crust in the Damaran-Lufilian orogenic belt, as also indicated by basement rocks and Cu-Co sulphides in stratiform Katangan metasediments which have a mean μ-value of 10.25 ± 0.12 in the Copperbelt region of Zambia and the Democratic Republic of Congo (formerly Zaire). The ²³²Th/²⁰⁴Pb isotope ratios of 43.08 and 40.42 for Kabwe and Tsumeb suggest Th-enriched source regions with ²³²Th/²³⁵U (κ-values) of 4.18 and 4.01, respectively. Model isotopic ages determined for the Kabwe (680 Ma) and Tsumeb (530 Ma) deposits indicate that the timing of the mineralisation was probably related to phases of orogenic activity associated with the Pan-African Lufilian and Damaran orogenies, respectively. Galena from the carbonate-hosted Kipushi Cu-Pb-Zn massive sulphide deposit in the Congo also has homogeneous lead isotope ratios, but its isotopic composition is comparable to that of the average global lead evolution curve for conformable massive sulphide deposits. The μ (9.84) and κ (3.69) values indicate a significant mantle component, and the isotopic age of the Kipushi deposit (456 Ma) suggests that the emplacement of the mineralisation was related to a post-tectonic phase of igneous activity in the Lufilian belt. The isotope ratios (^206/204Pb, ^207/204Pb, ^208/204Pb) of the three deposits are markedly different from the heterogeneous lead ratios of the Katangan Cu-Co stratiform mineralisation of the Copperbelt as well as those of the volcanogenic Nampundwe massive pyrite deposit in the Zambezi belt which typically define radiogenic linear trends on lead-lead plots. The host-rock dolomite of the Kabwe deposit also has homogeneous lead isotope ratios identical to the ore galena. This observation indicates contamination of the Kabwe Dolomite Formation with ore lead during mineralisation. Received: 8 September 1997 / Accepted: 21 August 1998     

Origin and regional significance of late Precambrian and early Palaeozoic granitoids in the Pan-African belt of Somalia

Granitoids within the Precambrian basement of north-eastern and southern Somalia are subdivided on the basis of geology, geochronology and petrology into three different assemblages. The post-kinematic assemblage in north-eastern Somalia ( 630 Ma) comprises granodiorites and granites which belong to a medium-K calc-alkaline suite. Average initial Sr, Nd and Pb isotopic ratios [Sr_i = 0.7048, _Nd = –1.8,²⁰⁶Pb/²⁰⁴Pb(i) = 17.704 and²⁰⁷Pb/²⁰⁴Pb(i) = 15.611] indicate that these melts were derived from a mantle or juvenile crustal source with only slight involvement of pre-existing crust as a contaminant. Two different assemblages are found in southern Somalia. The older assemblage is composed of crustal anatectic, synkinematic, parautochthonous granites ( 600 Ma) related to amphibolite facies retrogression of an intensively reworked pre-Pan-African crust [Sr_i = 0.7100, _Nd = –8.4,²⁰⁶Pb/²⁰⁴Pb(i) = 15.403 and²⁰⁷Pb/²⁰⁴Pb(i) = 15.259]. These monzo- and syenogranites are moderately potassic and peraluminous. The younger assemblage ( 470 Ma) consists of post-kinematic monzonites to syenogranites with A-type affinities. Initial Sr, Nd and Pb isotopic data for this metaluminous assemblage [Sr_i = 0.7114, _Nd = –13.1,²⁰⁷Pb/²⁰⁴Pb(i) = 16.913 and²⁰⁷Pb/²⁰⁴Pb(i) = 15.512] indicate a significant lower crustal component but, however, also a mantle signature. The late Proterozoic to early Palaeozoic granitoids in Somalia thus express contrasting regimes, characterized by strong juvenile input in the north, close to the Arabian-Nubian Shield, whereas intense crustal reworking with little addition of juvenile material prevailed in the south. Somalia was definitively not a cratonic area during the Pan-African, but a zone of high crustal mobility.     

Geology and Lead-Isotope Study of the Baiyinnuoer Zn-Pb-Ag Deposit, South Segment of the Da Hinggan Mountains, Northeastern China

The Baiyinnuoer deposit (32.74 Mt ore with grades of 5.44% Zn, 2.02% Pb and 31.36 g t^?1 Ag), the largest Zn‐Pb‐Ag deposit in northern China, is hosted by crystalline limestone and slate of the Early Permian Huanggangliang Formation. Detailed cross‐section mapping indicates stratigraphic and fold structural controls on the mineralization. The Zn‐Pb‐Ag mineralization is hosted predominantly by skarn, which occurs as bedding‐parallel lens that pinch out at the margins of the main economic zone. Three skarn stages are identified at the deposit: (i) garnet‐clinopyroxene; (ii) sulfides; and (iii) carbonate‐epidote. Lead isotopic compositions were determined for galena and sphalerite of the ores, whole rock samples of the Yanshanian granite and granodiorite, Permian marble and tuff, and Jurassic volcanic and subvolcanic rocks in and around the Baiyinnuoer area in order to discuss the sources of ore‐forming materials and the relationship between the ore formation and these whole rocks. Galena and sphalerite of the Baiyinnuoer ore have uniform isotopic ratios (²⁰⁶Pb/²⁰⁴Pb, 18.267–18.369; ²⁰⁷Pb/²⁰⁴Pb, 15.506–15.624; ²⁰⁸Pb/²⁰⁴Pb, 38.078–38.394) consistent with the granite and granodiorite (²⁰⁶Pb/²⁰⁴Pb, 18.252–18.346; ²⁰⁷Pb/²⁰⁴Pb, 15.504–15.560; ²⁰⁸Pb/²⁰⁴Pb, 38.141–38.320), whereas the ratios for Jurassic volcanic and subvolcanic rocks are variable and radiogenic (²⁰⁶Pb/²⁰⁴Pb, 18.468–18.614; ²⁰⁷Pb/²⁰⁴Pb, 15.521–15.557; ²⁰⁸Pb/²⁰⁴Pb, 38.304–38.375). These results indicate that the mineralization was not related to the Jurassic volcanism, but to the Yanshanian magmatism. The Permian strata may have a slight contribution to the mineralization. All features show that the Baiyinnuoer deposit is related to the Yanshanian granitic magmatism, and can be classified as a zinc‐lead‐silver skarn deposit.     

Primitive and contaminated basalts from the Southern Rocky Mountains,U.S.A.

Basalts in the Southern Rocky Mountains province have been analyzed to determine if any of them are primitive. Alkali plagioclase xenocrysts armored with calcic plagioclase seem to be the best petrographic indicator of contamination. The next best indicator of contamination is quartz xenocrysts armored with clinopyroxene. On the rocks and the region studied, K₂O apparently is the only major element with promise of separating primitive basalt from contaminated basalt inasmuch as it constitutes more than 1 % in all the obviously contaminated basalts. K₂O: lead (> 4 ppm) and thorium (> 2 ppm) contents and Rb/Sr (> 0.035) are the most indicative of the trace elements studied. Using these criteria, three basalt samples are primitive (although one contains 1.7% K₂O) and are similar in traceelement contents to Hawaiian and Eastern Honshu, Japan, primitive basalts.Contamination causes lead isotope ratios, ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb, to become less radiogenic, but it has little or no effect on ⁸⁷Sr/⁸⁶Sr. We interpret the effect on lead isotopes to be due to assimilation either of lower crustal granitic rocks, which contain 5–10 times as much lead as basalt and which have been low in U/Pb and Th/Pb since Precambrian times, or of upper crustal Precambrian or Paleozoic rocks, which have lost much of their radiogenic lead because of heating prior to assimilation. The lack of definite effects on strontium isotopes may be due to the lesser strontium contents of granitic crustal rocks relative to basaltic rocks coupled with lack of a large radiogenic enrichment in the crustal rocks.Lead isotope ratios were found to be less radiogenic in plagioclase separates from an obviously contaminated basalt than in the primitive basalts. The feldspar separate that is rich in sodic plagioclase xenocrysts was found to be similar to the whole-rock composition for ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb whereas a more dense fraction probably enriched in more calcic plagioclase phenocrysts is more similar to the primitive basalts in lead isotope ratios.The primitive basalts have: ²⁰⁶Pb/²⁰⁴Pb 18.09–18.34, ²⁰⁷Pb/²⁰⁴Pb 15.5, ²⁰⁸Pb/²⁰⁴Pb 37.6–37.9, ⁸⁷Sr/⁸⁶Sr 0.704–0.705. In the primitive basalts from the Southern Rocky Mountains the values of ²⁰⁶Pb/²⁰⁴Pb are similar to values reported by others for Hawaiian and eastern Honshu basalts and abyssal basalts, whereas ²⁰⁸Pb/²⁰⁴Pb tends to be equal to or a little less radiogenic than those from the oceanic localities. ⁸⁷Sr/⁸⁶Sr appears to be equal to or a little greater than those of the oceanic localities. These ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios are distinctly less radiogenic and ⁸⁷Sr/⁸⁶Sr values are about equal to those reported by others for volcanic islands on oceanic ridges and rises.Publication authorized by the Director, U.S. Geological Survey     

Age and sources of gold mineralization in the Marmato mining district, NW Colombia: A Miocene–Pliocene epizonal gold deposit

Epigenetic gold mineralization occurs in the Marmato mining district, within the Calima Terrain of the Setentrional Andes, Colombia. Regional rocks associated with this mineralization include: graphite- and chlorite-schists of the Arquia Complex; metamorphosed during the Cretaceous, Miocene sandstones, shales and conglomerates of the Amagá Formation; as well as pyroclastic rocks (clasts of basalt, andesites and mafic lavas) and subvolcanic andesitic/dacitic bodies of the Combia Formation (9 to 6 Ma). The subvolcanic Marmato stock hosts mesothermal and epithermal low-sulfidation Au–Ag ores in the form of distensional veins, stockwork, and quartz veinlets within brecciated zones. Ore minerals are pyrite, sphalerite and galena with subordinate chalcopyrite, arsenopyrite, pyrrhotite, argentite and native gold/electrum.Sericitized plagioclase from a porphyry dacite yielded a K–Ar age of 5.6 ± 0.6 Ma, interpreted as the age of ore deposition. This is in close agreement with the age of reactivation of the Cauca–Romeral Fault System (5.6 ± 0.4 Ma), which bounds the Calima Terrain. A porphyry andesite–dacite (6.7 ± 0.1 Ma), hosting the Au–Ag veins, shows a measured ⁸⁷Sr/⁸⁶Sr between 0.70440 and 0.70460, ε_Nd between + 2.2 and + 3.2 and ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios of 18.964 to 19.028; 15.561 to 15.570; and 38.640 to 38.745, respectively. The ⁸⁷Sr/⁸⁶Sr and ε_Nd values of rocks from the Arquia Group range from 0.70431 to 0.73511 and − 12.91 to + 10.0, respectively, whereas the corresponding Pb isotopic ratios (²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb) range from 18.948 to 19.652; 15.564 to 15.702; and 38.640 to 38.885, respectively. ⁸⁷Sr/⁸⁶Sr and ε_Nd values obtained on sulfides from the gold quartz veins, which occur at shallow and intermediate levels, range from 0.70500 to 0.71210 and from − 1.11 to + 2.40. In the deepest veins, ε_Nd values lie between + 1.25 and + 3.28 and the ⁸⁷Sr/⁸⁶Sr of calcite and pyrite fall between 0.70444 and 0.70930. The ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios of all mineralization are in the ranges 18.970 to 19.258; 15.605 to 15.726 and 38.813 to 39.208, respectively. Carbonates have an average ⁸⁷Sr/⁸⁶Sr ratio of 0.70445, which is within the range of values measured in the host dacite. The Sr isotopic data indicate that carbonic fluids have a restricted hydrothermal circulation within the host igneous body, while the Sr, Pb and Nd isotopic compositions of the sulfides suggest that the fluids not only circulated within the Marmato stock, but also throughout the Arquia Complex, inferring that these rocks offer a potential target for mineral exploration. Based on geological and geochronological evidence, the epizonal Marmato gold ores formed during the Miocene to Pliocene, as a result of cooling of the Marmato stock and reactivation along a crustal-scale fault zone related to thermal processes in an accretionary oceanic–continental plate orogen.     

Temporal variation of isotope and rare earth element abundances in volcanic rocks from Guam: implications for the evolution of the Mariana Arc

Volcanic rocks exposed on Guam were erupted during the Late Middle Eocene (Facpi Fm.), Late Eocene-Oligocene (Alutom Fm.) and Miocene (Umatac Fm.). Four magma series are recognized: the boninite series (44 m.y.b.p.), the tholeiite and calc-alkaline series, which were erupted along with boninite series lavas at 32–36 m.y.b.p. and high-K lavas of the Umatac Fm. (14 m.y.b.p.). Isotope and and rare earth element (REE) characteristics of the four magma series are distinct. Boninite series lavas have U-shaped REE patterns, relatively low ¹⁴³Nd/¹⁴⁴Nd (0.51294–0.51298), and high ²⁰⁶Pb/²⁰⁴Pb (19.0–19.2). Tholeiite series lavas are LREE (light REE) depleted, and have high ¹⁴³Nd/¹⁴⁴Nd (0.51304–0.51306) and low ²⁰⁶Pb/²⁰⁴Pb (18.4–18.5). Calc-alkaline series lavas have Sr, Nd and Pb isotope ratios similar to tholeiite series lavas, but flat to U-shaped REE patterns. Umatac Fm. lavas are strongly LREE-enriched, and have higher ⁸⁷Sr/ ⁸⁶Sr (0.70375–0.70380) and ²⁰⁷Pb/²⁰⁴Pb relative to ²⁰⁶Pb/ ²⁰⁴Pb than Facpi and Alutom Fm. lavas. Boninite and tholeiite series magmas, erupted in the position of the Palau-Kyushu Ridge, were probably derived from distinct mantle sources having OIB and N-MORB-like isotopic characteristics, together with fluids derived from subducted Pacific plate basalt. Calc-alkaline series lavas were most likely derived from the tholeiite series by extensive crystal fractionation, wallrock contamination and magma mixing. Lavas of the Umatac Fm., erupted in the position of the West Mariana Ridge, may include up to 2–3% subducted sediment, similar to some active Mariana arc lavas.     

Petrogenesis of isotopically unusual Pliocene olivine leucitites from Deep Springs Valley, California

High-K mafic alkalic lavas (5.4 to 3.2 wt% K₂O) from Deep Springs Valley, California define good correlations of increasing incompatible element (e.g., Sr, Zr, Ba, LREE) and compatible element contents (e.g., Ni, Cr) with increasing MgO. Strontium and Nd isotope compositions are also correlated with MgO; ⁸⁷Sr/⁸⁶Sr ratios decrease and ɛ_Nd values increase with decreasing MgO. The Sr and Nd isotope compositions of these lavas are extreme compared to most other continental and oceanic rocks; ⁸⁷Sr/⁸⁶Sr ratios range from 0.7121 to 0.7105 and ɛ_Nd values range from −16.9 to −15.4. Lead isotope ratios are relatively constant, ²⁰⁶Pb/²⁰⁴Pb ∼17.2, ²⁰⁷Pb/²⁰⁴Pb ∼15.5, and ²⁰⁸Pb/²⁰⁴Pb ∼38.6. Depleted mantle model ages calculated using Sr and Nd isotopes imply that the reservoir these lavas were derived from has been distinct from the depleted mantle reservoir since the early Proterozoic. The Sr-Nd-Pb isotope variations of the Deep Springs Valley lavas are unique because they do not plot along either the EM I or EM II arrays. For example, most basalts that have low ɛ_Nd values and unradiogenic ²⁰⁶Pb/²⁰⁴Pb ratios have relatively low ⁸⁷Sr/⁸⁶Sr ratios (the EM I array), whereas basalts with low ɛ_Nd values and high ⁸⁷Sr/⁸⁶Sr ratios have radiogenic ²⁰⁶Pb/²⁰⁴Pb ratios (the EM II array). High-K lavas from Deep Springs Valley have EM II-like Sr and Nd isotope compositions, but EM I-like Pb isotope compositions. A simple method for producing the range of isotopic and major- and trace-element variations in the Deep Springs Valley lavas is by two-component mixing between this unusual K-rich mantle source and a more typical depleted mantle basalt. We favor passage of MORB-like magmas that partially fused and were contaminated by potassic magmas derived from melting high-K mantle veins that were stored in the lithospheric mantle. The origin of the anomalously high ⁸⁷Sr/⁸⁶Sr and ²⁰⁸Pb/²⁰⁴Pb ratios and low ɛ_Nd values and ²⁰⁶Pb/²⁰⁴Pb ratios requires addition of an old component with high Rb/Sr and Th/Pb ratios but low Sm/Nd and U/Pb ratios into the mantle source region from which these basalts were derived. This old component may be sediments that were introduced into the mantle, either during Proterozoic subduction, or by foundering of Proterozoic age crust into the mantle at some time prior to eruption of the lavas. Received: 28 February 1997 / Accepted: 9 July 1998     

Contemporary lead concentration and stable lead isotope ratio distribution in forest moss across the Czech Republic

Lead concentrations and stable lead isotopes (²⁰⁴Pb, ²⁰⁶Pb, ²⁰⁷Pb, ²⁰⁸Pb) were measured in forest moss samples (Pleurozium schreberi or Scleropodium purum) collected at 273 sites across the Czech Republic during 2010. Continuously decreasing median Pb concentrations in moss were documented over the last two decades: 1995: 11 mg/kg, 2000: 5.66 mg/kg, 2005: 4.94 mg/kg and 2010: 2.85 mg/kg. Several local anomalies have decreased in scale, the overall regional distribution patterns remained, however, the same. The regional Pb isotope ratio distributions show that the ratios show little variation for a large central part of the country and provide the large-scale background isotope ratios for the Czech Republic of about ²⁰⁴Pb/²⁰⁶Pb = 0.0550, ²⁰⁶Pb/²⁰⁷Pb = 1.167, ²⁰⁶Pb/²⁰⁸Pb = 0.478 and ²⁰⁷Pb/²⁰⁸Pb = 0.409 for 2010. This background Pb isotope ratio signal in moss has been locally (900–7500 km²) modified by specific Pb isotopic ratio signals caused by deposition of Pb emissions from known local anthropogenic Pb emission sources, such as industrial combustion of local coal, and a variety of industrial enterprises (metallurgical, engineering and glass works). At some sites where mining of uranium and polymetallic ores took place the moss samples show also a locally specific Pb isotope signal. The in terms of area affected largest deviations in the Pb-isotope ratios, e.g., in the Bohemian Massif, may be due to the input of geogenic dust.