Direct dating of hydrothermal W mineralization: U-Pb age for hübnerite (MnWO4), Sweet Home Mine, Colorado

We have investigated the potential of hübnerite for U-Pb dating. Hübnerite forms typically at medium to low-temperatures in a wide range of pneumatolytic-hydrothermal mineral deposits, particularly porphyry molybdenum and Sn-specialized granites. Hübnerite from the Sweet Home Mine (Alma, Colorado) formed in a Pb-rich, U-poor environment, but still developed relatively radiogenic Pb isotopic compositions. The low Pb_common contents in hübnerite (0.075 to 0.155 ppm) demonstrate that Pb is efficiently excluded from the crystal lattice. In contrast, U may substitute for Mn. The U-Pb data of hübnerite scatter. Most of the scatter originates from samples with ²⁰⁶Pb/²⁰⁴Pb values below 50, where Pb_blank contributes up to 30% to Pb_total. Using the least radiogenic galena Pb, samples with ²⁰⁶Pb/²⁰⁴Pb values above 70 have overlapping ²⁰⁶Pb∗/²³⁸U and ²⁰⁷Pb∗/²³⁵U values and yield a ²⁰⁶Pb/²³⁸U age of 25.7 ± 0.3 Ma (2σ). Late stage apatite from the Sweet Home Mine yields a ²⁰⁶Pb/²⁰⁴Pb-²³⁸U/²⁰⁴Pb isochron corresponding to an age of 24.8 ± 0.5 Ma (2σ). A comparison of the U-Pb hübnerite ages with literature ⁴⁰Ar/³⁹Ar ages on earlier sericite and the U-Pb age on later apatite suggests that (i) hübnerite yields accurate U-Pb ages and (ii) the evolution of the Sweet Home mineralization from greisen-type mineralization to medium-temperature hydrothermal vein mineralization took place in a few hundred thousand years at most. Aqueous low-N₂-bearing and aqueous inclusions in the dated hübnerite have homogenization temperatures between 325 and 356 °C and moderate salinity (up to 6.7 wt% NaCl equiv.). Thus, hübnerite represents one of the rare examples of a mineral that can be dated accurately and carries petrological information.     

The origin of geochemical diversity of lunar mantle sources inferred from the combined U-Pb, Rb-Sr, and Sm-Nd isotope systematics of mare basalt 10017

The results of our combined U-Pb, Rb-Sr, and Sm-Nd isotope study of mare basalt 10017 contribute to the understanding of the petrogenetic processes involved in the origin of geochemical diversity in lunar mare basalt sources, as well as the U-Pb isotope systematics of the Moon. The Rb-Sr, Sm-Nd, and ²³⁸U-²⁰⁶Pb isotope systems yield concordant crystallization ages of 3.633 ± 0.057 Ga, 3.678 ± 0.069 Ga, and 3.616 ± 0.098 Ga, respectively. The ²³⁵U-²⁰⁷Pb isochron yields an older, though still concordant, age of 3.80 ± 0.12 Ga. Neither the ²⁰⁶Pb-²⁰⁷Pb system nor U-Pb concordia system yields an age for 10017 that is concordant with the age determined from the Sm-Nd, Rb-Sr, and ²³⁸U-²⁰⁶Pb systems. The initial ⁸⁷Sr/⁸⁶Sr of 10017 is 0.69941 ± 7 and the initial ε_Nd is +3.2 ± 0.4. Initial Pb isotopic compositions, determined from the U-Pb isochrons, are ²⁰⁶Pb/²⁰⁴Pb_i = 31 ± 11 and ²⁰⁷Pb/²⁰⁴Pb_i = 34 ± 15. Together, these initial Pb compositions constrain the μ value of the 10017 source to be 70 ± 30, assuming a single-stage Pb growth model. This is considerably lower than μ values typically estimated for mare basalt sources (∼100-600). Regardless, the μ values calculated for the sources of mare basalts, as well as other lunar samples, show a range that is larger than can be explained by fractionation of U from Pb solely by crystallization of silicate phases and ilmenite during magma ocean solidification and formation of lunar mantle sources. The U-Pb isotope systematics may reflect late-stage formation of a sulfide phase, which strongly fractionates Pb from U but has minimal effect on Rb/Sr or Sm/Nd compositions, during crystallization of the lunar magma ocean.     

The U-Pb systematics of angrite Sahara 99555

Angrite Sahara 99555 (hereafter SAH), precisely dated by Baker et al. (Baker J., Bizzarro M., Wittig N., Connelly J. and Haack H. (2005) Early planetesimal melting from an age of 4.5662 Gyr for differentiated meteorites. Nature436, 1127-1131), has been proposed as a new reference point for the early Solar System timescale and for calculation of the revised minimum age of our Solar System. The Pb-Pb age of SAH of 4566.18 ± 0.14 Ma, reported by Baker et al., differs from the Pb-Pb age of D’Orbigny, another basaltic angrite, of 4564.42 ± 0.12 Ma (Amelin Y. (2008) U-Pb ages of angrites. Geochim. Cosmochim. Acta72, 221-232), despite the fact that the relative ⁵³Mn-⁵³Cr and ¹⁸²Hf-¹⁸²W ages of these meteorites are identical. Here I report U-Pb data for 21 whole rock and pyroxene fractions from SAH, analyzed using the same approach as D’Orbigny (Amelin, 2008). These fractions contain between 1.3 and 8.9 pg of total common Pb, slightly more than analytical blank. Measured ²⁰⁶Pb/²⁰⁴Pb ratios are between 625 and 2817 for D’Orbigny, blank-corrected ²⁰⁶Pb/²⁰⁴Pb ratios are between 1173 and 6675. Eight acid-washed whole rock fractions yielded an isochron age of 4564.86 ± 0.38 Ma, MSWD = 1.5. Data for pyroxene fractions plot mostly above the whole rock isochron, and do not form a linear array in ²⁰⁷Pb/²⁰⁶Pb vs. ²⁰⁴Pb/²⁰⁶Pb isochron coordinates. The ²⁰⁷Pb^∗/²⁰⁶Pb^∗ model dates of the pyroxene fractions vary from 4563.8 ± 0.3 to 4567.1 ± 0.5 Ma. The difference between whole rock and pyroxene U-Pb systematics may be a result of re-distribution of radiogenic Pb at a mineral grain scale several million years after crystallization. Complexities of Sm-Nd, Lu-Hf, and possibly ²⁶Al-²⁶Mg mineral systematics of SAH, described previously, may be related to the same process that caused the re-distribution of radiogenic Pb. Disturbance of isotopic chronometers renders SAH an imperfect anchor for the early Solar System timescale. The problems with age determination revealed by the studies of SAH call for greater attention in Pb-isotopic dating of angrites and other achondrites.     

U-Pb ages of angrites

Precise U-Pb ages, determined with double spike (²⁰²Pb-²⁰⁵Pb) thermal ionization m1ass spectrometry, are reported for angrites Angra dos Reis (AdoR), Lewis Cliff 86010 (LEW), and D’Orbigny. Nineteen of 23 acid-washed pyroxene fractions from these meteorites and whole rock fractions from D’Orbigny contain between 0.5 and 1.3 pg of total common Pb, indistinguishable from analytical blank. Measured ²⁰⁶Pb/²⁰⁴Pb ratios in these fractions are between 6300 and 14,100 for AdoR, 1160-4500 for LEW, and 608-8500 for D’Orbigny. Blank-corrected ²⁰⁶Pb/²⁰⁴Pb ratios for all three meteorites vary from 2160 to over 100,000. These fractions yielded precise and reproducible ²⁰⁷Pb^∗/²⁰⁶Pb^∗ dates with the average values of 4557.65 ± 0.13 Ma for AdoR, 4558.55 ± 0.15 Ma for LEW, and 4564.42 ± 0.12 Ma for D’Orbigny. Pb-Pb isochrons including data with slightly elevated common Pb, and U-Pb upper concordia intercepts, yield similar dates. The implications of these new Pb-isotopic ages of angrites are threefold. First, they demonstrate that AdoR and LEW are not coeval, and the group of “slowly cooled” angrites is therefore genetically diverse. Second, the new age of LEW suggests an upward revision of ⁵³Mn-⁵³Cr “absolute” ages by 0.7 Ma. Third, a precise age of D’Orbigny allows consistent linking of the ⁵³Mn-⁵³Cr and ²⁶Al-²⁶Mg extinct nuclide chronometers to the absolute lime scale.     

Ore genesis and hydrothermal evolution of the Huanggang skarn iron–tin polymetallic deposit,southern Great Xing'an Range: Evidence from fluid inclusions and isotope analyses

The southern Great Xing'an Range is one of the most important metallogenic belts in northern China, and contains numerous Pb–Zn–Ag–Cu–Sn–Fe–Mo deposits. The Huanggang iron–tin polymetallic skarn deposit is located in the Sn-polymetallic metallogenic sub-belt. Skarns and iron orebodies occur as lenses along the contact between granite plutons and the Lower Permian Huanggangliang Formation marble or Dashizhai Formation andesite. Field evidence and petrographic observations indicate that the three stages of hydrothermal activity, i.e., skarn, oxide and sulfide stages, all contributed to the formation of the Huanggang deposit.The skarn stage is characterized by the formation of garnet and pyroxene, and high-temperature, hypersaline hydrothermal fluids with isotopic compositions that are similar to those of typical magmatic fluids. These fluids most likely were generated by the separation of brine from a silicate melt instead of being a product of aqueous fluid immiscibility. The iron oxide stage coincides with the replacement of garnet and pyroxene by amphibole, chlorite, quartz and magnetite. The hydrothermal fluids of this stage are represented by L-type fluid inclusions that coexist with V-type inclusions with anomalously low δD values (approximately − 100 to − 116‰). The decrease in ore fluid δ¹⁸O_H2O values with time coincides with marked decreases in the fluid salinity and temperature. Based on the fluid inclusion and stable isotopic data, the ore fluid evolved by boiling of the magmatic brine. The sulfide stage is characterized by the development of sphalerite, chalcopyrite, fluorite, and calcite veins, and these veins cut across the skarns and orebodies. The fluids during this stage are represented by inclusions with a variable but continuous sequence of salinities, mainly low-salinity inclusions. These fluids yield the lowest δ¹⁸O_H2O values and moderate δD values ( − 1.6 to − 2.8‰ and − 101 to − 104‰, respectively). The data indicate that the sulfide stage fluids originated from the mixing of residual oxide-stage fluids with various amounts of meteoric water. Boiling occurred during this stage at low temperatures.The sulfur isotope (δ³⁴S) values of the sulfides are in a narrow range of − 6.70 to 4.50‰ (mean = − 1.01‰), and the oxygen isotope (δ¹⁸O) values of the magnetite are in a narrow range of 0.1 to 3.4‰. Both of these sets of values suggest that the ore-forming fluid is of magmatic origin. The lead isotope compositions of the ore (²⁰⁶Pb/²⁰⁴Pb = 18.252–18.345, ²⁰⁷Pb/²⁰⁴Pb = 15.511–15.607, and ²⁰⁸Pb/²⁰⁴Pb = 38.071–38.388) are consistent with those of K-feldspar granites (²⁰⁶Pb/²⁰⁴Pb = 18.183–18.495, ²⁰⁷Pb/²⁰⁴Pb = 15.448–15.602, ²⁰⁸Pb/²⁰⁴Pb = 37.877–38.325), but significantly differ from those of Permian marble (²⁰⁶Pb/²⁰⁴Pb = 18.367–18.449, ²⁰⁷Pb/²⁰⁴Pb = 15.676–15.695, ²⁰⁸Pb/²⁰⁴Pb = 38.469–38.465), which also suggests that the ore-forming fluid is of magmatic origin.     

In situ Pb and bulk Sr isotope analysis of the Yinchanggou Pb-Zn deposit in Sichuan Province (SW China): Constraints on the origin and evolution of hydrothermal fluids

The Yinchanggou Pb-Zn deposit, located in southwestern Sichuan Province, western Yangtze Block, is stratigraphically controlled by late Ediacaran Dengying Formation and contains >0.3 Mt of metal reserves with 11 wt% Pb + Zn. A principal feature is that this deposit is structurally controlled by normal faults, whereas other typical deposits nearby (e.g. Maozu) are controlled by reverse faults. The origin of the Yinchanggou deposit is still controversial. Ore genetic models, based on conventional whole-rock isotope tracers, favor either sedimentary basin brine, magmatic water or metamorphic fluid sources. Here we use in situ Pb and bulk Sr isotope features of sulfide minerals to constrain the origin and evolution of hydrothermal fluids. The Pb isotope compositions of galena determined by femtosecond LA-MC-ICPMS are as follows: ²⁰⁶Pb/²⁰⁴Pb = 18.17–18.24, ²⁰⁷Pb/²⁰⁴Pb = 15.69–15.71, ²⁰⁸Pb/²⁰⁴Pb = 38.51–38.63. These in situ Pb isotope data overlap with bulk-chemistry Pb isotope compositions of sulfide minerals (²⁰⁶Pb/²⁰⁴Pb = 18.11–18.40, ²⁰⁷Pb/²⁰⁴Pb = 15.66–15.76, ²⁰⁸Pb/²⁰⁴Pb = 38.25–38.88), and both sets of data plotting above the Pb evolution curve of average upper continental crust. Such Pb isotope signatures suggest an upper crustal source of Pb. In addition, the coarse-grained galena in massive ore collected from the deep part has higher ²⁰⁶Pb/²⁰⁴Pb ratios (18.18–18.24) than the fine-grained galena in stockwork ore sampled from the shallow part (²⁰⁶Pb/²⁰⁴Pb = 18.17–18.19), whereas the latter has higher ²⁰⁸Pb/²⁰⁴Pb ratios (38.59–38.63) than the former (²⁰⁸Pb/²⁰⁴Pb = 38.51–38.59). However, both types of galena have the same ²⁰⁷Pb/²⁰⁴Pb ratios (15.69–15.71). This implies two independent Pb sources, and the metal Pb derived from the basement metamorphic rocks was dominant during the early phase of ore formation in the deep part, whereas the ore-hosting sedimentary rocks supplied the majority of metal Pb at the late phase in the shallow part. In addition, sphalerite separated from different levels has initial ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.7101 to 0.7130, which are higher than the ore formation age-corrected ⁸⁷Sr/⁸⁶Sr ratios of country sedimentary rocks (⁸⁷Sr/⁸⁶Sr_200 Ma = 0.7083–0.7096), but are significantly lower than those of the ore formation age-corrected basement rocks (⁸⁷Sr/⁸⁶Sr_200 Ma = 0.7243–0.7288). Again, such Sr isotope signatures suggest that the above two Pb sources were involved in ore formation. Hence, the gradually mixing process of mineralizing elements and associated fluids plays a key role in the precipitation of sulfide minerals at the Yinchanggou ore district. Integrating all the evidence, we interpret the Yinchanggou deposit as a strata-bound, normal fault-controlled epigenetic deposit that formed during the late Indosinian. We also propose that the massive ore is formed earlier than the stockwork ore, and the temporal-spatial variations of Pb and Sr isotopes suggest a certain potential of ore prospecting in the deep mining area.     

Genesis of the Huangshaping W–Mo–Cu–Pb–Zn polymetallic deposit in Southeastern Hunan Province,China: Constraints from fluid inclusions,trace elements,and isotopes

The Huangshaping polymetallic deposit is located in southeastern Hunan Province, China. It is a world-class W–Mo–Pb–Zn–Cu skarn deposit in the Nanling Range Metallogenic Belt, with estimated reserves of 74.31 Mt of W–Mo ore at 0.28% WO₃ and 0.07% Mo, 22.43 Mt of Pb–Zn ore at 3.6% Pb and 8.00% Zn, and 20.35 Mt of Cu ore at 1.12% Cu. The ore district is predominantly underlained by carbonate formations of the Lower Carboniferous period, with stocks of quartz porphyry, granite porphyry, and granophyre. Skarns occurred in contact zones between stocks and their carbonate wall rocks, which are spatially associated with the above-mentioned three types of ores (i.e., W–Mo, Pb–Zn, and Cu ores).Three types of fluid inclusions have been identified in the ores of the Huangshaping deposit: aqueous liquid–vapor inclusions (Type I), daughter-mineral-bearing aqueous inclusions (Type II), and H₂O–CO₂ inclusions (Type III). Systematic microthermometrical, laser Raman spectroscopic, and salinity analyses indicate that high-temperature and high-salinity immiscible magmatic fluid is responsible for the W–Mo mineralization, whereas low-temperature and low-salinity magmatic-meteoric mixed fluid is responsible for the subsequent Pb–Zn mineralization. Another magmatic fluid derived from deep-rooted magma is responsible for Cu mineralization.Chondrite-normalized rare earth element patterns and trace element features of calcites from W–Mo, Pb–Zn, and Cu ores are different from one another. Calcite from Cu ores is rich in heavy rare earth elements (187.4–190.5 ppm), Na (0.17%–0.19%), Bi (1.96–64.60 ppm), Y (113–135 ppm), and As (9.1–29.7 ppm), whereas calcite from W–Mo and Pb–Zn ores is rich in Mn (> 10.000 ppm) and Sr (178–248 ppm) with higher Sr/Y ratios (53.94–72.94). δ¹⁸O values also differ between W–Mo/Pb–Zn ores (δ¹⁸O = 8.10‰–8.41‰) and Cu ores (δ¹⁸O = 4.34‰–4.96‰), indicating that two sources of fluids were, respectively, involved in the W–Mo, Pb–Zn, and Cu mineralization.Sulfur isotopes from sulfides also reveal that the large variation (4‰–19‰) within the Huangshaping deposit is likely due to a magmatic sulfur source with a contribution of reduced sulfate sulfur host in the Carboniferous limestone/dolomite and more magmatic sulfur involved in the Cu mineralization than that in W–Mo and Pb–Zn mineralization. The lead isotopic data for sulfide (galena: ²⁰⁶Pb/²⁰⁴Pb = 18.48–19.19, ²⁰⁷/²⁰⁴Pb = 15.45–15.91, ²⁰⁸/²⁰⁴Pb = 38.95–39.78; sphalerite: ²⁰⁶Pb/²⁰⁴Pb = 18.54–19.03, ²⁰⁷/²⁰⁴Pb = 15.60–16.28, ²⁰⁸/²⁰⁴Pb = 38.62–40.27; molybdenite: ²⁰⁶Pb/²⁰⁴Pb = 18.45–19.21, ²⁰⁷/²⁰⁴Pb = 15.53–15.95, ²⁰⁸/²⁰⁴Pb = 38.77–39.58 chalcopyrite: ²⁰⁶Pb/²⁰⁴Pb = 18.67–19.38, ²⁰⁷/²⁰⁴Pb = 15.76–19.90, and ²⁰⁸/²⁰⁴Pb = 39.13–39.56) and oxide (scheelite: ²⁰⁶Pb/²⁰⁴Pb = 18.57–19.46, ²⁰⁷/²⁰⁴Pb = 15.71–15.77, ²⁰⁸/²⁰⁴Pb = 38.95–39.13) are different from those of the wall rock limestone (²⁰⁶Pb/²⁰⁴Pb = 18.34–18.60, ²⁰⁷/²⁰⁴Pb = 15.49–15.69, ²⁰⁸/²⁰⁴Pb = 38.57–38.88) and porphyries (²⁰⁶Pb/²⁰⁴Pb = 17.88–18.66, ²⁰⁷/²⁰⁴Pb = 15.59–15.69, ²⁰⁸/²⁰⁴Pb = 38.22–38.83), suggesting Pb²⁰⁶-, U²³⁸-, and Th ²³²-rich material are involved in the mineralization. The Sm–Nd isotopes of scheelite (ε_Nd(t) = − 6.1 to − 2.9), garnet (ε_Nd(t) = − 6.8 to − 6.1), and calcite (ε_Nd(t) = − 6.3) from W–Mo ores as well as calcite (ε_Nd(t) = − 5.4 to − 5.3) and scheelite (ε_Nd(t) = − 2.9) from the Cu ores demonstrate suggest more mantle-derived materials involved in the Cu mineralization.In the present study we conclude that two sources of ore-forming fluids were involved in production of the Huangshaping W–Mo–Pb–Zn–Cu deposit. One is associated with the granite porphyry magmas responsible for the W–Mo and then Pb–Zn mineralization during which its fluid evolved from magmatic immiscible to a magmatic–meteoritic mixing, and the other is derived from deep-rooted magma, which is related to Cu-related mineralization.     

Uranium-lead isotope systematics of Mars inferred from the basaltic shergottite QUE 94201

Uranium-lead ratios (commonly represented as ²³⁸U/²⁰⁴Pb = μ) calculated for the sources of martian basalts preserve a record of petrogenetic processes that were active during early planetary differentiation and formation of martian geochemical reservoirs. To better define the range of μ values represented by the source regions of martian basalts, we completed U-Pb elemental and isotopic analyses on whole rock, mineral and leachate fractions from the martian meteorite Queen Alexandra Range 94201 (QUE 94201). The whole rock and silicate mineral fractions have unradiogenic Pb isotopic compositions that define a narrow range (²⁰⁶Pb/²⁰⁴Pb = 11.16-11.61). In contrast, the Pb isotopic compositions of weak HCl leachates are more variable and radiogenic. The intersection of the QUE 94201 data array with terrestrial Pb in ²⁰⁶Pb/²⁰⁴Pb-²⁰⁷Pb/²⁰⁴Pb-²⁰⁸Pb/²⁰⁴Pb compositional space is consistent with varying amounts of terrestrial contamination in these fractions. We calculate that only 1-7% contamination is present in the purified silicate mineral and whole rock fractions, whereas the HCl leachates contain up to 86% terrestrial Pb. This terrestrial Pb contamination generated a ²⁰⁶Pb-²⁰⁷Pb array in the QUE fractions that appears to represent an ancient age, which contrasts with a much younger crystallization age of 327 ± 10 Ma derived from Rb-Sr and Sm-Nd isochrons (Borg L. E., Nyquist L. E., Taylor L. A., Wiesmann H. and Shih C. -Y. (1997) Constraints on Martian differentiation processes from Rb-Sr and Sm-Nd isotopic analyses of the basaltic shergottite QUE 94201. Geochim. Cosmochim. Acta61, 4915-4931). Despite the contamination, and accepting 327 ± 10 Ma as the crystallization age, we use the U-Pb data to determine the initial ²⁰⁶Pb/²⁰⁴Pb of QUE 94201 to be 11.086 ± 0.008 and to calculate the μ value of its mantle source to be 1.82 ± 0.01. The μ value calculated for the QUE 94201 source is the lowest determined for any martian basalt source, and, when compared to the highest values determined for martian basalt sources, indicates that μ values in martian source reservoirs vary by at least a factor of two. Additionally, the range of source μ values indicates that the μ value of bulk silicate Mars is approximately three. The amount of variation in the μ values of the mantle sources (μ ∼ 2-4) is greater than can be explained by igneous processes involving silicate phases alone. We suggest the possibility that a small amount of sulfide crystallization may generate greater extents of U-Pb fractionation during formation of the mantle sources of martian basalts.     

U-Th-Pb and Lu-Hf isotopic constraints on the evolution of sub-continental lithospheric mantle, French Massif Central

We have carried out a Pb double-spike and Lu-Hf isotope study of clinopyroxenes from spinel-facies mantle xenoliths entrained in Cenozoic intraplate continental volcanism of the French Massif Central (FMC). U-Th-Pb and Lu-Hf isotope systematics verify the existence of different lithospheric domains beneath the northern and southern FMC. Northern FMC clinopyroxenes have extreme Lu/Hf ratios and ultra-radiogenic Hf (ε_Hf = +39.6 to +2586) that reflect ∼15-25% partial melting in Variscan times (depleted mantle model ages ∼360 Ma). Zr, Hf and Th abundances in these clinopyroxenes are low and unaffected by hydrous/carbonatitic metasomatism that overprinted LILE and light REE abundances and caused decoupling of Lu/Hf-Sm/Nd ratios and Nd-Hf isotopes (ε_Nd = +2.1 to +91.2). Pb isotopes of northern FMC clinopyroxenes are radiogenic (²⁰⁶Pb/²⁰⁴Pb > 19), and typically more so than the host intraplate volcanic rocks. ²³⁸U/²⁰⁴Pb ratios range from 17 to 68, and most samples have distinctively low ²³²Th/²³⁸U (<1) and ²³²Th/²⁰⁴Pb (3-22). Clinopyroxenes from southern FMC lherzolites are generally marked by overall incompatible trace element enrichment including Zr, Hf and Th abundances, and have Pb isotopes that are similar to or less radiogenic than the host volcanic rocks. Hf isotope ratios are less radiogenic (ε_Hf = +5.4 to +41.5) than northern FMC mantle and have been overprinted by silicate-melt-dominated metasomatism that affected this part of FMC mantle. Major element and Lu concentrations of clinopyroxenes from southern FMC harzburgites are broadly similar to northern FMC clinopyroxenes and suggest they experienced similar degrees of melt extraction as northern FMC mantle. ²³⁸U/²⁰⁴Pb (53-111) and ²³²Th/²⁰⁴Pb ratios (157-355) of enriched clinopyroxenes from the southern FMC are extreme and significantly higher than the intraplate volcanic rocks. In summary, mantle peridotites from different parts of the FMC record depletion at ∼360 Ma during Variscan subduction, followed by differing styles of enrichment. Northern FMC mantle was overprinted by a fluid/carbonatitic metasomatic agent that carried elements like U, Pb, Sr and light REE. In contrast, much of the southern FMC mantle was metasomatised by a small-degree partial silicate melt resulting in enrichment of all incompatible trace elements. The extreme mantle ²³⁸U/²⁰⁴Pb (northern and southern FMC), ²³²Th/²³⁸U (northern FMC) and ²³²Th/²⁰⁴Pb ratios (southern FMC), coupled with unremarkable present-day Pb isotope ratios, constrain the timing of enrichment. Mantle metasomatism is a young feature related to melting of the upwelling mantle responsible for Cenozoic FMC volcanism, rather than subduction-related metasomatism intimately associated with mantle depletion during the Variscan orogeny. The varying metasomatic styles relate to pre-existing variations in the thickness of the continental lithospheric lid, which controlled the extent to which upwelling mantle could ascend and melt. In the northern FMC, a thicker and more refractory lithospheric lid (?80 km) only allowed incipient degrees of melting resulting in fluid/carbonatitic metasomatism of the overlying sub-continental lithospheric mantle. The thinner lithospheric lid of the southern FMC (?70 km) allowed larger degrees of melting and resulted in silicate-melt-dominated metasomatism, and also focused the location of the volcanic fields of the FMC above this region.     

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.     

Plume-lithosphere interaction beneath Mt. Cameroon volcano, West Africa: Constraints from U-Th-Ra and Sr-Nd-Pb isotope systematics

Precise measurements of ²³⁸U-²³⁰Th-²²⁶Ra disequilibria in lavas erupted within the last 100 yr on Mt. Cameroon are presented, together with major and trace elements, and Sr-Nd-Pb isotope ratios, to unravel the source and processes of basaltic magmatism at intraplate tectonic settings. All samples possess ²³⁸U-²³⁰Th-²²⁶Ra disequilibria with ²³⁰Th (18-24%) and ²²⁶Ra (9-21%) excesses, and there exists a positive correlation in a (²²⁶Ra/²³⁰Th)-(²³⁰Th/²³⁸U) diagram. The extent of ²³⁸U-²³⁰Th-²²⁶Ra disequilibria is markedly different in lavas of individual eruption ages, although the (²³⁰Th/²³²Th) ratio is constant irrespective of eruption age. When U-series results are combined with Pb isotope ratios, negative correlations are observed in the (²³⁰Th/²³⁸U)-(²⁰⁶Pb/²⁰⁴Pb) and (²²⁶Ra/²³⁰Th)-(²⁰⁶Pb/²⁰⁴Pb) diagrams. Shallow magma chamber processes like magma mixing, fractional crystallization and wall rock assimilation do not account for the correlations. Crustal contamination is not the cause of the observed isotopic variations because continental crust is considered to have extremely different Pb isotope compositions and U/Th ratios. Melting of a chemically heterogeneous mantle might explain the Mt. Cameroon data, but dynamic melting under conditions of high D_U and D_U/D_Th, long magma ascent time, or disequilibrium mineral/melt partitioning, is required. The most plausible scenario to produce the geochemical characteristics of Mt. Cameroon samples is the interaction of melt derived from the asthenospheric mantle with overlying sub-continental lithospheric mantle which has elevated U/Pb (>0.75) and Pb isotope ratios (²⁰⁶Pb/²⁰⁴Pb > 20.47) due to late Mesozoic metasomatism.     

Jurassic magmatism related Pb-Zn-W-Mo polymetallic mineralization in the central Nanling Range,South China: Geochronologic,geochemical, and isotopic evidence from the Huangshaping deposit

The Nanling Range in South China is characterized by extensive Mesozoic magmatism and coeval nonferrous and rare metal mineralization. Huangshaping is a world-class Pb-Zn-W-Mo polymetallic skarn deposit in the central Nanling Range. Magmatic rocks occurring in this ore district include quartz porphyry, granite porphyry, granophyre, dacite porphyry, and aplite, with only the first three granitoids genetically associated with polymetallic mineralization. Most of the orebodies are constrained within the contact zones as skarn and veins between these granitic stocks and the carbonate wall rocks.Since the age of the quartz porphyry is still controversial, and studies of the dacite porphyry and aplite are absent, we focus on these magmatic rocks first. LA-ICP-MS zircon U-Pb dating suggests that the crystallization ages of the quartz porphyry, dacite porphyry, and aplite are 154.3 ± 1.9 Ma, 158.1 ± 0.8 Ma, and 148.4 ± 3.4 Ma, respectively. Combined with previously published age data, we infer the evolutionary sequence of magmatic rocks should be dacite porphyry → quartz porphyry → granite porphyry (granophyre) → aplite. The quartz porphyry, dacite porphyry, and aplite yield high contents of high field strength elements (Zr + Nb + Ce + Y = 255–440 ppm), high ratios of 10,000 × Ga/Al (2.6–3.2), and prominent depletions in Ba, Sr, Eu, P, and Ti, indicating their crustal affinities to A-type granites. They have negative ε_Nd(t) values (−9.4 to −7.0) and high initial Pb isotopic ratios (²⁰⁶Pb/²⁰⁴Pb_i = 18.307–18.644, ²⁰⁷Pb/²⁰⁴Pb_i = 15.689–15.742, ²⁰⁸Pb/²⁰⁴Pb_i = 38.589–38.986), suggesting that they were probably derived by partial melting of ancient granulitic crustal materials.The sulfide minerals exhibit a wide range of δ³⁴S_V-CDT values from −22.6 to 24.2‰, with ²⁰⁶Pb/²⁰⁴Pb of 17.669–19.708, ²⁰⁷Pb/²⁰⁴Pb of 15.492–15.714, and ²⁰⁸Pb/²⁰⁴Pb of 37.880–39.789, indicating that sulfur, lead, and other associated metals were derived from a mixture of magmatic components and the Carboniferous wall rocks. Fluid inclusions in pyrrhotite, sphalerite, and marmatite samples have ³He/⁴He ratios of 0.12 to 1.53 Ra, with calculated mantle helium proportions of 1.3 to 18.9%, indicating a predominantly crustal origin for the ore fluids, with minor inputs from the mantle. The Huangshaping deposit is a typical example of the genetic relationship both spatially and temporally between Jurassic magmatism and polymetallic metallogeny in the Nanling Range.     

Pb/Pb geochronology, petrography and chemistry of Zr-rich accessory minerals (zirconolite, tranquillityite and baddeleyite) in mare basalt 10047

In situ U-Pb isotopic measurements were carried out by ion microprobe on the Zr-rich accessory minerals zirconolite [CaZrTi₂O₇], tranquillityite [Fe₈²⁺(ZrY)₂Ti₃Si₃O₂₄] and baddeleyite [ZrO₂] in low-K, high-Ti mare basalt 10047 collected during the Apollo 11 mission. The analysed minerals are concentrated in pockets of late-stage mesostasis that comprises an intergrowth of silica, barian K-feldspar and Si-Al-K glass, from a phaneritic, subophitic, basalt comprising mainly pyroxene, plagioclase, ilmenite, cristobalite and troilite. Most Zr-rich minerals are unaltered, however, some tranquillityite is replaced by a complex intergrowth of zirconolite, baddeleyite, ilmenite and fayalite, suggesting that the mineral became unstable during crystallization. Several baddeleyite crystals have also undergone alteration to secondary zircon. Zirconolite was analysed in thin section 10047,11 and tranquillityite and baddeleyite in 10047,227, using a ∼6 μm primary ion beam. Both zirconolite and tranquillityite have significant U and low initial Pb contents, and are highly suitable for Pb/Pb dating. Fifteen analyses of zirconolite give a ²⁰⁷Pb/²⁰⁶Pb age of 3708 ± 7 Ma (²⁰⁷Pb/²⁰⁶Pb:²⁰⁴Pb/²⁰⁶Pb isochron; 95% confidence, including renormalisation of ratios) and twenty-five analyses of tranquillityite give 3710 ± 6 Ma. The ²⁰⁷Pb/²⁰⁶Pb dates are consistent with each other and refine results from an earlier study. Baddeleyite data were less precise, mainly due to lower secondary ionisation efficiency. Our results show that zirconolite and tranquillityite can provide precise isotopic dates and, given their presence in other samples, they represent important U-Pb chronometers for refining lunar geology.     

LA-MC-ICPMS Pb-Pb dating of rutile from slowly cooled granulites: Confirmation of the high closure temperature for Pb diffusion in rutile

Rapid Pb-Pb dating of natural rutile crystals by laser ablation multiple-collector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) is investigated as a tool for constraining geological temperature-time histories. LA-MC-ICPMS was used to analyse Pb isotopes in rutile from granulite-facies rocks from the Reynolds Range, Northern Territory, Australia. The resultant ages were compared with previous U-Pb zircon and monazite age determinations and new mica (muscovite, phlogopite, and biotite) Rb-Sr ages from the same metamorphic terrane. Rutile crystals ranging in size from 3.5 to 0.05 mm with ?20 ppm Pb were ablated with a 300-25 μm diameter laser beam. Crystals larger than 0.5 mm yielded sufficiently precise ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb ratios to correct for the presence of common Pb, and individual rutile crystals often exhibited sufficient Pb isotopic heterogeneity to allow isochron calculations to be performed on replicate analyses of a single crystal. The mean of 12 isochron ages is 1544 ± 8 Ma (2 SD), with isochron ages for single crystals having uncertainties as low as ±1.3 Myr (2 SD). The ²⁰⁷Pb-²⁰⁶Pb ages calculated without correction for common Pb are typically <0.5% higher than the common-Pb-corrected isochron ages reflecting the very minor amounts of common Pb present in the rutile. The LA-MC-ICPMS method described samples only the outer 0.1-0.2 mm of the rutile crystals, resulting in a grain size-independent apparent closure temperature (T_c) for Pb diffusion in rutile that is less than the T_c of monazite ?0.1 mm in diameter, but significantly higher than the Rb-Sr system in muscovite (550 °C), phlogopite (435 °C) and biotite (400 °C). Even small rutile crystals are extremely resistant to isotopic resetting. For the established slow cooling rate of ca. 3 °C/Myr, the T_c for Pb diffusion in the analysed rutile is ca. 630 °C. This is in excellent agreement with recent experimental results that indicate that rutile has a higher T_c than previously thought (ca. 600-640 °C for rutile 0.1-0.2 mm diameter cooled at 3 °C/Myr; near 600 °C [Cherniak D.J., 2000. Pb diffusion in rutile. Contrib. Mineral. Petrol. 139, 198-207], versus 400 °C [Mezger, K., Hanson G.N., Bohlen S.R., 1989a. High precision U-Pb ages of metamorphic rutile: applications to the cooling history of high-grade terranes. Earth Planet. Sci. Lett. 96, 106-118.] for 1 °C/Myr), and with current T_c estimates for monazite and other high temperature geochronometers, which have been revised upwards in recent years. The new rutile ages, together with the other geochronological data from the region, support the interpretation that the Reynolds Range underwent prolonged slow cooling on a conductive geotherm, under nearly steady-state conditions. Slow cooling at ca. 3 °C/Myr persisted for at least 40 Myr followed the peak of high-T/low-P metamorphism to granulite-facies conditions, and probably continued at ca. 2-3 °C/Myr for ca. 200 Myr overall.     

Evidence for distinct proportions of subducted oceanic crust and lithosphere in HIMU-type mantle beneath El Hierro and La Palma, Canary Islands

Shield-stage high-MgO alkalic lavas from La Palma and El Hierro (Canary Islands) have been characterized for their O-Sr-Nd-Os-Pb isotope compositions and major-, trace-, and highly siderophile-element (HSE: Os, Ir, Ru, Pt, Pd, Re) abundances. New data are also reported for associated evolved rocks, and entrained xenoliths. Clear differences in Pd/Ir and isotopic ratios for high Os (>50 ppt) lavas from El Hierro (δ¹⁸O_olivine = 5.17 ± 0.08‰; ⁸⁷Sr/⁸⁶Sr = 0.7029 to 0.7031; ε_Nd = +5.7 to +7.1; ¹⁸⁷Os/¹⁸⁸Os = 0.1481 to 0.1750; ²⁰⁶Pb/²⁰⁴Pb = 19.1 to 19.7; Pd/Ir = 6 ± 3) versus those from La Palma (δ¹⁸O_olivine = 4.87 ± 0.18‰; ⁸⁷Sr/⁸⁶Sr = 0.7031 to 0.7032; ε_Nd = +5.0 to +6.4; ¹⁸⁷Os/¹⁸⁸Os = 0.1421 to 0.1460; ²⁰⁶Pb/²⁰⁴Pb = 19.5 to 20.2; Pd/Ir = 11 ± 4) are revealed from the dataset.Crustal or lithospheric assimilation during magma transport cannot explain variations in isotopic ratios or element abundances of the lavas. Shallow-level crystal-liquid fractionation of olivine, clinopyroxene and associated early-crystallizing minerals (e.g., spinel and HSE-rich phases) controlled compatible element and HSE abundances; there is also evidence for sub-aerial degassing of rhenium. High-MgO lavas are enriched in light rare earth elements, Nb, Ta, U, Th, and depleted in K and Pb, relative to primitive mantle abundance estimates, typical of HIMU-type oceanic island basalts. Trace element abundances and ratios are consistent with low degrees (2-6%) of partial melting of an enriched mantle source, commencing in the garnet stability field (?110 km). Western Canary Island lavas were sulphur undersaturated with estimated parental melt HSE abundances (in ppb) of 0.07 ± 0.05 Os, 0.17 ± 0.16 Ir, 0.34 ± 0.32 Ru, 2.6 ± 2.5 Pt, 1.4 ± 1.2 Pd, 0.39 ± 0.30 Re. These estimates indicate that Canary Island alkali basalts have lower Os, Ir and Ru, but similar Pt, Pd and Re contents to Hawai’ian tholeiites.The HIMU affinities of the lavas, in conjunction with the low δ¹⁸O_olivine and high ²⁰⁶Pb/²⁰⁴Pb for La Palma, and elevated ¹⁸⁷Os/¹⁸⁸Os for El Hierro implies melting of different proportions of recycled oceanic crust and lithosphere. Our preferred model to explain isotopic differences between the islands is generation from peridotitic mantle metasomatised by <10% pyroxenite/eclogite made from variable portions of similar aged recycled oceanic crust and lithosphere. The correspondence of radiogenic ²⁰⁶Pb/²⁰⁴Pb, ¹⁸⁷Os/¹⁸⁸Os, elevated Re/Os and Pt/Os, and low-δ¹⁸O in western Canary Island lavas provides powerful support for recycled oceanic crust and lithosphere to generate the spectrum of HIMU-type ocean island basalt signatures. Persistence of geochemical heterogeneities throughout the stratigraphies of El Hierro and La Palma demonstrate long-term preservation of these recycled components in their mantle sources over relatively short-length scales (∼50 km).     

The sources of ore-forming material in the low-sulfidation epithermal Wulaga gold deposit,NE China: Constraints from S,Pb isotopes and REE pattern

The Wulaga gold deposit, located in Heilongjiang province, NE China, is a subvolcanic rock-hosted, low-sulfidation epithermal gold deposit, and has an Au reserve of about 84 tons. The gold mineralization occurs in a crypto-explosive breccia, and is spatially and temporally associated with an Early Cretaceous granodioritic porphyry. Three individual stages of mineralization have been identified in the Wulaga gold deposit: an early white quartz-euhedral vein stage, a fine-grained pyrite–marcasite–stibnite–chalcedony stage, and a late calcite–pyrite stage. The sulfur isotopic values of sulfide minerals vary in a wide range from − 4 to 4.9‰, but are concentrated in the range of − 3 to 0‰, implying that sulfur in the hydrothermal fluids was derived from magmatic volatiles. Lead isotopic results of the granodioritic porphyry (²⁰⁶Pb/²⁰⁴Pb = 18.341–18.395, ²⁰⁷Pb/²⁰⁴Pb = 15.507–15.523, ²⁰⁸Pb/²⁰⁴Pb = 38.174–38.251) and sulfide minerals (²⁰⁶Pb/²⁰⁴Pb = 18.172–18.378, ²⁰⁷Pb/²⁰⁴Pb = 15.536–15.600, ²⁰⁸Pb/²⁰⁴Pb = 38.172–38.339) are comparatively consistent and clustered together between the orogenic and upper mantle lines, indicating the lead in the ores is closely related to the parent magma of the granodioritic porphyry. The REE patterns of fluid inclusions trapped in sulfides are similar to those of the granodioritic porphyry, which confirms the magmatic origin of the REE in the hydrothermal fluids. The characteristics of S and Pb isotopes and REE suggest that the ore-forming materials of the Wulaga gold deposit are partly magmatic in origin, and related to a high-level hydrous granodioritic magma.     

Lead isotopic signatures of wine and vineyard soils—tracers of lead origin

The Pb contents and ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb isotopic ratios were studied in the soils and wines (2004 harvest) of three vineyard areas of the Czech Republic. The areas differ in their geological basements and anthropogenic loading. The isotopic compositions of wine in areas with intensive industry (Most, North Bohemia ²⁰⁶Pb/²⁰⁷Pb_wine = 1.178 ± 0.004) and the agricultural areas of Central Bohemia (Roudnice nad Labem ²⁰⁶Pb/²⁰⁷Pb_wine = 1.176 ± 0.007) are similar to the Pb isotopic composition of airborne particulate material typical of polluted and industrial environments (²⁰⁶Pb/²⁰⁷Pb = 1.17–1.19). The isotopic composition of wine from Prague (²⁰⁶Pb/²⁰⁷Pb_wine = 1.174 ± 0.003) is different from that of the soil, which was severely contaminated in the past by vehicular Pb (²⁰⁶Pb/²⁰⁷Pb_soil = 1.147–1.168). This fact shows that interception of airborne Pb by plants is greater than its uptake by the root system.     

Archaeological reconstruction of medieval lead production: Implications for ancient metal provenance studies and paleopollution tracing by Pb isotopes

The identification of metal provenance is often based on chemical and Pb isotope analyses of materials from the operating chain, mainly ores and metallic artefacts. Such analyses, however, have their limits. Some studies are unable to trace metallic artefacts or ingots to their ore sources, even in well-constrained archaeological contexts. Possible reasons for this difficulty are to be found among a variety of limiting factors: (i) problems of ore signatures, (ii) mixing of different ores (alloys), (iii) the use of additives during the metallurgical process, (iv) metal recycling and (v) possible Pb isotopic fractionation during metal production. This paper focuses on the issue of Pb isotope fractionation during smelting to address the issue of metal provenance. Through an experimental reconstruction of argentiferous Pb production in the medieval period, an attempt was made to better understand and interpret the Pb isotopic composition of ore smelting products. It is shown that the measured differences (outside the total external uncertainties of 0.005 (2*sd) for ²⁰⁶Pb/²⁰⁴Pb ratios) in Pb signatures measured between ores, slag and smoke are not due to Pb mass fractionation processes, but to (1) ore heterogeneity (Δ²⁰⁶Pb/²⁰⁴Pb_slag-ores = 0.066) and (2) the use of additives during the metallurgical process (Δ²⁰⁶Pb/²⁰⁴Pb_slag-ores = 0.083). Even if these differences are due to causes (1) and/or (2), smoke from the ore reduction appears to reflect the ore mining area without a significant disturbance of its Pb signature for all the isotopic ratios (Δ²⁰⁶Pb/²⁰⁴Pb_smokes-ores = 0.026). Thus, because the isotopic heterogeneity of the mining district and additives is averaged in slags, slag appears as the most relevant product to identify ancient metal provenance. Whereas aiming at identifying a given mine seems beyond the possibilities provided by the method, searching for the mining district through analysis of the smelting workshop materials should provide a more appropriate approach in cases where no archaeological evidence of ancient mining is available. Furthermore, smoke Pb isotopic composition does not seem to be significantly affected by the metallurgical process. Paleopollution recorded in peat deposits could help to detect ancient mining production and workshops. Integrated collaboration between mining archaeologists and geochemists appears crucial to achieve this goal.     

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.