Complex magmatic and impact history prior to 4.1 Ga recorded in zircon from Apollo 17 South Massif aphanitic breccia 73235

Sample 73235 is one of several aphanitic impact melt breccias collected by the Apollo 17 mission at stations 2 and 3 on the slopes of the South Massif. This study presents a detailed investigation of internal structures and U-Pb ages of large zircon grains from this breccia sample. New data combined with the results of previous studies of zircon grains from the same location indicate that most zircon clasts in breccias from stations 2 and 3 formed during multiple magmatic events between 4.37 and 4.31 Ga, although the oldest zircon crystallized at about 4.42 Ga and the youngest at 4.21 Ga. In addition, zircons from the aphanitic breccias record several impact events prior to the ∼3.9 Ga Late Heavy Bombardment. The results indicate that the zircons probably crystallized at different locations within the Procellarum KREEEP Terrane and were later excavated and modified by several impacts and delivered to the same locality within separate ejecta blankets. This locality became a source of material that formed the aphanitic impact melt breccias of the South Massif during a ∼3.9 Ga impact. However, the zircons, showing old impact features, are not modified by this ∼3.9 Ga impact event suggesting that (i) this common source area was located at the periphery of excavation cavity, and (ii) the > 3.9 Ga ages recorded by the zircon grains could date large (basin-forming) events as significant as major later (∼3.9 Ga) collisions such as Imbrium and Serenitatis.     

The contribution of the sensitive high-resolution ion microprobe (SHRIMP) to lunar geochronology

The sensitive high-resolution ion microprobe (SHRIMP) developed at the Australian National University (ANU) was the first of the high-resolution ion microprobes. The impact of this instrument on geochronological research over the last twenty years has been immense. This is particularly so for lunar geochronology where it has opened up avenues of research that were not possible using conventional TIMS techniques. The great advantage of SHRIMP is that it provides a means for determining precise U–Pb isotopic ratios on selected micron-size areas on polished grains of zircon and other U-bearing minerals. One of the first projects undertaken on the newly invented SHRIMP I was an investigation of U–Pb ages of lunar zircon. Using SHRIMP, multiple analyses could be made on areas of individual zircons to test the stability of U–Pb systems in shocked grains. Also, by analysing grains “in situ”, textural relationships between the analysed zircon and the components of the sample breccia could be used in the interpretation of the SHRIMP data. As a result of this research it was realised that most lunar zircons have ages up to 500 Ma older than the Imbrium and Serenitatis impacts at ca. 3.9 Ga, demonstrating that the zircons have not been affected by the these impact events although heating and shock effects have profoundly disturbed other dating systems. This has opened the way for research into the early lunar magmatic and bombardment record. For example, recent SHRIMP results have revealed profound differences in the ages of zircons from breccias from the Apollo 14 and Apollo 17 sample sites, raising new questions about the evolution of lunar magmatism. Also, multiple SHRIMP analyses on complex lunar zircons have shown that these grains can record U–Pb disturbance by later impact events. SHRIMP U–Pb age determinations on phosphates in lunar meteorites has identified lunar events not recognised in samples from the Apollo program. SHRIMP-based research on lunar materials is ongoing and, in combination with other chemical and structural evidence, continues to stimulate new ideas on the early evolution of the Moon.     

Reworking of Earth's first crust: Constraints from Hf isotopes in Archean zircons from Mt. Narryer,Australia

Discoveries of >4 Ga old zircon grains in the northwest Yilgarn of Western Australia led to the conclusion that evolved crust formed on the Earth within the first few 100 Ma after accretion. Little is known, however, about the fate of the first crust that shaped early Earth's surface. Here we report combined solution and laser-ablation Lu–Hf–U–Pb isotope analyses of early Archean and Hadean detrital zircon grains from different rocks of the Narryer Gneiss Complex (NGC), Yilgarn Craton, Western Australia. The zircons show two distinct groups with separate evolutionary trends in their Hf isotopes. The majority of the zircon grains point to separation from a depleted mantle reservoir at ∼3.8–3.9 Ga. The second Hf isotope trend implies reworking of older Hadean zircon grains. The major trend starting at 3.8–3.9 Ga defined by the Hf isotopes corresponds to a Lu/Hf that is characteristic for felsic crust and consequently, the primary sources for these zircons presumably had a chemical composition characteristic of continental crust. Reworked Hadean crust appears to have evolved with a similar low Lu/Hf, such that the early crust was probably evolved with respect to Lu–Hf distributions. The co-variation of Hf isotopes vs. age in zircon grains from Mt. Narryer and Jack Hills zircon grains implies a similar crustal source for both sediments in a single, major crustal domain. Age spectra and associated Hf isotopes in the zircon grains strongly argue for ongoing magmatic reworking over hundreds of millions of years of the felsic crustal domain in which the zircon grains formed. Late-stage metamorphic zircon grains from the Meeberrie Gneiss unit yield a mean U–Pb age of 3294.5 ± 3.2 Ma with initial Hf isotopes that correspond to the evolutionary trend defined by older NGC zircon grains and overlap with other detrital zircon grains, proving their genetic relationship. This ‘Meeberrie event’ is interpret here as the last reworking event in the precursor domain before final deposition. The continuous magmatic activity in one crustal domain during the Archean is recorded by the U–Pb ages and Hf isotope systematics of zircon grains and implies reworking of existing crust. We suspect that the most likely driving force for such reworking of crustal material is ongoing crustal collision and subduction. A comparison of Hf isotope signatures of zircon grains from other Archean terranes shows that similar trends are recognised within all sampled Archean domains. This implies either a global trend in crustal growth and reworking, or a genetic connection of Archean terranes in close paleo-proximity to each other. Notably, the Archean Acasta gneiss (Canada) shows a similar reworking patterns to the Yilgarn Craton of Hadean samples implying either a common Hadean source or amalgamation at the Hadean–Archean transition.     

Proterozoic volcanism in the Jack Hills Belt,Western Australia: Some implications and consequences for the World's oldest zircon population

Rare felsic volcanic rocks of dacitic to rhyolitic composition occur in the central part of the Jack Hills metasedimentary belt in the Narryer Terrane of Western Australia, interleaved with clastic sedimentary rocks and amphibolite. Representative samples of the four identified felsic volcanic units reveal a similar complex pattern of zircon age distribution, with all samples containing zircon populations at ∼3.3–3.4, ∼3.0–3.1, ∼2.6 and ∼1.8–1.9 Ga. The ∼3.3–3.4 Ga zircons show well-developed oscillatory zoning in cathodoluminescence (CL) images and are interpreted as inherited igneous zircon derived from granitic precursors, similar to the ∼3.3 Ga trondhjemitic granitoids currently exposed along the northern and southern margins of the belt. The ∼3.0–3.1 Ga zircons also reveal well-developed oscillatory zoning in CL and are most likely derived from granitoid and/or volcanic rocks of this age, as recorded in the Murchison domain to the south and possibly also present in the Narryer Terrane. The ∼2.6 Ga population matches the age of nearby late Archean granitoids intruding the Jack Hills belt and their oscillatory zoning and U–Th chemistry is consistent with their origin from such a source. The youngest discrete group of zircon grains, with ages ranging from ∼1970 to ∼1775 Ma, show strong oscillatory zoning and average Th/U ratios of 0.76, features consistent with an igneous origin. These younger zircons are therefore interpreted as defining the age of crystallisation of the volcanic rocks. These results establish that the Jack Hills metasedimentary belt contains significant post-Archean components. Taken together with similar results obtained from zircon occurring as detrital grains in clastic sedimentary rocks at Jack Hills, these results overturn the generally-accepted view that the belt is entirely Archean in age and that sedimentation was completed around 3.0 Ga ago. Instead, there is a distinct possibility that much of the material currently exposed in the Jack Hills belt formed in the Proterozoic. A further implication of this study is that the metamorphism affecting these rocks also occurred in the Proterozoic and consequently the rocks should not be considered as forming an Archean greenstone or metasedimentary belt. The paucity of zircons >4 Ga in the known Proterozoic sedimentary rocks and their total absence in the felsic volcanic rocks suggests that such ancient source rocks were no longer present in the area.     

The formation and chronology of the PAT 91501 impact-melt L chondrite with vesicle-metal-sulfide assemblages

The L chondrite Patuxent Range (PAT) 91501 is an 8.5-kg unshocked, homogeneous, igneous-textured impact melt that cooled slowly compared to other meteoritic impact melts in a crater floor melt sheet or sub-crater dike [Mittlefehldt D. W. and Lindstrom M. M. (2001) Petrology and geochemistry of Patuxent Range 91501 and Lewis Cliff 88663. Meteoritics Planet. Sci. 36, 439-457]. We conducted mineralogical and tomographic studies of previously unstudied mm- to cm-sized metal-sulfide-vesicle assemblages and chronologic studies of the silicate host. Metal-sulfide clasts constitute about 1 vol.%, comprise zoned taenite, troilite, and pentlandite, and exhibit a consistent orientation between metal and sulfide and of metal-sulfide contacts. Vesicles make up ∼2 vol.% and exhibit a similar orientation of long axes. ³⁹Ar-⁴⁰Ar measurements probably date the time of impact at 4.461 ± 0.008 Gyr B.P. Cosmogenic noble gases and ¹⁰Be and ²⁶Al activities suggest a pre-atmospheric radius of 40-60 cm and a cosmic ray exposure age of 25-29 Myr, similar to ages of a cluster of L chondrites. PAT 91501 dates the oldest known impact on the L chondrite parent body. The dominant vesicle-forming gas was S₂ (∼15-20 ppm), which formed in equilibrium with impact-melted sulfides. The meteorite formed in an impact melt dike beneath a crater, as did other impact melted L chondrites, such as Chico. Cooling and solidification occurred over ∼2 h. During this time, ∼90% of metal and sulfide segregated from the local melt. Remaining metal and sulfide grains oriented themselves in the local gravitational field, a feature nearly unique among meteorites. Many of these metal-sulfide grains adhered to vesicles to form aggregates that may have been close to neutrally buoyant. These aggregates would have been carried upward with the residual melt, inhibiting further buoyancy-driven segregation. Although similar processes operated individually in other chondritic impact melts, their interaction produced the unique assemblage observed in PAT 91501.     

The complex age of orthogneiss protoliths exemplified by the Eoarchaean Itsaq Gneiss Complex (Greenland): SHRIMP and old rocks

Field studies integrated with cathodoluminescence petrography and SHRIMP U–Pb dating of zircons from >150 orthogneisses and metatonalites from the Eoarchaean Itsaq Gneiss Complex (southern West Greenland) shows that only a minority contain ≥3840 Ma zircons, whereas the majority carry only younger ones. Rocks containing ≥3840 Ma zircons vary from very rare single-phase metatonalites to more common complexly banded tonalitic migmatites. The former metatonalites have simple oscillatory-zoned ≥3840 Ma zircon with limited recrystallisation and overgrowth, whereas the more common migmatites have much more complicated zircon populations with both ≥3840 Ma and 3650–3600 Ma oscillatory-zoned zircon, more extensive recrystallisation and widespread complex core-rim multiple growth relationships.     

Soil Cd,Cu, Pb and Zn contaminants around Mount Isa city,Queensland, Australia: Potential sources and risks to human health

This article investigates the relationship between soil Cd, Cu, Pb and Zn contaminants and the location and activities of the Pb–Zn–Ag and Cu mines at Mount Isa, Queensland, Australia. Analysis of the data focuses primarily on soil Pb distributions and concentrations because of their potential impact on children’s health. The Xstrata Mount Isa Mines lease (XMIM) is Australia’s leading emitter of numerous contaminants to the environment, including Cu and Pb, and the mining-related activities have been linked causally to the findings of a 2008 study that showed 11.3% of local children (12–60 months) have blood Pb levels >10 μg/dL. Queensland government authorities and Xstrata Mount Isa Mines Pty Ltd maintain that contaminants within environmental systems around Mount Isa are largely the result of near-surface mineralization. The evidence for whether the contamination is derived from XMIM or other possible sources, such as the natural weathering of ore-rich bedrock, is investigated using data from surface and subsurface soil chemistry, atmospheric modelling of metal contaminants from mining and smelting operations and local geological and associated geochemical studies. Sixty surface soil samples collected from sites adjacent to houses, parks and schools throughout Mount Isa city were analyzed for their total extractable Cd, Cu, Pb and Zn concentrations in the <2 mm to >180 μm (coarser) and <180 μm (finer) grain size fractions. Concentrations in the finer size fraction reveal a range of values: Cd – 0.7–12.5 ppm; Cu – 31–12,100 ppm; Pb – 8–5770 ppm; Zn – 26–11,100 ppm, with several samples exceeding Australian residential health investigation guidelines. Spatial analysis shows that surface soil metal concentrations are significantly higher within 2 km of XMIM compared to more distant samples, and that more than 1000 property lots are at risk of having detrimentally high soil Pb levels. Determination of metal concentrations in 49 samples from eight soil pits shows that surface samples (0–2 cm) are enriched significantly relative to those at depth (10–20 cm), suggesting an atmospheric depositional origin. AUSPLUME air dispersal modelling of Pb originating from the Cu and Pb smelter stacks and mine site fugitive sources confirms that Pb is deposited across the urban area, during periods of the year (∼20%/a) when the wind blows from the direction of XMIM towards the urban area and disperses dusts from the uncovered spoil and road surfaces, as well as from stack emission sources. Although there are some spatially restricted outcrops of Pb close to the surface in parts of the urban area, the Cu-ore body is ∼244 m below the surface. However, enriched and significantly correlated surface soil concentrations of Cu and Pb (Pearson correlation 0.879, p = 0.000) in and around the urban area of Mount Isa can only be explained by atmospheric transport and deposition of metals from the adjoining mining and smelting operations. The results from this study provide unequivocal evidence that both historic and ongoing emissions from XMIM are contaminating the urban environment. Given the ongoing Pb poisoning issues in Mount Isa children, it is clear that remediation, reductions in mine emissions and more stringent regulatory actions are warranted.     

Paleoproterozoic gabbronoritic and granitic magmatism in the northern margin of the North China craton: Evidence of crust–mantle interaction

Paleoproterozoic Xuwujia gabbronorites in the northern margin of the North China craton occur as dykes, sills and small plutons intruded into khondalite (aluminous paragneisses, sedimentary protoliths deposited at ca. 2.0–1.95 Ga), and as numerous entrained bodies and fragments of variable scales in the Liangcheng granitoids (ca. 1.93–1.89 Ga). These gabbronoritic dykes are present at all locations where ca. 1.93–1.92 Ga ultra-high-temperature metamorphism is recorded in the khondalite. A gabbronorite sample from the Hongmiaozi dyke gives zircon ²⁰⁷Pb/²⁰⁶Pb mean ages of 1954 ± 6 Ma (core domains) and 1925 ± 8 Ma (rim domains). These ages, as well as previously reported ages, constrain the age of mafic magmatism to be at ca. 1.96–1.92 Ga (∼1.93 Ga). One sample from the Xigou gabbro intruded by the Liangcheng granitoids gives a zircon ²⁰⁷Pb/²⁰⁶Pb mean age of 1857 ± 4 Ma, which is interpreted as the age of a metamorphic overprint. The Xuwujia gabbronorites comprise mainly gabbronorite compositions, as well as some norite, olivine gabbronorite, monzonorite, quartz gabbronorite, and quartz monzonorite. Chemically, they are tholeiitic and can be divided into two groups: a high-Mg group (6.2–22.9 wt.% MgO) and a relatively low-Mg group (2.2–5.7 wt.% MgO). The high-Mg group shows negative Eu-anomalies (Eu/Eu* = 0.53–0.72), slight light rare earth element enrichment (La/Yb_N = 0.56–1.53), and small negative anomalies in high field-strength elements. The ?Nd (t = 1.93 Ga) values vary from +0.3 to +2.4. The low-Mg group shows varied Eu-anomalies (Eu/Eu* = 0.48–1.05), and is enriched in light rare earth elements (La/Yb_N = 1.51–11.98). The majority shows negative anomalies in high field-strength elements (e.g., Th, Nb, Zr, and Ti). Initial ?Nd (at 1.93 Ga) values for low-Mg gabbronorites vary from −5.0 to 0. The Xuwujia gabbronorites possibly experienced assimilation of crust, and fractional crystallization of initially olivine and hypersthene (the high-Mg group), and then olivine, clinopyroxene, and plagioclase (the low-Mg group). The slightly younger Liangcheng granitoids consist of garnet-bearing granite, granodiorite and quartz-rich granitic compositions. They are intermediate to felsic calc-alkaline rocks, thought to be derived from surrounding metasedimentary crust. Xigou gabbro could represent early cumulates. The granitoids have relatively high-Mg numbers (up to 54), and show some chemical affinities with the gabbronorites, which could have resulted from incorporation of gabbronoritic melts. The occurrence and chemical variations of the Xuwujia gabbronorites and Liangcheng granitoids can be interpreted to have resulted from crust–mantle interaction, with mingling and partial mixing of mantle (gabbronoritic) and crustal (granitic) melts. The Xuwujia gabbronorites originated from a mantle region with high potential temperatures (∼1550 °C), possibly associated with a plume or more likely a ridge-subduction-related mantle upwelling event. They could have had extremely high primary intrusion temperatures (up to 1400 °C). Emplacement of these magmas was likely responsible for the extensive crustal anatexis (Liangcheng granitoids) and the local ultra-high-temperature metamorphism. These sequences may have followed ca. 1.95 Ga continent–continent (arc?) juxtaposition and were themselves followed by significant regional uplift and exhumation in the northern margin of the North China craton.     

Geochronology and geochemistry of Middle Devonian mafic dykes in the East Kunlun orogenic belt,Northern Tibet Plateau: Implications for the transition from Prototethys to Paleotethys orogeny

The tectonic transition from Prototethys to Paleotethys orogeny in the East Kunlun orogenic belt is not completely clear, and is a major unresolved geologic issue in Northern Tibet Plateau. Here, we present zircon geochronology, whole-rock elemental and zircon Hf isotopic geochemistry for newly discovered mafic dykes in the East Kunlun orogenic belt, to provide constraints on this issue. The studied mafic dykes are hornblende gabbros, consisting of hornblende (60–65 vol.%), plagioclase (15–25 vol.%) and augite and biotite (0–5 vol.%). LA–ICP–MS zircon U–Pb dating shows that these mafic dykes were emplaced at about 393 Ma. All the mafic dykes are characterized by high contents of CaO (8.82–11.48 wt.%), MgO (9.07–11.39 wt.%), V (275–336 ppm), Cr (370–467 ppm) and Ni (78.3–120 ppm), with high Mg# (63–67), flat CI-normalized REE distribution and depleted ?Hf(t) values (2.03–5.35), showing tholeiitic affinities and geochemical characteristics similar to those of mid-ocean ridge basalts. They were derived from low degree (about 5–15%) partial melting of a fertile spinel lherzolite source, which have been metasomatized by fluids introduced to the mantle by former subducted slab. The geologic–petrologic evidence suggests that the mafic dykes were emplaced in a shift tectonic setting related to continental rifting, which was caused by the extensional collapse related to the lithospheric thinning after the Prototethys orogeny. The delamination-induced thermal disturbance and extensional decompression triggered partial melting of the mantle and the emplacement of the mafic dykes. Combined with previous work, we propose that the Middle Devonian mafic dykes may be the early magmatic response to the transition from Prototethys to Paleotethys marking the opening of the Paleotethys in the East Kunlun orogenic belt.     

Thermal events documented in Hadean zircons by ion microprobe depth profiles

We report the first U-Th-Pb ion microprobe depth profiles of four Hadean zircons from the Jack Hills and Mount Narryer supracrustal belts of the Narryer Gneiss Complex (NGC), Western Australia. This ultra-high spatial resolution technique probes the age and origin of sub-micron features in individual crystals that can record episodes of zircon growth. Near-surface grain dates of 2700 Ma or older are coincident with post-depositional growth/modification. Some ages may coincide with documented pre-deposition metamorphic events for the NGC and igneous emplacement at ca. 3700 Ma. Separate events that do not correlate in time with known geologic episodes prior to the preserved rock record are also present on pre-4000 Ma zircons. We find evidence for a ∼3.9 Ga event, which is coterminous within age uncertainty with one or several large basin-forming impacts (e.g. Nectaris) on the Moon attributed to the late heavy bombardment of the inner solar system.     

Geochemistry of highly acidic mine water following disposal into a natural lake with carbonate bedrock

Acid mine drainage (AMD) from the Zn–Pb(–Ag–Bi–Cu) deposit of Cerro de Pasco (Central Peru) and waste water from a Cu-extraction plant has been discharged since 1981 into Lake Yanamate, a natural lake with carbonate bedrock. The lake has developed a highly acidic pH of ∼1. Mean lake water chemistry was characterized by 16,775 mg/L acidity as CaCO₃, 4330 mg/L Fe and 29,250 mg/L SO₄. Mean trace element concentrations were 86.8 mg/L Cu, 493 mg/L Zn, 2.9 mg/L Pb and 48 mg/L As, which did not differ greatly from the discharged AMD. Most elements showed increasing concentrations from the surface to the lake bottom at a maximal depth of 41 m (e.g. from 3581 to 5433 mg/L Fe and 25,609 to 35,959 mg/L SO₄). The variations in the H and O isotope compositions and the element concentrations within the upper 10 m of the water column suggest mixing with recently discharged AMD, shallow groundwater and precipitation waters. Below 15 m a stagnant zone had developed. Gypsum (saturation index, SI ∼ 0.25) and anglesite (SI ∼ 0.1) were in equilibrium with lake water. Jarosite was oversaturated (SI ∼ 1.7) in the upper part of the water column, resulting in downward settling and re-dissolution in the lower part of the water column (SI ∼ −0.7). Accordingly, jarosite was only found in sediments from less than 7 m water depth. At the lake bottom, a layer of gel-like material (∼90 wt.% water) of pH ∼1 with a total organic C content of up to 4.40 wet wt.% originated from the kerosene discharge of the Cu-extraction plant and had contaminant element concentrations similar to the lake water. Below the organic layer followed a layer of gypsum with pH 1.5, which overlaid the dissolving carbonate sediments of pH 5.3–7. In these two layers the contaminant elements were enriched compared to lake water in the sequence As < Pb ≈ Cu < Cd < Zn = Mn with increasing depth. This sequence of enrichment was explained by the following processes: (i) adsorption of As on Fe-hydroxides coating plant roots at low pH (up to 3326 mg/kg As), (ii) adsorption at increasing pH near the gypsum/calcite boundary (up to 1812 mg/kg Pb, 2531 mg/kg Cu, and 36 mg/kg Cd), and (iii) precipitation of carbonates (up to 5177 mg/kg Zn and 810 mg/kg Mn; all data corrected to a wet base). The infiltration rate was approximately equal to the discharge rate, thus gypsum and hydroxide precipitation had not resulted in complete clogging of the lake bedrocks.     

Eoarchean–Paleoproterozoic zircon inheritance in Japanese Permo-Triassic granites (Unazuki area,Hida Metamorphic Complex): Unearthing more old crust and identifying source terrranes

U–Pb zircon geochronology of two Permo-Triassic granites (samples OT-52 and OT-272 with ages of 229 ± 8 Ma and 256 ± 2 Ma, respectively) in the Unazuki area, Hida Metamorphic Belt, southwest Japan, revealed the presence of Eoarchean to Paleoproterozoic inheritance. Inheritance is consistent with both samples showing low zircon saturation temperatures for their bulk compositions. In OT-52, dark in CL, low Th/U zircon domains have a mean ²⁰⁷Pb/²⁰⁶Pb age of 1940 ± 17 Ma, which is consistent with an age of 1937 ± 6 Ma for anatexis in the Precambrian Busan gneiss complex in Korea. Eoarchaean inherited zircons with ²⁰⁷Pb/²⁰⁶Pb ages from ca. 3750 to 3550 Ma are common in OT-272 but are few in OT-52, suggesting a source from rocks with affinities to those in the Anshan area in the northeast China part of the North China Craton. On the other hand, a Hida Metamorphic Belt metasedimentary gneiss into which the granites were intruded contains ca. 1840, 1130, 580, 360, 285 and 250 Ma zircons (Sano et al., 2000). These ages suggest that the Unazuki Mesozoic granites did not originate from proximal Hida Metamorphic Complex rocks, but instead from unrelated rocks obscured at depth. The predominance of Eoarchean to Paleoproterozoic age components, and the marked lack of 900–700 Ma components suggest that the source was the (extended?) fringe of the North China Craton, rather than from Yangtze Craton crust. The Mesozoic evolution of Japan and its linkages to northeast Asia are discussed in the context of these results.     

Proterozoic mafic magmatism in Siberian craton: An overview and implications for paleocontinental reconstruction

We present a summary of late Paleoproterozoic to Neoproterozoic mafic magmatism in the Siberian craton, including recently published U–Pb and ⁴⁰Ar–³⁹Ar dates. These new precise ages suggest that at least some of the previously published K–Ar ages of Siberian mafic bodies should be ignored. The time–space geochronological chart, or the ‘barcode’ of mafic magmatic events shows significant differences between northern and southern Siberia. Both are characterized by ∼1900–1700 Ma magmatic events, but then there was an almost 1 Ga mafic magmatic ‘pause’ in south Siberia until ∼800 Ma. Meanwhile there are indications of multiple mafic magmatic events in North Siberia (Anabar shield and Olenek uplift) between ∼1600 and 1000 Ma. A series of magmatic events probably related to the breakup of Rodinia occurred in southern Siberia after ∼800 Ma. So far, there are no indications of late Neoproterozoic mafic magmatism in North Siberia. Ca. 1000–950 Ma mafic sills were reported from Meso- to Neo-Proterozoic sedimentary successions in the Sette-Daban area on the east side of the Siberian craton, but their tectonic setting is debated. Recent Ar–Ar dates of ∼1750 Ma for NW-trending dykes in the Aldan and Anabar shields, together with similar-age NNE-trending Baikal uplift dykes in south-eastern Siberia suggest the existence of a giant radial dyke swarm possibly related to a mantle plume centred in the Vilyui River area.     

Neoproterozoic SHRIMP U–Pb zircon ages of silica-rich Dokhan Volcanics in the North Eastern Desert,Egypt

Chronology of Neoproterozoic volcanosedimentary successions remains controversial for many regions of the Arabian–Nubian Shield, including the Dokhan Volcanics of NE Egypt. New U–Pb zircon SHRIMP ages have been obtained for 10 silica-rich ignimbrites and two subvolcanic dacitic bodies, mapped as Dokhan Volcanics, from the North Eastern Desert of Egypt. Crystallization ages range between 592 ± 5 and 630 ± 6 Ma (Early Ediacaran). Apparently, the late consolidation of the Arabian–Nubian Shield was accompanied by the evolution of isolated volcanic centres and basin systems which developed during a period of approx. 40 Ma, independently in space and time and probably under changing tectonic regimes. The obtained age data together with other previously published reliable ages for Dokhan Volcanics suggest two main pulses of volcanic activity: 630–623 Ma and 618–592 Ma. Five samples contain inherited zircons, with ages of 669, 715–746, 847 and 1530 Ma, supporting models that North Eastern Desert crust is mainly juvenile Neoproterozoic crust.     

The biogeochemistry of atmospherically derived Pb in the boreal forest of Sweden

The use of stable Pb isotopes for tracing Pb contamination within the environment has strongly increased our understanding of the fate of airborne Pb contaminants within the boreal forest. This paper presents new stable Pb isotope (²⁰⁶Pb/²⁰⁷Pb ratio) measurements of solid soil samples, stream water (from a mire outlet and a stream draining a forest dominated catchment) and components of Picea abies (roots, needles and stemwood), and synthesizes some of the authors’ recent findings regarding the biogeochemistry of Pb within the boreal forest. The data clearly indicate that the biogeochemical cycling of Pb in the present-day boreal forest ecosystem is dominated by pollution Pb from atmospheric deposition. The ²⁰⁶Pb/²⁰⁷Pb ratios of the mor layer (O-horizon), forest plants and stream water (mainly between 1.14 and 1.20) are similar to atmospheric Pb pollution (1.14–1.19), while the local geogenic Pb of the mineral soil (C-horizon) has high ratios (>1.30). Roots and basal stemwood of the analyzed forest trees have higher ²⁰⁶Pb/²⁰⁷Pb ratios (1.15–1.30) than needles and apical stemwood (1.14–1.18), which indicate that the latter components are more dominated by pollution derived Pb. The low ²⁰⁶Pb/²⁰⁷Pb ratios of the mor layer suggest that the upward transport of Pb as a result of plant uptake is small (<0.04 mg m⁻² a⁻¹) in comparison to atmospheric inputs (∼0.5 mg m⁻² a⁻¹) and annual losses with percolating soil-water (∼2 mg m⁻² a⁻¹); consequently, the Pb levels in the mor layer are now decreasing while the pool of Pb in the mineral soil is increasing. Streams draining mires appear more strongly affected by pollution Pb than streams from forested catchments, as indicated by Pb concentrations about three times higher and lower ²⁰⁶Pb/²⁰⁷Pb ratios (1.16 ± 0.01 in comparison to 1.18 ± 0.02). To what extent stream water Pb levels will respond to the build-up of Pb in deeper mineral soil layers remains uncertain.     

A protracted timeline for lunar bombardment from mineral chemistry,Ti thermometry and U–Pb geochronology of Apollo 14 melt breccia zircons

New zircon U–Pb and trace element investigations from Apollo 14 lunar impact breccia sample #14311 reveal at least three distinct (Concordia, 2σ) age populations at 4334 ± 10, 4245 ± 10 and 3953 ± 10 Ma. Titanium-in-zircon thermometry (Ti ^xln ) results correlated with U–Pb ages range from ~800–1200 ºC. Lattice strain models used to infer zircon versus whole-rock rare earth element contents, and partitioning calculations against lunar impact breccia component compositions, quantitatively constrain formation conditions for the different age populations. A compilation of new data with published work shows that Apollo 14 zircons older than ca. 4300 Ma formed by igneous processes associated with lunar crust formation. Compositional variability in the ca. 4240 Ma zircon age population is interpretable, however, via a mixture of inherited and melt-generated components from one or more large impacts perhaps related to a marked increase in bombardment flux. Ages from the youngest zircon group at ca. 3950 Ma coincide with the classical “late heavy bombardment” (LHB) as documented from previous lunar geochronologies. These results lend support to the idea that instead of a simple unimodal LHB scenario, or a monotonic decline in impacts, the Moon was battered by multiple cataclysms since ca. 4240 Ma. Such a “Picket fence”-like bombardment to the Moon best describes the mode and tempo of impacts that accompanied the late stages of solar system formation and giant planet migration.     

Correlated microanalysis of zircon: Trace element, δO, and U-Th-Pb isotopic constraints on the igneous origin of complex >3900 Ma detrital grains

The origins of >3900 Ma detrital zircons from Western Australia are controversial, in part due to their complexity and long geologic histories. Conflicting interpretations for the genesis of these zircons propose magmatic, hydrothermal, or metamorphic origins. To test the hypothesis that these zircons preserve magmatic compositions, trace elements [rare earth elements (REE), Y, P, Th, U] were analyzed by ion microprobe from a suite of >3900 Ma zircons from Jack Hills, Western Australia, and include some of the oldest detrital zircons known (4400-4300 Ma). The same ∼20 μm domains previously characterized for U/Pb age, oxygen isotope composition (δ¹⁸O), and cathodoluminescence (CL) zoning were specifically targeted for analysis. The zircons are classified into two types based on the light-REE (LREE) composition of the domain analyzed. Zircons with Type 1 domains form the largest group (37 of 42), consisting of grains that preserve evolved REE compositions typical of igneous zircon from crustal rocks. Grains with Type 1 domains display a wide range of CL zoning patterns, yield nearly concordant U/Pb ages from 4400 to 3900 Ma, and preserve a narrow range of δ¹⁸O values from 4.7‰ to 7.3‰ that overlap or are slightly elevated relative to mantle oxygen isotope composition. Type 1 domains are interpreted to preserve magmatic compositions. Type 2 domains occur in six zircons that contain spots with enriched light-REE (LREE) compositions, here defined as having chondrite normalized values of La_N > 1 and Pr_N > 10. A subset of analyses in Type 2 domains appear to result from incorporation of sub-surface mineral inclusions in the analysis volume, as evidenced by positively correlated secondary ion beam intensities for LREE, P, and Y, which are anti-correlated to Si, although not all Type 2 analyses show these features. The LREE enrichment also occurs in areas with discordant U/Pb ages and/or high Th/U ratios, and is apparently associated with past or present radiation damage. The enrichment is not attributed to hydrothermal alteration, however, as oxygen isotope ratios in Type 2 domains overlap with magmatic values of Type 1 domains, and do not appear re-set as might be expected from dissolution or ion-exchange processes operating at variable temperatures. Thus, REE compositions in Type 2 domains where mineral inclusions are not suspected are best interpreted to result from localized enrichment of LREE in areas with past or present radiation damage, and with a very low fluid/rock ratio. Correlated in situ analyses allow magmatic compositions in these complex zircons to be distinguished from the effects of secondary processes. These results are additional evidence for preservation of magmatic compositions in Jack Hills zircons, and demonstrate the benefits of detailed imaging in studies of complicated detrital zircons of unknown origin. The data reported here support previous interpretations that the majority of >3900 Ma zircons from the Jack Hills have an origin in evolved granitic melts, and are evidence for the existence of continental crust very early in Earth’s history.     

The Pb-Pb age of Angrite SAH99555 revisited

Representing a suite of well-preserved basaltic meteorites with reported ages from 4566.18 ± 0.14 Ma to 4557.65 ± 0.13 Ma, angrites have been recurring targets for cross-calibrating extinct and absolute chronometers. However, inconsistencies exist in the available chronological data set, including a 4566.18 ± 0.14 Ma Pb-Pb age reported 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] for Sahara 99555 (herein SAH99555) that is significantly older than a Pb-Pb age for D’Orbigny, despite the two meteorites yielding indistinguishable Hf-W and Mn-Cr ages. We re-evaluate the Pb-Pb age of SAH99555 using a stepwise dissolution procedure on a whole rock fragment and a pyroxene separate. The combined data set yields a linear array that reflects a mixture of radiogenic Pb and terrestrial contamination and corresponds to an age of 4564.58 ± 0.14 Ma, which is 1.60 ± 0.20 Ma younger than that reported 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]. Our conclusion that SAH99555 crystallized at 4564.58 ± 0.14 Ma requires that all initial Pb was removed in the first progressive dissolution steps, an assertion supported by linearity of data generated by stepwise dissolution of a single fragment and the removal of an obvious highly-radiogenic component early in the dissolution process. We infer that the linear array defined 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] and their older age reflects a ternary mixture of Pb with constant relative proportions of highly-radiogenic initial Pb and radiogenic Pb with varying amounts of a terrestrial contamination. This requires that the phase harboring the initial Pb is insoluble in 2 M HCl, the only acid applied to the samples 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] prior to dissolution.     

Estimation of lead sources in a Japanese cedar ecosystem using stable isotope analysis

Anthropogenic Pb affects the environment worldwide. To understand its effect on forest ecosystem, Pb isotope ratios were determined in precipitation, various components of vegetation, the forest floor, soil and parent material in a Japanese cedar (Cryptomeria japonica D. Don) forest stand. The average ²⁰⁶Pb/²⁰⁷Pb ratio in bulk precipitation was 1.14 ± 0.01 (mean ± SD), whereas that in the subsoil (20–130 cm) was 1.18 ± 0.01. Intermediate ratios ranging from 1.15 to 1.16 were observed in the vegetation, the forest floor, and the surface soil (0–10 cm). Using the ²⁰⁶Pb/²⁰⁷Pb ratios, the contribution of anthropogenic sources to Pb accumulated in the forest were estimated by the simple binary mixing model. Sixty-two percent of the Pb in the forest floor, 71% in the vegetation, and 55% in the surface soil (0–10 cm) originated from anthropogenic sources, but only 16% in the sub-surface soil (10–20 cm) was anthropogenic. These results suggest that internal Pb cycling occurs mainly between surface soil and vegetation in a Japanese cedar ecosystem, and that anthropogenic Pb strongly influences Pb cycling. Although the Japanese cedar ecosystem has a shallow forest floor, very little atmospherically derived Pb migrated downward over 10 cm in depth.     

Seasonal variability in the input of lead, barium and indium to Law Dome, Antarctica

Lead (Pb) isotopic compositions and concentrations, and barium (Ba) and indium (In) concentrations have been determined at monthly resolution in five Law Dome (coastal Eastern Antarctica) ice core sections dated from ∼1757 AD to ∼1898 AD. ‘Natural’ background Pb concentrations in ∼1757 AD average ∼0.2 pg g⁻¹ and can be attributed to mineral dust and volcanic emissions, with ²⁰⁶Pb/²⁰⁷Pb ratios reaching up to 1.266 ± 0.002. From ∼1887 AD to ∼1898 AD, Pb concentrations reached ∼5 pg g⁻¹ and ²⁰⁶Pb/²⁰⁷Pb ratios decreased to 1.058 ± 0.001 as a result of additional inputs of Pb from anthropogenic sources. Seasonal variability in the late 1880s has been investigated by decoupling volcanic Pb from the total measured Pb concentrations, revealing spring and autumn maxima, and consistent winter minima, in anthropogenic Pb and mineral dust (Ba) concentrations. We link this variability to the annual cycle in the position and strength of the Antarctic Circumpolar Trough and, the Southern Ocean westerly winds to the north of the trough region. During the autumn and spring seasons, these systems increase in strength, transporting more impurity laden air from the Southern Hemisphere continental regions to Eastern Antarctica and Law Dome. As this Pb is isotopically identical to that emitted from south-eastern Australia (Broken Hill, Port Pirie) this implies a relatively direct air trajectory pathway from southern Australia to Law Dome (Eastern Antarctica).