From commodity to money: The rise of silver coinage around the Ancient Mediterranean (sixth-first centuries bce).

The reasons why the Western Mediterranean, especially Carthage and Rome, resisted monetization relative to the Eastern Mediterranean are still unclear. We address this question by combining lead (Pb) and silver (Ag) isotope abundances in silver coinage from the Aegean, Magna Graecia, Carthage and Roman Republic. The clear relationships observed between 109Ag/107Ag and 208Pb/206Pb reflect the mixing of silver ores or silver objects with Pb metal used for cupellation. The combined analysis of Ag and Pb isotopes reveals important information about the technology of smelting. The Greek world extracted Ag and Pb from associated ores, whereas, on the Iberian Peninsula, Carthaginians and Republican-era Romans applied Phoenician cupellation techniques and added exotic Pb to Pb-poor Ag ores. Massive Ag recupellation is observed in Rome during the Second Punic War. After defeating the Carthaginians and the Macedonians in the late second century bce, the Romans brought together the efficient, millennium-old techniques of silver extraction of the Phoenicians, who considered this metal a simple commodity, with the monetization of the economy introduced by the Greeks.

Author Correction: 2600-years of stratospheric volcanism through sulfate isotopes.

The authors became aware of a mistake in the data and axis labeling in Fig. 2 in the original version of the Article. Specifically, the authors mistakenly copied and pasted a formula for background correction instead of the actual values. As a result of this, Fig. 3 was updated to replace the incorrect label 'sulfate flux (kg km-2)' with the correct 'sulfate concentrations (ng g-1)' on the far-left y-axes in both panels, and to add the correct data for Δ33S, as given by the red dotted lines. The correct version of Fig. 3 is shown below as Fig. 1, which replaced the previous incorrect version, shown below as Fig. 2. This has been corrected in both the PDF and the HTML versions of the Article. The findings and interpretations in the original Article are based on the correct dataset, and this error does not affect the original discussion or conclusions of the Article. The authors apologize for the confusion caused by this mistake.

2600-years of stratospheric volcanism through sulfate isotopes.

High quality records of stratospheric volcanic eruptions, required to model past climate variability, have been constructed by identifying synchronous (bipolar) volcanic sulfate horizons in Greenland and Antarctic ice cores. Here we present a new 2600-year chronology of stratospheric volcanic events using an independent approach that relies on isotopic signatures (Δ33S and in some cases Δ17O) of ice core sulfate from five closely-located ice cores from Dome C, Antarctica. The Dome C stratospheric reconstruction provides independent validation of prior reconstructions. The isotopic approach documents several high-latitude stratospheric events that are not bipolar, but climatically-relevant, and diverges deeper in the record revealing tropospheric signals for some previously assigned bipolar events. Our record also displays a collapse of the Δ17O anomaly of sulfate for the largest volcanic eruptions, showing a further change in atmospheric chemistry induced by large emissions. Thus, the refinement added by considering both isotopic and bipolar correlation methods provides additional levels of insight for climate-volcano connections and improves ice core volcanic reconstructions.

A Zn isotope perspective on the rise of continents.

Zinc isotope abundances are fairly constant in igneous rocks and shales and are left unfractionated by hydrothermal processes at pH < 5.5. For that reason, Zn isotopes in sediments can be used to trace the changing chemistry of the hydrosphere. Here, we report Zn isotope compositions in Fe oxides from banded iron formations (BIFs) and iron formations of different ages. Zinc from early Archean samples is isotopically indistinguishable from the igneous average (δ(66) Zn ~0.3‰). At 2.9-2.7 Ga, δ(66) Zn becomes isotopically light (δ(66) Zn < 0‰) and then bounces back to values >1‰ during the ~2.35 Ga Great Oxygenation Event. By 1.8 Ga, BIF δ(66) Zn has settled to the modern value of FeMn nodules and encrustations (~0.9‰). The Zn cycle is largely controlled by two different mechanisms: Zn makes strong complexes with phosphates, and phosphates in turn are strongly adsorbed by Fe hydroxides. We therefore review the evidence that the surface geochemical cycles of Zn and P are closely related. The Zn isotope record echoes Sr isotope evidence, suggesting that erosion starts with the very large continental masses appearing at ~2.7 Ga. The lack of Zn fractionation in pre-2.9 Ga BIFs is argued to reflect the paucity of permanent subaerial continental exposure and consequently the insignificant phosphate input to the oceans and the small output of biochemical sediments. We link the early decline of δ(66) Zn between 3.0 and 2.7 Ga with the low solubility of phosphate in alkaline groundwater. The development of photosynthetic activity at the surface of the newly exposed continents increased the oxygen level in the atmosphere, which in turn triggered acid drainage and stepped up P dissolution and liberation of heavy Zn into the runoff. Zinc isotopes provide a new perspective on the rise of continents, the volume of carbonates on continents, changing weathering conditions, and compositions of the ocean through time.

Cryptic striations in the upper mantle revealed by hafnium isotopes in southeast Indian ridge basalts.

The Earth's mantle is isotopically heterogeneous on length scales ranging from centimetres to more than 10(4) kilometres. This heterogeneity originates from partial melt extraction and plate tectonic recycling, whereas stirring during mantle convection tends to reduce it. Here we show that mid-ocean ridge basalts from 2,000 km along the southeast Indian ridge (SEIR) display a bimodal hafnium isotopic distribution. This bimodality reveals the presence of ancient compositional striations (streaks) in the Indian Ocean upper mantle. The number density of the streaks is described by a Poisson distribution, with an average thickness of approximately 40 km. Such a distribution is anticipated for a well-stirred upper mantle, in which heterogeneity is continually introduced by plate tectonic recycling, and redistributed by viscous stretching and convective refolding.

Heterogeneous Hadean hafnium: evidence of continental crust at 4.4 to 4.5 ga.

The long-favored paradigm for the development of continental crust is one of progressive growth beginning at approximately 4 billion years ago (Ga). To test this hypothesis, we measured initial 176Hf/177Hf values of 4.01- to 4.37-Ga detrital zircons from Jack Hills, Western Australia. epsilonHf (deviations of 176Hf/177Hf from bulk Earth in parts per 10(4)) values show large positive and negative deviations from those of the bulk Earth. Negative values indicate the development of a Lu/Hf reservoir that is consistent with the formation of continental crust (Lu/Hf approximately 0.01), perhaps as early as 4.5 Ga. Positive epsilon(Hf) deviations require early and likely widespread depletion of the upper mantle. These results support the view that continental crust had formed by 4.4 to 4.5 Ga and was rapidly recycled into the mantle.

A short timescale for terrestrial planet formation from Hf-W chronometry of meteorites.

Determining the chronology for the assembly of planetary bodies in the early Solar System is essential for a complete understanding of star- and planet-formation processes. Various radionuclide chronometers (applied to meteorites) have been used to determine that basaltic lava flows on the surface of the asteroid Vesta formed within 3 million years (3 Myr) of the origin of the Solar System. Such rapid formation is broadly consistent with astronomical observations of young stellar objects, which suggest that formation of planetary systems occurs within a few million years after star formation. Some hafnium-tungsten isotope data, however, require that Vesta formed later (approximately 16 Myr after the formation of the Solar System) and that the formation of the terrestrial planets took a much longer time (62(-14)(+4504) Myr). Here we report measurements of tungsten isotope compositions and hafnium-tungsten ratios of several meteorites. Our measurements indicate that, contrary to previous results, the bulk of metal-silicate separation in the Solar System was completed within <30 Myr. These results are completely consistent with other evidence for rapid planetary formation, and are also in agreement with dynamic accretion models that predict a relatively short time (approximately 10 Myr) for the main growth stage of terrestrial planet formation.

Evidence from Sardinian basalt geochemistry for recycling of plume heads into the Earth's mantle.

Up to 10 per cent of the ocean floor consists of plateaux--regions of unusually thick oceanic crust thought to be formed by the heads of mantle plumes. Given the ubiquitous presence of recycled oceanic crust in the mantle source of hotspot basalts, it follows that plateau material should also be an important mantle constituent. Here we show that the geochemistry of the Pleistocene basalts from Logudoro, Sardinia, is compatible with the remelting of ancient ocean plateau material that has been recycled into the mantle. The Sr, Nd and Hf isotope compositions of these basalts do not show the signature of pelagic sediments. The basalts' low CaO/Al2O3 and Ce/Pb ratios, their unradiogenic 206Pb and 208Pb, and their Sr, Ba, Eu and Pb excesses indicate that their mantle source contains ancient gabbros formed initially by plagioclase accumulation, typical of plateau material. Also, the high Th/U ratios of the mantle source resemble those of plume magmas. Geochemically, the Logudoro basalts resemble those from Pitcairn Island, which contain the controversial EM-1 component that has been interpreted as arising from a mantle source sprinkled with remains of pelagic sediments. We argue, instead, that the EM-1 source from these two localities is essentially free of sedimentary material, the geochemical characteristics of these lavas being better explained by the presence of recycled oceanic plateaux. The storage of plume heads in the deep mantle through time offers a convenient explanation for the persistence of chemical and mineralogical layering in the mantle.

40K-(40)Ar constraints on recycling continental crust into the mantle

Extraction of potassium into magmas and outgassing of argon during melting constrain the relative amounts of potassium in the crust with respect to those of argon in the atmosphere. No more than 30% of the modern mass of the continents was subducted back into the mantle during Earth's history. It is estimated that 50 to 70% of the subducted sediments are reincorporated into the deep continental crust. A consequence of the limited exchange between the continental crust and the upper mantle is that the chemistry of the upper mantle is driven by exchange of material with the deep mantle.

Hf-Nd isotope evidence for a transient dynamic regime in the early terrestrial mantle

Modern basalts have seemingly lost all 'memory' of the primitive Earth's mantle except for an ambiguous isotopic signal observed in some rare gases. Although the Earth is expected to have reached a thermal steady state within several hundred million years of accretion, it is not known how and when the initial chemical fractionations left over from planetary accretion (and perhaps a stage involving a magma ocean) were overshadowed by fractionations imposed by modern-style geodynamics. Because of the lack of samples older than 4 Gyr, this early dynamic regime of the Earth is poorly understood. Here we compare published Hf-Nd isotope data on supracrustals from Isua, Greenland, with similar data on lunar rocks and the SNC (martian) meteorites, and show that, about 3.8 Gyr ago, the geochemical signature of the Archaean mantle was partly inherited from the initial differentiation of the Earth. The observed features seem to indicate that the planet at that time was still losing a substantial amount of primordial heat. The survival of remnants from an early layering in the modern deep mantle may account for some unexplained seismological, thermal and geochemical characteristics of the Earth as observed today.

Hf isotope evidence for pelagic sediments in the source of hawaiian basalts

Lead, oxygen, and osmium isotopic ratios measured on Hawaiian basalts can be matched with the isotopic ratios inferred for recycled ancient oceanic crust. High-precision hafnium isotopic data for lavas from several Hawaiian volcanoes identify old pelagic sediments in their source. These observations support the recycling hypothesis, whereby the mantle source of ocean island basalts includes ancient subducted oceanic crust. Hyperbolic lead-hafnium isotopic relations among Hawaiian basalts further indicate that upper mantle material is not involved in the production of hot spot basalts.

Lu-Hf Isotope Systematics of Garnet Pyroxenites from Beni Bousera, Morocco: Implications for Basalt Origin.

Six garnet pyroxenites from Beni Bousera, Morocco, yield a mean lutetium-hafnium age of 25 +/- 1 million years ago and show a wide range in hafnium isotope compositions (varepsilonHf = -9 to +42 25 million years ago), which exceeds that of known basalts (0 to +25). Therefore, primary melts of garnet pyroxenites cannot be the source of basalts. The upper mantle may be an aggregate of pyroxenites that were left by the melting of oceanic crust at subduction zones and peridotites that were contaminated by the percolation of melts from these pyroxenites. As a consequence, the concept of geochemical heterogeneities as passive tracers is inadequate. Measured lutetium-hafnium partitioning of natural minerals requires a reassessment of some experimental work relevant to mantle melting in the presence of garnet.

Short-lived chemical heterogeneities in the archean mantle with implications for mantle convection.

The neodymium isotope and samarium-neodymium systematics of 2.7-billion-year-old mantle-derived magmas indicate that the lifetime of chemical heterogeneities was much shorter in the Archean mantle than in the modern mantle. Isotopic evidence is compatible with a Rayleigh number 100 times larger and convection 10 times faster in the Late Archean compared with the present-day mantle. Modern plate tectonics thus may be an improbable analog for the Archean. Chemical heterogeneities in the mantle may originate upon magma migration and mineralogical phase changes rather than by recycling of oceanic and continental crust.

Dialysis-associated arthropathy: secondary ion mass spectrometry evidence of aluminum silicate in beta 2-microglobulin amyloid synovial tissue and articular cartilage.

The role of aluminum accumulation in articular tissues of patients affected by dialysis-associated arthropathy (DAA) is questioned. The aim of this work is to identify the nature of these aluminum accumulations by the use of secondary ion mass spectrometry (SIMS). Al/Si ratios of about 1, measured by SIMS, strongly suggest for the first time the presence of aluminum silicates and possibly aluminum hydroxides in amyloid synovial tissue and articular cartilage of 1 patient with DAA and aluminum intoxication. This is thermodynamically consistent with the total dissolved Al and Si contents and pH measured in the synovial fluids. These results are similar to the abnormal Al distribution recently found by SIMS in the forebrain of chronic renal dialysis patients and to the amorphous aluminum silicates identified in the core of senile plaques in Alzheimer's disease.