The lead and copper isotopic composition of copper ores from the Sierra Morena (Spain)

The paper presents lead and copper isotope analyses of 51 copper ore samples from the Sierra Morena, South of Spain. They are from ancient mines of the Iberian Peninsula collected by Claude Domergue during various field campaigns in the central Sierra Morena from 1965 to 1975. Most samples consist of copper oxide minerals such as malachite, azurite and chrysocolla and stem from the surficial sections of the ore deposits. The aim of the study was to supplement the existing reference data bank on lead isotopic compositions of ancient copper mines from the Iberian Peninsula. This is particularly important for the Sierra Morena for which data exist mostly for lead-zinc but not for copper ores. The lead isotope ratios range from 18.165 to 19.712 (206Pb/204Pb), 0.797 to 0.859 (207Pb/206Pb) and 1.955 to 2.108 (208Pb/206Pb). Two separate fields can be distinguished with a major field intermediate between the ore deposits from SW and SE Spain and a second at higher 208Pb/206Pb values. Copper isotopes were analysed additionally to provide further constraints for provenance studies. The copper isotope ratios δ65Cu of the copper oxide samples are mostly positive and higher on average than those of sulphide minerals. They are a potential tool to distinguish between either sulphide ore or oxide ore deposit derived artefacts.En este artículo, presentamos los resultados de los análisis isotópicos (plomo y cobre) llevados a cabo sobre 51 muestras de mineral de cobre de Sierra Morena, Sur de España. Las muestras provienen de minas antiguas de la Península Ibérica, que habían sido recogidas por Claude Domergue en el curso de sus prospecciones en Sierra Morena central, entre 1965 y 1975. La mayoría de las muestras consiste de minerales de óxido de cobre como malaquita, azurita y crisocola que se encuentran en la superficie de los depósitos. El objetivo de este estudio es de contribuir a la base hoy disponible de datos de isótopos de plomo de las antiguas minas de cobre en la Península Ibérica. Este objetivo es particularmente importante puesto que la mayoría de los datos publicados de Sierra Morena se refieren a minerales de plomo-zinc. Las proporciones de isótopos de plomo varían entre 18.165 y 19.713 206Pb/204Pb, de 0.797 a 0.859 207Pb/206Pb, y de 1.955 a 2.108 208Pb/206Pb. Se pueden distinguir dos zonas independientes: una zona principal que se sitúa entre los depósitos de España del sudoeste y sudeste y una segunda zona con las proporciones de isótopos de plomo más altas. Además, los isótopos del cobre fueron analizados para suplir restricciones adicionales en los estudios de proveniencia. Las proporciones de isótopos de cobre, δ65Cu/63Cu, fueron analizadas en los óxidos de cobre y son en la mayor parte positivas y mas altas en medio que las proporciones δ65Cu de los sulfuros de cobre. Los resultados presentan un instrumento eficiente para distinguir los artefactos elaborados de minerales de sulfuros de cobre o de minerales de óxido de cobre

Exact steady state solution of the Boltzmann equation: A driven 1-D inelastic Maxwell gas

The exact nonequilibrium steady state solution of the nonlinear Boltzmann equation for a driven inelastic Maxwell model was obtained by Ben-Naim and Krapivsky [Phys. Rev. E 61, R5 (2000)] in the form of an infinite product for the Fourier transform of the distribution function $f(c)$. In this paper we have inverted the Fourier transform to express $f(c)$ in the form of an infinite series of exponentially decaying terms. The dominant high energy tail is exponential, $f(c)\simeq A_0\exp(-a|c|)$, where $a\equiv 2/\sqrt{1-\alpha^2}$ and the amplitude $A_0$ is given in terms of a converging sum. This is explicitly shown in the totally inelastic limit ($\alpha\to 0$) and in the quasi-elastic limit ($\alpha\to 1$). In the latter case, the distribution is dominated by a Maxwellian for a very wide range of velocities, but a crossover from a Maxwellian to an exponential high energy tail exists for velocities $|c-c_0|\sim 1/\sqrt{q}$ around a crossover velocity $c_0\simeq \ln q^{-1}/\sqrt{q}$, where $q\equiv (1-\alpha)/2\ll 1$. In this crossover region the distribution function is extremely small, $\ln f(c_0)\simeq q^{-1}\ln q$.Comment: 11 pages, 4 figures; a table and a few references added; to be published in PR

Inclusions in sublithospheric diamonds: Glimpses of deep Earth

Diamonds originate in the deep roots of ancient continental blocks (cratons) that extend into the diamond stability field beneath about 140 km. Over the last two decades, rare diamonds derived from even greater depths—the deep upper mantle, the transition zone (410-660 km), and the lower mantle—have been recognized. Inclusions in diamonds from the deep upper mantle and the transition zone document sources of basaltic composition, possibly related to subduction of old oceanic crust back into Earth's mantle. Diamonds from the lower mantle carry inclusions that largely confirm predictions of the composition and mineralogy of the deep mantle based on a “pyrolite” (primitive peridotitic) composition of silicate Earth. For some inclusions, however, the chemical evidence again points to a connection with subducting oceanic slabs, possibly ponding at the top of the lower mantle

Peridotitic diamonds from Namibia: constraints on the composition and evolution of their mantle source

About half the diamonds studied from the Cenozoic placer deposits along the Namibian coast belong to the peridotitic suite. The peridotitic mantle source is heterogeneous ranging from lherzolitic to strongly Ca depleted (down to 0.24 wt.% CaO in garnet) and shows large variations in Cr/Al ratio, illustrated by very low to very high Cr2O3 contents in garnet (2.6–17.3 wt.%). The Cr-rich end of this range includes exceptionally high Cr2O3 contents in Mg-chromite (70.7 wt.%) and clinopyroxene (3.6 wt.%). Garnet-olivine thermometry appears to indicate two groups, one that equilibrated at temperatures between 1200 and 1220°C and a second between 960 and 1100°C. Combined estimates of pressure and temperature based on garnet-orthopyroxene pairs indicate a large variance in geothermal gradients, corresponding to 38–42 mW/m2 surface heat flow. The trace-element composition of peridotitic garnet inclusions (determined by SIMS) also indicates large diversity. Two principal groups, corresponding to different styles of metasomatic source enrichment, are recognized. The first group ranges from extremely LREEN-depleted patterns, through trough-shaped REEN to sinusoidal patterns with the position of the first peak gradually moving from the LREEN to the MREEN. This series of REE patterns is interpreted to reflect a range of metasomatic agents with decreasing LREE/HREE. Only in the case of the two garnets with REEN peaking at Sm–Eu is this process connected with enrichment in Zr, without significant introduction of Y and Ti. The metasomatism responsible is interpreted as reflecting percolation of CHO-fluids through harzburgite under sub-solidus conditions. A second group of garnets shows an increase from LREEN–MREEN and almost flat (lherzolitic garnet) to moderately declining MREEN–HREEN at super-chondritic levels. This second style of metasomatism is caused by an agent carrying HFSE and showing only moderate enrichment in LREE over HREE, which points towards silicate melts

Li abundances in inclusions in diamonds from the upper and lower mantle

Lithium abundances in inclusions in diamonds of peridotitic, websteritic, eclogitic (including garnets with majoritic component) and lower mantle paragenesis were determined with the ion microprobe. The partitioning of Li both between olivine and clinopyroxene and clinopyroxene and garnet appears to be pressure-dependent in peridotites. More importantly, garnets containing a majorite component show a dramatic increase in Li solubility so that even for mildly majoritic garnets Dcpx/majorite is smaller than one. Lower mantle ferropericlase is a sink for lithium, containing several hundred times more Li than coexisting Mg-perovskite. Lithium decreases in olivine inclusions with increasing forsterite content, which we interpret as reflecting a depletion event in the protoliths of the inclusions. We also infer that lithium was not re-enriched in the silicate phases by a metasomatic agent during diamond formation unlike other trace elements like REE and HFSE. Depletion on partial melting and no re-enrichment also seems to hold for the eclogitic suite of inclusions where cpx's (and deduced bulk composition) have similar Li abundances as in the peridotitic suite and are significantly lower than in crustal eclogites. For the lower mantle bulk, lithium estimates give values four to five times higher than primitive mantle. This may relate either to local enrichment through fluid/melt metasomatism similarly as for spinel lherzolites or high Li abundances in lower mantle diamonds sources are inherited from crustal protoliths

Mineral inclusions in diamonds from the Panda kimberlite, Slave Province, Canada

Tappert, Ralf; Stachel, Thomas; Harris, Jeffrey W.; Shimizu, Nobumichi; Brey, Gerhard P

Eclogitic and websteritic diamond sources beneath the Limpopo Belt - is slab-melting the link?

Trace-element concentrations in eclogitic and websteritic inclusions in diamonds from Venetia (South Africa) were analysed using an ion microprobe (SIMS). Garnets of both parageneses show similar, positive LREEN/HREEN slopes, but eclogitic garnets have higher MREE and almost flat MREEN–HREEN, and are also different in having significantly higher Sr and Zr. The occurrence of negative and positive Eu anomalies in garnets and clinopyroxenes of both parageneses points towards feldspar fractionation and accumulation in a magmatic precursor, suggesting subducted oceanic crust as a common protolith. Assuming equilibrium between clinopyroxene and garnet included in the same diamond, a bulk eclogite was reconstructed from these inclusions plus (expected) accessory rutile. The whole rock has a trace-element pattern lying between oceanic gabbro and EMORB, but is depleted in highly incompatible elements relative to these possible precursors. Quantitative modelling shows that relative and absolute trace-element abundances of the reconstructed eclogite and the hypothetical oceanic precursor agree if the latter is subjected to a loss of partial melts after subduction into the eclogite stability field. Major- and trace-element characteristics of websteritic inclusions could imply a more mafic precursor, which may have been part of a heterogeneous oceanic crust. However, new experimental data show that major- and trace-element compositions of websteritic inclusions in diamond are consistent with a mixing model in which they result from the reaction of slab-derived melts with surrounding mantle peridotite. This reaction generates major element contents that are intermediate between those of eclogitic and peridotitic sources whereas trace-element characteristics, such as Eu anomalies, are inherited from the melt source

Diamond formation and source carbonation: mineral associations in diamonds from Namibia

Mineral inclusions in diamonds from Namibia document a range of mantle sources, including eclogitic, websteritic and peridotitic parageneses. Based on unusual textural features a group of inclusions showing websteritic, peridotitic and transitional chemical features is assigned to an 'undetermined suite' (12% of the studied diamonds). The mutual characteristic of this group is the occurrence of lamellar intergrowths of clinopyroxene and orthopyroxene. In addition, the 'undetermined suite' is associated with a number of uncommon phases: in one diamond MgCO3 is enclosed by clinopyroxene. Other minerals that form touching inclusions with the pyroxene lamellae are (1) a SiO2 phase observed in three diamonds, together with CaCO3 in one of them, (2) phlogopite and a Cr-rich 'titanate' (probably lindsleyite). The inclusions document a metamorphic path of decreasing pressures and temperatures after entrapment in diamond. First, homogeneous low-Ca clinopyroxenes were entrapped at high temperatures. They subsequently exsolved orthopyroxene and probably also SiO2 (coesite) on cooling along a P,T trajectory that did not allow garnet to be exsolved as well. Phlogopite, carbonates and LIMA phases are the result of overprint of a peridotitic source rock by a carbon-rich agent. The resulting unusual, olivine-free mineral association and the host diamonds are interpreted as products of extensive carbonation of the peridotite

Ferropericlase - a lower mantle phase in the upper mantle

Experiments on compositions along the join MgO–NaA3+Si2O6 (A=Al, Cr, Fe3+) show that sodium can be incorporated into ferropericlase at upper mantle pressures in amounts commonly found in natural diamond inclusions. These results, combined with the observed mineral parageneses of several diamond inclusion suites, establish firmly that ferropericlase exists in the upper mantle in regions with low silica activity. Such regions may be carbonated dunite or stalled and degassed carbonatitic melts. Ferropericlase as an inclusion in diamond on its own is not indicative of a lower mantle origin or of a deep mantle plume. Coexisting phases have to be taken into consideration to decide on the depth of origin. The composition of olivine will indicate an origin from the upper mantle or border of the transition zone to the lower mantle and whether it coexisted with ferropericlase in the upper mantle or as ringwoodite. The narrow and flat three phase loop at the border transition zone—lower mantle together with hybrid peridotite plus eclogite/sediments provides an explanation for the varying and Fe-rich nature of the diamond inclusion suite from Sao Luiz, Brazil