Volatile Chalcophile Elements Research Articles

Chondritic mercury isotopic composition of Earth and evidence for evaporative equilibrium degassing during the formation of eucrites

Variations in the abundances of moderately volatile elements (MVE) are one of the most fundamental geochemical differences between the terrestrial planets. Whether these variations are the consequence of nebular processes, planetary volatilization, differentiation or late accretion is still unresolved. The element mercury is the most volatile of the MVE and is a strongly chalcophile element. It is one of the few elements that exhibit large mass-dependent (MDF) and mass-independent (MIF) isotopic fractionations for both odd (odd-MIF, Δ199Hg and Δ201Hg) and even (even-MIF, Δ200Hg) Hg isotopes in nature, which is traditionally used to trace Hg biogeochemical cycling in surface environments. However, the Hg isotopic composition of Earth and meteorites is not well constrained. Here, we present Hg isotopic data for terrestrial basaltic, trachytic and granitic igneous samples. These rocks are isotopically lighter (δ202Hg = −3.3 ± 0.9‰; 1 standard deviation) than sedimentary rocks that have previously been considered to represent the terrestrial Hg isotope composition (δ202Hg=−0.7±0.5‰; 1 standard deviation). We show degassing during magma emplacement induces MIF that are consistent with kinetic fractionation in these samples. Also presented is a more complete dataset for chondritic (carbonaceous, ordinary and enstatite) meteorites, which are consistent with previous work for carbonaceous chondrites (positive odd-MIF) and ordinary chondrites (no MIF), and demonstrate that some enstatite chondrites exhibit positive odd-MIF, similar to carbonaceous chondrites. The terrestrial igneous rocks fall within the range of chondritic compositions for both MIF and MDF. Given the fact that planetary differentiation (core formation, evaporation) would contribute to Hg loss from the silicate portion of Earth and would likely fractionate Hg isotopes from chondritic compositions, we suggest that the budget of the mantle Hg is dominated by late accretion of chondritic materials to Earth, as also suggested for other volatile chalcophile elements (S, Se, Te). Considering the Hg isotopic signatures, materials with compositions similar to CO chondrites or ordinary chondrites are the most likely late accretion source candidates. Finally, eucrite meteorites, which are highly depleted in volatile elements, are isotopically heavier than chondrites and exhibit negative odd-MIF. The origin of volatile depletion in eucrites has been vigorously debated. We show that Δ199Hg versus Δ201Hg relationships point toward an equilibrium nuclear field shift effect, suggesting that volatile loss occurred during a magma ocean phase at the surface of the eucrite parent body, likely the asteroid 4-Vesta.

Volatile Chalcophile Elements in Native Sulfur from a Submarine Hydrothermal System at Kueishantao, Offshore NE Taiwan

We analyzed sulfur isotopes, trace elements and chalcophile elements (Se, Te, As, Sb, and Hg) in the native sulfur matrix from the Kueishantao hydrothermal system and conducted a systematic micro-analytical investigation. The sulfur matrix lacked all measured metals (e.g., Fe, Cu) and rare earth elements (REEs) while being significantly enriched in Te, As, Se (750–1500 ppm), Sb (around 100 ppm) and some Hg. The δ34S data (0.2–2.4‰) suggest a magmatic source leached from igneous rocks and a small contribution of seawater sulfates to the sulfur in hydrothermal deposits. Correlations between Te, As, Sb, and S (r2 = 0.30–0.61) indicate that these elements behave coherently in magmatic-hydrothermal processes. The enrichment factors and content ratios of these elements demonstrate their abundance in the sulfur matrix and minor fractionation after being partitioned into the metallic melt and forming a separate vapor phase to transport. Our study focuses on the native sulfur matrix in a shallow-water volcanic hydrothermal system, to which relatively little attention has previously been paid. This will expand our understanding of hydrothermal precipitates. The study of volatile chalcophile elements in the matrix will provide significant information about their sources, distributions and other geochemical behaviors in magmatic-hydrothermal processes and help to understand the Kueishantao hydrothermal circulation better.

Accretion and core formation: The effects of sulfur on metal–silicate partition coefficients

The accretion of the Earth was marked by the high-pressure segregation of the core, accompanied by dissolution of about 10% of one or more “light” elements into the metal. Cosmochemical data suggest that, of these 10% “light” elements, the core contains ∼1.7% S (Dreibus and Palme, 1996) and there is evidence that volatile elements such as S accreted to the Earth late in planetary growth, plausibly as a sulfide “matte” (O’Neill, 1991). Given that metallurgical data indicate that dissolution of even small amounts of sulfur in liquid Fe can have profound effects on the activities of some trace components, we have undertaken a study of the affect of S on the metal–silicate partitioning of a number of the most important chalcophile and siderophile elements.We performed experiments at 1.5GPa and 1460–1650°C on metal–silicate partitioning of W, Mo, Ni, Co, Cu, Ag, Mn, Cd, Tl, Cr, Sb, In, Pb, Ga, Ge, V and Zn under conditions where the S content of the metal was varied from 0 to 37wt%. Mn and Ag were found to exhibit the highest ratio of chalcophile to siderophile behaviour while W, Ga and Sb are the most “chalcophobic” of the elements studied. In terms of the 1-parameter epsilon model (Wagner, 1962) we derived values for each element at 1600°C as follows (negative values indicate chalcophile behaviour): εCuS=-2.57;εMnS=-6.41;εAgS=-4.15;εSbS=4.36;εCdS=-3.78;εInS=-0.24;εTlS=-6.21;εGaS=6.54;εPbS=-3.73;εCrS=-3.70;εGeS=7.03;εVS=-3.14;εZnS=-1.68;εMoS=2.27;εWS=6.47;εNiS=2.17;εCoS=2.40.We use these new data in conjunction with published pressure–temperature dependences of metal–silicate partitioning to test the effects of accreted S on the calculated trace element concentrations in bulk silicate Earth. The approach employs a continuous accretion model in which the oxidation state of the Earth and pressure of core segregation both increase during accretion. We find that, without addition of S in the latter stages of accretion, the Mo/W ratio of silicate Earth would be several times larger than that observed. Addition of ∼2% S accompanied by small amounts of carbon in the last 15% of accretion, however, enables us to match the observed concentrations of these elements in silicate Earth. This confirms an earlier conclusion that the Mo/W ratio of silicate Earth requires late sulfide addition to the core (Wade et al., 2012).Further support for late sulfide addition to the core comes from the depletion factors of volatile chalcophile elements Cu, Ga, Sb, Ag, Zn, Pb, Cd, In and Tl in silicate Earth relative to lithophile elements of similar volatility. We find that depletions of these elements are well correlated with their partition coefficients into sulfide (FeS) liquids at 1.5GPa and temperatures of 1460–1650°C. In contrast there is essentially no correlation between their depletion factors and sulfur-free liquid Fe–silicate partition coefficients.

Isotopic fractionation of Cu in tektites

Tektites are terrestrial natural glasses of up to a few centimeters in size that were produced during hypervelocity impacts on the Earth's surface. It is well established that the chemical and isotopic composition of tektites is generally identical to that of the upper terrestrial continental crust. Tektites typically have very low water content, which has generally been explained by volatilization at high temperature; however, the exact mechanism is still debated. Because volatilization can fractionate isotopes, comparing the isotopic composition of volatile elements in tektites with those of their source rocks may help to understand the physical conditions during tektite formation. Interestingly, volatile chalcophile elements (e.g., Cd and Zn) seem to be the only elements for which isotopic fractionation is known so far in tektites. Here, we extend this study to Cu, another volatile chalcophile element. We have measured the Cu isotopic composition for 20 tektite samples from the four known different strewn fields. All of the tektites (except the Muong Nong-types) are enriched in the heavy isotopes of Cu (1.98 < delta(61)Cu < 6.99) in comparison to the terrestrial crust (delta(65)Cu approximate to 0) with no clear distinction between the different groups. The Muong Nong-type tektites and a Libyan Desert Glass sample are not fractionated, (delta(65)Cu approximate to 0) in comparison to the terrestrial crust. To refine the Cu isotopic composition of the terrestrial crust, we also present data for three geological reference materials (delta(65)Cu approximate to 0). An increase of delta(65)Cu with decreasing Cu abundance probably reflects that the isotopic fractionation occurred by evaporation during heating. A simple Rayleigh distillation cannot explain the Cu isotopic data and we suggest that the isotopic fractionation is governed by a diffusion-limited regime. Copper is isotopically more fractionated than the more volatile element Zn (delta(66/64)Zn up to 2.49 parts per thousand). This difference of behavior between Cu and Zn is predicted in a diffusion-limited regime, where the magnitude of the isotopic fractionation is regulated by the competition between the evaporative flux and the diffusive flux at the diffusion boundary layer. Due to the difference of ionic charge in silicates (Zn(2+) vs. Cu(+)), Cu has a diffusion coefficient that is larger than that of Zn by at least two orders of magnitude. Therefore, the larger isotopic fractionation in Cu than in Zn in tektites is due to the significant difference in their respective chemical diffusivity. (C) 2009 Elsevier Ltd. All rights reserved.

The geochemistry of the volatile trace elements As, Cd, Ga, In and Sn in the Earth’s mantle: New evidence from in situ analyses of mantle xenoliths

The abundances of 30 trace elements, including the volatile chalcophile/siderophile elements As, Cd, Ga, In and Sn were determined by laser ablation ICP-MS in minerals of 19 anhydrous and 5 hydrous spinel peridotite xenoliths from three continents. The majority of samples were fertile lherzolites with more than 5% clinopyroxene; several samples have major element compositions close to estimates of the primitive mantle. All samples have been previously analysed for bulk-rock major, minor and lithophile trace elements. They cover a wide range of equilibration temperatures from about 850 to 1250 °C and a pressure range from 0.8 to 3.0 GPa. A comparison of results from bulk-rock analyses with concentrations obtained from combining silicate and oxide mineral data with modal mineralogy, gave excellent agreement, with the exception of As. Arsenic is the only element analysed that has high concentrations in sulphides. For all other elements sulphides can be neglected as host phases in these mantle rocks. The major host phase for Cd, In and Sn is clinopyroxene and if present, amphibole. Cadmium and In appear to behave moderately incompatibly during mantle melting similar to Yb. The data yield new and more reliable mantle abundances for Cd (35 ± 7 ppb), In (18 ± 3 ppb) and Sn (91 ± 28 ppb). The In value is similar to the Mg and CI-normalized Zn abundance of the mantle, although In is cosmochemically more volatile than Zn. The high In content suggests a high content of volatile elements in general in proto-Earth material. The lower relative abundances of volatile chalcophile elements such as Cd, S, Se and Te might be explained by sulphide segregation during core formation. The very low relative abundances of volatile and highly incompatible lithophile elements such as Br, Cl and I, and also C, N and rare gases, imply loss during Earth accretion, arguably by collisional erosion from differentiated planetesimals and protoplanets.

Cadmium, indium, tin, tellurium, and sulfur in oceanic basalts: Implications for chalcophile element fractionation in the Earth

Concentrations of S, Cd, In, Sn, and Te are reported for 80 samples of mid‐ocean ridge basalt (MORB), submarine and subaerial ocean island basalt (OIB) and submarine arc lavas. Cadmium, In, and Sn are moderately incompatible, and Te is compatible during partial melting. Cadmium is particularly uniform, consistent with a homogeneous distribution in the mantle. Tellurium is more variable (1–6 ppb) and is notably higher in Loihi, ranging up to 29 ppb, the most likely explanation for which is accumulation of Cu‐bearing sulfide. The average Cd/Dy ratio is the same (0.027) for OIB glasses, MORB glasses and the continental crust, yielding a primitive mantle Cd concentration of ∼18 ppb. Indium, despite being more volatile, is less depleted than Cd and the other very volatile chalcophile elements Pb, Bi, Tl, and Hg. From the depletion of In we deduce that core formation depleted the silicate Earth in Cd, Pb, Bi, Tl, and Hg by between factors of 5 and 10. The In depletion yields concentrations of C, S, Se, and Te in the core of C ∼1.2%, S &gt; 2.4%, Se &gt; 7.1 ppm, and Te &gt; 0.89 ppm. The Moon appears to be enriched in Te relative to the silicate Earth. Either a significant fraction of the Moon was derived from a more Te‐rich body or the silicate Earth's inventory of chalcophile and siderophile elements was depleted by further terrestrial core growth after formation of the Moon.

Fragments of ancient lunar crust: Petrology and geochemistry of ferroan noritic anorthosites from the Descartes region of the Moon

Clasts of ferroan noritic anorthosite from Apollo 16 breccia 67016 have mineralogical and geochemical affinities with pristine ferroan anorthosites and therefore may represent primary igneous rocks from the lunar crust. The textures of these clasts document a complex history involving magmatic crystallization, brecciation, subsolidus recrystallization, and sulfide metasomatism. Nonetheless, the major, minor, and trace element compositions of their minerals, as determined by electron and proton microprobe, show that the clasts are essentially monomict and belong to the ferroan anorthositic suite of lunar highlands rocks. The low bulk Ni contents, low Ni Co ratios, and ancient SmNd isotopic age (≥4.5 Ga; Alibert et al., 1994) of the clasts are consistent with this interpretation. Strontium and gallium contents of plagioclase in the clasts show that their parental magma was depleted in Ga relative to Sr by a factor of about 30 relative to carbonaceous chondrites. This depletion of Ga, which is both moderately volatile and moderately siderophile, probably reflects volatile loss from the Moon rather than extraction of metal. The parental magma from which these clasts originally crystallized was enriched in Sr by about 4–6X relative to proposed bulk Moon compositions, which implies either that ferroan anorthosites crystallized late in the evolution of a lunar magma ocean, or that their parental magma was a basaltic partial melt. Bulk major and trace element compositions of these clasts are remarkably similar to that of the average upper crust of the Moon, which suggests that igneous ferroan noritic anorthosite such as that found in the North Ray Crater breccias and soils may be a significant primary component of the lunar crust. The ferroan noritic anorthosite clasts in 67016 are unusual among lunar samples for their abundance of troilite, and for the evidence of metasomatic introduction of volatile chalcophile elements such as Cu, Zn, Ni, Sb, and Se. Anhydrous COSCl vapors are the most likely transport agent for these metals, which would be more consistent with an indigenous lunar origin for the volatiles rather than a cometary or meteoritic source.

An extremely low [formula omitted] source in the Moon: UThPb, SmNd, RbSr, and [formula omitted] isotopic systematics and age of lunar meteorite Asuka 881757

We have undertaken UThPb, SmNd, RbSr, and 40Ar 39Ar isotopic studies on Asuka 881757, a coarse-grained basaltic lunar meteorite whose chemical composition is close to low-Ti and very low-Ti (VLT) mare basalts. The PbPb internal isochron obtained for acid leached residues of separated mineral fractions yields an age of 3940 ± 28 Ma, which is similar to the U-Pb (3850 ± 150 Ma) and Th-Pb (3820 ± 290 Ma) internal isochron ages. The Sm-Nd data for the mineral separates yield an internal isochron age of 3871 ± 57 Ma and an initial 143Nd 144Nd value of 0.50797 ± 10. The Rb-Sr data yield an internal isochron age of 3840 ± 32 Ma ( λ( 87Rb) = 1.42 × 10 −11 yr −1 ) and a low initial 87Sr 86Sr ratio of 0.69910 ± 2. The 40Ar 39Ar age spectra for a glass fragment and a maskelynitized plagioclase are relatively flat and give a weighted mean plateau age of 3798 ± 12 Ma. We interpret these ages to indicate that the basalt crystallized from a melt 3.87 Ga ago (the Sm-Nd age) and an impact event disturbed the Rb-Sr system and completely reset the K-Ar system at 3.80 Ga. The slightly higher Pb-Pb age compared to the Sm-Nd age could be due to the secondary Pb (from terrestrial and/or lunar surface Pb contamination) that remained in the residues after acid leaching. Alternatively, the following interpretation is also possible; the meteorite crystallized at 3.94 Ga (the Pb-Pb age) and the Sm-Nd, Rb-Sr, and K-Ar systems were disturbed by an impact event at 3.80 Ga. The crystallization age obtained here is older than those reported for low-Ti basalts (3.2–3.5 Ga) and for VLT basalts (3.4 Ga), but similar to ages of some mare basalts, indicating that the basalt may have formed from a magma related to a basin-forming event (Imbrium?). The age span for VLT basalts from different sampling sites suggest that they were erupted over a wide area during an interval of at least ~500 million years. The impact event that thermally reset the K-Ar system of Asuka 881757 must have been post-Imbrium (perhaps Orientale) in age. The lead isotopic composition of Asuka 881757 is nonradiogenic compared with typical Apollo mare basalts and the estimated 238U 204Pb (μ) value for the basalt source is 10 ± 3. This source-μ value is the lowest so far measured for lunar rocks. A large positive ϵ Nd value (7.4 ± 0.5) and the time averaged 147Sm 144Nd ratio for the basalt source are similar to those for some Apollo 12, 15, and 17 basalts, suggesting a LREE-depleted mantle, which is consistent with the global magma ocean hypothesis. The U-Th-Pb, Sm-Nd, and Rb-Sr data on Asuka 881757 suggest that the basalt was derived from a low U Pb , low Rb Sr , and high Sm Nd source region, mainly composed of olivine and orthopyroxene with minor amounts of plagioclase (or clinopyroxene) and with sulfides enriched in volatile chalcophile elements. The basalt source may be deep in origin and different in chemistry from those previously estimated from studies of Apollo and Luna mare basalts, indicating heterogeneous sources for mare basalts.

Core formation in the Earth and Shergottite Parent Body (SPB): Chemical evidence from basalts

Constraints on processes of core formation in terrestrial planets may be inferred from the abundances of siderophile and chalcophile elements in their mantles. Of particular interest is a comparison of processes of core formation in the Earth and in the Shergottite Parent Body (SPB), a terrestrial planet tentatively inferred to be Mars. To this end, we (i) present new INAA and RNAA analyses of the non-Antarctic SNC meteorites, (ii) infer the composition of the SPB mantle from the compositions of the SNC meteorites, (iii) infer the composition of the Earth's mantle from the compositions of terrestrial basalts, and (iv) deconvolve the effects of volatile depletion, core formation, and mineral/melt fractionation on the abundances of siderophile and chalcophile elements in the SPB and the Earth. Element abundances in the mantles of the SPB and the Earth are estimated from element/element correlations observed among basalt samples. In basalts from the SPB (the SNC meteorites), four groups of covariant elements are observed: highly incompatible, moderately incompatible, indifferent and compatible. From correlations within these groups, the SPB mantle is found to be depleted in volatile elements, and strongly depleted in siderophile and chalcophile elements. For the Earth, the element/element correlation method gives a mantle composition similar to previous estimates. Compared to the Earth, the SPB mantle is richer in moderately siderophile elements (e.g., W, P), consistent with its inferred higher oxidation state. Chalcophile elements in the SPB mantle are more depleted than in the Earth's mantle, particularly when compared to estimates of the original abundances of volatile chalcophile elements in the two planets. In the SPB mantle, the NiCo ratio is nonchondritic, in contrast to the chondritic ratio in the Earth's mantle. Abundances of siderophile and chalcophile elements in the SPB mantle may be modelled by equilibrium with solid metal and metallic sulfide liquid, with some metal and sulfide trapped in the mantle (i.e., homogeneous accretion and inefficient core formation). Neither this model nor a heterogeneous accretion model is satisfactory in explaining element abundances in the Earth's mantle, particularly the abundances of Ni, Co, Mo, and W. Nevertheless it appears that core formation in the SPB and the Earth left quite different chemical signatures in their planetary mantles.

Chemical and physical studies of type 3 chondrites—V: The enstatite chondrites

We report instrumental neutron activation analysis determinations of 19 major, minor and trace elements in three enstatite chondrites. Based on these, and literature data on the bulk and mineral composition of enstatite chondrites, we discuss the history of the type 3 or unequilibrated enstatite chondrites, and their relationship with the other enstatite chondrites. The type 3 enstatite chondrites have E chondrite lithophile element abundances and their siderophile element abundances place them with the EH chondrites, well resolved from the EL chondrites. Moderately volatile chalcophile elements are at the low end of the EH range and Cr appears to be intermediate between EH and EL. We suggest that the type 3 enstatite chondrites are EH chondrites which have suffered small depletions of certain chalcophile elements through the loss of shock-produced sulfurous liquids. The oxygen isotope differences between type 3 and other enstatite chondrites is consistent with equilibration with the nebula gas ~30° higher than the others, or with the loss of a plagioclase-rich liquid. The mineral chemistry of the type 3 chondrites is consistent with either low temperature equilibration, or, in some instances, with shock effects.