Isotopic composition of zinc, copper, and iron in lunar samples

We determined by ICP-MS the concentrations and isotopic ratios of Fe, Cu, and Zn in the Ti-rich lunar basalt 74275, in the lunar orange glass 74220, and in up to 10 lunar soils, namely, 14163, 15231, 64501, 66041, 68841, 69941, 70011, 72501, 75081, and 76501. Two analyses of zinc in lunar basalt 74275 give δ⁶⁶Zn = 0.17‰ and 0.75‰, values within the range of those measured in terrestrial basalts; copper in lunar basalt 74275 has δ⁶⁵Cu  +1.4‰, which is isotopically heavier than values observed in terrestrial basalts. In the orange glass, we measured δ⁵⁶Fe = −0.24‰, δ⁶⁵Cu = −0.42‰, and δ⁶⁶Zn  −3.6‰. These values of δ are more negative than those obtained for 74275 and for typical lunar basalts, but for Cu, comparable to those observed in terrestrial sulfides and meteorites. In lunar soils we found 0.11‰  δ⁵⁶Fe  0.51‰, 2.6‰  δ⁶⁵Cu  4.5‰, and 2.2‰  δ⁶⁶Zn  6.4‰. Insofar as we can generalize from a small sample set, S, Fe, Cu, Zn, and Cd show similar trends in isotopic fractionation on the Moon. Lunar basalts have nearly terrestrial isotopic ratios. Relative to the lunar basalt 74275, the pyroclastic glass 74220 is enriched in the lighter isotopes of Fe, Cu, and Zn, and the soils are enriched in the heavier isotopes of Fe, Cu, and Zn. The patterns in the basalts are likely inherited from the source material; the light-isotope enrichments seen in the orange glass originated during lava fountaining or, less probably, during partial condensation of vapor; and the heavy-isotope enrichments in the lunar soils were likely created by a combination of processes that included micrometeorite vaporization and sputtering. In the orange glass, the light-isotope enrichments (relative to lunar basalts) of Zn are larger than those of Cu. If these enrichments reflect accurately the isotopic composition of the gas, they suggest that Cu is more volatile than Zn in the liquid from which the gas derived. A simple model built on the known flux of micrometeorites to the lunar surface and a published estimate that micrometeorites generate 10 times their own mass of vapor, predicts heavy-isotope enrichments comparable to those observed in soils but only if the regolith gardening rate is set at about one twentieth of the generally accepted value of 1 cm/My. This discrepancy may reflect the difference in the time constants for micrometeorite milling and decimeter-scale gardening, or the importance of sputtering.     

Geochemical relation between gas hydrates and water venting in the seismic blanking zone on the northern Cascadia continental margin offshore Vancouver Island, Canada

The isotopic composition (δD and δ¹⁸O) and chloride concentration (Cl⁻) of pore waters from the northern Cascadia continental margin offshore Vancouver Island were measured to characterize the relations between the water flow regime and the distribution, formation and dissociation of gas hydrates. The δD values of pore waters in gas hydrate-bearing sediments are slightly higher ( 1‰) than those of seawater as the result of gas hydrate dissociation during core recovery and handling. Within the seismic blanking zone, the δD values were slightly lower (− 1‰) than values measured from sites outside the blanking area (0‰). We attribute these differences to 1) distillation of D-rich water during hydrate formation in the center of the blanking zone and 2) limited migration of pore water between inside and outside of the blanking zone due to different fluid fluxes. In contrast, the δ¹⁸O values and Cl⁻ concentrations do not show significant spatial variation due to decreased isotopic fractionation of oxygen and small fraction of chloride relative to hydrogen isotope during gas hydrate formation. The δD value of pore water, therefore, appears to be a sensitive indicator of gas hydrate occurrence. We estimate that gas hydrate occupied at least 2.0 to 6.3% of sediment pore space using δD distribution in this area.     

Silicon isotope fractionation between plant parts in banana: In situ vs. in vitro

We recently showed that silicon isotopic fractionation in banana (Musa acuminata Colla, cv Grande Naine) was related to phytolith production, and therefore to silica content in plant. The present study focuses on isotopic fractionation between the different plant parts. Silicon isotopic compositions were measured using a Nu plasma multicollector plasma source mass spectrometer (MC–ICP–MS) operating in dry plasma mode. The results are expressed as δ²⁹Si relatively to the NBS28 standard, with an average precision and accuracy of ± 0.08‰ (± 2σ). On mature banana (Musa acuminata Colla, cv Grande Naine) from Cameroon, δ²⁹Si ranged from + 0.13‰ in the petiole to + 0.49‰ in the lamina, yielding to a 0.36‰ change towards heavier isotopic composition in the upper parts of the plant. This strongly accords with results obtained on in vitro banana plantlets cultivated in hydroponics, where the δ²⁹Si increase from pseudostems to lamina is 0.26‰. These preliminary results on in situ banana show a trend of intra-plant fractionation comparable with that of in vitro hydroponics banana plantlets and with previous data obtained on bamboo.     

Iron isotopes in acid mine waters and iron-rich solids from the Tinto–Odiel Basin (Iberian Pyrite Belt, Southwest Spain)

The isotopic composition of Fe was determined in water, Fe-oxides and sulfides from the Tinto and Odiel Basins (South West Spain). As a consequence of sulfide oxidation in mine tailings both rivers are acidic (1.45 < pH < 3.85) and display high concentrations of dissolved Fe (up to 420 mmol l^− 1) and sulphates (up to 1190 mmol l^− 1).The δ⁵⁶Fe of pyrite-rich samples from the Rio Tinto and from the Tharsis mine ranged from − 0.56 ± 0.08‰ to + 0.25 ± 0.1‰. δ⁵⁶Fe values for Fe-oxides precipitates that currently form in the riverbed varied from − 1.98 ± 0.10‰ to 1.57 ± 0.08‰. Comparatively narrower ranges of values (− 0.18 ± 0.08‰ and + 0.21 ± 0.14‰) were observed in their fossil analogues from the Pliocene–Pleistocene and in samples from the Gossan (the oxidized layer that formed through exposure to oxygen of the massive sulfide deposits) (− 0.36 ± 0.12‰ to 0.82 ± 0.07‰). In water, δ⁵⁶Fe values ranged from − 1.76 ± 0.10‰ to + 0.43 ± 0.05‰.At the source of the Tinto River, fractionation between aqueous Fe(III) and pyrite from the tailings was less than would be expected from a simple pyrite oxidation process. Similarly, the isotopic composition of Gossan oxides and that of pyrite was different from what would be expected from pyrite oxidation. In rivers, the precipitation of Fe-oxides (mainly jarosite and schwertmannite and lesser amounts of goethite) from water containing mainly (more than 99%) Fe(III) with concentrations up to 372 mmol l^− 1 causes variable fractionation between the solid and the aqueous phase (− 0.98‰ < Δ⁵⁶Fe_{solid–water} < 2.25‰). The significant magnitude of the positive fractionation factor observed in several Fe(III) dominated water may be related to the precipitation of Fe(III) sulphates containing phases.     

Diagenetic mineralization in Pennsylvanian coals from Indiana, USA: C/C and O/O implications for cleat origin and coalbed methane generation

Cleats and fractures in southwestern Indiana coal seams are often filled with authigenic kaolinite and/or calcite. Carbon- and oxygen-stable isotope ratios of kaolinite, calcite, and coalbed CO₂ were evaluated in combination with measured values and published estimates of δ¹⁸O of coalbed paleowaters that had been present at the time of mineralization. δ¹⁸O_mineral and δ¹⁸O_water values jointly constrain the paleotemperature of mineralization. The isotopic evidence and the thermal and tectonic history of this part of the Illinois Basin led to the conclusion that maximum burial and heat-sterilization of coal seams approximately 272 Ma ago was followed by advective heat redistribution and concurrent precipitation of kaolinite in cleats at a burial depth of < 1600 m at  78 ± 5 °C. Post-Paleozoic uplift, the development of a second generation of cleats, and subsequent precipitation of calcite occurred at shallower burial depth between  500 to  1300 m at a lower temperature of 43 ± 6 °C. The available paleowater in coalbeds was likely ocean water and/or tropical meteoric water with a δ¹⁸O_water  − 1.25‰ versus VSMOW. Inoculation of coalbeds with methanogenic CO₂-reducing microbes occurred at an even later time, because modern microbially influenced ¹³C-enriched coalbed CO₂ (i.e., the isotopically fractionated residue of microbial CO₂ reduction) is out of isotopic equilibrium with ¹³C-depleted calcite in cleats.     

Feldspathic clasts in Yamato-86032: Remnants of the lunar crust with implications for its formation and impact history

Low concentrations of Th and Fe in the Yamato (Y)-86032 bulk meteorite support earlier suggestions that Y-86032 comes from a region of the moon far distant from the Procellarum KREEP Terrain (PKT), probably from the lunar farside. ³⁹Ar–⁴⁰Ar, Rb–Sr, Sm–Nd, and Sm-isotopic studies characterize the chronology of Y-86032 and its precursors in the mega regolith. One of the rock types present in a light gray breccia lithology is an anorthosite characterized by plagioclase with An 93, i.e., more sodic than lunar FANs, but with very low ⁸⁷Rb/⁸⁶Sr and ⁸⁷Sr/⁸⁶Sr similar to those of FANs. (FAN stands for Ferroan Anorthosite). This “An93 anorthosite” has Nd-isotopic systematics similar to those of nearside norites. A FAN-like “An97 anorthosite” is present in a second light-colored feldspathic breccia clast and has a more negative ε_Nd value consistent with residence in a LREE-enriched environment as would be provided by an early plagioclase flotation crust on the Lunar Magma Ocean (LMO). This result contrasts with generally positive values of ε_Nd for Apollo 16 FANs suggesting the possibility of assymetric development of the LMO. Other possible explanations for the dichotomy in ε_Nd values are advanced in the text. The Y-86032 protolith formed at least 4.43 ± 0.03 Ga ago as determined from a Sm–Nd isochron for mineral fragments from the breccia clast composed predominantly of An93 anorthosite and a second clast of more varied composition. We interpret the mineral fragments as being predominatly from a cogenetic rock suite. An ³⁹Ar–⁴⁰Ar age of 4.36–4.41 ± 0.035 Ga for a third clast composed predominantly of An97 anorthosite supports an old age for the protolith. Initial ¹⁴³Nd/¹⁴⁴Nd in that clast was −0.64 ± 0.13 ε-units below ¹⁴³Nd/¹⁴⁴Nd in reservoirs having chondritic Sm/Nd ratios, consistent with prior fractionation of mafic cumulates from the LMO. A maximum in the ³⁹Ar–⁴⁰Ar age spectrum of 4.23 ± 0.03 Ga for a second sample of the same feldspathic breccia clast probably reflects some diffusive ⁴⁰Ar loss. Lack of solar wind and lunar atmosphere implanted Ar in the light gray breccia clast allows determination of an ³⁹Ar/⁴⁰Ar age of 4.10 ± 0.02 Ga, which is interpreted as the time of initial brecciation of this litholgy. After correction for implanted lunar atmosphere ⁴⁰Ar, impact melt and dark regolith clasts give Ar ages of 3.8 ± 0.1 Ga implying melt formation and final breccia assembly 3.8 Ga ago. Some breccia lithologies were exposed to thermal neutron fluences of 2 × 10¹⁵ n/cm², only about 1% of the fluence experienced by some other lunar highlands meteorites. Other lithologies experienced neutron fluences of 1 × 10¹⁵ n/cm². Thus, Y-86032 spent most of the time following final brecciation deeply buried in the megaregolith. The neutron fluence data are consistent with cosmogenic ³⁸Ar_cos cosmic ray exposure ages of 10 Ma. Variations among differing lithologies in the amount of several regolith exposure indicators, including cosmogenic noble gas abundances, neutron capture induced variations in Sm isotopic abundances, and Ir contents, are consistent with a period of early (>3.8 Ga ago) lunar regolith exposure, subsequent deep burial at >5 m depth, and ejection from the moon 7–10 Ma ago.     

Equilibrium H/H fractionations in organic molecules. II: Linear alkanes, alkenes, ketones, carboxylic acids, esters, alcohols and ethers

Equilibrium ²H/¹H fractionation factors (α_eq) for various H positions in alkanes, alkenes, ketones, carboxylic acids, esters, alcohols, and ethers were calculated between 0 and 100 °C using vibrational frequencies from ab initio QM calculations (B3LYP/6-311G**). Results were then corrected using a temperature-dependent linear calibration curve based on experimental data for H_α in ketones (Wang et al., 2009). The total uncertainty in reported α_eq values is estimated at 10–20‰. The effects of functional groups were found to increase the value of α_eq for H next to electron-donating groups, e.g. OR, OH or O(CO)R, and to decrease the value of α_eq for H next to electron-withdrawing groups, e.g. (CO)R or (CO)OR. Smaller but significant functional group effects are also observed for H_β and sometimes H_γ. By summing over individual H positions, we estimate the equilibrium fractionation relative to water to be −90‰ to −70‰ for n-alkanes and around −100‰ for pristane and phytane. The temperature dependence of these fractionations is very weak between 0 and 100 °C. Our estimates of α_eq agree well with field data for thermally mature hydrocarbons (δ²H values between −80‰ and −110‰ relative to water). Therefore the observed δ²H increase of individual hydrocarbons and the disappearance of the biosynthetic δ²H offset between n-alkyl and linear isoprenoid lipids during maturation of organic matter can be confidently attributed to H exchange towards an equilibrium state. Our results also indicate that many n-alkyl lipids are biosynthesized with δ²H values that are close to equilibrium with water. In these cases, constant down-core δ²H values for n-alkyl lipids cannot be reliably used to infer a lack of isotopic exchange.     

Chemical and chronologic complexity in the convecting upper mantle: Evidence from the Taitao ophiolite, southern Chile

Exposure of the ca. 6 Ma Taitao ophiolite, Chile, located 50 km south of the Chile Triple Junction, allows detailed chemical and isotopic study of rocks that were recently extracted from the depleted mantle source of mid-ocean ridge basalts (DMM). Ultramafic and mafic rocks are examined for isotopic (Os, Sr, Nd, and O), and major and trace element compositions, including the highly siderophile elements (HSE). Taitao peridotites have compositions indicative of variable extents of partial melting and melt extraction. Low δ¹⁸O values for most whole rock samples suggest some open-system, high-temperature water–rock interaction, most likely during serpentinization, but relict olivine grains have δ¹⁸O values consistent with primary mantle values. Most of the peridotites analyzed for Nd–Sr isotopes have compositions consistent with estimates for the modern DMM, although several samples are characterized by ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd indicative of crustal contamination, most likely via interactions with seawater. The peridotites have initial ¹⁸⁷Os/¹⁸⁸Os ratios that range widely from 0.1168 to 0.1288 (γ_Os = −8.0 to +1.1), averaging 0.1239 (γ_Os = −2.4), which is comparable to the average for modern abyssal peridotites. A negative correlation between the Mg^# of relict olivine grains and Os isotopic compositions of whole rock peridotites suggests that the Os isotopic compositions reflect primary mantle Re/Os fractionation produced by variable extents of partial melting at approximately 1.6 Ga. Recent re-melting at or near the spatially associated Chile Ridge further modified these rocks, and Re, and minor Pt and Pd were subsequently added back into some rocks by late-stage melt–rock or fluid–rock interactions.In contrast to the peridotites, approximately half of the mafic rocks examined have whole rock δ¹⁸O values within the range of mantle compositions, and their Nd and Sr isotopic compositions are all generally within the range of modern DMM. These rocks have initial ¹⁸⁷Os/¹⁸⁸Os ratios, calculated for 6 Ma, that range from 0.126 (γ_Os = −1) to as high as 0.561 (γ_Os = +342). The Os isotopic systematics of each of these rocks may reflect derivation from mixed lithologies that include the peridotites, but may also include pyroxenites with considerably more radiogenic Os than the peridotites. This observation supports the view that suprachondritic Os present in MORB derives from mixed mantle source lithologies, accounting for some of the worldwide dichotomy in ¹⁸⁷Os/¹⁸⁸Os between MORB and abyssal peridotites.The collective results of this study suggest that this >500 km³ block of the mantle underwent at least two stages of melting. The first stage occurred at 1.6 Ga, after which the block remained isolated and unmixed within the DMM. A final stage of melting recently occurred at or near the Chile Ridge, resulting in the production of at least some of the mafic rocks. Convective stirring of this mantle domain during a >1 Ga period was remarkably inefficient, at least with regard to Os isotopes.     

Investigation of the fate of nitrogen in Palaeozoic shales of the Central European Basin

Nitrogen geochemistry of Upper Carboniferous shales from the Central European Basin (CEB) was investigated by elemental analysis, stable isotope mass spectrometry and non-isothermal pyrolysis. Total N-contents of Namurian shales from four deep wells (4400–7000 m) in NE Germany ranged between 520 and 2680 ppm. Up to 90% of this nitrogen occurs as ammonium in minerals with δ¹⁵N values between + 1‰ and + 3.5‰. Low nitrogen contents (down to 460 ppm) and high δ¹⁵N values (up to + 5.6‰) in one well in the basin centre suggest a large-scale release of nitrogen associated with isotopic fractionation. Pyrolytic liberation of N₂ from pelagic Namurian A shales of NW and NE Germany occurred at significantly lower temperatures than from paralic Namurian B shales and terrestrial Westphalian samples. On-line isotope analysis of N₂ liberated between 400 and 1200 °C indicates the presence of precursor pools with different thermal stability and nitrogen isotopic composition.     

Two magma series and associated ore deposit types in the Permian Emeishan large igneous province, SW China

The Late Middle Permian ( 260 Ma) Emeishan large igneous province in SW China contains two magmatic series, one comprising high-Ti basalts and Fe-rich gabbroic and syenitic intrusions, the other low-Ti basalts and mafic–ultramafic intrusions. The Fe-rich gabbros are spatially and temporally associated with syenites. Each series is associated with a distinctive type of mineralization, the first with giant Fe–Ti–V oxide ore deposits such as Panzhihua and Baima, the second with Ni–Cu–(PGE) sulfide deposits such as Jinbaoshan, Limahe and Zhubu. New SHRIMP zircon U–Pb isotopic data yielded 263 ± 3 Ma for the Limahe intrusion, 261 ± 2 Ma for the Zhubu intrusion and 262 ± 2 Ma for a syenitic intrusion. These new age dates, together with previously reported SHRIMP zircon U–Pb ages, suggest that all these intrusions are contemporaneous with the Emeishan flood basalts and formed during a major igneous event at ca. 260 Ma.The oxide-bearing intrusions have higher Al₂O₃, FeO (as total iron) and total alkalis (Na₂O + K₂O) but lower MgO than the sulfide-bearing intrusions. All intrusions are variably enriched in LREE relative to HREE. The oxide-bearing intrusions display positive Nb- and Ti-anomalies and in certain cases negative Zr–Hf anomalies, whereas the sulfide-bearing intrusions have obvious negative Nb- and Ti-anomalies, a feature of crustal contamination. Individual intrusions have relatively small ranges of Nd(t) values. All the intrusions, however, have Nd(t) values ranging from − 3.9 to + 4.6, and initial ⁸⁷Sr/⁸⁶Sr ratios from 0.7039 to 0.7105. The syenites have very low MgO (< 2 wt.%) but highly variable Fe₂O₃ (2.5 to 13 wt.%) with initial ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.7039 to 0.7089. Magmas from both series could have derived by melting of a heterogeneous mantle plume: the high-Ti series from a Fe-rich, more fertile source and the low-Ti series from a Fe-poor, more refractory source. In addition, the low-Ti series underwent significant crustal contamination. The two magma series evolved along different paths that led to distinct mineralization styles.     

Oxygen isotopic fractionation during inorganic calcite precipitation ― Effects of temperature, precipitation rate and pH

Stable oxygen isotopic fractionation during inorganic calcite precipitation was experimentally studied by spontaneous precipitation at various pH (8.3 < pH < 10.5), precipitation rates (1.8 < log R < 4.4 μmol m^− 2 h^− 1) and temperatures (5, 25, and 40 °C) using the CO₂ diffusion technique.The results show that the apparent stable oxygen isotopic fractionation factor between calcite and water (α_{calcite–water}) is affected by temperature, the pH of the solution, and the precipitation rate of calcite. Isotopic equilibrium is not maintained during spontaneous precipitation from the solution. Under isotopic non-equilibrium conditions, at a constant temperature and precipitation rate, apparent 1000lnα_{calcite–water} decreases with increasing pH of the solution. If the temperature and pH are held constant, apparent 1000lnα_{calcite–water} values decrease with elevated precipitation rates of calcite. At pH = 8.3, oxygen isotopic fractionation between inorganically precipitated calcite and water as a function of the precipitation rate (R) can be described by the expressions

at 5, 25, and 40 °C, respectively.The impact of precipitation rate on 1000lnα_{calcite–water} value in our experiments clearly indicates a kinetic effect on oxygen isotopic fractionation during calcite precipitation from aqueous solution, even if calcite precipitated slowly from aqueous solution at the given temperature range. Our results support Coplen's work [Coplen T. B. (2007) Calibration of the calcite–water oxygen isotope geothermometer at Devils Hole, Nevada, a natural laboratory. Geochim. Cosmochim. Acta 71, 3948–3957], which indicates that the equilibrium oxygen isotopic fractionation factor might be greater than the commonly accepted value.     

Geology, mineralogy and stable isotope geochemistry of the Kabwe carbonate-hosted Pb–Zn deposit, Central Zambia

The carbonate-hosted Kabwe Pb–Zn deposit, Central Zambia, has produced at least 2.6 Mt of Zn and Pb metal as well as minor amounts of V, Cd, Ag and Cu. The deposit consists of four main epigenetic, pipe-like orebodies, structurally controlled along NE–SW faults. Sphalerite, galena, pyrite, minor chalcopyrite, and accessory Ge-sulphides of briartite and renierite constitute the primary ore mineral assemblage. Cores of massive sulphide orebodies are surrounded by oxide zones of silicate ore (willemite) and mineralized jasperoid that consists largely of quartz, willemite, cerussite, smithsonite, goethite and hematite, as well as numerous other secondary minerals, including vanadates, phosphates and carbonates of Zn, Pb, V and Cu.Galena, sphalerite and pyrite from the Pb–Zn rich massive orebodies have homogeneous, negative sulphur isotope ratios with mean δ³⁴S_CDT permil (‰) values of − 17.75 ± 0.28 (1σ), − 16.54 ± 0.0.27 and − 15.82 ± 0.25, respectively. The Zn-rich and Pb-poor No. 2 orebody shows slightly heavier ratios of − 11.70 ± 0.5‰ δ³⁴S for sphalerite and of − 11.91 ± 0.71‰ δ³⁴S for pyrite. The negative sulphur isotope ratios are considered to be typical of sedimentary sulphides produced through bacterial reduction of seawater sulphate and suggest a sedimentary source for the sulphur.Carbon and oxygen isotope ratios of the host dolomite have mean δ¹³C_PDB and δ¹⁸O_SMOW values of 2.89‰ and 27.68‰, respectively, which are typical of marine carbonates. The oxygen isotope ratios of dolomite correlate negatively to the SiO₂ content introduced during silicification of the host dolomite. The depletion in ¹⁸O in dolomite indicates high temperature fluid/rock interaction, involving a silica- and ¹⁸O-rich hydrothermal solution.Two types of secondary fluid inclusions in dolomite, both of which are thought to be related to ore deposition, indicate temperatures of ore deposition in the range of 257 to 385 and 98 to 178 °C, respectively. The high temperature fluid inclusions contain liquid + vapour + solid phases and have salinities of 15 to 31 eq. wt.% NaCl, whereas the low temperature inclusions consist of liquid + vapour with a salinity of 11.5 eq. wt.% NaCl.Fluid transport may have been caused by tectonic movements associated with the early stages of the Pan-African Lufilian orogeny, whereas ore deposition within favourable structures occurred due to changes in pressure, temperature and pH in the ore solution during metasomatic replacement of the host dolomite. The termination of the Kabwe orebodies at the Mine Club fault zone and observed deformation textures of the ore sulphides as well as analysis of joint structures in the host dolomite, indicate that ore emplacement occurred prior to the latest deformation phase of the Neoproterozoic Lufilian orogeny.     

A low δLi lower crustal component: Evidence from an alkalic intraplate volcanic series (Chaîne des Puys, French Massif Central)

The intraplate volcanic suite of the Chaîne des Puys (French Massif Central) shows a complete petrologic range, from alkali basalts to trachytes. The significant variations of trace elements and radiogenic isotopes along the series strongly support the occurrence of crustal assimilation associated with fractional crystallization (AFC). The least contaminated basalts are clearly related to a HIMU-type reservoir (²⁰⁶Pb/²⁰⁴Pb > 19.6; ⁸⁷Sr/⁸⁶Sr < 0.7037; ε_Nd > + 4). The behavior of radiogenic isotopes suggests that the most likely crustal contaminants are meta-sediments located in the lower crust.The Li isotopic compositions of the lavas range from high δ⁷Li (> + 7‰) in basalts to lighter values in more evolved lavas (down to δ⁷Li ≈ 0‰). The mantle component, expressed in the least evolved lavas, has a heavy Li isotopic signature, in good agreement with previous δ⁷Li measurements of OIB lavas with HIMU affinities. The evolution of Li isotopic compositions throughout the volcanic series is in agreement with the AFC model suggested by the Sr–Nd–Pb isotopic systems. Although the behavior of Li isotopes during assimilation processes is currently poorly constrained, our calculations suggest that at least a portion of the lower crust beneath the Chaîne des Puys is characterized by a light Li isotopic composition (δ⁷Li < − 5‰).     

Carbon biogeochemistry of the Betsiboka estuary (north-western Madagascar)

Madagascar’s largest estuary (Betsiboka) was sampled along the salinity gradient during the dry season to document the distribution and sources of particulate and dissolved organic carbon (POC, DOC) as well as dissolved inorganic carbon (DIC). The Betsiboka was characterized by a relatively high suspended matter load, and in line with this, low DOC/POC ratios (0.4–2.5). The partial pressure of CO₂ (pCO₂) was generally above atmospheric equilibrium (270–1530 ppm), but relatively low in comparison to other tropical and subtropical estuaries, resulting in low average CO₂ emission to the atmosphere (9.1 ± 14.2 mmol m⁻² d⁻¹). Despite the fact that C4 vegetation is reported to cover >80% of the catchment area, stable isotope data on DOC and POC suggest that C4 derived material comprises only 30% of both pools in the freshwater zone, increasing to 60–70% and 50–60%, respectively, in the oligohaline zone due to additional lateral inputs. Sediments from intertidal mangroves in the estuary showed low organic carbon concentrations (<1%) and δ¹³C values (average −19.8‰) consistent with important inputs of riverine imported C4 material. This contribution was reflected in δ¹³C signatures of bacterial phospholipid derived fatty acids (i + a15:0), suggesting the potential importance of terrestrial organic matter sources for mineralization and secondary production in coastal ecosystems.     

Graphite oxidation in the Apollo 17 orange glass magma: Implications for the generation of a lunar volcanic gas phase

An Apollo 17 picritic orange glass composition has been used to experimentally investigate the conditions at which graphite would oxidize to form a CO-rich gas, and ultimately produce lunar fire-fountain eruptions. Isothermal decompression experiments run above the A17 orange glass liquidus temperature (>1350 °C) suggest that the initial CO-rich gas phase produced by graphite oxidation would be generated during magma ascent at a pressure of 40 MPa, 8.5 km beneath the lunar surface. Additional experiments with 2000 ppm S and 1000 ppm Cl showed that the presence of these dissolved gas species would not affect the depth of graphite oxidation, verifying that the first volcanic gas phase would be generated by the oxidation of graphite.A simple ideal chemical mixing model for calculating melt FeO activity in a Fe-metal/silicate melt system was tested with a series of 0.1 MPa controlled oxygen fugacity experiments. Agreement between the model and experiments allows the model to be used to calculate oxygen fugacity in picritic lunar glass compositions such as the A17 orange glass. Using this model in a reanalysis of chemical equilibria between the natural A17 orange glass melt and the metal spherules (Fe₈₅Ni₁₄Co₁) trapped within the glass beads indicates a log oxygen fugacity of −11.2, 0.7 log units, more oxidized than previous estimates. At the A17 orange glass liquidus temperature (1350 ± 5 °C), this f_O2 corresponds to a minimum pressure of 41 MPa on the graphite–C–O surface. The fact that the same critical graphite oxidation pressure was determined in decompression experiments and from the Fe–FeO activity model for the natural A17 orange glass–metal assemblage strongly supports this pressure (8.5 km depth) for volcanic gas formation in lunar basalts. Generation of a gas by oxidation of C in ascending magma is likely to have been important in getting dense lunar magmas to the surface as well as in generating fire-fountain eruptions. The vesicles common in many lunar basalts and the ubiquitous Fe-metal in these rocks are also likely generated by the oxidation of carbon. The presence of carbon in the lunar basalts and the recent discovery of ppm levels of water in lunar basalts indicate that at least parts of the lunar interior still contained volatiles at 3.9 bybp.     

Oxygen isotope composition of annually banded modern and mid-Holocene travertine and evidence of paleomonsoon floods, Grand Canyon, Arizona, USA

Holocene and modern travertine formed in spring-fed Havasu Creek of the Grand Canyon, Arizona, was studied to determine the factors governing its oxygen-isotope composition. Analysis of substrate-grown travertine indicates that calculated calcite-formation temperatures compare favorably with measured water temperatures, and include silt-rich laminae deposited by monsoon-driven floods. Ancient spring-pool travertine is dated by U-series at 7380 ± 110 yr and consists of 14 travertine-silt couplets of probable annual deposition. One hundred eighty high-resolution δ¹⁸O analyses of this mid-Holocene sample average −11.0‰ PDB. The average value for modern travertine is 0.5‰ lower, perhaps because mid-Holocene temperature was higher or there was proportionally greater summer recharge. δ¹⁸O cyclicity in the mid-Holocene travertine has average amplitude of 1.9 ± 0.5‰ PDB, slightly less than the inferred modern-day annual temperature range of Havasu Creek. The annual temperature range might have been reduced during the 14-yr interval compared to present, although other non-temperature factors could account for the muted annual variation. Silt-rich laminae within isotopically lower calcite in the modern and mid-Holocene travertine verifies the seasonal resolution of both samples, and suggests that similar temperature-precipitation conditions, as well as monsoon-generated summer floods, prevailed in the mid-Holocene as they do throughout the Grand Canyon region today.     

Fractionation of silicon isotopes during biogenic silica dissolution

Silicon isotopes have been investigated for their potential to reveal both past and present patterns of silicic acid utilization, primarily by diatoms, in surface waters of the ocean. Interpretation of this proxy has thus far relied on characteristic trends in the isotope composition of the dissolved and particulate silicon pools in the upper ocean, as driven by biological fractionation during the production of biogenic silica (bSiO₂, or opal) by diatoms. However, other factors which may influence the silicon isotope composition of diatom opal, particularly post-formational aging and maturation processes, remain largely uninvestigated. Here, we report a consistent fractionation of silicon isotopes during the physicochemical dissolution of diatom bSiO₂ suspended in seawater under closed conditions. This fractionation acts counter to that occurring during bSiO₂ production and at about half its absolute magnitude, with dissolution discriminating against the release of the heavier isotopes of silicon at an enrichment factor ε_DSi–BSi of −0.55‰, corresponding to a fractionation factor α_30/28 of 0.99945. The enrichment factor did not vary with source material, indicating the lack of a significant species effect, or with temperature from 3 to 20 °C. Thus, the dissolution of bSiO₂ produces dissolved silicon with a δ³⁰Si value that is 0.55‰ more negative than its parent bSiO₂, an effect that must be accounted for when interpreting oceanic δ³⁰Si distributions. The δ³⁰Si values of both the dissolved and particulate silicon pools increased linearly as dissolution progressed, implying a measurable (±0.1‰) change in the relative δ³⁰Si of opal samples whenever the difference in preservation efficiency between them is >20%. This effect could account for 10–30% of the difference in diatom δ³⁰Si values observed between glacial and interglacial conditions. It is unlikely, however, that the inferred maximum possible change in δb³⁰SiO₂ of +0.55‰ would be manifested in situ, as a high mean percentage of dissolution would include complete loss of the more soluble members of the diatom assemblage.     

Carbon and nitrogen utilization in two species of Red Sea corals along a depth gradient: Insights from stable isotope analysis of total organic material and lipids

We examined the utilization of carbon and nitrogen in two common Red Sea coral species (Stylophora pistillata and Favia favus), differing in colony morphology and polyp size, along a depth gradient down to 60 m. We describe the changes in C/N ratios and in the stable isotope composition of carbon and nitrogen of coral’s tissue and algal symbionts. We also measured the carbon isotopic composition of the lipid fraction extracted from both coral tissue and algal symbionts in order to reveal the changes in the carbon source utilized by the host coral for lipid synthesis.The results show that for both species, δ¹³C decreases by 7–8‰ in animal tissue, algal symbionts and in the lipid fractions as depth increases. However, in contrast to previous reports, the difference between δ¹³C values of coral tissue and algal symbionts does not increase with depth. δ¹⁵N values of coral tissue and algal symbionts in both species do not correlate with depth suggesting that the heterotrophic capacity of these corals does not increase with depth. δ¹³C values of tissue lipids were depleted by an average of 3.5‰ compared to δ¹³C of the entire tissue at all depths. δ¹³C values of algal lipids were depleted by an average of 2‰ compared to δ¹³C of the entire zooxanthellae at all depths, indicating high efficiency of carbon recycling between the two symbiotic partners along the entire gradient. The depletion of lipids is attributed to the fractionation mechanism during lipid synthesis. In addition, for both species, δ¹³C values of algal lipids were enriched compared with δ¹³C of tissue lipids. In S. pistillata, the difference between δ¹³C values of tissue lipids and algal lipids increased linearly with depth, indicating a change in the sources of carbon utilized by the coral for lipid synthesis below 20 m from an autotrophic to a heterotrophic source. However, in F. favus, this average difference was 4 times larger compared to shallow S. pistillata and was constant along the entire depth gradient, suggesting that F. favus uses heterotrophically-acquired carbon for lipid synthesis regardless of depth. Overall, F. favus exhibited enriched δ¹³C and δ¹⁵N values compared to S. pistillata along the entire gradient. We attribute these differences to both morphological differences (i.e. colony morphology, tissue thickness and polyp size) between the two species and to a higher heterotrophy/autotrophy ratio in F. favus at all depths. The C/N ratio in S. pistillata tissue decreased with increasing water depth whereas in F. favus it remained constant. This reflects a higher heterotrophic capacity in the large polyped F. favus, at all depths.     

Glide systems of hematite single crystals in deformation experiments

The critical resolved shear stresses (CRSSs) of hematite crystals were determined in compression tests for r-twinning, c-twinning and {a}<m>-slip in the temperature range 25 °C to 400 °C, at 400 MPa confining pressure, and a strain rate of 10^− 5 s^− 1 by Hennig-Michaeli, Ch., Siemes, H., 1982. Experimental deformation of hematile crstals betwen 25 °C and 400 °C at 400 MPa confining pressure. In: Schreyer, W. (Ed.) High Pressure Research in Geoscience, Schweizerbart'sche Verlagsbuchhandlung, Stuttgart, p. 133–150. In the present contribution newly performed experiments on hematite single crystals at temperatures up to 800 °C at strain rates of 10^− 5 s^− 1 and 300 MPa confining pressure extends the knowledge about the CRSS of twin and slip modes. Optical observations, neutron diffraction goniometry, SEM forescatter electron images and electron backscatter diffraction are applied in order to identify the glide modes. Both twinning systems and {a}<m>-slip were confirmed by these methods. Besides the known glide systems the existence of the (c)<a>-slip system could be stated. Mechanical data establish that the CRSS of r-twinning decreases from 140 MPa at 25 °C to  5 MPa at 800 °C and for {a}<m>-slip from > 560 MPa at 25 °C to  40 MPa at 700 °C. At room temperature the CRSS for c-twinning is around 90 MPa and at 600 °C  60 MPa. The data indicate that the CRSSs above 200 °C seem to be between the values for r-twinning and {a}<m>-slip. For (c)<a>-slip only the CRSS at 600 °C could be evaluated to  60 MPa. Exact values are difficult to determine because other glide systems are always simultaneously activated.     

Oxygen isotopic compositions of chondrules: Implications for evolution of oxygen isotopic reservoirs in the inner solar nebula

We review the oxygen isotopic compositions of minerals in chondrules and compound objects composed of a chondrule and a refractory inclusion, and bulk oxygen isotopic compositions of chondrules in unequilibrated ordinary, carbonaceous, enstatite, and Kakangari-like chondrites, focusing on data acquired using secondary ion mass-spectrometry and laser fluorination coupled with mass-spectrometry over the last decade. Most ferromagnesian chondrules from primitive (unmetamorphosed) chondrites are isotopically uniform (within 3–4‰ in Δ¹⁷O) and depleted in ¹⁶O (Δ¹⁷O>−7‰) relative to amoeboid olivine aggregates (AOAs) and most calcium–aluminum-rich inclusions (CAIs) (Δ¹⁷O<−20‰), suggesting that these classes of objects formed in isotopically distinct gaseous reservoirs, ¹⁶O-poor and ¹⁶O-rich, respectively. Chondrules uniformly enriched in ¹⁶O (Δ¹⁷O<−15‰) are exceptionally rare and have been reported only in CH chondrites. Oxygen isotopic heterogeneity in chondrules is mainly due to the presence of relict grains. These appear to consist of chondrules of earlier generations and rare refractory inclusions; with rare exceptions, the relict grains are ¹⁶O-enriched relative to chondrule phenocrysts and mesostasis. Within a chondrite group, the magnesium-rich (Type I) chondrules tend to be ¹⁶O-enriched relative to the ferrous (Type II) chondrules. Aluminum-rich chondrules in ordinary, enstatite, CR, and CV chondrites are generally ¹⁶O-enriched relative to ferromagnesian chondrules. No systematic differences in oxygen isotopic compositions have been found among these chondrule types in CB chondrites. Aluminum-rich chondrules in carbonaceous chondrites often contain relict refractory inclusions. Aluminum-rich chondrules with relict CAIs have heterogeneous oxygen isotopic compositions (Δ¹⁷O ranges from −20‰ to 0‰). Aluminum-rich chondrules without relict CAIs are isotopically uniform and have oxygen isotopic compositions similar to, or approaching, those of ferromagnesian chondrules. Phenocrysts and mesostases of the CAI-bearing chondrules show no clear evidence for ¹⁶O-enrichment compared to the CAI-free chondrules. Spinel, hibonite, and forsterite of the relict refractory inclusions largely retained their original oxygen isotopic compositions. In contrast, plagioclase and melilite of the relict CAIs experienced melting and ¹⁶O-depletion to various degrees, probably due to isotopic exchange with an ¹⁶O-poor nebular gas. Several igneous CAIs experienced isotopic exchange with an ¹⁶O-poor nebular gas during late-stage remelting in the chondrule-forming region. On a three-isotope diagram, bulk oxygen isotopic compositions of most chondrules in ordinary, enstatite, and carbonaceous chondrites plot above, along, and below the terrestrial fractionation line, respectively. Bulk oxygen isotopic compositions of chondrules in altered and/or metamorphosed chondrites show evidence for mass-dependent fractionation, reflecting either interaction with a gaseous/fluid reservoir on parent asteroids or open-system thermal metamorphism. Bulk oxygen isotopic compositions of chondrules and oxygen isotopic compositions of individual minerals in chondrules and refractory inclusions from primitive chondrites plot along a common line of slope of 1, suggesting that only two major reservoirs (gas and solids) are needed to explain the observed variations. However, there is no requirement that each had a permanently fixed isotopic composition. The absolute (²⁰⁷Pb–²⁰⁶Pb) and relative (²⁷Al–²⁶Mg) chronologies of CAIs and chondrules and the differences in oxygen isotopic compositions of most chondrules (¹⁶O-poor) and most refractory inclusions (¹⁶O-rich) can be interpreted in terms of isotopic self-shielding during UV photolysis of CO in the initially ¹⁶O-rich (Δ¹⁷O−25‰) parent molecular cloud or protoplanetary disk. According to these models, the UV photolysis preferentially dissociates C¹⁷O and C¹⁸O in the parent molecular cloud and in the peripheral zones of the protoplanetary disk. If this process occurs in the stability field of water ice, the released atomic ¹⁷O and ¹⁸O are incorporated into water ice, while the residual CO gas becomes enriched in ¹⁶O. During the earliest stages of evolution of the protoplanetary disk, the inner solar nebula had a solar H₂O/CO ratio and was ¹⁶O-rich. During this time, AOAs and the ¹⁶O-rich CAIs and chondrules formed. Subsequently, the inner solar nebula became H₂O- and ¹⁶O-depleted, because ice-rich dust particles, which were depleted in ¹⁶O, agglomerated outside the snowline (5 AU), drifted rapidly towards the Sun and evaporated. During this time, which may have lasted for 3 Myr, most chondrules and the ¹⁶O-depleted igneous CAIs formed. We infer that most chondrules formed from isotopically heterogeneous, but ¹⁶O-depleted precursors, and experienced isotopic exchange with an ¹⁶O-poor nebular gas during melting. Although the relative roles of the chondrule precursor materials and gas–melt isotopic exchange in establishing oxygen isotopic compositions of chondrules have not been quantified yet, mineralogical, chemical, and isotopic evidence indicate that Type I chondrules may have formed in chemical and isotopic equilibrium with nebular gas of variable isotopic composition. Whether these variations were spatial or temporal are not known yet.