Burial of redox-sensitive metals and organic matter in the equatorial Indian Ocean linked to precession

Authigenic metals (uranium, cadmium, and molybdenum), organic carbon (OC) and total C₃₇ alkenone (totC₃₇) concentrations were measured for the last 350 kyr in core MD900963, located in the eastern equatorial Arabian Sea. Authigenic metal concentrations on a carbonate-free basis range between 1 and 17 ppm, 0.5 and 6 ppm, and 0.5 and 4 ppm for U, Cd, and Mo, respectively. The profiles are characterized by well-defined 23 kyr cycles between oxic and mildly suboxic conditions. The redox-sensitive metal profiles also follow variations in the concentrations of OC (0.2-0.9%) and alkenones (0.2-6.7 ppm). The coupled variations in inorganic and organic constituents are attributed to a 23-kyr cycle in primary production above site MD900963, as suggested by clear correlations with independent micropaleontologic proxies (primary productivity indices based on foraminifera and coccoliths and fragmentation of foraminiferal shells). The 23-kyr cycles do appear to be primarily driven by productivity rather than changes in bottom water oxygen. Comparison with other records indicates that if this interpretation is correct, productivity variations across much of the Indian Ocean have been dominated by precessional forcing, with high productivity in phase with low summer insolation in the Northern Hemisphere. This interpretation contrasts with the traditional attribution of enhanced productivity in the Indian Ocean with periods of high summer insolation.     

Implications of Nb/U, Th/U and Sm/Nd in plume magmas for the relationship between continental and oceanic crust formation and the development of the depleted mantle

The Nb/U and Th/U of the primitive mantle are 34 and 4.04 respectively, which compare with 9.7 and 3.96 for the continental crust. Extraction of continental crust from the mantle therefore has a profound influence on its Nb/U but little influence on its Th/U. Conversely, extraction of midocean ridge-type basalts lowers the Th/U of the mantle residue but has little influence on its Nb/U. As a consequence, variations in Th/U and Nb/U with Sm/Nd can be used to evaluate the relative importance of continental and basaltic crust extraction in the formation of the depleted (Sm/Nd enriched) mantle reservoir.This study evaluates Nb/U, Th/U, and Sm/Nd variations in suites of komatiites, picrites, and their associated basalts, of various ages, to determine whether basalt and/or continental crust have been extracted from their source region. Emphasis is placed on komatiites and picrites because they formed at high degrees of partial melting and are expected to have Nb/U, Th/U, and Sm/Nd that are essentially the same as the mantle that melted to produce them. The results show that all of the studied suites, with the exception of the Barberton, have had both continental crust and basaltic crust extracted from their mantle source region. The high Sm/Nd of the Gorgona and Munro komatiites require the elevated ratios seen in these suites to be due primarily to extraction of basaltic crust from their source regions, whereas basaltic and continental crust extraction are of subequal importance in the source regions of the Yilgarn and Belingwe komatiites. The Sm/Nd of modern midocean ridge basalts lies above the crustal extraction curve on a plot of Sm/Nd against Nb/U, which requires the upper mantle to have had both basaltic and continental crust extracted from it.It is suggested that the extraction of the basaltic reservoir from the mantle occurs at midocean ridges and that the basaltic crust, together with its complementary depleted mantle residue, is subducted to the core-mantle boundary. When the two components reach thermal equilibrium with their surroundings, the lighter depleted component separates from the denser basaltic component. Both are eventually returned to the upper mantle, but the lighter depleted component has a shorter residence time in the lower mantle than the denser basaltic component. If the difference in the recycling times for the basaltic and depleted components is ∼1.0 to 1.5 Ga, a basaltic reservoir is created in the lower mantle, equivalent to the amount of basalt that is subducted in 1.0 to 1.5 Ga, and that reservoir is isolated from the upper mantle. It is this reservoir that is responsible for the Sm/Nd ratio of the upper mantle lying above the trend predicted by extraction of continental crust on the plot of Sm/Nd against Nb/U.     

Isotopic partitioning between scallop shell calcite and seawater: effect of shell growth rate

The relationship between molluscan shell growth rate and skeletal δ¹⁸O and δ¹³C was investigated in a detailed field study for the scallop, Pecten maximus. Seasonal variation in shell growth rate was found to be a governing factor influencing shell δ¹⁸O and δ¹³C. At low shell growth rates, shell δ¹⁸O were more positive (of the order +0.4‰) and δ¹³C more negative (up to −2‰) as compared with predicted values for precipitation of inorganic calcite in isotopic equilibrium with seawater. The deviations in δ¹⁸O were hypothesized as reflecting possible differences in solution carbonate chemistry at the site of mineralization in the extrapallial fluid as compared with that of the external seawater medium. The deviations in shell δ¹³C were consistent with incorporation of isotopically depleted respiratory ¹³C (i.e., a metabolic effect). A trend toward more depleted shell δ¹⁸O and δ¹³C values occurred at higher shell growth rates, with negative δ¹⁸O values as compared with predicted equilibrium at shell growth rates above 0.13 mm per day. These simultaneous negative deviations in skeletal δ¹⁸O and δ¹³C were interpreted as resulting from a kinetic effect. The implications for environmental reconstruction from molluscan isotopic records are discussed in light of a model of isotopic behavior based on the findings of the study.     

Oxygen fugacity and geochemical variations in the martian basalts: implications for martian basalt petrogenesis and the oxidation state of the upper mantle of Mars

The oxygen fugacity of the Dar al Gani 476 martian basalt is determined to be quartz-fayalite-magnetite (QFM) −2.3 ± 0.4 through analysis of olivine, low-Ca pyroxene, and Cr-spinel and is in good agreement with revised results from Fe-Ti oxides that yield QFM −2.5 ± 0.7. This estimate falls within the range of oxygen fugacity for the other martian basalts, QFM −3 to QFM −1. Oxygen fugacity in martian basalts correlates with ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd, and La/Yb ratios, indicating that the mantle source of the basalts is reduced and that assimilation of crust-like material controls the oxygen fugacity. This allows constraints to be placed on the oxidation state of the martian mantle and on the nature of assimilated crustal material. The assimilated material may be the product of early and extensive hydrothermal alteration of the martian crust, or it may be amphibole- or phlogopite-bearing basaltic rock within the crust. In either case, water may play a significant role in the oxidation of basaltic magmas on Mars, although it may be secondary to assimilation of ferric iron-rich material.     

δC of low-molecular-weight organic acids generated by the hydrous pyrolysis of oil-prone source rocks

Low-molecular-weight (LMW) aqueous organic acids were generated from six oil-prone source rocks under hydrous-pyrolysis conditions. Differences in total organic carbon-normalized acid generation are a function of the initial thermal maturity of the source rock and the oxygen content of the kerogen (OI). Carbon-isotope analyses were used to identify potential generation mechanisms and other chemical reactions that might influence the occurrence of LMW organic acids. The generated LMW acids display increasing ¹³C content as a function of decreasing molecular weight and increasing thermal maturity. The magnitudes of observed isotope fractionations are source-rock dependent. These data are consistent with δ¹³C values of organic acids presented in a field study of the San Joaquin Basin and likely reflect the contributions from alkyl-carbons and carboxyl-carbons with distinct δ¹³C values. The data do not support any particular organic acid generation mechanism. The isotopic trends observed as a function of molecular weight, thermal maturity, and rock type are not supported by either generation mechanisms or destructive decarboxylation. It is therefore proposed that organic acids experience isotopic fractionation during generation consistent with a primary kinetic isotope effect and subsequently undergo an exchange reaction between the carboxyl carbon and dissolved inorganic carbon that significantly influences the carbon isotope composition observed for the entire molecule. Although generation and decarboxylation may influence the δ¹³C values of organic acids, in the hydrous pyrolysis system described, the nondestructive, pH-dependent exchange of carboxyl carbon with inorganic carbon appears to be the most important reaction mechanism controlling the δ¹³C values of the organic acids.     

Generation of mid-ocean ridge basalts at pressures from 1 to 7 GPa

We propose a model for the generation of average MORBs based on phase relations in the CaO-MgO-Al₂O₃-SiO₂-CO₂ system at pressures from 3 to 7 GPa and in the CaO-MgO-Al₂O₃-SiO₂-Na₂O-FeO (CMASNF) system at pressures from ∼0.9 to 1.5 GPa. The MELT seismic tomography (Forsyth et al., 2000) across the East Pacific Rise shows the largest amount of melt centered at ∼30-km depth and lesser amounts at greater depths. An average mantle adiabat with a model-system potential temperature (T_p) of 1310°C is used that is consistent with this result. In the mantle, additional minor components would lower solidus temperatures ∼50°C, which would lower T_p of the adiabat for average MORBs to ∼1260°C. The model involves generation of carbonatitic melts and melts that are transitional between carbonatite and kimberlite at very small melt fractions (<0.2%) in the low-velocity zone at pressures of ∼2.6 to 7 GPa in the CMAS-CO₂ system, roughly the pressure range of the PREM low-velocity zone. These small-volume, low-viscosity melts are mixed with much larger volumes of basaltic melt generated at the plagioclase-spinel lherzolite transition in the pressure range of ∼0.9 to 1.5 GPa.In this model, solidus phase relations in the pressure range of the plagioclase-spinel lherzolite transition strongly, but not totally, control the major-element characteristics of MORBs. Although the plagioclase-spinel lherzolite transition suppresses isentropic decompression melting in the CMAS system, this effect does not occur in the topologically different and petrologically more realistic CMASNF system. On the basis of the absence of plagioclase from most abyssal peridotites, which are the presumed residues of MORB generation, we calculate melt productivity during polybaric fractional melting in the plagioclase-spinel lherzolite transition interval at exhaustion of plagioclase in the residue. In the CMASN system, these calculations indicate that the total melt productivity is ∼24%, which is adequate to produce the oceanic crust. The residual mineral proportions from this calculation closely match those of average abyssal peridotites.Melts generated in the plagioclase-spinel lherzolite transition are compositionally distinct from all MORB glasses, but do not have a significant fractional crystallization trend controlled by olivine alone. They reach the composition field of erupted MORBs mainly by crystallization of both plagioclase and olivine, with initial crystallization of either one of these phases rapidly joined by the other. This is consistent with phenocryst assemblages and experimental studies of the most primitive MORBs, which do not show an olivine-controlled fractionation trend. The model is most robust for the eastern Pacific, where an adiabat with a T_p of ∼1260°C is supported by the MELT seismic data and where the global inverse correlation of (FeO)₈ with (Na₂O)₈ is weak. Average MORBs worldwide also are well modeled. A heterogeneous mantle consisting of peridotite of varying degrees of major-element depletion combined with phase-equilibrium controls in the plagioclase-spinel lherzolite transition interval would produce the form of the global correlations at a constant T_p, which suggests a modest range of T_p along ridges. Phase-composition data for the CMASNF system are presently not adequate for quantitative calculation of (FeO)₈-(Na₂O)₈-(CaO/Al₂O₃)₈ systematics in terms of this model. The near absence of basalts in the central portion of the Gakkel Ridge suggests a lower bound for T_p along ridges of ∼1240°C, a potential temperature just low enough to miss the solidus for basalt production at ∼0.9 GPa. An upper bound for T_p is poorly constrained, but the complete absence of picritic glasses in Iceland and the global ridge system suggests an upper bound of ∼1400°C. In contrast to some previous models for MORB generation that emphasize large potential temperature variations in a relatively homogeneous peridotitic mantle, our model emphasizes modest potential temperature variations in a peridotitic mantle that shows varying degrees of heterogeneity. Calculations indicate that melt productivity changes from 0 to 24% for a change in T_p from 1240 to 1260°C, effectively producing a rapid increase to full crustal thickness or decrease to none as ridges appear and disappear.