Trace element mobility during sub-seafloor alteration of basaltic glass from Ocean Drilling Program site 953 (off Gran Canaria)

Trace element concentrations of altered basaltic glass shards (layer silicates) and zeolites in volcaniclastic sediments drilled in the volcanic apron northeast of Gran Canaria during Ocean Drilling Program (ODP) leg 157 document variable element mobilities during low-temperature alteration processes in a marine environment. Clay minerals (saponite, montmorillonite, smectite) replacing volcanic glass particles are enriched in transition metals and rare earth elements (REE). The degree of retention of REE within the alteration products of the basaltic glass is correlated with the field strength of the cations. The high field-strength elements are preferentially retained or enriched in the alteration products by sorption through clay minerals. Most trace elements are enriched in a boundary layer close to the interface mineral-altered glass. This boundary layer has a key function for the physico-chemical conditions of the subsequent alteration process by providing a large reactive surface and by lowering the fluid permeability. The release of most elements is buffered by incorporation into secondary precipitates (sodium-rich zeolites, phillipsite, Fe- and Mn-oxides) as shown by calculated distribution coefficients between altered glasses and authigenic minerals. Chemical fluxes change from an open to a closed system behavior during prograde low-temperature alteration of volcaniclastic sediments with no significant trace metal flux from the sediment to the water column.     

Occurrence of naphthalenesulfonates and their condensates with formaldehyde in a landfill leachate and their transport behavior in groundwater of the Upper Rhine Valley, Germany

. Naphthalenesulfonates and their condensation products with formaldehyde are manufactured in the chemical industry for broad application as tanning agents, dispersing agents, and as superplasticizers for concrete. With the disposal of waste they have found their way into the aquatic environment. Five monomeric naphthalenesulfonates and a group of dimeric sulfonated naphthalene-formaldehyde condensates (SNFC) were identified in the leachate and in groundwater observation wells downstream in the plume of the Karlsruhe-West landfill, situated in the Upper Rhine Valley in southwest Germany. For the main monomer of technical SNFC products, 2-naphthalenesulfonate (2-NS), the concentration in the leachate was 170 µg l^–1, which decreased to 9.5 µg l^–1 at a distance of about 300 m from the boundary of the landfill. In the Merdingen tracer test field, the transport of these compounds was studied under more controlled conditions in two tracer experiments with (1) two model compounds, and (2) a technical SNFC product and uranine as a reference tracer. In these experiments, the monomeric naphthalenesulfonates and the SNFC with n=2 behave as conservative tracers. Thus, the findings of the landfill study were supported by these results. Higher molecular SNFC were strongly retarded, which is attributed to adsorption to soil particles. The results of the second tracer experiment suggest a degradation of 2-NS and 2,6-naphthalenedisulfonate (2,6-NDS) after adaptation of the microorganisms in the groundwater aquifer as a consequence of the first tracer experiment.     

Water quality variation and clam growth: Is pH really a non-issue in estuaries?

A tandem deployment system was used to critically evaluate relationships between important water chemistry parameters (pH, salinity, dissolved oxygen) and biotic performance based on clam growth. The effects of environmental conditions on growth of juvenile clams,Mercenaria mercenaria, were determined after 7-day field deployments in cages at reference sites from 1998 to 2000. Continuous measurements of the overlying water chemistry parameters were monitored by deploying an in situ water quality instrument (Hydrolab Datasonde) at the same time. While salinity was identified as an important determinant of clam growth over wide salinity ranges (10–35‰), pH was also found to be a very important parameter, especially in low-salinity regimes (<25‰). Average pH measurements ranged from 7.2 to 7.8; minimal pHs ranged from 6.9 to 7.6. The results indicated that when average pH levels fell below 7.5 or minimum pH levels fell below 7.2, growth rates were <50% that of clams deployed under higher pH conditions. Estuarine systems are generally perceived as being well-buffered so pH is frequently assumed to be unimportant, but our results suggest that pH levels can decline in estuarine systems to levels that can adversely affect biological responses. The potential impacts on biological resources of even moderate decreases in pH, particularly in systems that naturally tend to have lower pH conditions, may be more important than previously realized.     

Impact of suboxia on sinking particulate organic carbon: Enhanced carbon flux and preferential degradation of amino acids via denitrification

Fluxes of particulate organic carbon (POC) through the oxygen deficient waters in the eastern tropical North Pacific were found to be relatively less attenuated with depth than elsewhere in the eastern North Pacific. The attenuation coefficient (b) for the flux was found to be 0.40 versus the composite value of 0.86 determined by Martin et al. (1987). To examine this further, sinking POC was collected using sediment traps and allowed to degrade in oxic and suboxic experiments. Using a kinetic model, it was found that degradation proceeded at similar rates (roughly 0.8 day⁻¹) under oxic and suboxic conditions, but a greater fraction of bulk POC was resistant to degradation in the suboxic experiments (61% vs. 23%). Amino acids accounted for 37% of POC collected at 75m, but following degradation the value dropped to 17% and 16% in the oxic and suboxic experiments respectively. POC collected from 500m was 10% amino acids. The non-AA component of POC collected at 75m was not degraded under suboxic conditions, while under oxic conditions it was. These results suggest that microbes degrading OC under suboxic conditions via denitrification preferentially utilize nitrogen-rich amino acids. This preferential degradation of amino acids suggests that 9% more nitrogen may be lost via water column denitrification than is accounted for when a more “Redfieldian” stoichiometry for POC is assumed.     

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.     

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.