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.     

Portable autonomous vertical profiler for estuarine applications

The design and implementation of a portable autonomous vertical profiler are documented and example data sets from a mesotidal estuary and a microtidal, wind-driven estuary are presented. The profiler sampling range dynamically adjusts to changes in water column depth, and a typical vertical sampling resolution of 4 cm is attained. Example data show the onset and vertical and temporal extent of stratification in the water column. The profiler is ideal for water quality monitoring programs in shallow estuaries that require frequent profiles of hydrographic, chemical, and biological parameters that can be measured in situ.     

The osmium isotopic composition of convecting upper mantle deduced from ophiolite chromites

Chromites separated from the upper mantle or lower crustal portions of 18 ophiolites ranging in age from 900 Ma to 50 Ma are examined for Re-Os isotopic systematics. The ophiolites include both MORB and back arc types, although most are from supra-subduction zone (SSZ) settings. The chromites are robust indicators of the initial Os isotopic compositions of the systems sampled. There is very limited range in calculated initial γ_Os values, with the entire group averaging +1.31. Least squares linear regression of the age of chromite formation (in Ga) versus initial ¹⁸⁷Os/¹⁸⁸Os of a filtered suite yields a slope of −0.0058±0.0019 (2σ) and a present day intercept of 0.12809±0.00085 (2σ), equivalent to a γ_Os value of +0.9±0.6. Of the suite of 51 samples analyzed, 68% lie within ±1% of this evolution trajectory.Although most of the samples formed in SSZ environments, there is little evidence to suggest modification of the mantle Os isotopic composition via radiogenic melts or fluids derived from subducting slabs. The ophiolite data are interpreted as representative of the convecting upper mantle and suggest that the present isotopic composition of the convecting upper mantle averages approximately 1.2% less radiogenic than the estimated minimum composition of the primitive upper mantle of 0.1296±8 (Meisel et al., 2001). The most likely explanation for the difference is the formation, subduction and isolation of some portion of the mafic oceanic crust. Using models based on the assumption that the convecting upper mantle comprises 50% of the total mass of the mantle, and that the average isolation period for subducted oceanic crust is 1.5 to 2.0 Ga, it is estimated that approximately 2 to 3% of the total mass of the mantle is composed of subducted mafic oceanic crust that remains isolated from the convecting upper mantle. Because the isotopic compositions of the DMM and PUM overlap within uncertainties, however, the results do not require any isolated slab component.     

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.     

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.