Iron colloids/organic matter associated transport of major and trace elements in small boreal rivers and their estuaries (NW Russia)

The chemical status of major and trace elements (TE) in various boreal small rivers and watershed has been investigated along a 1500-km transect of NW Russia. Samples were filtered in the field through a progressively decreasing pore size (5, 0.8 and 0.22 μm; 100, 10, and 1 kD) using a frontal filtration technique. All major and trace elements and organic carbon (OC) were measured in filtrates and ultrafiltrates. Most rivers exhibit high concentration of dissolved iron (0.2–4 mg/l), OC (10–30 mg/l) and significant amounts of trace elements usually considered as immobile in weathering processes (Ti, Zr, Th, Al, Ga, Y, REE, V, Pb). In (ultra)filtrates, Fe and OC are poorly correlated: iron concentration gradually decreases upon filtration from 5 μm to 1 kD whereas the major part of OC is concentrated in the <1–10 kD fraction. This reveals the presence of two pools of colloids composed of organic-rich and Fe-rich particles. According to their behavior during filtration and association with these two types of colloids, three groups of elements can be distinguished: (i) species that are not affected by ultrafiltration and are present in the form of true dissolved inorganic species (Ca, Mg, Li, Na, K, Sr, Ba, Rb, Cs, Si, B, As, Sb, Mo) or weak organic complexes (Ca, Mg, Sr, Ba), (ii) elements present in the fraction smaller than 1–10 kD prone to form inorganic or organic complexes (Mn, Co, Ni, Zn, Cu, Cd, and, for some rivers, Pb, Cr, Y, HREE, U), and (iii) elements strongly associated with colloidal iron in all ultrafiltrates (P, Al, Ga, REE, Pb, V, Cr, W, Ti, Ge, Zr, Th, U). Based on size fractionation results and taking into account the nominal pore size for membranes, an estimation of the effective surface area of Fe colloids was performed. Although the total amount of available surface sites on iron colloids (i.e., 1–10 μM) is enough to accommodate the nanomolar concentrations of dissolved trace elements, very poor correlation between TE and surface sites concentrations was observed in filtrates and ultrafiltrates. This strongly suggests a preferential transport of TE as coprecipitates with iron oxy(hydr)oxides. These colloids can be formed on redox boundaries by precipitation of Fe(III) from inflowing Fe(II)/TE-rich anoxic ground waters when they meet well-oxygenated surface waters. Dissolved organic matter stabilizes these colloids and prevents their aggregation and coagulation. Estuarine behavior of several trace elements was studied for two small iron- and organic-rich rivers. While Si, Sr, Ba, Rb, and Cs show a clear conservative behavior during mixing of freshwaters with the White sea, Al, Pb and REE are scavenged with iron during coagulation of Fe hydroxide colloids.     

Origin of fine-scale sheeted granites by incremental injection of magma into active shear zones: examples from the Pilbara Craton, NW Australia

In the Archaean Pilbara Craton of Western Australia, three zones of heterogeneous centimetre- to metre-scale sheeted granites are interpreted to represent high-level, syn-magmatic shear zones. Evidence for the syn-magmatic nature of the shear zones include imbricated and asymmetrically rotated metre-scale orthogneiss xenoliths that are enveloped by leucogranite sheets that show no significant internal strain. At another locality, granite sheets have a strong shape-preferred alignment of K-feldspar, suggesting magmatic flow, while the asymmetric recrystallisation of the grain boundaries indicates that non-coaxial deformation continued acting upon the sheets under sub-solidus conditions. Elsewhere, randomly oriented centimetre-wide leucogranite dykes are realigned at a shear zone boundary to form semi-continuous, layer-parallel sheets within a magma-dominated, dextral shear zone.

It is proposed that the granite sheets formed by the incremental injection of magmas into active shear zones. Magma was sheared during laminar flow to produce the sheets that are aligned sub-parallel to the shear zone boundary. Individual sheets are fed by individual dykes, with up to 1000s of discrete injections in an individual shear zone. The sheets often lack microstructural evidence for magmatic flow, either because the crystal content of the magma was too low to record internal strain, or because of later recrystallisation.     

Hydrothermal Redistribution of Rare—Earth Elements in Pingxiang Dacite,Guangxi

Distribution of the rare-earth elements (REE) in dacite has been studied so as to get a better understanding of the migration behavior of REE during alteration. Both unaltered and altered samples were collected in an unpolluted area of Guangxi Zhuang Autonomous Region, southwest China. The REE concentrations were analyzed by ICP-MS. It is concluded that the REE were enriched during dacite alteration in varying degrees. The chondrite-normalized REE patterns of altered samples approximately maintain the characteristics of unaltered samples. However, if we normalize the REE concentrations of altered samples with unaltered dacite, fractionation of REE will appear. The LREE are more enriched than HREE in all altered samples with the LREE possibly precipitated as carbonate minerals. Both positive and negative Eu anomalies exist. Enrichment, immobility and depletion are noticed for the element Lu. Heavy mineral alteration, difference in stability constant between carbonate LREE and HREE complexes, downward migration of weathering fluid and microenvironment change may be responsible for the fractionation of REE in the altered dacite.     

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.     

A comparison of early juvenile red drum densities among various habitat types in Galveston Bay, Texas

Seagrass meadows are often cited as important nursery areas for newly settled red drum even though many estuaries, such as Galveston Bay, Texas, support large numbers of red drum and have limited seagrass cover, suggesting the use of alternate nursery areas. We examined patterns of habitat use for newly settled red drum at six sampling areas in Galveston Bay; two areas had seagrass beds and four areas had no seagrass. We measured densities in different habitat types using epibenthic sleds and enclosure samplers. Peak recruitment of young red drum to the estuary occurred during September through December. Highest densities of new settlers were found in seagrass meadows (primarilyHalodule wrightii), but when seagrass was absent, the highest densities of red drum occurred along theSpartina alterniflora marsh edge interface. Densities were relatively low on nonvegetated bottom away from the marsh edge. We also examined density patterns in other habitat types at selected sampling areas and found no red drum within marsh vegetation away from the marsh edge interface (5 and 10 m into the marsh interior). Oyster reefCrassostrea virginica was sampled using lift nets, and we found no red drum using this habitat, although adjacent seagrass and marsh interface habitats were used. Even though red drum densities in marsh edge were low relative to seagrass, the large areal extent of marshes in the bay complex probably makes marsh edge the most important nursery habitat for red drum in Galveston Bay.     

Kinetics of Mn(II) oxidation by Leptothrix discophora SS1

The kinetics of Mn(II) oxidation by the bacterium Leptothrix discophora SS1 was investigated in this research. Cells were grown in a minimal mineral salts medium in which chemical speciation was well defined. Mn(II) oxidation was observed in a bioreactor under controlled conditions with pH, O₂, and temperature regulation. Mn(II) oxidation experiments were performed at cell concentrations between 24 mg/L and 35 mg/L, over a pH range from 6 to 8.5, between temperatures of 10°C and 40°C, over a dissolved oxygen range of 0 to 8.05 mg/L, and with L. discophora SS1 cells that were grown in the presence of Cu concentrations ranging from zero to 0.1 μM. Mn(II) oxidation rates were determined when the cultures grew to stationary phase and were found to be directly proportional to O₂ and cell concentrations over the ranges investigated. The optimum pH for Mn(II) oxidation was approximately 7.5, and the optimum temperature was 30°C. A Cu level as low as 0.02 μM was found to inhibit the growth rate and yield of L. discophora SS1 observed in shake flasks, while Cu levels between 0.02 and 0.1 μM stimulated the Mn(II) oxidation rate observed in bioreactors. An overall rate law for Mn(II) oxidation by L. discophora as a function of pH, temperature, dissolved oxygen concentration (D.O.), and Cu concentration is proposed. At circumneutral pH, the rate of biologically mediated Mn(II) oxidation is likely to exceed homogeneous abiotic Mn(II) oxidation at relatively low (≈μg/L) concentrations of Mn oxidizing bacteria.     

Morphologic and spectral investigation of exceptionally well-preserved bacterial biofilms from the Oligocene Enspel formation, Germany

The fossilised soft tissues of a tadpole and an associated coprolitic structure from the organic-rich volcanoclastic lacustrine Upper Oligocene Enspel sediments (Germany) were investigated using high-resolution imaging techniques and nondestructive in situ surface analysis. Total organic carbon analysis of the coprolite and the sediment revealed values of 28.9 and 8.9% respectively. The soft tissues from the tadpole and the coprolite were found to be composed of 0.5 to 1 μm-sized spheres and rod shapes. These features are interpreted as the fossil remains of bacterial biofilms consisting probably of heterotrophic bacteria and fossilised extracellular polymeric substances. They became fossilised while in the process of degrading the organic matter of the organism and the coprolite. Comparison with a modern marine biofilm revealed morphologic details identical to those observed in the fossil bacterial biofilms. Although the fossil biofilms on both macrofossils exhibited identical microtextures, their mode of preservation was inhomogeneous and varied between calcium phosphate and an as yet unidentified mineral phase consisting mainly of Si, Ca, Ti, P, and S, but also showing the presence of Mg, Al, and Fe. The coprolite consists purely of fossilised bacterial cells in a densely packed arrangement and associated fossilised extracellular polymeric substances.In addition to preliminary imaging and energy-dispersive X-ray analysis, both the fossil biofilms and the sediment were investigated by nondestructive in situ analysis using time of flight-secondary ion mass spectroscopy (ToF-SIMS). The mass spectra obtained on the coprolite in mass-resolved chemical mapping mode allowed the tentative identification of a number of organic secondary ion species. Some spectra appear to indicate the presence of bacterial hopanoids, but further work using standard techniques such as gas chromatography mass spectroscopy is needed to conclusively verify the presence of these substances. Nevertheless, ToF-SIMS chemical maps were successfully correlated with electron microscopy images, allowing the correlation of molecular spectra, the spatial distribution of individual organic species, and specific morphologic features to demonstrate the potential of this approach in the analysis of microfossils.     

Source and H2O content of high-MgO magmas in island arc settings: an experimental study of a primitive calc-alkaline basalt from St. Vincent, lesser antilles arc

Liquidus phase relationships have been determined for a high-MgO basalt (STV301: MgO=12.5 wt%, Ni=250 ppm, Cr=728 ppm) from Black Point, St Vincent (Lesser Antilles arc). Piston-cylinder experiments were conducted between 7.5 and 20 kbar under both hydrous and oxidizing conditions. AuPd capsules were used as containers. Compositions of supraliquidus glasses and mass-balance calculations show that Fe loss is < 10% in the majority of experiments. Two series of water concentrations in melt were investigated: (i) 1.5 wt% and (ii) 4.5 wt% H₂O, as determined by SIMS analyses on quenched glasses and with the by difference technique. The Fe³⁺/Fe²⁺ partitioning between Cr-Al spinel and melt and olivine-spinel equilibria show that oxidizing fO₂ were imposed (NNO + 1.5 for the 1.5 wt% H₂O series, NNO + 2.3 for the 4.5 wt% H₂O series). For both series of water concentrations, the liquid is multiply-saturated with a spinel lherzolite phase assemblage on its liquidus, at 1235°C, 11.5 kbar (1.5 wt% H₂O) and 1185°C, 16 kbar (4.5 wt% H₂O). Liquidus phases are homogeneous and comparable to typical mantle compositions. Mineral-melt partition coefficients are generally identical to values under anhydrous conditions. The modal proportion cpx/opx on the liquidus decreases from the 1.5 wt% to the 4.5 wt% H₂O series. The experimental data are consistent with STV301 being a product of partial melting of lherzolitic mantle. Conditions of multiple saturation progressively evolve toward lower temperatures and higher pressures with increasing melt H₂O concentration. Phase equilibria constraints, i.e., the necessity of preserving the mantle signature seen in high-MgO and picritic arc basalts, and glass inclusion data suggest that STV301 was extracted relatively dry (∼ 2 wt% H₂O) from its mantle source. However, not all primary arc basalts are extracted under similarly dry conditions because more hydrous melts will crystallize during ascent and will not be present unmodified at the surface. From degrees of melting calculated from experiments on KLB-1, extraction of a 12.5 wt% MgO melt with ∼ 2 wt% H₂O would require a H₂O concentration of 0.3 wt% in the sub-arc mantle. For mantle sources fluxed with a slab-derived hydrous component, extracted melts may contain up to ∼ 5.5 wt% H₂O.     

Comparative Re-Os systematics of chondrites: Implications regarding early solar system processes

A suite of 47 carbonaceous, enstatite, and ordinary chondrites are examined for Re-Os isotopic systematics. There are significant differences in the ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os ratios of carbonaceous chondrites compared with ordinary and enstatite chondrites. The average ¹⁸⁷Re/¹⁸⁸Os for carbonaceous chondrites is 0.392 ± 0.015 (excluding the CK chondrite, Karoonda), compared with 0.422 ± 0.025 and 0.421 ± 0.013 for ordinary and enstatite chondrites (1σ standard deviations). These ratios, recast into elemental Re/Os ratios, are as follows: 0.0814 ± 0.0031, 0.0876 ± 0.0052 and 0.0874 ± 0.0027, respectively. Correspondingly, the ¹⁸⁷Os/¹⁸⁸Os ratios of carbonaceous chondrites average 0.1262 ± 0.0006 (excluding Karoonda), and ordinary and enstatite chondrites average 0.1283 ± 0.0017 and 0.1281 ± 0.0004, respectively (1σ standard deviations). The new results indicate that the Re/Os ratios of meteorites within each group are, in general, quite uniform. The minimal overlap between the isotopic compositions of ordinary and enstatite chondrites vs. carbonaceous chondrites indicates long-term differences in Re/Os for these materials, most likely reflecting chemical fractionation early in solar system history.A majority of the chondrites do not plot within analytical uncertainties of a 4.56-Ga reference isochron. Most of the deviations from the isochron are consistent with minor, relatively recent redistribution of Re and/or Os on a scale of millimeters to centimeters. Some instances of the redistribution may be attributed to terrestrial weathering; others are most likely the result of aqueous alteration or shock events on the parent body within the past 2 Ga.The ¹⁸⁷Os/¹⁸⁸Os ratio of Earth’s primitive upper mantle has been estimated to be 0.1296 ± 8. If this composition was set via addition of a late veneer of planetesimals after core formation, the composition suggests the veneer was dominated by materials that had Re/Os ratios most similar to ordinary and enstatite chondrites.