Uranium speciation and stability after reductive immobilization in aquifer sediments

It has generally been assumed that the bioreduction of hexavalent uranium in groundwater systems will result in the precipitation of immobile uraninite (UO₂). In order to explore the form and stability of uranium immobilized under these conditions, we introduced lactate (15 mM for 3 months) into flow-through columns containing sediments derived from a former uranium-processing site at Old Rifle, CO. This resulted in metal-reducing conditions as evidenced by concurrent uranium uptake and iron release. Despite initial augmentation with Shewanella oneidensis, bacteria belonging to the phylum Firmicutes dominated the biostimulated columns. The immobilization of uranium (∼1 mmol U per kg sediment) enabled analysis by X-ray absorption spectroscopy (XAS). Tetravalent uranium associated with these sediments did not have spectroscopic signatures representative of U-U shells or crystalline UO₂. Analysis by microfocused XAS revealed concentrated micrometer regions of solid U(IV) that had spectroscopic signatures consistent with bulk analyses and a poor proximal correlation (μm scale resolution) between U and Fe. A plausible explanation, supported by biogeochemical conditions and spectral interpretations, is uranium association with phosphoryl moieties found in biomass; hence implicating direct enzymatic uranium reduction. After the immobilization phase, two months of in situ exposure to oxic influent did not result in substantial uranium remobilization. Ex situ flow-through experiments demonstrated more rapid uranium mobilization than observed in column oxidation studies and indicated that sediment-associated U(IV) is more mobile than biogenic UO₂. This work suggests that in situ uranium bioimmobilization studies and subsurface modeling parameters should be expanded to account for non-uraninite U(IV) species associated with biomass.     

Geochemical processes in a Mediterranean Lake: a high-resolution study of the last 4,000 years in Zoñar Lake,southern Spain

High-resolution geochemical analysis of a 6-m-long sediment core from Zoñar Lake, southern Spain, provides a detailed characterization of major changes in lake and watershed processes during the last 4,000 years. Geochemical variables were used as paleolimnological indicators and complement Zoñar Lakes’s paleoenvironmental reconstruction based on sedimentological and biological proxies, which define periods of increasing allochthonous input to the lake and periods of dominant autochthonous sedimentation. Chemical ratios identify periods of endogenic carbonate formation (higher Ca/Al, Sr/Al and Ba/Al ratios), evaporite precipitation (higher S/Al, Sr/Al ratios), and anoxic conditions (higher Mo/Al, U/Th ratios and Eu anomaly). Higher productivity is marked by elevated organic carbon content and carbonate precipitation (Mg/Ca). Hydrological reconstruction for Zoñar Lake was based on sedimentological, mineralogical and biological proxies, and shows that lower lake levels are characterized by Sr-rich sediments (a brackish lake with aragonite) and S-rich sediments (a saline lake with gypsum), while higher lake levels are characterized by sediments enriched in elements associated with alumino-silicates (Al, K, Ti, Fe, trace and rare earth elements), reflecting fresher conditions. Geochemical indicators also mark periods of higher detrital input to the lake related to human activity in the watershed: (1) during the Iberian Roman Humid Period (650 BC–AD 300), around the onset of the Little Ice Age (AD 1400), during the relatively drier Post-Roman and Middle Ages (AD 800–1400), and over the last 50 years, due to mechanized farming practices. Heavy metal enrichment in the sediments (Cu and Ni) suggests intensification of human activities during the Iberian Roman Period, and the use of fertilizers during the last 50 years.     

Alteration of bottom roughness by benthic organisms in a sandy coastal environment

This work deals with the potential influence of benthic communities on the sediment dynamics of the coastal zone, and specifically with the modifications to bottom roughness caused by communities and their effects on wave propagation across the coastal profile. Time-series of video observations of the sea bottom on the Ebro delta coast were analysed in order to estimate the bottom roughness associated with physical and biological morphological components and the sediment reworking rates caused by epifaunal organisms. Biological roughness was mainly caused by ophiuroids and tanatocenosis of bivalve and gastropod shells, which changed their abundance during the study period. The total biological roughness (K_bio) ranged between 0.27 and 0.81 cm and represented a significant part (<20%) of the total form drag roughness. Flattening of ripples caused by bioturbation was observed under low-energy conditions. Surface sediment perturbation and bioturbation rates were also estimated. Based on these observations a wave propagation model was applied in order to carry out a sensitivity analysis of the significance of biological roughness on wave dissipation in the study area under different wave conditions.     

Soil fertility evolution and landscape dynamics in a Mediterranean area: a case study in the Sant Llorenç Natural Park (Barcelona, NE Spain)

The cartography of land covers was used to study fertility and soil evolution in a mountainous Mediterranean area during the anthropocene period ( Crutzen P J 2002 Geology of mankind Nature 415 23). The aim was to determine changes in fertility as agricultural lands were abandoned in the 14 000 hectare area that constitutes Sant Llorenç del Munt Natural Park in a pre-coastal Catalan mountain range (north-eastern Iberian Peninsula). The analysis of land covers using vegetation maps, orthorectified images and aerial photography has allowed us to differentiate six vegetation groups: holm-oak wood, pine grove, oak wood, scrub, active agricultural fields and abandoned agricultural fields. The anthropic covers over the past 100 years were subdivided into five categories: active fields and those abandoned over four time periods. Study variables include field shape (concave, convex, flat), orientation (north, south) and slope (ranging from 12º to 24º). The parameters used for the physical-chemical soil analysis included organic material, phosphorous and potassium; fertility was classified based on groups, types and classes. The results indicate that even when the visual appearance of certain landscapes is similar, the edaphic characteristics may be very different. Changes induced by human disturbance share this phenomenon. Therefore, land management should be considered globally, taking into account vegetation, soils and water as interdependent factors, since it is their interaction that produces landscape and most affects its evolution over time.     

Pyrite formation driven by MSW landfill leachate in the Madrid Basin, Spain

The role of municipal solid waste (MSW) landfill leachate on the genesis of minor amounts of pyrite associated with gypsum in an otherwise predominantly evaporitic sequence was studied in geological and geochemical terms. The potential association between landfill leachate and the conditions required for bacterial reduction of sulfate and fixation of H₂S as pyrite were examined. The lithological column was generally found to contain little or no Fe. The δ³⁴S values for sulfates were consistent with previously reported data; however, the measured δ¹⁸O values were slightly higher. Sulfides disseminated in the marl/lutite exhibited higher δ³⁴S values (≈−8‰) than gypsum-coating pyrite crystals (δ³⁴S < −30‰). Dissolution of gypsum to sulfate and the supply of metabolizable organic matter and Fe required for H₂S fixation as sulfides may have originated from landfill leachate. Intermittent availability of leachate, a result of the precipitation regime, can facilitate sulfur disproportionation and lead to fractionations as high as      

Dissolution of arsenopyrite (FeAsS) and galena (PbS) in the presence of desferrioxamine-B at pH 5

Microorganisms and higher plants produce biogenic ligands, such as siderophores, to mobilize Fe that otherwise would be unavailable. In this paper, we study the stability of arsenopyrite (FeAsS), one of the most important natural sources of arsenic on Earth, in the presence of desferrioxamine (DFO-B), a common siderophore ligand, at pH 5. Arsenopyrite specimens from mines in Panasqueira, Portugal (100-149 μm) that contained incrustations of Pb, corresponding to elemental Pb as determined by scanning electron microscopy-electron diffraction spectroscopy (SEM-EDX), were used for this study. Batch dissolution experiments of arsenopyrite (1 g L⁻¹) in the presence of 200 μM DFO-B at initial pH (pH₀) 5 were conducted for 110 h. In the presence of DFO-B, release of Fe, As, and Pb showed positive trends with time; less dependency was observed for the release of Fe, As, and Pb in the presence of only water under similar experimental conditions. Detected concentrations of soluble Fe, As, and Pb in suspensions containing only water were found to be ca. 0.09 ± 0.004, 0.15 ± 0.003, and 0.01 ± 0.01 ppm, respectively. In contrast, concentrations of soluble Fe, As, and Pb in suspensions containing DFO-B were found to be 0.4 ± 0.006, 0.27 ± 0.009, and 0.14 ± 0.005 ppm, respectively. Notably, the effectiveness of DFO-B for releasing Pb was ca. 10 times higher than that for releasing Fe. These results cannot be accounted for by thermodynamic considerations, namely, by size-to-charge ratio considerations of metal complexation by DFO-B. As determined by SEM-EDX, elemental sample enrichment analysis supports the idea that the Fe-S subunit bond energy is limiting for Fe release. Likely, the mechanism(s) of dissolution for Pb incrustations is independent and occurs concurrently to that for Fe and As. Our results show that dissolution of arsenopyrite leads to precipitation of elemental sulfur, and is consistent with a non-enzymatic mineral dissolution pathway. Finally, speciation analyses for As indicate variability in the As(III)/As(V) ratio with time, regardless of the presence of DFO-B or water. At reaction times <30 h, As(V) concentrations were found to be 50-70%, regardless of the presence of DFO-B. These results are interpreted to indicate that transformations of As are not imposed by ligand-mediated mechanisms. Experiments were also conducted to study the dissolution behavior of galena (PbS) in the presence of 200 μM at pH₀ 5. Results show that, unlike arsenopyrite, the dissolution behavior of galena shows coupled increases in pH with decreases in metal solubility at t > 80 h. Oxidative dissolution mechanisms conveying sulfur oxidation bring about the production of {H⁺}. However, dissolution data trends for arsenopyrite and galena indicate {H⁺} consumption. It is plausible that the formation of Pb species is dependent on {H⁺} and {OH⁻}, namely, stable surface hydroxyl complexes of the form (pH₅₀ 5.8) and for pH values 5.8 or above.     

Lipid biogeochemistry of Phormidium and Microcoleus mats

A study on the predominant sources of organic matter and the main diagenetic processes in two different cyanobacterial mats from evaporite-controlled environments was performed. Fatty acids, hydrocarbons, alcohols, ketones and aldehydes were anlyzed in selected millimetre and submillimetre core sections. The changes in lipid composition were evaluated by comparison with the vertical distributions of the populations observed by optic microscopy and with the lipid patterns of enrichment cultures of species such as cyanobacteria, diatoms, purple bacteria, sulphate-reducers and methanogens obtained from the mats.The cyanobacteria Phormidium valderianum and Microcoleus chthonoplastes are the predominant primary producers, and occur almost as monocultures in the respective top layers. However, these mat-forming organisms only leave minor features in the solvent-extractable lipid sedimentary record. The predominant fatty acid distributions parallel the composition observed in the enrichment cultures of purple bacteria and appear mixed with acids characteristic of heterotrophic eubacteria such as sulphate-reducers. The concentrations of these lipids are, however, 5–10 times lower than the cyanobacterial acids from the top layer. De novo heterotrophic eubacterial synthesis is also observed in cases such as the highly branched isoprenoid eicosenes, the major hydrocarbon in the deep layers (>2 mm) of the Phormidium mat. Other major diagenetic changes involve dehydration and hydrogenation. These two processes take place concurrently under anoxic conditions and have been observed among the sterols and the isoprenoid alcohols. Significant amounts of 5ß(H)-stanols were observed in the more reducing sections where molecular indicators of methanogenic bacteria were also found.     

Can light intensity cause shifts in natural product and bacterial profiles of the sponge Aplysina aerophoba?

The potential role of microbial consortia on sponge chemistry is well known. However, how environmental factors affect microbial and chemical profiles and how these shifts affect the sponge holobiont are far from being understood. This study experimentally investigated the effect of light on both the concentration of secondary metabolites and the bacterial assemblages of the sponge Aplysina aerophoba. We quantified major brominated alkaloids (BAs) using a high‐performance liquid chromatography system coupled with a UV‐detector and analysed sponge‐associated bacteria using denaturing gradient gel electrophoresis of 16S rRNA gene amplicons. We identified distinct chemical and bacterial profiles between the ectosome and the choanosome of A. aerophoba. The abundance of most secondary metabolites increased regardless of the illumination regime. We found that the probability of occurrence of three microbial phylotypes (operational taxonomic units 84, 86 and 87) was strongly associated with increasing concentrations of three brominated compounds (aerophobin‐1, aplysinamisin‐1 and isofistularin‐3). Although the role of these bacteria remains uninvestigated, these associations between natural products and specific microbial phylotypes outline further hypotheses that will improve our understanding of the organization and functioning of these complex host–symbiont interactions.