Iron isotopes constrain biologic and abiologic processes in banded iron formation genesis

The voluminous 2.5 Ga banded iron formations (BIFs) from the Hamersley Basin (Australia) and Transvaal Craton (South Africa) record an extensive period of Fe redox cycling. The major Fe-bearing minerals in the Hamersley-Transvaal BIFs, magnetite and siderite, did not form in Fe isotope equilibrium, but instead reflect distinct formation pathways. The near-zero average δ⁵⁶Fe values for magnetite record a strong inheritance from Fe³⁺ oxide/hydroxide precursors that formed in the upper water column through complete or near-complete oxidation. Transformation of the Fe³⁺ oxide/hydroxide precursors to magnetite occurred through several diagenetic processes that produced a range of δ⁵⁶Fe values: (1) addition of marine hydrothermal , (2) complete reduction by bacterial dissimilatory iron reduction (DIR), and (3) interaction with excess that had low δ⁵⁶Fe values and was produced by DIR. Most siderite has slightly negative δ⁵⁶Fe values of ∼ −0.5‰ that indicate equilibrium with Late Archean seawater, although some very negative δ⁵⁶Fe values may record DIR. Support for an important role of DIR in siderite formation in BIFs comes from previously published C isotope data on siderite, which may be explained as a mixture of C from bacterial and seawater sources.Several factors likely contributed to the important role that DIR played in BIF formation, including high rates of ferric oxide/hydroxide formation in the upper water column, delivery of organic carbon produced by photosynthesis, and low clastic input. We infer that DIR-driven Fe redox cycling was much more important at this time than in modern marine systems. The low pyrite contents of magnetite- and siderite-facies BIFs suggests that bacterial sulfate reduction was minor, at least in the environments of BIF formation, and the absence of sulfide was important in preserving magnetite and siderite in the BIFs, minerals that are poorly preserved in the modern marine record. The paucity of negative δ⁵⁶Fe values in older (Early Archean) and younger (Early Proterozoic) BIFs suggests that the extensive 2.5 Ga Hamersley-Transvaal BIFs may record a period of maximum expansion of DIR in Earth’s history.     

Surface complexation of U(VI) on goethite (α-FeOOH)

Sorption of U(VI) to goethite is a fundamental control on the mobility of uranium in soil and groundwater. Here, we investigated the sorption of U on goethite using EXAFS spectroscopy, batch sorption experiments and DFT calculations of the energetics and structures of possible surface complexes. Based on EXAFS spectra, it has previously been proposed that U(VI), as the uranyl cation , sorbs to Fe oxide hydroxide phases by forming a bidentate edge-sharing (E2) surface complex, >Fe(OH)₂UO₂(H₂O)_n. Here, we argue that this complex alone cannot account for the sorption capacity of goethite (α-FeOOH). Moreover, we show that all of the EXAFS signal attributed to the E2 complex can be accounted for by multiple scattering. We propose that the dominant surface complex in CO₂-free systems is a bidentate corner-sharing (C2) complex, (>FeOH)₂UO₂(H₂O)₃ which can form on the dominant {101} surface. However, in the presence of CO₂, we find an enhancement of UO₂ sorption at low pH and attribute this to a (>FeO)CO₂UO₂ ternary complex. With increasing pH, U(VI) desorbs by the formation of aqueous carbonate and hydroxyl complexes. However, this desorption is preceded by the formation of a second ternary surface complex (>FeOH)₂UO₂CO₃. The three proposed surface complexes, (>FeOH)₂UO₂(H₂O)₃, >FeOCO₂UO₂, and (>FeOH)₂UO₂CO₃ are consistent with EXAFS spectra. Using these complexes, we developed a surface complexation model for U on goethite with a 1-pK model for surface protonation, an extended Stern model for surface electrostatics and inclusion of all known UO₂-OH-CO₃ aqueous complexes in the current thermodynamic database. The model gives an excellent fit to our sorption experiments done in both ambient and reduced CO₂ environments at surface loadings of 0.02-2.0 wt% U.     

Spectroscopic investigation of uranyl(VI) and citrate coadsorption to Al2O3

ATR-FTIR spectroscopy is used to understand the adsorption of uranyl-citrate complexes to Al₂O₃. Spectral data indicate that uranyl-citrate complexes partially dissociate upon adsorption, allowing full or partial hydrolysis of the uranyl ion. K_ads values determined for free citrate adsorption are similar to those for citrate in uranyl-citrate complexes, indicating that the complexation of uranyl by citrate does not significantly affect the ability of citrate to bond with the surface. The isotherm data also indicate enhanced citrate adsorption to Al₂O₃ in the presence of uranyl, suggesting that uranyl may be the central link between two citrate ligands, and that uranyl is associated with the surface through a bridging citrate ligand. Finally, uranyl-citrate complexes interact with citrate adsorbed to Al₂O₃ through outer sphere interactions.     

Seasonal patterns of carbon chemistry and isotopes in tufa depositing groundwaters of southwestern Japan

Annually laminated carbonates, known as tufas, commonly develop in limestone areas and typically record seasonal patterns of oxygen- and carbon-isotope compositions. δ¹⁸O values are principally controlled by seasonal changes of water temperature, whereas δ¹³C values are the result of complex reactions among the gaseous, liquid, and solid sources of carbon in the system. We examined the processes that cause the seasonal patterns of δ¹³C in groundwater systems at three tufa-depositing sites in southwestern Japan by applying model calculations to geochemical data. Underground inorganic carbon species are exchanged with gaseous CO₂, which is mainly introduced to the underground hydrological system by natural atmospheric ventilation and by diffusion of soil air. These processes control the seasonal pattern of δ¹³C, which is low in summer and high in winter. Among the three sites we investigated, we identified two extreme cases of the degree of carbon exchange between liquid and gaseous phases. For the case with high radiocarbon composition (Δ¹⁴C) and low pCO₂, there was substantial carbon exchange because of a large contribution of atmospheric CO₂ and a small water mass. For the other extreme case, which was characterized by low Δ¹⁴C and high pCO₂, the contribution of atmospheric CO₂ was small and the water mass was relatively large. Our results suggest that at two of the three sites water residence time within the soil profile was longer than 1 year. Our results also suggested a short residence time (less than 1 year) of water in the soil profile at the site with the smallest water mass, which is consistent with large seasonal amplitude of the springwater temperature variations. The Δ¹⁴C value of tufas is closely related to the hydrological conditions in which they are deposited. If the initial Δ¹⁴C value of a tufa-depositing system is stable, ¹⁴C-chronology can be used to date paleo-tufas.     

An absolute paleotemperature record from 10 to 6 Ka inferred from fluid inclusion D/H ratios of a stalagmite from Vancouver Island, British Columbia, Canada

By using continuous helium flow during the crushing of calcite speleothem samples, we are able to recover liberated inclusion waters without isotopic fractionation. A paleotemperature record for the Jacklah Jill Cave locality, Vancouver Island, BC, was obtained from a 30-cm tall stalagmite that grew 10.3-6.3 Ka ago, using δ¹⁸O values of the crushed calcite and of the inclusion water as inferred from its δD. It is found that the locality experienced mean annual temperature variations up to 11 °C over a 4-Ka period in the early Holocene. At the beginning of the period, local temperature quickly increased from a minimum of ∼1 °C to around 10 °C, but this early climate optimum, about 3 °C warmer than today, only lasted for ∼1200 years. About 8.6 Ka ago, temperature had declined to ∼7 °C, approximately the same as the modern cave temperature. Since then, the study area has experienced only minor temperature fluctuations, but there was a brief fall to ∼4 °C at around 7 Ka ago, which might be caused by a short lived expansion of local alpine glaciers. The long-term T-dependence of δD was 1.47‰/°C, identical to the value in modern precipitation.     

Kinetics of Cd sorption, desorption and fixation by calcite: A long-term radiotracer study

Time-dependent sorption and desorption of Cd on calcite was studied over 210 days utilizing ¹⁰⁹Cd as a tracer to distinguish between ‘labile’ and ‘non-labile’ forms of sorbed Cd. Stabilizing the calcite suspensions for 12 months under atmospheric P_CO2 and controlled temperature was necessary to reliably follow Cd dynamics following initial sorption. Results revealed time-dependant Cd sorption and marked desorption hysteresis by calcite under environmentally relevant conditions. Data obtained were fitted to a first-order kinetic model and a concentric shell diffusion model. Both models described the progressive transfer of Cd²⁺ to a less reactive form within calcite and subsequent desorption of Cd subject to different initial contact times. The kinetic model provided a better fit to the combined sorption and desorption data (R² = 0.992). It differentiates between two ‘pools’ of sorbed Cd²⁺ on calcite, ‘labile’ and ‘non-labile’, in which labile sorbed Cd is in immediate equilibrium with the free Cd²⁺ ion activity in solution whereas non-labile Cd is kinetically restricted. For the diffusion model (R² = 0.959), the rate constants describing Cd dynamics in calcite produced a half-life for Cd desorption of ∼175 d, for release to a ‘zero-sink’ solution. Results from this study allow comment on the likely mechanisms occurring at the calcite surface following long-term Cd sorption.     

Silicon isotope fractionation in bamboo and its significance to the biogeochemical cycle of silicon

A systematic investigation on silica contents and silicon isotope compositions of bamboos was undertaken. Seven bamboo plants and related soils were collected from seven locations in China. The roots, stem, branch and leaves for each plant were sampled and their silica contents and silicon isotope compositions were determined. The silica contents and silicon isotope compositions of bulk and water-soluble fraction of soils were also measured. The silica contents of studied bamboo organs vary from 0.30% to 9.95%. Within bamboo plant the silica contents show an increasing trend from stem, through branch, to leaves. In bamboo roots the silica is exclusively in the endodermis cells, but in stem, branch and leaves, the silica is accumulated mainly in epidermal cells. The silicon isotope compositions of bamboos exhibit significant variation, from −2.3‰ to 1.8‰, and large and systematic silicon isotope fractionation was observed within each bamboo. The δ³⁰Si values decrease from roots to stem, but then increase from stem, through branch, to leaves. The ranges of δ³⁰Si values within each bamboo vary from 1.0‰ to 3.3‰. Considering the total range of silicon isotope composition in terrestrial samples is only 7‰, the observed silicon isotope variation in single bamboo is significant and remarkable. This kind of silicon isotope variation might be caused by isotope fractionation in a Rayleigh process when SiO₂ precipitated in stem, branches and leaves gradually from plant fluid. In this process the Si isotope fractionation factor between dissolved Si and precipitated Si in bamboo (α_pre-sol) is estimated to be 0.9981. However, other factors should be considered to explain the decrease of δ³⁰Si value from roots to stem, including larger ratio of dissolved H₄SiO₄ to precipitated SiO₂ in roots than in stem. There is a positive correlation between the δ³⁰Si values of water-soluble fractions in soils and those of bulk bamboos, indicating that the dissolved silicon in pore water and phytoliths in soil is the direct sources of silicon taken up by bamboo roots. A biochemical silicon isotope fractionation exists in process of silicon uptake by bamboo roots. Its silicon isotope fractionation factor (α_bam-wa) is estimated to be 0.9988. Considering the distribution patterns of SiO₂ contents and δ³⁰Si values among different bamboo organs, evapotranspiration may be the driving force for an upward flow of a silicon-bearing fluid and silica precipitation. Passive silicon uptake and transportation may be important for bamboo, although the role of active uptake of silicic acid by roots may not be neglected. The samples with relatively high δ³⁰Si values all grew in soils showing high content of organic materials. In contrast, the samples with relatively low δ³⁰Si values all grew in soil showing low content of organic materials. The silicon isotope composition of bamboo may reflect the local soil type and growth conditions. Our study suggests that bamboos may play an important role in global silicon cycle.     

Cr-spinel/olivine and Cr-spinel/liquid nickel partition coefficients from natural samples

The Nernst partition coefficient of nickel (D^Ni) between Cr-spinel and silicate melt in natural systems has been investigated using mid-ocean ridge basalts (MORB) and other volcanic rocks. The Cr-spinel/olivine D^Ni values in volcanic rocks are between 1.2 and 0.3, indicating that the Cr-spinel/liquid D^Ni values vary from slightly higher to significantly lower than the olivine/liquid D^Ni values in natural systems. The Cr-spinel/liquid D^Ni values from the MORB samples vary between 6 and 11, slightly higher than those from the S-bearing experiments of Satari et al. [Satari P., Brenan J. M., Horn I. and McDonough W. F. (2002) Experimental constraints on the sulfide- and chromite-silicate melt partitioning behavior of rhenium and platinum-group elements. Economic Geology97, 385-398]. The results of the MORB samples and the experiments of Satari et al. (2002) indicate a negative correlation between the Cr-spinel/liquid D^Ni and the X_Cr values in Cr-spinels (Cr cation number on the basis of 3 total cations in the spinel structure). Variations of Cr-spinel/liquid D^Ni values with Cr-spinel compositions can be estimated from an empirical equation based on the results of the MORB samples and the experiments by Satari et al. (2002). The choice of Cr-spinel/liquid D^Ni = 10 for numerical modeling by Righter et al. [Righter K., Leeman W. P. and Hervig R. L. (2006) Partitioning of Ni, Co, and V between spinel-structured oxides and silicate melts: importance of spinel composition. Chemical Geology227, 1-25] is reasonable for basaltic systems. For picritic and komatiitic systems a lower value of ∼5 is more appropriate.     

Low-oxygen and chemical kinetic constraints on the geochemical niche of neutrophilic iron(II) oxidizing microorganisms

Neutrophilic iron oxidizing bacteria (FeOB) must actively compete with rapid abiotic processes governing Fe(II) oxidation and as a result have adapted to primarily inhabit low-O₂ environments where they can more successfully compete with abiotic Fe(II) oxidation. The spatial distribution of these microorganisms can be observed through the chemical gradients they affect, as measured using in situ voltammetric analysis for dissolved Fe(II), Fe(III), O₂, and FeS_(aq). Field and laboratory determination of the chemical environments inhabited by the FeOB were coupled with detailed kinetic competition studies for abiotic and biotic oxidation processes using a pure culture of FeOB to quantify the geochemical niche these organisms inhabit. In gradient culture tubes, the maximum oxygen levels, which were associated with growth bands of Sideroxydans lithotrophicus (ES-1, a novel FeOB), were 15-50 μM. Kinetic measurements made on S. lithotrophicus compared biotic/abiotic (killed control) Fe oxidation rates. The biotic rate can be a significant and measurable fraction of the total Fe oxidation rate below O₂ concentrations of approximately 50 μM, but biotic Fe(II) oxidation (via the biotic/abiotic rate comparison) becomes difficult to detect at higher O₂ levels. These results are further supported by observations of conditions supporting FeOB communities in field settings. Variablity in cell densities and cellular activity as well as variations in hydrous ferrous oxide mineral quantities significantly affect the laboratory kinetic rates. The microbial habitat (or geochemical niche) where FeOB are active is thus largely controlled by the competition between abiotic and biotic kinetics, which are dependent on Fe(II) concentration, P_O2, temperature and pH in addition to the surface area of hydrous ferric oxide minerals and the cell density/activity of FeOB. Additional field and lab culture observations suggest a potentially important role for the iron-sulfide aqueous molecular cluster, FeS_(aq), in the overall cycling of iron associated with the environments these microorganisms inhabit.     

Anaerobic oxidation of methane (AOM) in marine sediments from the Skagerrak (Denmark): II. Reaction-transport modeling

A steady-state reaction-transport model is applied to sediments retrieved by gravity core from two stations (S10 and S13) in the Skagerrak to determine the main kinetic and thermodynamic controls on anaerobic oxidation of methane (AOM). The model considers an extended biomass-implicit reaction network for organic carbon degradation, which includes extracellular hydrolysis of macromolecular organic matter, fermentation, sulfate reduction, methanogenesis, AOM, acetogenesis and acetotrophy. Catabolic reaction rates are determined using a modified Monod rate expression that explicitly accounts for limitation by the in situ catabolic energy yields. The fraction of total sulfate reduction due to AOM in the sulfate-methane transition zone (SMTZ) at each site is calculated. The model provides an explanation for the methane tailing phenomenon which is observed here and in other marine sediments, whereby methane diffuses up from the SMTZ to the top of the core without being consumed. The tailing is due to bioenergetic limitation of AOM in the sulfate reduction zone, because the methane concentration is too low to engender favorable thermodynamic drive. AOM is also bioenergetically inhibited below the SMTZ at both sites because of high hydrogen concentrations (∼3-6 nM). The model results imply there is no straightforward relationship between pore water concentrations and the minimum catabolic energy needed to support life because of the highly coupled nature of the reaction network. Best model fits are obtained with a minimum energy for AOM of ∼11 kJ mol⁻¹, which is within the range reported in the literature for anaerobic processes.