Iron isotope fractionation during microbially stimulated Fe(II) oxidation and Fe(III) precipitation

Interpretation of the origins of iron-bearing minerals preserved in modern and ancient rocks based on measured iron isotope ratios depends on our ability to distinguish between biological and non-biological iron isotope fractionation processes. In this study, we compared ⁵⁶Fe/⁵⁴Fe ratios of coexisting aqueous iron (Fe(II)_aq, Fe(III)_aq) and iron oxyhydroxide precipitates (Fe(III)_ppt) resulting from the oxidation of ferrous iron under experimental conditions at low pH (<3). Experiments were carried out using both pure cultures of Acidothiobacillus ferrooxidans and sterile controls to assess possible biological overprinting of non-biological fractionation, and both SO₄²⁻ and Cl⁻ salts as Fe(II) sources to determine possible ionic/speciation effects that may be associated with oxidation/precipitation reactions. In addition, a series of ferric iron precipitation experiments were performed at pH ranging from 1.9 to 3.5 to determine if different precipitation rates cause differences in the isotopic composition of the iron oxyhydroxides. During microbially stimulated Fe(II) oxidation in both the sulfate and chloride systems, ⁵⁶Fe/⁵⁴Fe ratios of residual Fe(II)_aq sampled in a time series evolved along an apparent Rayleigh trend characterized by a fractionation factor α_{Fe(III)aq-Fe(II)aq} ∼ 1.0022. This fractionation factor was significantly less than that measured in our sterile control experiments (∼1.0034) and that predicted for isotopic equilibrium between Fe(II)_aq and Fe(III)_aq (∼1.0029), and thus might be interpreted to reflect a biological isotope effect. However, in our biological experiments the measured difference in ⁵⁶Fe/⁵⁴Fe ratios between Fe(III)_aq, isolated as a solid by the addition of NaOH to the final solution at each time point under N₂-atmosphere, and Fe(II)_aq was in most cases and on average close to 2.9‰ (α_{Fe(III)aq-Fe(II)aq} ∼ 1.0029), consistent with isotopic equilibrium between Fe(II)_aq and Fe(III)_aq. The ferric iron precipitation experiments revealed that ⁵⁶Fe/⁵⁴Fe ratios of Fe(III)_aq were generally equal to or greater than those of Fe(III)_ppt, and isotopic fractionation between these phases decreased with increasing precipitation rate and decreasing grain size. Considered together, the data confirm that the iron isotope variations observed in our microbial experiments are primarily controlled by non-biological equilibrium and kinetic factors, a result that aids our ability to interpret present-day iron cycling processes but further complicates our ability to use iron isotopes alone to identify biological processing in the rock record.     

Fine‐grained,spinel‐rich inclusions from the reduced CV chondrite Efremovka: II. Oxygen isotopic compositions

Abstract— Oxygen isotopes have been measured by ion microprobe in individual minerals (spinel, Al‐Ti‐diopside, melilite, and anorthite) within four relatively unaltered, fine‐grained, spinel‐rich Ca‐Al‐rich inclusions (CAIs) from the reduced CV chondrite Efremovka. Spinel is uniformly ¹⁶O‐rich (Δ¹⁷O ≤ ?20‰) in all four CAIs; Al‐Ti‐diopside is similarly ¹⁶O‐rich in all but one CAI, where it has smaller ¹⁶O excesses (‐15‰ ≤ Δ¹⁷O ≤ ?10‰). Anorthite and melilite vary widely in composition from ¹⁶O‐rich to ¹⁶O‐poor (‐22‰ ≤ Δ¹⁷O ≤ ?5‰). Two of the CAIs are known to have group II volatility‐fractionated rare‐earth‐element patterns, which is typical of this variety of CAI and which suggests formation by condensation. The association of such trace element patterns with ¹⁶O‐enrichment in these CAIs suggests that they formed by gas‐solid condensation from an ¹⁶O‐rich gas. They subsequently experienced thermal processing in an ¹⁶O‐poor reservoir, resulting in partial oxygen isotope exchange. Within each inclusion, oxygen isotope variations from mineral to mineral are consistent with solid‐state oxygen self‐diffusion at the grain‐to‐grain scale, but such a model is not consistent with isotopic variations at a larger scale in two of the CAIs. The spatial association of ¹⁶O depletions with both elevated Fe contents in spinel and the presence of nepheline suggests that late‐stage iron‐alkali metasomatism played some role in modifying the isotopic patterns in some CAIs. One of the CAIs is a compound object consisting of a coarse‐grained, melilite‐rich (type A) lithology joined to a fine‐grained, spinel‐rich one. Melilite and anorthite in the fine‐grained portion are mainly ¹⁶O‐rich, whereas melilite in the type A portion ranges from ¹⁶O‐rich to ¹⁶O‐poor, suggesting that oxygen isotope exchange predated the joining together of the two parts and that both ¹⁶O‐rich and ¹⁶O‐poor gaseous reservoirs existed simultaneously in the early solar nebula.     

Formulation and characterization of an appropriate lime-based mortar for use with a porous limestone

Several studies have shown that the degradation of architectural monuments constructed using Tuffeau stones from Val de Loire region of France over a period of time are often related to use of mortars that are not compatible with the Tuffeau stones. For this reason, it is important to ensure physico-chemical compatibility between Tuffeau and the mortar. To alleviate differences in compatibility characteristics, a mortar is prepared from hydrated lime and aggregates obtained from the crushing of Tuffeau stone and used in this study. The key parameters that influence the strength and durability characteristics such as mechanical resistance, water transfer properties, and physico-chemical properties were identified and studied. Based on these studies, recommendations are offered for the preparation of a more compatible mortar that can be used in the construction and restoration of monuments using Tuffeau stone.     

Composition and flight periodicity of adult caddisflies in New Zealand hill‐country catchments of contrasting land use

A total of 6085 adult Trichoptera (excluding Hydroptilidae) representing 12 families, 31 genera, and 56 species were collected by a combination of Malaise net and light trapping from July 1998 to July 1999 at three hill‐country sites of contrasting catchment land use (100% native forest, a pasture site with native forest headwaters, and 100% pasture) in the Waikato, northern New Zealand. Forty‐eight species of Trichoptera were collected from Malaise nets and 45 species from light traps. Eleven species of Trichoptera were only ever collected from the Malaise nets and seven species from only the light traps. At the native forest site, Malaise nets collected more species and taxa of conservation interest than did light traps, possibly reflecting diurnal activity or non‐attraction to light by some species. Several species of Trichoptera showed site specificity and most of these were found at the native forest site. Twenty‐eight species were active for at least 6 months of the year with at least four species active all year. A minimum overnight air temperature of at least 9°C was required to induce Trichoptera flight activity, but large‐scale flight activity may require temperatures greater than 14°C. Trichoptera with free‐living and net spinning larvae exhibited extended flight periods, and for three species examined there were bi‐modal activity peaks. Adult caddisflies with cased larvae which grazed on epilithic food resources generally had reduced flight periods and one species had a well‐defined, synchronous periodicity. These findings suggest flight periodicity may partly be a functional response to larval food availability.     

Design Considerations and Evaluation of a Collaborative, Spatio-Temporal Decision Support System

Collaborative spatial decision support systems (C‐SDSS) have been used to help groups of stakeholders understand data and search for opportunities at resolving local and regional decision problems in various domains including land use, trans‐ portation, and water resources. The key issue in designing an effective C‐SDSS is the anticipation of user information needs. Knowledge of user information needs can guide system designers in achieving a C‐SDSS that fits the decision process. In this paper we present a design approach that is informed by stakeholder concerns, as part of a user needs assessment. The approach is based on the premise that knowing stakeholders’ concerns can help anticipate user information needs and consequently lead to a more usable C‐SDSS. We demonstrate the approach with the example of a spatio‐temporal decision problem involving conjunctive water administration in the Boise River Basin in southwestern Idaho. The spatial dimension of the decision task involves delineating the areas of conjunctive water administration while the temporal dimension involves selecting the year in which a given area will start to be administered. We show how the elicitation of stakeholder concerns leads to functional specification of a collaborative spatio‐temporal decision support system.     

Gas-partitioning tracer test to quantify trapped gas during recharge

Dissolved helium and bromide tracers were used to evaluate trapped gas during an infiltration pond experiment. Dissolved helium preferentially partitioned into trapped gas bubbles, or other pore air, because of its low solubility in water. This produced observed helium retardation factors of as much as 12 relative to bromide. Numerical simulations of helium breakthrough with both equilibrium and kinetically limited advection/dispersion/retardation did not match observed helium concentrations. However, better fits were obtained by including a decay term representing the diffusive loss of helium through interconnected, gas-filled pores. Calculations indicate that 7% to more than 26% of the porosity beneath the pond was filled with gas. Measurements of laboratory hydraulic properties indicate that a 10% decrease in saturation would reduce the hydraulic conductivity by at least one order of magnitude in the well-sorted sandstone, but less in the overlying soils. This is consistent with in situ measurements during the experiment, which show steeper hydraulic gradients in sandstone than in soil. Intrinsic permeability of the soil doubled during the first six months of the experiment, likely caused by a combination of dissolution and thermal contraction of trapped gas. Managers of artificial recharge basins may consider minimizing the amount of trapped gas by using wet, rather than dry, tilling to optimize infiltration rates, particularly in well-sorted porous media in which reintroduced trapped gas may cause substantial reductions in permeability. Trapped gas may also inhibit the amount of focused infiltration that occurs naturally during ephemeral flood events along washes and playas.     

Ion microprobe isotopic measurements of individual interplanetary dust particles

Ion microprobe measurements of D/H ratios in individual fragments of eight stratospheric dust particles give δD values ranging from ?386 to +2534‰ relative to SMOW. The δD values in five particles far exceed those in terrestrial samples and prove that the samples are interplanetary dust particles (IDPs). The hydrogen isotopic composition is heterogeneous on a scale of a few microns demonstrating that the dust is unequilibrated. Measurements of D/H ratios in conjunction with elemental and molecular ion signals in different fragments of individual IDPs show that a carbonaceous phase, not water, is the carrier of the D enrichments. Previous infrared transmission measurements have shown that IDPs fall into three main spectral classes. Particles from two of those three IR classes show large D/H ratios. Two particles studied from the third class do not. However, one of these contains solar flare tracks and is extraterrestrial. Thus, most, but not all, IDPs contain hydrogen with a non-terrestrial isotopic composition.Carbon isotopic measurements on fragments of three IDPs give ratios similar to terrestrial values and show a largely uniform isotopic composition for a given particle. Small, but significant, differences in δ¹³C of ~40‰ between particles are seen. No correlations between the hydrogen and carbon isotopic compositions are observed.The magnesium and silicon isotopic compositions of fragments of three IDPs are found to be normal within measurement errors.     

Using Soil Magnetic Properties to Determine the Onset of Pleistocene Human Settlement at Gledswood Shelter 1, Northern Australia

In regions that lack built structures or stratified open archaeological sites, such as precolonial Australia, rockshelters are a major source of detailed information for understanding the nature and timing of human occupation. A key concern is that the proposed ages for the earliest archaeological sites are based on luminescence dating of sediments, rather than directly of cultural materials, leaving the association between the sediments and evidence of human activity questionable. Here, we present evidence of magnetic enhancement associated with cultural horizons within the deposits of a Pleistocene rockshelter in interior northern Queensland. Soil magnetic studies combined with experimental burning show that magnetically enhanced sediments in Gledswood Shelter 1 are the result of anthropogenic burning of hearth fires, which burn hotter and for a longer time than natural wild fires. These techniques appear to work in this setting because of the nature of the local geology and the geological antiquity of the landscape. Susceptibility and frequency dependence of susceptibility signatures provide a critical tool to resolve that human occupation starts at 2.2 m depth within a stratigraphic section. In conjunction with luminescence dating, soil magnetic studies provide an opportunity for archaeologists to resolve the timing of human settlement in Australia and other intracratonic plate settings.     

Reappraisal of early Paleogene CCD curves: foraminiferal assemblages and stable carbon isotopes across the carbonate facies of Perth Abyssal Plain

Bulk carbonate content, planktic and benthic foraminiferal assemblages, stable isotope compositions of bulk carbonate and Nuttallides truempyi (benthic foraminifera), and non-carbonate mineralogy were examined across ∼30 m of carbonate-rich Paleogene sediment at Deep Sea Drilling Project (DSDP) Site 259, on Perth Abyssal Plain off Western Australia. Carbonate content, mostly reflecting nannofossil abundance, ranges from 3 to 80% and generally exceeds 50% between 35 and 57 mbsf. A clay-rich horizon with a carbonate content of about 37% occurs between 55.17 and 55.37 mbsf. The carbonate-rich interval spans planktic foraminiferal zones P4c to P6b (∼57–52 Ma), with the clay-rich horizon near the base of our Zone P5 (upper)—P6b. Throughout the studied interval, benthic species dominate foraminiferal assemblages, with scarce planktic foraminifera usually of poor preservation and limited species diversity. A prominent Benthic Foraminiferal Extinction Event (BFEE) occurs across the clay-rich horizon, with an influx of large Acarinina immediately above. The δ¹³C records of bulk carbonate and N. truempyi exhibit trends similar to those observed in upper Paleocene–lower Eocene (∼57–52 Ma) sediment from other locations. Two successive decreases in bulk carbonate and N. truempyi δ¹³C of 0.5 and 1.0‰ characterize the interval at and immediately above the BFEE. Despite major changes in carbonate content, foraminiferal assemblages and carbon isotopes, the mineralogy of the non-carbonate fraction consistently comprises expanding clay, heulandite (zeolite), quartz, feldspar (sodic or calcic), minor mica, and pyrolusite (MnO₂). The uniformity of this mineral assemblage suggests that Site 259 received similar non-carbonate sediment before, during and after pelagic carbonate deposition. The carbonate plug at Site 259 probably represents a drop in the CCD from ∼57 to 52–51 Ma, as also recognized at other locations.