Evidence for equilibrium iron isotope fractionation by nitrate-reducing iron(II)-oxidizing bacteria

Iron isotope fractionations produced during chemical and biological Fe(II) oxidation are sensitive to the proportions and nature of dissolved and solid-phase Fe species present, as well as the extent of isotopic exchange between precipitates and aqueous Fe. Iron isotopes therefore potentially constrain the mechanisms and pathways of Fe redox transformations in modern and ancient environments. In the present study, we followed in batch experiments Fe isotope fractionations between Fe(II)_aq and Fe(III) oxide/hydroxide precipitates produced by the Fe(III) mineral encrusting, nitrate-reducing, Fe(II)-oxidizing Acidovorax sp. strain BoFeN1. Isotopic fractionation in ⁵⁶Fe/⁵⁴Fe approached that expected for equilibrium conditions, assuming an equilibrium Δ⁵⁶Fe_{Fe(OH)3-Fe(II)aq} fractionation factor of +3.0‰. Previous studies have shown that Fe(II) oxidation by this Acidovorax strain occurs in the periplasm, and we propose that Fe isotope equilibrium is maintained through redox cycling via coupled electron and atom exchange between Fe(II)_aq and Fe(III) precipitates in the contained environment of the periplasm. In addition to the apparent equilibrium isotopic fractionation, these experiments also record the kinetic effects of initial rapid oxidation, and possible phase transformations of the Fe(III) precipitates. Attainment of Fe isotope equilibrium between Fe(III) oxide/hydroxide precipitates and Fe(II)_aq by neutrophilic, Fe(II)-oxidizing bacteria or through abiologic Fe(II)_aq oxidation is generally not expected or observed, because the poor solubility of their metabolic product, i.e. Fe(III), usually leads to rapid precipitation of Fe(III) minerals, and hence expression of a kinetic fractionation upon precipitation; in the absence of redox cycling between Fe(II)_aq and precipitate, kinetic isotope fractionations are likely to be retained. These results highlight the distinct Fe isotope fractionations that are produced by different pathways of biological and abiological Fe(II) oxidation.     

Catchment-scale observations at the Niwot Ridge long-term ecological research site

The Niwot Ridge and Green Lakes Valley (NWT) long-term ecological research (LTER) site collects environmental observations spanning both alpine and subalpine regimes. The first observations began in 1952 and have since expanded to nearly 300 available datasets over an area of 99 km² within the north-central Colorado Rocky Mountains that include hydrological (n = 101), biological (n = 79), biogeochemical (n = 62), and geographical (n = 56) observations. The NWT LTER database is well suited to support hydrologic investigations that require long-term and interdisciplinary data sets. Experimentation and data collection at the NWT LTER are designed to characterize ecological responses of high-mountain environments to changes in climate, nutrients, and water availability. In addition to the continuation of the many legacy NWT datasets, expansion of the breadth and utility of the NWT LTER database is driven by new initiatives including (a) a catchment-scale sensor network of soil moisture, temperature, humidity, and snow-depth observations to understand hydrologic connectivity and (b) snow-albedo alteration experiments using black sand to evaluate the effects of snow-disappearance on ecosystems. Together, these observational and experimental datasets provide a substantial foundation for hydrologic studies seeking to understand and predict changes to catchment and local-scale process interactions.     

Neoproterozoic evolution and Cambrian reworking of ultrahigh temperature granulites in the Eastern Ghats Province,India

The time‐scales and P–T conditions recorded by granulite facies metamorphic rocks permit inferences about the geodynamic regime in which they formed. Two compositionally heterogeneous cordierite–spinel‐bearing granulites from Vizianagaram, Eastern Ghats Province (EGP), India, were investigated to provide P–T–time constraints using petrography, phase equilibrium modelling, U–Pb geochronology, the rare earth element composition of zircon and monazite, and Ti‐in‐zircon thermometry. These ultrahigh temperature (UHT) granulites preserve discrete compositional layering in which different inferred peak assemblages are developed, including layers bearing garnet–sillimanite–spinel, and others bearing orthopyroxene–sillimanite–spinel. These mineral associations cannot be reproduced by phase equilibrium modelling of whole‐rock compositions, indicating that the samples became domainal on a scale less than that of a thin section, even at UHT conditions. Calculation of the P–T stability fields for six compositional domains within which the main rock‐forming minerals are considered to have attained equilibrium suggests peak metamorphic conditions of ~6.8–8.3 kbar at ~1,000°C. In most of these domains, the subsequent evolution resulted in the growth of cordierite and final crystallization of melt at an elevated (residual) H₂O‐undersaturated solidus, consistent with <1 kbar of decompression. Concordant U–Pb ages obtained by SHRIMP from zircon (spread 1,050–800 Ma) and monazite (spread 950–800 Ma) demonstrate that crystallization of these minerals occurred during an interval of c. 250 Ma. By combining LA‐ICP‐MS U–Pb zircon ages with Ti‐in‐zircon temperatures from the same analysis sites, we show that the crust may have remained above 900°C for a minimum of c. 120 Ma between c. 1,000 and c. 880 Ma. Overall, the results suggest that, in the interval 1,050 to 800 Ma, the evolution of the Vizianagaram granulites culminated with UHT conditions from c. 1,000 Ma to c. 880 Ma, associated with minor decompression, before further zircon crystallization at c. 880–800 Ma during cooling to the solidus. However, these rocks are adjacent to the Paderu–Anantagiri–Salur crustal block to the NW that experienced counterclockwise P–T–t paths, and records similar UHT peak metamorphic conditions (7–8 kbar, ~950°C) followed by near‐isobaric cooling, and has a similar chronology during the Neoproterozoic. The limited decompression inferred at Vizianagaram may be explained by partial exhumation due to thrusting of this crustal block over the adjacent Paderu–Anantagiri–Salur crustal block. The residual granulites in both blocks have high concentrations of heat‐producing elements and likely remained hot at mid‐crustal depths throughout a period of relative tectonic quiescence in the interval 800–550 Ma. During the Cambrian Period, the EGP was located in the hinterland of the Denman–Pinjarra–Prydz orogen. A later concordant population of zircon dated at 511 ± 6 Ma records crystallization at temperatures of ~810°C. This age may record a low‐degree of melting due to limited influx of fluid into hot, weak crust in response to convergence of the Crohn craton with a composite orogenic hinterland comprising the Rayner terrane, EGP, and cratonic India.     

Closed system behaviour of argon in osumilite records protracted high‐T metamorphism within the Rogaland–Vest Agder Sector,Norway

Here, we present results of the first ⁴⁰Ar/³⁹Ar dating of osumilite, a high‐T mineral that occurs in some volcanic and high‐grade metamorphic rocks. The metamorphic osumilite studied here is from a metapelitic rock within the Rogaland–Vest Agder Sector, Norway, an area that experienced regional granulite facies metamorphism and subsequent contact metamorphism between 1,100 Ma and 850 Ma. The large grain size (~1 cm) of osumilite in the studied rock, which preserves a nominally anhydrous assemblage, increases the potential for large portions of individual grains to have remained essentially unaffected by the effects of diffusive argon loss, potentially preserving prograde ages. Step‐heating diffusion experiments yielded a maximum activation energy of ~461 kJ/mol and a pre‐exponential factor of ~8.34 × 10⁸ cm²/s for Ar diffusion in osumilite. These parameters correspond to a relatively high closure temperature of ~620°C for a cooling rate of 10°C/Ma in an osumilite crystal with a 175 µm radius. Fragments of osumilite separated from the sample preserve a range of ages between c. 1,070 and 860 Ma. The oldest ages are inferred to date the growth of coarse‐grained osumilite during prograde granulite facies regional metamorphism, which pre‐date contact metamorphism that has historically been ascribed to the growth of osumilite in the region. The majority of fragments record ages between c. 920 and 860 Ma, inferred to reflect the growth of osumilite and/or diffusive argon loss during contact metamorphism. The retention of old ⁴⁰Ar/³⁹Ar dates was facilitated by the low diffusivity of Ar in osumilite (i.e. a closed system), large grain sizes, and anhydrous metamorphic conditions. The ability to date osumilite with the ⁴⁰Ar/³⁹Ar method provides a valuable new thermochronometer that may constrain the timing and duration of high‐T magmatic and metamorphic events.     

Atmospheric control of the cooling rate of impact melts and cryolavas on Titan’s surface

As on Earth, Titan’s atmosphere plays a major role in the cooling of heated surfaces. We have assessed the mechanisms by which Titan’s atmosphere, dominantly N₂ at a surface pressure of 1.5 × 10⁵ Pa, cools a warm or heated surface. These heated areas can be caused by impacts generating melt sheets and (possibly) by endogenic processes emplacing cryolavas (a low-temperature liquid that freezes on the surface). We find that for a cooling cryolava flow, lava lake, or impact melt body, heat loss is mainly driven by atmospheric convection. Radiative heat loss, a dominant heat loss mechanism with terrestrial silicate lava flows, plays only a minor role on Titan. Long-term cooling and solidification are dependent on melt sheet or flow thickness, and also local climate, because persistent winds will speed cooling. Relatively rapid cooling caused by winds reduces the detectability of these thermal events by instruments measuring surface thermal emission. Because surface temperature drops by ≈50% within ≈1 day of emplacement, fresh flows or impact melt may be difficult to detect via thermal emission unless an active eruption is directly observed. Cooling of flow or impact melt surfaces are orders of magnitude faster on Titan than on airless moons (e.g., Enceladus or Europa).Although upper surfaces cool fast, the internal cooling and solidification process is relatively slow. Cryolava flow lengths are, therefore, more likely to be volume (effusion) limited, rather than cooling-limited. More detailed modeling awaits constraints on the thermophysical properties of the likely cryomagmas and surface materials.     

Edge adapted wavelets,solar magnetic activity,and climate change

The continuous wavelet transform is adapted to account for signal truncation through renormalization and by modifying the shape of the analyzing window. Comparison is made of the instant, integrated, and mean wavelet power with previous algorithms. The edge adapted and renormalized admissible wavelet transforms are used to estimate the level of solar magnetic activity from the sunspot record. The solar activity is compared to Oerlemans’ temperature reconstruction and to the Central England Temperature record. A correlation is seen for years between 1610 and 1990, followed by a strong deviation as the recently observed temperature increases.     

Metal-catalyzed degradation and racemization of amino acids in iron sulfate brines under simulated martian surface conditions

Recent lines of evidence indicate that Mars may have been substantially warmer and wetter, raising questions about whether the planet’s surface was once more conducive to the possibility of life. To better constrain the extent of preservation of ancient amino acid biosignatures, the effects of metal ions and UV radiation were investigated with respect to the rates of diagenesis of amino acids in metal-rich sulfate brines. Individual experimental results indicate that the oxidation rates of amino acids loosely followed trends characteristic of a radiolytic oxidation mechanism that is dependent on variations in side-chain constituents. Relative rates of racemization only show a limited dependence on the presence of metals; overall, rates of racemization in the presence of metals in solution are an order of magnitude slower than oxidation and both are several orders of magnitude faster than previously reported. This increase in rate constant is indicative of an extremely efficient catalytic enhancement of this destructive diagenetic pathway. These findings imply that chiral life-detection strategies should focus on specific geochemical environments that exhibit relatively slow rates of both degradation and racemization. Episodic liquid water during periods of increased water activity on the martian surface may have significant implications for the oxidation of organic matter through secondary diagenetic reactions and may act as a leveling mechanism for organic compounds.