Density functional theory predictions of equilibrium isotope fractionation of iron due to redox changes and organic complexation

We present molecular orbital/density functional theory (MO/DFT) calculations that predict a greater isotopic fractionation in redox reactions than in reactions involving ligand exchange. The predicted fractionation factors, reported as 1000·ln(^56-54α), associated with equilibrium between Fe-organic and Fe-H₂O species were <1.6‰ in vacuo and <1.2‰ in solution when the oxidation state of the system was held constant. These fractionation factors were significantly smaller than those predicted for equilibrium between different oxidation states of Fe, for which 1000·ln(^56-54α) was >2.7‰ in vacuo and >2.2‰ in solution when the bound ligands were unchanged. The predicted ⁵⁶Fe/⁵⁴Fe ratio was greater in complexes containing Fe³⁺ and in complexes with shorter Fe-O bond lengths; both of these trends follow previous theoretical results. Our predictions also agree with previous experimental measurements that suggest that the largest biological fractionations will be associated with processes that change the oxidation state of Fe, and that identification of biologically controlled Fe isotope fractionation may be difficult when abiotic redox fractionations are present in the system. The models studied here also have important implications for future theoretical isotope calculations, because we have discovered the necessity of using vibrational frequencies instead of reduced masses when predicting reduced partition functions in aqueous-phase species.     

Oxygen isotope heterogeneity of the mantle beneath the Canary Islands: a discussion of the paper of Gurenko et al.

Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) report laser-assisted fluorination (LF) and secondary ionization mass spectrometry (SIMS) ¹⁸O/¹⁶O datasets for olivine grains from the Canary Islands of Gran Canaria, Tenerife, La Gomera, La Palma and El Hierro. As with prior studies of oxygen isotopes in Canary Island lavas (e.g. Thirlwall et al. Chem Geol 135:233–262, 1997; Day et al. Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010), these authors find variations in δ¹⁸O_ol (~4.6–6.0 ‰) beyond that measured for mantle peridotite olivine (Mattey et al. Earth Planet Sci Lett 128:231–241, 1994) and interpret this variation to reflect contributions from pyroxenite-peridotite mantle sources. Furthermore, Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) speculate that δ¹⁸O_ol values for La Palma olivine grains measured by LF (Day et al. Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010) may be biased to low values due to the presence of altered silicate, possibly serpentine. The range in δ¹⁸O_ol values for Canary Island lavas are of importance for constraining their origin. Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) took a subset (39 SIMS analyses from 13 grains from a single El Hierro lava; EH4) of a more extensive dataset (321 SIMS analyses from 110 grains from 16 Canary Island lavas) to suggest that δ¹⁸O_ol is weakly correlated (R ² = 0.291) with the parameter used by Gurenko et al. (Earth Planet Sci Lett 277:514–524, 2009) to describe the estimated weight fraction of pyroxenite-derived melt (Xpx). With this relationship, end-member δ¹⁸O values for HIMU-peridotite (δ¹⁸O = 5.3 ± 0.3 ‰) and depleted pyroxenite (δ¹⁸O = 5.9 ± 0.3 ‰) were defined. Although the model proposed by Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) implicates similar pyroxenite-peridotite mantle sources to those proposed by Day et al. (Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010) and Day and Hilton (Earth Planet Sci Lett 305:226–234, 2011), there are significant differences in the predicted δ¹⁸O values of end member components in the two models. In particular, Day et al. (Geochim Cosmochim Acta 74:6565–6589, 2010) proposed a mantle source for La Palma lavas with low-δ¹⁸O (<5 ‰), rather than higher-δ¹⁸O (c.f. the HIMU-peridotite composition of Gurenko et al. in Contrib Mineral Petrol 162:349–363, 2011). Here we question the approach of using weakly correlated variations in δ¹⁸O_ol and the Xpx parameter to define mantle source oxygen isotope compositions, and provide examples of why this approach appears flawed. We also provide reasons why the LF datasets previously published for Canary Island lavas remain robust and discuss why LF and SIMS data may provide complementary information on oxygen isotope variations in ocean island basalts (OIB), despite unresolved small-scale uncertainties associated with both techniques.     

Decompression and H<Subscript>2</Subscript>O exsolution driven crystallization and fractionation: development of a new model for low-pressure fractional crystallization in calc-alkaline magmatic systems

Magma ascent, decompression-induced H₂O exsolution and crystallization is now recognized as an important process in hydrous subduction zone magmas. During the course of such a process calculations suggest that the ascent rate of a degassing and crystallizing mafic magma will be greater than crystal settling velocities. Thus, any crystals formed as a consequence of volatile exsolution will remain suspended in the magma. If the magma erupts before the percentage of suspended crystals reaches the critical crystallinity value for mafic magma (~55 vol.%) it will produce the commonly observed crystal rich island arc basalt lava. If the magma reaches its critical crystallinity before it erupts then it will stall within the crust. Extension of compaction experiments on a 55 vol.% sand-Karo syrup suspension at different temperatures (and liquid viscosities) to the likely viscosities of interstitial andesitic to dacitic liquid within such a stalled magma suggest that small amounts (up to ~10%) can be expelled on a time scale of 1–10 years. The expelled liquid can create a new intermediate to silicic body of magma that is related to the original mafic magma via fractional crystallization. The short time scale for liquid expulsion indicate that decompression-induced H₂O exsolution and crystallization can be an important mechanism for fractional crystallization. Based on this assumption a general model of decompression-induced crystallization and fractionation is proposed that explains many of the compositional, mineralogical and textural features of Aleutian (and other andesites).     

Textured organic surfaces associated with the Ediacara biota in South Australia

The Ediacaran Period takes its name from the fossils of the Ediacara biota, which represent the first appearance of large and diverse assemblages of organisms in the fossil record. Although the global record of these distinctive body fossils is now well known, a previously unrecognized megascopic organic record of textured organic surfaces (TOS) occurs in the Ediacara biota. However, TOS is also a feature over a wider range of paleoenvironmental settings, where body fossils are unknown, in Ediacaran siliciclastic successions that have been studied in Australia, Namibia and western North America.Paleoecological analysis of successive bedding planes of strata from the late Ediacaran Rawnsley Quartzite in the Flinders Ranges of South Australia, reveals that TOS represent the most common organic features in bedding-surface assemblages of the Ediacara biota. The TOS consist of preserved, patterned assemblages of textured organic mats, fibers and simple tubular body fossils. Complex Ediacara body fossils while striking for their distinctive body plans, and dominating some of the beds, are relatively minor components of combined overall surface area. Many elements of TOS have previously been miss-diagnosed as trace fossils, which are in practice limited to two or at most three morphotypes that indicate the presence of Bilateria. Although TOS represent a simpler grade of organismic construction than discrete and more complex Ediacara body fossils, they were preserved in a similar manner. Marked variability in all components of the biota between successive surfaces suggests that Ediacara ecologies fluctuated at short intervals despite an apparently consistent sedimentary regime.     

Volcano monitoring in NZ and links to SW Pacific via the Wellington VAAC

Monitoring for natural hazards like earthquakes, volcanic eruptions and landslides in New Zealand is under taken by GNS Science through the GeoNet project, funded by the Earthquake Commission (EQC). The volcano monitoring function, which includes seismograph and GPS networks, visual observations, webcams, deformation, gas and chemical measurements, assesses the status of New Zealand’s 12 active volcanoes and disseminates warnings as necessary. Interaction with the Wellington VAAC addresses aviation concerns. Near-real-time data is obtained from the monitoring networks and processed via two data centres, with two Duty Officers who respond to pager alerts. Through the National Civil Defence Plan, the volcano monitoring function is delegated to GNS Science, which is responsible for setting the volcanic alert level at each volcano. The Alert level is then used by responding agencies, industries, utility providers and the public to set their response. The New Zealand alert level system is based on the current status of the volcano, and is not necessarily predictive. The aviation industry is one of these responding industries. As a consequence of the 1995 and 1996 eruptions of Ruapehu volcano, it became apparent that the aviation industry required more information than the standard VAAC data and an additional service known as VAAS (NZ Volcanic Ash Advisory System) was established by MetService NZ and GNS Science. This arrangement provides enhanced services to the airlines and ensures rapid dissemination and quantification of information like SIGMET and NOTAM. GNS Science has informal relationships with similar geological based organisations in SW Pacific countries, especially Vanuatu and the Solomon Islands, and is able to quantify information about eruptions in those countries. Similarly, MetService NZ has relationships and is able to obtain pilot reports and updates from the meteorological and air traffic control organisations.     

Modifications of resonant column and torsional shear device for the large strain

Conventional RC/TS (resonant column and torsional shear) devices use a specimen with an aspect ratio (height-to-diameter) of 2:1 and this generates a maximum shear strain in the sample of about 1.5% at the maximum rotation of the driving system. The objective of this study is to modify the RC/TS device to generate higher strain amplitude. The modifications include a new base pedestal to overcome the limitations in the travel of the drive system and modification of the coil wiring to increase torque. The effects of the new coil wire on torque in the electromagnetic drive system were evaluated and the application of the modified device was illustrated using sand soil.     

The potential impact of herbivores on the susceptibility of the marsh plantSagittaria lancifolia to saltwater intrusion in coastal wetlands

The objective of this study was to experimentally evaluate the effects of simulated herbivory on the ability of a freshwater marsh plant to recover from temporary saltwater intrusion such as can be caused by tropical storms. Sods containingSagittaria lancifolia, a dominant plant in interior coastal marshes, were manipulated in the field so as to subject plants to a pulse of 15‰ salt water for a duration of 1 wk. In addition to the exposure to salt water, some plants were also subjected to both short-term and long-term flooding treatments of 20 cm, and to simulated herbivory (clipping). Following exposure to salt water, plants were allowed to recover over the winter and were harvested the next June. Neither simulated herbivory, nor salinity, nor flooding caused any long-term effect either singly or in pairwise combinations. However, when plants were subjected to herbivory, salt water, and flooding simultaneously, reduced growth and plant death occurred. These results suggest that high levels of grazing by herbivores may increase the susceptibility of coastal marsh plants to damage from saltwater intrusion. *** DIRECT SUPPORT *** A01BY073 00002     

Multicomponent reactive transport modeling of uranium bioremediation field experiments

A reaction network integrating abiotic and microbially mediated reactions has been developed to simulate biostimulation field experiments at a former Uranium Mill Tailings Remedial Action (UMTRA) site in Rifle, Colorado. The reaction network was calibrated using data from the 2002 field experiment, after which it was applied without additional calibration to field experiments performed in 2003 and 2007. The robustness of the model specification is significant in that (1) the 2003 biostimulation field experiment was performed with 3 times higher acetate concentrations than the previous biostimulation in the same field plot (i.e., the 2002 experiment), and (2) the 2007 field experiment was performed in a new unperturbed plot on the same site. The biogeochemical reactive transport simulations accounted for four terminal electron-accepting processes (TEAPs), two distinct functional microbial populations, two pools of bioavailable Fe(III) minerals (iron oxides and phyllosilicate iron), uranium aqueous and surface complexation, mineral precipitation and dissolution. The conceptual model for bioavailable iron reflects recent laboratory studies with sediments from the UMTRA site that demonstrated that the bulk (∼90%) of initial Fe(III) bioreduction is associated with phyllosilicate rather than oxide forms of iron. The uranium reaction network includes a U(VI) surface complexation model based on laboratory studies with Rifle site sediments and aqueous complexation reactions that include ternary complexes (e.g., calcium-uranyl-carbonate). The bioreduced U(IV), Fe(II), and sulfide components produced during the experiments are strongly associated with the solid phases and may play an important role in long-term uranium immobilization.