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.     

Holocene History of the Bering Sea Bowhead Whale (Balaena mysticetus) in Its Beaufort Sea Summer Grounds off Southwestern Victoria Island, Western Canadian Arctic

The fossil remains of 43 bowhead whales were mapped on the raised beaches of western Wollaston Peninsula, Victoria Island, Canadian Arctic, near the historic summer range limit of the Bering Sea stock in the Beaufort Sea. The elevations and radiocarbon ages of the remains demonstrate that the bowhead ranged commonly into the region following the submergence of Bering Strait at ca. 10,000 ¹⁴C yr B.P. until ca. 8500 ¹⁴C yr B.P. During the same interval, bowheads ranged widely from the Beaufort Sea to Baffin Bay. Subsequently, no whales reached Wollaston Peninsula until ca. 1500 ¹⁴C yr B.P. Late Holocene populations evidently were small, or occupations were brief, in comparison to those of the early Holocene. Although the late Holocene recurrence may relate to the expansion of pioneering Thule whalers eastward from Alaska, there are few Thule sites and limited evidence of Thule whaling in the area surveyed to support this suggestion.     

Spatial and isotopic analysis of watershed soil loss and reservoir sediment accumulation rates in Lake Anna, Virginia, USA

Soil erosion and associated sedimentation are a threat to the sustainable use of surface water resources through the loss of volume storage capacity and conveyance of pollutants to receiving water bodies. The RUSLE2 empirical model and isotopic sediment core analyses were used to evaluate watershed erosion and reservoir sediment accumulation rates for Lake Anna, in Central Virginia. A sediment flux rate of 66,000 Mg/year was estimated from the upper basin and land use was determined to be the primary factor contributing to soil erosion. Barren lands and agricultural activities were estimated to contribute the most sediment (>20 Mg/ha/year), whereas forested and herbaceous landscapes were less likely to erode (<0.3 Mg/ha/year). Eleven separate ²¹⁰Pb-based estimates of sediment accumulation were used to construct reservoir-scale sedimentation rates. Sedimentation rates in the upper reaches of the reservoir were variable, ranging from 2.3 to 100 Mg/ha/year, with a median rate of 8.4 Mg/ha/year. Historical sedimentation showed an increase in annual accumulation from 1972 to present. Based on these data the reservoir has experienced a 2% loss of volume storage capacity since impoundment in 1972. Results from this study indicate that Lake Anna is not currently experiencing excessive sedimentation and erosion problems. However, the predominance of highly erosive soils (soil erodibility factor >0.30) within the watershed makes this system highly vulnerable to future anthropogenic stressors.     

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.     

Late Quaternary Bison diminution on the Great Plains of North America: evaluating the role of human hunting versus climate change

Body size changes of Bison and mortality age structure data document the effects of climate-driven environmental change and human hunting pressure on large mammals in North America. Morphometric and mortality data are drawn from 58 archaeological and 9 paleontological localities dating between 37,000 and 250 calBP. Proxy information on body size is based on measurements recorded on 901 adult calcanei (os calcis) and 1026 humeri. In addition, published mortality profiles from 24 archaeological faunal assemblages spanning the last 14,000 years were used to approximate the age structure of bison populations. These results suggest that dramatic diminution in bison body size occurred in several short bursts, rather than a continuous gradual decline. These periods of rapid size reduction correlate with times of ecological reorganization, when aridity-driven changes in grasslands decreased forage quality and availability. Mortality age data indicate that the decrease in body size occurred in a context where there was no evidence for a progressively severe juvenile bias in bison populations. Overall, it appears that the changes in body size were a reaction to environmental conditions rather than the result of human predation pressure.     

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.