Stable Fe isotope fractionations produced by aqueous Fe(II)-hematite surface interactions

Stable Fe isotope fractionations were investigated during exposure of hematite to aqueous Fe(II) under conditions of variable Fe(II)/hematite ratios, the presence/absence of dissolved Si, and neutral versus alkaline pH. When Fe(II) undergoes electron transfer to hematite, Fe(II) is initially oxidized to Fe(III), and structural Fe(III) on the hematite surface is reduced to Fe(II). During this redox reaction, the newly formed reactive Fe(III) layer becomes enriched in heavy Fe isotopes and light Fe isotopes partition into aqueous and sorbed Fe(II). Our results indicate that in most cases the reactive Fe(III) that undergoes isotopic exchange accounts for less than one octahedral layer on the hematite surface. With higher Fe(II)/hematite molar ratios, and the presence of dissolved Si at alkaline pH, stable Fe isotope fractionations move away from those expected for equilibrium between aqueous Fe(II) and hematite, towards those expected for aqueous Fe(II) and goethite. These results point to formation of new phases on the hematite surface as a result of distortion of Fe-O bonds and Si polymerization at high pH. Our findings demonstrate how stable Fe isotope fractionations can be used to investigate changes in surface Fe phases during exposure of Fe(III) oxides to aqueous Fe(II) under different environmental conditions. These results confirm the coupled electron and atom exchange mechanism proposed to explain Fe isotope fractionation during dissimilatory iron reduction (DIR). Although abiologic Fe(II)_aq - oxide interaction will produce low δ⁵⁶Fe values for Fe(II)_aq, similar to that produced by Fe(II) oxidation, only small quantities of low-δ⁵⁶Fe Fe(II)_aq are formed by these processes. In contrast, DIR, which continually exposes new surface Fe(III) atoms during reduction, as well as production of Fe(II), remains the most efficient mechanism for generating large quantities of low-δ⁵⁶Fe aqueous Fe(II) in many natural systems.     

Composite titanomagnetite-ferrian ilmenite grains and correlative magnetic components in a dacite with self-reversed TRM

Electron microprobe and reflected light microscopic examinations confirm the presence of composite grains of ferrian ilmenite with X_ilm = 0.53 and titanomagnetite with X_usp = 0.13 in a dacite with self-reversed TRM. A parallel TRM component associated with titanomagnetite and a reversed component associated with self-reversing ferrian ilmenite are the principal NRM components. A subordinate, parallel component is associated with ferrian ilmenite which is not magnetically coupled to an “χ-phase”. The natural self-reversing properties are mainly a consequence of the dacite's high quenching temperature, calculated at 862–864°C using the Fe—Ti oxide geothermometer, and are most consistent with the self-reversal mechanism proposed by Lawson et al. [9].The conduction of thermal demagnetization and TRM induction tests in air had a much greater effect on the Fe—Ti oxides than did natural cooling, and resulted in significant oxidation with the consequent modification of some magnetic properties and the formation of another reversed TRM component. The subdivision of titanomagnetite grains by oxidation along fractures decreased its effective grain size and caused an apparent increase in its magnetic intensity, in addition to a slight increase in its resistance to alternating field demagnetization. The χ-phase associated with the reversed NRM component, with 0.42 > X_ilm 0.31, became Fe-enriched during the earlier stages of heat treatment. It is suggested that after heating at 600°C for two hours or more, this χ-phase exsolves as titanohematite with X_ilm < 0.33. The ferrian ilmenite host is consequently enriched in Ti, and another χ-phase much closer in composition to the host generates a reversed TRM component with T_b < 200°C.     

Beyond headline mitigation numbers: we need more transparent and comparable NDCs to achieve the Paris Agreement on climate change

Nationally determined contributions (NDCs) were key to reaching the Paris Agreement and will be instrumental in implementing it. Research was quick to identify the ‘headline numbers’ of NDCs: if these climate action plans were fully implemented, global mean warming by 2100 would be reduced from approximately 3.6 to 2.7°C above pre-industrial levels (Höhne et al. Climate Pol 17:1–17, 2016; Rogelj et al. Nature 534:631–639, 2016). However, beyond these headline mitigation numbers, NDCs are more difficult to analyse and compare. UN climate negotiations have so far provided limited guidance on NDC formulation, which has resulted in varying scopes and contents of NDCs, often lacking details concerning ambitions. If NDCs are to become the long-term instrument for international cooperation, negotiation, and ratcheting up of ambitions to address climate change, then they need to become more transparent and comparable, both with respect to mitigation goals, and to issues such as adaptation, finance, and the way in which NDCs are aligned with national policies. Our analysis of INDCs and NDCs (Once a party ratifies the Paris Agreement, it is invited to turn its Intended Nationally Determined Contribution (INDC) into an NDC. We refer to results from our INDC analysis rather than our NDC analysis in this commentary unless otherwise stated.) shows that they omit important mitigation sectors, do not adequately provide details on costs and financing of implementation, and are poorly designed to meet assessment and review needs.     

Caldera resurgence during magma replenishment and rejuvenation at Valles and Lake City calderas

A key question in volcanology is the driving mechanisms of resurgence at active, recently active, and ancient calderas. Valles caldera in New Mexico and Lake City caldera in Colorado are well-studied resurgent structures which provide three crucial clues for understanding the resurgence process. (1) Within the limits of ⁴⁰Ar/³⁹Ar dating techniques, resurgence and hydrothermal alteration at both calderas occurred very quickly after the caldera-forming eruptions (tens of thousands of years or less). (2) Immediately before and during resurgence, dacite magma was intruded and/or erupted into each system; this magma is chemically distinct from rhyolite magma which was resident in each system. (3) At least 1?km of structural uplift occurred along regional and subsidence faults which were closely associated with shallow intrusions or lava domes of dacite magma. These observations demonstrate that resurgence at these two volcanoes is temporally linked to caldera subsidence, with the upward migration of dacite magma as the driver of resurgence. Recharge of dacite magma occurs as a response to loss of lithostatic load during the caldera-forming eruption. Flow of dacite into the shallow magmatic system is facilitated by regional fault systems which provide pathways for magma ascent. Once the dacite enters the system, it is able to heat, remobilize, and mingle with residual crystal-rich rhyolite remaining in the shallow magma chamber. Dacite and remobilized rhyolite rise buoyantly to form laccoliths by lifting the chamber roof and producing surface resurgent uplift. The resurgent deformation caused by magma ascent fractures the chamber roof, increasing its structural permeability and allowing both rhyolite and dacite magmas to intrude and/or erupt together. This sequence of events also promotes the development of magmatic–hydrothermal systems and ore deposits. Injection of dacite magma into the shallow rhyolite magma chamber provides a source of heat and magmatic volatiles, while resurgent deformation and fracturing increase the permeability of the system. These changes allow magmatic volatiles to rise and meteoric fluids to percolate downward, favouring the development of hydrothermal convection cells which are driven by hot magma. The end result is a vigorous hydrothermal system which is driven by magma recharge.     

The geomorphology and evolution of a large barrier spit: Farewell Spit,New Zealand

Farewell Spit is a 25 km long barrier spit that marks the end of a littoral drift system, almost 1000 km in length that runs along South Island, New Zealand. The spit is composed of barchan dunes over 20 m high, sand sheets over 1 km wide and vegetated linear dunes. Analysis of aerial photography indicates a rapid colonization of the spit by vegetation which has expanded in area by 75% since 1950. Vegetation colonization preferentially occurs on the southern side of the spit, with its northern margin characterized by barchan dunes which migrate at rates of up to 64 m/yr. Sand sourced from longshore drift appears to be the primary source of beach sediment, which is then transported into the dune field by the persistent westerly winds of the Roaring 40s. While there has been significant dune roll‐over on the surface of the spit, its overall area has remained much the same for the past 54 years. Occasional cyclone events cause erosion, but this is balanced by aeolian sediment transport. It would appear that extension of the subaerial portion of the spit is related to the development of shells banks at its downdrift end which are periodically welded to the main spit by dune extension. Farewell Spit therefore provides an ideal example of a barrier environment where longshore sediment supply and aeolian transport dominates geomorphic evolution. This differentiates the study site from other barrier environments where overwash or tidal inlet development often characterizes recent landform evolution. Copyright © 2010 John Wiley & Sons, Ltd.     

Extreme <Superscript>15</Superscript>N Depletion in Seagrasses

Seagrass beds form an important part of the coastal ecosystem in many parts of the world but are very sensitive to anthropogenic nutrient increases. In the last decades, stable isotopes have been used as tracers of anthropogenic nutrient sources and to distinguish these impacts from natural environmental change, as well as in the identification of food sources in isotopic food web reconstruction. Thus, it is important to establish the extent of natural variations on the stable isotope composition of seagrass, validating their ability to act as both tracers of nutrients and food sources. Around the world, depending on the seagrass species and ecosystem, values of seagrass N normally vary from 0 to 8?‰ δ¹⁵N. In this study, highly unusual seagrass N isotope values were observed on the east coast of Qatar, with significant spatial variation over a scale of a few metres, and with δ¹⁵N values ranging from +2.95 to ?12.39?‰ within a single bay during March 2012. This pattern of variation was consistent over a period of a year although there was a seasonal effect on the seagrass δ¹⁵N values. Seagrass, water column and sediment nutrient profiles were not correlated with seagrass δ¹⁵N values and neither were longer-term indicators of nutrient limitation such as seagrass biomass and height. Sediment δ¹⁵N values were correlated with Halodule uninervis δ¹⁵N values and this, together with the small spatial scale of variation, suggest that localised sediment processes may be responsible for the extreme isotopic values. Consistent differences in sediment to plant ¹⁵N discrimination between seagrass species also suggest that species-specific nutrient uptake mechanisms contribute to the observed δ¹⁵N values. This study reports some of the most extreme, negative δ¹⁵N values ever noted for seagrass (as low as ?12.4?‰) and some of the most highly spatially variable (values varied over 15.4?‰ in a relatively small area of only 655 ha). These results are widely relevant, as they demonstrate the need for adequate spatial and temporal sampling when working with N stable isotopes to identify food sources in food web studies or as tracers of anthropogenic nutrients.     

Effect of salinity and temperature on survival and development of young zebra (Dreissena polymorpha) and quagga (Dreissena bugensis) mussels

We reared larval zebra mussels,Dreissena polymorpha, and quagga mussels,D. bugensis, through and beyond metamorphosis (settlement) at salinities of 0–8‰. Juvenile zebra mussels gradually acclimated to 8‰ and 10‰ have been reared at these salinities for over 8 mo. Tolerance to both higher temperatures and higher salinities increases with larval age in both species (though zebra mussel embryos and larvae have a greater degree of salinity tolerance than quagga mussel embryos and larvae). Thus, only 6% of 3-day-old zebra mussel veligers survived after exposure to 4‰ for 8 additional days, whereas there was 22% survival of veligers placed in 4‰ at day 13 and grown to settlement 11 d later. Zebra mussel pediveligers, acclimated to increasing salinity in 2‰ increments beginning at day 23, continued to survive and grow in 8‰ after 5-mo exposure, though the growth rates of these juveniles were significantly less than those of juveniles reared in lower salinities. Quagga mussels did not metamorphose and settle as quickly as zebra mussel pediveligers. No quagga mussel pediveligers had settled before exposure to artificial fresh water (AFW), 2‰ 4‰, 6‰, and 8‰ on day 30. Percent settlement of these quagga mussel juveniles (based on 100% survival at the start of experiments on day 30) was 90% in AFW, 67% at 2‰, 69% at 4‰, 46% at 6‰, and 0.1% at 8‰.