Large-scale atmospheric circulation forms and their impact on air temperature in Europe and northern Asia

Air temperature variations in Europe and northern Asia are strongly affected by atmospheric circulation. A large-scale study of temperature signals is presented, using a newly available global gridded daily temperature dataset. Major types of European Grosswetterlagen (large-scale weather patterns) and the Russian Vangengeim–Girs classification are compared in their spatial applicability to air temperatures within the past 110 years (1901–2010). The consistency of spatial patterns in the three most recent decades (1981–2010) is investigated, and temperature changes are interpreted against the backdrop of changes in character and frequency of circulation patterns. Both classifications largely explain the observed temperature variability. Spatial patterns are large-scale and strong in both regions, especially in winter. Both spatial extent and signal magnitude show a distinct seasonality with maximum values in winter and minimum ones in summer. Spatial patterns show little changes in Europe; yet the ability to explain temperature variability in northern Asia decreased within 1981–2010. European winter warming corresponds to increased maritime and to decreased continental air mass inflow, superimposed on the general warming trend. Northern Asian winter warming is partly explainable by circulation changes in January and February, but to a lesser extend in December. These results may be used to advance input variables of global climate models and to improve their performance in the European–Northern Asian area.     

Equity and efficiency in adaptation finance: initial experiences of the Adaptation Fund

The Adaptation Fund, established under the Kyoto Protocol of the United Nations Framework Convention on Climate Change (UNFCCC), has now been approving funding for adaptation projects for more than two years. Given its particular institutional status and specific focus on concrete adaptation, it is particularly relevant to study the initial experiences of it for any future upscaling of international adaptation finance, despite the fact that its own resources are getting scarce. Alternative rationales for allocating funds, based on equity and efficiency concerns at both international and subnational levels, are here tested against the criteria and priorities of the Fund and decisions made on project approval. It is concluded that equity concerns appear to be the primary motivation and that allocation is de facto made between states rather than by considering inequity between subnational communities. However, the currency of vulnerability for determining equitable outcomes in allocation decisions has not been formalized, despite its central importance to the Fund. Instead, uniform national caps have been introduced. Such an equality approach can be considered inequitable. Finally, it is noted that although the Adaptation Fund Board has continuously developed its proposal review practices and adopted a learning-by-doing approach, it should provide both a further specification of the evaluation criteria and a compilation of best practices from approved proposals, and moreover enhance the transparency of the review process, all of which would clarify its core priorities for current and future project proponents.     

Cross-national patterns of governance mechanisms in nationally determined contributions (NDCs) under the Paris Agreement

ABSTRACT

The continuous submission and scaling-up of Nationally Determined Contributions (NDCs) constitutes a key feature of the Paris Agreement. In their NDCs, states propose governance mechanisms for implementation of climate action, in turn distinguishing appropriate roles for the state in climate governance. Clarity on Parties’ suggested roles for the state makes explicit assumptions on the premise of climate policy, in turn contributing to enhanced transparency in negotiations on the scaling-up of NDCs. This also speaks to ongoing debates on roles for the state in climate governance literature. This article identifies the governance mechanisms proposed by states in their NDCs and the roles for the state envisioned by those governance mechanisms, and also examines how cross-national patterns of roles for the state break or converge with conventional patterns of international politics. The analysis shows that states propose a plurality of roles, which to different extents may be complementary or conflictual. We conclude that income, region, and the Annexes under the United Nations Framework Convention on Climate Change (UNFCCC) are important for understanding suggested roles for the state, but that there are nuances to be further explored. We argue that this paper has three key findings: i) a majority of states rely on market mechanisms to implement their NDCs while rules on implementation and assessment of market mechanisms are still an outstanding issue in the negotiations, meaning that resolving this issue will be essential; ii) the process for evaluating and assessing qualitative governance mechanisms needs to be specified; and iii) increased awareness of differing views on the state’s roles makes explicit different perspectives on what constitutes an ambitious and legitimate contribution to combating climate change.

Key policy insights

• A majority of states (> 75%) envision the state as regulator (creating and strengthening legislation), market facilitator (creating and maintaining market structures), or facilitator (creating more favourable material conditions for climate-friendly behaviour).

• Greater awareness of differing views on roles for the state can increase understanding of different perspectives on ambition and legitimacy of contributions, in turn facilitating trust in negotiations.

• A distinction between substantive and procedural qualitative governance mechanisms and their function and interaction would facilitate the stocktaking dialogues.

     

Effect of KCl on melting in the Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript>–MgSiO<Subscript>3</Subscript>–H<Subscript>2</Subscript>O system at 5 GPa

To examine the effect of KCl-bearing fluids on the melting behavior of the Earth’s mantle, we conducted experiments in the Mg₂SiO₄–MgSiO₃–H₂O and Mg₂SiO₄–MgSiO₃–KCl–H₂O systems at 5 GPa. In the Mg₂SiO₄–MgSiO₃–H₂O system, the temperature of the fluid-saturated solidus is bracketed between 1,200–1,250°C, and both forsterite and enstatite coexist with the liquid under supersolidus conditions. In the Mg₂SiO₄–MgSiO₃–KCl–H₂O systems with molar Cl/(Cl + H₂O) ratios of 0.2, 0.4, and 0.6, the temperatures of the fluid-saturated solidus are bracketed between 1,400–1,450°C, 1,550–1,600°C, and 1,600–1,650°C, respectively, and only forsterite coexists with liquid under supersolidus conditions. This increase in the temperature of the solidus demonstrates the significant effect of KCl on reducing the activity of H₂O in the fluid in the Mg₂SiO₄–MgSiO₃–H₂O system. The change in the melting residues indicates that the incongruent melting of enstatite (enstatite = forsterite + silica-rich melt) could extend to pressures above 5 GPa in KCl-bearing systems, in contrast to the behavior in the KCl-free system.     

A Zonal Pathway for NADW in the South Atlantic

Several large deployments of neutrally buoyant floats took place within the Antarctic Intermediate (AAIW), North Atlantic Deep Water (NADW), and the Antarctic Bottom Water (AABW) of the South Atlantic in the 1990s and a number of hydrographic sections were occupied as well. Here we use the spatially and temporally averaged velocities measured by these floats, combined with the hydrographic section data and various estimates of regional current transports from moored current meter arrays, to determine the circulation of the three major subthermocline water masses in a zonal strip across the South Atlantic between the latitudes of 19°S and 30°S. We concentrate on this region because the historical literature suggests that it is where the Deep Western Boundary Current containing NADW bifurcates. In support of this notion, we find that a net of about 5 Sv. of the 15–20 Sv that crosses 19°S does continue zonally eastward at least as far as the Mid-Atlantic Ridge. Once across the ridge it takes a circuit to the north along the ridge flanks before returning to the south in the eastern half of the Angola Basin. The data suggest that the NADW then continues on into the Indian Ocean. This scheme is discussed in the context of distributions of dissolved oxygen, silicate and salinity. In spite of the many float-years of data that were collected in the region a surprising result is that their impact on the computed solutions is quite modest. Although the focus is on the NADW we also discuss the circulation for the AAIW and AABW layers.     

Diel Aquatic CO<Subscript>2</Subscript> System Dynamics of a Bermudian Mangrove Environment

Mangrove ecosystems play an important, but understudied, role in the cycling of carbon in tropical and subtropical coastal ocean environments. In the present study, we examined the diel dynamics of seawater carbon dioxide (CO₂) and dissolved oxygen (DO) for a mangrove-dominated marine ecosystem (Mangrove Bay) and an adjacent intracoastal waterway (Ferry Reach) on the island of Bermuda. Spatial and temporal trends in seawater carbonate chemistry and associated variables were assessed from direct measurements of dissolved inorganic carbon, total alkalinity, dissolved oxygen (DO), temperature, and salinity. Diel pCO₂ variability was interpolated across hourly wind speed measurements to determine variability in daily CO₂ fluxes for the month of October 2007 in Bermuda. From these observations, we estimated rates of net sea to air CO₂ exchange for these two coastal ecosystems at 59.8 ± 17.3 in Mangrove Bay and 5.5 ± 1.3 mmol m⁻² d⁻¹ in Ferry Reach. These results highlight the potential for large differences in carbonate system functioning and sea-air CO₂ flux in adjacent coastal environments. In addition, observation of large diel variability in CO₂ system parameters (e.g., mean pCO₂: 390–2,841 μatm; mean pH_T: 8.05–7.34) underscores the need for careful consideration of diel cycles in long-term sampling regimes and flux estimates.     

Partitioning of Ca and Al between forsterite and silicate melt in dynamic systems with implications for the origin of Ca,Al‐rich forsterites in primitive meteorites

Abstract— We report the results of dynamic crystallization experiments that were specifically designed to study the dependence of Ca and Al partitioning between forsterite and melt in rapidly cooling Caand Al‐rich melts. The partitioning of Ca between olivine and silicate melt is found to be independent of the cooling rate within the range of 1.5 to 1000°C/hr and at CaO contents of up to 25 wt%. Within analytical uncertainty, our data plot on the equilibrium partitioning curve obtained by Libourel (1999). The partitioning behavior of Al at high cooling rates is more complex. Aluminum is much more heterogenously distributed in the olivine and the co‐existing melt than Ca. But, no systematic trend of Al partition coefficient with cooling rate is observed. We apply the results of the experiments to the formation of meteoritic forsterites with relatively high contents of Ca and Al. Although these forsterites are found frequently inside chondrules, the Ca contents of their host chondrules are far too low to crystallize these high Ca‐forsterites. This is also true for very rapid cooling of chondrule melts. The parental melt of these forsterites requires CaO contents above 20 wt%.     

Ductile deformation of garnet in mylonitic gneisses from the Münchberg Massif (Germany)

Mylonitic gneisses from the Münchberg Massif contain single grains (type I) and polycrystalline aggregates (type II) of garnet displaying a distinct elongation parallel to a macroscopic lineation which is interpreted as the result of ductile deformation. Lattice-preferred orientations of quartz (textures) symmetrical to the macroscopic foliation and lineation and the lack of rotational microfabrics indicate that the bulk deformation was pure shear at least during the latest strain increments. Garnet textures measured by EBSD together with microprobe analyses demonstrate that these two structural types of garnet can be related to two different processes of ductile deformation: (1) For the single grains stretching can be attributed to diffusion creep along grain boundary zones (Coble creep). The related mass transfer is indicated by the fact that primary growth zones are cut off at the long faces of the grains while the related strain shadow domains do not show comparable chemical zoning. Pressure solution and precipitation suitable to produce similar structures can be largely ruled out because retrogressive reactions pointing to the presence of free hydrous fluids are missing. (2) For the polycrystalline garnet aggregates consisting of cores grading into fine-grained mantles, dislocation creep and associated rotation recrystallization can be assumed. Continuous lattice rotation from the core to the outer polycrystalline rim allow a determination of the related dominant slip systems which are {100}<010> and equivalent systems according to the cubic lattice symmetry. The same holds for garnets which appear to be completely recrystallized. For this type of fine-grained aggregates an alternative nucleation model is discussed. Due to penetrative dislocation glide in connection with short range diffusion and the resulting lattice rotation, primary growth zones are strongly disturbed.Since for the considered rock unit of the Münchberg Massif peak metamorphic temperatures between 630 and 670 °C can be assumed, this study clearly demonstrates that the inferred processes of ductile garnet deformation can occur not only in HT regimes as often suggested in the literature even if embedded within a matrix of “low-strength” minerals like quartz, feldspars and micas.     

The structure of monomeric and dimeric uranyl adsorption complexes on gibbsite: A combined DFT and EXAFS study

We investigated the structure of uranyl sorption complexes on gibbsite (pH 5.6-9.7) by two independent methods, density functional theory (DFT) calculations and extended X-ray absorption fine structure (EXAFS) spectroscopy at the U-L_III edge. To model the gibbsite surface with DFT, we tested two Al (hydr)oxide clusters, a dimer and a hexamer. Based on polarization, structure, and relaxation energies during geometry optimization, the hexamer cluster was found to be the more appropriate model. An additional advantage of the hexamer model is that it represents both edges and basal faces of gibbsite. The DFT calculations of (monomeric) uranyl sorption complexes show an energetic preference for the corner-sharing versus the edge-sharing configuration on gibbsite edges. The energy difference is so small, however, that possibly both surface species may coexist. In contrast to the edge sites, sorption to basal sites was energetically not favorable. EXAFS spectroscopy revealed in all investigated samples the same interatomic distances of the uranyl coordination environment (R_U-Oax ≈ 1.80 Å, R_U-Oeq ≈ 2.40 Å), and towards the gibbsite surface (R_U-O ≈ 2.87 Å, R_U-Al ≈ 3.38 Å). In addition, two U-U distances were observed, 3.92 Å at pH 9.7 and 4.30 Å at pH 5.6, both with coordination numbers of ∼1. The short U-U distance is close to that of the aqueous uranyl hydroxo dimer, UO₂(OH)₂, reported as 3.875 Å in the literature, but significantly longer than that of aqueous trimers (3.81-3.82 Å), suggesting sorption of uranyl dimers at alkaline pH. The longer U-U distance (4.30 Å) at acidic pH, however, is not in line with known aqueous uranyl polymer complexes. Based on the EXAFS findings we further refined dimeric surface complexes with DFT. We propose two structural models: in the acidic region, the observed long U-U distance can be explained with a distortion of the uranyl dimer to form both a corner-sharing and an edge-sharing linkage to neighboring Al octahedra, leading to R_U-U = 4.150 Å. In the alkaline region, a corner-sharing uranyl dimer complex is the most favorable. The U-O path at ∼2.87 Å in the EXAFS spectra arises from the oxygen atom linking two Al cations in corner-sharing arrangement. The adsorption structures obtained by DFT calculations are in good agreement with the structural parameters from EXAFS analysis: U-Al (3.394 Å), U-U (3.949 Å), and U-O (2.823 Å) for the alkaline pH model, and U-Al (3.279 Å), U-U (4.150 Å), and U-O (2.743 Å) for the acidic pH model. This work shows that by combining EXAFS and DFT, consistent structural models for uranyl sorption complexes can be obtained, which are relevant to predict the migration behavior of uranium at nuclear facilities.     

Multi-metal contaminant dynamics in temporarily flooded soil under sulfate limitation

In many river basins, floodplain soils have accumulated a variety of metal contaminants, which might be released during periods of flooding. We investigated the dynamics of copper, cadmium, lead, zinc, and nickel in a contaminated freshwater floodplain soil under a realistic sulfate-limited flooding regime in microcosm experiments. We found that most contaminants were initially mobilized by processes driven by the reductive dissolution of Fe(III) and Mn(IV, III) (hydr)oxides. Subsequently, bacterial sulfate respiration resulted in the transformation of the entire available sulfate (2.3 mmol/kg) into chromous reducible sulfur (CRS). Cu K-edge X-ray absorption fine structure (XAFS) spectroscopy revealed that the soil Cu speciation changed from predominantly Cu(II) bound to soil organic matter (SOM) intermittently to 14% metallic Cu(0) and subsequently to 66% copper sulfide (Cu_xS). These Cu_xS precipitates accounted for most of the formed CRS, suggesting that Cu_xS was the dominant sulfide phase formed in the flooded soil. Sequential metal extractions, in agreement with CRS results, suggested that easily mobilizable Cd was completely and Pb partially sequestered in sulfide precipitates, controlling their dissolved concentrations to below detection limits. In contrast, Zn and Ni (as well as Fe) were hardly sequestered into sulfide phases, so that micromolar levels of dissolved Zn and Ni (and millimolar dissolved Fe(II)) persisted in the reduced soil. The finding that Cu, Cd, and Pb were sequestered (but hardly any Zn, Ni, and Fe) is consistent with the thermodynamically predicted sulfide ladder following the increasing solubility products of the respective metal sulfides. The observation that Cd and Pb were sequestered in sulfides despite the presence of remaining SOM-bound Cu(II) suggested that the kinetics of Cu(II) desorption, diffusion, and/or Cu_xS precipitation interfered with the sulfide ladder. We conclude that the dynamics of multiple metal contaminants are intimately coupled under sulfate limitation by the relative thermodynamic stabilities and formation kinetics of the respective metal sulfides.