Nanogeochemistry of hydrothermal magnetite

Magnetite from hydrothermal ore deposits can contain up to tens of thousands of parts per million (ppm) of elements such as Ti, Si, V, Al, Ca, Mg, Na, which tend to either structurally incorporate into growth and sector zones or form mineral micro- to nano-sized particles. Here, we report micro- to nano-structural and chemical data of hydrothermal magnetite from the Los Colorados iron oxide–apatite deposit in Chile, where magnetite displays both types of trace element incorporation. Three generations of magnetites (X–Z) were identified with concentrations of minor and trace elements that vary significantly: SiO₂, from below detection limit (bdl) to 3.1 wt%; Al₂O₃, 0.3–2.3 wt%; CaO, bdl–0.9 wt%; MgO, 0.02–2.5 wt%; TiO₂, 0.1–0.4 wt%; MnO, 0.04–0.2 wt%; Na₂O, bdl–0.4 wt%; and K₂O, bdl–0.4 wt%. An exception is V₂O₃, which is remarkably constant, ranging from 0.3 to 0.4 wt%. Six types of crystalline nanoparticles (NPs) were identified by means of transmission electron microscopy in the trace element-rich zones, which are each a few micrometres wide: (1) diopside, (2) clinoenstatite; (3) amphibole, (4) mica, (5) ulvöspinel, and (6) Ti-rich magnetite. In addition, Al-rich nanodomains, which contain 2–3 wt% of Al, occur within a single crystal of magnetite. The accumulation of NPs in the trace element-rich zones suggest that they form owing to supersaturation from a hydrothermal fluid, followed by entrapment during continuous growth of the magnetite surface. It is also concluded that mineral NPs promote exsolution of new phases from the mineral host, otherwise preserved as structurally bound trace elements. The presence of abundant mineral NPs in magnetite points to a complex incorporation of trace elements during growth, and provides a cautionary note on the interpretation of micron-scale chemical data of magnetite.     

Long-term ocean simulations in FESOM: evaluation and application in studying the impact of Greenland Ice Sheet melting

The Finite Element Sea-ice Ocean Model (FESOM) is formulated on unstructured meshes and offers geometrical flexibility which is difficult to achieve on traditional structured grids. In this work, the performance of FESOM in the North Atlantic and Arctic Ocean on large time scales is evaluated in a hindcast experiment. A water-hosing experiment is also conducted to study the model sensitivity to increased freshwater input from Greenland Ice Sheet (GrIS) melting in a 0.1-Sv discharge rate scenario. The variability of the Atlantic Meridional Overturning Circulation (AMOC) in the hindcast experiment can be explained by the variability of the thermohaline forcing over deep convection sites. The model also reproduces realistic freshwater content variability and sea ice extent in the Arctic Ocean. The anomalous freshwater in the water-hosing experiment leads to significant changes in the ocean circulation and local dynamical sea level (DSL). The most pronounced DSL rise is in the northwest North Atlantic as shown in previous studies, and also in the Arctic Ocean. The released GrIS freshwater mainly remains in the North Atlantic, Arctic Ocean and the west South Atlantic after 120 model years. The pattern of ocean freshening is similar to that of the GrIS water distribution, but changes in ocean circulation also contribute to the ocean salinity change. The changes in Arctic and sub-Arctic sea level modify exchanges between the Arctic Ocean and subpolar seas, and hence the role of the Arctic Ocean in the global climate. Not only the strength of the AMOC, but also the strength of its decadal variability is notably reduced by the anomalous freshwater input. A comparison of FESOM with results from previous studies shows that FESOM can simulate past ocean state and the impact of increased GrIS melting well.

     

The distribution of late-Quaternary woody taxa in northern Eurasia: evidence from a new macrofossil database

We present a database of late-Quaternary plant macrofossil records for northern Eurasia (from 23° to 180°E and 46° to 76°N) comprising 281 localities, over 2300 samples and over 13,000 individual records. Samples are individually radiocarbon dated or are assigned ages via age models fitted to sequences of calibrated radiocarbon dates within a section. Tree species characteristic of modern northern forests (e.g. Picea, Larix, tree-Betula) are recorded at least intermittently from prior to the last glacial maximum (LGM), through the LGM and Lateglacial, to the Holocene, and some records locate trees close to the limits of the Scandinavian ice sheet, supporting the hypothesis that some taxa persisted in northern refugia during the last glacial cycle. Northern trees show differing spatio-temporal patterns across Siberia: deciduous trees were widespread in the Lateglacial, with individuals occurring across much of their contemporary ranges, while evergreen conifers expanded northwards to their range limits in the Holocene.     

Quality assessment of COSMIC/FORMOSAT-3 GPS radio occultation data derived from single- and double-difference atmospheric excess phase processing

This study evaluates the quality of GPS radio occultation (RO) atmospheric excess phase data derived with single- and double-difference processing algorithms. A spectral analysis of 1 s GPS clock estimates indicates that a sampling interval of 1 s is necessary to adequately remove the GPS clock error with single-difference processing. One week (May 2–8, 2009) of COSMIC/FORMOSAT-3 data are analyzed in a post-processed mode with four different processing strategies: (1) double-differencing with 1 s GPS ground data, (2) single-differencing with 30 s GPS clock estimates (standard COSMIC Data Analysis and Archival Center product), (3) single-differencing with 5 s GPS clocks, and (4) single-differencing with 1 s GPS clocks. Analyses of a common set of 5,596 RO profiles show that the neutral atmospheric bending angles and refractivities derived from single-difference processing with 1 s GPS clocks are the highest quality. The random noise of neutral atmospheric bending angles between 60 and 80 km heights is about 1.50e−6 rad for the single-difference cases and 1.74e−6 rad for double-differencing. An analysis of pairs of collocated soundings also shows that bending angles derived from single-differencing with 1 s GPS clocks are more consistent than with the other processing strategies. Additionally, the standard deviation of the differences between RO and high-resolution European Center for Medium range Weather Forecasting (ECMWF) refractivity profiles at 30 km height is 0.60% for single-differencing with 1 and 5 s GPS clocks, 0.68% for single-differencing with 30 s clocks, and 0.66% for double-differencing. A GPS clock-sampling interval of 1 s or less is required for single- and zero-difference processing to achieve the highest quality excess atmospheric phase data for RO applications.     

Low heavy-element photospheric abundance: a challenge for solar modeling

Recent spectroscopic data pointing to low heavy-element abundances Z pose a severe problem for solar-structure modeling. The low-Z abundances imply a lower opacity and a relatively shallow convective zone, both of which are in obvious contradiction with the observed helioseismic sound-speed profile. This paper presents a series of solar models with different heavy-element abundances. The SAHA-S equation of state and OPAL opacities properly take into account the respective heavy-element abundances. Diffusion of individual elements is also included in the models. Sound-speed profiles are compared with inversion results and it is shown that the models with low Z are in disagreement with the inversion data. Even combining the effect of diffusion, overshooting and mixing for the sound-speed profile did not lead to a solution of the low-Z problem. Models with varied neon abundance have also been computed. It turned out that a substantial increase of the neon abundance could produce a model in agreement with the sound-speed inversion but the required abundance increase would be unrealistic. The effect of the neon enhancement on the adiabatic exponent profile in the convection zone is also presented.     

Sulfur speciation in the upper Black Sea sediments

We report solid phase sulfur speciation of six cores from sediments underlying oxic, suboxic and anoxic-sulfidic waters of the Black Sea. Our dataset includes the five sulfur species [pyrite-sulfur, acid volatile sulfides (AVS), zerovalent sulfur (S(0)), organic polysulfides (RS_x), humic sulfur] together with reactive iron and manganese, as quantified by dithionite extraction, and total organic carbon. Pyrite – sulfur was the major phase in all cores [200-400 µmol (g dry wt)^- 1] except for the suboxic core. However, zerovalent sulfur and humic sulfur also reached very significant levels: up to about 109 and 80 µmol (g dry wt)^- 1, respectively. Humic sulfur enrichment was observed in the surface fluff layers of the eastern central basin sediments where Unit-1 type depositional conditions prevail. Elemental sulfur accumulated as a result of porewater sulfide oxidation by reactive iron oxides in turbidities from the anoxic basin margin and western central basin sediments. The accumulation of elemental sulfur to a level close to that of pyrite-S in any part of central Black Sea sediments has never been reported before and our finding indicates deep basin turbidites prevent the build-up of dissolved sulfide in the sediment. This process also contributes to diagenetic pyrite formation whereas in the non-turbiditic parts of the deep basin water column formed (syngenetic) pyrite dominates the sulfur inventory. In slope sediments under suboxic waters, organic sulfur (humic sulfur + organic polysulfides) account for 33-42% of total solid phase S, indicating that the suboxic conditions favor organosulfur formation. Our study shows that the interactions between depositional patterns (Unit 1 vs. turbidite), redox state of overlying waters (oxic-suboxic-sulfidic) and organic matter content determine sulfur speciation and enable the accumulation of elemental sulfur and organic sulfur species close to a level of pyrite-S.     

Analysis of climate policy targets under uncertainty

Although policymaking in response to the climate change threat is essentially a challenge of risk management, most studies of the relation of emissions targets to desired climate outcomes are either deterministic or subject to a limited representation of the underlying uncertainties. Monte Carlo simulation, applied to the MIT Integrated Global System Model (an integrated economic and earth system model of intermediate complexity), is used to analyze the uncertain outcomes that flow from a set of century-scale emissions paths developed originally for a study by the U.S. Climate Change Science Program. The resulting uncertainty in temperature change and other impacts under these targets is used to illustrate three insights not obtainable from deterministic analyses: that the reduction of extreme temperature changes under emissions constraints is greater than the reduction in the median reduction; that the incremental gain from tighter constraints is not linear and depends on the target to be avoided; and that comparing median results across models can greatly understate the uncertainty in any single model.     

Studies of bright flat-spectrum radio quasar 3C 454.3 at high and very-high-energies

Blazars are the subclass of active galactic nuclei (AGNs) which includes the Flat Spectrum Radio Quasars (FSRQ) and BL Lacertae (BL Lac) objects. Variability on the short- and long-time scale in all the wide energy ranges from radio up to gamma-ray emission is a special characteristic of blazars. Multi-wavelength studies of the flaring activity and variability of blazars can serve as a tool to probe the physical properties of the near the core regions and processes responsible for the observed features. 3C 454.3 is a bright FSRQ that is intensively studied through the wide range of electromagnetic spectrum. It has shown remarkably high activity since 2000. The long-term observations of 3C 454.3 at 800 GeV–100 TeV energies with the SHALON telescope were started in 1998 year. A number of activity periods were found. The most significant flaring state of 3C 454.3 at TeV energies was detected in the SHALON observational period of November–December 2010. This increase is correlated with the flares at a lower energy range in observations of Fermi-LAT. The direct association of the significant changes of gamma-ray flux with strong core radio flares are not clear but observed correlations and lags in multi-wavelength activity may point to the complexity of the emission processes in blazars connected with disturbance propagating in the jet.     

Fast data assimilation using a nonlinear Kalman filter and a model surrogate: An application to the Columbia River estuary

A fast and adjoint-free nonlinear data assimilation (DA) system was developed to simulate 3D baroclinic circulation in estuaries, leveraging two recently developed technologies: (1) a nonlinear model surrogate that executes forward simulation three orders of magnitude faster than a forward numerical circulation code and (2) a nonlinear extension to the reduced-dimension Kalman filter that estimates the state of the model surrogate. The noise sources in the Kalman filter were calibrated using empirical cross-validation and accounted for errors in model and model forcing.The DA system was applied to assimilate in situ measurements of water levels, salinities, and temperatures in simulations of the Columbia River estuary. To validate the DA results, we used a combination of cross-validation studies, process-oriented studies, and tests of statistical and dynamical consistency. The validation studies showed that DA improved the representation of several important processes in the estuary, including nonlinear tidal propagation, salinity intrusion, estuarine residual circulation, heat balance, and response of the estuary to coastal winds.