Natural manganese oxide: Combined analytical approach for solid characterization and arsenic retention

To understand the retention of As on a natural manganese sand, the structural, textural and chemical properties of the solid were first investigated by combining scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron-energy-loss spectroscopy (EELS), X-ray diffraction (XRD), BET N₂ gas adsorption, diffuse reflectance Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) analysis. Manganese sand could be mainly described as a mixture of a phyllomanganate, lithiophorite [(Al,Li)MnO₂(OH)₂], and pyrolusite (MnO₂). Iron particle, kaolinite and gibbsite type-phases were also observed. Particles organization led to the presence of a mesoporosity with pore diameters ranging from 100 to 200 Å and a specific surface area of 23 m² g⁻¹. Contact with an As(V) solution (0.67 mmol L⁻¹) led to an average fractional surface coverage of 0.4. Both As (V) and (III) were present on the surface of the sand in a 1:1 ratio. As(V) was sorbed on lithiophorite-type particles through surface complexation type reaction. As(III) was thought to result from As(V) reduction mechanism on iron particles.     

Andesite and dacite genesis via contrasting processes: the geology and geochemistry of El Valle Volcano,Panama

The easternmost stratovolcano along the Central American arc is El Valle volcano, Panama. Several andesitic and dacitic lava flows, which range in age 5–10 Ma, are termed the old group. After a long period of quiescence (approximately 3.4 Ma), volcanic activity resumed approximately 1.55 Ma with the emplacement of dacitic domes and the deposition of dacitic pyroclastic flows 0.9–0.2 Ma. These are referred to as the young group. All of the samples analyzed are calc-alkaline andesites and dacites. The mineralogy of the two groups is distinct; two pyroxenes occur in the old-group rocks but are commonly absent in the young group. In contrast, amphibole has been found only in the young-group samples. Several disequilibrium features have been observed in the minerals (e.g., oscillatory zoning within clinopyroxenes). These disequilibrium textures appear to be more prevalent among the old- as compared with the young-group samples and are most likely the result of magma-mixing, assimilation, and/or polybaric crystallization. Mass-balance fractionation models for major and trace elements were successful in relating samples from the old group but failed to show a relationship among the young-group rocks or between the old- and young-group volcanics. We believe that the old-group volcanics were derived through differentiation processes from basaltic magmas generated within the mantlewedge. The young group, however, does not appear to be related to more primitive magmas by differentiation. The young-group samples cannot be related by fractionation including realistic amounts of amphibole. Distinctive geochemical features of the young group, including La/Yb ratios〉15, Yb〈1, Sr/Y〉150, and Y〈6, suggest that these rocks were derived from the partial melting of the subducted lithosphere. These characteristics can be explained by the partial melting of a source with residual garnet and amphibole. Dacitic material with the geochemical characteristics of subducted-lithosphere melting is generated apparently only where relatively hot crust is subducted, based on recent work. The young dacite-genesis at El Valle volcano is related to the subduction of relatively hot lithosphere.     

Tourmalinites from the Eastern Sierras Pampeanas, Argentina

In the eastern Sierras Pampeanas, Central Argentina, tourmalinites and coticules are found in close association with stratabound scheelite deposits in metamorphic terranes. In Sierra Grande (Agua de Ramón and Ambul districts) and Sierra de Altautina, tourmalinites are associated with stratabound scheelite deposits related to orthoamphibolites. In the Pampa del Tamboreo area, tourmalinites are located in biotite schists stratigraphically related to acid to intermediate metavolcanic rocks and scheelite-bearing quartzites.The mineral chemistry and boron isotopic compositions of tourmalinite-hosted and vein-hosted tourmalines are investigated. Overall, the tourmalines belong to the dravite-schorl series and are generally aluminous; Fe/(Fe+Mg) ranges from 0.33 to 0.85, Al/(Al+Fe+Mg) from 0.66 to 0.76 and the amount of X-site vacancy (0.12–0.48) indicates significant foitite components. Their boron isotopic compositions (δ¹¹B) are from −24.0‰ to−15.0‰.Similar mineral chemistries and boron isotopic values for tourmaline in tourmalinites related to stratabound scheelite mineralisation and in tungsten-bearing quartz veins suggest a common source for the boron and probably the tungsten. The field, chemical and isotopic relationships are consistent with tungsten and boron in quartz-vein deposits being remobilised from stratabound scheelite and tourmalinite, dominantly by liquid-state transfer associated with regional shear zones. Tungsten and boron in the original sedimentary sequence (now meta-exhalites) are ascribed to volcanogenic exhalations.     

The Removal of Dissolved Metals by Hydroxysulphate Precipitates during Oxidation and Neutralization of Acid Mine Waters, Iberian Pyrite Belt

This study examines the removal of dissolved metals during the oxidation and neutralization of five acid mine drainage (AMD) waters from La Zarza, Lomero, Esperanza, Corta Atalaya and Poderosa mines (Iberian Pyrite Belt, Huelva, Spain). These waters were selected to cover the spectrum of pH (2.2–3.5) and chemical composition (e.g., 319–2,103 mg/L Fe; 2.85–33.3 g/L SO₄⁼) of the IPB mine waters. The experiments were conducted in the laboratory to simulate the geochemical evolution previously recognized in the field. This evolution includes two stages: (1) oxidation of dissolved Fe(II) followed by hydrolysis and precipitation of Fe(III), and (2) progressive pH increase during mixing with fresh waters. Fe(III) precipitates at pH < 3.5 (stages 1 and 2) in the form of schwertmannite, whereas Al precipitates during stage 2 at pH 5.0 in the form of several hydroxysulphates of variable composition (hydrobasaluminite, basaluminite, aluminite). During these stages, trace elements are totally or partially sorbed and/or coprecipitated at different rates depending basically on pH, as well as on the activity of the SO₄⁼ anion (which determines the speciation of metals). The general trend for the metals which are chiefly present as aqueous free cations (Pb²⁺, Zn²⁺, Cu²⁺, Cd²⁺, Mn²⁺, Co²⁺, Ni²⁺) is a progressive sorption at increasing pH. On the other hand, As and V (mainly present as anionic species) are completely scavenged during the oxidation stage at pH < 3.5. In waters with high activities (> 10⁻¹) of the SO ₄⁼ ion, some elements like Al, Zn, Cd, Pb and U can also form anionic bisulphate complexes and be significantly sorbed at pH < 5. The removal rates at pH 7.0 range from around 100% for As, V, Cu and U, and 60–80% for Pb, to less than 20% for Zn, Co, Ni and Mn. These processes of metal removal represent a significant mechanism of natural attenuation in the IPB.     

Identifying Key Sources of Uncertainty in Climate Change Projections

What sources of uncertainty shouldbe included in climate change projections and whatgains can be made if specific sources of uncertaintyare reduced through improved research?DIALOGUE, anintegrated assessment model, has been used to answerthese questions. Central in the approach of DIALOGUEis the concept of parallel modeling, i.e., for eachstep in the chain from emissions to climate change anumber of equivalent models areimplemented. The followingconclusions are drawn:The key source of uncertainty in global temperatureprojections appears to be the uncertainty inradiative forcing models. Within this group ofmodels uncertainty within aerosol forcing models isabout equal to the total forcing of greenhouse gasmodels. In the latter group CO₂ is dominant.The least important source of uncertainty appears tobe the gas cycle models. Within this group of modelsthe role of carbon cycle models is dominant.Uncertainty in global temperature projections hasnot been treated consistently in the literature.First, uncertainty should be calculated as a productof all uncertainty sources. Second, aparticular choice of a base year for global warmingcalculations influences the ranking of uncertainty.Because of this, a comparison of ranking resultsacross different studies is hampered. We argue that`pre-Industrial' is the best choice for studies onuncertainty.There is a linear relationship between maximumuncertainty in the year 2100 and cumulativeemissions of CO₂ over the period 1990–2100:higher emissions lead to more uncertainty.     

The intracloud/cloud-to-ground lightning ratio in Southeastern Brazil

The intracloud to cloud-to-ground lightning flash ratio (Z) has been estimated for the first time in Southeastern Brazil and in the tropical region using the Lightning Imaging Sensor (LIS) and Brazilian lightning detection network (BrasilDat) lightning data obtained from 1999 to 2005. Geographical variations of Z and their relation to elevation, latitude, precipitation, total lightning density and percentage of positive CG lightning will be discussed. Daily variations of Z will also be presented. The results suggest that Z values are similar to studies outside the tropics and that are influenced by orographic features.     

Climate change hotspots mapping: what have we learned?

In the past 5 years there has been a proliferation of efforts to map climate change “hotspots” — regions that are particularly vulnerable to current or future climate impacts, and where human security may be at risk. While some are academic exercises, many are produced with the goal of drawing policy maker attention to regions that are particularly susceptible to climate impacts, either to mitigate the risk of humanitarian crises or conflicts or to target adaptation assistance. Hotspots mapping efforts address a range of issues and sectors such as vulnerable populations, humanitarian crises, conflict, agriculture and food security, and water resources. This paper offers a timely assessment of the strengths and weaknesses of current hotspots mapping approaches with the goal of improving future efforts. It also highlights regions that are anticipated, based on combinations of high exposure, high sensitivity and low adaptive capacity, to suffer significant impacts from climate change.     

Countergradient Fluxes of Conserved Variables in the Clear convective and Stratocumulus-topped Boundary Layer: The role of the Entrainment Flux

Large-eddy simulations of a clear convective boundary layer (CBL)and a stratocumulus-topped boundary layer are studied. Bottom-upand a top-down scalars were included in the simulations, and theprinciple of linear superposition of variables was applied toreconstruct the fields of any arbitrary conserved variable.This approach allows a systematic analysis of countergradient fluxesas a function of the flux ratio, which is defined as the ratio betweenthe entrainment flux and the surface flux of the conserved quantity.In general, the turbulent flux of an arbitrary conserved quantityis counter to the mean vertical gradient if the heights where thevertical flux and the mean vertical gradient change sign do notcoincide. The regime where the flux is countergradient is thereforebounded by the so-called zero-flux and zero-gradient heights. Becausethe vertical flux changes sign only if the entrainment flux has anopposite sign to the surface flux, countergradient fluxes arepredominantly found for negative flux ratios. In the CBL the fluxratio for the virtual potential temperature is, to a good approximation,constant, and equal to -0.2. Only if the moisture contribution to thevirtual potential temperature is negligibly small will the flux ratio forthe potential temperature be equal to this value. Otherwise, theflux ratio for the potential temperature can have any arbitrary(negative) value, and, as a consequence, the fluxes for thepotential temperature and the virtual potential temperature willbe countergradient at different heights. As a practical application ofthe results, vertical profiles of the countergradient correction termfor different entrainment-to-surface-flux ratios are discussed.     

Fingerprinting of the Atlantic meridional overturning circulation in climate models to aid in the design of proxy investigations

It is desirable to design proxy investigations that target regions where properties reconstructed from calibrated parameters potentially carry high-fidelity information concerning changes in large-scale climate systems. Numerical climate models can play an important role in this task, producing simulations that can be analyzed to produce spatial “fingerprints” of the expected response of various properties under a variety of different scenarios. We will introduce a new method of fingerprinting the Atlantic meridional overturning circulation (AMOC) that not only provides information concerning the sensitivity of the response at a given location to changes in the large-scale system, but also quantifies the linearity, monotonicity and symmetry of the response. In this way, locations that show high sensitivities to changes in the AMOC, but that exhibit, for example, strongly nonlinear behavior can be avoided during proxy investigations. To demonstrate the proposed approach we will use the example of the response of seawater temperatures to changes in the strength of the AMOC. We present results from an earth-system climate model which has been perturbed with an idealized freshwater forcing scenario in order to reduce the strength of the AMOC in a systematic manner. The seawater temperature anomalies that result from the freshwater forcing are quantified in terms of their sensitivity to the AMOC strength in addition to the linearity and monotonicity of their response. A first-order reversal curve (FORC) approach is employed to investigate and quantify the irreversibility of the temperature response to a slowing and recovering AMOC. Thus, FORCs allow the identification of areas that are unsuitable for proxy reconstructions because their temperature versus AMOC relationship lacks symmetry.     

Quantifying Arctic contributions to climate predictability in a regional coupled ocean-ice-atmosphere model

The relative importance of regional processes inside the Arctic climate system and the large scale atmospheric circulation for Arctic interannual climate variability has been estimated with the help of a regional Arctic coupled ocean-ice-atmosphere model. The study focuses on sea ice and surface climate during the 1980s and 1990s. Simulations agree reasonably well with observations. Correlations between the winter North Atlantic Oscillation index and the summer Arctic sea ice thickness and summer sea ice extent are found. Spread of sea ice extent within an ensemble of model runs can be associated with a surface pressure gradient between the Nordic Seas and the Kara Sea. Trends in the sea ice thickness field are widely significant and can formally be attributed to large scale forcing outside the Arctic model domain. Concerning predictability, results indicate that the variability generated by the external forcing is more important in most regions than the internally generated variability. However, both are in the same order of magnitude. Local areas such as the Northern Greenland coast together with Fram Straits and parts of the Greenland Sea show a strong importance of internally generated variability, which is associated with wind direction variability due to interaction with atmospheric dynamics on the Greenland ice sheet. High predictability of sea ice extent is supported by north-easterly winds from the Arctic Ocean to Scandinavia.