The infrared dielectric properties of maghemite, γ-Fe2O3, from reflectance measurement on pressed powders

The infrared complex permittivity functions of three varieties of maghemite, γ-Fe₂O₃, having different degrees of vacancy ordering, have been determined from their IR reflectance spectra, measured at near to normal incidence on pressed powder pellets. The optical constants therefrom obtained have been verified by using them in the simulation of the corresponding absorption spectra for KBr-diluted pellets, and these are in excellent agreement with the experimental spectra. All calculations are based on a procedure for the estimation of the effective dielectric function of a mixture, which incorporates percolation features, recently developed by the authors.     

Effect of heat treatment on tourmaline from Brazil

The crystal-chemical behaviour of tourmaline from Araçuaí, Minas Gerais state, Brazil, when subjected to heating in air atmosphere has been studied by several techniques, including EMPA, UV–Vis, TGA, and Mössbauer spectroscopy. The tourmaline samples are typically intermediate members of the elbaite-schorl series. The origin of colour and of its change after treatment has been discussed in terms of local disorder, presence of metal transition elements, oxidation of ferrous iron at the octahedral site, and simultaneous trap of the excess electron. These findings may be used to enhance the colour in tourmaline crystals or generate wanted colour changes.     

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.     

A new algorithm to estimate sky condition based on 5 minutes-averaged values of clearness index and relative optical air mass

Summary This work describes a new algorithm to characterize sky condition in intervals of 5 min using four categories of sun exposition: apparent sun with cloud reflection effects; apparent sun without cloud effects; sun partially concealed by clouds; and sun totally concealed by clouds. The algorithm can also be applied to estimate hourly and daily sky condition in terms of the traditional three categories: clear, partially cloudy and cloudy day. It identifies sky conditions within a confidence interval of 95% by minimizing local climate and measurement effects. This is accomplished by using a logistic cumulative probability function to characterize clear sky and Weibull cumulative probability function to represent cloudy sky. Both probability functions are derived from frequency distributions of clearness index, based on 5 minutes-averaged values of global solar irradiance observed at the surface during a period of 6 years in Botucatu, Southeastern of Brazil. The relative sunshine estimated from the new algorithm is statistically comparable to the one derived from Campbell-Stocks sunshine recorder for both daily and monthly values. The new method indicates that the highest frequency of clear sky days occurs in Botucatu during winter (66%) and the lowest during the summer (38%). Partially cloudy condition is the dominant feature during all months of the year.     

Mean flow-transient perturbation interaction in the Southern Hemisphere: a simulation using a variable-resolution GCM

The ability of an atmospheric general circulation model to reproduce fundamental features of the wintertime extratropical Southern Hemisphere (SH) circulation is evaluated with emphasis on the daily variability of the SH mean flow and the mean flow-transient perturbations interaction. Two 10-year simulations using a new version of the LMDZ GCM with a stretched grid scheme centered at 45 °S and forced by climatological SST are performed: a high (144Ꮡ) and low (64Ꭹ) horizontal resolution runs. The performance of both simulations was determined by comparing several simulated fields (zonal wind, temperature, kinetic energy, transient eddy momentum and heat fluxes, Eliassen-Palm fluxes, Eady growth rate and baroclinic conversion term) against the European Centre for Medium Range Weather Forecast reanalyses (ERA). High and low-resolution simulations are similar in many respects; in particular, both experiments reproduce the main patterns of the southern extratropical large-scale circulation satisfactorily. Increasing resolution does not improve universally some spurious aspects of the low resolution simulation (e.g. the cold bias in the high polar troposphere, the debilitated subtropical jet, the low baroclinic conversion rate). Those aspects present little sensitivity to the model resolution. The interaction between transient eddies and zonal mean flow are examined. The low-resolution experiment is able to qualitatively represent the acceleration/deceleration of the mean flow by transient perturbations, south/north of 30 °S with an accuracy similar to that of the high-resolution experiment. Although both experiments represent the baroclinic structure of the mean flow satisfactorily, the model underestimates some transient properties due to the underestimation of the baroclinic conversion term in middle latitudes. Such misrepresentation does not improve with increasing resolution and is related to the relatively weak meridional temperature gradient and the inadequate geographical distribution of the eddy heat fluxes. In particular, the eddy kinetic energy is always underestimated. Eddy kinetic energy does not improve convincingly with increasing resolution, suggesting that the adequate representation of the storm tracks is highly influenced by the physical parametrizations.     

Witnessing North Atlantic westerlies variability from ships’ logbooks (1685–2008)

A monthly index based on the persistence of the westerly winds over the English Chanel is constructed for 1685–2008 using daily data from ships’ logbooks and comprehensive marine meteorological datasets. The so-called Westerly Index (WI) provides the longest instrumental record of atmospheric circulation currently available. Anomalous WI values are associated with spatially coherent climatic signals in temperature and precipitation over large areas of Europe, which are stronger for precipitation than for temperature and in winter and summer than in transitional seasons. Overall, the WI series accord with the known European climatic history, and reveal that the frequency of the westerlies in the eastern Atlantic during the twentieth century and the Late Maunder Minimum was not exceptional in the context of the last three centuries. It is shown that the WI provides additional and complementary information to the North Atlantic Oscillation (NAO) indices. The analysis of WI series during the industrial era indicates an overall good agreement with the winter and high-summer NAO, with the exception of several multidecadal periods of weakened correlation. These decoupled periods between the frequency and the intensity of the zonal flow are interpreted on the basis of several sources of non-stationarity affecting the centres of the variability of the North Atlantic and their teleconnections. Comparisons with NAO reconstructions and long instrumental indices extending back to the seventeenth century suggest that similar situations have occurred in the past, which call for caution when reconstructing the past atmospheric circulation from climatic proxies. The robustness and extension of its climatic signal, the length of the series and its instrumental nature make the WI an excellent benchmark for proxy calibration in Europe and Greenland.     

Response of single benthic metrics and multi-metric methods to anthropogenic pressure gradients, in five distinct European coastal and transitional ecosystems

In recent times many benthic indices have been proposed to assess the ecological quality of marine waters worldwide. In this study we compared single metrics and multi-metric methods to assess coastal and transitional benthic status along human pressure gradients in five distinct environments across Europe: Varna bay and lake (Bulgaria), Lesina lagoon (Italy), Mondego estuary (Portugal), Basque coast (Spain) and Oslofjord (Norway). Hence, 13 single metrics (abundance, number of taxa, and several diversity and sensitivity indices) and eight of the most common indices used within the European Water Framework Directive (WFD) for benthic assessment were selected: index of size spectra (ISS), Benthic assessment tool (BAT), Norwegian quality index (NQI), Multivariate AMBI (M-AMBI), Benthic quality index (BQI), (Benthic ecosystem quality index (BEQI), Benthic index based on taxonomic sufficiency (BITS), and infaunal quality index (IQI). Within each system, sampling sites were ordered in an increasing pressure gradient according to a preliminary classification based on professional judgement. The different indices are largely consistent in their response to pressure gradient, except in some particular cases (i.e. BITS, in all cases, or ISS when a low number of individuals is present). Inconsistencies between indicator responses were most pronounced in transitional waters (i.e. IQI, BEQI), highlighting the difficulties of the generic application of indicators to all marine, estuarine and lagoonal environments. However, some of the single (i.e. ecological groups approach, diversity, richness) and multi-metric methods (i.e. BAT, M-AMBI, NQI) were able to detect such gradients both in transitional and coastal environments, being these multi-metric methods more consistent in the detection than single indices. This study highlights the importance of survey design and good reference conditions for some indicators. The agreement observed between different methodologies and their ability to detect quality trends across distinct environments constitutes a promising result for the implementation of the WFD’s monitoring plans. Moreover, these results have management implications, regarding the dangers of misclassification, uncertainty in the assessment, use of conflicting indices, and testing and validation of indices.     

The effect of El Niño Southern Oscillation cycles on the decadal scale suspended sediment behavior of a coastal dry‐summer subtropical catchment

Rivers display temporal dependence in suspended sediment–water discharge relationships. Although most work has focused on multi‐decadal trends, river sediment behavior often displays sub‐decadal scale fluctuations that have received little attention. The objectives of this study were to identify inter‐annual to decadal scale fluctuations in the suspended sediment–discharge relationship of a dry‐summer subtropical river, infer the mechanisms behind these fluctuations, and examine the role of El Niño Southern Oscillation climate cycles. The Salinas River (California) is a moderate sized (11 000 km²), coastal dry‐summer subtropical catchment with a mean discharge (Q_mean) of 11.6 m³ s^?1. This watershed is located at the northern most extent of the Pacific coastal North America region that experiences increased storm frequency during El Niño years. Event to inter‐annual scale suspended sediment behavior in this system was known to be influenced by antecedent hydrologic conditions, whereby previous hydrologic activity regulates the suspended sediment concentration–water discharge relationship. Fine and sand suspended sediment in the lower Salinas River exhibited persistent, decadal scale periods of positive and negative discharge corrected concentrations. The decadal scale variability in suspended sediment behavior was influenced by inter‐annual to decadal scale fluctuations in hydrologic characteristics, including: elapsed time since small (~0.1 × Q_mean), and moderate (~10 × Q_mean) threshold discharge values, the number of preceding days that low/no flow occurred, and annual water yield. El Niño climatic activity was found to have little effect on decadal‐scale fluctuations in the fine suspended sediment–discharge relationship due to low or no effect on the frequency of moderate to low discharge magnitudes, annual precipitation, and water yield. However, sand concentrations generally increased in El Niño years due to the increased frequency of moderate to high magnitude discharge events, which generally increase sand supply. Copyright © 2014 John Wiley & Sons, Ltd.     

The use of the exponent K(q) function to delimit homogeneous regions in regional frequency analysis of extreme annual daily rainfall

The regional frequency analysis of extreme annual rainfall data is a useful methodology in hydrology to obtain certain quantile values when no long data series are available. The most crucial step in the analysis is the grouping of sites into homogeneous regions. This work presents a new grouping criterion based on some multifractal properties of rainfall data. For this purpose, a regional frequency analysis of extreme annual rainfall data from the Maule Region (Chile) has been performed. Daily rainfall data series of 53 available stations have been studied, and their empirical moments scaling exponent functions K(q) have been obtained. Two characteristics parameters of the K(q) functions (γ_max and K(0)) have been used to group the stations into three homogeneous regions. Only five sites have not been possible to include into any homogenous regions, being the local frequency analysis of extreme daily rainfall the most appropriate method to be used at these locations. Copyright © 2014 John Wiley & Sons, Ltd.