Distribution of trace elements in filtered and non filtered aqueous fractions: Insights from rivers and streams of Sardinia (Italy)

The distribution of several trace elements in different aqueous fractions has been studied in running waters from Sardinia (Italy). Trace elements and major components were determined in water samples collected at high- and low-discharge from rivers (90 samples) and streams (70 samples). At selected sites, total (non filtered samples) and dissolved (0.4 μm and 0.015 μm pore-size filtered samples) amounts of trace elements were determined, and the composition of the solid matter retained on the filters was investigated for estimating the eventual interrelationship. The elements B, Li, Rb, Sr, Ba, As, Sb, Mo, Tl and U in the studied waters showed small differences between total and dissolved amounts; dissolved concentrations were higher under low flow conditions, when the contribution of rainwater to the rivers was minimum; their concentrations were often correlated with total dissolved solids (TDS), and appeared to be related to the intensity of water-rock interaction processes. The elements Al, Fe, Mn, Pb, Zn, Cd, Cu, Co, Ni, Cs, Y, REE and Th were not related to TDS and/or major ions; they showed higher concentrations under high flow conditions; marked differences occurred between total and dissolved amounts; much lower concentrations were generally observed in the water filtered through 0.015 μm than in the water filtered through 0.4 μm, especially when sampling was carried out after heavy rain events that enhanced the load of solid matter in the water. These observations indicate an aqueous transport via sorption processes on very fine particles, such as Fe-oxide/hydroxide and clay mineral particles, which have been inferred by SEM-EDX analyses of the matter retained on the filters.     

The Burren: a glacial,karstic and biokarstic expression of a limestone plateau in western Ireland

The term glaciokarst describes a landscape where both glacial and karstic processes have contributed to geomorphological evolution and has been applied to a range of environments from the high arctic to the alpine Mediterranean. Nevertheless, glaciokarstic environments globally often exhibit significant variation in geomorphological processes and landforms due to these geographical differences. The Burren, County Clare, Republic of Ireland, is often quoted as a quintessential glaciokarstic landscape. However, the Burren and other similar environments would appear to lean towards one end of the glaciokarst spectrum, where solutional and biological processes have been dominant throughout the Holocene, in contrast to ice‐dominated glaciokarsts where karstic and biokarstic processes are temperature‐limited and cryospheric processes remain the principal geomorphological agents. Holocene landscape evolution and the development of a range of meso‐, micro‐ and nano‐scale karren features on limestone surfaces appears to be largely biokarstic in origin. Karstification of many glacially scoured limestone pavements would have begun under acidic soil cover, with biological soil processes contributing to smooth, rounded cryptokarstic surface forms. Holocene soil erosion is attributed to anthropogenic activity, climatic fluctuations and the evolution of the karstic groundwater system leading to vertical soil loss through widening grikes. Exposed limestone pavements subject to subaerial conditions often exhibit extensive lichen colonization which has been shown to influence the overall rate of karstification and contribute to the development of micro‐ and meso‐scale bioweathering features. Where cryptokarstic features have been exhumed from beneath soil cover, their evolution under subaerial conditions leads to intermediate, polygenetic karren features. In light of our current understanding of the Burren landscape, it is proposed that the term glaciobiokarstic may be a better expression to encompass the biological processes that have played a fundamental role in the evolution of the Burren and similar landscapes, without neglecting the contribution of glacial and inorganic karstic processes. Copyright © 2016 John Wiley & Sons, Ltd.     

Reconstruction of annual winter rainfall since A.D.1579 in central-eastern Spain based on calcite laminated sediment from Lake La Cruz

We present the first winter (December to March) rainfall reconstruction based in a novel proxy, the thickness of annual calcite laminations preserved in Lake La Cruz (central–eastern Spain). A previous calibration analysis between laminae thickness and the instrumental data series (1950 to present) indicated a highly significant correlation with winter rainfall. Therefore this study attempts the winter rainfall reconstruction since the onset of laminations (1579 a.d.) by means of the calibration function previously developed. The verification analysis between inferred annual values and earlier instrumental data (1859–1949) confirms the suitability of this novel proxy and the reliability of the series reconstructed. The reconstructed series show the fluctuating character of winter rainfall in the western Mediterranean area; interdecadal dry periods alternated with wetter periods following, in a board sense, the pattern recorded by documentary sources in other regions of the Iberian Peninsula. At present times regional winter rainfall anomalies are highly correlated with the phase of the North Atlantic Oscillation (NAO). However the time series analysis showed the dominance of nonstationary components at high frequencies of the climate signal over the last four centuries suggesting that the connection between winter rainfall and the NAO has not been stable over time and also other modes of variability, not only NAO, may have conditioned winter rainfall variability.     

Sun–earth relationship inferred by tree growth rings in conifers from Severiano De Almeida,Southern Brazil

This study of Sun–Earth relationships is based on tree growth rings analysis of araucarias (Araucaria angustifolia) collected at Severiano de Almeida (RS) Brazil. A chronology of 359 years was obtained, and the classical method of spectral analysis by iterative regression and wavelet method was applied to find periodicities and trends contained in the tree growth. The analysis of the dendrochronological series indicates representative periods of solar activity of 11 (Schwabe cycle), 22 (Hale cycle), and 80 (Gleissberg cycle) years. The result shows the possible influence of the solar activity on tree growth in the last 350 years. Periods of 2–7 years were also found and could represent a response of the trees to local climatic conditions. Good agreement between the time series of tree growth rings and the 11 year solar cycle was found during the maximum solar activity periods.     

Patterns of rare earth and other trace elements in different size fractions of clays of Campanian–Maastrichtian deposits from the Portuguese western margin (Aveiro and Taveiro Formations)

The Upper Cretaceous (Campanian–Maastrichtian) Taveiro and Aveiro Formations belong to the northern sector of the Lusitanian basin (Portuguese western margin). The Taveiro Formation was deposited in alluvial fans, including mud flow beds, lakes and sinuous rivers. The Aveiro Formation was deposited in a flat region with low hydrodynamics channels, with the formation of a barrier island-tidal system. The reconstruction of this sedimentary basin may be difficult due to its complex architecture. This work aims a methodology to be used in the reconstruction of Cretaceous sedimentary environments of the Lusitanian basin, through the establishment of geochemical patterns of different size fractions of those deposits. Chemical analysis was performed by instrumental neutron activation analysis (INAA), and the mineralogical composition obtained by X-ray diffractometry (XRD). The whole rock and different size fractions (? ≥ 125 μm, 63–125 μm, 20–63 μm, 2–20 μm and ? < 2 μm) of selected samples were studied aiming the rare earth elements (REE) and other trace elements distribution and its correlation with the grain size and mineralogy.The results obtained for the studied Cretaceous sediments showed that REE patterns and other trace elements distribution in the different size fractions may be used as a tool to differentiate deposits within and between sedimentary formations. Within the Taveiro Formation, REE are concentrated in the silt fractions (20–63 μm and 2–20 μm) of the Reveles deposit, and in the clay size fraction of S. Pedro deposit, which is richer in kaolinite. The 1st transition elements, particularly Zn, are correlated with the presence of smectite in the clay fraction of Reveles deposit. In the sand and silt size fractions (>2 μm) of samples from Taveiro Formation correlations were found between: Ga and 1st transition elements, and phyllosilicates; Cs and mica; and Rb and Ba, and K–feldspars.The Bustos deposit (Aveiro Formation) samples are very fine-grained and with a high proportion of the fine silt fraction where REE are concentrated, especially the heavy ones. Incorporation of MREE, Co and U in carbonates of the coarser fraction appears to occur. The abundances of the 1st transition elements, Ga and As, are correlated with phyllosilicates.Significant differences were found in the trace elements patterns of the various analysed size fractions of the Lusitanian basin of Cretaceous sediments, between and even within formations, which can be used as a methodological approach for a fine paleogeographic reconstruction.     

Mobility of aqueous contaminants at abandoned mining sites: insights from case studies in Sardinia with implications for remediation

Public awareness of environmental health issues has increased significantly in recent years, creating the need for detailed scientific studies that can identify potential environmental problems. This paper reports the results of hydrogeochemical surveys carried out in Sardinia, an Italian region with a long mining history. When mining operations in Sardinia ceased, actions for limiting the potential adverse effects of mine closure on the water system were not undertaken. Drainages from flooded mines and seeps from mining residues left on the ground are the main mining-related sources of contamination in Sardinia. Due to the proximity of mining sites to water resources and land that is within reach of animals and humans, the major risks to human health are associated with the direct discharge of contaminated waters into the streams and soils located down-gradient of the abandoned mines. Results of hydrogeochemical surveys carried out under different seasonal conditions showed that the dispersion of toxic and harmful elements (As, Cd, Ni, Pb, Sb and Zn) increases during the rainy season, especially under high runoff conditions. These results should help regional and national authorities to address present environmental regulations, particularly those regarding the quality of water resources. Furthermore, the results might be useful elsewhere for planning remediation actions at abandoned mining sites. Lessons learned by past mining in Sardinia indicate that correct disposal and management of mining residues should be mandatory from the beginning of exploitation and processing at each active mine. This would allow reduction of the environmental risks as well as the cost of remediation.     

Metal binding by humic acids in recent sediments from the SW Iberian coastal area

The concentrations of Cu, Zn, Cr, Ni, Pb, As, Mn and Co were determined by Inductively Coupled Plasma–Mass Spectrometry both in recent sediments from different locations of the Huelva littoral (SW Iberian Peninsula) and in their humic acid (HA) fractions in order to evaluate distribution and binding capacity of those trace elements to HAs. In addition, elemental composition (C, N, S) and δ¹³C values were determined to appraise the sources of organic matter in the area. This study involved the comparison of selected samples taken from different environments including the estuary of the Guadiana River, the main fluvial system of the region, the Tinto and Odiel estuary system and the proximal shelf. Significant positive correlations were found among Cu, Zn, As and Pb in bulk sediments, suggesting a common origin of all of those elements: the mining activities and pyrite deposits located hinterland. On the other hand, results for Cr, Co and Ni pointed to the basic rocks from the low basin of the Guadiana River as their main source. Elemental (C, N) and isotopic (δ¹³C) composition of sediments indicated a significant contribution of autochthonous plankton in coastal shelf sediments, whereas estuarine and riverine sediments showed a major contribution of terrestrial biomass. Geochemical values for their corresponding HAs suggested a greater terrestrial contribution in the sedimentary OM of the coastal shelf sediments than in bulk sediments, which evidenced the influence of coastal currents and sediment fluxes. Humic acids sequester considerable amounts of Cu and Zn contributing to reduce the bioavailability of these contaminants.     

Weathering of ordinary chondrites from the Atacama Desert,Chile, by Mössbauer spectroscopy and synchrotron radiation X‐ray diffraction

Some terrestrial areas have climatic and geomorphologic features that favor the preservation, and therefore, accumulation of meteorites. The Atacama Desert in Chile is among the most important of such areas, known as DCA. This desert is the driest on Earth, one of the most arid, uninhabitable localities with semiarid, arid, and hyper‐arid conditions. The meteorites studied here were collected from within the DCA of San Juan and Pampa de Mejillones, located, respectively, in the Central Depression and the Coastal Range of the Atacama Desert. ⁵⁷Fe Mössbauer spectroscopy was used for quantitative analysis of the degree of weathering of the meteorites, through the determination of the proportions of the various Fe‐bearing phases and in particular the amount of oxidized iron in terrestrial alteration products. The abundance of ferric ions in weathered chondrites can be related to specific precursor compositions and to the level of terrestrial weathering. The aim of the study was the identification, quantification, and differentiation of the weathering products in the ordinary chondrites found in the San Juan and the Pampa de Mejillones areas of the Atacama Desert. The ⁵⁷Fe Mössbauer spectroscopy study was complemented by synchrotron radiation X‐ray diffraction and magnetic susceptibility measurements. The results allow a clear differentiation of the rate of weathering in meteorite samples collected from the San Juan versus the Pampa de Mejillones areas of the Atacama Desert.