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.     

Structural-stratigraphic control on the Umitaka Spur gas hydrates of Joetsu Basin in the eastern margin of Japan Sea

Integrated geological, geochemical, and geophysical exploration since 2004 has identified massive accumulation of gas hydrate associated with active methane seeps on the Umitaka Spur, located in the Joetsu Basin on the eastern margin of Japan Sea. Umitaka Spur is an asymmetric anticline formed along an incipient subduction zone that extends throughout the western side of the Japanese island-arc system. Seismic surveys recognized chimney structures that seem strongly controlled by a complex anticlinal axial fault system, and exhibit high seismic amplitudes with apparent pull-up structures, probably due to massive and dense accumulation of gas hydrate. Bottom simulating reflectors are widely developed, in particular within gas chimneys and in the gently dipping eastern flank of the anticline, where debris can store gas hydrates that may represent a potential natural gas resource. The axial fault system, the shape of the anticline, and the carrier beds induce thermogenic gas migration to the top of the structure, and supply gas to the gas hydrate stability zone. Gas reaching the seafloor produces strong seepages and giant plumes in the sea water column.     

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.     

Water quality and risk assessment of dug wells: a case study for a poor community in the city of São Paulo, Brazil

Sparsely populated areas, or peripheral communities commonly lack access to a public water supply and sewerage systems. The inhabitants of these areas must make use of excavated wells to provide their water needs, and cesspits for domestic wastewater disposal. These on-site sanitation systems can release pathogens and nutrients into shallow groundwater. These poor communities urgently require cheap and efficient techniques for the detection of sanitary conditions, in order to prevent contamination of the water resources supplied by dug wells. The sanitary risk assessment methodology, applied in an irregular settlement south of the city of São Paulo, was based on a questionnaire with yes/no questions (risk factors), which allowed the identification of problems related to the well construction and operation, and the presence of potential contamination sources in its vicinity. These risk factors were compared against nitrate and bacterial analysis using the clustering statistical method, to verify the relationship between contamination and certain aspects surveyed in the questionnaire. Questions that were more related to contaminated wells were those concerning the presence of cover and its integrity; gaps between mouth and cover; the surrounding pavement and presence of ground irregularities; infiltration in the well casing; water-suspended materials; and proximity to contamination sources. Contamination models based on variograms allowed to observe that bacterial contamination presented a strong localized component, which was associated frequently with the way residents handled the wells, whereas nitrate contamination was related more to a regional (spatial) component; that is, the distance between wells and cesspits.     

Volcanic soil formation in Calabria (southern Italy): The Cecita Lake geosol in the late Quaternary geomorphological evolution of the Sila uplands

This paper focuses on the main morphological, physical, chemical and mineralogical features of an andic-like soil, widely outcropping in the Sila upland plateau of Calabria (southern Italy), and its potential role in tephrostratigraphy. A multidisciplinary and multiscale approach allowed identification of this soil as a “masked” distal archive of volcanic products, developed on granite rocks and sediments with a coeval pyroclastic input during pedogenesis. The study demonstrates that the contribution of volcanic parent materials can be successfully hypothesized and assessed even in the absence, limited extent or poor preservation of primary eruptive products. The soil has an Andisol-like appearance, despite laboratory data that do not match the entire suite of diagnostic criteria for the Andisol taxonomic order. Geomorphological, stratigraphic and pedologic results, coupled with tephrostratigraphic and radiometric data, concur to suggest a Late Pleistocene(?) to Holocene age of the Andisol-like soil. In particular, the rhyolitic chemical composition of small-sized glass fragments (identified by SEM–EDS analyses) indicates soil genesis contributed by volcanic ash, probably sourced from Aeolian Arc explosive activity spanning the last 30 ka. Accordingly, the evidence of limited relict clay illuviation and the specific type of pedogenesis allowing the development of andic properties (in turn related to the neoformation of clay minerals from the weathering of volcanic glass) are consistent with a climatic shift from a seasonally-contrasted to a constantly humid pedoenvironment. This change can be ascribed to the Lateglacial(?) or Early–Middle Holocene to Late Holocene transition. Calibrated AMS ¹⁴C dates performed on charcoal fragments sampled from three representative soil profiles, provide Late Holocene ages (3136 ± 19, 343 ± 16 and 92 ± 24 yr BP), in accord with archaeological finds. On the basis of the consistent stratigraphic position, lateral continuity and wide extent, the soil can be considered a good pedostratigraphic marker in the Sila highlands and is informally defined as the “Cecita Lake geosol”. It supplies valuable time constraints for the underlying (occasionally overlying) deposits and/or soils. Moreover, it allows regional-scale morphostratigraphic correlations and detailed reconstruction of Late Pleistocene–Holocene geomorphic events in Calabria, a very suitable region for distal tephra deposition in the central Mediterranean peri-volcanic area. The effects of high-energy volcanic eruptions are interfingered with or superimposed by other geomorphic processes and climatic or anthropogenic signals.     

The influence of variable topography on the depositional behaviour of pyroclastic density currents: The examples of the Upper Pollara eruption (Salina Island,southern Italy)

Stratigraphic reconstruction of the Upper Pollara eruption has allowed for the inference of eruptive mechanisms and the distillation of a sedimentological model for pyroclastic density currents (PDCs) moving across variable topography. The pre-eruptive topography in the study area was characterised by a tuff ring-like morphology, with both inward and outward dipping slopes. Highly viscous, moderately porphyritic, dacitic to rhyolitic magmas fed the eruption, which was characterised by a Vulcanian eruptive style. The stratigraphic succession was divided into five eruption units (EUs), which result from different phases of the eruption separated by stases. Sustained columns occurred only during EU1, while PDC generation dominates EU2–5. Lithofacies analysis of the PDC deposits indicates the prevalence of massive coarse-grained deposits on the inner slopes of the Pollara crater, which are interpreted as the deposits of a flow-boundary zone dominated by granular flow or fluid escape regimes. Dune-bedded, massive to stratified lithofacies dominate the outer slopes of the Pollara crater, and are interpreted as the deposits of PDCs with flow-boundary zones in which traction played a major role. Thin, massive PDC deposits are exposed on the sub-horizontal Malfa terrace, and are interpreted as representative of flow-boundary zones dominated by a granular flow regime. The occurrence of stacked deposits indicates that most of the PDCs were characterised by unsteady pulsatory behaviour, with development of trains of pulses during their transport. The downcurrent lithofacies transitions observed for the Upper Pollara deposits have finally been compared with other similar lithofacies associations which have been described for short-lived PDCs at tuff rings, in order to discuss the influence of pre-eruptive topography on lithofacies association.     

Removal of Copper,Nickel and Zinc Ions from Aqueous Solution by Chitosan‐8‐Hydroxyquinoline Beads

In this work, 8‐hydroxyquinoline is used as the active sites in cross‐linked chitosan beads with epichlorohydrin (CT‐8HQ). The CT‐8HQ material was shaped in bead form and used for heavy metal removal from aqueous solution. The study was carried out at pH 5.0 with both batch and column methods and the maximum adsorption capacity of metal ions by the CT‐8HQ was attained in 4 h in the batch experiment. The adsorption capacity order was: Cu²⁺ > Ni²⁺ > Zn²⁺ for both mono‐ and multi‐component systems with batch conditions. From breakthrough curves with column conditions, the adsorption capacity followed the order Cu²⁺ > Zn²⁺ > Ni²⁺ for both mono‐ and multi‐component systems. The CT‐8HQ beads maintained good metal adsorption capacity for all five cycles with absorbent restoration achieved with the use of 1.0 mol L^–1 HCl solution, with 90% regeneration.     

Study of Metal Distribution in Raw and Screened Swine Manure

The growth of industrial swine production over the last few years has led to a growth in concern over effluents generated by the activity. Several elements, mainly toxic metals, can be present in swine wastewater and can have a serious environmental impact. It is important, therefore, to know the metal concentration before the discharge of wastewater. In this work the temporal metal distribution in swine manure and its potential reduction using coarse (2 mm) and fine (<0.45 μm) liquid‐solid separation techniques were investigated. In order to do this, different swine manure sample preparation methods for Al, Ba, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sr and Zn determination by Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES) were tested. The acid mixtures used to digest the manure sample significantly affected the metal recovery. Good analyte recoveries were observed with nitric acid/hydrogen peroxide mixtures or nitric acid/perchloric acid mixtures. Sulfuric acid/hydrogen peroxide mixtures produced inconsistent results and poor recoveries, mainly for Ba and Pb. It was observed that metal concentrations in swine manure varied greatly with time, up to one order of magnitude, due to changes in swine production such as feed and animal numbers. Metals concentrations observed in the raw wastewater exceeded Brazilian limits for discharge into water bodies and recommendations for agricultural use. Results obtained from the liquid‐solid separation study showed that metals in the raw swine manure were not removed with coarse screening. However, the major fraction of metals were removed by filtration (0.45 μm), with the exception of Na, K and Sr. Thus, the use of liquid‐solid separation techniques that capture the fine solid fractions (and associated metals) from raw manure can have a favorable impact on the environment and contribute to swine production wastewater treatment.     

New Approach to Study Extended Evolution of Supergranular Flows and Their Advection of Magnetic Elements

Using velocity and magnetogram data extracted from the full-disk field of view of MDI during the 1999 Dynamics Program, we have studied the dynamics of small-scale magnetic elements (3–7 Mm in size) over time periods as long as six days while they are readily visible on the solar disk. By exploiting concurrent time series of magnetograms and Doppler images, we have compared the motion of magnetic flux elements with the supergranular velocity field inferred from the correlation tracking of mesogranular motions. Using this new method (which combines the results from correlation tracking of mesogranules with detailed analysis of simultaneous magnetograms), it is now possible to correlate the motions of the velocity field and magnetic flux for long periods of time and at high temporal resolution. This technique can be utilized to examine the long-term evolution of supergranulation and associated magnetic fields, for it can be applied to data that span far longer time durations than has been possible previously. As tests of its efficacy, we are able to use this method to verify many results of earlier investigations. We confirm that magnetic elements travel at approximately 350 m s ^–1 throughout the duration of their lifetime as they are transported by supergranular outflows. We also find that the positions of the magnetic flux elements coincide with the supergranular network boundaries and adjust as the supergranular network itself evolves over the six days of this data set. Thus we conclude that this new method permits us to study the extended evolution of the supergranular flow field and its advection of magnetic elements. Since small-scale magnetic elements are strongly advected by turbulent convection, their dynamics can give important insight into the properties of the subsurface convection.