Age and depositional environment of the Draa Sfar massive sulfide deposit, Morocco

The Draa Sfar mineralization consists of two main stratabound orebodies, Sidi M’Barek and Tazacourt, located north and south of the Tensift River (“Oued Tessift”), respectively. Each orebody is comprised by at least two massive sulfide lenses. The hosting rocks are predominantly black shales, although minor rhyolitic rocks are also present in the footwall to the southern orebody. Shales, rhyolitic volcanic rocks, and massive sulfides are all included into the Sarhlef Series, which is recognized as one of the main stratigraphic units of the Moroccan Variscan Meseta. Hydrothermal activity related with an anomalous thermal gradient, together with a high sedimentation rate in a tectonically driven pull-apart marine basin, favored the accumulation of organic-rich mud in the deepest parts of the basin and the sedimentary environment suitable for massive sulfide deposition and preservation. This took place by replacement of the hosting unlithified wet mud below the sediment–water interface. Geochemical data suggest a sedimentary environment characterized by oxic water column and anoxic sediment pile with the redox boundary below the sediment–water interface. The low oxygen availability within the sediment pile inhibited oxidation and pyritization of pyrrhotite. Biostratigraphic analysis, based on the palynological content of the hosting black shales, restricts the age of the sulfides to the Asbian substage (mid-Mississippian). This age is consistent with earlier geochronological constraints.     

Late Carboniferous porphyry copper mineralization at La Voluntad,Neuquén,Argentina: Constraints from Re–Os molybdenite dating

The La Voluntad porphyry Cu–Mo deposit in Neuquén, Argentina, is one of several poorly known porphyry-type deposits of Paleozoic to Early Jurassic age in the central and southern Andes. Mineralization at La Voluntad is related to a tonalite porphyry from the Chachil Plutonic Complex that intruded metasedimentary units of the Piedra Santa Complex. Five new Re–Os molybdenite ages from four samples representing three different vein types (i.e., quartz–molybdenite, quartz–sericite–molybdenite and quartz–sericite–molybdenite ± chalcopyrite–pyrite) are identical within error and were formed between ~312 to ~316 Ma. Rhenium and Os concentrations range between 34 to 183 ppm and 112 to 599 ppb, respectively. The new Re–Os ages indicate that the main mineralization event at La Voluntad, associated to sericitic alteration, was emplaced during a time span of 1.7 ± 3.2 Ma and that the deposit is Carboniferous in age, not Permian as previously thought. La Voluntad is the oldest porphyry copper deposit so far recognized in the Andes and indicates the presence of an active magmatic arc, with associated porphyry style mineralization, at the proto-Pacific margin of Gondwana during the Early Pennsylvanian.     

Aerobic methanotrophy at ancient marine methane seeps: A synthesis

The molecular fingerprints of the chemosynthesis based microbial communities at methane seeps tend to be extremely well preserved in authigenic carbonates. The key process at seeps is the anaerobic oxidation of methane (AOM), which is performed by consortia of methanotrophic archaea and sulphate reducing bacteria. Besides the occurrence of ¹³C depleted isoprenoids and n-alkyl chains derived from methanotrophic archaea and sulphate reducing bacteria, respectively, ¹³C depleted triterpenoids have been reported from a number of seep deposits. In order to evaluate the significance of these apparently non-AOM related molecular fossils, the biomarker inventories of one Campanian and two Miocene methane seep limestones are compared. These examples provide strong evidence that methane was not solely oxidized by an anaerobic process. Structural and carbon isotope data reveal that aerobic methanotrophy was common at some ancient methane seeps as well. The Miocene Marmorito limestone contains abundant 3β-methylated hopanoids (δ¹³C: −100‰). Most likely, 3β-methylated hopanepolyols, prevailing in aerobic methanotrophs, were the precursor lipids of these compounds. A series of isotopically depleted 4-methylated steranes (lanostanes; δ¹³C: −80‰ to −70‰) and similarly isotopically depleted 17β(H),21β(H)-32-hopanoic acid in the Miocene Pietralunga seep limestone also are derived probably from aerobic methanotrophs. Lanosterol, which is known to be produced by aerobic methanotrophs, is the most likely precursor of 4-methylated steranes. Less obvious is the origin of 8,14-secohexahydrobenzohopanes (δ¹³C: −110‰ to −107‰) in Late Cretaceous seep limestones. These hopanoids probably reflect early degradational products of precursor lipids locally produced by seep endemic aerobic methanotrophs.     

Soil contamination from urban and industrial activity: example of the mining district of Linares (southern Spain)

The Linares region (southern Spain) has been subjected to two important sources of pollution: the intensive mining works and the urban-industrial activity. To obtain a geochemical characterisation of the soil, 31 trace elements were analysed and 669 soil samples were collected. By means of clustering analysis, we identified groups of elements and grid squares in which relations could be established concerning soil lithology, urban and industrial activities and the degree of pollution impact; in addition, we were able to characterise the geochemical background of the study area. The multivariate study led us to identify four factors. Particularly important was factor 2, which represented the elements associated with mineral paragenesis (Cu, Pb, As, Co, Mn, Zn, Sn, Ba). This factor also contains elements related with an urban-industrial activity, such as Pb, Cu, Zn, As and Ba. Furthermore, we identified factor 4, associating Ni, V and Cr, and which is related to the use of fuels.     

Trace elements contamination of agricultural soils affected by sulphide exploitation (Iberian Pyrite Belt,Sw Spain)

Agricultural soils of the Riotinto mining area (Iberian Pyrite Belt) have been studied to assess the degree of pollution by trace elements as a consequence of the extraction and treatment of sulphides. Fifteen soil samples were collected and analysed by ICP-OES and INAA for 51 elements. Chemical analyses showed an As–Cu–Pb–Zn association related with the mineralisation of the Iberian Pyrite Belt. Concentrations were 19–994 mg kg⁻¹ for As, 41–4,890 mg kg⁻¹ for Pb, 95–897 mg kg⁻¹ for Zn and of 27–1,160 mg kg⁻¹ for Cu. Most of the samples displayed concentrations of these elements higher than the 90th percentile of the corresponding geological dominium, which suggests an anthropogenic input besides the bedrock influence. Samples collected from sediments were more contaminated than leptosols because they were polluted by leachates or by mining spills coming from the waste rock piles. The weathering of the bedrock is responsible for high concentrations in Co, Cr and Ni, but an anthropogenic input, such as wind-blown dust, seems to be indicative of the high content of As, Cu, Pb and Zn in leptosols. The metal partitioning patterns show that most trace elements are associated with Fe amorphous oxy-hydroxides, or take part of the residual fraction. According to the results obtained, the following mobility sequence is proposed for major and minor elements: Mn, Pb, Cd, > Zn, Cu > Ni > As > Fe > Cr. The high mobility of Pb, Cu and Zn involve an environmental risk in this area, even in soils where the concentrations are not so high.     

Origin of nickel in water solution of the chalk aquifer in the north of France and influence of geochemical factors

In the north of France, high registers of nickel are sometimes recorded within the chalk aquifer. In a confined context, the presence of pyrite in the covering clays or in the marcasite nodules encrusted in the clay may constitute a natural source of trace metals. With an objective of sanitary control, the limits of chemical contents regulating the quality of water destined for human consumption have been lowered by the European Framework Directive in the field of water policy (2000/60/EC). As a result, nickel limits have been reduced from 50 to 20 μg/l. The analyses, carried out on three water catchment fields in our area of study, were centred on variable parameters (Eh, O₂(d), pH, Conductivity, T°), major elements (SO₄, NO₃) and metals (Fe, Ni, Mn, Co). The acquired data enabled us to identify from one hand, the conditions which are presented within the site, special thanks to the evolution of nitrate and iron contents and on the other hand, the natural origin (geological) of nickel for two of the three sites studied based essentially on the evaluation of the Nickel/Cobalt ratio. Thus, on the first site, the evolution of nickel content and nitrate content showed the influence of the phenomenon of denitrification on the re-mobilisation of the nickel. Whereas on the second site, a high variation of total iron content and oxygen dissolved in solution highlighted a particular phenomenon of oxidation of the pyrite through molecular oxygen. Finally, the correlation with the sulphates clearly showed behaviour of the nickel, once released, that was entirely dependent on the phenomenon of adsorption on the iron and manganese hydroxides.     

Space–time distribution of ancient and active alluvial karst subsidence: examples from the central Ebro Basin,Spain

Space and time variations of alluvial karst subsidence in the central Ebro Basin are analysed in trenches (paleodolines), aerial photographs (historical dolines) and field surveys (present-day active dolines). The measured subsidence rates, as well as a comparison between densities of paleodolines computed in randomly selected scan-lines and density of active dolines computed in maps, suggest that present-day subsidence in favourable areas is more intense than that of Pleistocene times. According to diachronic maps drawn from (a) different aerial photographs taken after 1946 and (b) field surveys on deformations in urbanized areas, subsidence behaved as a nearly steady process while the whole area was used for agriculture. In contrast, rapid changes (through periods of several tens of years) have occurred in urbanized areas, in which dolines expand their boundaries through small marginal collapses, shifting sharply their sinking centres to neighbouring sites. These rapid changes do not have an equivalent in observed paleodolines.     

Mineralogy and geochemistry of the Texeo Cu–Co mine site (NW Spain): screening tools for environmental assessment

The Cu–Co–Ni Texeo mine has been the most important source of Cu in NW Spain since Roman times and now, approximately 40,000 m³ of wastes from mine and metallurgical operations, containing average concentrations of 9,263 mg kg⁻¹ Cu, 1,100 mg kg⁻¹ As, 549 mg kg⁻¹ Co, and 840 mg kg⁻¹ Ni, remain on-site. Since the cessation of the activity, the abandoned works, facilities and waste piles have been posing a threat to the environment, derived from the release of toxic elements. In order to assess the potential environmental pollution caused by the mining operations, a sequential sampling strategy was undertaken in wastes, soil, surface and groundwater, and sediments. First, screening field tools were used to identify hotspots, before defining formal sampling strategies; so, in the areas where anomalies were detected in a first sampling stage, a second detailed sampling campaign was undertaken. Metal concentrations in the soils are highly above the local background, reaching up to 9,921 mg kg⁻¹ Cu, 1,373 mg kg⁻¹ As, 685 mg kg⁻¹ Co, and 1,040 mg kg⁻¹ Ni, among others. Copper concentrations downstream of the mine works reach values up to 1,869 μg l⁻¹ and 240 mg kg⁻¹ in surface water and stream sediments, respectively. Computer-based risk assessment for the site gives a carcinogenic risk associated with the presence of As in surface waters and soils, and a health risk for long exposures; so, trigger levels of these elements are high enough to warrant further investigation.     

Modeling of water–rock interactions in an aquitard of sandy clay in the coastal area near Beihai,China

Unconsolidated sand, gravel and clay deposits near Beihai and in the Leizhou Peninsula in southern China form an unconfined aquifer, aquitard and a confined aquifer. Water and soil samples were collected from the two aquifers in the coastal Beihai area for the determination of chemical compositions, minerals and soluble ions. Hydrogeochemical modeling of three flow paths through the aquitard are carried out using PHREEQC to determine water–rock interactions along the flow paths. The results indicate that the dissolution of anorthite, fluorite, halite, rhodochrosite and CO₂, and precipitation of potash feldspar and kaolinite may be occurring when groundwater leaks through the aquitard from the unconfined aquifer to the confined aquifer. Cation exchanges between Na and Ca can also happen along the flow paths.     

Assessment of sandstone deterioration at Ta Keo temple (Angkor): first results and future prospects

A first application of geomorphological methods to the assessment of sandstone deterioration at Angkor is presented. Damage diagnosis was carried out on the first eastern tier of the central pyramid of the 1,000 year-old Ta Keo temple. Methods combine field observations and measurements at 230 sampling points, high-resolution lasergrammetry and stereophotogrammetry on a 2-m² test zone, and SEM observations. The first results indicate that decay operates through a synergistic combination of weathering phenomena dominated by scaling and solution, and exhibits a high spatial variability. Percentages of deteriorated surfaces vary from 17.6 to 93.8%, and average stone recession values from 0.00 to 2.71 cm (minimum) and 0.34 to 5.49 cm (maximum). On the test-zone, stereophotogrammetry and 3D-mapping of the present and reconstructed initial states using lasergrammetry indicate that erosion scars up to 6 cm deep have formed since 1963. On the whole, the amount of deteriorated surfaces more than tripled between 1963 and 2008. The degree of implication of salts in stone decay remains unclear for most efflorescences are composed of calcite (CaCO3), with secondary importance of barite (BaSO4) and gypsum (CaSO₄·2H₂O). Future prospects aim to evaluate the impact on stone decay of the clearing out of the temple from the forest in the 1920s.