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.     

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.     

Anthropogenic influence on trace element geochemistry of healing mud (peloid) from Makirina Cove (Croatia)

Due to their balneotherapeutic features, the organic-rich sediments in Makirina Cove are an important source of healing mud. An environmental geochemistry approach using normalization techniques was applied to evaluate the anthropogenic contribution of trace metals to sediments used as healing mud. Sediment geochemistry was found to be associated with land-use change and storm events, as well as with proximity of a road with heavy traffic in the summer months. Local valley topography preferentially channels lithogenic and pollutant transport to the cove. Concentrations and distribution of trace metals indicate lithogenic (Ni, Cr, Co) and anthropogenic (Pb, Cu, Zn and Se) contributions to the sediments. The calculation of enrichment factors indicates a moderate (EFs between 2–3.5) input of anthropogenic Cu and Pb in surficial sediments to a depth of 10 cm. Patients using the Makirina Cove sediments as healing mud could be to some extent exposed to enhanced uptake of metals from anthropogenic sources via dermal contact.     

Environmental risk evaluation of the use of mine spoils and treated sewage sludge in the ecological restoration of limestone quarries

The ecologic restoration criteria in areas degraded from extraction activities require making use of their mine spoils. These materials do not meet fertility conditions to guarantee restoration success and therefore, need the incorporation of organic amendments to obtain efficient substratum. Reducing the deficiencies in the organic material and restoration material nutrients with the contribution of treated sewage sludge is proposed in this work. This experiment was based on a controlled study using columns. The work was conducted with two mine spoils, both very rich in calcium carbonate. The first mineral, of poor quality, came from the formation of aggregates of crushed limestone (Z). The other residual material examined originated in limestone extraction, formed by the levels of interspersed non-limestone materials and the remains of stripped soils (D). Two treatments were undertaken (30,000 and 90,000 kg/ha of sewage sludge), in addition to a control treatment. The water contribution was carried out with a device that simulated either short-duration rain or a flooding irrigation system in order to cover the surface and then percolate through the soil. The collection of leached water took place 24 h after the applications. Different parameters of the leached water were determined, including pH, electrical conductivity, nitrate anions, ammonium, phosphates, sulphates and chlorides. The values obtained for each irrigation application are discussed, and the nitrate values obtained were very elevated.     

Stable isotope study of the Archaean rocks of the Vredefort impact structure,central Kaapvaal Craton,South Africa

The Vredefort dome in the Kaapvaal Craton was formed as a result of the impact of a large meteorite at 2.02 Ga. The central core of Archaean granitic basement rocks is surrounded by a collar of uplifted and overturned strata of the Witwatersrand Supergroup, exposing a substantial depth section of the Archaean crust. Orthogneisses of the core show little variation in whole-rock δ ¹⁸O value, with the majority being between 8 and 10‰, with a mean of 9.2‰ (n = 35). Quartz and feldspar have per mil differences that are consistent with O-isotope equilibrium at high temperatures, suggesting minimal interaction with fluids during subsequent cooling. These data refute previous suggestions that the Outer Granite Gneiss (OGG) and Inlandsee Leucogranofels (ILG) of the core represent middle and lower crust, respectively. Granulite-facies greenstone remnants from the ILG have δ ¹⁸O values that are on average 1.5‰ higher than the ILG host rocks and are unlikely, therefore, to represent the residuum from the partial melting event that formed the host rock. Witwatersrand Supergroup sedimentary rocks of the collar, which were metamorphosed at greenschist-to amphibolite-facies conditions, generally have lower δ ¹⁸O values than the core rocks with a mean value for metapelites of 7.7‰ (n = 45). Overall, through an ∼20 km thick section of crust, there is a general increase in whole-rock δ ¹⁸O value with increasing depth. This is the reverse of what is normal in the crust, largely because the collar rocks have δ ¹⁸O values that are unusually low in comparison with metamorphosed sedimentary rocks worldwide. The collar rocks have δD values ranging from −35 to −115‰ (average −62‰, n = 29), which are consistent with interaction with water of meteoric origin, having a δD of about −25 to −45‰. We suggest that fluid movement through the collar rocks was enhanced by impact-induced secondary permeability in the dome structure. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Upwelling, species, and depth effects on coral skeletal cadmium-to-calcium ratios (Cd/Ca)

Skeletal cadmium-to-calcium (Cd/Ca) ratios in hermatypic stony corals have been used to reconstruct changes in upwelling over time, yet there has not been a systematic evaluation of this tracer’s natural variability within and among coral species, between depths and across environmental conditions. Here, coral skeletal Cd/Ca ratios were measured in multiple colonies of Pavona clavus, Pavona gigantea and Porites lobata reared at two depths (1 and 7 m) during both upwelling and nonupwelling intervals in the Gulf of Panama (Pacific). Overall, skeletal Cd/Ca ratios were significantly higher during upwelling than during nonupwelling, in shallow than in deep corals, and in both species of Pavona than in P. lobata. P. lobata skeletal Cd/Ca ratios were uniformly low compared to those in the other species, with no significant differences between upwelling and nonupwelling values. Among colonies of the same species, skeletal Cd/Ca ratios were always higher in all shallow P. gigantea colonies during upwelling compared to nonupwelling, though the magnitude of the increase varied among colonies. For P. lobata, P. clavus and deep P. gigantea, changes in skeletal Cd/Ca ratios were not consistent among all colonies, with some colonies having lower ratios during upwelling than during nonupwelling. No statistically significant relationships were found between skeletal Cd/Ca ratios and maximum linear skeletal extension, δ¹³C or δ¹⁸O, suggesting that at seasonal resolution the Cd/Ca signal was decoupled from growth rate, coral metabolism, and ocean temperature and salinity, respectively. These results led to the following conclusions, (1) coral skeletal Cd/Ca ratios are independent of skeletal extension, coral metabolism and ambient temperature/salinity, (2) shallow P. gigantea is the most reliable species for paleoupwelling reconstruction and (3) the average Cd/Ca record of several colonies, rather than of a single coral, is needed to reliably reconstruct paleoupwelling events.     

Benthic fluxes of mercury species in a lagoon environment (Grado Lagoon,Northern Adriatic Sea,Italy)

The role of the major biogeochemical processes in Hg cycling at the sediment–water interface was investigated in the Grado Lagoon (Northern Adriatic Sea). This wetland system has been extensively contaminated from the Idrija Hg Mine (Slovenia) through the Isonzo River suspended load carried by tidal fluxes. Three approaches were used to study the sediment–water exchange of total Hg (THg), methylmercury (MeHg), reactive Hg (RHg) and dissolved gaseous Hg (DGHg): (1) estimation of diffusive fluxes from porewater and overlying water concentrations, (2) measurements of benthic fluxes using a deployed light benthic chamber in situ and (3) measurements of benthic fluxes during oxic–anoxic transition with a laboratory incubation experiment. The THg solid phase, ranging between 9.5 and 14.4 μg g⁻¹, showed slight variability with depth and time. Conversely, MeHg contents were highest (up to 21.9 ng g⁻¹) at the surface; they tended to decrease to nearly zero concentration with depth, thus suggesting that MeHg production and accumulation occur predominantly just below the sediment–water interface. Porewater MeHg concentrations (0.9–7.9 ng L⁻¹, 0.15–15% of THg) varied seasonally; higher contents were observed in the warmer period. The MeHg diffusive fluxes (up to 17 ng m⁻² day⁻¹) were similar to those in the nearby Gulf of Trieste [Covelli, S., Horvat, M., Faganeli, J., Brambati, A., 1999. Porewater distribution and benthic flux of mercury and methylmercury in the Gulf of Trieste (Northern Adriatic Sea). Estuar. Coast. Shelf Sci. 48, 415–428], although the lagoon sediments contained four-fold higher THg concentrations. Conversely, the THg diffusive fluxes in the lagoon (up to 110 ng m⁻² day⁻¹) were one- to two-fold higher than those previously estimated for the Gulf of Trieste. The diurnal MeHg benthic fluxes were highest in summer at both sites (41,000 and 33,000 ng m⁻² day⁻¹ at the fishfarm and in the open lagoon, respectively), thus indicating the influence of temperature on microbial processes. The diurnal variations of dissolved THg and especially MeHg were positively correlated with O₂ and inversely with DIC, suggesting an important influence of benthic photosynthetic activities on lagoon benthic Hg cycling, possibly through the production of organic matter promptly available for methylation. The results from the dark chamber incubated in the laboratory showed that the regeneration of dissolved THg was slightly affected by the oxic–anoxic transition. Conversely, the benthic flux of MeHg was up to 15-fold higher in sediments overlain by O₂ depleted waters. In the anoxic phase, the MeHg fluxes proceeded in parallel with Fe fluxes and the methylated form reached approximately 100% of dissolved THg. The MeHg is mostly released into overlying water (mean recycling efficiency of 89%) until the occurrence of sulphide inhibition, due to scavenging of the available Hg substrate for methylation. The results suggest that sediments in the Grado Lagoon, especially during anoxic events, should be considered as a primary source of MeHg for the water column.     

Origins of high pH mineral waters from ultramafic rocks, Central Portugal

This paper reviews the geochemical, isotopic (²H, ¹⁸O, ¹³C, ³H and ¹⁴C) and numerical modelling approaches to evaluate possible geological sources of the high pH (11.5)/Na–Cl/Ca–OH mineral waters from the Cabeço de Vide region (Central-Portugal). Water–rock interaction studies have greatly contributed to a conceptual hydrogeological circulation model of the Cabeço de Vide mineral waters, which was corroborated by numerical modelling approaches. The local shallow groundwaters belong to the Mg–HCO₃ type, and are derived by interaction with the local serpentinized rocks. At depth, these type waters evolve into the high pH/Na–Cl/Ca–OH mineral waters of Cabeço de Vide spas, issuing from the intrusive contact between mafic/ultramafic rocks and an older carbonate sequence. The Cabeço de Vide mineral waters are supersaturated with respect to serpentine indicating that they may cause serpentinization. Magnesium silicate phases (brucite and serpentine) seem to control Mg concentrations in Cabeço de Vide mineral waters. Similar δ²H and δ¹⁸O suggest a common meteoric origin and that the Mg–HCO₃ type waters have evolved towards Cabeço de Vide mineral waters. The reaction path simulations show that the progressive evolution of the Ca–HCO₃ to Mg–HCO₃ waters can be attributed to the interaction of meteoric waters with serpentinites. The sequential dissolution at CO₂ (g) closed system conditions leads to the precipitation of calcite, magnesite, amorphous silica, chrysotile and brucite, indicating that the waters would be responsible for the serpentinization of fresh ultramafic rocks (dunites) present at depth. The apparent age of Cabeço de Vide mineral waters was determined as 2790 ± 40 a BP, on the basis of ¹⁴C and ¹³C values, which is in agreement with the ³H concentrations being below the detection limit.