An approximation to short-term evolution and sediment transport pathways along the littoral of Cadiz Bay (SW Spain)

This work presents the results of a beach-monitoring program carried out in the Bay of Cadiz (SW Spain), which consists of urban, natural and nourished beaches. In the present study, 24 topographic profiles have been monthly monitored during the 1996–1998 period, in order to draw the morphodynamic behavior of this coast and the general characterization of short-term coastal trends. This way, total volumetric budgets have been calculated for each beach profile in order to group beaches in different erosive/accreting sectors. Studied beaches recorded both erosion and accretion: the greatest accretionary trends have been observed at Aguadulce, La Costilla and Rota beaches, with values ranging from 30 to 70 m³/m. The largest erosion episodes have been recorded in the southernmost end of Valdelagrana spit, with values over 50 m³/m, and in Rota and Vistahermosa, after nourishment works. Main erosion and accretion pathways have been related to the existence of natural and human structures, which blocked the longshore drift suggesting the existence of littoral cells.     

Structural and physiographic control on the Holocene marine sedimentation in the bay of Cadiz (SW Spain)

The Quaternary tectonic activity in the Gulf of Cadiz has considerably influenced the depositional regime and distribution of Holocene marine deposits. The aim of this work is to determine the nature of the recent sedimentary filling in the Bay of Cadiz sea bottom and adjacent continental shelf and to establish the main controlling factors on the Holocene marine sedimentation.

The sedimentary record indicates siliciclastic sedimentation supplied from the continent, with alternating episodes of high and low sedimentation rates. The recent sedimentary evolution of this marine area was controlled by the Late Quaternary eustatic fluctuations. Bathymetric, geophysical and drilling data have been employed to prepare a detailed isopach map of the non-consolidated recent sedimentary cover. Thickness distribution shows significant variations related to the infilling of former fluvial palaeochannels incised during the Late Pleistocene lowstand, and highly controlled by the structural neotectonic trends of faults and joints: NNW-SSE, NNE-SSW and ENE-WSW. The general distribution of isopachs in this area is clearly influenced by these morphostructural lines, which controlled the sedimentary processes during the Holocene. These results are coherent with the main regional neotectonic structures previously described in the nearby continental area, and confirm their prolongation towards the marine domain.     

Carbon Dioxide and Methane Emissions from Mangrove-Associated Waters of the Andaman Islands,Bay of Bengal

We estimated CO₂ and CH₄ emissions from mangrove-associated waters of the Andaman Islands by sampling hourly over 24 h in two tidal mangrove creeks (Wright Myo; Kalighat) and during transects in contiguous shallow inshore waters, immediately following the northeast monsoons (dry season) and during the peak of the southwest monsoons (wet season) of 2005 and 2006. Tidal height correlated positively with dissolved O₂ and negatively with pCO₂, CH₄, total alkalinity (TAlk) and dissolved inorganic carbon (DIC), and pCO₂ and CH₄ were always highly supersaturated (330–1,627 % CO₂; 339–26,930 % CH₄). These data are consistent with a tidal pumping response to hydrostatic pressure change. There were no seasonal trends in dissolved CH₄ but pCO₂ was around twice as high during the 2005 wet season than at other times, in both the tidal surveys and the inshore transects. Fourfold higher turbidity during the wet season is consistent with elevated net benthic and/or water column heterotrophy via enhanced organic matter inputs from adjacent mangrove forest and/or the flushing of CO₂-enriched soil waters, which may explain these CO₂ data. TAlk/DIC relationships in the tidally pumped waters were most consistent with a diagenetic origin of CO₂ primarily via sulphate reduction, with additional inputs via aerobic respiration. A decrease with salinity for pCO₂, CH₄, TAlk and DIC during the inshore transects reflected offshore transport of tidally pumped waters. Estimated mean tidal creek emissions were ～23–173 mmol m^?2 day^?1 CO₂ and ～0.11–0.47 mmol m^?2 day^?1 CH₄. The CO₂ emissions are typical of mangrove-associated waters globally, while the CH₄ emissions fall at the low end of the published range. Scaling to the creek open water area (2,700 km²) gave total annual creek water emissions ～3.6–9.2?×?10¹⁰ mol CO₂ and 3.7–34?×?10⁷ mol CH₄. We estimated emissions from contiguous inshore waters at ～1.5?×?10¹¹ mol CO₂?year^?1 and 2.6?×?10⁸ mol CH₄?year^?1, giving total emissions of ～1.9?×?10¹¹ mol CO₂?year^?1 and ～3.0?×?10⁸ mol CH₄?year^?1 from a total area of mangrove-influenced water of ～3?×?10⁴ km². Evaluating such emissions in a range of mangrove environments is important to resolving the greenhouse gas balance of mangrove ecosystems globally. Future such studies should be integral to wider quantitative process studies of the mangrove carbon balance.     

Groundwater,Acid and Carbon Dioxide Dynamics Along a Coastal Wetland,Lake and Estuary Continuum

Coastal wetlands are hotspots for biodiversity and biological productivity, yet the hydrology and carbon cycling within these systems remains poorly understood due to their complex nature. By using a novel spatiotemporal approach, this study quantified groundwater discharge and the related inputs of acidity and CO₂ along a continuum of a modified coastal acid sulphate soil (CASS) wetland, a coastal lake and an estuary under highly contrasting hydrological conditions. To increase the resolution of spatiotemporal data and advance upon previous methodologies, we relied on automated observations from four simultaneous time-series stations to develop multiple radon mass balance models to estimate groundwater discharge and related groundwater inputs of acidity and dissolved inorganic carbon (DIC), along with surface water to atmosphere CO₂ fluxes. Spatial surveys indicated distinct acid hotspots with minimum surface water pH of 2.91 (dry conditions) and 2.67 (flood conditions) near a non-remediated (drained) CASS area. Under flood conditions, groundwater discharge accounted for ～14.5 % of surface water entering the lake. During the same period, acid discharge from the acid sulphate soil section of the continuum produced ～4.8 kg H₂SO₄?ha^?1 day^?1, a rate much higher than previous studies in similar systems. During baseflow conditions, the low pH water was rapidly buffered within the estuarine lake, with the pH increasing from 4.22 to 6.07 over a distance of ～250 m. The CO₂ evasion rates within the CASS were extremely high, averaging 2163?±?125 mmol m^?2 day^?1 in the dry period and 4061?±?259 mmol m^?2 day^?1 under flood conditions. Groundwater input of DIC could only account for 0.4 % of this evasion in the dry conditions and ～5 % during the flood conditions. We demonstrated that by utilising a spatiotemporal (multiple time-series stations) approach, the study was able to isolate distinct zones of differing hydrology and biogeochemistry, whilst providing more reasonable groundwater acid input estimates and air–water CO₂ flux estimates than some traditional sampling designs. This study highlights the notion that modified CASS wetlands can release large amounts of CO₂ to the atmosphere because of high groundwater acid inputs and extremely low surface water pH.     

Experiments on Methane Displacement by Carbon Dioxide in Large Coal Specimens

Carbon dioxide (CO₂) is considered to be the most important greenhouse gas in terms of overall effect. CO₂ geological storage in coal beds is of academic and industrial interest because of economic synergies between greenhouse gas sequestration and coal bed methane (CH₄) recovery by displacement/adsorption. Previously, most work focused on either theoretical analyses and mathematical simulations or gas adsorption?Cdesorption experiments using coal particles of millimeter size or smaller. Those studies provided basic understanding of CH₄ recovery by CO₂ displacement in coal fragments, but more relevant and realistic investigations are still rare. To study the processes more realistically, we conducted experimental CH₄ displacement by CO₂ and CO₂ sequestration with intact 100?×?100?×?200?mm coal specimens. The coal specimen permeability was measured first, and results show that the permeability of the specimen is different for CH₄ and CO₂; the CO₂ permeability was found to be at least two orders of magnitude greater than that for CH₄. Simultaneously, a negative exponential relationship between the permeability and the applied mean stress on the specimen was found. Under the experimental stress conditions, 17.5?C28.0 volumes CO₂ can be stored in one volume of coal, and the displacement ratio CO₂?CCH₄ is as much as 7.0?C13.9. The process of injection, adsorption and desorption, displacement, and output of gases proceeds smoothly under an applied constant pressure differential, and the CH₄ content in the output gas amounted to 20?C50% at early stages, persisting to 10?C16% during the last stage of the experiments. Production rate and CH₄ fraction are governed by complex factors including initial CH₄ content, the pore and fissure fabric of the coal, the changes in this fabric as the result of differential adsorption of CO₂, the applied stress, and so on. During CO₂ injection and CH₄ displacement, the coal can swell from effects of gas adsorption and desorption, leading to changes in the microstructure of the coal itself. Artificial stimulation (e.g. hydraulic fracturing) to improve coalbed transport properties for either CO₂ sequestration or enhanced coal bed methane recovery will be necessary. The interactions of large-scale induced fractures with the fabric at the scale of observable fissures and fractures in the laboratory specimens, as well as to the pore scale processes associated with adsorption and desorption, remain of profound interest and a great challenge.     

Sedimentological and paleoenvironmental characterisation of transgressive sediments on the Guadiana Shelf (Northern Gulf of Cadiz, SW Iberia)

During the transgression following the Last Glacial Maximum, four backstepping parasequences were deposited on the northern Gulf of Cádiz shelf (SW Iberia). In contrast to other areas on the shelf, these transgressive deposits are at, or very close to, the surface to the southeast of the Guadiana Estuary mouth. This is particularly true for transgressive parasequence T_C, possibly associated with the Younger Dryas event, and the youngest parasequence T_D, probably linked to a slow-down in sea-level rise at around 8.2 ka BP, both of which form a sandy transgressive bulge on the upper middle shelf.The older and more distal parasequence T_C is characterised on seismic records by convex low-angle sigmoidal clinoforms, and contains high amounts of quartz and bioclasts. In contrast, the younger and more proximal parasequence T_D shows relatively steep concave prograding clinoforms, and contains high amounts of quartz and other terrigenous components, but comparatively low amounts of bioclasts. Furthermore, the difference in age between both parasequences is clearly marked by a difference in the content of glauconite.The results indicate that sediments found in parasequence T_C are associated with deposition related to storm events, with frequent reworking of components, and the more proximal and younger sediments in T_D are the result of rapid sediment accumulation related to floods in the Guadiana River basin, possibly during the transition from a dry cold period to a warmer more humid period, when vegetation cover was lowest and flood frequency increased.Additionally, accumulations of terrigenous components directly associated with the Guadiana River basin found on the outer shelf indicate that, at least during the beginning of the transgression, overflow channels active during large-scale flood events may have spilled material to an area located immediately to the south of the Guadiana Estuary mouth.     

Mineralogy and geochemistry of platinum-group elements in the Aguablanca Ni-Cu deposit (SW Spain)

Summary The Aguablanca Ni-Cu-(PGE) magmatic sulphide deposit is associated with a magmatic breccia located in the northern part of the Aguablanca gabbro (SW, Iberia). Three types of ores are present: semi-massive, disseminated, and chalcopyrite-rich veined ore. The principal ore minerals are pyrrhotite, pentlandite and chalcopyrite. A relatively abundant platinum-group mineral (PGM) assemblage is present and includes merenskyite, melonite, michenerite, moncheite and sperrylite. Moreover, concentrations of base and precious metals and micro-PIXE analyses were obtained for the three ore-types. The mineralogy and the mantle-normalised chalcophile element profiles strongly suggest that semi-massive ore represents mss crystallisation, whereas the disseminated ore represents an unfractionated sulphide liquid and the chalcopyrite-rich veined ore a Cu-rich sulphide liquid. Palladium-bearing minerals occur commonly enclosed within sulphides, indicating a magmatic origin rather than hydrothermal. The occurrences and the composition of these minerals suggest that Pd was initially dissolved in the sulphides and subsequently exsolved at low temperatures to form bismutotellurides. Negative Pt and Au anomalies in the mantle-normalised chalcophile element profiles, a lack of Cu-S correlation and textural observations (such as sperrylite losing its euhedral shape when in contact with altered minerals) suggest partial remobilisation of Pt, Au and Cu by postmagmatic hydrothermal fluids after the sulphide crystallisation. Authors’ addresses: R. Pi?a, L. Ortega, R. Lunar, Departamento de Cristalografía y Mineralogía, Facultad de Geología, Universidad Complutense de Madrid, ES-28040 Madrid, Spain; F. Gervilla, Facultad de Ciencias, Instituto Andaluz de Ciencias de la Tierra, Universidad de Granada-CSIC, Avda. Fuentenueva, s/n, ES-18002 Granada, Spain     

Dynamics of contaminants in phosphogypsum of the fertilizer industry of Huelva (SW Spain): From phosphate rock ore to the environment

The dynamics of trace elements from phosphate rock ore to the environment in a phosphoric acid plant located in SW Spain and the impact of phosphogypsum wastes were investigated through total digestion and BCR-sequential extraction. Based on total concentration, element transfer factors as criteria for examining the potential environmental risk of waste with respect to ore rock were calculated, and it was observed that most trace elements are only transferred into phosphogypsum at rates of 2–12%. However, based on those concentrations that are likely to be most readily mobile in the environment, phosphogypsum acts as a higher emission source of contaminants than the original rock. About 100 million tonnes of phosphogypsum are stack-piled in a dump of 1200 ha over salt-marshes of an estuary formed by the confluence of the Tinto and Odiel rivers. Phosphogypsum has been applied, at the recommended rate of 20–25 t/ha since 1978–2001, to improve fertility and reduce Na saturation in agricultural soils of the Guadalquivir river valley (140 km²). Phosphogypsum capacity as a source of mobile contaminants in three environmental scenarios (water leaching, exposure to oxidising and reducing conditions) was quantified by combining sequential extraction and waste mass. The amounts of mobile contaminants that could be released for every tonne of phosphogypsum are approximately 7 × 10² g Sr, 1.1 × 10² g Fe, 55 g Y, 30 g Ce, 12 g Cr, 11 g Ti, 5 g Zn, 4 g each of Cu and Pb, 3 g each of V and Cd, 2 g each of As and Ni and 1 g U. Multiplying these amounts by 100 Mt and 20–25 t/ha, it is possible to calculate risk assessments of phosphogypsum for both estuarine zones, e.g. in a hypothetical stack collapse and waste spilling, and agricultural soils, respectively.     

Organic matter accumulation during the Holocene in the Guadalquivir marshlands (SW Spain)

The distribution of biomarker compounds and magnetic susceptibility observed in the sediment from a 20 m core drilled in the marshlands of the estuarine region of the Guadalquivir River (southwest coast of Spain) has allowed us to reconstruct the palaeoenvironmental evolution of this area during the Holocene. Several organic compounds (n‐alkanes, n‐ketones, n‐alkanols, n‐alkanoic acids and organic sulphur), as well as different biomarker ratios, have been used to show changing environmental conditions through time. These geochemical proxies suggest good preservation of the organic matter, although some diagenesis has occurred to particular organic compounds, especially the n‐alkanoic acids. Our data indicate a major allochthonous supply of terrestrial plants, with less influence from aquatic plants or algae through the core. There are markedly different palaeoenvironmental conditions between the uppermost 5 m (last 6 ka cal. B.P.) and the rest of the core. From 5 m (ca 6 ka cal. B.P.) to 19 m (ca 8 ka cal. B.P.) depth the palaeoenvironmental conditions were almost constant. Based on organic sulphur content and n‐alkane content logs, anoxic conditions prevailed from 8 to 6 ka cal. B.P., while oxic conditions with enhanced convection of water (prevalence of fluvial input), and consequently a greater organic matter supply, predominated in the upper 5 m of the core. Similarly, little variation in the magnetic susceptibility profile below 5 m indicates stable environmental conditions, while in the upper 5 m conditions shifted to one with elevated water input and clastic sediment supply. This is linked to palaeofloral alterations in the Guadiamar/Guadalquivir drainage basins and/or anthropogenic effects. We propose that from ca 8 to 6 ka cal. B.P. a stable landscape physiognomy in the surroundings of the estuarine area of the Guadalquivir River, with a predominance of pines and grassland. However, over the last 6 ka cal. B.P. a variation in the terrestrial plant biomarker compounds suggests an alternation of relatively dry and humid phases and/or the impact of human populations on altering the vegetation community have occurred. Copyright © 2007 John Wiley & Sons, Ltd.     

Contrasting Carbon Dioxide Inputs and Exchange in Three Adjacent New England Estuaries

Four surveys of the adjacent Cocheco, Bellamy, and Oyster estuaries reveal spatial heterogeneity with respect both to river-born carbon dioxide (CO₂) fluxes and CO₂ exchange with the atmosphere (−17 to 51 mmol m⁻² day⁻¹), a finding partially explained by CO₂ inputs from contributing watersheds. Nonuniform nutrient and organic carbon loading from upstream rivers and within the estuaries is considered as a mechanism resulting in the variability between estuaries. Conditions during the surveys included spring river runoff and phytoplankton blooms, drought with baseline river flow, and a historic flood which led to a large CO₂ release to the atmosphere. This study highlights the variability of CO₂ transport and release found between proximate estuaries over a wide range of flow conditions.     

Carbon Dioxide Fluxes and Their Environmental Control in a Reclaimed Coastal Wetland in the Yangtze Estuary

Large areas of natural coastal wetlands have suffered severely from human-driven damages or conversions (e.g., land reclamations), but coastal carbon flux responses in reclaimed wetlands are largely unknown. The lack of knowledge of the environmental control mechanisms of carbon fluxes also limits the carbon budget management of reclaimed wetlands. The net ecosystem exchange (NEE) in a coastal wetland at Dongtan of Chongming Island in the Yangtze estuary was monitored throughout 2012 using the eddy covariance technique more than 14 years after this wetland was reclaimed using dykes to stop tidal flooding. The driving biophysical variables of NEE were also examined. The results showed that NEE displayed marked diurnal and seasonal variations. The monthly mean NEE showed that this ecosystem functioned as a CO₂ sink during 9 months of the year, with a maximum value in September (?101.2 g C m^?2) and a minimum value in November (?8.2 g C m^?2). The annual CO₂ balance of the reclaimed coastal wetland was ?558.4 g C m^?2 year^?1. The ratio of ecosystem respiration (ER) to gross primary production (GPP) was 0.57, which suggests that 57 % of the organic carbon assimilated by wetland plants was consumed by plant respiration and soil heterotrophic respiration. Stepwise multiple linear regressions suggested that temperature and photosynthetically active radiation (PAR) were the two dominant micrometeorological variables driving seasonal variations in NEE, while soil moisture (M _s) and soil salinity (PS_s) played minor roles. For the entire year, PAR and daytime NEE were significantly correlated, as well as temperature and nighttime NEE. These nonlinear relationships varied seasonally: the maximum ecosystem photosynthetic rate (A _max), apparent quantum yield (?), and Q ₁₀ reached their peak values during summer (17.09 μmol CO₂?m^?2 s^?1), autumn (0.13 μmol CO₂?μmol^?1 photon), and spring (2.16), respectively. Exceptionally high M _s or PS_s values indirectly restricted ecosystem CO₂ fixation capacity by reducing the PAR sensitivity of the NEE. The leaf area index (LAI) and live aboveground biomass (AGB_L) were significantly correlated with NEE during the growing season. Although the annual net CO₂ fixation rate of the coastal reclaimed wetland was distinctly lower than the unreclaimed coastal wetland in the same region, it was quite high relative to many inland freshwater wetlands and estuarine/coastal wetlands located at latitudes higher than this site. Thus, it is concluded that although the net CO₂ fixation capacity of the coastal wetland was reduced by land reclamation, it can still perform as an important CO₂ sink.     

Interaction between sedimentary processes,historical pollution and microfauna in the Tinto Estuary (SW Spain)

The analysis of a short core collected in the Tinto Estuary (SW Spain) permits to delimitate the influence of historical mining activities on sediments and microfauna (Foraminifera and Ostracoda). In very shallow palaeochannels of the middle estuary, a first mining period (~3,600 cal years BP) caused high sediment pollution by Cu, with a significant diminution of the palaeontological record due to continuous acid mining drainage processes. In this core, the polluted levels derived from both Roman extractions (2,000–1,900 years BP) and the extensive mining activities between 1870 and 1935 have been eroded. The 1,800–200 years BP period is characterized by a limited mining activity and an important improvement of this ecosystem. In addition, the effects of recent industrial wastes have been limited in this area.     

A new approach to landslide geomorphological mapping using the Open Source software in the Olvera area (Cadiz, Spain)

This paper presents the preliminary results of a geomorphological survey of the Olvera area (Cadiz province, Betic Ranges, Spain) and the use of the Geographic Information System (GIS) Open Source (OS) software plus Database Management System (DBMS) for making available and distributing the landslide data over the Web. In the geomorphologic survey, different landforms have been identified in the area, including structural, anthropogenic, fluvial, karst, and slope forms. In particular, the majority of the slope forms are complex (from topple to rotational slides and falls), but there are also minor forms like debris flows and mudslides. To manage geomorphological data, an Open Source GIS was used, which contained the following components: QuantumGIS, System for Automated Geoscientific Analyses (SAGA), GIS and Geographic Resources Analysis Support System (GRASS), GIS for Digital Elevation Model (DEM) generation. A key aim was to make the project-derived data available over the Web. This was achieved using MapServer which allows for the representation of the derived geospatial data with pMapper providing the graphical Web interface. Our study highlights the process dynamics of run-off erosion in Olvera derived through the use of advanced computer-based mapping tools. The resulting map products and interpretations are available via the Internet. To date, derivative maps have been produced to improve maintenance of roads and transport and of the construction of new infrastructure.     

Chesapeake Bay Plume Morphology and the Effects on Nutrient Dynamics and Primary Productivity in the Coastal Zone

To determine the effects of the Chesapeake Bay outflow plume on the coastal ocean, nutrient concentrations and climatology were evaluated in conjunction with nitrogen (N) and carbon (C) uptake rates during a 3-year field study. Sixteen cruises included all seasons and captured high- and low-flow freshwater input scenarios. Event-scale disturbances in freshwater flow and wind speed and direction strongly influenced the location and type of plume present and thus the biological uptake of N and C. As expected, volumetric primary productivity rates did not always correlate with chlorophyll a concentrations, suggesting that high freshwater flow does not translate into high productivity in the coastal zone; rather, high productivity was observed during periods where recycling processes may have dominated. Results suggest that timing of meteorological events, with respect to upwelling or downwelling favorable conditions, plays a crucial role in determining the impact of the estuarine plume on the coastal ocean.     

Utility of clay Minerals in the Determination of Sedimentary Transport Patterns in the Bay of Cadiz and the Adjoining Continental Shelf (SW-Spain)

The contents and the distribution of clay minerals in modern sediments of the Cadiz bay and the continental shelf have been studied aiming to establish the sedimentary exchange model and the pathways followed by the clay fraction between the bay and the adjoining continental shelf. The most abundant clay minerals in the muddy sediments consist mainly of illite, smectite, interstratified illite-smectite, kaolinite and chlorite. The application of factor analysis method (PCA) to clay minerals data are considered to be useful in the determination of sedimentary transport patterns. The data from clay mineral assemblages, and their distribution map, make possible to establish the fine sediments transport paths in the study area using clay mineral as natural tracers. This model of transport takes in consideration the facies distribution, the supplies sources and the way of fine sediments are incorporated to the marine environment.

Two flows paths have been established: the outflows coming from Cadiz bay and the littoral zones; and the inflows coming from external marine zones of the bay. These flows are controlled by tidal currents and the morphology of the coast. The action of surge and the marine currents, specially the Atlantic Surface Water flow, are also important in the transport of fine sediments coming from sources located to the north of the study zone.     

Origin and metamorphic evolution of rocks with braunite and pyrophanite from the Iberian Massif (SW Spain)

Summary ?Rocks containing braunite from the Ossa-Morena central belt (Iberian Massif, SW Spain) have been studied; these include nodules and layers of braunite (association I), Mn-slates (association II) and Mn-metatuffs (associations III and IV). Geochemical features of braunite nodules such as Mn/Fe ratios around 2, positive Ce-anomalies and good correlations among Mn, Fe, Co, Cu and REE contents indicate that the protolith of the braunite-nodules was precipitated from oxidising sea water. Greenschist facies Hercynian metamorphism reduced initial Mn⁴⁺ to Mn³⁺ and Mn²⁺. High initial fO₂ of oxide beds (association I) limited reduction to the formation of braunite. Reduction continued until the formation of garnet + piemontite (associations II and III), and pyroxmangite + pyrophanite (association IV). Ti-rich braunites (up to 6.8% of TiO₂) occur in slates and metatuffs in which the (Mn + Fe)/Ti ratio of the whole rock is lower than 30, while braunites have lower Ti contents in slates and metatuffs with (Mn + Fe)/Ti ratios around 90. Fe-rich braunite crystallized in rocks with Mn²⁺ oxide and silicate where low Mn³⁺/Mn²⁺ in the whole rock facilitated substitution of Fe³⁺ for Mn³⁺. Received January 30, 2002; revised version accepted May 7, 2002 Published online November 22, 2002     

Sludge weathering and mobility of contaminants in soil affected by the Aznalcollar tailing dam spill (SW Spain)

As a result of the collapse of the Aznalcollar mine tailings dam, a large extension of the Guadiamar valley in SW Spain was covered with a layer of pyrite sludge. Although most of the sludge was removed, a small amount remains in the soil, constituting a potential source of water pollution. A column experiment was carried out in order to determine the rate of sludge oxidation in the soil, and the existence of metal retention processes. The column was filled with a mixture of sludge and a sandy soil common in the region. At different time intervals, the column was leached with water and the resulting solution analysed.

The pH of the water dropped to values around 2 after 260 days and then remained constant due to the buffering role of silicate dissolution. The concentration of Zn, Cd and Co in the leachates matched the expected values from flow-through experiments at atmospheric oxygen pressure. This indicates that oxygen diffusion in the pores was complete. Moreover, no efficient processes existed for retaining Zn, Cd and Co, which formed soluble salts and were entirely incorporated into the infiltrating water. During the first 2 months of the experiment, when pH was higher than 4.5, the concentrations of Fe and Al were very low. Saturation indices showed that the solution was in equilibrium with amorphous Fe(OH)₃ and Al(OH)₃. Subsequently, at lower pH values, jarosite [(Na,K)Fe₃(SO₄)₂(OH)₆] formed. This solid phase was identified by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). Jarosite was also responsible for the depletion of As, Pb, Sb and probably Tl in the water resulting from infiltration.     

Oxidative dissolution of pyritic sludge from the Aznalcóllar mine (SW Spain)

As a result of the collapse of a mine tailing dam, a large extension of the Guadiamar valley was covered with a layer of pyritic sludge. Despite the removal of most of the sludge, a small amount remained in the soil, constituting a potential risk of water contamination. The kinetics of the sludge oxidation was studied by means of laboratory flow-through experiments at different pH and oxygen pressures. The sludge is composed mainly of pyrite (76%), together with quartz, gypsum, clays, and sulphides of zinc, copper, and lead. Trace elements, such as arsenic and cadmium, also constitute a potential source of pollution. The sludge is fine grained (median of 12 μm) and exhibits a large surface (BET area of 1.4±0.2 m² g⁻¹).

The dissolution rate law of sludge obtained is r=10^{−6.1(±0.3)} [O₂(aq)]^0.41(±0.04) a_H+^0.09(±0.06) g_sludge m⁻² s⁻¹ (22 °C, pH=2.5–4.7). The dissolution rate law of pyrite obtained is r=10^{−7.8(±0.3)} [O₂(aq)]^0.50(±0.04) a_H+^0.10(±0.08) mol m⁻² s⁻¹ (22 °C, pH=2.5–4.7). Under the same experimental conditions, sphalerite dissolved faster than pyrite but chalcopyrite dissolves at a rate similar to that of pyrite. No clear dependence on pH or oxygen pressure was observed. Only galena dissolution seemed to be promoted by proton activity. Arsenic and antimony were released consistently with sulphate, except at low pH conditions under which they were released faster, suggesting that additional sources other than pyrite such as arsenopyrite could be present in the sludge. Cobalt dissolved congruently with pyrite, but Tl and Cd seemed to be related to galena and sphalerite, respectively.

A mechanism for pyrite dissolution where the rate-limiting step is the surface oxidation of sulphide to sulphate after the adsorption of O₂ onto pyrite surface is proposed.     

Palaeoecology of Late Triassic marine assemblages from the proto-Atlantic Basin (Ayamonte,SW Spain)

The Triassic represents a critical period that attests to the diversification of marine ecosystems. This paper analyses the stratigraphy of the easternmost Mesozoic series of the Algarve Basin in the Ayamonte sector (SW Spain). Two sets forming this series are described. The first, mainly siliciclastic, was deposited in continental contexts represented by fluvial and lacustrine environments with bioturbation associated with swamp-like environments (Taenidium) or with plain alluvial sediments (Labyrintichnus terrerensis, Planolites). This ichnoassemblage corresponds to the ichnofacies of Scoyenia. The second set, is carbonate-dominated and shows a remarkable palaeontological content comprising bivalves and gastropods, which made it possible to review our current knowledge of the regional stratigraphy of the Triassic in this area. Trigonodus-Isocyprina form this association for bivalves and Coeslostylina and Coeslostylina-Spirostylus-Mathilda for gastropods allowing to infer a Late Triassic (Carnian-Rhaetian) age for the Ayamonte area. The characteristic trace fossils of the carbonate sections are represented by Thalassinoides Treptichnus pollardi and Helminthoidichnites tenuis, which belong to the proximal expression of the Cruziana ichnofacies. Shallow marginal, low energy, and brackish and locally lacustrine conditions are inferred for this carbonate-dominated set, alternating with episodes of normal salinity, and towards the top, with punctuated episodes of higher energy. This palaeoenvironmental context is congruent with the palaeogeographical scenario conditioned by the existence of a threshold of major order that would indicate the initial breaking of Pangea and the opening of the Tethys in the eastern Mediterranean.