Calcareous skeletons of sea urchins as indicators of heavy metals pollution. Portman Bay, Spain

 Portman Bay presents elevated quantities of metals and heavy metals in the sediments and rocky outcrops. The calcitic skeletons of the sea urchins that live there present elevated concentrations of Mn, Fe, Zn, and Pb (249, 273, 32, and 59 ppm) in comparison with control zones (beach of La Vila) where the concentrations for these elements are 5, 7, 8, and 2 ppm, respectively. Two species of sea urchins have been studied: Paracentrotus lividus and Arbacia lixula. The different compositions between the plates and the spines of their skeletons have also been studied. Received: 20 November 1995 · Accepted: 25 January 1996     

Distribution of heavy metals in the Piscinas beach sediments (SW Sardinia, Italy)

We have studied sediments of the Piscinas beach (SW Sardinia, Italy), which is supplied by two streams that wash mine dumps of abandoned lead and zinc mines at Montevecchio and Ingurtosu, situated inland from the supply basin of the beach itself. A study of the texture, mineralogy and geochemistry of the sediments was conducted for the purpose of assessing the possible influence of the mine waste on the composition of the sediments, looking for any anomalous enrichments in heavy metals. Furthermore, to evaluate and quantify metal release into the sea, samples of Posidonia oceanica, a bioaccumulator marine plant, were also examined. The results indicate that the distribution of heavy metals in the foreshore sediments is particularly affected by the contribution of the streams, while in the shoreface the distribution is affected by the currents that disperse the sediments both out to sea and southwards. The metal contents of the Posidonia oceanica are correlated with the different stages of activity of the mines. Received: 28 January 1998 · Accepted: 22 April 1998     

Mine waste dumps and heavy metal pollution in abandoned mining district of Boccheggiano (Southern Tuscany, Italy)

 Mining activity in the Boccheggiano-Fontalcinaldo area (Southern Tuscany) dates back at least to the 16th century AD and lasted up to very recent times. Copper-rich hydrothermal veins, massive pyrite deposits, and their gossans were exploited. Two mine waste dumps (Fontalcinaldo, Fontebona), one flotation tailings impoundment (Gabellino), and one roasting/smelting waste dump (Merse-Ribudelli) in the study area were selected to ascertain the environmental effects of such protracted mining activity. Primary waste mineralogy is mainly characterized by pyrite, gypsum, quartz, carbonates, chlorites, and micas. Secondary oxidation mineralogy includes Fe and Cu sulfates and hydroxy sulfates, Cu carbonates, Fe and Al oxyhydroxides, and other phases [neogenic cassiterite at Fontalcinaldo; probable calkinsite, (Ce,La)₂(CO₃)₃· 4H₂O, at Fontebona]. Mine waste samples show extremely variable contents of toxic elements (Cu, Pb, Zn, Bi, Cd, As), with average values in the order of hundreds to thousands of parts per million (except for Bi and Cd). In some samples, the abundance of proper minerals of these metals cannot account for the entire metal load. Conceivably, either solid solution substitutions or adsorption processes contribute to the intake of released metals into newly formed minerals. Release and transport of pollutants was affected to variable degrees by acid-neutralization processes. The highest metal and acid concentrations occur close to the investigated wastes and rapidly decrease moving downstream some hundreds of meters or less, with the partial exception for Mn and Fe. Other than dilution effects, this phenomenon may be ascribed to metal adsorption and precipitation of solid phases. Received: 16 April 1995 · Accepted: 14 December 1995     

Mobilization and attenuation of heavy metals within a nickel mine tailings impoundment near Sudbury, Ontario, Canada

 The oxidation and the subsequent dissolution of sulfide minerals within the Copper Cliff tailings area have led to the release of heavy metals such as Fe, Ni, and Co to the tailings pore water. Dissolved concentrations in excess of 10 g/l Fe and 2.2 g/l Ni have been detected within the shallow pore water of the tailings, with increasing depth these concentrations decrease to or near analytical detection limits. Geochemical modelling of the pore-water chemistry suggests that pH-buffering reactions are occurring within the shallow oxidized zones, and that secondary phases are precipitating at or near the underlying hardpan and transition zones. Mineralogical study of the tailings confirmed the presence of goethite, jarosite, gypsum, native sulfur, and a vermiculite-type clay mineral. Goethite, jarosite, and native sulfur form alteration rims and pseudo-morphs of the sulfide minerals. Interstitial cements, composed of goethite, jarosite, and gypsum, locally bind the tailings particles, forming hardpan layers. Microprobe analyses of the goethite indicate that it contains up to 0.6 weight % Ni, suggesting that the goethite is a repository for Ni. Other sinks detected for heavy metals include jarosite and a vemiculite-type clay mineral which locally contains up to 1.6 weight % Ni. To estimate the mass and distribution of heavy metals associated with the secondary phases within the shallow tailings, a series of chemical extractions was completed. The experimental design permitted four fractions of the tailings to be evaluated independently. These four fractions consisted of a water-soluble, an acid-leachable, and a reducible fraction, as well as the whole-rock total. Twenty-five percent of the total mass of heavy metals was removed in the acid-leaching experiments, and 100% of the same components were removed in the reduction experiments. The data suggest that precipitation/coprecipitation reactions are providing an effective sink for most of the heavy metals released by sulfide mineral oxidation. In light of these results, potential decommissioning strategies should be evaluated with the recognition that changing the geochemical conditions may alter the stability of the secondary phases within the shallow tailings. Received: 9 April 1997 · Accepted: 21 July 1997     

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.     

Heavy metals in Oka river sediments (Urdaibai National Biosphere Reserve, northern Spain): lithogenic and anthropogenic effects

 The Oka River basin is located in the Urdaibai National Biosphere Reserve, North Spain. In order to obtain a preliminary view of its environmental conditions, nitric acid extractable Fe, Mn, Zn, Pb, Cu, Cr, Ni and Co, organic matter content (L.O.I.), geochemical fractionation of heavy metals and mineralogical composition were analysed in surficial sediments (fraction <63 μm) collected in October 1991. Relatively high concentrations of metals occurred in a sampling site upstream, due to a local natural enrichment controlled by weathering of volcanic rocks. Geochemical fractionation confirmed the lithogenic origin of metals, which were mainly associated to the detrital phase. The significant increase of heavy metals found in some samples collected in the municipal area of Gernika suggested a pollution effect, related to anthropogenic wastes. Large amounts of metallic slags have been found mixed with the sediments upstream from this locality. Nevertheless, in view of their composition, it is unlikely that these slags constitute a significant source of heavy metals in the studied area. In a second sampling in October 1997 an apparent decreasing trend in some heavy metal levels was noted, particularly for Pb and Cu. Nowadays, enrichment factors relative to background values confirm moderate anthropogenic influence on Zn, Pb, Cu, Cr and Ni concentrations. However, heavy metal levels in the Oka river sediments are much lower than those detected in other major rivers of the Basque Country (Nervión, Urumea, Deba). Received: 7 July 1997 · Accepted: 4 July 1998     

Water contamination and remedial measures at the Troya abandoned Pb-Zn mine (The Basque Country, Northern Spain)

 This article describes a case of contamination of a karstic aquifer by abandoning an underground mine exploiting sulphide ore body. To exploit the ore, the aquifer was drained and the water level declined about 230 m, drying up the spring that had drained the aquifer up to that moment. When the mining activity ceased, the piezometric level recovered and contaminated water began to flow out from a mine adit. The water is high in sulphates and dissolved Fe, although the pH is neutral. When this water reached the nearby creek, the fish population was eliminated, principally due to the presence of toxic metals and the precipitation of Fe hydroxides. The contamination originated in an area of the partially flooded mine rooms where the ore is in contact with both air and water. The acidity generated by pyrite oxidation is neutralized by calcite dissolution. Presently, the mine water is diverted to the old tailings pond which functions as an aerobic wetland. This action has allowed the fish population in the creek to be restored. Received: 20 January 1999 · Accepted: 15 March 1999     

Heavy metals in freshly deposited sediments of the Gomati River (a tributary of the Ganga River): effects of human activities

 The concentrations of various metals (Cr, Cu, Co, Fe, Mn, Ni, Pb, Zn, and Cd) were determined in recently deposited surface sediments of the Gomati River in the Lucknow urban area. Markedly elevated concentrations (milligrams per kilogram) of some of the metals, Cd (0.26–3.62), Cu (33–147), Ni (45–86), Pb (25–77), and Zn (90–389) were observed. Profiles of these metals across the Lucknow urban stretch show a progressive downstream increase due to additions from 4 major drainage networks discharging the urban effluents into the river. The degree of metal contamination is compared with the local background and global standards. The geoaccumulation index order for the river sediments is Cd>Zn>Cu>Cr>Pb. Significant correlations were observed between Cr and Zn, Cr and Cu, Cu and Zn and total sediment carbon with Cr and Zn. This study reveals that the urbanization process is associated with higher concentrations of heavy metals such as Cd, Cu, Cr, Pb, and Zn in the Gomati River sediments. To keep the river clean for the future, it is strongly recommended that urban effluents should not be overlooked before their discharge into the river. Received: 16 February 1996 · Accepted: 29 February 1996     

Mineralogical and geochemical signature of mine waste contamination, Tresillian River, Fal Estuary, Cornwall, UK

The mineralized district of SW England was one of the world's greatest mining areas, with mining commencing in the Bronze age, peaking in the 1850s to 1890s, but still continuing to the present day. Consequently, it is not surprising that mining has had a major impact on the environmental geochemistry of SW England. In this study, the mineralogical and geochemical signature of mine waste contamination within the Fal Estuary at Tresillian, Cornwall, has been examined. A pulse of mine waste contamination is recognized at approximately 50?cm below present day sediment surface. Sn, As, Cu, Pb, and Zn are all enriched within this contaminated interval with up to 1800 mg?kg^–1 Sn, 290 mg?kg^–1 As, 508 mg?kg^–1 Pb, 2210 mg?kg^–1 Zn, and 1380 mg?kg^–1 Cu. Within this interval, the dominant minerals present include chalcopyrite, arsenopyrite, pyrite, cassiterite, Fe–Ti oxides (ilmenite and ?rutile), wolframite, sphalerite, baryte, zircon, monazite, tourmaline and xenotime. In addition, man-made slag products commonly occur. The exact timing of the release of mine waste into the estuary is poorly constrained, but probably occurred during or immediately following the peak in mining activity in the nearby Camborne-Redruth district, which was between 1853 and 1893. The mine waste may have entered the estuary either via the Tresillian River and its tributaries or via Calenick Creek and the Truro River and/or the Carnon River which flows into Rostronguet Creek.     

Hydrogeochemical analysis of salinization processes in the coastal aquifer of Oropesa (Castellón, Spain)

 The coastal aquifer of Oropesa is affected by salinization processes undoubtedly associated with intense groundwater exploitation for agriculture supply. The aquifer corresponds geologically to a tectonic depression with Plioquaternary fill. Hydrogeologically, this aquifer is detrital, with intergranular porosity, which receives substantial recharge from adjacent Mesozoic aquifers. Contact with the sea, in addition to the presence of cultivated soil requiring extreme exploitation of groundwater, frequently give rise to processes of seawater intrusion. The present research is an attempt to understand the saltwater intrusion in this aquifer, using hydrochemical analyses of the behavior of certain minor ions that could help in the characterization process. In the case of the Oropesa sector, groundwater salinization does not appear to be attributable solely to the intrusion of seawater, but there are also anomalies related largely to the geology of the sector and its surroundings, the type of recharge, the hydrodynamic conditions in the specific area, etc. Received: 23 January 1995 · Accepted: 12 September 1995     

Use of sample color to estimate oxidized Fe content in mine waste rock

 Color, a readily perceived feature of natural earth materials, including mine waste, often represents compositional variation as a result of oxidative processes involving Fe. Near surface samples from excavated trenches in a mine-waste rock pile were collected to investigate the relationship between color and contents of Fe, Cu, and S. The silt+clay fraction (<0.05 mm) was isolated from recognizable colored material of the bulk sample for determination of pH, total and extractable Fe and Cu, and bulk mineralogy. Rock fragments within the pile exhibited coatings of crystalline gypsum and amorphous Fe. These coatings result from weathering (secondary products) and play important roles in surface reactions of waste rock piles, such as adsorption of anions (SO₄ ^2–) or coprecipitation of Fe with Cu. The correlation between color (Hurst method) and extractable Fe was high. Although color is influenced by site conditions such as original mineral composition, materials handling, weathering conditions etc., the results suggest that color measurements may provide an inexpensive and rapid estimation for secondary iron compounds and associated sorbed elements. Received: 5 April 1998 · Accepted: 30 June 1998     

Surface analysis of particles in mine tailings by time-of-flight laser-ionization mass spectrometry (TOF-LIMS)

  Time-of-flight laser-ionization mass spectrometry was applied to study the chemical composition of mineral particle surfaces in a sulphide-rich mine-tailings impoundment. This surface-sensitive technique provides chemical information from surfaces of irregularly shaped mineral particles (both conductive and insulators) less than 100 μm in diameter, which are considered to be representative of particle surface coatings in the tailings pile (after drying). In addition, depth profiles in the mineral particles were obtained. The combination of speed of analysis (1 min), small beam-diameter (2–4 μm), surface sensitivity (2–10 nm), trace-element sensitivity, and capability to analyze rough surfaces makes this method useful as a complement to studies of pore-water geochemistry and tailings mineralogy. As an example, the behavior of Pb and As in the Kidd Creek tailings dam near Timmins, Ontario, Canada, was studied, using a combination of surface analyses, and pore-water geochemical data. Received: 22 February 1995 / Accepted: 6 January 1996     

Testing the ability of bentonite-amended natural zeolite (clinoptinolite) to remove heavy metals from liquid waste

 The design of environmentally sound liquid waste containment structures has become a crucial task in engineering applications due to ever increasing groundwater contamination from such sites. Construction of such structures usually requires a bottom liner of low hydraulic conductivity as part of the design. In order to reduce the hazards associated with liquid wastes including landfill leachate, bentonite-amended natural zeolite is proposed as an alternative to conventional earthen liners. Among many contaminants associated with liquid wastes, heavy metals are the most dangerous ones. This paper deals with determining the ability of natural zeolite to remove heavy metals from aqueous waste. For this purpose, crushed natural zeolite (clinoptinolite) is amended with commercial powdered bentonite to yield a soil mixture low in permeability and high in ion-exchange capacity. Leachate from a conventional landfill is used as the percolation fluid. Concentrations of certain heavy metals in the effluent fluid percolated through the bentonite-zeolite mixture are compared with that of initial leachate. The conclusion is reached that certain metals are efficiently removed from the influent solution by the soil matrix whereas some ions do not show significant reduction in concentration. This is attributed to high hydraulic conductivity of the bentonite-zeolite mixture.     

Source of pollution as a factor controlling distribution of heavy metals in bottom sediments of Chechło River (south Poland)

 The influence of sources of effluents on pollution of bottom sediments of the small Chechło River (23 km long, mean discharge 1.5 m³ s^–1) in southern Poland was examined through analysis of heavy metals distribution in transverse and longitudinal cross sections. Underground waters from a Pb–Zn mine cause very high concentrations of Zn, Cd, and Pb in both fractions investigated (<1 mm and <0.063 mm) of sediments in the active channel zone, whereas sedimentation of huge amounts of suspended matter discharged from oil refinery cause concentrations of heavy metals in fine fractions rather uniform in cross sections. In the lowest reach, with relatively reduced contamination, the highest concentration both in fine and coarse fractions occurs close to the river banks and in the deepest points of the channel. The lowest concentrations have been found at the points of strongest reworking and accumulation of sandy material in the riverbed. Received: 25 April 1995 · Accepted: 11 September 1995     

Comparison of color, chemical and mineralogical compositions of mine drainage sediments to pigment

 Forty-three untreated and actively and passively (wetland) treated coal mine drainage sediments and five yellow-red pigments were characterized using X-ray fluorescence, fusion-inductively coupled plasma atomic emission spectroscopy, X-ray diffraction, and tristimulus colorimeter. Primary crystalline iron-bearing phases were goethite and lepidocrocite, and iron phases converted to hematite upon heating. Quartz was nearly ubiquitous except for synthetic pigments. Gypsum, bassinite, calcite, and ettringite were found in active treatment sediments. Iron concentrations from highest to lowest were synthetic pigment>wetland sediment>natural pigment>active treatment (untreated sediments varied more widely), and manganese was highest in actively treated sediments. Loss on ignition was highest for passively treated sediments. No clear trends were observed between quantified color parameters (L*, a*, b*, and Redness Index) and chemical compositions. Because sediments from passive treatment are similar in chemistry, mineralogy, and color to natural pigments, the mine drainage sediments may be an untapped resource for pigment. Received: 29 December 1997 · Accepted: 11 May 1998     

Environmental geochemistry of the Gulf Creek copper mine area, north-eastern New South Wales, Australia

 Past mining and smelting of sulphide ore (pyrite-chalcopyrite-sphalerite) at the abandoned Gulf Creek mine has resulted in a stream highly contaminated by acid mine drainage (pH: 2.2–3.4), as well as degradation of local soil and vegetation. Physical dispersion of secondary metal-bearing minerals from abandoned ore and waste dumps into Gulf Creek and adsorption and coprecipitation of dissolved metals and metalloids in the stream bed cause elevated Ag, As, Cd, Cu, Fe, Pb and Zn values in stream sediments. The bioavailability of individual heavy metals to freshwater organisms changes downstream, however, selective bioaccumulation processes in algae reject readily bioavailable Zn and concentrate less bioavailable Cu. Polluted soils in the vicinity of the mine and smelter sites are subject to continuing soil erosion and either support no vegetation, or a depauperate flora with certain species showing bioaccumulation of metals and resistance to high metal contents. Rehabilitation of disturbed areas should involve covering and sealing sulphidic mine waste or removal of ore and waste dumps, installation of a physical and chemical plant or construction of a wetland environment (plus anoxic lime drains), and import of topsoil and planting of local, metal-tolerant plant species. Received: 17 March 1998 / Accepted: 6 October 1998     

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.     

Speciation and solubility relationships of Al, Cu and Fe in solutions associated with sulfuric acid leached mine waste rock

 Solutions from oxidized waste rock originating from an acid-leached waste dump were studied. The dissolution data suggest that after the majority of the soluble solid phases are removed, remaining solid phases continued to buffer the solutions in the acidic pH range. Incorporating the solution data into MINTEQA2 identified controls on the solubility of Al, Cu and Fe at pH values from about 2.5 to slightly over 5. Sulfate appears to play a significant role in the formation of solubility controlling solid phases for Al and Cu. This is not the case for Fe, and is suggested that Fe and Cu solubility may be controlled by cupric ferrite at low pH values. Received: 5 April 1998 · Accepted: 27 July 1998     

Heavy metal pollution in freshly deposited sediments of the Yamuna River (the Ganges River tributary): a case study from Delhi and Agra urban centres, India

 The Yamuna River sediments, collected from Delhi and Agra urban centres, were analysed for concentration and distribution of nine heavy metals by means of atomic adsorption spectrometry. Total metal contents varied in the following ranges (in mg/kg): Cr (157–817), Mn (515–1015), Fe (28,700–45,300), Co(11.7–28.4), Ni (40–538), Cu (40–1204), Zn (107–1974), Pb (22–856) and Cd (0.50–114.8). The degree of metal enrichment was compared with the average shale concentration and shows exceptionally high values for Cr, Ni, Cu, Zn, Pb and Cd in both urban centres. In the total heavy metal concentration, anthropogenic input contains 70% Cr, 74% Cu, 59% Zn, 46% Pb, 90% Cd in Delhi and 61% Cr, 23% Ni, 71% Cu, 72% Zn, 63% Pb, 94% Cd in Agra. A significant correlation was observed between increasing Cr, Ni, Zn, and Cu concentrations with increasing total sediment carbon and total sediment sulfur content. Based on the Müller's geoaccumulation index, the quality of the river sediments can be regarded as being moderately polluted to very highly polluted with Cr, Ni, Cu, Zn, Pb and Cd in the Delhi and Agra urban centres. The present sediment analysis, therefore, plays an important role in environmental measures for the Yamuna River and the planning of these city centres. Received: 21 June 1999 · Accepted: 1 October 1999     

Stable isotopes and heavy metal distribution in Dreissena polymorpha (Zebra Mussels) from western basin of Lake Erie, Canada

 Dreissena polymorpha is an exotic freshwater bivalve species which was introduced into the Great Lakes system in the fall of 1985 through the release of ballast water from European freighters. Utilizing individual growth rings of the shells, the stable isotope distribution (δ¹⁸O and δ¹³C) was determined for the life history of selected samples which were collected from the western basin of Lake Erie. These bivalves deposit their shell in near equilibrium with the ambient water and thus reflect any annual variation of the system in the isotopic records held within their shells. Observed values for δ¹⁸O range from -6.64 to –9.46‰ with an average value of –7.69‰ PDB, while carbon values ranged from –0.80 to –4.67‰ with an average value of –1.76‰ PDB. Dreissena polymorpha shells incorporate metals into their shells during growth. Individual shell growth increments were analyzed for Pb, Fe, Mg, Mn, Cd, Cu, and V concentrations. The shells show increased uptake of certain metals during periods of isotopic enrichment which correspond with warmer water temperatures. Since metals are incorporated into the shells, the organism may be useful as a biomonitor of metal pollution within aquatic environments. Received: 31 October 1996 · Accepted: 21 May 1997