Supergene mineralization in mining residues of the Matchless cupreous pyrite deposit (Namibia)—a clue to the origin of modern and fossil duricrusts in semiarid climates

Mineralogical, geochemical, sedimentological and microbiological investigations of the evolution of supergene mineralization of mining residues at Matchless chalcopyrite–pyrite deposit (Namibia) have delineated what may be called “the minero-stratigraphy of tailings”. The encrustations of the supergene or secondary mineralization have originated from alteration of sulfides and carbonates of the primary mineralization and from chemical agents (e.g. lime, phosphate) added during processing of ore. The variation in tailings discharge and the early diagenetic alteration led to a pronounced bedding and the development of distinct layers within the tailings impoundment: (1) gypsum–carbonate (e.g. huntite), (2) gypsum–sulfate (e.g. melanterite), (3) gypsum–phosphate (e.g. brushite), (4) gypsum–chloride (e.g. halite), (5) sulfate–gypsum efflorescence (e.g. copiapite).Deposition and early diagenesis of tailings may be described as follows: During deposition of tailings, oxidation began because of relocations of the discharge point. Phyllosilicate-rich layers form local aquatards and minimize solution homogenization in the succeeding cycles of deposition. The whole impoundment is a series of paleo-oxidation zones on which the current oxidation in the vadose zone is being superimposed. Low-pH zones, even though some are now in the saturated part of the impoundment, owe their low pH to low dolomite content, reflecting variations in the input of primary minerals. Excess pyrite and Fe hydrolysis is still generating acidity and the formation of a typical “gossan-type” profile is in progress. The modern hardpans in the tailings may, during late diagenesis, eventually evolve to duricrusts analogous to those duricrusts that have largely been studied in geological series prevalently of Cenozoic age.     

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     

Release,transport and attenuation of metals from an old tailings impoundment

The oxidation of sulfide minerals from mine wastes results in the release of oxidation products to groundwater and surface water. The abandoned high-sulfide Camp tailings impoundment at Sherridon, Manitoba, wherein the tailings have undergone oxidation for more than 70 a, was investigated by hydrogeological, geochemical, and mineralogical techniques. Mineralogical analysis indicates that the unoxidized tailings contain nearly equal proportions of pyrite and pyrrhotite, which make up to 60 wt% of the total tailings, and which are accompanied by minor amounts of chalcopyrite and sphalerite, and minute amounts of galena and arsenopyrite. Extensive oxidation in the upper 50 cm of the tailings has resulted in extremely high concentrations of dissolved SO₄ and metals and As in the tailings pore water (pH < 1, 129,000 mg L⁻¹ Fe, 280,000 mg L⁻¹ SO₄, 55,000 mg L⁻¹ Zn, 7200 mg L⁻¹ Al, 1600 mg L⁻¹ Cu, 260 mg L⁻¹ Mn, 110 mg L⁻¹ Co, 97 mg L⁻¹ Cd, 40 mg L⁻¹ As, 15 mg L⁻¹ Ni, 8 mg L⁻¹ Pb, and 3 mg L⁻¹ Cr). The acid released from sulfide oxidation has been extensive enough to deplete carbonate minerals to 6 m depth and to partly deplete Al-silicate minerals to a 1 m depth. Below 1 m, sulfide oxidation has resulted in the formation of a continuous hardpan layer that is >1 m thick. Geochemical modeling and mineralogical analysis indicate that the hardpan layer consists of secondary melanterite, rozenite, gypsum, jarosite, and goethite. The minerals indicated mainly control the dissolved concentrations of SO₄, Fe, Ca and K. The highest concentrations of dissolved metals are observed directly above and within the massive hardpan layer. Near the water table at a depth of 4 m, most metals and SO₄ sharply decline in concentration. Although dissolved concentrations of metals and SO₄ decrease below the water table, these concentrations remain elevated throughout the tailings, with up to 60,600 mg L⁻¹ Fe and 91,600 mg L⁻¹ SO₄ observed in the deeper groundwater. During precipitation events, surface seeps develop along the flanks of the impoundment and discharge pore water with a geochemical composition that is similar to the composition of water directly above the hardpan. These results suggest that shallow lateral flow of water from a transient perched water table is resulting in higher contaminant loadings than would be predicted if it were assumed that discharge is derived solely from the deeper primary water table. The abundance of residual sulfide minerals, the depletion of aluminosilicate minerals in the upper meter of the tailings and the presence of a significant mass of residual sulfide minerals in this zone after 70 a of oxidation suggest that sulfide oxidation will continue to release acid, metals, and SO₄ to the environment for decades to centuries.     

Water management for acid mine drainage control at the polymetallic Zn–Pb–(Ag–Bi–Cu) deposit Cerro de Pasco, Peru

The geochemical and mineralogical study of the Quiulacocha tailings impoundment has shown that the hydrological connection of the three studied mine-waste systems at Cerro de Pasco (Pyrite-rich waste-rock dump Excelsior, old tailings impoundment Quiulacocha, and the active tailings impoundment Ocroyoc) is a critical concern for effective acid mine drainage (AMD) control and mine-waste management. The Quiulacocha tailings covered 114 ha, comprising 79 Mt of tailings, which contained  50 wt.% pyrite, and are located at 4340 m altitude in a tropical puna climate with about 1025 mm/a rainfall and 988 mm/a of evaporation. The tailings were partially overlain by the Excelsior waste-rock dump, which contains about 26,400,000 m³ of waste rocks that cover 94 ha and contained  60 wt.% of pyrite, which origin from a massive pyrite-quartz replacement body. Therefore, these two mine-waste deposits had a direct hydrological connection, resulting in the export of AMD produced at Excelsior towards Quiulacocha. In the Quiulacocha impoundment there are two different types of tailings recognized, that interact with the AMD from Excelsior: 1) Zn–Pb-rich tailings and 2) Cu–As-rich tailings. During the sampling, the Zn–Pb-rich part of Quiulacocha was not producing important excesses of AMD from the oxidation zone, since the pH increased to near neutral values at 1 m depth. The underlying tailings were still able to neutralize the acidity produced in the oxidation zone through sulfide oxidation by the carbonates (mainly dolomite and siderite) contained in the Zn–Pb mineral assemblage. The main source of AMD in this mine-waste system is the Excelsior waste-rock dump. Its acid seepage infiltrates into Quiulacocha forming a Fe–Zn–Pb plume with a pH 5.5–6.1 and containing up to 7440 mg/L Fe, 627 mg/L Zn, and 1.22 mg/L Pb. The plume was detected at 10–13 m depth in the stratigraphy of Quiulacocha tailings. Additionally, the AMD seepage outcropping at the base of the Excelsior waste-rock dump was channeled on the tailings surface into the Quiulacocha pond (pH 2.3), which covered the Cu–As-rich tailings. Infiltration of this Fe(III)-rich AMD increased tailings oxidation in the southwestern part of the impoundment, and subsequently liberated arsenic by enargite oxidation. Additionally, the AMD collected in the Quiulacocha pond was pumped into the active Ocroyoc tailings impoundment, where sulfide oxidation was strongly enhanced by the input of dissolved Fe(III). Therefore, the AMD management and a hydrological separation of the different mine-waste systems could be a first step to prevent further extension of the AMD problem in order to prevent increased sulfide oxidation by Fe(III)-rich solutions.     

Ore-microscopic and geochemical characteristics of gold-bearing sulfide minerals,El Sid Gold mine,Eastern Desert,Egypt

Gold deposits at El Sid are confined to hydrothermal quartz veins which contain pyrite, arsenopyrite, sphalerite and galena. These veins occur at the contact between granite and serpentinite and extend into the serpentinite through a thick zone of graphite schist. Gold occurs in the mineralized zone either as free gold in quartz gangue or dissolved in the sulfide minerals. Ore-microscopic study revealed that Au-bearing sulfides were deposited in two successive stages with early pyrite and arsenopyrite followed by sphalerite and galena. Gold was deposited during both stages, largely intergrown with sphalerite and filling microfractures in pyrite and arsenopyrite.Spectrochemical analyses of separated pyrite, arsenopyrite, sphalerite and galena showed that these sulfides have similar average Au contents. Pyrite is relatively depleted in Ag and Te. This suggests that native gold was deposited in the early stage of mineralization. Arsenopyrite and galena show relatively high concentrations of Te. They are also respectively rich in Au and Ag. Tellurides are, thus, expected to be deposited together with arsenopyrite and galena.     

The effects of hardpan layers on the water chemistry from the leaching of pyrrhotite-rich tailings material

Column leaching experiments were used to determine the effects of an iron-rich hardpan layer, on the rate of tailings oxidation and the composition of leachate waters, from the Renison Bell tailings dams in western Tasmania, Australia. One-meter-long PVC columns, filled with tailings, cover material (Cassiterite Flotation Tailings) and hardpan samples from the tailings dams, were leached over a period of 14 weeks. Under dry cover conditions, when hardpan was present, the solute loads peaked at 21–49 days (Fe at 2,294 ppm and SO ₄ ^2- at 4,700 ppm), and stabilised at much lower concentrations after 9 weeks. In contrast, the solute loads steadily increased over time in the column where hardpan was absent (SO ₄ ^2- from 1,800 to 3,100 ppm, and Fe from 407 to 1,692 ppm). Under saturated cover conditions, the solute concentrations in the leachate also increased with time (SO ₄ ^2-from 1,900 to 17,000 ppm, and Fe from 480 to 8,500 ppm). The presence of a hardpan layer between the reactive tailings and cover material has been found to improve leachate water chemistry and lessen the rate of sulphide oxidation.     

Mineralogical and geochemical characterization of the Old Tailings Dam,Australia: Evaluating the effectiveness of a water cover for long-term AMD control

Establishing a shallow water cover over tailings deposited in a designated storage facility is one option to limit oxygen diffusion and retard oxidation of sulfides which have the potential to form acid mine drainage (AMD). The Old Tailings Dam (OTD) located at the Savage River mine, western Tasmania contains 38 million tonnes of pyritic tailings deposited from 1967 to 1982, and is actively generating AMD. The OTD was constructed on a natural gradient, resulting in sub-aerial exposure of the southern area, with the northern area under a natural water cover. This physical contrast allowed for the examination of tailings mineralogy and geochemistry as a function of water cover depth across the OTD. Tailings samples (n = 144, depth: ≤ 1.5 m) were collected and subjected to a range of geochemical and mineralogical evaluations. Tailings from the southern and northern extents of the OTD showed similar AMD potential based on geochemical (NAG pH range: 2.1 to 4.2) and bulk mineralogical parameters, particularly at depth. However, sulfide alteration index (SAI) assessments highlighted the microscale contrast in oxidation. In the sub-aerial zone pyrite grains are moderately oxidized to a depth of 0.3 m (maximum SAI of 6/10), under both gravel fill and oxidized covers, with secondary minerals (e.g., ferrihydrite and goethite) developed along rims and fractures. Beneath this, mildly oxidized pyrite is seen in fresh tailings (SAI = 2.9/10 to 5.8/10). In the sub-aqueous zone, the degree of pyrite oxidation demonstrates a direct relationship with cover depth, with unoxidized, potentially reactive tailings identified from 2.5 m, directly beneath an organic-rich sediment layer (SAI = 0 to 1/10). These findings are broadly similar to other tailings storage facilities e.g., Fox Lake, Sherritt-Gordon ZnCu mine, Canada and Stekenjokk mine, Sweden where water covers up to 2 m have successfully reduced AMD. Whilst geotechnical properties of the OTD restrict the extension of the water cover, pyrite is enriched in cobalt (up to 2.6 wt%) indicating reprocessing of tailings as an alternative management option. Through adoption of an integrated mineralogical and geochemical characterization approach for tailings assessment robust management strategies after mine closure can be developed.     

Arsenic mobility in weathered gold mine tailings under a low-organic soil cover

Historical gold mining operations in Nova Scotia, Canada, resulted in numerous deposits of publicly accessible, arsenic (As)-rich mine waste that has weathered in situ for 75–150 years, resulting in a wide range of As-bearing secondary minerals. The geochemical heterogeneity of this mine waste creates a challenge for identifying a single remediation approach that will limit As mobility. A 30-cm-thick, low-organic content soil cover was evaluated in a laboratory leaching experiment where, to simulate natural conditions, the equivalent of 2 years of synthetic rainwater was leached through each column and two dry seasons were incorporated into the leaching protocol. Each column was a stratigraphic representation of the four major tailings types found at the historical Montague and Goldenville gold mine districts: hardpan tailings, oxic tailings, wetland tailings, and high Ca tailings. Hardpan tailings released acidic, As-rich waters (max 12 mg/L) under the soil cover but this acidity was buffered by surrounding oxic tailings. Leachate from the oxic tailings was circumneutral, with average As concentrations between 4.4 and 9.7 mg/L throughout the experiment. The presence of carbonates in the high Ca tailings resulted in near-neutral to weakly alkaline leachate pH values and average As concentrations between 2.1 and 6.1 mg/L. Oxidation of sulfides in the wetland tailings led to acidic leachate over time and a decrease in As concentrations to values that were generally less than 1 mg/L. This study shows that the use of a low-organic content soil cover does not create reducing conditions that would destabilize oxidized, As-bearing secondary phases in these tailings. However, oxygen penetration through the cover during dry seasons would continue to release As to tailings pore waters via sulfide oxidation reactions.     

Influence of hardpan layers on arsenic mobility in historical gold mine tailings

Hardpans, or cemented layers, form by precipitation and cementation of secondary minerals in mine tailings and may act as both physical and chemical barriers. Precipitation of secondary minerals during weathering of tailings can sequester metal(loid)s, thereby limiting their release to the environment. At Montague Gold Mines in Nova Scotia, tailings are partially cemented by the Fe arsenate mineral scorodite (FeAsO₄·2H₂O). Previous studies have shown that the formation of scorodite can effectively limit aqueous As concentrations due to its relatively low solubility (<1 mg/L at pH 3–4) and high As content (43–52 wt.% As₂O₅, this study). Co-existing waters and solids were sampled at Montague Gold Mines to identify present-day field conditions influencing scorodite precipitation and dissolution, and to better understand the mineralogical and chemical relationship between hardpan and tailings. In addition to scorodite, hardpan cements were found to include amorphous Fe arsenate and Fe oxyhydroxide. Nearly all hardpan is associated with historical arsenopyrite-bearing concentrate which provides a source of acidity, As⁵⁺ and Fe³⁺ for secondary mineral precipitation. Pore waters sampled from the hardpan have pH values ranging from 2.43 to 7.06. Waters with the lowest pH values also have the highest As concentrations (up to 35.8 mg/L) and are associated with the most extensive hardpan and greatest amount of weathered sulfide. Samples from areas with discontinuous hardpan and less sulfide have near-neutral pH and lower As concentrations. Detailed petrographic observations indicate that the identity and stability of As-bearing secondary minerals depends on the continued availability of sulfide concentrate. The results of this study are being used to develop remediation strategies for highly weathered, hardpan-bearing tailings that consider the stability of both primary and secondary minerals under various cover scenarios.     

Experimental study on prevention of acid mine drainage by silica coating of pyrite waste rocks with amorphous silica solution

Acid mine drainage (AMD) is a widespread environmental problem associated with working and abandoned mining operations. It results from the microbial oxidation of pyrite in the presence of water and air, affording an acidic solution that contains toxic metal ions. Pyrite microencapsulation, utilizing silica coating, is a novel approach for controlling AMD that has been shown to be very effective in controlling pyrite oxidation. The roles of the solution pH and silica concentration in the formation mechanism for the AMD-preventing coating were investigated. A silica coating can be formed from silica solution at pH 7, at which the amount of Fe eluted from pyrite into the solution is small. No coating was formed at other pH values, and the amounts of eluted Fe were larger than at pH 7, especially at pH 11. The silica coating forms from 2,500 to 5,000 mg/L silica solutions, but not from 0 or 1,000 mg/L silica solutions. The coating formation rate was slower in the 2,500 mg/L silica solution than in the 5,000 mg/L silica solution. The formation of silica coating on pyrite surfaces depends on three main steps: formation of Fe(OH)₃ on the surface of pyrite, reaction between Fe(OH)₃ and silicate in the solution on the pyrite surface, and growth of the silica layer on the first layer of silica. The best pH condition to enable these steps was around 7, and the silica coating formation rate can be controlled by the concentration of silica.     

Diagenetic formation of gypsum and dolomite in a cold‐water coral mound in the Porcupine Seabight,off Ireland

Authigenic gypsum was found in a gravity core, retrieved from the top of Mound Perseverance, a giant cold‐water coral mound in the Porcupine Basin, off Ireland. The occurrence of gypsum in such an environment is intriguing, because gypsum, a classic evaporitic mineral, is undersaturated with respect to sea water. Sedimentological, petrographic and isotopic evidence point to diagenetic formation of the gypsum, tied to oxidation of sedimentary sulphide minerals (i.e. pyrite). This oxidation is attributed to a phase of increased bottom currents which caused erosion and enhanced inflow of oxidizing fluids into the mound sediments. The oxidation of pyrite produced acidity, causing carbonate dissolution and subsequently leading to pore‐water oversaturation with respect to gypsum and dolomite. Calculations based on the isotopic compositions of gypsum and pyrite reveal that between 21·6% and 28·6% of the sulphate incorporated into the gypsum derived from pyrite oxidation. The dissolution of carbonate increased the porosity in the affected sediment layer but promoted lithification of the sediments at the sediment‐water interface. Thus, authigenic gypsum can serve as a signature for diagenetic oxidation events in carbonate‐rich sediments. These observations demonstrate that fluid flow, steered by environmental factors, has an important effect on the diagenesis of coral mounds.     

Pyrite formation driven by MSW landfill leachate in the Madrid Basin, Spain

The role of municipal solid waste (MSW) landfill leachate on the genesis of minor amounts of pyrite associated with gypsum in an otherwise predominantly evaporitic sequence was studied in geological and geochemical terms. The potential association between landfill leachate and the conditions required for bacterial reduction of sulfate and fixation of H₂S as pyrite were examined. The lithological column was generally found to contain little or no Fe. The δ³⁴S values for sulfates were consistent with previously reported data; however, the measured δ¹⁸O values were slightly higher. Sulfides disseminated in the marl/lutite exhibited higher δ³⁴S values (≈−8‰) than gypsum-coating pyrite crystals (δ³⁴S < −30‰). Dissolution of gypsum to sulfate and the supply of metabolizable organic matter and Fe required for H₂S fixation as sulfides may have originated from landfill leachate. Intermittent availability of leachate, a result of the precipitation regime, can facilitate sulfur disproportionation and lead to fractionations as high as      

Characterisation of the Sarcheshmeh copper mine tailings,Kerman province,southeast of Iran

Mineral processing operation at the Sarcheshmeh porphyry copper mine has produced huge quantities of tailings materials containing sulphide minerals in particular pyrite. These tailings materials were geochemically and mineralogically characterised to assess pyrite and chalcopyrite oxidation, acid mine drainage generation, and trace element mobility to lead development of a proper remediation plan. Five vertical trenches up to 4.2 m deep were excavated from the tailings surface, and 70 solid samples were taken in 0.3 m intervals. The samples were first mineralogically analysed. Pyrite was the main sulphide mineral found in the tailings. The gangue minerals include quartz ± muscovite–illite ± chlorite ± albite ± orthoclase ± halite. The samples were geochemically analysed for total concentrations of 62 elements, paste pH, SO₄ ^2?, CO₃ ^2?, and HCO₃ ^?. The maximum concentrations of SO₄ ^2? (1,300, 1,170, 1,852, 1,960 and 837 mg/L) were observed at a depth of 0.9 m in profiles A, B, C, D and E, respectively. The tailings have a high acid-producing potential and low acid-neutralising potential (pyrite 4–6 wt %, calcite 1 wt %). Fe₂(SO₄)₃, CuSO₄, MgSO₄ and MnSO₄ were the dominant secondary sulphate minerals in the tailings. The lowest pH values (2.9, 3 and 3) were measured at a depth of 0.3 m in the profiles A, B and C, 3.9 at a depth of 0.6 m in the profile D and 3 at a depth of 0.9 m in the profile E. The upper portions of the profiles C (1.8 m) and D (2.1 m) were moderately oxidised, while oxidation in the profiles A, B and E did not extend more than 1.2, 1.2 and 1.5 m beneath the tailings surface. Zn, Pb, Rb, U, Hf, Nd, Zr and Ga show almost a constant trend with depth. Cd, Sr, Th, La and Ce increased with increasing depth of the tailings materials while, Co, V, Ti, Cr, Cu, As, Mn, Ag, Mo and Ni exhibit initially a decreasing trend from tailings surface to the depths that vary between 0.9 and 1.2. They then remained constant with the depth. The results show pyrite and chalcopyrite oxidation at surface layers of the tailings and subsequent leaching of the oxidation products and trace elements by infiltrated atmospheric precipitation.     

Geoecology of ecosystem recovery at an inactive coal mine site,New Zealand

Ecological restoration of the Wangaloa coal mine in southern New Zealand is hindered by a range of geoecological factors. The site has some substrate acidification (down to pH 1) and acid rock drainage with discharge waters initially down to pH 4, although this has since risen to ca. pH 6. Surface and ground waters develop elevated sulfate (up to 700 mg/kg) during oxidation of pyrite in coal and quartz in waste rock. Coal has elevated boron content (up to 450 mg/kg) and surface waters on coal-rich waste rock have up to 6 mg/L dissolved boron. Evaporation causes formation of salt encrustations dominated by gypsum with minor boron salts. Boron is bioavailable and may be at toxic levels (>200 mg/kg) in some plants. Quartz-rich waste rock is readily eroded, and develops a cm-scale low-nutrient quartz pebble armouring layer with low water retention properties. All waste rocks including loess siltstone have low nutrient contents, and low moisture retention properties, that are barely sufficient for plant establishment. Native plants introduced to the site during rehabilitation have grown on loess substrate (up to fivefold increase in height over 3 years), with poor or no growth on coal-rich and quartz-rich substrates. In contrast, natural colonisation of manuka (Leptospermum scoparium) has been most effective at revegetation on even the most hostile substrates. This natural revegetation has been facilitated by islands of manuka established accidentally during 60 years of mining history. Manuka from local genetic stock is most viable for this revegetation, and introduced manuka seedlings have had a 70% mortality rate. Natural plant colonisation is the key step in overall ecosystem recovery, and invertebrates rapidly colonise beneath new shrubs irrespective of the nature of the substrate from vegetation islands that have high invertebrate numbers and species richness.     

A sulfur isotope study of volcanogenic massive sulfide deposits of the Eastern Black Sea province,Turkey

Kuroko-type massive sulfide deposits of the Eastern Black Sea province of Turkey are related to the Upper Cretaceous felsic lavas and pyroclastic rocks, and associated with clay and carbonate alteration zones in the footwall and hangingwall lithologies. A complete upward-vertical section of a typical orebody consists of a stringer-disseminated sulfide zone composed mainly of pyrite and chalcopyrite; a massive pyrite zone; a massive yellow ore consisting mainly of chalcopyrite and pyrite; a black ore made up mainly of galena and sphalerite with minor amounts of chalcopyrite, bornite, pyrite and various sulfosalts; and a barite zone. Most of the deposits in the province are associated with gypsum in the footwall or hangingwall. The paragenetic sequence in the massive ore is pyrite, sphalerite, chalcopyrite, bornite, galena and various sulfosalts, with some overlap between the mineral phases. Massive, stringer and disseminated sulfides from eight kuroko-type VMS deposits of the Eastern Black Sea province have a ³⁴S range of 0–7 per mil, consistent with the ³⁴S range of felsic igneous rocks. Sulfides in the massive ore at Madenköy (4.3–6.1 per mil) differ isotopically from sulfides in the stringer zone (6.3–7.2 per mil) suggesting a slightly increased input of H₂S derived from marine sulfate with time. Barite and coarse-grained gypsum have a ³⁴S range of 17.7–21.5 per mil, a few per mil higher than the ³⁴S value of contemporaneous seawater sulfate. The deposits may, therefore, have formed in restricted basins in which bacterial reduction of sulfate was taking place. Fine-grained, disseminated gypsum at Kutlular and Tunca has ³⁴S values (2.6–6.1 per mil) overlapping those of ore sulfides, indicating sulfide oxidation during waning stages of hydrothermal activity.     

Effect of acid mine drainage on a karst basin: a case study on the high-As coal mining area in Guizhou province,China

Acid mine drainage (AMD) is a common pollution in mining areas due to the oxidation of pyrite and associated sulfide minerals at mines, tailings and mine dumps. Elevated metals (Fe, Mn, Al) and metalloids (As, Hg) in AMD would deteriorate the local aquatic environment and influence the water supply. A carbonate basin with deposits of high-arsenic coal in Xingren County, southwestern China, was chosen to study the behavior of As and other chemical constituents along a river receiving AMD. Heavy metals (Fe, Mn) and major ions such as (Ca²⁺, Mg²⁺, Cl⁻, SO₄ ²⁻) in surface water, and As in sediment and surface water were analyzed. It was found that high concentrations of SO₄ ²⁻ (1,324–7,560 mg/L) and Fe (369–1,472 mg/L) in surface water were mainly controlled by the interactions between water and rocks such as the oxidation of pyrite in the local coal seams, precipitation and adsorption of iron minerals. Although ubiquitous carbonate minerals in the bedrock and the riverbeds, low pH (<3) water was maintained until 2 km downstream from the AMD source due to the Fe(hydro)oxide minerals coating on the surface of carbonate minerals to restrain the neutralization of acidic water. Moreover, the formation of Fe(hydro)oxide precipitations absorbed As was dominated the attenuation of As from water to sediment. Whereas, the dilution also played an important role in decrease of As in river water.     

Mineralogical and geochemical behavior of mill tailing material produced from lead-zinc skarn mineralization,Hanover, Grant County,New Mexico,USA

Mineral extraction and processing, especially metal mining, produces crushed and milled waste; such material, exposed to weathering, poses the potential threat of environmental contamination. In this study, mill tailings from inactive Pb-Zn mines in New Mexico, southwest USA, have been examined for their potential environmental impacts by means of detailed mineralogical and geochemical characterization. The principal ore minerals remaining in the tailings material are sphalerite, chalcopyrite, and very minor galena, smithsonite, and cerrusite, accompanied by the gangue minerals pyrite, pyrrhotite, magnetite, hematite, garnet, pyroxene, quartz, and calcite. White precipitate occurring on tailings surfaces is composed of gypsum and hydrated magnesium sulfates. Pyrite is mostly unaltered or shows only micron-scale rims of oxidation (goethite/hematite) in some surface samples. This iron oxide rim on pyrite is the only indication of weathering-derived minerals found by microscopy. There are variations in element concentrations with depth that reflect primary variations through time as the tailings ponds were filled. Cadmium and Zn concentrations increase with depth and Ag and Pb are low for the uppermost core samples, while Cu, Ni, and Co concentrations are generally high for the uppermost core samples. These elemental distributions indicate that little or no leaching has taken place since emplacement of the tailings because no accumulation or enrichment of these metals is observed in Hanover tailings, even in reducing portions of tailings piles. Element concentrations of surface samples surrounding the tailings reflect underlying mineralized zones rather than tailings-derived soil contamination. We observed no successive decreasing metal concentrations in prevalent wind directions away from the tailings. Stream sediment samples from Hanover Creek have somewhat elevated Zn, Cd, and Pb concentrations in areas that receive sediments from erosion of the tailings. However, input from tributaries downstream of the ponds appears to be principal source of heavy metals in Hanover Creek. The results of this study indicate that there is low risk for groundwater heavy-metal contamination from Hanover tailings. Tailings material do not show significant geochemical oxidation/alteration or metal leaching with depth. Our studies indicate that neutralizing minerals present in the tailings are sufficient to keep the tailings material chemically stable. Geochemically, however, tailings materials are being eroded and may pose a threat to Hanover Creek via siltation.     

Middle Miocene to Pleistocene sedimentary record of rift evolution in the southern Albert Rift (Uganda)

This study presents an almost complete Middle Miocene to Pleistocene sequence of synrift sediments in the western branch of the East African Rift. The studied succession is exposed in several patches on an eastward tilted block between the northern tip of the Rwenzori Block and the eastern shoulder of the Albert Rift. In this position, it reaches a maximum thickness of 600 m of which 350 m have been logged systematically by analysing lithofacies and sediment architecture. Stratigraphic subdivision of the succession relies on published biostratigraphic data of endemic mollusc associations and their correlation across East Africa. The synrift sediments encountered are siliciclastics ranging from clay to coarse gravel with gypsum and ferrugineous interlayers or impregnations. Lithofacies and architectural analysis indicate alluvial plain, delta plain, nearshore, delta front, or lacustrine depositional environments. Based on the vertical stacking pattern, prograding and retrograding trends of the depositional environments, and climatic indicators (e.g. conservation of feldspar, gypsum, and/or iron hydroxide precipitation), four evolutionary phases can be distinguished: (i) a first phase between ca. 14.5 and 10.0 Ma is characterised by bedload-dominated fluvial environment with massive sandy to gravelly bedforms, feldspar-rich sands, rare iron impregnations and relatively low accommodation space. This phase is interpreted as pre- and early synrift sedimentation under a semiarid climate. (ii) From ca. 10.0 to 4.5 Ma predominantly fine-grained siliciclastics were deposited in a distal fluvial plain to lacustrine setting characterised by limited accommodation space. Fluctuation of thin beds, dominance of clay and frequent iron impregnations point to a more humid climate with seasonality and weak tectonic activity. (iii) During the third phase between 4.5 and 2.0 Ma delta plain and nearshore deposits with frequent ferrugineous impregnations and rich mollusc associations occurred, indicating a humid period with lake-level highstands and accelerated subsidence. (iv) During the final sedimentary interval between 2.0 and 1.5 Ma gravel units reoccurred with less iron- but more carbonate and gypsum impregnations, and arkosic sandstones. This phase recorded a general aridisation trend most probably caused by the upcoming rain barrier of the Rwenzori Mountains together with accelerated rift-flank uplift and strong subsidence of the rift floor. The results of this study are of particular importance for delineating key controls on sedimentation in the Albert Rift.     

Coupled thermal, hydraulic and geochemical evolution of pyritic tailings in unsaturated column experiments

The evolution of pore-water and the composition of solid phases in the vadose zone of pyritic tailings was studied by means of unsaturated column experiments. Several columns of water-saturated mine tailings were dried during 125 days under controlled laboratory conditions. The columns were dismantled at four successive drying stages and the evolution of pore-water, mineralogy, water content and temperature was characterized.Sulfide and aluminosilicate minerals present in the waste dissolved, releasing sulfate and other solutes (mainly Fe, Zn, Cu, Al, Mg and Ca) to the pore-water. Evaporation caused a crust of efflorescent, water-soluble sulfates to develop over the complete top surface of the columns and into the pores of the underlying waste material. This crust, which has also been identified in the field, changed the hydraulic properties of the tailings and produced a decrease in the evaporation rate of the columns. Moreover, these water-soluble precipitates (mainly rozenite, szomolnokite, halotrichite, hexahydrite, mirabilite and gypsum) acted as temporary sinks for Cd, Pb, Co and Ni, which could be released to the surface run-off or the groundwaters during rainfall events under field conditions.Pore-water evolution was determined not only by geochemical processes (dissolution of sulfides and aluminosilicates, precipitation of secondary phases) but also by thermal and hydraulic processes. Progressive dilution was observed in the lower part of the columns. Dilution was caused by the thermally driven vapor flux from the top of the column to its colder bottom and subsequent condensation therein. This process, which may also occur in tailings under sub-arid climate, played a key role on the evolution of pore-water with increasing drying.