Supergene features and evolution of gossans capping massive sulphide deposits in the Iberian Pyrite Belt

Twelve massive sulphide deposits from the Iberian Pyrite Belt (IPB) show well-preserved iron caps, some of which were mined during the last century to recover precious metals (e.g., Tharsis, Rio Tinto, San Miguel). Field observations and correlation assays between the distinct mineral sequences at different deposits suggest that all the gossans were developed under similar conditions and have undergone the same geological events. All the gossans have a mushroom-like morphology in sharp contact with the underlying massive sulphide orebodies. In most cases these are located over an apparent supergene enrichment zone rich in secondary sulphides. Some gossans extend into tongues of alluvial heterolithic breccias consisting of eroded transported gossans displaced as far as several hundred meters away from their sources. The distribution of major minerals throughout the gossan profiles (goethite, hematite, quartz and jarosite) and the statistical analysis of the geochemical data distinguish three separate zones, with gradual contacts roughly parallel to the current topography: (1) the lower zone dominated by goethite and subordinate jarosite, with significant enrichment in S, As, P, Pb, Sn, Sb, Ag and Au; (2) the middle or principal zone dominated by goethite and lacking jarosite, which is depleted in S, and As, as well as heavy and precious metals; and (3) the upper zone near the surface, mainly composed of hematite and quartz with only weak anomalies in P, Pb and Sn. The origin and variations occurred in the profiles are explained by a three-stage process. This involves an initial acidic stage of gossan development centred on the oxidation of sulphides that lead to the formation of the first Fe-rich oxyhydroxides and sulphates (mainly goethite and jarosite, respectively). Over time, a progressive stage of maturity is reached progressively downwards through the gossan profile due to the intensification of the oxidation and leaching processes. The ongoing gossan formation produced alteration and reprecipitation of pre-existing oxyhydroxides, the loss of the majority of the previously sorbed heavy metals, and a major dilution of trace elements especially in the zones near the surface. The main results of this stage of formation are the production of heavy metal-depleted oxyhydroxides, most commonly goethite and hematite, and the disappearance of jarosite. Subsequently, local uplift of the gossanous rocks by neotectonic movements facilitated the rejuvenation of the oxidation of the ores. This final stage complicated the previously developed zonation with the formation of jarosite in mature areas. Possible major breaks in this gossan development ocurred in Messinian times (7–8 Ma) and at the beginning of the Early Quaternary (1–2 Ma?).     

Distribution and partitioning of major and trace elements in pyrite-bearing sediments of a Mediterranean coastal lagoon

The formation of iron sulphide minerals exerts significant control on the behaviour of trace elements in sediments. In this study, three short sediment cores, retrieved from the remote Antinioti lagoon (N. Kerkyra Island, NW Greece), are investigated concerning the solid phase composition, distribution, and partitioning of major (Al, Fe) and trace elements (Cd, Cu, Mn, Pb, and Zn). According to ²¹⁰Pb, the sediments sampled correspond to depositions of the last 120 years. The high amounts of organic carbon (4.1–27.5%) result in the formation of Fe sulphides, predominantly pyrite, already at the surface sediment layers. Pyrite morphologies include monocrystals, polyframboids, and complex FeS–FeS₂ aggregates. According to synchrotron-generated micro X-ray fluorescence and X-ray absorption near-edge structure spectra, authigenically formed, Mn-containing, Fe(III) oxyhydroxides (goethite type) co-exist with pyrite in the sediments studied. Microscopic techniques evidence the formation of galena, sphalerite and CuS, whereas sequential extractions show that carbonates are important hosts for Mn, Cd, and Zn. However, significant percentages of non-lattice held elements are bound to Fe/Mn oxyhydroxides that resist reductive dissolution (on average 60% of Pb, 46% of Cd, 43% of Zn and 9% of Cu). The partitioning pattern changes drastically in the deeper part of the core that is influenced by freshwater inputs. In these sediments, the post-depositional pyritization mechanism, illustrated by overgrowths of Fe monosulphides on pre-existing pyrite grains, results in relatively high degree of pyritization that reaches 49% for Cd, 66% for Cu, 32% for Zn and 7% for Pb.     

Geological and anthropogenic influences on sediment metal composition in the upper Paracatu River Basin, Brazil

This work reports a geochemical study of sediments from the upper Paracatu River Basin. The objective is to define the influences of Au, Zn, and Pb mineral deposits and mining activities on the sediment metal sources, distribution, and accretion. The samples were analyzed using ICP/OES, AAS, and XRD techniques and were treated with principal components analysis and the geo-accumulation index. The main geochemical processes that control the sediment composition are pyrite oxidation, muscovite weathering, carbonate dissolution, and the erosion of oxisols enriched with Zn and Pb. The upper Rico Stream has high Al, Fe, Cu, Cr, Co, and Mn concentrations due erosion of oxisols and pyrite oxidation and muscovite alteration present in the parental rock. The artisanal alluvial gold mining increased the primary rock-minerals?? weathering and Hg sediment concentration. The lower Escuro River and Santa Catarina Stream are enriched with Zn and Pb due the erosion of metal-rich soils formed over galena, sphalerite, calamine, and willemite mineral deposits located upstream. Elements such as Ca, Mg, and Ba have low concentrations throughout the sampled area due the high solubility of these metals-bearing minerals. The dispersion of metals is limited by the basin geomorphology and their affinity to silt-clayey minerals and Fe and Mn oxides and hydroxides in circumneutral pH waters.     

Arsenic and metal mobility from Au mine tailings in Rodalquilar (Almería,SE Spain)

In the old mining area of Rodalquilar, mine wastes, soil and sediments were characterized and the results revealed high concentration of Au, Ag, As, Bi, Cu, Fe, Mn, Pb, Se, Sb and Zn in tailings and sediments. The contaminant of greatest environmental concern is As. The mean concentration in the tailings was 679.9, and 345 mg/kg in the sediments of Playazo creek. The groundwater samples from the alluvial aquifer showed high concentration of Al, As, Cd, Fe, Hg, Mn, Ni, Pb, Se, Sb and Zn and very high concentration of chloride and sulfate, which were above the concentration defined in the European standards for drinking water. The presence of As in groundwater may be caused by the oxidation of arsenian pyrite, the possible As desorption from goethite and ferrihydrite and the jarosite dissolution. Groundwater concentrations of Cd, Fe, Mn, and possibly Cu, were associated with low values of Eh, indicating the possible dissolution of oxy-hydroxides of Fe and Mn. The mobility of metals in the column experiments show the release of Al, Fe, Mn, Cr, Cu, Ni, V and Zn in significant concentrations but below the detected values in groundwater. However, As, Cd, Sb, Se Pb and Au, are generally mobilized in concentrations above the detected values in groundwater. The possible mass transfer processes that could explain the presence of the contaminants in the aquifer and the leachates was simulated with the PHREEQC numerical code and revealed the possible dissolution of the following mineral phases: jarosite, natrojarosite, arsenian pyrite, alunite, chlorite, kaolinite and calcite.     

Heavy metal partitioning in river sediments severely polluted by acid mine drainage in the Iberian Pyrite Belt

This study provides a geochemical partitioning pattern of Fe, Mn and potentially toxic trace elements (As, Cd, Cr, Cu, Ni, Pb, Zn) in sediments historically contaminated with acid mine drainage, as determined by using a 4-step sequential extraction scheme. At the upperstream, the sediments occur as ochreous precipitates consisting of amorphous or poorly crystalline oxy-hydroxides of Fe, and locally jarosite, whereas the estuarine sediments are composed mainly of detrital quartz, illite, kaolinite, feldspars, carbonates and heavy minerals, with minor authigenic phases (gypsum, vivianite, halite, pyrite). The sediments are severely contaminated with As, Cd, Cu, Pb and Zn, especially in the vicinity of the mining pollution sources and some sites of the estuary, where the metal concentrations are several orders of magnitude above background levels. Although a significant proportion of Zn, Cd and Cu is present in a readily soluble form, the majority of heavy metals are bonded to reducible phases, suggesting that Fe oxy-hydroxides have a dominant role in the metal accumulation. In the estuary, the sediments are potentially less reactive than in the riverine environment, because relevant concentrations of heavy metals are immobilised in the crystalline structure of minerals.     

Mineralogical controls on element dispersion in regolith over two mineralised shear zones near the Peak, Cobar, New South Wales

Effective exploration for polymetallic ore deposits in the Cobar region is hampered by incomplete knowledge of the mineralogical controls on element dispersion in the different regolith-landform settings throughout the area. A detailed mineralogical and geochemical study of regolith profiles over two major mineralised shear zones in a strongly weathered but dominantly erosional setting has delineated the important host minerals for a range of base metal cations. Iron oxides/oxyhydroxides, particularly goethite and to a much lesser extent hematite, are major hosts for Pb, Cu, and Zn as substituted/adsorbed cations and as constituents of associated or intergrown minerals, probably including members of the jarosite–alunite group. Correlations between elements and major regolith minerals suggest that goethite is also a host phase for As, Bi and Sb. Minor manganese minerals, including lithiophorite and cryptomelane group minerals, also host base metals in appreciable amounts. No clear association was found between gold and any particular secondary mineral. It is likely that gold is present largely as elemental gold particles associated with a range of minerals.Sampling strategies for geochemical exploration in variably leached and stripped regolith in the Cobar area should take into account the relative abundance of goethite and manganese oxides/oxyhydroxides within the profiles and overlying lag. Goethite would appear to be the preferred sampling medium for base metals. Highly ferruginous lag has a high proportion of hematite with variable maghemite and very low manganese oxide contents. Most of the base metal content in this surface material is strongly bound to the crystalline oxides/oxyhydroxides. More work is required to understand the effects of surface transformation of goethite to hematite and maghemite on the mobility and distribution of base metal cations in soil and ferruginous lags.     

Mine drainage from the weathering of sulfide minerals and magnetite

Pyrite and pyrrhotite are the principal minerals that generate acid drainage in mine wastes. Low-pH conditions derived from Fe-sulfide oxidation result in the mobilization of contaminant metals (such as Zn, Cd, Ni and Cr) and metalloids (such as As) which are of environmental concern. This paper uses data from detailed mineralogical and geochemical studies conducted at two Canadian tailings impoundments to examine the mineralogical changes that pyrite, pyrrhotite, sphalerite and magnetite undergo during and after sulfide oxidation, and the subsequent release and attenuation of associated trace elements. The stability of sphalerite in tailings impoundments generally is greater than that of pyrrhotite, but less than pyrite. Dissolved Ni and Co derived from Fe sulfides, and to a lesser extent, dissolved Zn and Cd from sphalerite, are commonly attenuated by early-formed Fe oxyhydroxides. As oxidation progresses, a recycling occurs due to continued leaching from low-pH pore waters and because the crystallinity of Fe oxyhydroxides gradually increases which decreases their sorptive capacity. Unlike many other elements, such as Cu, Pb and Cr, which form secondary minerals or remain incorporated into mature Fe oxyhydroxides, Zn and Ni become mobile. Magnetite, which is a potential source of Cr, is relatively stable except under extremely low-pH conditions. A conceptual model for the sequence of events that typically occurs in an oxidizing tailings impoundment is developed outlining the progressive oxidation of a unit of mine waste containing a mixed assemblage of pyrrhotite and pyrite.     

Heavy metal anomalies in the Tinto and Odiel River and estuary system,Spain

The Tinto and Odiel rivers drain 100 km from the Rio Tinto sulphide mining district, and join at a 20-km long estuary entering the Atlantic Ocean. A reconnaissance study of heavy metal anomalies in channel sand and overbank mud of the river and estuary by semi-quantitative emission dc-arc spectrographic analysis shows the following upstream to downstream ranges in ppm (μg g^?1): As 3,000 to <200, Cd 30 to <0.1, Cu 1,500 to 10, Pb 2,000 to <10, Sb 3000 to <150, and Zn 3,000 to <200. Organic-rich (1.3–2.6% total organic carbon, TOC), sandysilty overbank clay has been analyzed to represent suspended load materials. The high content of heavy metals in the overbank clay throughout the river and estuary systems indicates the importance of suspended sediment transport for dispersing heavy metals from natural erosion and anthropogenic mining activities of the sulfide deposit. The organic-poor (0.21–0.37% TOC) river bed sand has been analyzed to represent bedload transport of naturally-occurring sulfide minerals. The sand has high concentrations of metals upstream but these decrease an order of magnitude in the lower estuary. Although heavy metal contamination of estuary mouth beach sand has been diluted to background levels estuary mud exhibits increased contamination apparently related to finer grain size, higher organic carbon content, precipitation of river-borne dissolved solids, and input of anthropogenic heavy metals from industrial sources. The contaminated estuary mud disperses to the inner shelf mud belt and offshore suspended sediment, which exhibit metal anomalies from natural erosion and mining of upstream Rio Tinto sulphide lode sources (Pb, Cu, Zn) and industrial activities within the estuary (Fe, Cr, Ti). Because heavy metal contamination of Tinto-Odiel river sediment reaches or exceeds the highest levels encountered in other river sediments of Spain and Europe, a detailed analysis of metals in water and suspended sediment throughout the system, and epidemiological analysis of heavy metal effects in humans is appropriate.     

The distribution of elements between co-existing phases in some marine ferromanganese-oxide deposits

Analyses of ferromanganese oxides from the Indian and Atlantic Oceans for the elements Mn, Fe, Co, Ni, Cu, Zn, Pb, Ca, AI, Ti, Cr and Cd have helped to elucidate some of the controls on their geochemistry. In most samples virtually all of the Mn and much of the Fe are present as acid-reducible phyllomanganates and Fe oxyhydroxides respectively. By contrast, in samples in which goethite was identified, much of the Fe and significant amounts of the Mn. are not acid-reducible. The partition patterns of the minor elements reflect to varying extents the mineralogy of the hydrous Mn and Fe oxide phases. In δ-Mn-O₂-rich samples the ratio of adsorbed to crystallographically-bound Ni. Cu and Zn, is higher than in todorokite-rich samples, but in each case these metals are virtually entirely phyllomanganate-associated. In goethite-rich samples, however, significant amounts of Ni. Cu and Zn may be associated with the goethite itself rather than with phyllomanganate minerals. Cobalt shows very close association with the phyllomanganates irrespective of the specific mineralogy, but Pb behaves in a way which cannot yet be fully characterised. The non-reducible fractions of the samples contain most of the Ca, Al. Ti and Cr. Some Ca however is also present in the phyllomanganates.     

Trace metal occurrence in a mineralised and a non-mineralised spodosol in northern Sweden

In order to determine the metal-bearing phases with special emphasis on Cu, a sequential extraction has been carried out on seven soil samples from a sulphide-bearing spodosol profile in Liikavaara Östra, close to the Aitik Copper Mine in northern Sweden. A reference spodosol profile with very low abundances of sulphides located far from anthropogenic emissions was also studied. Five fractions were selected for the extraction: (I) CH₃COONa-extractable (exchangeable/adsorbed/carbonate); (II) Na₄P₂O₇-extractable (labile organics); (III) 0.25 M NH₂OH·HCl-extractable (amorphous Fe oxyhydroxides/Mn oxides); (IV) 1 M NH₂OH·HCl-extractable (crystalline Fe oxides); and (V) KClO₃/HCl-extractable (organics and sulphides). The distribution of trace elements (Co, Cr, Cu, Ni, Pb and Zn) in the profile in Liikavaara Östra is different from that in the reference profile. Possible explanations for these differences are (i) the presence of sulphides in the soil, (ii) atmospheric deposition of dust derived from mining activities at the Aitik Copper Mine, and (iii) mineralogical heterogeneities inherited from the deposition of the till. There is no straightforward correlation between the amount of the extracted phases and the metal extractability in the soils. This fact indicates that other factors are important for the retention of trace metals as well. The data presented in this study suggest that Co, Cr and Ni, to a fairly large extent, are associated with the organic matter in the B-horizon in both profiles, while in the C-horizon in Liikavaara Östra, sulphides are probably the more important carriers of these elements. For Co and Ni, Fe oxyhydroxides seem to be important. Most of the Cr occurred in the residual remaining after the leaching procedure. Copper and Zn seem to be associated with the organic matter to some extent in the B-horizon. The concentration of Cu in the C-horizon in Liikavaara Östra is high (2310 ppm), but only a very small fraction is likely to be hosted by sulphides. It is concluded that the major part of Cu in the C-horizon and a prominent fraction in the B-horizon in Liikavaara Östra are associated with some secondary phase that is extractable during extractions III and IV. Possible candidates for this phase are goethite and inclusions of native Cu in weathered biotite.     

Weathering of the New Albany Shale, Kentucky, USA: I. Weathering zones defined by mineralogy and major-element composition

Comprehensive understanding of chemical and mineralogical changes induced by weathering is valuable information when considering the supply of nutrients and toxic elements from rocks. Here minerals that release and fix major elements during progressive weathering of a bed of Devonian New Albany Shale in eastern Kentucky are documented. Samples were collected from unweathered core (parent shale) and across an outcrop excavated into a hillside 40 year prior to sampling. Quantitative X-ray diffraction mineralogical data record progressive shale alteration across the outcrop. Mineral compositional changes reflect subtle alteration processes such as incongruent dissolution and cation exchange. Altered primary minerals include K-feldspars, plagioclase, calcite, pyrite, and chlorite. Secondary minerals include jarosite, gypsum, goethite, amorphous Fe(III) oxides and Fe(II)-Al sulfate salt (efflorescence). The mineralogy in weathered shale defines four weathered intervals on the outcrop—Zones A–C and soil. Alteration of the weakly weathered shale (Zone A) is attributed to the 40-a exposure of the shale. In this zone, pyrite oxidization produces acid that dissolves calcite and attacks chlorite, forming gypsum, jarosite, and minor efflorescent salt. The pre-excavation, active weathering front (Zone B) is where complete pyrite oxidation and alteration of feldspar and organic matter result in increased permeability. Acidic weathering solutions seep through the permeable shale and evaporate on the surface forming abundant efflorescent salt, jarosite and minor goethite. Intensely weathered shale (Zone C) is depleted in feldspars, chlorite, gypsum, jarosite and efflorescent salts, but has retained much of its primary quartz, illite and illite–smectite. Goethite and amorphous FE(III) oxides increase due to hydrolysis of jarosite. Enhanced permeability in this zone is due to a 14% loss of the original mass in parent shale. Denudation rates suggest that characteristics of Zone C were acquired over 1 Ma. Compositional differences between soil and Zone C are largely attributed to illuvial processes, formation of additional Fe(III) oxides and incorporation of modern organic matter.     

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     

The mineralogy and geochemistry of the weathering profile of the Teutonic Bore Cu-Pb-Zn-Ag sulphide deposit

The Cu-Zn-Pb-Ag sulphide deposit at Teutonic Bore is a stratiform deposit of apparent volcanogenic origin in Archaean metabasaltic rocks in the Yilgarn Block of Western Australia. The area has moderate topographic relief, and has been weathered to a depth of about 75 m, which is about 40 m below the present water table. Part of the deposit, before mining commenced, was exposed at the surface as a gossan, samples of which contained between 500 and 1000 ppm Zn, Cu and Sb, and in excess of 1000 ppm Pb, Sn and As.The primary ore has weathered to supergene sulphides, then to an oxide assemblage containing abundant secondary ore minerals, then to leached oxides, and finally to surface gossan. The strong geochemical signature of the gossan is attributed partly to elements chemically combined with Fe oxides, partly to the presence of several stable secondary ore minerals, and partly to the presence of unweathered primary minerals. Diagnostic boxwork textures, except for those of pyrite, are not well developed.     

Metal speciation and attenuation in stream waters and sediments contaminated by landfill leachate

The degree of metal contamination (Zn, Pb, Cu, Ni, Cd) has been investigated in the vicinity of an old unmonitored municipal landfill in Prague, Czech Republic, where the leachate is directly drained into a surface stream. The water chemistry was coupled with investigation of the stream sediment (aqua regia extract, sequential extraction, voltammetry of microparticles) and newly formed products (SEM/EDS, XRD). The MINTEQA2 speciation-solubility calculation showed that the metals (Zn, Pb, Cu, Ni) are mainly present as carbonate complexes in leachate-polluted surface waters. These waters were oversaturated with respect to Fe(III) oxyhydroxides, calcite (CaCO₃) and other carbonate phases. Three metal attenuation mechanisms were identified in leachate-polluted surface waters: (i) spontaneous precipitation of metal-bearing calcite exhibiting significant concentrations of trace elements (Fe, Mn, Mg, Sr, Ba, Pb, Zn, Ni); (ii) binding to Fe(III) oxyhydroxides (mainly goethite, FeOOH) (Pb, Zn, Cu, Ni); and (iii) preferential bonding to sediment organic matter (Cu). These processes act as the key scavenging mechanisms and significantly decrease the metal concentrations in leachate-polluted water within 200 m from the direct leachate outflow into the stream. Under the near-neutral conditions governing the sediment/water interface in the landfill environment, metals are strongly bound in the stream sediment and remain relatively immobile.     

Minerals in the Triassic carbonaceous silicites of Sikhote Alin

Over 60 minerals, including native elements, intermetallic compounds, haloids, sulfides, sulfates, arsenides, oxides and hydroxides, silicates, borosilicates, wolframates, phosphates and REE phosphates, were established in Triassic siliceous rocks of Sikhote Alin. Allothigenic and authigenic minerals in the carbonaceous silicites were formed over a long period through several stages. Judging from morphology, chemical composition, and structural position, K-feldspar (K-Fsp), illite, kaolinite, metahalloysite, monazite, xenotime, zircon, rutile, or its polymorphs are the disintegration products of sialic rocks of continental crust. Authigenic sulfides are dominated by diagenetic pyrite (fine-crystalline, microglobular, framboidal, as well as those developed after biogenic siliceous and carbonate fragments), which has been formed prior to precipitation of siliceous cement and lithification of siliceous rocks. Most of other sulfides (sphalerite, galena, chalcopyrite, pyrrhotite, argentite, pentlandite, antimonite, ulmanite, and bravoite), arsenides and sulfoarsenides (arsenopyrite, nickeline, skutterudite, cobaltite, glaucodot, and gersdorffite), wolframates (scheelite and wolframite), intermetallides (Cu₂Zn, Cu₃Zn₂, Cu₃Zn, Cu₄Zn, CuSn, Cu₄Sn, Cu₈Sn, Cu₄Zn₂Ni, Ni₂Cu₂Zn, Ni₄Cd), and native elements (Au, Pd, Ag, Cu, Fe, W, Ni, Se) were crystallized later (during catagenesis after the lithification and brecciation of siliceous beds) from metals involved in the easily mobile fractions of bitumens. Supergene mineral formation was mainly expressed in the sulfide oxidation and replacement of diagenetic pyrite by jarosite and iron hydroxides.     

Heavy metal contamination in the Arieş river catchment, western Romania: Implications for development of the Roşia Montană gold deposit

The Abrud–Arieş river system, western Romania, is subject to ongoing mining activity associated with Cu, Pb and Zn ore extraction. The catchment contains what is believed to be Europe's largest unutilized Au deposit at Roşia Montană that is planned to be exploited by open-cast mining techniques. The magnitude and environmental significance of metal (Cd, Cu, Pb, and Zn) concentrations in surface water and river channel sediment have been investigated along a 140 km reach of the Rivers Abrud and Arieş and 9 tributaries affected by mining. The speciation of sediment-bound metals was established using a 4-stage sequential extraction procedure (SEP) that identified four chemical phases: (1) exchangeable, (2) Fe/Mn oxides, (3) organic matter/sulphides and (4) residual. Peak solute and sediment-bound metal concentrations were found to occur in the River Abrud downstream of the EM Bucium mine and in mining-affected tributaries, with up to 71% of sites containing sediment metal concentrations in excess of Dutch intervention values. The River Arieş was found to be much less polluted than the River Abrud, with only Cu showing concentrations above guideline values, as a consequence of porphyry Cu mineralization in the catchment. The magnitude and spatial extent of metal pollution is influenced by local physico-chemical conditions and hydrological linkages between mining and local river systems. Sediment-bound Cd and Zn were found to be predominantly associated with the exchangeable phase of the sediment (9–74% and 6–65%, respectively), whilst Fe/Mn oxides (5–76%) and organic matter/sulphides (1–45%) generally accounted for a majority of Pb and Cu partitioning, respectively. Sites of environmentally significant sediment-metal pollution were identified in the Rivers Abrud and Arieş where exchangeable metal concentrations exceeded Dutch intervention values. The implications of metal contamination in the Arieş river basin to the proposed mining development at Roşia Montana are discussed in relation to other contaminated Romanian catchments and with the EU Water Framework Directive.     

Supergene alteration of sulphides,VI. The binding of Cu,Ni, Zn,Co and Pb with gossan (iron-bearing) minerals

The results of experimentally coprecipitating the base metals Cu, Ni, Zn, Co and Pb with iron as it is oxidised and hydrolised are presented in conjunction with the data from anodically weathering 19 different sulphide ore electrodes.At pH-values above 6 the base metals are shown to be retained in the solid precipitates with Fe“Ni, Fe“Zn and Fe“Co pyroaurite-type phases forming. A 7–8-Å interlayer spacing predominates at higher pH while at the pH of 6–7 where the base metals become more soluble, a 10–11-Å spacing forms. The Fe“Cu system gives posnjakite and brochantite phases that are likely to have a high Fe content, as well as the oxides tenorite and cuprite. The base metals can be leached out of these precipitates if they are acted on by weakly acid leachants, but alkaline leaching shows retention of the base metals.Below pH 6 the base metals are more soluble, with Cu and Pb being retained to some degree in the precipitates as Fe-oxyhydroxide minerals form.In the light of experiments that show the mechanisms involved in the formation of all of these phases, two mechanisms for the formation of iron minerals during the weathering of sulphides to gossans are discussed. One at higher pH that gives rise to retention of base metals with the iron minerals, and the other giving rise to a low pH and the solubilising of the base metals.     

The spatial distribution and source of arsenic, copper, tin and zinc within the surface sediments of the Fal Estuary, Cornwall, UK

ABSTRACT Estuarine sediments commonly form major sinks for contaminants released during industrial activity. Many industrial processes lead to the release of metals initially in solution, which can then be adsorbed on to, for example, Fe hydroxides or clay minerals. However, in the mining industry, there are two major contaminant waste streams: (1) metals discharged in solution via mine drainage; and (2) particulate grains of the ore‐forming or related minerals released after ore processing. The release of particulate waste can have a major long‐term impact on environmental geochemistry. In this study, we have mapped the distribution of arsenic, copper, tin and zinc within the surficial sediments of the Fal Estuary, Cornwall, UK, an area that drains a historically important polymetallic mining district. There are clear spatial variations in the contaminants, with the highest levels (> 2800 p.p.m. As, > 5000 p.p.m. Cu, > 3000 p.p.m. Sn and > 6000 p.p.m. Zn) within Restronguet Creek on the western side of the estuary. Mineralogical studies show that small (< 20 µm) grains of detrital arsenopyrite, chalcopyrite, cassiterite and sphalerite are very abundant within the surface sediments. Most of the sulphide grains are fractured, but mineralogically unaltered, although some grains show alteration rims caused by oxidation of the sulphides. The geochemistry and mineralogy are indicative of sediment supply from the discharge of particulate waste into the estuary during historical mining activity. Subsequently, this particulate waste has been largely physically and biologically reworked within the surface sediments. Although considerable effort has been made to minimize contaminants released via mine drainage into the estuary, the potential flux of contaminants present within the intertidal and subtidal sediments has not been addressed. Benthic invertebrates living within the area have adapted to be metal tolerant, and it is likely that the dominant source of bioavailable metals is a result of alteration of the particulate mine waste present within the intertidal and subtidal sediments.     

Different types of fine-grained sediments associated with acid mine drainage in the Libiola Fe–Cu mine area (Ligurian Apennines,Italy)

Different types of fine-grained chemical precipitates were characterized in the surroundings of the pyrite-chalcopyrite mine of Libiola (Northern Italy). Both water chemistry and sediment composition were used to investigate metal mobility near the mine area. Local drainage waters were very acidic (with a pH as low as 2.5) and were rich in dissolved metals (Fe, Al, Cu, Zn, Mn, Ni). Sediments associated with low pH water (pH <4.5) were ochreous mixtures of schwertmannite and goethite with traces of jarosite. Their chemistry was dominated by Fe and they had, compared to other sediments investigated, low concentrations of other metals. When the acidity decreased gradually, other precipitates formed. At a pH of approximately 5, a poorly crystalline, whitish, Al-rich precipitate occurred. At a pH between 6 and 7, a poorly crystalline, blue, Cu (Zn) rich phase was present. These “sequential” precipitation events progressively reduced the metal loading typical of the acidic mine water when there was a gradual mixing with normal water. When a sudden mixing between normal waters (pH ∼8, Ca–HCO₃, low metal bearing) and acidic waters took place, a rapid flocculation occurred of mixed precipitates containing Fe, Al and trace elements.     

Mineralogical controls on mine drainage of the abandoned Ervedosa tin mine in north-eastern Portugal

The Ervedosa Mine, in north-eastern Portugal, has Sn-bearing quartz veins containing cassiterite and sulphides that cut Silurian schists and a Sn-bearing muscovite granite. These veins were mined for Sn and As₂O₃ until 1969. Cassiterite, the main Sn ore, has alternate lighter and darker growth-zones. The darker zones are richer in Fe, Nb, Ta and Ti, but poorer in Sn than the adjoining lighter zones. Exsolution blebs of ferrocolumbite, manganocolumbite, Ti ixiolite, rutile, ilmenite and rare wolframite were found in the darker zones. Arsenopyrite is the most abundant sulphide and contains inclusions of pyrrhotite, bismuth, bismuthinite and matildite. Other sulphides are pyrite, sphalerite, chalcopyrite and stannite. Secondary solid phases consisting mainly of hydrate sulphate complexes of Al, Fe, Ca and Mg (aluminocopiapite, copiapite, halotrichite, pickeringite, gypsum and alunogen, meta-alunogen) occur at the surface of the Sn-bearing quartz veins and their wall rocks (granite and schist), while oxides, hydroxides, arsenates and residual mineral phases (albite, muscovite and quartz) occur in mining tailings. Toxic acid mine waters (acid mine drainage AMD), which have high conductivity and significant concentrations of As, SO₄ and metal (Cu, Zn, Pb, Fe, Mn, Cd, Ni and Co), occur in an area directly affected by the mine. Surface stream waters outside this area have low conductivity and a pH that is almost neutral. Metal and As concentrations are also lower. Stream waters within the impact area have an intermediate composition, falling between that of the AMD and the natural stream waters outside impact area. Waters associated directly with mineralised veins must not be used for human consumption or agriculture.