Trace elements contamination of agricultural soils affected by sulphide exploitation (Iberian Pyrite Belt,Sw Spain)

Agricultural soils of the Riotinto mining area (Iberian Pyrite Belt) have been studied to assess the degree of pollution by trace elements as a consequence of the extraction and treatment of sulphides. Fifteen soil samples were collected and analysed by ICP-OES and INAA for 51 elements. Chemical analyses showed an As–Cu–Pb–Zn association related with the mineralisation of the Iberian Pyrite Belt. Concentrations were 19–994 mg kg⁻¹ for As, 41–4,890 mg kg⁻¹ for Pb, 95–897 mg kg⁻¹ for Zn and of 27–1,160 mg kg⁻¹ for Cu. Most of the samples displayed concentrations of these elements higher than the 90th percentile of the corresponding geological dominium, which suggests an anthropogenic input besides the bedrock influence. Samples collected from sediments were more contaminated than leptosols because they were polluted by leachates or by mining spills coming from the waste rock piles. The weathering of the bedrock is responsible for high concentrations in Co, Cr and Ni, but an anthropogenic input, such as wind-blown dust, seems to be indicative of the high content of As, Cu, Pb and Zn in leptosols. The metal partitioning patterns show that most trace elements are associated with Fe amorphous oxy-hydroxides, or take part of the residual fraction. According to the results obtained, the following mobility sequence is proposed for major and minor elements: Mn, Pb, Cd, > Zn, Cu > Ni > As > Fe > Cr. The high mobility of Pb, Cu and Zn involve an environmental risk in this area, even in soils where the concentrations are not so high.     

Mineralogical and geochemical alteration of Hitura sulphide mine tailings with emphasis on nickel mobility and retention

Weathering of Hitura (W Finland) nickel sulphide mine tailings and release of heavy metals into pore water was studied with mineralogical (optical and electron microscopy, X-ray diffraction) and geochemical methods (selective extractions). Tailings were composed largely of serpentine, micas and amphiboles with only minor carbonates and sulphides. Sulphides, especially pyrrhotite, have oxidized intensively in the shallow tailings in 10–15 years, but a majority of the tailings have remained unchanged. Oxidation has resulted in depletion of carbonates, slightly decreased pH, and heavy metal (Ni, Zn) release in pore water as well as in the precipitation of secondary Fe precipitates. Nevertheless, in the middle of the tailings area, where the oxidation front moves primarily downward, released heavy metals have been adsorbed and immobilized with these precipitates deeper in the oxidation zone. In contrast to what was seen in pore water pH, but in accordance with static tests of the previous studies, the neutralisation potential ratio (NPR) calculated based on the mineralogical composition and the total sulphur content suggested that tailings are ‘not potentially acid mine drainage (AMD) generating’. However, the calculated buffering capacity of the tailings resulted largely from the abundant serpentine because of the low carbonate content. Despite its slow weathering rate, serpentine may buffer the acidity to some extent through ion exchange processes in fine ground tailings. Nevertheless, in practice, acid production capacity of the tailings depends primarily on the balance between Ca–Mg carbonates and iron sulphides. NPR calculation based on carbonate and sulphur contents suggested, that the Hitura tailings are ‘likely AMD generating’. The study shows that sulphide oxidation can be significant in mobilisation of heavy metals even in apparently non-acid producing, low sulphide tailings. Therefore, prevention of oxygen diffusion into tailings is also essential in this type of sulphide tailings.     

Geochemical stream sediment survey in Winder Valley, Balochistan, Pakistan

A pilot scale geochemical survey of sediments from the Winder Stream (SW Pakistan) and its tributaries was carried out. The Winder Stream mainly receives sediment from the southern extensions of the Mor and Pab Ranges in the District of Lasbela (Balochistan). In these two mountain ranges, rocks from Jurassic to Cretaceous age are exposed. Rocks of the Ferozabad Group comprise of carbonates and siliciclastics of Lower–Middle Jurassic age and occupy the dominant part of the Mor Range. These strata host syngenetic and epigenetic Zn–Pb–Ba mineralizations of Stratiform Sediment-Hosted (SSH) and Mississippi Valley Type (MVT) deposits.Quantitative estimates of mobile and immobile elements were made from active stream sediments of the Winder stream and its tributaries. The samples were analyzed for Ag, Zn, Pb, Cu, Ni, Co, V, Mn, Fe and Ba using atomic absorption spectroscopy. The abundance of these elements is discussed in relation to local geological conditions such as bedrock, climate, weathering, mobility and pH of the dispersing waters. A number of Zn anomalies have been distinguished in the study area. Kharrari (Zn, 360 ppm), Sand (Zn, 340 ppm) and Draber (Zn, 210 ppm) are demarcated as new areas for Zn mineralization. The present study also indicates prospects of Ag, Cu and V in the rocks of the Mor Range.Relationships between various elements have been identified from scattergrams and reflect genetic associations. Whereby the positive correlation between Cu–Zn (0.55, n=18) and Cu–Pb (0.63) is related to possible sulphide mineralization.     

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.     

细菌浸铜技术在紫金山铜矿的应用

介绍了生物浸矿技术在紫金山铜矿的应用及在这一过程中发现的一些问题，并提出了有待进一步解决的一些问题。     

Pressure fluctuations and the formation of the PGE-rich Merensky and chromitite reefs, Bushveld Complex

The Merensky Reef and the underlying Upper Group 2 chromitite layer, in the Critical Zone of the Bushveld Complex, host much of the world’s platinum-group element (PGE) mineralization. The genesis is still debated. A number of features of the Merensky Reef are not consistent with the hypotheses involving mixing of magmas. Uniform mixing between two magmas over an area of 150 by 300 km and a thickness of 3–30 km seems implausible. The Merensky Reef occurs at the interval where Main Zone magma is added, but the relative proportions of the PGE in the Merensky Reef are comparable to those of the Critical Zone magma. Mineral and isotopic evidence in certain profiles through the Merensky Unit suggest either mixing of minerals, not magmas, and in one case, the lack of any chemical evidence for the presence of the second magma. The absence of cumulus sulphides immediately above the Merensky Reef is not predicted by this model. An alternative model is proposed here that depends upon pressure changes, not chemical processes, to produce the mineralization in chromite-rich and sulphide-rich reefs. Magma was added at these levels, but did not mix. This addition caused a temporary increase in the pressure in the extant Critical Zone magma. Immiscible sulphide liquid and/or chromite formed. Sinking sulphide liquid and/or chromite scavenged PGE (as clusters, nanoparticles or platinum-group minerals) from the magma and accumulated at the floor. Rupturing of the roof resulted in a pressure decrease and a return to sulphur-undersaturation of the magma.     

Interactions between sediment chemistry and frenulate pogonophores (Annelida) in the north-east Atlantic

The small frenulate pogonophores (Annelida: Pogonophora a.k.a. Siboglinidae) typically inhabit muddy sediments on the continental slope, although a few species occur near hydrothermal vents and cold seeps. We present data on the distribution and habitat characteristics of several species on the European continental shelf and slope from 48°N to 75°N and show how the animals interact with the chemistry of the sediments. The environments inhabited include: shallow (30 m), organic-rich, fjord sediments; slope sediments (1000–2200 m) and methane seeps at 330 m depth. All the species studied obtain nutrition from endosymbiotic bacteria. They take up reduced sulphur species, or in one case, methane, through the posterior parts of their tubes buried in the anoxic sediment. We conclude that most species undertake sulphide ‘mining’, a mechanism previously demonstrated in the bivalves Lucinoma borealis and Thyasira sarsi. These pogonophores participate in the sulphur cycle and effectively lower the sulphide content of the sediments. Our results show that the abundance of frenulate pogonophores increases with increasing sedimentation and with decreasing abundance of other benthos, particularly bioturbating organisms. The maximum sustainable carrying capacity of non-seep sediments for frenulate pogonophores is limited by the rate of sulphate reduction.     

Dissolved oxygen variations in alpine glacial meltwaters

Recent models of chemical weathering in alpine glacial meltwaters suggest that sulphide oxidation is a major source of solute in the distributed component of the subglacial hydrological system. This reaction requires O₂, and may lower dissolved oxygen levels to below saturation with respect to the atmosphere. This should result in an inverse association between SO₇^2- and dissolved oxygen saturation. However, measurements of O₂ saturation in bulk meltwaters draining the Haut Glacier d'Arolla, Switzerland, show that there is a positive association between SO₄^2- and O₂ saturation. The O₂ content of glacial meltwaters depends on the initial content of snow and icemelt, which may be controlled by the rate of melting, and the kinetic balance between O₂ losses (e.g. sulphide oxidation, microbial respiration) and gains (e.g. diffusion of O₂ into solution).     

Three mechanisms of ore re-mobilisation during amphibolite facies metamorphism at the Montauban Zn–Pb–Au–Ag deposit

The relative importance of mechanical re-mobilisation, hydrothermal dissolution and re-precipitation, and sulphide melting in controlling redistribution of metals during concurrent metamorphism and deformation is evaluated at the middle amphibolite facies Montauban deposit in Canada. As at many other deposits, ductile deformation was important in driving mechanical re-mobilisation of massive sulphides from limb regions into hinge regions of large-scale folds and is thus the most important for controlling the economics of Pb and Zn distribution. Two possible stages of hydrothermally driven re-mobilisation are discussed, each of which produces characteristically different alteration assemblages. Prograde hydrothermal re-mobilisation is driven by pyrite de-sulphidation and concurrent chlorite dehydration and is thus an internally driven process. At Montauban, the H₂S-rich fluid generated through this process allowed re-mobilisation of gold into the wall rock, where it was deposited in response to sulphidation of Fe Mg silicates. Retrograde hydrothermal re-mobilisation is an externally driven process, whereby large volumes of fluids from outside the deposit may dissolve and re-precipitate metals, and cause hydration of silicate minerals. This second hydrothermally driven process is not recognised at Montauban. Sulphide melting occurred as temperatures neared the peak metamorphic conditions. Melting initiated in the massive sulphides through arsenopyrite breakdown, and a small volume of melt was subsequently re-mobilised into the wall rock. Trace element partitioning and fractional crystallisation of this melt generated a precious metal-rich fractionate, which remained mobile until well after peak metamorphism. Thus, prograde hydrothermal re-mobilisation and sulphide melting were the most important mechanisms for controlling the distribution of Au and Ag.     

Mobility of Al, Co, Cr, Cu, Fe, Mn, Ni and V in sulphide-bearing fine-grained sediments exposed to atmospheric O2: an experimental study

 The major aim was to increase our knowledge on the behaviour of Al, Co, Cr, Cu, Fe, Mn, Ni and V in sulphide-bearing fine-grained sediments exposed to atmospheric oxygen. Samples of this type of sediment collected in a previous investigation at eight sites in western Finland were digested in HClO₄-HNO₃-HCl-HF at 200  °C and in HCl:HNO₃:H₂O at 95  °C (aqua regia), and subjected to extractions with ammonium acetate and hydrogen peroxide. Metals and S in the leachates were determined with ICP-AES. The results of the chemical analyses are compared with previously reported experimental data. The concentrations of Al and Fe in the sulphide-bearing fine-grained sediments are about 7% and 5%, respectively. Of the trace metals studied, Mn is most abundant followed in decreasing order by V>Cr>Ni>Cu>Co. On oxidation of the sediments, high proportions of Co, Mn and Ni, intermediate proportions of Cu but low proportions of Fe, Al, Cr and V are released. The extent of the release of a metal on oxidation is controlled either by (1) the level to which the pH of the sediments drops on oxidation (Al, Cu, Cr, V), (2) the amount of the metal associated with easily reduced phases (metal sulphides) in the sediments (Ni, Co) or (3) the sum of the amount associated with reduced phases and adsorbed on soil compounds (Mn). No control of the release of Fe on oxidation of the sediments was identified. Based on the results of the study it is argued that artificial drainage and the subsequent oxidation of sulphide-bearing sediments will result in extensive leaching of Co, Mn and Ni, moderate leaching of Cu and limited leaching of Cr and V into drainages. The major elements, Fe and Al, have the potential to be mobilised and leached in large amounts, though the proportions mobilised/leached will remain low. It is suggested that the identification of sulphide-bearing sediments with a high potential of metal release should be based on determination of metals in easily mobilised reduced compounds (dissolved e.g. in H₂O₂) and of the level to which the pH of the sediments drops on oxidation. Received: 16 October 1997 · Accepted: 9 March 1998