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. 相似文献
The early diagenesis of trace elements (V, Cr, Co, Cu, Zn, As, Cd, Ba, U) in anoxic sediments of the Achterwasser, a shallow lagoon in the non-tidal Oder estuary in the Baltic Sea, was investigated in the context of pyrite formation. The dissolved major redox parameters show a two-tier distribution with transient signals in the occasionally re-suspended fluid mud layer (FM) and a permanently established diagenetic sequence in the sediment below. Intense microbial respiration leads to rapid depletion of O2 within the uppermost mm of the FM. The reduction zones of Mn, Fe and sulfate overlap in the FM and in the permanently anoxic sediment section which appears to be a typical feature of estuarine sediments, under low-sulfate conditions. Degrees of pyritization (DOP) range from 50% in the FM to remarkably high values > 90% at 50 cm depth. Pyrite formation at the sediment surface is attributed to the reaction of Fe-monosulfides with intermediate sulfur species via the polysulfide pathway. By contrast, intense pyritization in the permanently anoxic sediment below is attributed to mineral growth via adsorption of aqueous Fe-sulfide complexes onto pyrite crystals which had originally formed in the surface layer.The studied trace elements show differential behavior patterns which are closely coupled to the diagenetic processes described above: (i) Zn, Cu and Cd are liberated from organic matter in the thin oxic layer of the sediment and diffuse both upwards across the sediment/water boundary and downwards to be trapped as monosulfides, (ii) V, Cr, Co and As are released during reductive dissolution of Mn- and Fe-oxyhydroxides, (iii) U removal from pore water occurs concomitantly to Fe reduction in the FM and is attributed to reduction of U(VI) to U(IV), (iv) the Ba distribution is controlled by reductive dissolution of authigenic barite in the sulfate reduction zone coupled with upward diffusion and re-precipitation. The incorporation of trace elements into pyrite is most intense for Co, Mn and As, intermediate for Cu and Cr and little to negligible for U, Zn, Cd, V and Ba. The observed trend is largely in agreement with previous studies and may be explained with differing rates for ligand exchange. Slow and fast ligand exchange and thus precipitation kinetics are also displayed by downcore increasing (Mn, Cr, Co and As) or constantly low (Zn, Cu, Cd) pore water concentrations. The downward increasing degrees of trace metal pyritization (DTMP) for Co, Cu, Zn and As are, in analogy to pyrite growth, assigned to adsorption of sulfide complexes or As oxyanions onto preexisting pyrite minerals. 相似文献
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. 相似文献
Interatomic potential parameters have been derived at simulated temperatures of 0 K and 300 K to model pyrite FeS2. The predicted pyrite structures are within 1% of those determined experimentally, while the calculated bulk modulus is within 7%. The model is also able to simulate the properties of marcasite, even though no data for this phase were included in the fitting procedure. There is almost no difference in results obtained for pyrite using the two potential sets; however, when used to model FeS2 marcasite, the potential fitted at 0 K performs better. The potentials have also been used to study the high-pressure behaviour of pyrite up to 44 GPa. The calculated equation of state gives good agreement with experiment and shows that the Fe–S bonds shorten more rapidly that the S–S dimer bonds. The behaviour of marcasite at high pressure is found to be similar to that of pyrite. 相似文献
The chemical composition of pyrite in coal can be used to investigate its geological and mineralogical origin. In this paper, high-resolution time-of-flight secondary ion mass spectrometry (TOF-SIMS) was used to study the chemical composition of various pyrite forms in the No. 9 coal seam (St,d=3.46%) from the Wuda Coalfield, Inner Mongolia, northern China. These include bacteriogenic, framboidal, massive, cell-filling, fracture-filling, and nodular pyrites. In addition to Fe+ (54Fe+, 56Fe+, 57Fe+), other fragment ions were detected in bacteriogenic pyrites, such as 27Al+, Si+ (28Si+, 29Si+, 30Si+), 40Ca+, Cu+ (63Cu+, 65Cu+), Zn+ (64Zn+, 66Zn+, 67Zn+, 68Zn+), Ni+ (58Ni+, 60Ni+, 62Ni+), and C3H7+. TOF-SIMS images show bacteriogenic pyrites are relatively rich in Cu, Zn, and Ni, suggesting that bacteria probably play an important role in the enrichment of Cu, Zn, and Ni during their formation. Intense positive secondary ion fragments from framboidal aggregates, such as 27Al+, 28Si+, 29Si+, AlO+, CH2+, C3H3+, C3H5+, and C4H7+, indicate that formation of the framboidal aggregates may have occurred together with clay mineral and organic matter, which probably serve as the binding substance. The intense ions of 28Si+ and 27Al+ from massive pyrites also suggest that their pores incorporated clay minerals during crystallization. Together with the lowest 28Si+/23Na+ value, the intense organic positive secondary ion peaks from cell-filling pyrites, such as C3H3+, C3H5+, C3H7+, and C4H7+, indicate that pyrite formation may have accompanied dissolution or disintegration of the cell. The intense P+ peak was observed only in the fracture-filling pyrite and the highest 28Si+/23Na+ value of fracture-filling pyrite reflects its epigenetic origin. Together with XRD and REEs data, the stronger 40Ca+ in nodular pyrite than other pyrite forms shows seawater influence during its formation. 相似文献
The mineralogic residence and abundance of trace metals is an important environmental issue. Data from the USGS coal quality database show that potentially toxic elements, including Hg, As, Mo, Se, Cu, and Tl are enriched in a subset of coal samples in the Black Warrior Basin of Alabama, USA. Although the coal as-mined typically is low in these elements, localized enrichments occur in high-pyrite coals and near faults. Microscopic analyses demonstrate that the residence of these elements is dominantly in a late-stage pyrite associated with structurally disrupted coal. Further, our data suggest addition of Hg to the coal matrix as well. The source of these trace elements was hydrothermal fluids driven into the Black Warrior Basin by Alleghanian age tectonism. 相似文献
Based on back scattered electron images and electron micro-probe analysis results, four alteration layers, including a transition layer, a reticulated ferric oxide layer, a nubby ferric oxide layer and a cellular ferric oxide layer, were identified in the naturally weathering products of pyrite. These layers represent a progressive alteration sequence of pyrite under weathering conditions. The cellular ferric oxide layer correlates with the strongest weathering phase and results from the dissolution of nubby ferric oxide by acidic porewater. Leaching coefficient was introduced to better express the response of element mobility to the degree of pyrite weathering. Its variation shows that the mobility of S, Co and Bi is stronger than As, Cu and Zn. Sulfur in pyrite is oxidized to sulfuric acid and sulfate that are basically released into to porewater, and heavy metals Co and Bi are evidently released by acid dissolution. As, Cu and Zn are enriched in ferric oxide by adsorption and by co-precipitation, but they would re-release to the environment via desorption or dissolution when porewater pH becomes low enough. Consequently, Co, Bi, As, Cu and Zn may pose a substantial impact on water quality. Considering that metal mobility and its concentration in mine waste are two important factors influencing heavy metal pollution at mining-impacted sites, Bi and Co are more important pollutants in this case. 相似文献