Environmental impact of the former Pb–Zn mining and smelting in East Belgium

In the mining district of Plombières-La Calamine (East Belgium), extensive Pb–Zn mining activities resulted in an important contamination of overbank sediments along the Geul river. Moreover, a huge amount of heavy metals is stored in a dredged mine pond tailing, which is located along the river. In the dredged mine pond tailing sediments, Pb–Zn minerals control the solubility of Zn, Pb and Cd. Although Pb, Zn and Cd display a lower solubility in overbank sediments compared to the mine tailing pond sediments, elevated concentrations of Pb, Zn and Cd are still found in the porewater of the overbank sediments. The considerable ‘actual’ and ‘potential’ mobility of Zn, Pb and Cd indicates that the mine pond tailing sediments and the overbank sediments downstream from the mine pond tailing represent a considerable threat for the environment. Besides the chemical remobilisation of metals from the sediments, the erosion of overbank sediments and the reworking of riverbed sediments act as a secondary source of pollution.     

Developments in the characterisation of waste materials for environmental impact assessment purposes

The characterisation of waste is entering a new phase with the latest developments of characterisation leaching tests and associated modelling capabilities. The currently applied too simple testing approaches lead to poor choices in waste management. With the increased insight in release controlling processes chemical speciation aspects can be addressed even in the most complex and heterogeneous waste materials. From a composition perspective materials may be highly variable, but often materials are far more consistent in their leaching behaviour. This aspect should be exploited more extensively as it holds the key to treat waste materials in such a way that long term solutions are achieved rather than reaching temporary gains.     

堆浸生产黄金浸出周期浅析

云南富源胜境关金矿开发生产初期，运用堆浸理论，根据矿山工业场地实际和矿石的物理化学性质，及矿石中的有害杂质(组织)的含量，多次试验、调整技术参数(堆浸场地物理性质、矿石粒度、矿堆高度、矿堆渗透性、氰化物浓度、浸出液碱性、浸出温度、喷淋强度、吸附流速或流量等)，完善浸出工艺，缩短浸出周期，提高浸出率，取得了良好的经济效益。     

Pristine and reacted surfaces of pyrrhotite and arsenopyrite as studied by X-ray absorption near-edge structure spectroscopy

Fe L-, S L-, and O K-edge X-ray absorption spectra of natural monoclinic and hexagonal pyrrhotites, Fe_1-xS, and arsenopyrite, FeAsS, have been measured and compared with the spectra of minerals oxidized in air and treated in aqueous acidic solutions, as well as with the previous XPS studies. The Fe L-edge X-ray absorption near-edge structure (XANES) of vacuum-cleaved pyrrhotites showed the presence of, aside from high-spin Fe²⁺, small quantity of Fe³⁺, which was higher for a monoclinic mineral. The spectra of the essentially metal-depleted surfaces produced by the non-oxidative and oxidative acidic leaching of pyrrhotites exhibit substantially enhanced contributions of Fe³⁺ and a form of high-spin Fe²⁺ with the energy of the 3d orbitals increased by 0.3–0.8 eV; low-spin Fe²⁺ was not confidently distinguished, owing probably to its rapid oxidation. The changes in the S L-edge spectra reflect the emergence of Fe³⁺ and reduced density of S s–Fe 4s antibonding states. The Fe L-edge XANES of arsenopyrite shows almost unsplit e_g band of singlet Fe²⁺ along with minor contributions attributable to high-spin Fe²⁺ and Fe³⁺. Iron retains the low-spin state in the sulphur-excessive layer formed by the oxidative leaching in 0.4 M ferric chloride and ferric sulphate acidic solutions. The S L-edge XANES of arsenopyrite leached in the ferric chloride, but not ferric sulphate, solution has considerably decreased pre-edge maxima, indicating the lesser admixture of S s states to Fe 3d orbitals in the reacted surface layer. The ferric nitrate treatment produces Fe³⁺ species and sulphur in oxidation state between +2 and +4.     

Arsenic and lead mobility: From tailing materials to the aqueous compartment

This study concerns the mineralogy of the tailings of a former Ag–Pb mine (Auzelles district, France) and the contribution of the waste materials to the heavy metal dissemination in the environment. Accumulation of metals in fish flesh was reported and this pollution is attributed to past mining activities. Tailings were studied to establish the major transfer schemes of As and Pb in order to understand their mobility that leads to contamination of a whole ecosystem. Mineralogical investigation, solubility and compliance tests were performed to assess the stability of the metal-bearing phases. Among the various metallic elements measured, As and Pb show the highest bulk concentrations (up to 0.7% and 6.3% respectively) especially for samples presenting near neutral pH values. According to X-ray diffraction (XRD), Scanning Electron Microscopy (SEM-EDX), Electron Probe Micro-Analysis (EPMA) and micro-Raman spectrometry (μRS), tailings mineralogy still contain primary minerals such as sulfides (e.g., galena, pyrite), phosphates (monazite, apatite) and/or carbonates (e.g., (hydro-)cerussite, dolomite, siderite). Sulfates (e.g., anglesite, lanarkite, plumbojarosite and beudantite) are the main secondary metal-bearing phases with other interesting phases accounting for metals mobility such as Fe and/or Pb and/or Mn oxides (e.g., lepidocrocite, goethite -up to 15 wt% of Pb was measured-, plumboferrite-type phase, mimetite). The lowest Pb solubilities were obtained at pH 8–9 and at a larger range than for As for which the lowest solubilities are reached around pH 6–7. At this minimum solubility pH value, Pb concentrations released still over exceed the National Environmental Quality Standards (NEQS), whatever the samples. The highest solubility is reached at pH 2 for both elements whatever the considered sample. This represents up to 51% of total Pb and up to 46% of total As remobilized and concentrations exceeding the NEQS. As and Pb released mainly depends on the Fe/Mn oxides (e.g., goethite, lepidocrocite) and carbonates (cerussite) which are the less stable phases. Compliance tests also show that Pb concentrations released are higher than the upper limit for hazardous waste landfills. Determination of the mineralogy allows understanding both the solubility and leaching test experiments results, as well as to forecast the impact of the residues on the water quality at a mid-term scale.     

Bacterially-mediated weathering of crystalline and amorphous Cu-slags

Two types of Cu-slags (CS: crystalline massive slag and GS: granulated amorphous slag) exhibiting a different chemical and mineral phase composition were compared with respect to their susceptibility to bacterial weathering using Pseudomonas aeruginosa (n° CIP 105094). Abiotic conditions e.g. sterile growth medium and ultrapure water were used for comparison. The experiments were extended up to 112 days with a systematic liquid phase renewal every 14 days. The results revealed significant release of elements in the bacterially mediated weathering experiments. Concentrations of elements (Si, Fe, Cu, Zn and Pb) in the biotic solutions were increased at least by 20% up to 99% compared to abiotic ones. From 3 to 77% of the leached elements were associated to the fraction >0.22 μm. Scanning electron microscope observations demonstrated greater weathering of mineral phases in biotic experiments than in abiotic ones which is in accordance with the solution chemistry exhibiting higher concentrations of elements leached in biotic set-ups. In the case of CS, glass and sulfides weathering was yet observed in abiotic experiment, whereas partial dissolution of fayalite (Fe₂SiO₄) was solely affected by the presence of bacteria. GS having a higher bulk content of metallic elements was found to be more stable than sulfide-bearing CS, while its (GS) glass matrix was found to weather easier under biotic conditions.     

Laboratory simulation of natural leaching processes of eastern USA oil shale

Raw and retorted spent oil shales from Kentucky, as well as soil and overburden materials, were subjected to laboratory and field leaching tests. Standard batch leaching tests grossly undervalue the amount of dissolved ions as measured in the field, being too brief to enable slow reactions of the mineral matrix, such as hydrolysis and oxidation of sulfides or reactions of acidic leachates with soluble components of the clays. Laboratory column tests, devised to closely simulate natural leaching processes, achieved concentration levels and elemental release patterns similar to those found in field tests. The column tests provide a reliable means to assess the leachability of metals in these materials.     

pH influence on sorption characteristics of heavy metal in the vadose zone

Sorption is an important process in the modelling and prediction of the movement of heavy metals in unsaturated clay barriers. This experimental study investigates the effect of pH changes in the acidic range on the sorption characteristics of heavy metals such as: lead, copper and zinc in an unsaturated soil. A series of one-dimensional coupled solute and moisture leaching column tests, using different heavy metal solutions, were conducted on an unsaturated illitic soil at varying pH values. Variations of volumetric water content (VWC) with distance were measured for different time durations, and concentrations of heavy metals in the liquid and solid phases were analysed. Partitioning coefficient profiles of contaminants along the soil column were determined for each individual layer in the soil.

Results from column leaching tests showed that the sorption characteristics of heavy metals are controlled by many factors which should be taken into consideration, i.e. the VWC, time of wetting, soil pH, and the influent heavy metal concentrations. Simplification of K_d as a constant and of the VWC as a linear function cannot be considered a good assumption and may lead to an improper evaluation of the sorption phenomena and also to serious errors in predicting contaminant transport through unsaturated soils.     

绿岩中金淋滤作用的实验研究

在200—550℃和60MPa条件下,以氯化物溶液对绿岩中金进行了淋滤实验,部分实验控制了氧逸度。实验结果显示,金的淋滤率与温度、溶液成分、酸碱度及氧逸度有关。在氧化和酸性溶液的实验中,淋滤率达50％以上。已查明金的淋滤作用受岩石中金溶解形成氯络合物的反应制约。因此,笔者认为花岗岩浆活动派生的酸性氯化物溶液话化迁移了绿岩中的金并富集成矿。     

Heavy Metal Load of Sediments of the River Gurk (Carinthia/Austria) — Merits and Limitations of Sequential Leaching Schwermetallbelastung des Sediments der Gurk in Kärnten — Vorzüge und Einschränkungen sequentieller Löseverfahren

By means of the analysis of sediments cored in the small river Gurk (Carinthia/Austria), the input of Ag, Cd, Ce, Cr, Hg, La, Mo, Ni, V, and W from a chemical industrial plant could be detected. To estimate the actual load, and to obtain data for comparison with other sites, both unsieved fine sediments and sediments sieved to 20 μm were investigated from the same cores. Environmental mobilities of toxic heavy metals (Co, Cr, Cu, Ni, Zn) have been shown by sequential leaching following Tessier/Förstner. In the last step, HNO₃ leaches a purely geogenic fraction, which is fairly constant along the investigated river. Whereas the additional Cr from the input of the chemical plant is mainly found in the oxalate-leachable fraction, short-time-load to unpolluted sediments in the laboratory is found mainly in hydroxylamine/acetic acid. Both is due to the high affinity of Cr to Fe- and Mn-oxides. Adsorption/desorption experiments reveal that the low carbonate content of the Gurk sediments increases the importance of Fe/Mn-oxides for the sorption of Cr compared to other samples containing carbonate. The Ni-load was primarily found in weak-acid-leachable and oxalate-leachable fractions. Similarly, the oxalate-leachable fraction is dominant for adsorption of other metals and phosphorus. Other interelement relationships among the amounts leached, which are attributable partly to carbonate-, silicate-, organic or coating phases, have been found by means of factor analyses together with marker fractions for each type.