Assessment of industrial by-products as amendments to stabilize antimony mine wastes.

The spread of antimony from mine wastes to the environment represents a matter of great concern due to its adverse effects on impacted ecosystems. There is an urgent need for developing and adopting sustainable and inexpensive measures to deal with this type of wastes. In this study the Sb leaching behavior of mine waste rocks and mine tailings derived from the exploitation of Sb ore deposits was characterized using standard batch leaching tests (TCLP and EN-12457-4) and column leaching essays. Accordingly, these mine wastes were characterized as toxic (>0.6 mg Sb L-1) and not acceptable at hazardous waste landfills (>5 mg Sb kg-1), showing also an ongoing Sb release under prolonged leaching conditions. Two industrial by-products were evaluated as amendments to stabilize them, namely deferrisation sludge (DFS) and a by-product derived from the treatment of aluminum salt slags (BP-Al). Mine wastes were amended with different doses (0-25%) of DFS or BP-Al and the performance of these treatments was evaluated employing also batch and column leaching procedures. The effectiveness of DFS to immobilize Sb was much higher than that exhibited by BP-Al. Thus, treatments with 25% BP-Al showed Sb immobilization levels of approximately 33-53%, whereas treatments with 5 and 25% DFS already attained Sb immobilization levels up to approximately 80-90 and 90-99%, respectively. Mine tailings amended with 5% DFS and mine waste rocks amended with 25% DFS decreased their leachable Sb contents below the limit for non-hazardous waste landfill acceptance (<0.7 mg Sb kg-1). Likewise, these DFS treatments were able to revert their toxic characterization. Moreover, the 25% DFS treatment showed to be a long-lasting stabilizing system, efficient at least during a leaching period equivalent to 10-year rainfall with a great Sb leaching reduction (close to 98%). After this long-term leaching process, DFS-treated mine wastes kept their non-hazardous and non-toxic characterization. The amorphous Fe (oxyhydr)oxides composing DFS were responsible for the important Sb removal capacity showed by this by-product. Thus, when DFS was applied to mine wastes mobile Sb was importantly fixed as non-desorbable Sb, showing also a considerable Sb removal capacity in presence of strong competing anions such as phosphate. The application of DFS as amendment presents a great potential to be used as a sustainable long-term stabilizing system of Sb mine wastes.

Antimony distribution and mobility in different types of waste derived from the exploitation of stibnite ore deposits.

Wastes derived from the exploitation of stibnite ore deposits were studied to determine their mineralogical, chemical, and environmental characteristics and establish the Sb distribution and the current and long-term risks of Sb mobilization. Representative samples of mine waste rocks, mine tailings, and smelting waste were studied by X-ray powder diffraction, polarized light microscopy, electron microprobe analysis, and digestion, leaching, and extraction procedures. The main Sb-bearing minerals and phases identified in the smelting waste were natrojarosite, iron (oxyhydr)oxides, mixtures of iron and antimony (oxyhydr)oxides, and tripuhyite; those in the mine tailings and mine waste rocks were iron (oxyhydr)oxides and/or mixtures of iron and antimony (oxyhydr)oxides. Iron (oxyhydr)oxides and natrojarosite had high Sb contents, with maximum values of 16.51 and 9.63 wt% Sb2O5, respectively. All three types of waste were characterized as toxic; the mine waste rocks and mine tailings would require pretreatment to decrease their leachable Sb content before they would be acceptable at hazardous waste landfills. Relatively little of the Sb was in desorbable forms, which accounted for <0.01 and <0.8% of the total Sb content in the smelting waste and mine waste rocks/mine tailings, respectively. Under reducing conditions, further Sb mobilization from mine waste rocks and mine tailings could occur (up to 4.6 and 3.3% of the total content, respectively), considerably increasing the risk that Sb will be introduced into the surroundings. Although the smelting waste had the highest total Sb content, it showed the lowest risk of Sb release under different environmental conditions. The significant Fe levels in the smelting waste facilitated the formation of various Fe compounds that greatly decreased the Sb mobilization from these wastes.

Characterization of secondary products in arsenopyrite-bearing mine wastes: influence of cementation on arsenic attenuation.

The secondary products of an arsenopyrite-bearing mine waste dump were characterized in order to ascertain their mineralogical, chemical and environmental features and to appraise their role in the abatement of As in the environment. To this purpose, representative surface samples of weathered sulfides (including cemented phases) and hardpan samples were collected and studied by X-ray powder diffraction (XRD), polarized light microscopy, electron microprobe analysis (EMPA), micro-Raman spectroscopy and digestion, extraction and leaching methods. Scorodite, amorphous ferric arsenates (AFA), elemental sulfur, hydronium jarosite, goethite, hematite and hydrous ferric oxides were the secondary products identified in the mine wastes. The hardpan was mainly constituted by gangue minerals, including sulfides (arsenopyrite and pyrite/marcasite) with different weathering degrees, cemented by cracked yellow phases corresponding to AFA with Fe/As molar ratios of 1.14-1.85 and elemental sulfur. These cracked compounds were also the binding agent in the other cemented phases. Hydronium jarosite and Fe (oxyhydr)oxides were enriched in As, showing values of 0.19-3.98 and 0.81-7.49 wt.% As2O5, respectively. The As leachability and lability from hardpan and cemented phases were not decreased as compared to those from the other weathered phases not showing cementation in the mine waste dump.

Arsenic distribution in a pasture area impacted by past mining activities.

Former mine exploitations entail a serious threat to surrounding ecosystems as after closure of mining activities their unmanaged wastes can be a continuous source of toxic trace elements. Quite often these mine sites are found within agricultural farming areas, involving serious hazards as regards product (feed/food) quality. In this work a grazing land impacted by the abandoned mine exploitation of an arsenical deposit was studied so as to evaluate the fate of arsenic (As) and other trace elements and the potential risks involved. With this aim, profile soil samples (0-50cm) and pasture plant species (Agrostis truncatula, Holcus annus and Leontodon longirostris) were collected at different distances (0-100m) from the mine waste dump and analyzed for their trace element content and distribution. Likewise, plant trace element accumulation from impacted grazing soils and plant trace element translocation were assessed. The exposure of livestock grazing animals to As was also evaluated, establishing its acceptability regarding food safety and animal health. International soil guideline values for As in grazing land soils (50mgkg-1) resulted greatly exceeded (up to about 20-fold) in the studied mining-affected soils. Moreover, As showed a high mobilization potential under circumstances such as phosphate application or establishment of reducing conditions. Arsenic exhibited relatively high translocation factor (TF) values (up to 0.32-0.89) in pasture plant species, reaching unsafe concentrations in their above-ground tissues (up to 32.9, 16.9 and 9.0mgkg-1 in Agrostis truncatula, Leontodon longirostris and Holcus annus, respectively). Such concentrations represent an elevated risk of As transfer to the high trophic-chain levels as established by international legislation. The limited fraction of arsenite found in plant roots should play an important role in the relatively high As root-to-shoot translocation shown by these plant species. Both soil ingestion and pasture intake resulted important entrance pathways of As into livestock animals, showing quite close contribution levels. The cow acceptable daily intake (ADI) of As regarding food safety was surpassed in some locations of the study area when the species Agrostis truncatula was considered as the only pasture feed. Restrictions in the grazing use of lands with considerable As contents where this plant was the predominant pasture species should be established in order to preserve food quality. Therefore, the exposure of livestock animals to As via both soil ingestion and pasture consumption should be taken into account to establish the suitability of mining-impacted areas for gazing.

Evaluation of ferrihydrite as amendment to restore an arsenic-polluted mine soil.

The effectiveness of ferrihydrite as amendment to restore the soil habitat functioning of a soil polluted with As by mining activities was evaluated. Its influence on As mobility and phytoavailability was also assessed. Soil treated with increasing amendment doses (0, 1, 2, and 5 %) were analyzed for soil microbiological parameters such as basal soil respiration and dehydrogenase, ß-glucosidase, urease, acid and alkaline phosphatase, and arylsulfatase activities. Batch leaching tests and plant growth experiments using ryegrass and alfalfa plants were performed. The treatment with ferrihydrite was effective to reduce As mobility and plant As uptake, translocation, and accumulation. Likewise, the soil microbiological status was generally improved as derived from basal soil respiration and dehydrogenase and acid and alkaline phosphatase activities, which showed increases up to 85, 45, 11, and 47 %, respectively, at a ferrihydrite addition rate of 5 %.

Mobility and phytoavailability of antimony in an area impacted by a former stibnite mine exploitation.

A mining area affected by the abandoned mine exploitation of a stibnite deposit was studied to establish the current and eventual environmental risks and to propose possible remediation practices. Soil and plant samples were collected at different places in this area and analyzed for their Sb content and distribution. Critical soil total concentrations of Sb were found, with values ranging from 585 to 3184 mg kg(-1) dry weight in the uppermost soil layer, and decreasing progressively with soil depth. The readily labile Sb contents represent <2% of the total concentrations, whereas the soil Sb contents more susceptible of being mobilized under changing environmental conditions attain values of about 4-9% of the total concentrations. Remediation measures should be undertaken to limit off-site migration of Sb. Within the tolerant plant community growing in this area, the shrub Daphne gnidium L. stands out for its relatively high root Sb accumulation and low Sb translocation, suggesting its feasibility to be used in Sb phytostabilization strategies.

Evaluation of different amendments to stabilize antimony in mining polluted soils.

Soil pollution with antimony is of increasing environmental concern worldwide. Measures for its control and to attenuate the risks posed to the ecosystem are required. In this study the application of several iron and aluminium oxides and oxyhydroxides as soil amendments was evaluated in order to assess their feasibility to stabilize Sb in mining polluted soils. Mine soils with different pollution levels were amended with either goethite, ferrihydrite or amorphous Al oxide at various ratios (0-10%). The effectiveness of such treatments was assessed by both batch and column leaching tests. The use of ferrihydrite or amorphous Al oxide proved to be highly effective to stabilize Sb. Immobilization levels of 100% were found when doses of 5% ferrihydrite or 10% amorphous Al oxide were applied, regardless of the soil Sb load. Column leaching studies also showed a high Sb leaching reduction (>75%) when soils were amended with 1% ferrihydrite or 5% amorphous Al oxide. Moreover, such treatments proved to simultaneously immobilize As and Pb in a great extent when soils were also polluted with such toxic elements.

Antimony, arsenic and lead distribution in soils and plants of an agricultural area impacted by former mining activities.

An agricultural area impacted by the former exploitation of an arsenical lead-antimony deposit was studied in order to assess the current and eventual environmental and health impacts. Samples of soils and cultivated (wheat) and spontaneously growing plants were collected at different distances from the mine pits and analyzed for the toxic element content and distribution. The soil total concentrations of Sb, As and Pb found in the uppermost soil layer (14.1-324, 246-758 and 757-10,660 mg kg(-1), respectively) greatly surpass their maximum tolerable levels in agricultural soils. Wheat grain Pb concentrations (0.068-1.36 mg kg(-1)) exceed the prescribed health standard, whereas Sb (<0.05-0.103 mg kg(-1)) and As (<0.05-0.126 mg kg(-1)) concentrations are below the permissible limits fixed for cereals. Of the spontaneously growing plants, Dactylis glomerata L. shows a relatively high root Pb accumulation and a very low Pb translocation, suggesting its feasibility to be used in Pb phytostabilization strategies.

Arsenic distribution in soils and plants of an arsenic impacted former mining area.

A mining area affected by the abandoned exploitation of an arsenical tungsten deposit was studied in order to assess its arsenic pollution level and the feasibility of native plants for being used in phytoremediation approaches. Soil and plant samples were collected at different distances from the polluting sources and analysed for their As content and distribution. Critical soil total concentrations of As were found, with values in the range 70-5330 mg kg(-1) in the uppermost layer. The plant community develops As tolerance by exclusion strategies. Of the plant species growing in the most polluted site, the shrubs Salix atrocinerea Brot. and Genista scorpius (L.) DC. exhibit the lowest bioaccumulation factor (BF) values for their aerial parts, suggesting their suitability to be used with revegetation purposes. The species Scirpus holoschoenus L. highlights for its important potential to stabilise As at root level, accumulating As contents up to 3164 mg kg(-1).

Study of arsenopyrite weathering products in mine wastes from abandoned tungsten and tin exploitations.

Arsenopyrite-rich wastes from abandoned tungsten and tin exploitations were studied to determine the composition and characteristics of the secondary phases formed under natural weathering conditions so as to assess their potential environmental risk. Representative weathered arsenopyrite-bearing rock wastes collected from the mine dumps were analysed using the following techniques: X-ray powder diffraction (XRD) analysis, polarizing microscopy analysis, electron microprobe analysis (EMPA) and microRaman and Mössbauer spectroscopies. Scorodite, pharmacosiderite and amorphous ferric arsenates (AFA) with Fe/As molar ratios in the range 1.2-2.5 were identified as secondary arsenic products. The former showed to be the most abundant and present in the different studied mining areas. Its chemical composition showed to vary in function of the original surrounding rock mineralogy in such a way that phosphoscorodite was found as the mineral variety present in apatite-containing geoenvirons. Other ever-present weathering phases were goethite and hydrous ferric oxides (HFO), displaying, respectively, As retained amounts about 1 and 20% (expressed as As(2)O(5)). The low solubility of scorodite, the relatively low content of AFA and the formation of compounds of variable charge, mostly of amorphous nature, with high capacity to adsorb As attenuate importantly the dispersion of this element into the environment from these arsenopyrite-bearing wastes.

Mercury in soils and plants in an abandoned cinnabar mining area (SW Spain).

An abandoned cinnabar mining area located in the South-West of Spain has been studied with the aim of assessing its mercury pollution level and enhancing the knowledge about the Hg soil/plant relationship. To do so, soils and plants were sampled near an inactive smelter and around two mining sites present in this area. Critical total Hg concentrations were found in the close environs of pollutant sources. These also show high levels of elemental Hg (up to 8 mg kg(-1)), but quite low exchangeable Hg contents (0.008-0.038 mg kg(-1)). Most plant specimens display in their aboveground tissues Hg concentrations comprised in the range 0.1-10 mg kg(-1), with a great proportion (50%) showing critical levels. Greater Hg contents were found in plant specimens growing in soils with higher elemental Hg concentrations. The plant species displaying the greatest Hg levels are either perennial species of small-medium size and/or showing medium-highly corrugated leaves, or annual plants of small size. Marrubium vulgare L., Bromus madritensis L. and Trifolium angustifolium L. are the plant species with the highest Hg contents (37.6, 12.7 and 9.0 mg kg(-1), respectively). Leaf specific surface seems an important feature in the atmospheric Hg uptake by plants.

Antimony distribution and mobility in topsoils and plants (Cytisus striatus, Cistus ladanifer and Dittrichia viscosa) from polluted Sb-mining areas in Extremadura (Spain).

A study about topsoil antimony distribution and mobility from the soils to the biomass has been afforded in three abandoned Sb mining areas located at Extremadura. Physico-chemical characteristics of the soils and total antimony levels were measured in soils and autochthonous plant species (Cytisus striatus, Cistus ladanifer and Dittrichia viscosa). Comparison with corresponding values in reference areas isolated from the mining activities is discussed. Antimony mobility in the soils was estimated by measuring the water extractable fraction; low results were obtained for the three soil areas, with no statistical differences. Plant ability to accumulate antimony was estimated by use of plant accumulation coefficients (PAC). Seasonal (spring vs. autumn) effects on the antimony content in the plant species. Cytisus striatus from Mari Rosa mine presented antimony excluder characteristics, whereas Dittrichia viscosa specimens growing in San Antonio mine showed a significant antimony bioaccumulation.

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Potentiometric stripping analysis (PSA) for monitoring of antimony in samples of vegetation from a mining area.

A potentiometric stripping analysis (PSA) method has been developed and checked for the fast and reliable determination of antimony in vegetation samples of Cistus ladanifer from a mining area in Badajoz, Southwest Spain. The method, modified from previous PSA methods for Sb in environmental samples, is based on dry ashing of the homogenized leaves, dissolution in hydrochloric acid, and PSA analysis on a mercury film plated on to a glassy carbon disk electrode. The influence of experimental variables such as the deposition potential, the deposition time, the signal stability and the calibration parameters, has been investigated. The method has been compared with an independent technique (instrumental neutron activation analysis) by analysis of standards and reference materials and comparison of the results. As a result of automation of the PSA equipment, the proposed method enables unattended analysis of 20 digested samples in a total time of 2 h, thus providing a useful tool for Sb monitoring of a large number of samples.