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1.
The pore-water geochemistry and mineralogy of tailings derived from a granitic tungsten deposit were characterized by collecting pore-water samples at discrete depth intervals throughout the tailings for the analysis of major and minor element concentrations. Mineralogical samples from the oxidation zone were analyzed by X-ray diffraction, scanning electron microscopy combined with energy dispersive X-ray spectroscopy (SEM/EDS), electron microprobe (EMP) combined with wavelength dispersive X-ray spectroscopy (WDS), and transmission electron microscopy (TEM). The oxidation of sulfide minerals in the near-surface tailings leads to a decrease in pore-water pH and elevated SO4, As, and metal concentrations. The unusual mineralogy of this deposit, compared with that of commonly studied base-metal and gold deposits, results in several unique geochemical characteristics. The dissolution of fluorite releases F into the pore water; the F forms strong complexes with Al and enhances the dissolution of aluminosilicate minerals within the oxidation zone. As a result, high Al concentrations (up to 151.7 mg/L) are detected in the near-neutral pore water in the oxidation zone. The combined dissolution of aluminosilicates and carbonate minerals maintains the pH near 10 in the pore water at depth. Elevated concentrations of W (up to 7.1 mg/L) are detected in the pore water throughout the tailings, likely as a result of the dissolution of wolframite. Consistent with geochemical model calculations, results from SEM/EDS, EMP/WDS and TEM/EDS analyses indicate that secondary minerals, which occur as orange-brown coatings on grains of primary-minerals, are Fe oxyhydroxides. Examples of these secondary minerals display a fibrous habit at high resolution in the TEM. One of these minerals, which contains substantial amounts of Al, As, and Si as impurities, was identified by selected-area electron diffraction (SAED) analyses to be goethite. Another mineral contains relatively high amounts of Si, Pb, Bi, and As, and SAED analyses suggest that the mineral is two-line ferrihydrite. 相似文献
2.
About a century of exploitation of the galena-arsenopyrite deposit of Baccu Locci in Sardinia (Italy) has caused a severe, persistent arsenic contamination that extends downstream from the mine for several kilometres. Differently from As, the contamination of lead in surface waters is only localised in the upper part of the mine despite very high Pb concentrations in geologic materials (waste rocks, tailings, stream sediments, soils) over the whole Baccu Locci stream catchment. The aqueous and solid speciation of Pb in various environmental media of the Baccu Locci system was determined by means of a combined analytical (ICP-MS, SEM-EDX, TEM-EDX, chemical extraction) and thermodynamic approach (PHREEQC). The study has pointed out that relatively little Pb (up to 30 µg/L) is initially released to surface waters (pH = 7–8, Eh = 0.4–0.6 V) very rapidly due to dissolution of anglesite that is the first product of galena oxidation. Subsequently, Pb is removed (down to 0.6 µg/L) by probable sorption onto hydrous ferric oxides (e.g. ferrihydrite) and/or possible precipitation of As-containing plumbojarosite that is the main secondary Pb-bearing phase in stream sediments/tailings along the Baccu Locci stream course. The latter hypothesis is controversial since it is reported from the literature that plumbojarosite is formed under acidic conditions, although there is contrary field evidence as well. Bearing in mind the uncertainties introduced from thermodynamic and analytical data, the solubility calculations indicate strong undersaturation of surface waters with respect to plumbojarosite (SI: ? 19.9 to ? 3.7). On the contrary arsenatian plumbojarosite is at or close to saturation (SI: ? 0.6 to 3.2) in most surface waters and beudantite is clearly above saturation (SI: 4.1 to 12.7). This suggests that the incorporation of As might increase the stability of plumbojarosite, extending it up to near-neutral conditions. As a consequence, Pb is prevented from being released downstream to surface waters, and dissolved Pb concentrations remain definitely below the Italian and WHO limits for drinking waters (50 µg/L and 10 µg/L, respectively). 相似文献
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4.
几种铁（氢）氧化物对溶液中磷的吸附作用对比研究 总被引：2，自引：0，他引：2
铁(氢)氧化物不仅是土壤中广泛存在的矿物,也是重要的矿物资源。表生地质作用形成的针铁矿、赤铁矿和无定形氢氧化铁都具有纳米尺度,具有很高的表面积,表现出对磷的专性吸附,是低浓度磷的潜在吸附材料。本文通过铁(氢)氧化物对水溶液中磷酸根的等温吸附实验,初步对比研究了针铁矿、合成氧化铁黄、赤铁矿和无定形氢氧化铁对水中低浓度磷的吸附作用。结果表明,无定形氢氧化铁对水溶液中磷酸根的吸附能力最强(对低浓度磷的吸附达到5.5mg/g),其次是氧化铁黄和针铁矿,赤铁矿的吸附能力最差。几种铁(氢)氧化物对磷吸附容量的差别主要受比表面积控制。无定形氢氧化铁、合成氧化铁黄、针铁矿、赤铁矿对磷的吸附符合Freundlich等温方程。针铁矿和赤铁矿对磷的吸附动力学符合双常数速率方程。 相似文献
5.
Mining and metallurgical processing of gold and base metal ores can lead to the release of arsenic into the aqueous environment as a result of the weathering and leaching of As-bearing minerals during processing and following disposal. Arsenic in process solutions and mine drainage can be effectively stabilized through the precipitation of ferrihydrite. However, under anaerobic conditions imposed by burial and waste cover systems, ferrihydrite is susceptible to microbial reduction. This research, stimulated by the paucity of information and limited understanding of the microbial reduction of arsenical ferrihydrite, was conducted on synthetic adsorbed and co-precipitated arsenical 6-line ferrihydrite (Fe/As molar ratio of 10/1) using Shewanella sp. ANA-3 and Shewanella putrefaciens CN32 in a chemically defined medium containing 0.045 mM phosphate concentration. Both bacteria were equally effective in their reducing abilities around pH 7, resulting in initial rates of formation of dissolved As(III) of 0.10 μM/h for the adsorbed, and 0.08 μM/h for the co-precipitated arsenical 6-line ferrihydrite samples. The solid phases in the post-reduction samples were characterized by powder X-ray diffraction (XRD), micro-XRD, scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron microprobe and X-ray absorption spectroscopy (XAS) techniques. The results indicate the formation of secondary phases such as a biogenic Fe(II)–As(III) compound, akaganeite, goethite, hematite and possibly magnetite during bacterial reduction experiments. Holes and bacterial imprints measuring about 1–2 μm were observed on the surfaces of the secondary phases formed after 1200 h of reduction. This study demonstrates the influence of Fe and As reducing bacteria on the release of significant concentrations of more mobile and toxic As(III) species from arsenical 6-line ferrihydrite, more readily from the adsorbed than from the co-precipitated ferrihydrite. 相似文献
6.
《Applied Geochemistry》2004,19(7):1065-1074
Potentially toxic metals exist in many reservoirs of surface water and therefore require an understanding of their occurrence, distribution, and mobility. The sediment accumulating at the bottom of the Dillon Reservoir, Colorado is contaminated with metals (Cu, Pb, Zn, Cd, Mo, etc.) that are primarily sorbed to Fe and Al hydroxides present in the sediment. The metals are derived from weathering of mineralized bedrock and mine tailings in the surrounding drainage basins. Sediment samples from the Dillon Reservoir were analyzed for major and trace elements and acidification experiments were performed to quantify the fraction of metals released from the sediment as a function of changes in pH. The highest percentages of metals are released from the sediment at low pH with the exception of Mo which has the highest percent released at near neutral pH. In addition, seasonal fluctuations in the concentrations of metals in the water of the Dillon Reservoir can be explained by changes in pH of as low as 0.2 pH units. 相似文献
7.
Sk. Md. Equeenuddin S. Tripathy P. K. Sahoo M. K. Panigrahi 《Environmental Earth Sciences》2010,60(4):723-731
The deposition of ochreous is common by a consequence of acid mine drainage (AMD). The ochreous precipitated from the AMD
sites around Tertiary coalfield of Assam, India were collected and characterized by X-ray diffractometry (XRD), Fe to S molar
ratio, ammonium oxalate acid (pH 3.0) extraction, fourier-transform infrared spectroscopy (FTIR), field emission scanning
electron microscopy (FESEM), scanning electron microscope (SEM) and transmission electron microscope (TEM). The ochreous mainly
consists of goethite, schwertmannite, ferrihydrite and jarosite. Mineralogy of ochreous was controlled by the pH whereas formation
of ferrihydrite was favored at high organic carbon content. Role of bacteria for the formation of secondary minerals was observed.
Mobility of metals was controlled by the ochreous, and they were also retained during the process of phase transformation
of poorly ordered iron-oxyhydroxysulfates into the stable forms. 相似文献
8.
A. Cristina Cismasu F. Marc Michel A. Patricia Tcaciuc Tolek Tyliszczak Gordon E. Brown Jr 《Comptes Rendus Geoscience》2011,343(2-3):210-218
A series of naturally occurring ferrihydrites sampled from an acid mine drainage environment were characterized and compared with synthetic 2-line ferrihydrite using high energy X-ray total scattering and pair distribution function analysis, Scanning Transmission X-ray Microscopy (STXM), Transmission Electron Microscopy (TEM), BET N2 surface area measurements, and chemical extractions in order to place constraints on their structural and physical properties as a function of composition. Overall, the short- and intermediate-range ordering of the natural samples is comparable to synthetic ferrihydrite. However, with increasing Al, Si, and organic matter contents, a decrease in particle size and an increase in structural disorder were observed. Silica is suspected to have a pronounced effect on the crystallinity of ferrihydrite as a result of its inhibitory effect on Fe polymerization and particle growth, and it is likely complexed at the surfaces of ferrihydrite nanoparticles. Aluminum, on the other hand may substitute for Fe3+ in natural ferrihydrite. Organic matter is pervasive and intimately associated with ferrihydrite aggregates, and its presence during ferrihydrite precipitation may have contributed to additional structural disorder. The increase in impurity content affects not only the particle size and structural order of ferrihydrite but may also have a significant effect on its surface reactivity. 相似文献
9.
Models of geochemical controls on elements of concern (EOCs; e.g., As, Se, Mo, Ni) in U tailings are dominated by ferrihydrite. However, the evolution of aqueous concentrations of Al and Mg through the Key Lake (KL) U mill bulk neutralization process indicates that secondary Al and Mg minerals comprise a large portion of the tailings solids. X-ray diffraction, Al K-edge XAS, and TEM elemental mapping of solid samples collected from a pilot-scale continuous-flow synthetic raffinate neutralization system of the KL mill indicate the secondary Al–Mg minerals present include Mg–Al hydrotalcite, amorphous Al(OH)3, and an amorphous hydrobasaluminite-type phase. The ferrihydrite present contains Al and may be more accurately described as Al–Fe(OH)3. In the final combined tailings sample (pH 10.5) collected from the model experiments using raffinate with Al, Mg, and Fe, solid phase EOCs were associated with Al–Fe(OH)3 and Mg–Al hydrotalcite. In model experiments using raffinate devoid of Fe, aqueous EOC concentrations decreased greatly at pH 4.0 (i.e., where ferrihydrite would precipitate) and largely remained in the solid phase when increased to the terminal pH of 10.5; this suggests Al–Mg minerals can control aqueous concentrations of EOCs in the raffinate in the absence of Fe. Maximum adsorption capacities for individual and mixtures of adsorbates by Mg–Al hydrotalcite were determined. A revised model of the geochemical controls in U mill tailings is presented in which Al and Mg minerals co-exist with Fe minerals to control EOC concentrations. 相似文献
10.
Martin R. Lee Mark E. Hodson Maureen MacKenzie Caroline L. Smith 《Geochimica et cosmochimica acta》2008,72(20):4962-4975
Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH 1 experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost ∼9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >∼2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction. 相似文献
11.
P. C. S. Carvalho A. M. R. Neiva M. M. V. G. Silva I. M. H. R. Antunes 《Environmental Earth Sciences》2014,71(5):2029-2041
Tailings deposited over the Castanheira, a stream which flows through the old Ag–Pb–Zn Terramonte mine area, showed a great potential environmental risk due to sulphide weathering, facilitated by the tailings–water interaction. The high concentrations of Al, Fe, Pb and Zn in the tailings are associated with the exchangeable, reducible and sulphide fractions and suggest sphalerite and pyrite occurrences. Oxidation of pyrite is responsible for the low pH values (3.38–4.89) of the tailings. The water from the Castanheira stream is not suitable for human consumption due to high concentrations of SO4 2?, Mn, Al, Cd, Ni, and Pb. The lowest concentrations of metals and metalloids were detected in downstream stretches of the Castanheira. However, As, Fe and Zn in deeper sediments tend to increase downstream. Significant concentrations of trivalent forms of arsenic were detected in water samples. In downstream stretches of the Castanheira, some free ions (Fe2+, Mn2+ and Zn2+) also predominate and the water is saturated with ferrihydrite, goethite, hematite, lepidocrosite and magnetite. 相似文献
12.
Authigenic clays in close textural relation to carbonate fluorapatite within finely laminated phosphate stromatolites of Upper Jurassic age have been studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and analytical electron microscopy (AEM). Stromatolite laminae consist of hexagonal prisms of francolite (sizes ranging between 0·1 and 1 μm) that are surrounded by poorly crystalline smectite and amorphous Fe–Si–Al oxyhydroxides. Microanalyses show that smectite is Fe rich, with highly variable composition, particularly regarding Fe and Si contents. Smectite has significant beidellitic, montmorillonitic and non-tronitic substitutions. Although the lack of fringe contrast in some areas adjacent to the smectite packets with 1·0–1·3 nm spacing is due to differences in orientation of layers, textural and analytical data clearly indicate the presence of Fe–Si–Al amorphous phases intimately intergrown with smectite. The occurrence of poorly crystalline smectite and associated amorphous phases within microbially precipitated stromatolite laminae, both as envelopes around, and as pore-fillings between extremely small calcium phosphate crystals, demonstrates authigenic smectite growth from a precursor Fe–Si–Al amorphous material. This material is formed in close association with a phosphate-rich precursor. The textural and structural relations, the preservation of chemical precursors of glauconite such as nontronitic montmorillonite, and the presence of Fe–Si–Al amorphous mineral phases, imply crystallization of the observed crystalline phases from synsedimentary (bacterially precipitated) amorphous precursors during early diagenesis in postoxic environments. Carbonate fluorapatite was the first phase to crystallize from the primary gel; smectite and associated amorphous Fe–Si–Al oxyhydroxides were the residual material of the crystallization process. The slow rate of transformation (at low temperatures) from Fe–Si–Al-rich gels to smectite, explains the textural relations between the poorly crystalline phases and the phosphate crystals, as well as the preservation of amorphous substances in relation to clays. Authigenic smectite represents the first step in glauconitization. 相似文献
13.
铁（氢）氧化物悬液中磷酸盐的吸附-解吸特性研究 总被引：2，自引：0，他引：2
铁（氢）氧化物对P的吸持和释放在一定程度上决定着P的生物有效性和水体富营养化。以两种环境中常见晶质铁氧化物（针铁矿和赤铁矿）为对照,采用X射线衍射（XRD）、透射电镜（TEM）、热重分析（TGA）和孔径分析以及动力学和吸附-解吸热力学平衡等技术方法,研究了弱晶质水铁矿对P吸附-解吸特性,并探讨了相关机制。实验表明,三种矿物对P的吸附分为起始的快速反应和随后的慢速反应,它们均符合准一级动力学过程,反应中OH释放明显滞后于P吸附,P吸附经历了从外围到内囤配位、单齿到多齿配位过渡的过程,与晶质氧化铁比,水铁矿吸附容量和OH释放量更大、慢速吸附反应更快、存在缓慢扩散反应阶段,吸附容量依次是：水铁矿（436μmol／m^2）〉针铁矿（262μmol／m^2）〉赤铁矿（228μmol／m^2）,针铁矿和赤铁矿吸附P符合L（Langmuir）模型,而水铁矿更符合F（Fremldlictl）模型。中性盐介质（KCl）中在最大吸附量时P的解吸率依次为：水铁矿（85％）〈针铁矿（10％）〈赤铁矿（125％）,柠檬酸通过配体解吸和诱导溶解两种机制促进P的解吸,最大吸附量时解吸率依次是：针铁矿（25％）〈水铁矿（32％）〈赤铁矿（50％）。 相似文献
14.
In this study, the retention of Ca and other metals (Pb, Cu, Fe, Zn and Mn) in the Oostriku peat bog (central Estonia) was modelled. Equilibrium sorption of metals on amorphous ferric oxyhydroxide and solid organic matter was simulated at steady-state. Ferric oxyhydroxide formation and possible precipitation of other metals (Mn, Pb and Cu) in the peat was also assessed. Evolution of metal sorption fronts along a peat profile over time was simulated with a dynamic model to test if metal–metal competition effects could cause Pb and Cu to sorb at higher amounts in the uppermost peat than in the lower peat, as observed in the field. The predicted sorbed amounts of metals were compared with those previously observed in the peat. In general, good agreement between both batch and dynamic model results and the independent observations at the Oostriku peat site was obtained. This suggests that the relatively simple model approach employed here might be generally useful for assessing other peat sites and similar applications. 相似文献
15.
Stable Fe isotope fractionations produced by aqueous Fe(II)-hematite surface interactions 总被引：1，自引：0，他引：1
Lingling Wu Brian L. Beard Eric E. Roden Christopher B. Kennedy 《Geochimica et cosmochimica acta》2010,74(15):4249-8833
Stable Fe isotope fractionations were investigated during exposure of hematite to aqueous Fe(II) under conditions of variable Fe(II)/hematite ratios, the presence/absence of dissolved Si, and neutral versus alkaline pH. When Fe(II) undergoes electron transfer to hematite, Fe(II) is initially oxidized to Fe(III), and structural Fe(III) on the hematite surface is reduced to Fe(II). During this redox reaction, the newly formed reactive Fe(III) layer becomes enriched in heavy Fe isotopes and light Fe isotopes partition into aqueous and sorbed Fe(II). Our results indicate that in most cases the reactive Fe(III) that undergoes isotopic exchange accounts for less than one octahedral layer on the hematite surface. With higher Fe(II)/hematite molar ratios, and the presence of dissolved Si at alkaline pH, stable Fe isotope fractionations move away from those expected for equilibrium between aqueous Fe(II) and hematite, towards those expected for aqueous Fe(II) and goethite. These results point to formation of new phases on the hematite surface as a result of distortion of Fe-O bonds and Si polymerization at high pH. Our findings demonstrate how stable Fe isotope fractionations can be used to investigate changes in surface Fe phases during exposure of Fe(III) oxides to aqueous Fe(II) under different environmental conditions. These results confirm the coupled electron and atom exchange mechanism proposed to explain Fe isotope fractionation during dissimilatory iron reduction (DIR). Although abiologic Fe(II)aq - oxide interaction will produce low δ56Fe values for Fe(II)aq, similar to that produced by Fe(II) oxidation, only small quantities of low-δ56Fe Fe(II)aq are formed by these processes. In contrast, DIR, which continually exposes new surface Fe(III) atoms during reduction, as well as production of Fe(II), remains the most efficient mechanism for generating large quantities of low-δ56Fe aqueous Fe(II) in many natural systems. 相似文献
16.
Hematite is a common primary/secondary mineral in mine drainage and mine waste settings that can adsorb dissolved metals and metalloids. This study explored the ability of synthetic hematite to retain one such contaminant, molybdate, on its surfaces under highly alkaline (pH = ∼10) conditions. X-ray diffraction (XRD), Raman spectroscopy (RS), scanning electron microscopy (SEM), and specific surface area (BET) analyses show that synthetic hematite particles are stable and able to adsorb molybdate. Raman spectra show that the hematite efficiently adsorbs molybdate and retains it on its surfaces via strong inner-sphere surface complexation. Inductively coupled plasma-mass spectrometry (ICP-MS) data indicate that hematite aged (7 and 9 days) at high and room temperatures (75 and 25 °C) retains adsorbed molybdate and that molybdate sorption increases with aging. SEM images show that aged hematite particles with adsorbed molybdate are similar in size and shape to pure hematite and exhibit no significant reduction in surface area. These findings are valuable for understanding the fate of Mo in mine wastes and mill tailings environments where the 2-line ferrihydrite to which it is adsorbed can transform to hematite. 相似文献
17.
《Australian Journal of Earth Sciences》2013,60(5):797-809
Sulfide‐rich materials comprising the waste at the abandoned Montalbion silver mine have undergone extensive oxidation prior to and after mining. Weathering has led to the development of an abundant and varied secondary mineral assemblage throughout the waste material. Post‐mining minerals are dominantly metal and/or alkali (hydrous) sulfates, and generally occur as earthy encrustations or floury dustings on the surface of other mineral grains. The variable solubility of these efflorescences combined with the irregular rainfall controls the chemistry of seepage waters emanating from the waste dumps. Irregular rainfall events dissolve the soluble efflorescences that have built up during dry periods, resulting in ‘first‐flush’ acid (pH 2.6–3.8) waters with elevated sulfate, Fe, Cu and Zn contents. Less‐soluble efflorescences, such as anglesite and plumbojarosite, retain Pb in the waste dump. Metal‐rich (Al, Cd, Co, Cu, Fe, Mn, Ni, Zn) acid mine drainage waters enter the local creek system. Oxygenation and hydrolysis of Fe lead to the formation of Fe‐rich precipitates (schwertmannite, goethite, amorphous Fe compounds) that, through adsorption and coprecipitation, preferentially incorporate As, Sb and In. Furthermore, during dry periods, evaporative precipitation of hydrous alkali and metal sulfate efflorescences occurs on the perimeter of stagnant pools. Flushing of the streambed by neutral pH waters during heavy rainfall events dissolves the efflorescences resulting in remobilisation and transport of sulfate and metals (particularly Cd, Zn) downstream. Thus, in areas of seasonal or irregular rainfall, secondary efflorescent minerals present in waste materials or drainage channels have an important influence on the chemistry of surface waters. 相似文献
18.
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. 相似文献
19.
The transformation of ferrihydrite to hematite by ageing at 92°C in solution has been studied using computer-fitted 57Fe Mössbauer spectra, together with X-ray diffraction and electron microscopy. The X-ray diffraction patterns show hematite is first discernible after 10 minutes ageing and after 30 minutes the hematite peaks are sharp and definite. Mössbauer spectroscopy at room temperature shows it is discernible after 60 minutes ageing but can be detected at liquid nitrogen temperature by 30 minutes. With further ageing the ferrihydrite progressively transforms to hematite and at 116 hours hematite is the only component. The electron micrographs show the ferrihydrite particles of 3–5 nm diameter coalesce to form hexagonal hematite platelets, initially of some 20 nm diameter, which increase to 30–40 nm with ageing.The Mössbauer spectra show the broadened ferric doublet resonance of ferrihydrite and the six-line magnetic hyperfine hematite resonance. Two closely overlapping ferric doublets were computer-fitted to the ferrihydrite resonance, the widths and dips of the component peaks within each doublet being constrained initially to be equal. As these constraints were relaxed, the widths and dips became unequal. This effect is related to the progressive ordering of the ferrihydrite structure as it ages to produce a partially magnetically ordered hematite structure, with a reduced magnetic field at room temperature of initially 473 kOe, increasing to 499 kOe with time. These results suggest a direct transformation of ferrihydrite to hematite, initiated by the coalescing of the ferrihydrite particles. 相似文献
20.
Maria Nesterova John Moreau Jillian F Banfield 《Geochimica et cosmochimica acta》2003,67(6):1185-1195
We studied biomimetic mineralization of self-assembling polymer matrices in order to develop a model for biomineralization of iron oxides in nature. High-resolution transmission electron microscopy (HRTEM), rheology, and fluorescence probe analyses show self-assembly of acidic polysaccharide alginic acid (Alg) to form fibrils in dilute solutions. The resulting Alg fibrils are subsequently mineralized by FeOOH in a biomimetically controlled process. Experiments were conducted in pH 9.2 solutions containing millimolar concentrations of iron at 38°C. The unperturbed state of the hybrid mineral-organic structures was studied by characterization of samples of interfacial films collected from an inorganic-organic interface. Progress of mineralization over a 4-week period was followed by HRTEM, energy-dispersive X-ray analysis, and selected area electron diffraction. Morphologies of hybrid structures determined by HRTEM, X-ray powder diffraction, Fourier transform infrared spectroscopy, energy-dispersive X-ray analysis, and selected area electron diffraction suggest formation of iron (III) oxyhydroxide phases and their assembly through a variety of mechanisms, possibly occurring simultaneously. An initial step involves precipitation of nanometer-scale amorphous particles and two-line ferrihydrite in bulk solution. Some nanoparticles assemble into chains that recrystallize to form akaganeite (β-FeOOH), presumably via a solid-state transformation pathway. Small organic molecules may mediate this process by stabilizing the akaganeite structure and controlling particle assembly. Ferrihydrite particles also bind to acidic polysaccharide fibrils and are transformed to ordered arrays of akaganeite. The parallel orientation of adjacent akaganeite nanocrystals may be inherited from the orientation of precursor ferrihydrite, possibly conferred during attachment of ferrihydrite to the polyacid fibrils. Alternatively, particle-particle interactions may induce orientation, leading to recrystallization. Subsequently, akaganeite is transformed to goethite that is characterized by nanoscale porosity and fine-scale twinning on {021}. Dislocation, twin, and nanopore microstructures are consistent with coarsening by nanoparticle assembly, possibly templated by the substrate. Nanoparticle assembly to generate biomimetic hybrid materials may be relevant to formation of complex natural biominerals in natural systems where mineral nanoparticles, small organic molecules, and more complex polymers coexist. 相似文献