Mobilization of colloidal ferrihydrite particles in porous media—An inner-sphere complexation approach

Prediction of colloid release and transport as affected by reactive species remains a significant challenge for field applications. In this paper, we report experimental and modeling results of ferrihydrite colloid release under the influence of citrate species. Using a 3-plane surface complexation model, equilibrium constants were obtained for the three proposed inner-sphere complexes by fitting a citrate adsorption isotherm on ferrihydrite at pH 4, and a pH adsorption envelop with 0.64 mM citrate. The constants were used in a reactive transport model for simulating reaction fronts of dissolved species during injection of citrate in ferrihydrite-coated quartz columns. Simulation results show that sorption alone may not adequately describe the breakthrough curves. Inclusions of ferrihydrite dissolution and re-adsorption of Fe(III) improve the prediction of dissolved species transport. Additionally, matrix diffusion may be needed for improved prediction. For the release of colloidal iron oxides it was shown that both oxide dissolution and interfacial repulsion controlled the process during complete breakthrough. However, the peak release of colloids, which occurred during the actual breakthrough of dissolved species, was mainly brought about by electric double layer forces. These particles underwent detachment-deposition-detachment cycles along the flow path, and emerged in the effluent with the major reaction front. To quantitatively predict colloid release, a semi-empirical linear correlation was established, linking the calculated electric potential to experimental colloid release rates. The model may be applied to the prediction and scaling of aquifer remediation studies involved in the injection of organic ligands to mobilize particle bound contaminants.     

Equilibrium studies on removal of lead (II) ions from aqueous solution by adsorption using modified red mud

In the present experimental study, solid waste was used as an adsorbent and the effectiveness of the adsorbent was increased by novel treatment methods. Red mud, acid-treated activated red mud and iron oxide-coated acid-treated activated red mud were used for the removal of lead (II). The structural and functional groups were identified to confirm the removal of lead (II) by powder X-ray diffraction and Fourier transform infrared spectroscopy analyses. The enhancement of surface area was confirmed by Brunauer–Emmett–Teller analysis. Batch adsorption experiment was also conducted, and various parameters such as the effect of adsorbent dosage, pH, contact time and initial ion concentration were analyzed and reported. Adsorption equilibrium data were investigated using Langmuir, Freundlich and Dubinin–Radushkevich isotherm models with three parameters, and the rate of reaction was examined through kinetic models. The results indicate that in particular a novel modified form of red mud, namely iron oxide-coated acid-treated activated red mud was well fitted in lead (II) removal compared with reported adsorbents. The Langmuir isotherm shows that the maximum adsorption of adsorbate per gram was greater than other adsorbents (27.02 mg/g). In Freundlich isotherm, the Freundlich constant n values lie between 1 and 10 indicate the favorable adsorption. The calculated n values for normal red mud, acid-treated activated red mud and iron oxide-coated acid-treated activated red mud were found to be 1.9, 2.1 and 2.0 respectively. The correlation coefficient value was higher and the rate of reaction follows the pseudo-second-order kinetic model.     

Synthesis,characterization of CdS/rectorite nanocomposites and its photocatalytic activity

CdS/rectorite nanocomposite was synthesized via a cation-exchange reaction followed by a sulfurization process. The obtained samples were characterized by using X-ray diffraction (XRD), fourier transform infrared spectra (FTIR), transmission electron microscope (TEM), UV-Vis diffuse reflectance spectra (DRS), and thermal analysis. The measured results indicate that CdS species in the composites exist in the form of pillars and nanoparticles, the crystallized CdS particles are in the hexagonal symmetry. The photocatalytic activities of the pillared nanocomposite were enhanced significantly comparing with the bare rectorite and the pure CdS. Moreover, the photostabilities of the obtained nanocomposites are also better than that of the pure CdS due to the hosts retard the photocorrosion of the CdS.     

Immobilization of Cd,Zn and Pb in sewage sludge using red mud

Sewage sludge is an inevitable end by-product of sewage treatment. Land application provides a cost-effective alternative for sewage sludge disposal. However, sewage sludge contains heavy metals that may limit its application. In this work, red mud was employed for the immobilization of heavy metals in sewage sludge. The effect of red mud amendment on heavy metal immobilization was evaluated using Toxicity Characteristic Leaching Procedure (TCLP) method. The TCLP results showed that the immobilization efficiency of Cd, Zn and Pb was 100, 92, and 82%, respectively, when sewage sludge was mixed with 10% red mud. Tests carried out in leaching columns demonstrated that heavy metal concentrations in the leachate of 10% red mud amended sludge were lower than those of the unamended sludge. Moreover, red mud decreased plant available heavy metal (Cd, Zn and Pb) content from 18.1, 17.2 and 14.6% to 6.9, 11.4 and 7.6%, respectively. Sequential chemical extraction experiments showed that after sludge was amended with 10% red mud, exchangeable fraction was reduced and iron and manganese oxides fraction was increased. Red mud amendment can effectively immobilize Cd, Zn and Pb in sewage sludge before land application.     

Constraining the colouration mechanisms of Cretaceous Oceanic Red Beds using diffuse reflectance spectroscopy

We have used diffuse reflectance spectroscopy to investigate the colouration mechanisms of hematite in Cretaceous Oceanic Red Beds (CORBs). Data for samples of CORBs from the Chuangde section in Tibet, Vispi Quarry section in Italy, and Core 12X of Ocean Drilling Program Hole 1049C in the North Atlantic were compared with calibration datasets obtained for hematite in different crystalline forms (kidney and specular hematite) and calcite matrix. Spectra for hematite in either pure form or in calibration datasets show that the centre of the reflection peak shifts to a longer wavelength and depth (D) decreases as the crystallinity of the hematite increases. Compared with specular hematite, the presence of just 0.5% of kidney hematite can cause a much deeper absorption peak and greater redness value, which indicates that kidney hematite has a higher colouration capacity than specular hematite. However, both kidney and specular hematite exhibit a good correlation between the redness value for each calibration dataset and the absorption peak depth. In all three studied sections, hematite is the main iron oxide mineral responsible for colouration. Spectral features such as absorption peak depth and peak centre reveal that hematite crystallinity gradually decreases from red shale to limestone to marl. Based on a spectral comparison of red shale in the Chuangde section before and after citrate–bicarbonate–dithionite (CBD) treatment, we found that two forms of hematite are present: a fine-grained and dispersed form, and a detrital form. The former is relatively poorly crystalline hematite, which has a much stronger colouration capacity than the detrital form. In the Vispi Quarry section and Core 12X of ODP Hole 1049C, a good correlation between the absorption peak depth of hematite and redness value indicates that the red colouration is caused by hematite of similar crystallinity in each section.     

Al2O3改良红黏土的力学试验研究

广西是我国铝业的生产大省,在生产金属铝的时候会产生污染物赤泥,由于赤泥结合的化学碱难以脱除,对地下水污染严重,大量的赤泥堆放,不仅占用了大片的土地,干燥的赤泥还会造成粉尘污染,有效地对赤泥进行回收利用已经成为当前迫在眉睫的任务。本次研究尝试使用作为赤泥主要成分之一的Al2O3的掺入,研究其对红黏土的物理力学性质的影响,本次试验采用掺入率分别为0、1%、2%、3%、4%,5个不同掺入比例Al2O3后的红黏土。对其进行液塑性试验,分析不同掺入率的红黏土的液塑性变化情况。通过击实试验,得出不同掺入率下红黏土的最大干密度、最优含水率。最后对红黏土重塑样进行三轴不固结不排水剪切试验,获得在同一含水率,不同掺入率、不同围压下的应力-应变关系曲线、弹性模量、抗剪强度参数的变化规律。试验结果表明：改良后的红黏土还是具有高液、塑限的特性,其状态为坚硬。随着掺入的Al2O3的量增加,其液限、塑限、塑性指数、含水率、最大干密度都降低;同等Al2O3掺入量的情况下,随着围压的增大抗剪强度增强,在同等围压下,随着Al2O3掺入量的增加抗剪强度呈先降低后增高的状态。     

Phenol and ammonium removal by using Fe-ZSM-5 synthesized by ammonium citrate iron source

Fe-ZSM-5 zeolites are important for many applications, especially for catalysis and volatile organic carbon removal. However, the inclusion of a high content of iron in the ZSM-5 structure is hindered due to the high pH required for hydrothermal synthesis. To overcome this problem, the synthesis of Fe-ZSM-5 zeolites with a novel iron chelate complex as the iron source (ammonium iron citrate) and a common iron source (iron chloride) was investigated. The synthesized materials were characterized by XRD, BET, SEM, FTIR, XPS and ICP. The total iron content was determined by ICP. Fe-ZSM-5 zeolites prepared by the ammonium iron citrate source method contain the highest iron concentration within the framework of a Mobil five structure, which has a high surface area and crystallinity. The prepared materials were used to remove phenol and ammonium. The catalytic results demonstrated that Fe-ZSM-5 prepared with ammonium iron citrate is the best catalyst.     

沉积物中铁氧化物的定量方法及其 在白垩纪大洋红层中的应用

赤铁矿和针铁矿是自然界中最稳定的两种铁氧化物,广泛存在于地球的各个圈层。很多沉积物的颜色都是由它们引 起的,它们的形成和保存具有重要的环境指示意义。实验室中赤铁矿和针铁矿的表征和鉴定手段很多,但受其含量低、结 晶差、颗粒细小难分离等因素的困扰以及某些测试方法自身的限制,能用于铁氧化物定量分析的方法很少。文中就常用的 基于X射线衍射（XRD） 和漫反射光谱（DRS） 的铁氧化物定量方法进行了系统评价。在定性分析的基础上,采用基于 XRD的K值法获得西藏床得剖面红色页岩中赤铁矿的含量为3.81％~8.11％,采用DRS与多元线性回归相结合的方法获得北 大西洋ODP1049C孔12X岩芯段棕色层中赤铁矿和针铁矿的含量分别为0.13％~0.82％和0.22%~0.81％,橙色层中赤铁矿和 针铁矿的含量分别为0.19%~0.46％和0.29%~0.67％。与其它分析结果的比较表明,这两种定量方法在白垩纪大洋红层中的 应用是可行的。但在实际应用时,首先要通过XRD和DRS相结合来提高定性分析的准确性,然后通过综合分析铁氧化物的 预判含量范围和结晶程度来选择合适的定量方法。     

稳定赤泥路用可行性与耐久性试验研究

水泥系结合料稳定赤泥应用于公路工程是消纳大宗工业固体废料赤泥的新技术路向。目前,路用稳定赤泥耐久性能的研究滞后于工程实践,为对此研究,进行稳定剂配比研究、干湿循环与冻融循环试验和微观试验。结果表明：水泥、石灰和磷石膏结合料稳定赤泥的标准强度最小为3.6 MPa,可满足路面稳定基层承载标准,且5级循环后试样质量损失趋于稳定。磷石膏比例由8%减小到2%,5级干湿循环后强度降低至1.69～3.69 MPa,强度损失率(BDR/%)达到35.1%～85.4%,5级冻融循环后强度降低至2.63～3.70 MPa,强度损失率(BDR/%)达到54.82%～79.79%,表明硫激发耦合效应的磷石膏掺量不宜超过赤泥用量的2%。此外,压汞试验研究揭示干湿与冻融循环导致试样大孔隙(直径>0.1μm)占比增加,并与强度呈显著负相关。综合承载性能与耐久性能试验,使用稳定赤泥替代公路道面水稳材料是可行的,最优配比为赤泥：水泥：石灰：磷石膏=100︰8︰2︰2。基于循环强度衰减特征,工程实践中施工期限制、早期养护质量等至关重要,且应严格控制稳定赤泥中的磷石膏掺量。     

Superoxide-mediated reduction of organically complexed iron(III): Impact of pH and competing cations (Ca)

The mechanism and kinetics of superoxide-mediated reduction of a variety of organic iron(III) complexes has been investigated over the pH range 7-9. Our experimental results show that the rate of iron(II) formation is a function of pH, ligand type and ligand concentration with the measured rate varying between 0.44 ± 0.07 and 39.25 ± 1.77 pM s⁻¹ in the systems investigated. Additionally, our results show that the presence of competing cations such as Ca²⁺ have a significant impact on iron(II) formation if the organic ligand is strongly complexed by Ca²⁺. Formation of iron(II) occurs by either (or, in some instances, both) reaction of superoxide with inorganic iron(III) after its dissociation from the complex (dissociative reduction) or by direct reaction of superoxide with the complex (non-dissociative reduction). In the presence of weak ligands, dissociative reduction (DR) dominates; however non-dissociative reduction (NDR) becomes important in the presence of either strongly binding ligands or high concentrations of weakly binding ligands. The major factors contributing to the pH dependence of the iron(II) formation rate are the complexation kinetics of inorganic iron(III) (which controls the DR contribution) and the reduction kinetics of the iron(III) complex (which controls the NDR contribution). The relative NDR contribution increases with increasing superoxide and ligand concentration and decreasing pH for all ligands examined. Since iron(II) formation occurring via NDR results in a significantly larger increase in the proportion of iron in free aquated form than does DR, this non-dissociative pathway of superoxide-mediated iron(III) reduction is particularly effective in increasing the lability of iron in aquatic systems.     

西北荒漠草甸植被光谱反射特征研究

选取位于西北干旱内陆地区的安西荒漠草场为观测试验区,分别对盐生低地草甸、极旱荒漠草甸和荒漠灌丛三类草地进行了地面反射光谱测定,并分析了主要荒漠草甸植被光谱反射的一般特征和红边参数特征,进而探讨了形成草地光谱特征差异的主要内在原因和影响因素。结果表明:在近红外波段,由于荒漠植被类别间叶片内部结构变化大,因此冠层光谱反射率差异较大;同一植被冠层光谱反射率的大小主要受植被长势的影响;受沙地背景的影响,在近红外波段,植被冠层的光谱反射率要明显小于叶片的光谱反射率;荒漠植被冠层光谱的红边也具有“双峰”现象,红边特征的参数表现为:沙地植被>绿洲植被>沙漠植被。对安西荒漠植被光谱特征的分析研究,对于研究干旱区荒漠植被的理化性能、遥感反演、植被分类、植被调查等都具有重要的意义。     

Iron Speciation of Mud Breccia from the Dushanzi Mud Volcano in the Xinjiang Uygur Autonomous Region, NW China

Organic-inorganic interactions occurring in petroleum-related mud volcanoes can help predict the chemical processes that are responsible for methane emissions to the atmosphere. Seven samples of mud breccia directly ejected from one crater were collected in the Dushanzi mud volcano, along with one argillite sample of the original reddish host rocks distal from the crater, for comparison purposes. The mineral and chemical compositions as well as iron species of all samples were determined using XRD, XRF and M?ssbauer spectroscopy, respectively. The results indicate that a series of marked reactions occurred in the mud volcano systems, more specifically in the mud breccia when compared to the original rocks. Changes mainly included: (1) some conversion of clay minerals from smectite into chlorite and illite, and the precipitation of secondary carbonate minerals such as calcite and siderite; (2) silicon depletion and significant elemental enrichment of iron, manganese, magnesium, calcium and phosphorus; and (3) transformation of iron from ferric species in hematite and smectite into ferrous species in siderite, chlorite and illite. These geochemical reactions likely induced the color changes of the original reddish Neogene argillite to the gray or black mud breccia, as a result of reduction of elements and/or alteration of minerals associated with the oxidation of hydrocarbons. Our results also suggest that greenhouse gases emitted from the mud volcanoes are lowered through a series of methane oxidation reactions and carbon fixation (i.e., through carbonate precipitation).     

不同含水率条件下赤泥掺量对红黏土力学性质及结构的影响

本文通过在不同含水量条件下对等比例赤泥改良红黏土的物理力学性质进行试验研究,研究含水量对赤泥红黏土的影响和作用机理。再通过电镜扫描,研究不同比例赤泥对红黏土微观结构的影响。试验结果表明,宏观上,掺入赤泥后红黏土随着含水量的增大,抗剪强度呈先增后减的趋势。压缩试验研究中,掺入赤泥的红黏土压缩性随含水量的增大整体呈降低趋势,下降幅度随着赤泥含量的增大而增大。微观上,不同赤泥含量的红黏土土样表面颗粒从团聚体向片状体变化,结构从疏松状态逐渐向致密状态过渡,孔隙减少使得赤泥红黏土的吸水能力减弱。     

黄土剖面中赤铁矿和针铁矿的定量分析与气候干湿变化研究

为了了解黄土剖面中赤铁矿和针铁矿的分布特征,文章采用对铁氧化物矿物灵敏的漫反射光谱法(DRS),开展了赤铁矿和针铁矿的鉴定和测定研究,提出了定量分析赤铁矿和针铁矿含量的DRS新方法.选择天然典型黄土和古土壤样品,首先采用柠檬酸盐-重碳酸盐-连二亚硫酸盐(CBD)方法去除其中成壤成因的铁氧化物矿物,以其为基体配制含不同赤铁矿和针铁矿的系列标样,然后进行DRS测试和多元逐步回归分析,分别建立测定赤铁矿和针铁矿含量的校准方程并加以检验.利用DRS方法,分析了多个黄土剖面的赤铁矿和针铁矿含量,发现黄土-古土壤剖面的赤铁矿/针铁矿比值可作为东亚季风干/湿变化的敏感指标.该比值较高时反映了干燥土壤环境,而较低时指示了潮湿土壤环境.对灵台和洛川剖面中赤铁矿/针铁矿比值的分析,初步揭示了2.6Ma年以来黄土高原东亚季风阶段性变强的特征.     

Feasibility of red mud neutralization with seawater using Taguchi’s methodology

In this study, feasibility of using seawater to neutralize alkaline red mud for its safe disposal has been studied using Taguchi’s design of experimental methodology. Parameters such as weight of red mud, volume of seawater, stirring time and temperature were tested at three levels to study their effect on response characteristic, i.e., pH of the neutralized slurry. The analysis of variance showed that volume of seawater added and quantity of red mud are the two significant parameters with 53.59 and 44.92 % contribution each, respectively. Under the optimized parameters, pH value of red mud slurry reaches to about 8.0 which is within disposable limits. When seawater or other Ca- and Mg-rich brines are added to caustic red mud, the pH of the mixture is reduced causing hydroxide, carbonate or hydroxy carbonate minerals to be precipitated. This mechanism of neutralization process has been explained with emphasis on chemical analysis, mineralogy and morphology of the neutralized red mud. The process improved the physical characteristics of red mud with entrained liquor becoming non-hazardous water with reduced alkalinity. The results would be extremely useful in the process of safe disposal of red mud.     

邻二氮菲分光光度法测定赤泥和石灰石混匀度

用盐酸提取赤泥和石灰石的混合料后,通过邻二氮菲分光光度法测定提取液中铁含量,进而求得混合料中氧化铁的质量分数,以此来衡量混匀度。结果表明,该法与重铬酸钾法比较,精密度和准确度均无显著性差异,测定混匀度的相对误差在±2%,且方法简便、快速、准确、对环境友好,可用于生产实时监控。     

Single-crystal infrared reflectivity of pure Mg2SiO2 forsterite and (Mg0.86,Fe0.14)2SiO4 olivine

New polarized infrared reflectance spectra of pure synthetic forsterite and natural Fo₈₆-olivine have been recorded from 5000 to 100cm^-1. Out of the 35 expected infrared active modes, 33 have been observed (8 B_1u, 12 B_2u, 13 B_3u). The observed frequency shift from pure forsterite to Fo₈₆-olivine is consistent with the higher mass of the substituted iron. The substitution of only 14% of iron also reduces the overal far-infrared reflectivity of olivine as compared to pure forsterite. Several discrepancies associated with previous studies of forsterite are explained by our investigation. We suggest that some of the previous investigations were complicated by polarization mixing.     

Model Test on Self-Weight Consolidation of the Red Mud Tailings Placed in the Karsts

The management of tailings depends on its consolidation behavior to great extent. The red mud tailings in Pingguo, Guangxi is of high water content and void ratio. The present paper takes the red mud aluminiferous tailings in Pingguo, Guangxi as prototype. Model tests were carried out to study the consolidation behavior of red mud aluminiferous tailings that were landfilled layer by layer. The layered settlement and the water discharge caused by self-weight consolidation were studied. The influence of the latter landfilled layer of red mud on the previous layer was analyzed. The results show that the settlement at the surface with time can be divided into two stages. During the first stage, a thin layer of water appeared and the thickness kept increasing at the top of the mud surface with the particle of red mud sinking. During the second stage, water drained from the mud and settlement developed slowly. Cracks developed at the surface due to evaporation and the red mud near the surface became unsaturated. When the previous landfilled layer consolidated to the degree that the water content was less than 40%, the later landfilled layer of red mud will have little influence on the settlement of previous landfilled layer.     

Iron speciation of sliding mud in Toyama Prefecture, Japan

It has been often observed that black mud recently formed and accumulated in slip planes that are closely associated with a progressing landslide in Japan. Mössbauer spectroscopy revealed that the composition of Fe species in the sliding mud is different from those in the debris rock and bedrock. The sliding mud contains more ferrous iron species, which indicates a relatively stronger reducing condition within the sliding zone than within the host rocks. In addition, the composition of Fe species, the total Fe and the volume of sliding mud also change with landslide development. Therefore, detailed Fe speciation in landslide profiles can be a useful approach to understanding the progress of a landslide and may also predict future sliding as well.     

Iron and chromium doped titanium dioxide nanotubes for the degradation of environmental and industrial pollutants

Pure titanate nanotubes and titanate nanotubes doped with iron (III) and chromium (III) were fabricated by the hydrothermal treatment in methanol and sodium hydroxide mixture. The fabricated nano tubes have high surface area, high aspect ratio, consisted of very good surface morphology and high metals dispersion. The morphology, crysralline phase, composition were characterized by powdered X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Barrett-Joyner-Halenda methods and X-ray photoelectron spectroscopy. The results showed that nanotubes possess anatase phase and are composed up of 8–12 nm in diameter and 360–400 nm in length. The band gap of the titanium dioxide nanotubes was determined using transformed diffuse reflectance spectroscopy according to the Kubelka-Munk theory, showed pronounced band gap decrease on doped titanium dioxide nanotubes. The photocatalytic activity of doped nanotubes were evaluated in terms of degradation of phenol and photoreduction of carbon dioxide into methanol and ethanol under Ultra violet and Infra red irradiation. It was found that with iron (III) and chromium (III) doped titanium dioxide nanotubes exhibited much higher photocatalytic activity than undoped titanate nanotubes.