A combined IR and XRD study of natural well crystalline goethites(α-FeOOH)

Goethite(a-FeOOH)is one of the most abundant minerals on the Earth surface,occurring in temperate,tropical and equatorial climates.Fe in goethite can be substituted by many cations such as Al,Ni for instance.A large amount of research has been conducted on the effect of varying elemental compositions(mainly Al-content)on the spectral features of goethites with most of the studies based on materials synthesized with different elemental ratios.The different elemental ratios,however,may not only affect the composition of the products but also their crystallinity and/or particle size and shape.Both parameters are known to affect results of both X-ray diffraction(XRD)and infrared spectroscopy(IR).These methods are predominantely used to characterize goethites.In the present study,therefore,a significant set of natural goethites was considered in order to investigate the effect of elemental composition on XRD and IR results.The focus was on crystallised samples which had a limited chemical variability but artefacts caused by the presence of admixtures could be excluded in most cases.First of all Rietveld refinement was optimized based on varying different parameters.A fairly good correlation of Rietveld derived crystallite sizes and specific surface area determined by N-adsorption(SSA)was found which proves the importance of considering the crystallite size parameters for Rietveld refinement and at the same times proves the quality of it.Using IR spectroscopy yet published relations of band position and Al-content could be confirmed despite the fact that the range of Al-contents was small.However,the band position of the Fe–O stretching,previously used as proxy for crystallinity assessment,was found to be least variable hence contradicting yet published results.Controversial results were also published for the effect of the Al-content on the position of the asymmetric FeOH stretching band at 450 cm.The goethites investigated in the present study indicate that the crystallite size determines the band position rather than the Al-content which is at least valid for the limited range of Al-contents.The results of the present study indicate that using synthetic sample sets bears the problem that more than one parameter might show systematic differences(e.g.crystallite size in a set of chemically varied goethites).The paper,therefore,provides IR reference data based on a set of natural well crystallised goethites.

Insights into the changes in the surface properties of goethite with Ni in the lattice in the presence of salicylhydroxamic acid:Experimental and density functional theory studies

Comparative experiments and theoretical analysis of the surface chemistry changes of goethite(GT)and goethite containing Ni(GTN)in the lattice in the presence of salicylhydroxamic acid(SA)were performed.It was revealed that in the presence of 100 g·t^(-1)of SA,the flotation recovery of GTN and GT increased with increasing pH,achieving a maximum recovery of 98.9%for both minerals at p H 8.3 and decreasing beyond that pH,with GTN having a slightly higher recovery than GT,except at pH 8.3.This was further confirmed by the higher complexation energies of GTN···SA(-883.87 kJ·mol^(-1))compared with GT···SA(-604.23 kJ·mol^(-1))resulting from covalent,closed-shell,and conventional hydrogen bonding.The higher adsorption of SA onto GTN relative to GT was due to the formation of aπ-hole in GTN,thereby promoting a higher interaction of the collector with the mineral.Thus,the presence of Ni in the GT lattice improves and decreases the adsorption and desorption of SA onto and from the mineral,respectively,compared with those onto and from GT.

Comparison of the effects of Ti-and Si-containing minerals on goethite transformation in the Bayer digestion of goethitic bauxite

Goethitic bauxite is a widely used raw material in the alumina industry.It is an essential prerequisite to clarify the effect of Ti-and Si-containing minerals on goethite transformation in the Bayer digestion process,which could efficiently utilize the Fe-and Al-containing minerals present in goethitic bauxite.In this work,the interactions between anatase or kaolinite with goethite during various Bayer digestion processes were investigated using X-ray diffraction (XRD),X-ray photoelectron spectroscopy (XPS),transmission electron microscopy (TEM),and scanning electron microscopy (SEM).The results showed that anatase and kaolinite hindered the transformation of goethite.Anatase exerted more significant effects than kaolinite due to the dense sodium titanate layer on the goethite surface after reacting with the sodium aluminate solution.Adding the reductant hydrazine hydrate could eliminate the retarding effect by inducing the transformation of goethite into magnetite.In this process,titanium was embedded into the magnetite lattice to form Ti-containing magnetite.Furthermore,the weakening of the interaction between magnetite and sodium aluminosilicate hydrate reduced the influence of kaolinite.As a validation of the above results,the reductive Bayer method resulted in the transformation of goethite into goethitic bauxite with 98.87% relative alumina digestion rate.The obtained red mud with 72.99wt% Fe2O3could be further utilized in the steel industry.This work provides a clear understanding of the transformative effects of Ti-and Si-containing minerals on iron mineral transformation and aids the comprehensive use of iron and aluminum in goethitic bauxite subjected to the reductive Bayer method.

In situ infiltration-precipitation processes in some rock systems

We carry out a chemical treatment(acidization or basification)of typical rock specimens in-situ,and characterize the emerging pattern resulting from the infil-tration-precipitation scenario.Galena and limestone sam-ples were treated with sulfuric acid,while pyrite was reacted with sodium hydroxide.Various infiltration tech-niques were employed,after selection of the most feasible method for each rock separately.The patterns of anglesite(PbSO_(4)),anhydrite(CaSO_(4))and goethite(FeOOH)depo-sition presented different alteration modes of the bare rock textures.Among the three deposited minerals,only the anhydrite(CaSO_(4))displayed a band stratification.The formation of a Liesegang pattern in the rock of highest porosity indicates a plausible correlation between the band formation and a minimum porosity requirement.A banded rock of compact texture could then be formed by a cementation mechanism,governing the long time evolution of the rock.

Mineralogy and crystal chemistry of a low grade nickel laterite ore

To acquire understanding of Ni enrichment from laterite ore,the mineralogy and crystal chemistry of a low grade limonite type nickel laterite ore sample assaying 0.97% Ni from Indonesia were studied using optical microscopy,X-ray diffraction（XRD）,scanning electron microscopy（SEM） and electron probe microanalysis（EPMA）.According to EPMA results,the mineral includes 80% goethite（（Fe,Ni,Al）O（OH）） with 0.87% Ni,15% silicate minerals with lizardite（（Mg,Fe,Ni）3Si2O5（OH）） and olivine（（Mg,Fe,Ni）2SiO4）,and 1.19% Ni,and other minor phases,such as hematite,maghemite,chromite and quartz,and no Ni was detected.The mineralogy of the laterite ore indicates that due to the complicated association of the various phases and the variable distribution of Ni,this refractory laterite ore can not be upgraded by traditional physical beneficiation processes.

Negative effects of dissolved organic compounds on settling performance of goethite in Bayer red mud

Goethite, a typical iron-containing monomineral in red mud, was synthesized under the simulated Bayer digestion condition during the alumina production. The effects of dissolved organic compounds including sodium formate, sodium acetate, sodium oxalate, sodium salicylate and disodium phthalate on the settling performance of goethite slurries were studied. The settling performance of the slurries was also investigated with the addition of self-made hydroxamated polyacrylamide flocculant （HCPAM）. The adsorption mechanism of dissolved organic compounds on the goethite surfaces was studied by FT-IR and XPS, respectively. The results show that the addition of organic compounds lowers the settling performance of the slurries and a deterioration in settling performance is observed in the order of sodium oxalate 〉 sodium salicylate （~ disodium phthalate） 〉 sodium formate 〉 sodium acetate. Moreover, HCPAM can efficiently eliminate the negative effects of sodium formate, sodium acetate and sodium oxalate on the settling performance of the goethite slurries, but it can only partially improve the settling performance of the goethite slurries containing sodium salicylate or disodium phthalate. FT-IR and XPS results show that these organic compounds are chemically adsorbed on the goethite surface.

Goethite Morphologies of Some Soils in South of Central China

The morphologies of goethites in latosol, red soils, yellow-brown soil and the paddy soils developed from red soils were studied in comparison with the morphology of synthetic goethite by means of the X-ray distraction, transmission electron microscopy and energy dispersive X-ray analysis. The synthetic goethite displayed acicular particles elongated in the c-direction. The goethites in the latosol, red soils and yellowbrown soil were platy particles stretched in two directions or isodimensional particles, and those in the paddy soils from red soils were acicular, short columnar, platy or isodimensional particles. Various morphologies of the goethites probably suggested their different dominant crystal faces, surface charge distribution and surface adsorption characteristics.

FT-IR, XPS, and DFT Study of Adsorption Mechanism of Sodium Acetohydroxamate onto Goethite or Hematite

The adsorption of sodium acetohydroxamate on the goethite or hematite surface was investi- gated by Fourier transform infrared spectroscopy （FT-IR）, X-ray photoemission spectroscopy and periodic plane-wave density functional theory （DFT） calculations. The core-level shifts and charge transfers of the adsorbed surface iron sites calculated by DFT with periodic in- terfacial structures were confronted to the X-ray photoemission experiments. FT-IR results reveal that the interracial structure of sodium acetohydroxamate adsorbed on the goethite or hematite surface may be assigned to a five-membered ring complex. In agreement with the adsorption energies determined by the DFT calculations, a five-membered ring complex is formed via bonding of one surface iron atom of goethite （101） or （100） to both oxygen atoms of hydroxamate group, and these two oxygen atoms of the hydroxamate group correspond- ingly attach to two neighboring iron atoms of the goethite surface. But a five-membered ring complex between two oxygen atoms of the hydroxamate group and one surface iron atom of hematite （001） is formed without any extra attachments. The calculated core-level shifts of Fe2p for the interracial structures are correspondingly in good agreement with the experimental observed one, which confirmed the reliability of the calculated results.

铁成分对硫化锌精矿的半导体性质及化学反应性的影响

硫化锌精矿(以下简称精矿)除含有主要元素锌与硫外,还含有其它元素,尤其是含有相当多的铁。在湿法处理精矿时,其铁成分的行为取决于铁的矿物存在形式。精矿中的铁可以铁闪锌矿[(Zn,Fe)S)、黄铁矿、黄铜矿的形式存在。铁闪锌矿的铁含量可在很大的范围内变化,其物理化学性质也随铁含量而变化,因此对精矿的湿法直接处理产生很大的影响。本文研究出一种可靠的、确定精矿矿物组成的化学分析方法,着重于测定铁在精矿各矿物中的分布,及铁闪锌矿铁含量的变化规律。在此基础上,实验研究了精矿中的铁(尤其是铁闪锌矿中的铁)对精矿的半导体性质的影响规律,应用半导体电化学原理讨论了精矿铁含量对精矿的直接浸出(常压、硫酸介质)的影响机理。

Effect of Reduction Associated with Organic Matter Decomposition on Magnetic Properties of Red Soils

Five soils derived from different parent materials were sampled from red soilregion of southern China and studied by magnetic methodology to understand to what extent ironreduction would affect soil magnetic properties and how iron reduction would affect the magneticminerals in soils. Reduction associated with organic matter decomposition strongly affected soilmagnetic parameters at low pH. The losses of original soil magnetic signals in terms of magneticsusceptibility (X), 'Soft' isothermal remanent magnetization ('Soft' IRM), anhysteretic remanentmagnetization (ARM) and saturation isothermal remanent magnetization (SIRM) at pH 4～6 during thetwo-month saturation treatment, were 66%～94%, 54%～90%, 64%～95% and 33%～83%, respectively. Thesechanges were interpreted as a consequence of substantial dissolution of maghaemite and haematite inthe soils. At pH 10, however, there was no significant magnetic change observed. Moreover, stablesingle domain soil maghaemite grains were also sensitive to reduction, which suggested that bothpedogenic and detrital maghaemite were not stable in acid and reducing environments. Goethite,instead, was the most stable iron form under reducing conditions.

Competitive and cooperative adsorption of arsenate and citrate on goethite

The fate of arsenic in natural environments is influenced by adsorption onto metal （hydr）oxides. The extent of arsenic adsorption is strongly affected by coexisting dissolved natural organic acids. Recently, some studies reported that there existed competitive adsorption between arsenate and citrate on goethite. Humic acid is known to interact strongly with arsenate by forming complexes in aqueous solution, hence it is necessary to undertake a comprehensive study of the adsorption of arsenate/citrate onto goethite in the presence of one another. The results showed that at the arsenate concentrations used in this study （0.006-0.27 mmol/L）, citrate decreased arsenate adsorption at acidic pH but no effect was observed at alkaline pH. In comparison, citrate adsorption was inhibited at acidic pH, but enhanced at alkaline pH by arsenate. This was probably due to the formation of complex between arsenate and citrate like the case of arsenate with humic acid. These results implied that the mechanism of the adsorption of arsenate and citrate onto goethite in the presence of one another involved not only competition for binding sites, but the cooperation between the two species at the watergoethite interface as well.

Types of Crystalline Iron Oxides and Phosphate Ad－sorption in Variable Charge Soils

The types, contents and morphologies of crystalline Fe oxides and their relations to phosphate adsorptionon the clay fractions in soils with variable charge in southern China were investigated by means of XRD, TEM,EMA and chemical analysis methods.Results indicated that the types and contents of crystalline Fe oxidesvaried with the soils examined. The dominant crystalline Fe oxide was hematite in the latosols and goethitesin the red soils.In yellow-brown soils, the only crystalline Fe oxide was goethite.The difference between Aldand Alo came mainly from the Al substituting for Fe in the pe oxides. The crystal morphology of goethiteappeared mainly as subrounded flat or iso-dimensional rather than acicular particles. Hematites occurredin plates of various thickness. Their MCDa/MCDc ratios in the latosols and red soils were generally above1.5 and below 1.5, respectively. The MCD values of goethites and hematites were 15-25nm and 20-35nm,and their specific surface areas were 80-120m￣2/g and 35-75m￣2/g, respectively.The goethite crystals weregenerally smaller. Variations of the total amounts of crystalline Fe oxi es in clay fractions were not related tophosphate adsorption. The types, contents and morphologies of crystalline Fe oxides in the soils remarkablyaffected phosphate adsorption characteristics of the soils. The phosphate adsorption of goethite was muchgreater than that of hematite. The higher the MCD /MCDc rotio of hematite, the lower the phosphateadsorption.

Study on kinetics of thermal decomposition of low LOI goethetic hematite iron ore

In the present study, the kinetics of thermal decomposition of hydrated minerals associated in natural hematite iron ores has been investigated in a fixed bed system using isothermal methods of kinetic analysis. Hydrated minerals in these hematite iron ores are kaolinite, gibbsite and goethite, which contribute to the loss on ignition(LOI) during thermal decomposition. Experiments in fixed bed have been carried out at variable bed depth(16, 32, 48 and 64 mm),temperature(400-1200 ℃) and residence time(30,45, 60 and 75 min) for iron ore samples. It is observed that beyond a certain critical bed depth(16 mm), 100% removal of LOI is not found possible even at higher temperature and higher residence time. Most of the solid-state reactions of isothermal kinetic analysis have been used to analyze the reaction mechanism. The raw data are modified to yield fraction reacted "α" versus time and used for developing various forms of "α" functions.f(α) is the inverse of first derivative of g(α) with respect to α. The study demonstrates that decomposition of hydrated mineral in hematite follows the chemical kinetics.The estimated activation energy values in all the experimental situations are found to high, of the order of 60 kJ/mol, reinstating that the reactions are indeed controlled by moving phase boundary and random nucleation.

Extraction of valuable metals from low nickel matte by calcified roasting-acid leaching process

A calcified roasting-acid leaching process was developed as a highly effective method for the extraction of valuable metals from low nickel matte in the presence of CaO additive. The influences of process parameters on the metal extraction were studied, including the roasting temperature, roasting time, addition of CaO, H2SO4 concentration and liquid-solid ratio. Under the optimum condition, 94.2% of Ni, 98.1% of Cu, 92.2% of Co and 89.3% of Fe were recovered. Additionally, 99.6% of Fe was removed from the leachate as goethite by a subsequent goethite iron precipitation process. The behavior and mechanism of CaO additive in the roasting process was clarified. The role of CaO is to prevent the formation of nonferrous metal ferrite phases by a preferential reaction with Fe2O3 during the roasting process. The metal oxides(Cu O and NixCu1-xO) remained stable during high-temperature roasting and were subsequently efficiently leached using a sulfuric acid solution.

Microwave-assisted reduction roasting–magnetic separation studies of two mineralogically different low-grade iron ores

The microwave-assisted reduction behaviours of two low-grade iron ores having a similar Fe content of 49wt%but distinctly different mineralogical and liberation characteristics were studied.Their performances in terms of the iron grade and recovery as obtained from statistically designed microwave(MW)roasting followed by low-intensity magnetic separation(LIMS)experiments were compared.At respective optimum conditions,the titano-magnetite ore(O1)could yield an iron concentrate of 62.57%Fe grade and 60.01%Fe recovery,while the goethitic ore(O2)could be upgraded to a concentrate of 64.4%Fe grade and 33.3%Fe recovery.Compared with the goethitic ore,the titanomagnetite ore responded better to MW heating.The characterization studies of the feed and roasted products obtained at different power and time conditions using X-ray diffraction,optical microscopy,vibrating-sample magnetometry,and electron-probe microanalysis explain the sequential reduction in the iron oxide phases.Finally,taking advantage of the MW absorbing character of the titano-magnetite ore,a blend of the same with the goethite-rich ore at a weight ratio of 60:40(O2:O1)was subjected to MW roasting that resulted in a concentrate of 61.57%Fe grade with a Fe recovery of 64.47%.

Roasting-induced phase change and its influence on phosphorus removal through acid leaching for high-phosphorus iron ore

In the present study, roasting-induced phase change and its influence on phosphorus removal via leaching has been investigated for high-phosphorus iron ore. The findings indicate that phosphorus in the ore is associated with goethite and exists mainly in amorphous Fe3PO7 phase. The phosphorus remains in the amorphous phase after being roasted below 300℃. Grattarolaite （Fe3PO7） is found in samples roasted at 600-700℃, revealing that phosphorus phase is transformed from the amorphous form to crystalline grattarolaite during roasting. Leaching tests on synthesized pure grattarolaite reveal a low rate of phosphorus removal by sulfiaric acid leaching. When the roasting tem- perature is higher than 800℃, grattarolaite is found to react with alumina to form aluminum phosphate, and the reactivity of grattarolaite with alumina increases with increasing roasting temperature. Consequently, the rate of phosphorus removal also increases with increasing roasting temperature due to the formation of acid-soluble aluminum phosphate.

Oxidation of As^Ⅲ by Several Manganese Oxide Minerals in Absence and Presence of Goethite

Oxidation of As^Ⅲ by three types of manganese oxide minerals affected by goethite was investigated by chemical analysis, equilibrium redox, X-ray diffraction （XRD） and transmission electron microscopy （TEM）. Three synthesized Mn oxide minerals of different types, birnessite, todorokite, and hausmannite, could actively oxidize As^Ⅲ to Asv, and greatly varied in their oxidation ability. Layer structured birnessite exhibited the highest capacity of As^Ⅲ oxidation, followed by the tunnel structured todorokite. Lower oxide hansmannite possessed much low capacity of As^Ⅲ oxidation, and released more Mn^2＋ than birnessite and todorokite during the oxidation. The maximum amount of Asv produced during the oxidation of As^Ⅲ by Mn oxide minerals was in the order： birnessite （480.4 mmol/kg） 〉 todorokite （279.6 mmol/kg） 〉 hansmannite （117.9 mmol/kg）. The oxidation capacity of the Mn oxide minerals was found to be relative to the composition, crystallinity, and surface properties. In the presence of goethite oxidation of As^Ⅲ by Mn oxide minerals increased, with maximum amounts of Asv being 651.0 mmol/kg for birnessite, 332.3 mmol/kg for todorokite and 159.4 mmol/kg for hansmannite. Goethite promoted As^Ⅲ oxidation on the surface of Mn oxide minerals through adsorption of the Asv produced, incurring the decrease of Asv concentration in solutions. Thus, the combined effects of the oxidation （by Mn oxide minerals）-adsorption （by goethite） lead to rapid oxidation and immobilization of As in soils and sediments and alleviation of the As^Ⅲ toxicity in the environments.

A Study of Chromium Adsorption on Natural Goethite Biomineralized with Iron Bacteria

Goethite, especially biogenic goethite, has high specific surface area and great capacity for the adsorption of many contaminants including metal ions and organic chelates. Chromium is a redox actively toxic metal ion that exists as either Cr^Ⅲ or Cr^Ⅵ in nature, and as such it is essential to understand its behavior of adsorption on natural goethite mineralized by iron bacteria, as Gallionella and Leptothrix in water body. The adsorption of Cr^3＋ and Cr^Ⅵ on naturally biomineralized goethite is studied in this paper. The results show that both Langmuir and Freundlich adsorption isothermal models are able to accurately describe the adsorption of these two ions. Investigation of SEM/EDS, TEM/EDS indicates that the two ions do not adsorb homogeneously on goethite owing to the different microstructures of goethite, and that the microspherical goethite has a greater adsorption capacity for chromium ions than the helical one. XPS data show that redox reaction of chromium on the surface of biomineralized goethite takes place in the adsorption of both Cr^3＋ and Cr^Ⅵ. The CrvI adsorbed on biogoethite is much easier to transform into CrIII than the oxidization of Cr^Ⅲ on the bio-goethite.

Adsorption of Acid Phosphatase on Minerals and Soil Colloids in Presence of Citrate and Phosphate

The aim of this work was to study the influence of phosphate and citrate, which are common inorganic and organic anions in soils, on the adsorption of acid phosphatase by kaolin, goethite and the colloids separated from yellow-brown soil (YBS) and latosol (LS) in central-south China. The YBS colloid has the major clay mineral composition of 1.4 nm mineral, illite and kaolinite while the LS colloid mainly contains kaolinite and oxides. The adsorption isotherm of acid phosphatase on the examined soil colloids and minerals fitted to the Langmuir model. The amount of enzyme adsorbed in the absence of ligands was in the order of YBS colloid > LS colloid > kaolin ≈ goethite. In the presence of phosphate or citrate, the amounts of the enzyme adsorbed followed the sequence YBS colloid > kaolin > LS colloid > goethite. The presence of ligands also decreased the binding energy between the enzyme and soil colloids or minerals. With the increase of ligand concentration from 10 mmol L-1 to 400 m mol L-1, different behaviors for the adsorption of enzyme were found in the colloid and mineral systems studied. A sharp decrease in enzyme adsorption was observed on goethite while gradual decreases of enzyme adsorption were recorded in the two soil colloid systems. However, no any decrease was found for the amount of enzyme adsorbed on kaolin at higher ligand concentrations. When phosphate or citrate was introduced to the system before the addition of enzyme, the ligands usually enhanced the adsorption of enzyme. The results obtained in this study suggested the important role of kaolinite mineral in the adsorption of enzyme molecules in acidic soils in the presence of various ligands.

Characterization of Iron Grains near the P/T Boundary in the Meishan Section of China

The Meishan section of China has been confirmed as the ＂Global Stratotype Section and Point＂ of the P/T boundary. In the section, the authors found several types of iron grains, including pyrite, pure iron grains and goethite. From the research of macro minerals, it is easy to find that the grains rich in iron appear from the bottom of the event layer of the section. In other words, it is probably residue of the geochemical catastrophe of that time. Therefore, it is important to trace the source of these iron grains and their relationships, which probably provides evidence for volcanic eruption or impact-volcanoes and has directive significance to the crisis during the P/T transitional period. Through the study of the characterization and relationships of these iron grains, the authors make a preliminary discussion on the P/T mass extinction.