Thermal transformations of akaganéite and lepidocrocite to hematite: assessment of possible precursors to Martian crystalline hematite

We examine the possibility that crystalline hematite (α-Fe₂O₃) deposits on Mars were derived from the precursor iron oxyhydroxide minerals akaganéite (β-FeOOH) or lepidocrocite (γ-FeOOH) and compare them to an earlier study of goethite (α-FeOOH) and magnetite (Fe₃O₄) precursors. Both the mid-infrared and visible/near infrared spectra of hematite are dependent upon the hematite precursor mineral and the temperature of transformation. Laboratory spectra are compared to spectra from the Mars Global Surveyor Thermal Emission Spectrometer (MGS-TES) and the Mars Exploration Rover (MER) Opportunity Mini-TES and Pancam experiments, allowing us to infer the formation environment of Martian crystalline hematite deposits. Akaganéite and lepidocrocite readily transform to hematite at temperatures of 300 and 500°C, respectively. The visible/near-infrared and mid-infrared spectra of akaganéite-derived hematite are poor matches to data returned from TES, Mini-TES, and Pancam. The spectra of lepidocrocite-derived hematite are slightly better fits, but previously published spectra of goethite-derived hematite still represent the best match to MGS and MER spectral data. The experiments demonstrate that hematite precursor mineralogy, temperature of formation, and crystal shape exert a strong control on the hematite spectra.     

长江三角洲全新世地层中潮滩沉积磁性特征及其古环境意义

对长江三角洲北翼江苏南通地区NT钻孔（长60.9 m）进行了系统的环境磁学分析,并结合岩性特征、粒度、漫反射光谱（DRS）等手段,探讨了全新世早、晚期潮滩沉积的磁性特征及其古环境意义。NT孔自下而上可分为6层（U1~U6层）,其中U2层下部（49.9~44.8 m）和U6层（7.5~0.3 m）为潮滩沉积,具有较低的退磁参数S比值及较高的硬剩磁（HIRM）和SIRM/χ,表明反铁磁性矿物如赤铁矿、针铁矿等含量和比例较高。结合漫反射光谱（DRS）分析,发现U6层上部盐沼（1.5~0.3 m）赤铁矿和针铁矿富集,U2层下部的盐沼仅富集赤铁矿。这一差异与U2层和U6层形成的时期和沉积环境有关。U2层形成于晚更新世晚期至早全新世,且曾长期暴露地表,有利于赤铁矿的形成,其后随着海平面的持续上升,盐沼不断垂向加积,始终处于水下环境,不利于针铁矿的形成;U6层形成于晚全新世三角洲海岸的进积过程中,氧化还原相互交替的环境有利于针铁矿的形成,后期成陆后的成土作用生成了较多的磁赤铁矿和赤铁矿。研究表明,全新世三角洲发育过程中,不同时期形成的盐沼具有不同的磁性特征,磁性特征的研究可以提供潮滩沉积环境演变的信息,对三角洲古环境重建研究具有重要意义。     

福建白垩系沙县组地层磁学特征及其环境意义

广泛分布于中国南方的白垩系巨厚地层被认为是河湖相沉积,蕴含着丰富的古气候古环境变化的信息。白垩纪是典型的温室时期,其气候特征可以为当代和未来温室气候研究提供重要借鉴。对位于中国东南的福建省三明市沙县和永安地区的白垩系沙县组典型地层进行了系统的环境磁学参数测量,结合漫反射光谱(DRS)和色度指标,探讨了该地层磁学特征及其环境指示意义和红色的成因。结果表明:1)红色调和黄色调地层的主要磁性矿物分别为赤铁矿和针铁矿,均含有顺磁性矿物和极少量的亚铁磁性矿物;2)相对于粗粒的砂岩,细粒的粉砂岩赤铁矿含量较高;3)红色赤铁矿与黄色针铁矿均形成于成岩阶段之前,具体形成阶段与形成原因需要具体分析;4)红色调地层的赤铁矿指示高温的气候环境;黄色调地层的针铁矿指示局部的湿润环境。磁学参数变化的具体环境指示意义需要进一步研究。     

Synchrotron-based X-ray study of iron oxide transformations in terraces from the Tinto-Odiel river system: Influence on arsenic mobility

Simultaneous analysis of micro-X-ray diffraction (μ-XRD) and micro-X-ray fluorescence (μ-XRF) based on synchrotron light sources, and electron microprobe (EMP) analyses, were performed on iron terrace samples taken from Tinto-Odiel river system from the Iberian Pyrite Belt (IBP, SW Iberian Peninsula). Iron terraces are formed during the oxidation and precipitation of dissolved iron along the riverbeds impacted by acid mine drainage (AMD). This paper includes the study of actively-forming current terraces and fossil terraces isolated from the stream courses due to the river migration over time. The results of the study of current terrace samples from AMD-affected streams of two IPB abandoned mines (Tinto Santa Rosa and Cueva de la Mora) showed that fresh precipitates at the surface are composed primarily of metastable schwertmannite, which is gradually transformed at depth over short-time scales into goethite. Sediments of ancient terraces are composed mainly of goethite, which most likely originated from the re-crystallization of a precursor schwertmannite. However, at century-time scale, goethite partially re-crystallizes to hematite due to diagenetic processes. The transformation rate of goethite into hematite is negatively correlated with grain size and the crystallinity of goethite. Moreover, this transformation is accompanied by an increase in grain size and a decrease in surface area of hematite, and a concomitant decrease in arsenic trapped in the solid. This increase in the arsenic mobility during the diagenetic maturation should be considered in the development of conceptual and analytical models describing long-term fate, transport and bioavailability of arsenic in environmental systems.     

The hematite–goethite enhancement model of loess and an ‘irregular’ case from Paks,Hungary

On the basis of a key model of the appearance of hematite and goethite in some Chinese and European loess successions, paleosols generally contain higher proportions of hematite formed by pedogenic processes during warm and humid interglacials, while loess contains sedimentary goethite deposited during colder, glacial periods. Rock magnetic measurements were conducted on samples from Paks (Hungary) loess, revealing an anomalous case. Sediments were found to contain higher amounts of hematite and/or goethite, while the well‐developed paleosols were found to be lacking in hematite but had significant amounts of magnetite and maghemite. This observation demonstrates that the character of pedogenic magnetic mineral alteration and neoformation differs from the hematite/goethite model; the model is therefore not applicable to the Paks succession, possibly due to differences in the regional paleoclimate and pedogenic environment. The results indicate the existence of a further model, in which hematite formation is not significant in the course of pedogenesis.     

Surface simulation studies of the hydration of white rust Fe(OH)2, goethite α-FeO(OH) and hematite α-Fe2O3

Computer modelling techniques were used to elucidate the hydration behaviour of three iron (hydr)oxide minerals at the atomic level: white rust, goethite and hematite. A potential model was first adapted and tested against the bulk structures and properties of eight different iron oxides, oxyhydroxides and hydroxides, followed by surface simulations of Fe(OH)₂, α-FeO(OH) and α-Fe₂O₃. The major interaction between the adsorbing water molecules and the surface is through interaction of their oxygen ions with surface iron ions, followed by hydrogen-bonding to surface oxygen ions. The energies released upon the associative adsorption of water range from 1 to 17 kJ mol⁻¹ for Fe(OH)₂, 26 to 80 kJ mol⁻¹ for goethite and 40 to 85 kJ mol⁻¹ for hematite, reflecting the increasing oxidation of the iron mineral. Dissociative adsorption at goethite and hematite surfaces releases larger hydration energies, ranging from 120 to 208 kJ mol⁻¹ for goethite and 76 to 190 kJ mol⁻¹ for hematite.The thermodynamic morphologies of the minerals, based on the calculated surface energies, agree well with experimental morphologies, where these are available. When the partial pressures required for adsorption of water from the gas phase are plotted against temperature for the goethite and hematite surfaces, taking into account experimental entropies for water, it appears that these minerals may well be instrumental in the retention of water during the cyclic variations in the atmosphere of Mars.     

Influence of the aging of Fe oxides on the decline of magnetic susceptibility of the Tertiary red clay in the Chinese Loess Plateau

Magnetic properties, free and active Fe oxides, grain size distribution and mineral assemblage of a Quaternary loess–Tertiary red clay (TRC) section in Lingtai County in the Chinese Loess Plateau were studied. The results suggest that the TRC of the Lingtai section shares similar aeolian characteristics with the overlying Quaternary loess-paleosol sequence (QLPS), but the former is generally more intensively weathered than the latter, as indicated by its higher citrate–bicarbonate–dithionite (CBD) extractable Fe (Fe_d), finer grain size and lower content of easily weathered primary minerals. However, magnetic susceptibility (χ_lf) and magnetic remanence (χ_arm, SIRM and SOFT etc.) of the main part of the TRC are significantly lower, implying the decline of ferrimagnetic minerals (FM). In contrast, hematite and goethite in the TRC is significantly enhanced, as indicated by its higher HIRM. The acid ammonium oxalate (AAO) extractable Fe (Fe_o) of the whole section sharply decreases with increasing age. Fe_o and Fe_o/Fe_d values of the section are significantly correlated with χ_lf. Especially in the TRC, the low values of Fe_o and Fe_o/Fe_d correspond to weak χ_lf. This suggests a significant influence of the age-related transformation of Fe oxides on the decline of FM in the TRC. Lower FM and higher hematite and/or goethite in the TRC further suggest the transformation of FM into hematite with the aging of Fe oxides during post-depositional processes, though more evidence is needed to understand the processes involved. χ_lf of the TRC in the Chinese Loess Plateau mostly cannot be regarded as a promising paleoclimatic proxy because its weak magnetism does not correlate to its strong pedogenesis.     

几种铁（氢）氧化物对溶液中磷的吸附作用对比研究

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。     

Comparative data on the volatile component composition of magma

Ferrihydrite (2.5 Fe₂O₂-4.5 H₂O) is an unstable colloidal mineral. It dissolves in highly alkaline solutions and is precipitated from them in the form of goethite. Jarosite is stable at very low pH but is decomposed at higher values of pH with separation of iron oxides. Experiments show that in rapid decomposition of jarosite a protohematite substance, ferrihydrite, is formed. This transformation occurs at moderate pH values when solutions percolate through the aggregates of jarosite. Ferrihydrite, an unstable colloidal hydrated oxide of ferric iron, changes spontaneously to stable hematite with time. Very slow decomposition of jarosite results in its replacement by iron hydroxide, goethite. Under laboratory conditions in alkaline solutions lepidocrocite may be obtained from jarosite. The synthesis of this iron hydroxide passes through a stage of intermediate products: ferrihydrite and hydrated ferric oxide - ferriprotolepidocrocite, formed by solution of ferrihydrite in strongly alkaline solutions. The transformation of ferriprotolepidocrocite into lepidocrocite may be regarded as a topotactic reaction. —Authors.     

Stable isotope and Rare Earth Element evidence for recent ironstone pods within the Archean Barberton greenstone belt, South Africa

There is considerable debate about the mode and age of formation of large (up to ∼200 m long) hematite and goethite ironstone bodies within the 3.2 to 3.5 Ga Barberton greenstone belt. We examined oxygen and hydrogen isotopes and Rare Earth Element (REE) concentrations of goethite and hematite components of the ironstones to determine whether these deposits reflect formation from sea-floor vents in the Archean ocean or from recent surface and shallow subsurface spring systems. Goethite δ¹⁸O values range from −0.7 to +1.0‰ and δD from −125 to −146‰, which is consistent with formation from modern meteoric waters at 20 to 25 °C. Hematite δ¹⁸O values range from −0.7 to −2.0‰, which is consistent with formation at low to moderate temperatures (40-55 °C) from modern meteoric water. REE in the goethite and hematite are derived from the weathering of local sideritic ironstones, silicified ultramafic rocks, sideritic black cherts, and local felsic volcanic rocks, falling along a mixing line between the Eu/Eu* and shale-normalized HREE_Avg/LREE_Avg values for the associated silicified ultramafic rocks and felsic volcanic rocks. Contrasting positive Ce/Ce* of 1.3 to 3.5 in hematite and negative Ce/Ce* of 0.2 to 0.9 in goethite provides evidence of oxidative scavenging of Ce on hematite surfaces during mineral precipitation. These isotopic and REE data, taken together, suggest that hematite and goethite ironstone pods formed from relatively recent meteoric waters in shallow springs and/or subsurface warm springs.     

Ferrimagnetic minerals in red paleosols of Pleistocene Epoch, eastern China

The type,grain size and origin of ferimagnetic minerals separated from red paleosols of pleistocene Epoch(Q2)in eastern China ,were studied by using mineral magnetic measurement,X-ray powder diffraction and electron microscopy.Results showed that the iron oxider in red paleosols were composed of hematite(α-Fe2O3),maghemite(γ-Fe2O3) and goethite(α-FeOOH),Mineral magnetic parameters and X-ray diffraction patterns indicated that maghemite was the dominant remanence carrier in red paleosols,which is characterized by superparamagnetic(SP) and stable single domain(SSD) grains,The variations of magnetic susceptibility(χ） ,anhysteretic magnetic susceptibility(χRAM）and saturation isothermal remanent magnetization(SIRM) for red paleosols following heating to various temperatures showed two peak values at 700℃ and 900℃.The spherulitic magnetic particles measuring 250-1000μm in diameter in red paleosols were separated by the magnetic separation method,indicating that these magnetic particles were an assemblage of superparamagnetic and stable single domain ferrimagnetic grains,It is suggested that the ferrimagnetic minerals of red paleosols be a pedogenic ferrimagnetic component under high temperature and high humid conditions in the Pleistocene Fpoch(Q2).It is concluded that the magnetism characteristics of red paleosols can be used to evaluate the environmental changes of Quaternary in eastern China.     

The βFeOOH to αFe2O3 phase transformation: Structural and magnetic phenomena

It is shown that under ambient atmospheric conditions heating causes the crystal structure of βFeOOH (synthetic akaganeite) to degenerate gradually into a quasi amorphous intermediate state, before the final phase transformation to αFe₂O₃ (hematite) takes place. Using X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and Mössbauer Spectroscopy, this amorphization process is monitored and the structural, morphological and magnetic features of the intermediate phase as a function of the isochronal heating temperature are discussed: the crystallites develop macropores on their surface, the adsorption capacity raises up to 10 percent of the initial mass, a third type of Fe³⁺ coordination, having an extremely large quadrupole splitting, is created and the Néel temperature, after an initial decrease, exhibits a sharp increase at higher heating temperatures. The magnetic behaviour of this intermediate phase at low temperatures and in high external fields suggests this antiferromagnet undergoes magnetic phase transitions (metamagnetism and spin flop) at unusually low critical fields.     

Field investigations and laboratory simulation of clogging in Lixi tailings dam of Jinduicheng,China

Clogging is one of the most important factors affecting the stability of the tailings dams. Firstly, this work investigates the clogging materials of Lixi tailings dam using ICP-AES, X-ray powder diffraction (XRD) and SEM analysis methods. The ICP-AES results indicate that Fe is the dominant element in the clogging materials. The iron contents of clogging samples collected from 2# radial-well pipe and the access hole of the starter dam are 54.35 and 40.24%, respectively. XRD spectra show that ferric hydroxide is the main initial component of the clogging materials. Other compounds such as akaganeite, hematite and goethite are products from ferric hydroxide transformation. Therefore, the clogging materials are a mixture of ferric hydroxide and its converted products. The clogging materials commonly exist in an amorphous form with a cluster microstructure when viewed under SEM. Secondly, this work uses a continuous flow column to simulate clogging in the laboratory, and the clogging materials are analyzed with XRD and SEM. The chemical analysis indicates that the iron content of the clogging materials from the experiment is 45.43%. XRD spectra show that hematite is the only compound detected. The clogging materials generated experimentally are also in amorphous cluster microstructure when viewed under SEM.     

Microplaty hematite ore in the Yilgarn Province of Western Australia: The geology and genesis of the Wiluna West iron ore deposits

The Wiluna West small (~ 130 Mt) high-grade bedded hematite ore deposits, consisting of anhedral hematite mesobands interbedded with porous layers of acicular hematite, show similar textural and mineralogical properties to the premium high-grade low-phosphorous direct-shipping ore from Pilbara sites such as Mt Tom Price, Mt Whaleback, etc., in the Hamersley Province and Goldsworthy, Shay Gap and Yarrie on the northern margin of the Pilbara craton. Both margins of the Pilbara Craton and the northern margin of the Yilgarn craton were subjected to sub-aerial erosion in the Paleoproterozoic era followed by marine transgressions but unlike the Hamersley Basin, the JFGB was covered by comparatively thin epeirogenic sediments and not subjected to Proterozoic deformation or burial metamorphism. The Joyner's Find greenstone belt (JFGB) in the Yilgarn region of Western Australia was exhumed by middle to late Cenozoic erosion of a cover of unmetamorphosed and relatively undeformed Paleoproterozoic epeirogenic sedimentary rocks that preserved the JFGB unaltered for nearly 2 Ga; thus providing a unique snapshot of the early Proterozoic environment.Acicular hematite, pseudomorphous after acicular iron silicate, is only found in iron ore and BIF that was exposed to subaerial deep-weathering in early Paleoproterozoic times (pre 2.2 Ga) and in the overlying unconformable Paleoproterozoic conglomerate derived from these rocks and is absent from unweathered rocks (Lascelles, 2002). High-grade ore and BIF weathered during later subaerial erosion cycles contain anhedral hematite and acicular pseudomorphous goethite. The acicular hematite was formed from goethite pseudomorphs of silicate minerals by dehydration in the vadose zone under extreme aridity during early Paleoproterozoic subaerial weathering.The principal high-grade hematite deposits at Wiluna West are interpreted as bedded ore bodies that formed from BIF by loss of chert bands during diagenesis and have been locally enriched to massive hematite by the introduction of hydrothermal specular hematite. No trace of chert bands are present in the deep saprolitic hematite and hematite–goethite ore in direct contrast to shallow supergene ore in which the trace of chert bands is clearly defined by goethite replacement, voids and detrital fill. Abundant hydrothermal microplaty hematite at Wiluna West is readily distinguished by its crystallinity.The genesis of the premium ore from the Pilbara Region has been much discussed in the literature and the discovery at Wiluna West provides a unique opportunity to compare the features that are common to both districts and to test genetic models.     

Coating a polystyrene well-plate surface with synthetic hematite,goethite and aluminium hydroxide for cell mineral adhesion studies in a controlled environment

Iron and aluminium oxides are available in many climatic regions and play a vital role in many environmental processes, including the interactions of microorganisms in contaminated soils and groundwater with their ambient environment. Indigenous microorganisms in contaminated environments often have the ability to degrade or transform those contaminants, a concept that supports an in situ remediation approach and uses natural microbial populations in order to bio-remediate polluted sites. These metal oxides have a relatively high pH-dependent surface charge, which makes them good candidates for studying mineral–bacterial adhesion. Given the importance of understanding the reactions that occur at metal oxide and bacterial cell interfaces and to investigate this phenomenon further under well-characterized conditions, some of the most common iron and aluminium oxides; hematite, goethite and aluminium hydroxide, were synthesized and characterized and a coating method was developed to coat polystyrene well-plates as a surface exposable to bacterial adhesion with these minerals (non-treated polystyrene-12 well-plates which are used for cell cultures). The coating process was designed in a way that resembles naturally coated surfaces in aquifers. Hematite, Fe₂O₃, was synthesized from acidic FeCl₃ solution, while goethite, FeOOH, and aluminium hydroxide, Al(OH)₃, were prepared from an alkaline solution of Fe(NO₃)₃ and Al(NO₃)₃. They were further characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR), potentiometric titration and contact angle measurements. Characterization results show that the pure phases of hematite, goethite and aluminium hydroxides are formed with a point of zero charge (PZC) of 7.5, 8.5 and 8.9, respectively. The coating process was based on the direct deposition of mineral particles from an aqueous suspension by evaporation. Then, altered polystyrene surface properties were analyzed using X-ray photoelectron spectroscopy (XPS), attenuated total reflection-Fourier transform infrared (ATR-IR), water drop contact angle measurements and vertical scanning interferometry (VSI). The surface analysis tests prove that the coated polystyrene surface has physicochemical properties that are similar to the reference synthetic hematite, goethite and aluminium hydroxide minerals. These prepared and well-characterized mineral well-plates are similar to naturally occurring surfaces in aquifers and enable us to study the different steps of bacterial adhesion and biofilm formation on these metal oxides under laboratory-controlled conditions.     

Evidence for a simple pathway to maghemite in Earth and Mars soils

Soil magnetism is greatly influenced by maghemite (γ-Fe₂O₃), the presence of which is usually attributed to the following: (1) heating of goethite in the presence of organic matter; (2) oxidation of magnetite (Fe₃O₄); or (3) dehydroxylation of lepidocrocite (γ-FeOOH). Formation of the latter two minerals in turn requires the presence of Fe(II) in the system. No laboratory experiment or soil study to date has shown whether maghemite can form from ferrihydrite, a poorly crystalline Fe(III) oxide [∼Fe_4.5(O,OH,H₂O)_13.5], below 250°C. However, ferrihydrite is the usual precursor of goethite (α-FeOOH) and hematite (α-Fe₂O₃), the most frequently occurring crystalline Fe(III) oxides in soils. Here is presented in vitro evidence that ferryhidrite can partly transform into maghemite at 150°C. This transformation occurs upon aging of ferrihydrite precipitated in the presence of phosphate or other ligands capable of ligand exchange with Fe-OH surface groups. This maghemite coexists with hematite and is a transient phase in the transformation of ferrihydrite to hematite, which is apparently stabilized by the adsorbed ligands. Its particle size is small (10 to 30 nm), and its X-ray diffraction pattern exhibits superstructure reflections. The possible formation of maghemite in Mars and in different Earth soils can partly be explained in the light of this pathway with minimal ad hoc assumptions.     

Genesis of superimposed hypogene and supergene Fe orebodies in BIF at the Madoonga deposit, Yilgarn Craton, Western Australia

The Madoonga iron ore body hosted by banded iron formation (BIF) in the Weld Range greenstone belt of Western Australia is a blend of four genetically and compositionally distinct types of high-grade (>55 wt% Fe) iron ore that includes: (1) hypogene magnetite–talc veins, (2) hypogene specular hematite–quartz veins, (3) supergene goethite–hematite, and (4) supergene-modified, goethite–hematite-rich detrital ores. The spatial coincidence of these different ore types is a major factor controlling the overall size of the Madoonga ore body, but results in a compositionally heterogeneous ore deposit. Hypogene magnetite–talc veins that are up to 3 m thick and 50 m long formed within mylonite and shear zones located along the limbs of isoclinal, recumbent F₁ folds. Relative to least-altered BIF, the magnetite–talc veins are enriched in Fe₂O_3(total), P₂O₅, MgO, Sc, Ga, Al₂O₃, Cl, and Zr; and depleted in SiO₂ and MnO₂. Mafic igneous countryrocks located within 10 m of the northern contact of the mineralised BIF display the replacement of primary igneous amphibole and plagioclase, and metamorphic chlorite by hypogene ferroan chlorite, talc, and magnetite. Later-forming, hypogene specular hematite–quartz veins and their associated alteration halos partly replace magnetite–talc veins in BIF and formed during, to shortly after, the F₂-folding and tilting of the Weld Range tectono-stratigraphy. Supergene goethite–hematite ore zones that are up to 150 m wide, 400 m long, and extend to depths of 300 m replace least-altered BIF and existing hypogene alteration zones. The supergene ore zones formed as a result of the circulation of surface oxidised fluids through late NNW- to NNE-trending, subvertical brittle faults. Flat-lying, supergene goethite–hematite-altered, detrital sediments are concentrated in a paleo-topographic depression along the southern side of the main ENE-trending ridge at Madoonga. Iron ore deposits of the Weld Range greenstone belt record remarkably similar deformation histories, overprinting hypogene alteration events, and high-grade Fe ore types to other Fe ore deposits in the wider Yilgarn Craton (e.g. Koolyanobbing and Windarling deposits) despite these Fe camps being presently located more than 400 km apart and in different tectono-stratigraphic domains. Rather than the existence of a synchronous, Yilgarn-wide, Fe mineralisation event affecting BIF throughout the Yilgarn, it is more likely that these geographically isolated Fe ore districts experienced similar tectonic histories, whereby hypogene fluids were sourced from commonly available fluid reservoirs (e.g. metamorphic, magmatic, or both) and channelled along evolving structures during progressive deformation, resulting in several generations of Fe ore.     

Structural constraints of ferric (hydr)oxides on dissimilatory iron reduction and the fate of Fe(II)

Due to the strong reducing capacity of ferrous Fe, the fate of Fe(II) following dissimilatory iron reduction will have a profound bearing on biogeochemical cycles. We have previously observed the rapid and near complete conversion of 2-line ferrihydrite to goethite (minor phase) and magnetite (major phase) under advective flow in an organic carbon-rich artificial groundwater medium. Yet, in many mineralogically mature environments, well-ordered iron (hydr)oxide phases dominate and may therefore control the extent and rate of Fe(III) reduction. Accordingly, here we compare the reducing capacity and Fe(II) sequestration mechanisms of goethite and hematite to 2-line ferrihydrite under advective flow within a medium mimicking that of natural groundwater supplemented with organic carbon. Introduction of dissolved organic carbon upon flow initiation results in the onset of dissimilatory iron reduction of all three Fe phases (2-line ferrihydrite, goethite, and hematite). While the initial surface area normalized rates are similar (∼10⁻¹¹ mol Fe(II) m⁻² g⁻¹), the total amount of Fe(III) reduced over time along with the mechanisms and extent of Fe(II) sequestration differ among the three iron (hydr)oxide substrates. Following 16 d of reaction, the amount of Fe(III) reduced within the ferrihydrite, goethite, and hematite columns is 25, 5, and 1%, respectively. While 83% of the Fe(II) produced in the ferrihydrite system is retained within the solid-phase, merely 17% is retained within both the goethite and hematite columns. Magnetite precipitation is responsible for the majority of Fe(II) sequestration within ferrihydrite, yet magnetite was not detected in either the goethite or hematite systems. Instead, Fe(II) may be sequestered as localized spinel-like (magnetite) domains within surface hydrated layers (ca. 1 nm thick) on goethite and hematite or by electron delocalization within the bulk phase. The decreased solubility of goethite and hematite relative to ferrihydrite, resulting in lower Fe(III)_aq and bacterially-generated Fe(II)_aq concentrations, may hinder magnetite precipitation beyond mere surface reorganization into nanometer-sized, spinel-like domains. Nevertheless, following an initial, more rapid reduction period, the three Fe (hydr)oxides support similar aqueous ferrous iron concentrations, bacterial populations, and microbial Fe(III) reduction rates. A decline in microbial reduction rates and further Fe(II) retention in the solid-phase correlates with the initial degree of phase disorder (high energy sites). As such, sustained microbial reduction of 2-line ferrihydrite, goethite, and hematite appears to be controlled, in large part, by changes in surface reactivity (energy), which is influenced by microbial reduction and secondary Fe(II) sequestration processes regardless of structural order (crystallinity) and surface area.     

Hazardous elements and amorphous nanoparticles in historical estuary coal mining area

In Brazil, intense coal exploitation activities have led to environmental deterioration, including soil mortification, water contamination, loss of ecosystem, and atmospheric contamination. In addition,considerable quantities of sulfur-rich residues are left behind in the mining area; these residues pose grave environmental issues as they undergo sulfide oxidation reactions. When sulfur oxides come in contact with water, extreme acid leachate is produced with great proportions of sulfate, and hazardous elements(HEs), which are identified as coal drainage(CMD). CMD is an environmental pollution challenge, particularly in countries with historic or active coal mines. To prevent CMD formation or its migration, the source must be controlled; however, this may not be feasible at many locations. In such scenarios, the mine water should be collected, treated, and discharged. In this study, data from 2005 to2010 was gathered on the geochemistry of 11 CMD discharges from ten different mines. There are several concerns and questions on the formation of nanominerals in mine acid drainage and on their reactions and interfaces. The detailed mineralogical and geochemical data presented in this paper were derived from previous studies on the coal mine areas in Brazil. Oxyhydroxides, sulfates, and nanoparticles in these areas possibly go through structural transformations depending on their size and formation conditions. The geochemistry of Fe-precipitates(such as jarosite, goethite, and hematite) existent in the CMD-generating coal areas and those that could be considered as a potential source of hazardous elements(HEs)(e.g., Cr) were also studied because these precipitates are relatively stable in extremely low pH conditions. To simplify and improve poorly ordered iron, strontium, and aluminum phase characterization, field emission scanning electron microscopy(FE-SEM), high-resolution transmission electron microscopy(HR-TEM), micro-Raman spectroscopy, and X-ray diffraction(XRD) and sequential extraction(SE) studies were executed on a set CMD samples from the Brazilian mines. This study aimed to investigate the role of both nanomineral and amorphous phase distribution throughout the reactive coal cleaning rejects profile and HEs removal from the water mine to provide holistic insights on the ecological risks posed by HEs, nanominerals, amorphous phases, and to assess sediments in complex environments such as estuaries.     

Twin formation in hematite during dehydration of goethite

Twin formation in hematite during dehydration was investigated using X-ray diffraction, electron diffraction, and high-resolution transmission electron microscopy (TEM). When synthetic goethite was heated at different temperatures between 100 and 800 °C, a phase transformation occurred at temperatures above 250 °C. The electron diffraction patterns showed that the single-crystalline goethite with a growth direction of [001]_G was transformed into hematite with a growth direction of [100]_H. Two non-equivalent structures emerged in hematite after dehydration, with twin boundaries at the interface between the two variants. As the temperature was increased, crystal growth occurred. At 800 °C, the majority of the twin boundaries disappeared; however, some hematite particles remained in the twinned variant. The electron diffraction patterns and high-resolution TEM observations indicated that the twin boundaries consisted of crystallographically equivalent prismatic (100) (010), and (1\(\bar{1}\)0) planes. According to the total energy calculations based on spin-polarized density functional theory, the twin boundary of prismatic (100) screw had small interfacial energy (0.24 J/m²). Owing to this low interfacial energy, the prismatic (100) screw interface remained after higher-temperature treatment at 800 °C.