Fe Oxide Minerals Research Articles

Shale Heavy Metal Isotope Records of Low Environmental O2 Between Two Archean Oxidation Events

Evidence of molecular oxygen (O2) accumulation at Earth’s surface during the Archean (4.0–2.5 billion years ago, or Ga) seems to increase in its abundance and compelling nature toward the end of the eon, during the runup to the Great Oxidation Event. Yet, many details of this late-Archean O2 story remain under-constrained, such as the extent, tempo, and location of O2 accumulation. Here, we present a detailed Fe, Tl, and U isotope study of shales from a continuous sedimentary sequence deposited between ∼2.6 and ∼2.5 Ga and recovered from the Pilbara Craton of Western Australia (the Wittenoom and Mt. Sylvia formations preserved in drill core ABDP9). We find a progressive decrease in bulk-shale Fe isotope compositions moving up core (as low as δ56Fe = –0.78 ± 0.08‰; 2SD) accompanied by invariant authigenic Tl isotope compositions (average ε205TlA = –2.0 ± 0.6; 2SD) and bulk-shale U isotope compositions (average δ238U = –0.30 ± 0.05‰; 2SD) that are both not appreciably different from crustal rocks or bulk silicate Earth. While there are multiple possible interpretations of the decreasing δ56Fe values, many, to include the most compelling, invoke strictly anaerobic processes. The invariant and near-crustal ε205TlA and δ238U values point even more strongly to this interpretation, requiring reducing to only mildly oxidizing conditions over ten-million-year timescales in the late-Archean. For the atmosphere, our results permit either homogenous and low O2 partial pressures (between 10−6.3 and 10−6 present atmospheric level) or heterogeneous and spatially restricted O2 accumulation nearest the sites of O2 production. For the ocean, our results permit minimal penetration of O2 in marine sediments over large areas of the seafloor, at most sufficient for the burial of Fe oxide minerals but insufficient for the burial of Mn oxide minerals. The persistently low background O2 levels implied by our dataset between ∼2.6 and ∼2.5 Ga contrast with the timeframes immediately before and after, where strong evidence is presented for transient Archean Oxidation Events. Viewed in this broader context, our data support the emerging narrative that Earth’s initial oxygenation was a dynamic process that unfolded in fits-and-starts over many hundreds-of-millions of years.

SSSAJ 2021 Publisher's Report

It is well-recognized and documented in the literature that a considerable fraction of the soil organic matter (SOM) is associated with Fe-oxide minerals (Lalonde et al., 2012; Zhao et al., 2016). Recent studies have also showed that the persistence of various classes of SOM may depend on soil Fe mineralogy (Zhao et al., 2020). Other laboratory studies with model mineral-associated organic matter (MAOM) moieties, which were primarily focused on the short-range ordered (SRO) Fe-mineral, such as ferrihydrite, either coated or coprecipitated with natural organic matter (NOM), have suggested that the mineral phase transformation and adsorption–desorption of SOM is rather complex but appears to be largely controlled by the C/Fe ratio of the MAOM moiety and geochemical conditions (Chen et al., 2015; Shimizu et al., 2013). It is also clear from multiple recent studies that the nature or type of SOM (microbial vs. plant-derived) adsorbed on mineral surfaces and the rate and extent of SOM biodegradation depend on the type of mineral (e.g., ferrihydrite, Fe-containing phyllosilicate minerals, calcite), and/or metal ions (e.g., Al, Fe, and Ca) (Christl & Kretzschmar, 2007; Rowley et al., 2020; Sheng et al., 2021; Sowers et al., 2018), that are associated with the SOM. Modeling studies that are primarily centered on achieving a better understanding of the effect of mineral type on SOM interactions with minerals and degradation are also reported (Andersen et al., 2016). These studies have improved the understanding of the nature and stability of MAOM in soils of varying types and under different conditions, positioning researchers to better predict the properties and stabilities of organo-mineral associations in soils. This special section includes a collection of studies that span across modeling efforts, modeling coupled with experimental studies, laboratory experimental studies on ferrihydrite–SOM systems that are subjected to anoxic conditions, a study that focused on the effect of temperature on C/Fe ratio of the ferrihydrite–SOM moieties, a laboratory study on the role of adsorbed extracellular polymeric substance (EPS) on acidity of selected soils, a study that used a tropical humid soil enriched in nanogoethite subjected to anaerobic conditions, and a study with a large set of soils from the National Ecological Observatory Network (NEON) subjected to selective chemical extractions to correlate extractable metal and SOM contents. Collectively, the set of papers included in this special section, as anticipated, clearly demonstrated that a fundamental mineral–SOM interaction understanding is essential to predict interplay between mineral and SOM and, more broadly, nutrient availability. Studies included in this Soil Science Society of America Journal special section have suggested that specific types of organic molecules are more likely to form associations with soil minerals (as well as cations), such as oxy-hydroxides, phyllosilicate minerals, and quartz. Additionally, certain mineral surfaces are more reactive, manipulating the stability of the organic molecules, or affecting their transport through the environment. A comprehensive understanding of the fate of Fe, Al, and SOM (and nutrients) during redox fluctuations and concurrent changes in porewater is critical for development of robust reactive transport models for different soil environments. Ravi K. Kukkadapu: Conceptualization; Supervision; Writing – original draft; Writing – review & editing. Qian Zhao: Conceptualization; Writing – original draft; Writing – review & editing. Nikolla P. Qafoku: Conceptualization; Writing – review & editing. The authors declare no conflict of interest.

Characterization and mode of occurrence of rare earth elements and yttrium in fly and bottom ash from coal-fired power plants in Java, Indonesia

Fly and bottom ash (FABA) produced primarily from coal combustion in a coal-fired power plant consists of fine particles of the organic and inorganic mixture and trace elements. Eight FABA samples from coal-fired power plants in Java, Indonesia, had been collected for composition and rare earth element and Yttrium (REY) mode of occurrence identification. The geochemical composition of both major and trace elements was determined by inductively coupled plasma-mass spectrometry/atomic emission spectrometry (ICP-MS/AES). Furthermore, the composition of FABA was identified by petrography with reflected light microscopy and X-ray diffraction (XRD) analysis. Simultaneously, scanning electron microscope determines the mode of occurrence of REY with an energy-dispersive X-ray (SEM–EDX). The study finds that the inorganic component of FABA consists of glass, Fe–Mg spinel, mullite, quartz, Fe-oxide mineral, and K-feldspar. In contrast, the organic component is dominated by unburned coal. Glass is the most abundant component with cenospheres as major and pleiospheres as minor constituents. Trace elements analysis indicates REY concentration with heavy REY (HREY) distribution pattern. Moreover, SEM–EDX analysis results show that Yttrium (Y) occurs in glass and has a low concentration in spinel. From the mode occurrence of REY, in particular Yttrium, it can be predicted that alkaline fusion followed by acid leaching will be the most appropriate extraction method to extract REY from Indonesian FABA.

Insights into paleoenvironment and chemical weathering as controls on arsenic accumulation in Late Pleistocene to Holocene aquifers

High As groundwater has been reported in aquifers comprising Late Pleistocene and Holocene sediments worldwide, and could be due to the depositional environment and sedimentological processes. To investigate the paleoenvironment and chemical weathering as mechanisms controlling the fate of As, this study characterized the elemental, clay mineral, and Li isotopic compositions of sediments of an As-contaminated aquifer in the Datong Basin, China. Indices for reconstructing chemical weathering conditions, for example, the Chemical Index of Alternation (CIA), indicate overall incipient to intermediate chemical weathering conditions in the Datong Basin during the Late Pleistocene to Holocene. The higher CIA values at depths of ∼20–∼85 m indicate stronger chemical weathering and a shift in climatic regime towards warm and humid conditions in Stage 2 compared to Stage 1 and Stage 3. Under such climatic conditions, intense chemical weathering favors the leaching of silicate-bound Fe and thus the production of various secondary Fe-oxide minerals. Besides, the positive relationship between CIA values and easily reducible Fe oxides further shows the enrichment of more weakly crystalline Fe-oxides during the depositional condition; this finding is also supported by the results of chemical extractions performed on the sediments. Moreover, the good correlations between total organic carbon (TOC) and both Fe/Na and As concentrations suggest the enrichment of As and OM along with Fe enrichment during chemical weathering; this is attributed to the adsorption or co-precipitation of As and OM on Fe minerals. Under warm and humid conditions, intense chemical weathering released a large amount of Fe minerals; As was also released due to stronger weathering of the terrestrial bedrock and sequestered by Fe oxides and organic matter, thus forming complexes involving As, Fe, and OM. FTIR and chemical extraction results confirm the formation of As–Fe-OM complexes during the geological history contributes to As enrichment and accumulation in the late Pleistocene sediments. These findings provide new insights into the interaction between the paleoenvironment and the accumulation of ferric oxides/hydroxides and OM, which serve as controlling mechanisms with respect to As enrichment in Late Pleistocene to Holocene sediments, and thus shed light on the sedimentogenesis of high As aquifers.

Determination of Band Structure of Naturally Occurring Goethite with Al Substitution: A Case Study of Zhushan Iron Zone.

The photocatalytic property of Fe oxide minerals has long been considered to play an important role in shaping modern terrestrial environments. However, due to the complexity of natural settings, a precise determination of the band structure of natural goethite has not been achieved. In this work, the mineralogical characteristics of natural goethite samples obtained from Zhushan, China, were systematically studied through X-ray diffraction, transmission electron microscopy, X-ray energy dispersive spectroscopy, and X-ray fluorescence spectroscopy. Afterward, the band structure for both natural and synthetic goethite samples was determined by synchrotron-based X-ray absorption and emission spectra and photoelectron spectroscopy. The band gap of natural goethite (2.25 eV) was narrower than that of its synthetic counterpart (2.55 eV), and the valence band position of natural goethite was slightly lifted (−5.06 eV) compared to that of synthetic goethite (−5.38 eV). Al doping in natural goethite crystal, as revealed by the mineralogical tests, was the main reason that contributed to this difference. The theoretical calculation showed the narrowed band gap was caused by the contribution of Al-2p orbits at the top of the valence band. Therefore, free electrons can be created under light irradiation with a shorter wavelength. The experiments showed that natural goethite can photo-catalytically degrade methyl orange, and the degradation efficiency was better (47.5%) than that of the synthetic goethite group (31.5%). This study, for the first time, revealed the band structure and confirmed the photocatalytic properties of natural goethite, which should play an important role in surface substance evolution and elemental cycling.

Effects of aluminum incorporation on the schwertmannite structure and surface properties.

Schwertmannite is a common nanomineral in acid sulfate environments such as Acid Mine Drainage (AMD) and Acid Sulfate Soils (ASS). Its high surface area and positively charged surface result in a strong affinity towards toxic oxyanions such as arsenate in solution. However, natural precipitation of schwertmannite also involves the accumulation of other impurities, in particular aluminum, an element that is often incorporated into the structure of Fe-oxide minerals, such as goethite and ferrihydrite, affecting their structural and surface properties. However, little is known about the effect of Al incorporation in schwertmannite on the removal capacity of toxic oxyanions found in AMD and ASS (e.g. arsenate). In this paper, schwertmannite samples with variable Al concentration were synthetized and employed in arsenate adsorption isotherm experiments at a constant pH of 3.5. Solid samples before and after arsenate adsorption were characterized using high energy X-ray diffraction and pair distribution function analyses in order to identify structural differences correlated with the Al content as well as variations in the coordination of arsenate adsorbed on the mineral surface. These analyses showed limited Al accumulation on schwertmannite (up to 5%) with a low effect on its structure. The maximum arsenate sorption capacity (258 mmolH2AsO4 molFe-1) was in the range of that with pure schwertmannite, but a higher proportion of inner-sphere coordination was observed. Finally, Al was found to desorb from schwertmannite, with adsorbed arsenate preventing this effect and increasing the stability of the mineral. These results are useful to interpret observations from the field, in particular from river water affected by AMD and ASS, where similar conditions are observed, and where aluminum incorporation is expected.

Effect of power plant operating conditions on fly ash and bottom ash composition: a case study from power plant in Lampung

Fly ash and Bottom ash (FA-BA) are solid waste produced from the coal-generated power plant. FA consists of fine powder particles with diameters varying from 0.5-100 µm, while BA consists of coarser particles with a diameter of 0.125-2 mm. FABA and feed coal samples were collected from the power plant in Lampung to distinguish the effect of power plant operating conditions on FABA composition. Feed coal characteristics were examined by proximate and petrography analysis. Organic and inorganic components of FABA were identified using petrography analysis, while the detailed mineralogical composition of FABA was determined using X-Ray diffraction analysis. Moreover, major oxides of the feed coal and FABA were determined using inductive ICP-AES. From the analysis, it was found that FA composition is mainly organic material in the form of unburned carbon (UC). The abundance of UC content (up to 74.68%) indicates the inefficiency of the coal combustion process. In terms of inorganic, quartz is the most abundant mineral found in the FABA sample, up to 50.15%, in contrast to the glass content that was only 17.41%. A minor amount of spinel (0.03-2.00%) was found associated with Fe-oxide mineral. Kaolinite was only found in the BA sample from a landfill source and interpreted as external input from the dumping ground. The high content of UC and quartz will decrease the compressive strength of the material construction product providing a negative impact on the utilization of FABA.

Paragenesis of gold mineralization at the Kiyuk Lake Project, Kivalliq Region, Nunavut, Canada

ABSTRACT Exploration for gold in Nunavut has been primarily focused on Archean greenstone belts in the north and coastal regions of the territory, resulting in large areas of underexplored terrain in the south. The Kiyuk Lake property is located in the underexplored southwest corner of the Kivalliq Region of Nunavut within the Hearne domain of the ∼1.9 Ga western Churchill Province. The property is hosted by Proterozoic calc-silicate and clastic sedimentary units of the Hurwitz Group (<2.4–1.9 Ga) and the unconformably overlying Kiyuk Group (1.9–1.83 Ga). Gold mineralization in Proterozoic sedimentary rocks is rare in the Canadian Shield, so the Rusty Zone at Kiyuk Lake presents a unique opportunity to study the enigmatic gold mineralization hosted in such sedimentary rocks. Mineralization at the Rusty Zone is hosted by an immature lithic wacke cut by thin intermediate dikes that are associated with hydrothermal breccias composed of Fe-carbonate, calcite, calcic-amphibole, Fe-sulfide, Fe-oxide minerals, and gold. Textural and timing relationships suggest that the gold mineralization is post-sedimentary and syn- to post-intrusion of intermediate dikes. Stable isotope thermometry suggests that mineralization took place between 450 and 600 °C, and geochronological studies indicate that the intrusion and mineralization occurred before or about 1.83 Ga. Using basement breaching thrusts faults as conduits to the surface, over-pressurization along a later normal fault is thought to be the primary cause for the localized breccia pipe that controls gold mineralization. The hydrothermal fluids are postulated to be volatile-rich aqueous solutions exsolved from a source of cooling magmas at depth. Although sub-economic at present, the occurrence of high-grade gold in a Paleoproterozoic basin such as Kiyuk Lake could signal a new opportunity for exploration for gold in the Canadian Shield.

Review on the interactions of arsenic, iron (oxy)(hydr)oxides, and dissolved organic matter in soils, sediments, and groundwater in a ternary system

High concentrations of arsenic (As) in groundwater threaten the environment and public health. Geogenically, groundwater As contamination predominantly occurs via its mobilization from underground As-rich sediments. In an aquatic ecosystem, As is typically driven by several underlying processes, such as redox transitions, microbially driven reduction of iron (Fe) oxide minerals, and release of associated As. Notably, dissolved As mobilized from soils and sediments exhibits high affinity for dissolved organic matter (DOM). Thus, high DOM concentrations can increase As mobility. Therefore, it is crucial to understand the complex interactions and biogeochemical cycling of As, DOM, and Fe oxides. This review collates knowledge regarding the fate of As in multicomponent As–DOM–Fe systems, including ternary complexes involving both Fe and DOM. Additionally, the release mechanisms of As from sediments into groundwater in the presence of both Fe and DOM have been discussed. The mechanisms of As mobilization/sorption at the solid–water interface can be affected by negatively charged DOM competing for sorption sites with As on Fe (oxy)(hydr)oxides and may be further modified by other anionic ubiquitous species such as phosphate, silicic acid, or sulfur. This review emphasizes the need for a comprehensive understanding of the impact of DOM, Fe oxides, and related biogeochemical processes on As mobilization to aquifers. The review identifies important knowledge gaps that may aid in developing applicable practices for preventing the spread of As contamination in aquatic resources and traditional soil management practices.

Factors controlling phosphorus mobility in nearshore aquifers adjacent to large lakes

Internal P stores in offshore lakebed sediments play an important role in lake nutrient dynamics. While P stores in nearshore aquifer sediments may also be important for nutrient dynamics, it is unclear whether P accumulates in these sediments, and if so, what factors control P accumulation and its potential later release from the sediments to nearshore waters. This knowledge gap was addressed by conducting field investigations at seven nearshore sites located along the shores of Lake Erie, Lake Huron and Lake Ontario, Canada, with more detailed dissolved and sediment phase characterization completed for two nearshore sites. PO4 concentrations were observed to be higher (>50 μg/L) in the more reducing nearshore aquifers compared to more oxidizing nearshore aquifers (<20 μg/L), despite similar total solid phase P concentrations at the sites. PO4 mobility in the nearshore aquifers was found to be closely linked to redox-driven Fe cycling. In the more reducing aquifers, dissolved PO4 was highest near the redox boundary present in the shallow sediments where oxic infiltrating surface water mixes with reducing groundwater. In the more oxidizing aquifers, solid phase characterization indicated that PO4 is sequestered to Fe oxide mineral phases throughout the nearshore aquifer which explains the low dissolved PO4. While pH was not found to be important for PO4 mobility at the study sites, batch laboratory experiments indicate that increased infiltration of more alkaline surface water into nearshore aquifers may promote PO4 release from the sediments. The study findings demonstrate that while internal P storage mechanisms in nearshore aquifer sediments may currently be limiting P loads to lakes, it is possible that P stores that build up over time may result in increased P loads to lakes in the future.

Photocatalytic oxidation of dissolved Mn(II) on natural iron oxide minerals

The energy conversion in Earth’s surface environments over geological history heavily involves the redox reactions of natural minerals. Natural Mn(III/IV) oxides and Mn2+(aq) is one of the most important redox couples that significantly dictate the electron flow in nature. Elucidating their formation and redox reactions is of critical importance for understanding numerous elemental cycles and the evolution of redox environments on Earth and other planets. Previous studies generally consider biotic processes as the dominant oxidation pathway for Mn2+(aq) in natural environments. In this study, we demonstrate rapid abiotic oxidation of Mn2+(aq) through photocatalytic reactions in the presence of natural Fe oxide minerals at rates comparable to those of currently known biotic/abiotic oxidation processes. Fe oxide minerals not only facilitate the electron transfer, but also serve as templates for the heterogeneous nucleation of tunnel structured Mn oxides. This finding highlights an important yet previously overlooked abiotic process on the formation of Mn oxides, which offers a new pathway for explaining the commonly observed co-occurrence of Fe and Mn oxide minerals in nature and the origin of diverse structures of Mn oxides.

Middle Stone Age mineral pigment procurement at Pinnacle Point 5–6 North, Western Cape province, South Africa

AbstractWe report on a multi‐method sourcing study of 35 mineral pigment artefacts from the Middle Stone Age site of Pinnacle Point 5–6 North (PP5–6 N), dating from about 90–50 ka. The artefacts were analysed and compared with geological samples from seven sources using neutron activation analysis (NAA), and supplemented by data from X‐ray diffraction (XRD) and scanning electron microscopy (SEM). Our preliminary results suggest that the occupants of PP5–6 N likely used at least two local and one currently unidentified and possibly non‐local Fe oxide mineral pigment sources. The mineral pigment artefacts derived from the latter source(s) exhibited manganese (Mn) enrichment with concentrations well above those observed in all sampled source deposits in the study area, suggesting a distinctive formation process. The proportions of the Mn‐enriched mineral pigment artefacts within the PP5–6 N assemblage vary over time, but tend to occur at higher rates in the glacial Marine Isotope Stage (MIS) 4 deposits, which holds potential implications for changes in the use of sources over time, increased mobility or increased exchange during this period.

Ligand Effects on Biotic and Abiotic Fe(II) Oxidation by the Microaerophile Sideroxydans lithotrophicus.

Organic ligands are widely distributed and can affect microbially driven Fe biogeochemical cycles, but effects on microbial iron oxidation have not been well quantified. Our work used a model microaerophilic Fe(II)-oxidizing bacterium Sideroxydans lithotrophicus ES-1 to quantify biotic Fe(II) oxidation rates in the presence of organic ligands at 0.02 atm O2 and pH 6.0. We used two common Fe chelators with different binding strengths: citrate (log KFe(II)-citrate = 3.20) and nitrilotriacetic acid (NTA) (log KFe(II)-NTA = 8.09) and two standard humic substances, Pahokee peat humic acid (PPHA) and Suwannee River fulvic acid (SRFA). Our results provide rate constants for biotic and abiotic Fe(II) oxidation over different ligand concentrations and furthermore demonstrate that various models and natural iron-binding ligands each have distinct effects on abiotic versus biotic Fe(II) oxidation rates. We show that NTA accelerates abiotic oxidation and citrate has negligible effects, making it a better laboratory chelator. The humic substances only affect biotic Fe(II) oxidation, via a combination of chelation and electron transfer. PPHA accelerates biotic Fe(II) oxidation, while SRFA decelerates or accelerates the rate depending on concentration. The specific nature of organic-Fe microbe interactions may play key roles in environmental Fe(II) oxidation, which have cascading influences on cycling of nutrients and contaminants that associate with Fe oxide minerals.

A chemical weathering control on the delivery of particulate iron to the continental shelf

The delivery of potentially reactive iron minerals to the marine environment exerts a major control on ocean and marine sediment biogeochemistry, including the preservation and burial of organic carbon. One aspect of the global iron cycle that has received little attention concerns the phase partitioning of iron in highly chemically-weathered sediments from (sub)tropical mountainous regions, where the sediment is commonly deposited directly onto adjacent continental margins. Here, we report the phase partitioning of particulate iron in surface seafloor sediments deposited from oxic bottom waters along the east coast of China, including the Bohai Sea, Yellow Sea and East China Sea, in addition to the continental shelf region adjacent to the (sub)tropical mountainous island of Hainan in the northern South China Sea. We document highly reactive (FeHR) to total iron (FeT) ratios for the Bohai Sea, Yellow Sea and East China Sea that are typical of global marine sediments deposited under oxic water column conditions. By contrast, FeHR/FeT ratios in Hainan offshore sediments are significantly elevated above normal oxic marine sediments. These Hainan offshore sediments display a strong positive correlation between FeHR/FeT ratios and the chemical index of alteration (CIA) weathering proxy, suggesting that the Fe speciation systematics are controlled by the intensity of chemical weathering. This observation is supported by additional geochemical data and Nd isotope analyses, which suggest a common source lithology for all the studied regions. The Hainan sediments thus document a specific scenario, whereby highly chemically weathered sediments from the mountainous Hainan region bypass the inner shore settings that commonly disproportionately trap Fe (oxyhydr)oxide minerals, depositing high concentrations of FeHR on the adjacent continental margin. Such enrichments likely aid in the preservation of organic carbon in marine sediments, suggesting that organic carbon preservation and burial may be enhanced by elevated FeHR in such settings. We also establish a set of essential criteria for potential recognition of chemical weathering-induced enrichments in FeHR/FeT ratios in ancient marine sediments.

Coal and coal ash characteristics to understand mineral transformation : A case study from Senakin coal field Indonesia

Coal ash is a material from coal combustion and recently is an economical source for the extraction of valuable elements such as rare earth elements and Yttrium (REY) and base metals. Eight coal samples from Senakin coal field were collected to identify their mineralogy composition in raw coal and coal ash. The ashing was carried out on coal samples at temperature 1000°C for 1 hour. The coal and coal ash samples were made polish section to identify the organic and inorganic constituents. In addition, the minerals in coal sampel were identified by X-ray diffraction analysis. From this study, organic constituent consist of vitrinite (60 – 71%), liptinite (22 – 33%) and inertinite (5 – 9%). Minerals found in coal are kaolinite (25,78 – 46,90), pyrite (24,16 – 38,38%), quartz (6,07 – 12,80%), gypsum (4,81 – 10,34%), chlorite (2,56 – 8,40%), jarosite (0,72 – 4,63%), hematite (0,96 – 3,81%), calcite (0,37 – 5,07%), Mg-calcite (0,11 – 3,20%), dolomite (1,35 – 3,55%), and siderite (1,22%). Coal ash is composed of organic and inorganic components. Organic components found is unburned coal (3,09 – 8,55%) derived from maceral which does not burn out, mainly inertinite group. While inorganic components found are fe-oxide mineral (40,36 – 54,55%), quartz (24,55 – 33,64%), mullite (5,09 – 7,82%), cenosphere (7,45 – 10,91%), pleiosphere (1,64 – 2,36%), pyrite (0,18 – 1,27%), and spinel (0,18 – 1,09%). Fe-oxide minerals are interpreted derived from Fe-bearing minerals in coal samples such as pyrite, hematite, and siderite. Kaolinite which is the dominant mineral in coal is transformed to cenosphere, pleiosphere, and mullite. Quartz in coal ash derived from quartz in the coal sample because ashing temperature does not exceed the melting temperature of quartz. Characterization of the coal ash component can be used as a reference for the extraction method of valuable elements.

Iron oxides catalyze the hydrolysis of polyphosphate and precipitation of calcium phosphate minerals

Interfacial chemistry of phosphorus (P) is important for understanding P sequestration and bioavailability in nature. Polyphosphate is a group of important P species in aquatic environments. The geochemical behaviors of polyphosphate at the mineral-water interface play critical roles in mediating aquatic P transformation, yet remain poorly constrained. This study investigates the hydrolysis of polyphosphate in the presence of four common iron (Fe) oxide minerals (ferrihydrite, hematite, goethite, lepidocrocite) and the subsequent precipitation of calcium phosphate minerals. Batch studies are combined with microscopic and spectroscopic characterizations to reveal P speciation and complexation state under varied solution chemistry (pH 6–9, 1 mM Ca2+, and artificial seawater). All four Fe oxides can hydrolyze polyphosphate and the hydrolysis rate and extent are both enhanced in the presence of Ca2+. In the presence of 1 mM Ca2+, the apparent hydrolysis rate fitted by first-order kinetic model follows the order of lepidocrocite > hematite > ferrihydrite > goethite. After normalization by specific surface area of Fe oxides, the hydrolysis rate is in the order of lepidocrocite ≈ goethite > hematite > ferrihydrite at pH 6, regardless of Ca2+ presence. At pH 7.5 and 9, the order of area-normalized apparent hydrolysis rate is lepidocrocite > goethite ≈ hematite > ferrihydrite. A terminal-only pathway via one-by-one cleavage of terminal phosphate groups is the dominant hydrolysis mechanism. Under alkaline conditions, amorphous calcium phosphate forms in the presence of Ca2+, which transforms to crystalline hydroxyapatite after long-term aging of 70 or 150 days. This study demonstrates the importance of natural minerals in controlling polyphosphate transformation into crystalline calcium phosphate minerals, and provides new insights for understanding P cycling and sequestration in the environment.

Identification of clays and Fe oxide minerals rich alteration zones using a Landsat 8 image of Pu Sam Cap area, Lai Chau

The hydrothermal alteration zones are the important sign for mineral exploration and can be identified by remote sensing images completely, but this is limited due to the effect of vegetable. We address this problem by a method called “Directed Principal Component Analysis” (DPCA) that involves calculating principal components on two input band ratio images. One ratio is a geological discriminant, confused by the presence of vegetation; the second ratio is chosen for its suitability as a vegetation index. DPCA applied on Landsat 8 image in Pu Sam Cap area, Lai Châu characteristied by argilic alteration, sericite alteration, etc., with the typical minerals like kaolinite, illite, etc., and pyrite, chalcopyrite, magnetite; specularite, etc., The results have identified Fe - rich zones in Bai Bang and Nam Tra areas; clay minerals are concentrated mainly in Nam Tra area and along the main faults. The results are also compared with previous research data and fieldtrip data that shows similarity and feasibility. This paper indicated limitation of Landsat image such as spatial resolution, spectral resolution, etc., when applied in the tropical area.

Months-long spike in aqueous arsenic following domestic well installation and disinfection: Short- and long-term drinking water quality implications

Exposure to high concentration geogenic arsenic via groundwater is a worldwide health concern. Well installation introduces oxic drilling fluids and hypochlorite (a strong oxidant) for disinfection, thus inducing geochemical disequilibrium. Well installation causes changes in geochemistry lasting 12 + months, as illustrated in a recent study of 250 new domestic wells in Minnesota, north-central United States. One study well had extremely high initial arsenic (1550 µg/L) that substantially decreased after 15 months (5.2 µg/L). The drilling and development of the study well were typical and ordinary; nothing observable indicated the very high initial arsenic concentration. We hypothesized that oxidation of arsenic-containing sulfides (which lowers pH) combined with low pH dissolution of arsenic-bearing Fe (oxyhydr)oxides caused the very high arsenic concentration. Geochemical equilibrium considerations and modeling supported our hypothesis. Groundwater equilibrium redox conditions are poised at the Fe(III)(s)/Fe(II)(aq) stability boundary, indicating arsenic-bearing Fe (oxyhydr)oxide mineral sensitivity to pH and redox changes. Changing groundwater geochemistry can have negative implications for home water treatment (e.g., reduced arsenic removal efficiency, iron fouling), which can lead to ongoing but unrecognized hazard of arsenic exposure from domestic well water. Our results may inform arsenic mobilization processes and geochemical sensitivity in similarly complex aquifers in Southeast Asia and elsewhere.

Microbe-Mineral Interaction and Novel Proteins for Iron Oxide Mineral Reduction in the Hyperthermophilic Crenarchaeon Pyrodictium delaneyi.

Dissimilatory iron reduction by hyperthermophilic archaea occurs in many geothermal environments and generally relies on microbe-mineral interactions that transform various iron oxide minerals. In this study, the physiology of dissimilatory iron and nitrate reduction was examined in the hyperthermophilic crenarchaeon type strain Pyrodictium delaneyi Su06. Iron barrier experiments showed that P. delaneyi required direct contact with the Fe(III) oxide mineral ferrihydrite for reduction. The separate addition of an exogenous electron shuttle (anthraquinone-2,6-disulfonate), a metal chelator (nitrilotriacetic acid), and 75% spent cell-free supernatant did not stimulate growth with or without the barrier. Protein electrophoresis showed that the c-type cytochrome and general protein compositions of P. delaneyi changed when grown on ferrihydrite relative to nitrate. Differential proteomic analyses using tandem mass tagged protein fragments and mass spectrometry detected 660 proteins and differential production of 127 proteins. Among these, two putative membrane-bound molybdopterin-dependent oxidoreductase complexes increased in relative abundance 60- to 3,000-fold and 50- to 100-fold in cells grown on iron oxide. A putative 8-heme c-type cytochrome was 60-fold more abundant in iron-grown cells and was unique to the Pyrodictiaceae There was also a >14,700-fold increase in a membrane transport protein in iron-grown cells. For flagellin proteins and a putative nitrate reductase, there were no changes in abundance, but a membrane nitric oxide reductase was more abundant on nitrate. These data help to elucidate the mechanisms by which hyperthermophilic crenarchaea generate energy and transfer electrons across the membrane to iron oxide minerals.IMPORTANCE Understanding iron reduction in the hyperthermophilic crenarchaeon Pyrodictium delaneyi provides insight into the diversity of mechanisms used for this process and its potential impact in geothermal environments. The ability of P. delaneyi to reduce Fe(III) oxide minerals through direct contact potentially using a novel cytochrome respiratory complex and a membrane-bound molybdopterin respiratory complex sets iron reduction in this organism apart from previously described iron reduction processes. A model is presented where obligatory H2 oxidation on the membrane coupled with electron transport and either Fe(III) oxide or nitrate reduction leads to the generation of a proton motive force and energy generation by oxidative phosphorylation. However, P. delaneyi cannot fix CO2 and relies on organic compounds from its environment for biosynthesis.

Diagenesis and Porosity Evolution of the Pachmarhi Sandstones (Early Triassic), Satpura Gondwana Basin, Central India

This study deals with the diagenetic history of the Pachmarhi Sandstones of Satpura Gondwana Basin, Central India. The sandstones are classified as quartz-arenite and sub-arkose type. Monocrystalline quartz grains dominate the detrital mineralogy followed by polycrystalline quartz grains, feldspars (more alkali-feldspar than plagioclase), rock fragments, detrital mica and heavy minerals. The diagenetic signatures observed in the Pachmarhi Sandstones include mechanical compaction, cementation (Fe-oxide, quartz overgrowths, calcite, matrix and clay minerals), replacement and dissolution of feldspar and calcite cement. The most commonly observed type of secondary porosity is dissolution of feldspars. The porosity loss is mainly due to cementation by pore occlusion and by early stage of mechanical compaction. In addition, several clay minerals occurred as pore-filling and pore-lining cements. The nature of various types of grain- to grain contacts suggests early cementation and consequent minor compaction. Among the various cements, calcite is the earliest followed by iron oxide while silica cementation occurred probably at a late stage. The carbonate cement formed during burial by dissolution and re-precipitation represents redistributed calcite which was buried with the sandstone. The iron cement was perhaps derived from weathering and leaching of ferromagnesian minerals of overlying Deccan traps. Silica cement was derived from the corrosion of quartz and feldspar grains. Types of grain contacts, minus-cement porosity and porosity reduction indicate a shallow depth of burial conditions for these sandstones.