Oxide Minerals Research Articles

Geochemical modelling on the role of redox reactions during hydrogen underground storage in porous media

Underground Hydrogen Storage (UHS) in porous media appears to be a promising means for large-scale hydrogen storage, underpinning the full-scale of hydrogen supply chain development. Hydrogen-brine-rock interactions play an important role in hydrogen conversion and contamination during hydrogen cycling process. While the redox reaction triggered by injected H2 and pre-existing O2 is unique in UHS compared to other types of gas subsurface storage, few research have been done to understand the role of redox reactions in hydrogen solubility, pH, and fewer works have looked beyond its process on hydrogen conversion and contamination, which may affect the stored H2 purity and storage efficiency. In this context, we examined the redox reactions on hydrogen-brine-minerals (e.g., calcite, siderite, quartz and pyrite) reactions as a function of dissolved oxygen concentration (from 5.5 to 5500 ppm), temperature, and pressure through geochemical modelling using geochemical solver PHREEQC.Our results showed that increasing dissolved oxygen concentration from 5.5 to 5500 ppm resulted in negligible impact on hydrogen solubility and pH for all tested minerals. As the sensitive minerals, siderite and calcite can react with H2 through the redox process, leading up to a certain hydrogen loss at the pressure of 20 MPa, respectively. Meanwhile, quartz and pyrite are insensitive minerals to hydrogen, causing less than 0.2% hydrogen loss at the same pressure condition. Our results indicate that the mineral oxidation due to the pre-existing O2 dissolved in formation brine played a negligible role in H2-brine-rock interactions. The results also showed that carbonate minerals such as siderite and calcite may act as electron acceptors, which triggered hydrogen dissociation and thus formed a strong reduction environment based on PHREEQC geochemical database. This process likely causes measurable hydrogen loss associated with abiotic geochemical reactions for the lifetime of the underground hydrogen storage operation. Taken together, we suggest that clean standstone reservoirs will signifcantly reduce the hydrogen conversion and contamination during underground hydrogen storage from abiotic geochemical perspective.

The Intensification of Prolonged Cooling Climate-Exacerbated Late Ordovician–Early Silurian Mass Extinction: A Case Study from the Wufeng Formation–Longmaxi Formation in the Sichuan Basin

The Late Ordovician–Early Silurian period was a significant transitional phase in geological history and has garnered global interest. This study focuses on the black shale series of the Wufeng Formation–Longmaxi Formation of the Upper Ordovician–Lower Silurian period in the Sichuan Basin. Based on the logging curves and lithological characteristics of the Yucan-1 Well, 46 black shale samples were collected from the target layer section for clay mineral XRD (46 samples) analysis and whole-rock XRF (14 samples) analysis. The results indicate that three third-order sequences (SQ1, SQ2, and SQ3) are present in the Wufeng Formation–Longmaxi Formation of the Yucan-1 Well, and two subfacies and three microfacies were identified. In conjunction with the characteristics as well as the characteristic parameters of whole-rock oxide and clay mineral content ((I/C), (S + I/S)/(I + C), CIA, CIA-error, CIW, PIA, MAP, and LST), the Wufeng Formation–Longmaxi Formation of the Yucan-1 Well is divided into three intervals. Interval I is the Wufeng Formation. During this interval, weathering intensity, surface temperature, and precipitation gradually decreased, while the climate shifted from warm and humid to cold and dry. This corresponds to two pulse-type biological extinction events and represents an interval of increasing organic carbon burial. Interval II encompasses the bottom-middle part of the Longmaxi Formation. Weathering intensity, surface temperature, and precipitation were characterized by smooth, low values. Subsequently, the climate was predominantly cold and dry. This was the primary interval of organic carbon enrichment. Interval III extends from the upper part to the top of the Longmaxi Formation. Weathering intensity, surface temperature, and precipitation gradually increased. The climate transitioned from cold and dry to warm and humid. Organic carbon burial gradually decreased, while sea levels dropped. This indicates that climate cooling was the primary controlling factor for this biological extinction event. In combination with previous divisions of graptolite zones in the Yucan-1 Well, it is postulated that this biological extinction event may primarily have been pulse extinction. The continuous cooling of the climate in the later period led to the continuous extinction of organisms that survived the disaster. Until approximately 438.76 Ma at the top of the Longmaxi Formation, the climate environment recovered to pre-extinction conditions, with a transition to a warm and humid climate again.

Metal Catalysis Acting on Nitriles in Early Earth Hydrothermal Systems.

Hydrothermal systems are areas in which heated fluids and organic molecules rush through basaltic material rich in metals and minerals. By studying malononitrile and acetonitrile, we examine the effects of metal and mineral nanoparticles on nitrile compounds in anoxic, hydrothermal conditions representing a prebiotic environment of early Earth. Polymerization, reduction, cyclization, and a phenomenon colloquially known as 'chemical gardening' (structure building via reprecipitation of metal compounds or complexing with organics) are all potential outcomes with the addition of metals and minerals. Reduction occurs with the addition of rhodium (Rh) or iron (II) sulfide (FeS), with positive identification of ethanol and ethylamine forming from acetonitrile reduction. We find that polymerization and insoluble product formation were associated with oxide minerals, metallic nickel (Ni), and metallic cobalt (Co) acting as catalysts. Oxide minerals strongly promoted polymerization into insoluble, tar-like products of nitriles. FeS, iron-nickel alloy (FeNi), and rhodium are unique cases that appear to act as reagents by actively participating in chemical gardening without returning to their initial state. Further, FeS tentatively had a phase change into the mineral parabutlerite. This research aims to identify metals and metal minerals that could best serve nitrile catalysis and reactions on early Earth.

Optimized photocatalytic performance of ZnS-SnO2 heterostructures for visible light driven mineralization of Acid violet 7 dye and inactivation of bacteria

The present study aims to decipher the defect-induced photocatalytic activity of ZnS-SnO2 heterostructure for visible light-assisted oxidative mineralization of Acid Violet 7 dye (AV7) and Escherichia coli (E. coli) bacterial disinfection. The prepared ZnS-SnO2 (60ZS) heterostructure/nanocomposite catalysts show improved optical and visible light absorption properties. Photoluminescence findings reveal the existence of defect energy levels/surface states associated with 60ZS heterostructure catalysts. Photo/Electrochemical studies show improved photocurrent response, high capacitance, lower charge transfer resistance, and improved charge-discharge behaviour in 60ZS heterostructure catalysts compared to individual components. The improved photocatalytic performance of 60ZS heterostructure is ascribed to the interactive effect of a reduction in the band gap, improved surface area, and enhanced lifetime of photogenerated charge carriers. The major reactive species that cause the degradation reaction have been identified, and a plausible AV7 dye degradation pathway has been proposed. The 60ZS heterostructure catalyst exhibits good stability and a recycled nature.

Geogenic, Anthropogenic, and Authigenic Minerals Hosting Arsenic and Antimony in Yellowknife Bay Sediments

Abstract Yellowknife Bay (Great Slave Lake, Northwest Territories, Canada) is a water body valued by surrounding communities for its subsistence, recreational, and cultural use. Located directly downstream of the former Giant Mine and Con Mine, Yellowknife Bay has received inputs from mine waste streams enriched in arsenic (As), antimony (Sb), and metals since the late 1930s. Lake sediments in Yellowknife Bay provide a record of metal(loid) contamination from aerially deposited roaster stack emissions, mine effluent, and Giant Mine tailings. A sediment sampling program was conducted in Yellowknife Bay to characterize As and Sb mineralogy using scanning electron microscopy-mineral liberation analysis. Mineralogical analysis of As- and Sb-hosted minerals in nine sediment cores suggests that arsenic trioxide (As2O3), originally deposited during the period of peak-mining emissions, has since been transformed into authigenic sulfides (interpreted to be realgar) down core from peak-mining emissions. Arsenic has also been attenuated by iron (Fe)-oxyhydroxides and roaster-generated iron oxides up-core from peak-mining emissions, near the sediment–water interface. The Sb-bearing minerals appear to be stable in Yellowknife Bay sediments, with no conclusive evidence of post-depositional mobility having been identified. The observed prevalence of arsenic trioxide in surface sediments proximal to Giant Mine suggests that As and Sb contamination is ongoing, likely from terrestrial weathering of contaminated soils and shoreline outcrops. Arsenic-bearing oxide minerals prevalent in surface sediments may become unstable should redox conditions in the hypolimnion change; prolonged anoxia could destabilize the As hosting minerals and release As to bottom waters. Therefore, long-term monitoring of the water column, including hypolimnion conditions, in Yellowknife Bay is recommended.

Chemical analysis and filtration efficiency of ceramic point-of-use water filters

Ceramic water filters (CWFs) are globally employed as a point-of-use water treatment technology. Although, there are no standards to regulate the use of these CWFs in developing countries, they are gaining acceptability for domestic water treatment. This study sought to assess and compare the efficiency of commercially available types of CWFs and to propose a consumer selection guide for the purchase and use of CWFs. The CWFs selected for the study were, Ball filter with activated carbon (BF + AC), Candle filter (CF), and Pot filter (PFcs) coated with colloidal silver. The elemental and mineral oxide composition of the selected CWFs were analysed with x-ray fluorescence method. Furthermore, the raw unfiltered water (from three different common sources), and the filtrates obtained with the CWFs were analysed for their physicochemical, metal ion removability, and microbial correction. The x-ray fluorescence analysis indicated that Al2O3 and SiO2 were the major mineral oxide compositions of the selected CWFs. These metal oxides were present in varying concentrations. The CWFs showed turbidity reduction of 74.28–99.40%, Mn and Fe reduction of 54.04–98.48% and 48.82–97.50% respectively. In addition, the total coliform reduction by the selected CWFs ranged from 2.31 to 76.97%. It was therefore observed from the results that, the efficiency of commercially available CWFs varied in the order BF + AC > CF > PFcs. BF + AC was the most efficient in both physicochemical and microbial correction of all water sources. CWF selection guide for consumers based on different sources of water which considered the physicochemical parameters, biological parameters and Water Quality Index was discussed. This has an implication for regulation and standardization of CWFs.

Contribution to the Ostracoda (crustacea) Fauna of the karstic region of Texas with the description of a new species

Iron oxide deposits in the form of crusts are examined in the field and in the laboratory with scanning electron microscopy. Samples came from two caves developed in different geological settings but assumed by previous studies to be of hydrothermal-hypogene origin. The relation of iron oxide crusts to cave wall and ceiling morphology created by the cave’s primary dissolution (speleogenesis), as well as to the formation of other speleothems, is investigated. Scanning electron microscope (SEM) elemental analysis showed a high iron content (20–78 % by weight) consistent with iron oxide minerals such as goethite, hematite, magnetite, etc. Three distinct types of iron oxide crusts were identified from the four samples that were analyzed: (1) high iron content crusts with some porosity formed on the host rock surface and discontinuities, (2) high iron content (but lower than type 1) crusts, including limestone clasts and pores originating from dissolved clasts, and (3) high iron content, significantly-porous crusts that are formed by a network of filaments that indicate microbial activity. The formation of these deposits in relation to other speleothems and to dissolution events is discussed.

Synthesis and characterization of cement clinker based on Tunisian dam sediments

Siltation is a permanent threat to the operation of dams since it reduces its storage capacity. In Tunisia, the annual siltation of dams is estimated at 22 Mm3 / year. Sediments currently cover 20% of the total capacity of the reservoirs, which could be a national water security issue in the years to come. Considering that sediments contain the oxides, SiO2. Al2O3. Fe2O3 and CaO, as main chemical constituents, a partial replacement of the raw materials in the cement production is suggested. This work concerns dam sediments from different regions in Tunisia. Characterisation results show that studied sediments are suitable for a beneficial reuse in the clinker production. However, according to the chemical composition, the incorporation rate of sediments in the raw mix varies from one sediment to another but still relatively important, ranging between 9 and 27 wt%. The characterization of produced clinkers show that mineralogy depends on minor oxides contents, especially SO3. MgO and equivalent Na2O. It has been proven that it is possible to substitute natural materials with 27.4 %SS sediment. The obtained clinker is characterized by the presence of M1 C3S and orthorhombic C3A. The high free lime content associated to incomplete alite formation can be surmounted by increasing slightly the clinkerization temperature.

Removal of arsenic from acidic liquors using chemical and autotrophic and mixed heterotrophic bacteria-produced biogenic schwertmannites

Arsenic penetrates human society through a variety of geological and anthropogenic processes, posing significant health hazards. Acid mine drainage, which contains high concentrations of heavy metals and sulfate, is formed by the biological oxidation of pyrite and other metal-containing sulfidic minerals and is a significant environmental hazard. Adsorption is a simple and effective method for removing arsenic from water. In this study, co-precipitation and adsorption of arsenic with biogenic and chemically produced iron-containing settleable precipitates, i.e. schwertmannites were studied. Autotrophic Leptospirillum ferrooxidans and heterotrophic mixed culture of Alicyclobacillus tolerans and Acidiphilium cryptum oxidized iron at rates from 18 to 23 mg/(L.h) in the presence of 5 and 10 mg/L As3+, and both cultures tolerated up to 100 mg As3+/L although Fe2+ oxidation rates decreased to 3–4 mg/(L.h). At Fe/As ratios of ≥20, As removal efficiencies of ≥95% were obtained by co-precipitation with Fe3+ at pH 3.5–4.5. Because schwertmannite precipitates produced by the heterotrophic culture formed crystals, it was studied for adsorptive removals of As3+ and As5+ and compared with chemically synthesized schwertmannites. As3+ (100 mg/L) adsorption onto biogenic and chemical schwertmannite were 25 and 44%, respectively, at pH 4. At 100 mg As5+/L, adsorption capacity and efficiency onto biogenic schwertmannite were 47 mg/g and 50%, respectively. At 300 mg As5+/L, adsorption capacity and efficiency onto chemical schwertmannite were 169 mg/g and 56%, respectively. In summary, biogenic schwertmannite has potential for As removal via co-precipitation with Fe3+ at pH 3.5–4.5 and Fe/As ratios of ≥20 due to low production cost from acidic mine drainage. In contrast to the schwertmannite generation methods, which are usually performed with autotrophic acidophilic bacteria in the literature, this efficient and modular schwertmannite production process and its evaluation on arsenic adsorption is an important potential in acidic mine drainage treatment containing arsenic.

Resolving dynamic mineral-organic interactions in the rhizosphere by combining in-situ microsensors with plant-soil reactive transport modeling

Associations between minerals and organic matter represent one of the most important carbon storage mechanisms in soils. Plant roots are major sources of soil carbon, and resolving the dynamics and dominance of microbial consumption versus mineral sorption of root-derived carbon is critical to understanding soil carbon storage. Here we integrate in-situ rhizosphere microsensor and plant physiological measurements with a 3-D plant-soil reactive transport model to explore the fate of dissolved organic carbon (DOC) in the rhizosphere, particularly its microbial consumption and interaction with Fe oxide minerals. Over several days, microdialysis probes at the root-soil interface of growing Vicia faba roots in live soil, revealed clear diel patterns of DOC concentration in the pore water. Daytime DOC spikes coincided with peaks in leaf-level photosynthesis rates and were accompanied by declining redox potential and dissolved oxygen as well as increasing pH in the rhizosphere. Incorporating microsensor data into our modeling framework showed that the measured rapid loss of DOC after each mid-day spike could not be explained by consumption via aerobic respiration, nor via anaerobic respiration dominated by Fe oxide reduction. Rather, in the model, a large fraction of rhizosphere DOC was rapidly immobilized each day by adsorption to Fe oxides. Further, modeled microbial Fe reduction (fueled by DOC) did not mobilize significant organic carbon from Fe oxides during the day. Instead, the model predicted equilibrium desorption of organic carbon from Fe oxides at night. This new mechanistic modeling framework, which couples aboveground plant physiological measurements with non-destructive high-resolution monitoring of rhizosphere processes, has great potential for exploring the dynamics and balance of the various microbial reactions and mineral interactions controlling carbon storage in soils.

Genesis of the Giant Huoshaoyun Non-Sulfide Zinc–Lead Deposit in Karakoram, Xinjiang: Constraints from Mineralogy and Trace Element Geochemistry

The Huoshaoyun zinc–lead deposit, a giant non-sulfide deposit in Xinjiang, is one of the most significant discoveries of zinc–lead deposit in China and globally in recent years. The deposit is dominated by zinc–lead non-sulfides, with minor occurrences of sulfides such as sphalerite, galena, and pyrite. The non-sulfide minerals include smithsonite, cerussite, anglesite, and Fe-oxide. This study focuses on the mineralogical characteristics of sulfide and non-sulfide ores, as well as the trace element characteristics of sphalerite, smithsonite, and Fe-oxide. Mineralogical analysis reveals that smithsonite is derived from the oxidation of primary sulfide minerals and can be classified into three types that are generated during different stages of supergene oxidation. The three types of smithsonite are formed through replacing the sphalerite and host limestone, as well as directly precipitating in the fissures and vugs. Trace element analysis of sphalerite indicates that it is rich in Cd, Tl, and Ge, but poor in Fe and Mn. The ore-forming temperature, calculated using the GGIMFis geothermometer, is mostly within the range of 100~150 °C. Moreover, the trace element characteristics, ore-forming temperature, and S and Pb isotope compositions of the sulfide ores of the Huoshaoyun deposit are similar to those of the Jinding and Duocaima MVT lead–zinc deposits, which are also located in the Eastern Tethyan zinc–lead belt. This suggests that the sulfide orebody in the Huoshaoyun Zn-Pb deposit could also be the MVT deposit. Study of the trace element of the non-sulfide minerals shows that the Mn and Cd are relatively enriched in smithsonite, while Ga, Ge, and Pb are enriched in Fe-oxide. This can be attributed to distinct geochemical properties of the trace elements in the non-sulfide minerals of the Huoshaoyun deposit and is consistent with those of the other oxidized MVT deposits, thus indicating the supergene oxidation process of this deposit.

Nomenclature of the triphylite group of minerals

Abstract. In this paper we present a Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA-CNMNC)-accepted scheme for the classification and nomenclature of the triphylite group of minerals. The general formula of those minerals is M1M2TO4, where M1 and M2 refer to cations in an octahedral coordination: M1 = □, Na, Li; M2 = Mn2+, Fe2+, Mg, Fe3+, Mn3+, and T to tetrahedrally coordinated P5+ cations. The group contains the Li-bearing phosphates triphylite [LiFe2+(PO4)] and lithiophilite [LiMn2+(PO4)] and their oxidation products heterosite [Fe3+(PO4)] and purpurite [Mn3+(PO4)], as well as the Na-bearing phosphates natrophilite [NaMn2+(PO4)] and karenwebberite [NaFe2+(PO4)]. The Li–Mg-bearing phosphate simferite has been redefined as LiMg(PO4). Ferrisicklerite and sicklerite correspond to intermediate phases in the triphylite–heterosite and lithiophilite–purpurite solid solutions; consequently, according to the CNMNC dominant-constituent rule, they are discredited. A new mineral oxidation sequence is defined, which considers the different oxidation capacity of iron and manganese, and therefore replaces the traditional Quensel–Mason sequence. The formula calculation procedure for Li-bearing species, based on electron microprobe analyses and single-crystal X-ray diffraction data, is also described.

Geochemical evaluation and environmental risk assessment of heavy metals: A case study from Ireland using Tellus stream sediment data (2011–2017)

A comprehensive assessment of the distribution, spatial mapping and ecological risk of heavy metals in stream sediments of 17 counties of Ireland based on the Tellus geochemical survey programme in Ireland was carried out. Average trace metal concentrations of chromium (Cr), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), vanadium (V), cobalt (Co), arsenic (As), and major and minor oxides iron oxide (Fe2O3), manganese oxide (MnO) in the stream sediments were above the background values, but lower than Irish sediment quality guidelines for livestock and Canadian sediment quality guidelines (ISQG); threshold effect level (TEL) and probable effect level (PEL). 69.65% of Ni, 22.13% of Zn, and 96.7% of Pb samples exceeded the low-effect-range (ERL) values, whereas only 21%, 1.80% and 0.69% of the same elements exceeded the median effect range (ERM) values. Hotspots of Zn (>12000 mg kg−1), Pb (>10,000 mg kg−1), Fe2O3 (61.38%), MnO (26%), Cr (>2300 mg kg−1) and Ni (874.2 mg kg−1) were observed at Wicklow, Dublin, Mayo, Galway and Cavan counties. Catchment geochemistry was identified for the presence of heavy metals in the stream sediments. The geo-accumulation index (Igeo) indicated Kildare to be the least contaminated county with Igeo < 0 for Cr, Ni, Cu, Zn, Pb and As for 50% of the samples. The enrichment factor (EF) indicated that some sites located in Mayo and Donegal were highly contaminated. PInemerow followed the trend, Tipperary > Dublin > Waterford > Monaghan > Donegal > Wexford > Galway > Wicklow > Cavan > Meath > Kilkenny > Leitrim > Mayo > Louth > Sligo > Kildare > Carlow. Based on potential ecological risk index (PERI), 83.1% of the sites posed low ecological risk (PERI <150), 11.9% sites posed moderate risk (150 < RI < 300) and high ecological risk was posed by 0.3% (PERI >1200) of the sites. Lithology, topography and anthropogenic factors influenced the distribution and ecological risks of heavy metals. Non-carcinogenic and carcinogenic risk for adults and children were above the recommended value.

Modeling the Liberation of Iron Ores with Different Grain Sizes Considering Intergranular Fracture

ABSTRACT Predicting the liberation distribution of minerals in comminuted ore particles is one of the fundamental problems in mineral processing. However, there is still no widely accepted liberation model due to the complexity of the mineral fracture mechanism. In this study, the shape constants of the cumulative beta distribution were further optimized based on the investigation of the liberation distribution and fracture mechanism of iron oxide minerals in three types of iron ores with different grain sizes by locked-cycle grinding and batch grinding to model the liberation distribution of iron oxide minerals with different grinding methods. The results showed that the liberation distribution of iron oxide minerals in the three types of iron ores with locked-cycle grinding and batch grinding was related to intergranular fracture proportion and the closeness of ore particle size and mineral grain size. By relating the shape constants of cumulative beta distribution to ore particle size, mineral grain size, and the proportion of intergranular fracture, the developed liberation model well predicted the liberation distribution of iron oxide minerals with different grinding methods and its coefficient of determination (R2) was between 0.85–0.93.

Eu(III) and Am(III) adsorption on aluminum (hydr)oxide minerals: surface complexation modeling

Americium is a highly radioactive actinide element found in used nuclear fuel. Its adsorption on aluminum (hydr)oxide minerals is important to study for at least two reasons: (i) aluminum (hydr)oxide minerals are ubiquitous in the subsurface environment and (ii) bentonite clays, which are proposed engineered barriers for the geologic disposal of used nuclear fuel, have the same ≡AlOH sites as aluminum (hydr)oxide minerals. Surface complexation modeling is widely used to interpret the adsorption behavior of heavy metals on mineral surfaces. While americium sorption is understudied, multiple adsorption studies for europium, a chemical analog, are available. In this study we compiled data describing Eu(III) adsorption on three aluminum (hydr)oxide minerals—corundum (α-Al2O3), γ-alumina (γ-Al2O3) and gibbsite (γ-Al(OH)3)—and developed surface complexation models for Eu(III) adsorption on these minerals by employing diffuse double layer (DDL) and charge distribution multisite complexation (CD-MUSIC) electrostatic frameworks. We also developed surface complexation models for Am(III) adsorption on corundum (α-Al2O3) and γ-alumina (γ-Al2O3) by employing a limited number of Am(III) adsorption data sourced from literature. For corundum and γ-alumina, two different adsorbed Eu(III) species, one each for strong and weak sites, were found to be important regardless of which electrostatic framework was used. The formation constant of the weak site species was almost 10,000 times weaker than the formation constant for the corresponding strong site species. For gibbsite, two different adsorbed Eu(III) species formed on the single available site type and were important for the DDL model, whereas the best-fit CD-MUSIC model for Eu(III)-gibbsite system required only one Eu(III) surface species. The Am(III)-corundum model based on the CD-MUSIC framework had the same set of surface species as the Eu(III)-corundum model. However, the log K values of the surface reactions were different. The best-fit Am(III)-corundum model based on the DDL framework had only one site type. Both the CD-MUSIC and the DDL model developed for Am(III)-γ-alumina system only comprised of one site type and the formation constant of the corresponding surface species was ~ 500 times stronger and ~ 700 times weaker than the corresponding Eu(III) species on the weak and the strong sites, respectively. The CD-MUSIC model for corundum and both the DDL and the CD-MUSIC models for γ-alumina predicted the Am(III) adsorption data very well, whereas the DDL model for corundum overpredicted the Am(III) adsorption data. The root mean square of errors of the DDL and CD-MUSIC models developed in this study were smaller than those of two previously-published models describing Am(III)-γ-alumina system, indicating the better predictive capacity of our models. Overall, our results suggest that using Eu(III) as an analog for Am(III) is practical approach for predicting Am(III) adsorption onto well-characterized minerals.Graphical

Acidification characteristics and its influencing factors of red paddy soil derived from four parent materials in Southeast of China

There are many types of parent materials of red paddy soil, however the acidification characteristics of paddy soil derived from different parent materials remain unclear in the past 40 years at Jiangxi Province, and the degree of soil properties on acidification is also still unknown. Therefore, four red paddy soil derived from Quaternary red earth (Qre), plate shale (P), red sand stone (Rs), granite (G) in Jiangxi Province was selected. We investigated the acidification characteristics and quantified the effect of soil factors on the acidification of red paddy soils derived from different parent materials. Results showed that related to the second soil survey (1980s), the pH of red paddy soil derived from four parent materials decreased by an average 0.47 unit, base saturation (BS%) decreased 13.93%, exchangeable acid (EA) and exchangeable aluminum (EAl) increased by 0.43 and 0.20 cmol·kg−1, respectively. The ∆pH of red paddy soil derived from Rs (0.56) and G (0.54) were higher than that of Qre (0.34) and P (0.32). The ∆BS% of of red paddy soil derived from G (22.53%) > Rs (17.61%) > Qre (8.27%) > P (2.66%). The ∆EA (0.76) and ∆EAl (0.62) of Rs is highest. The results of redundancy analysis (RDA) shown that soil properties of red paddy soil derived from four parent material could explain 43.1% variation of soil acidification. CEC7, silt, sand, and SOM could explain 36.3%, 4.6%, 1.4% and 1.2% variation of acidification, respectively. The difference of soil mineralogy including oxide and clay minerals is also the reason for the different acidizing characteristics of paddy soil derived from four parent material. Therefore, compared with the 1980s, there is significant acidification of red paddy soil in 2018 in Jiangxi Province. The acidification of red paddy soil derived from red sand stone and granite is higher than that of plate shale and Quaternary red earth. And, parent material affect acidification by soil physicochemical and mineralogical properties.

The giant ShangzhuangREE‐rich apatite deposit, western China: Genesis by ultramafic magma differentiation

The origin of giant rare earth element (REE)‐rich phosphorus deposits related to ultramafic rocks is unclear. To characterize the genetic linkage between ultramafic rocks and P–REE mineralization, we investigated the whole‐rock geochemistry, geochronology and Hf isotopic compositions, along with previously published data of barren and ore‐bearing clinopyroxenites from the giant Shangzhuang REE‐rich apatite deposit (containing about 51.1 million tonnes of P2O5and 157,400 tonnes of REEs) in the Lajishan suture, Western China. The P–REE ores and barren biotite clinopyroxenites are composed predominantly of clinopyroxene and biotite, with high levels of apatite, amphibole, allanite, sulfide and oxide minerals in the ore‐bearing samples. Zircon and allanite U–Pb ages for the barren and ore‐bearing clinopyroxenites indicate they were formed between 467 and 465 Ma. The barren and ore‐bearing samples are characterized by high CaO and low SiO2contents, as well as similar Hf isotope ratios (εHf[t]: +3.4 to +7.7), indicating that they represent an ultramafic magma system and have been derived from a similar source. They are enriched in light REEs and depleted in Nb–Ta–Zr–Hf–Ti, similar to arc‐related lavas found worldwide. The weakly evolved barren samples have high Ba/La, Rb/Y and Dy/Yb values, and their ages are coeval with calc‐alkaline granitic plutons in the belt, which postdate the formation of the Lajishan ophiolite by ~30 myr. This suggests that the primary magma originated from garnet peridotite mantle modified by subducted Proto‐Tethys oceanic crust‐derived fluids in an arc setting. The presence of apatite intergrowth with cumulus clinopyroxene without alteration features indicates that the deposit has a magmatic origin. The ore‐bearing clinopyroxenite contains higher contents of P, REEs, and high‐field‐strength elements than the barren clinopyroxenite, which could be attributed to the in situ accumulation of apatite and allanite in the residual magma. Thus, the formation of the P‐dominated orebodies results from phosphate saturation due to the extensive fractionation crystallization of clinopyroxene and biotite during magmatic evolution. REEs were primarily enriched in the late‐stage melt, which was compatible with apatite and allanite. We propose that the formation of the Shangzhuang REE‐rich apatite deposit can be attributed to a simple differentiation of ultramafic melts in an evolved magmatic system.

Evolution of pH, redox potential and solute concentrations in soil and drainage water at a cultivated acid sulfate soil profile

Land drainage lowers the soil water table, which triggers enhanced oxidation of iron sulfide minerals in acid sulfate soils, causing acidification of fields and posing environmental hazards to aquatic ecosystems. The objective of this study was to develop a model for investigating the effects of oxidation of iron sulfide minerals and the cation exchange capacity (CEC) on the long-term evolution of pH, redox potential and solute concentrations in soil water and drain discharge. Two electron acceptors (oxygen and ferric iron) were included in the model. The model was implemented in the HP1 modeling platform (coupled HYDRUS-1D and PHREEQC-3) and applied to an acid sulfate soil profile of an agricultural field in Finland. The geochemical part of the model was tested against field observations. A comparison of different model versions showed that CEC had an essential role in mimicking the observed pH profile of soil. The drain discharge water quality was similar in the model versions both with and without CEC, but the buffering effect of CEC could be seen as lower iron concentrations. The oxidation of metastable iron sulfide minerals was three times faster than the oxidation of pyrite. Descriptions for the oxidation of both two minerals and for CEC were required to conduct long-term simulations that reproduce the observed geochemical state of a drained agricultural field. The HP1 modeling platform facilitated the testing of alternative chemical transformation processes of an AS soil profile in response to increased drainage efficiency after subsurface drainage installation.

Plant ash prevents acid mine drainage from sulfur-bearing tailings through multiple actions — A low-cost alkaline material

Plant ash, an inexpensive alkaline material containing organic nutrients, can provide electron donors for microbial reactions and neutralize water acidity, making it an excellent candidate for use in preventing acid mine drainage production from tailings. However, the efficacy of using plant ash alone to treat tailings and the role of microorganisms remain unclear. Therefore, the effectiveness of plant ash in acid neutralization, inhibiting oxidation of sulfur-bearing minerals, and reducing acid mine drainage production is compared to that of three other alkaline materials—volcanic ash, limestone, and fly ash—in this study. Their potential microbial mechanisms are also explored. The 63-day experimental results showed that all four alkaline materials effectively neutralized the acidity of the sulfur-bearing tailings and dramatically decreased heavy metal leaching (Fe, Mn, Zn, Pb, As, and Cd). Plant ash had a higher removal efficiency of Fe (99.9%), Mn (94.0%), and Zn (99.7%) than the other three materials, which was related to its ability to provide better precipitation and adsorption conditions. XRD observed gypsum in each treatment column, the formation of a new phase of calcium carbonate was observed in the plant ash column, and SEM showed that precipitation wrapped around the surface of tailings inhibited their oxidation process. 16 S rRNA sequencing confirmed that plant ash could inhibit AMD production through microbial action. The plant ash column had higher biodiversity than the control column, and the eutrophic flora in the plant ash column could use organic matter to consume dissolved oxygen, inhibiting tailing oxidation; however, the growth of some reducing flora resulted in As reduction, causing a slight increase in As in the leachate.

Application of community data to surface complexation modeling framework development: Iron oxide protolysis

This study presents a comprehensive community data-driven surface complexation modeling framework for simulating potentiometric titration of mineral surfaces. Compiled community data for ferrihydrite, goethite, hematite, and magnetite are fit to produce representative protolysis constants that can reproduce potentiometric titration data collected from multiple literature sources. Using this framework, the impact of surface complexation model type and surface site density (SSD) on the fit quality and protolysis constants can be readily evaluated. For example, the non-electrostatic model yielded a poor data fit compared to diffuse double layer model and constant capacitance models due to the absence of known surface charge effects. Regardless of the choice of iron oxide mineral, pKa1 decreased with increasing SSD while the opposite tendency was observed for pKa2. This newly developed framework demonstrates a method to reconcile community data-wide potentiometric titration data using Findable, Accessible, Interoperable, Reusable data principles to produce mineral protolysis constants that improve robustness of surface complexation models for applications in metal sorption and reactive transport modeling. The framework is readily expandable (as community data increase) and extensible (as the number of minerals increase). The framework provides a path forward for developing self-consistent, comprehensive, and updateable surface complexation databases for surface complexation and reactive transport modeling.