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Accurate chronology of climatic shifts is critical to understand the controls on landscape and species evolution. Unfortunately, direct dating of continental climate change is hindered by the scarcity of dateable terrestrial products evidencing climatic shifts. Here we use ferruginous indurations from the arid landscapes of the Nullarbor Plain in southern Australia to constrain the timing of Plio‐Pleistocene aridification in the continental realm. We present (U‐Th)/He goethite data implying active induration processes between c. 2.7 and 2.4 Ma. Chemical‐mineralogical and petrographic examination suggests that formation of ferruginous indurations was linked with a decline of the groundwater table, driven by the rapid climatic shift from humid late Pliocene to arid early Pleistocene conditions. Combined with local to global climatic proxies, we conclude that ferruginous indurations are promising targets to obtain absolute ages on landscape evolution to refine continental climatic chronology and improve understanding of the environmental drivers of species diversification and extinction. Plain Language Summary The reconstruction of Earth's climate record is typically founded on the physicochemical properties of marine sediments. Continental sediments that yield time‐constrained climate information are rare, but important to interpret wider Earth system responses and the co‐evolution of regional climate, landscape, and biota. This study presents direct dating of continental climate change on the Nullarbor Plain to constrain its development as an important biogeographic barrier driving species diversification between SW‐ and SE‐Australia. Age dating of iron‐oxide cements constrains the waning availability of mobile water (e.g., groundwater) and the onset of drier conditions related to global Plio‐Pleistocene climate change. These findings demonstrate that iron‐oxides may provide an excellent continental archive to anchor major climate shifts and help understand associated terrestrial ecosystem change. Key Points (U‐Th)/He data from ferruginous indurations capture the onset of Plio‐Pleistocene aridification in southern Australia Correlation of induration age with other climatic proxies indicates that ferruginous indurations track terrestrial water table evolution Timing of aridification constrains evolution of important biogeographic barrier

Nanophase Fe-oxyhydroxides in freshwater ferromanganese nodules (FFN) from Green Bay, Lake Michigan, and adsorbed arsenate have been investigated by X-ray powder diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), Z-contrast imaging, and ab initio calculations using the density functional theory (DFT). The samples from northern Green Bay can be divided into two types: Fe-Mn nodules and Fe-rich nodules. The manganese-bearing phases are todorokite, birnessite, and buserite. The iron-bearing phases are feroxyhyte, nanophase goethite, two-line ferrihydrite, and nanophase FeOOH with guyanaite structure. Z-contrast images of the Fe-oxyhydroxides show ordered FeOOH nano-domains with guyanaite structure intergrown with nanophase goethite. The FeOOH nanophase is a precursor to the goethite. Henceforth, we will refer to it as \"proto-goethite.\" DFT calculations indicate that goethite is more stable than proto-goethite. Our results suggest that ordering between Fe and vacancies in octahedral sites result in the transformation from feroxyhyte to goethite through a proto-goethite intermediate phase. Combining Z-contrast images and TEM-EDS reveals that arsenate (AsO43-) tetrahedra are preferentially adsorbed on the proto-goethite (001) surface via tridentate adsorption. Our study directly shows the atomic positions of Fe-oxyhydroxides with associated trace elements. The methods can be applied for identifying structures of nanophases and adsorbed trace elements and heavy metals.

  The opposed transformation of arsenic (As) and cadmium (Cd) in paddy soil postures numerous challenges for their simultaneous remediation. An incubation study was conducted on the immobilization of Cd and As by biochar (BC), goethite (G), goethite-combined biochar (BC + G), and goethite-modified biochar (GBC). The results showed that biochar effectively immobilized Cd while significantly increasing As mobility, whereas goethite effectively immobilized As more than Cd. BC + G treatment significantly decreased toxicity characteristics leaching procedure (TCLP) and CaCl 2 -extractable Cd by 22.70% and 40.15%; meanwhile, TCLP and NaHCO 3 -As were significantly reduced by 38.25% and 31.87%, respectively, compared with the control. This study found that GBC was the optimum amendment within the immobilization efficiency for CaCl 2 -Cd (57.03%) and TCLP-As (61.11%). BC + G and GBC applications showed some interactions between biochar and goethite, which played an essential role in immobilizing Cd and As simultaneously. Therefore, GBC showed a great benefit in being a low-cost and efficient environmental amendment for Cd and As remediation in alkaline co-contaminated paddy soil.

Effective moisture (EM) distribution in the Indian summer monsoon (ISM) region is strongly related to regional topography. An understanding of climate change and the interactions between climate variables can help predict future climate variations. Here, we reconstruct a stack EM record for Southwest China over the past 90 kyr using environmental magnetism in lake sediment. The EM in Southwest China at the orbital scale was closely linked to precession‐induced change in North Hemisphere solar insolation, as well as the ISM variability. However, at the glacial‐interglacial scale, it was decoupled with ISM intensity, being wetter during glacial periods (weakened ISM) and drier during interglacial periods (enhanced ISM). Combined with modern meteorological observations, we suggest that the topographical barrier effect and temperature induced dryness are responsible for the decoupling between ISM intensity and EM. The terrestrial topography and temperature strongly influence EM distribution by altering the dynamics of onshore airflow and evapotranspiration. Plain Language Summary Effective moisture (EM) directly affects hydrological cycle and wider‐scale socio‐economic development. Reconstruction of prehistoric EM levels is essential for deeper understanding of the global climate system, developing climate models and improving prediction of future climate variations. Here, we reconstruct a high‐resolution EM record over the past ∼90,000 years from lake sediments in Tengchong, Yunnan province, Southwest China. We found that the variation of precession (shifts in the rotational axis of the Earth) and solar insolation are the key contributors to the EM variability at the orbital scale. Unusually, a wetter climate during the glacial period and relatively drier interglacial periods were observed in our records, which is opposite to those found in previous studies (arid glacial and humid interglacial) in monsoon regions, indicating a decoupling pattern between monsoon intensity and EM in study region. Based on a comprehensive analysis of the modern meteorological observations, we conclude that the topography and temperature exert a considerable role in modulating EM distribution and response to the decoupling pattern. Key Points The long‐term effective moisture (EM) record in Southwest China since ∼90 kyr was reconstructed The EM variability at the orbital scale in terrestrial Indian summer monsoon region is primarily dominated by precession The topographic barrier and temperature induced aridification contribute to the decoupling of monsoon intensity and EM

The current study assessed two concrete mixes prepared using dolomite and barite/limonite aggregates to shield against both energetic photons and neutrons. After that, a designed mix which comprised barite/goethite aggregates plus fine-powdered boron carbide additive, was proposed to improve the overall radiation shielding properties and in the same time, doesn’t compromise or even improve the physic-mechanical properties of the mature concrete. The assessment started first with intensive experimental investigations to investigate the prepared mixes’ shielding capabilities against both γ-rays and fast neutrons. Then, analytical computations were performed via number of reliable software programs such as; Phy-X, NXCom, MRCsC, JANIS-4, and MCNP5, in order to confirm the experimental results and to validate the created Monte-Carlo models. Finally, an intensive radiation shielding assessment for all concrete mixes understudy using, mainly, the validated MCNP models, was performed. The obtained results have revealed the superiority of barite mixes over the dolomite mix concerning attenuating photons moreover, the proposed designed mix has shown superiority over the other two prepared mixes considering shielding against; energetic photons, fast/thermal neutrons, and secondary emitted γ-rays, which nominates this mix to be a suitable universal shield that can be used even in mixed radiation fields.

Aims Many soil scientists think that soil phosphate exists as discrete compounds of iron, aluminium and calcium and, accordingly, use chemical fractionation schemes to identify these compounds. Methods We reacted a sample of goethite and a sample of aluminium oxide with a phosphate solution under conditions chosen to facilitate penetration of phosphate. Thus the sample of goethite had neither calcium nor aluminium present and similarly the sample of aluminium oxide had neither iron nor calcium. We included a sample of hydroxyapatite which had neither iron nor aluminium present. We subjected the samples to two fractionation procedures; the original Chang and Jackson ( 1957 ) method and a variant of it. Results For the phosphated goethite and aluminium oxide, energy dispersive X-ray spectra did not detect any discrete aluminium or iron phosphates; dissolution studies were consistent with penetration of phosphate. Both fractionation procedures detected discrete compounds even though none were present. They also detected iron, aluminium and calcium phosphates for samples for which they were not present. We also critically discuss other evidence for the existence of discrete iron, aluminium and calcium phosphates in soils. Conclusions Fractionation procedures designed to measure chemically specified phosphate fractions in soil are fallacious and should be abandoned.

Optimal pH conditions for efficient artificial photosynthesis, hydrogen/oxygen evolution reactions, and photoreduction of carbon dioxide are now successfully achievable with catalytic bipolar membranes-integrated water dissociation and in-situ acid-base generations. However, inefficiency and instability are severe issues in state-of-the-art membranes, which need to urgently resolve with systematic membrane designs and innovative, inexpensive junctional catalysts. Here we show a shielding and in-situ formation strategy of fully-interconnected earth-abundant goethite Fe +3 O(OH) catalyst, which lowers the activation energy barrier from 5.15 to 1.06 eV per HO − H bond and fabricates energy-efficient, cost-effective, and durable shielded catalytic bipolar membranes. Small water dissociation voltages at limiting current density (U LCD : 0.8 V) and 100 mA cm −2 (U 100 : 1.1 V), outstanding cyclic stability at 637 mA cm −2 , long-time electro-stability, and fast acid-base generations (H 2 SO 4 : 3.9 ± 0.19 and NaOH: 4.4 ± 0.21 M m −2 min −1 at 100 mA cm −2 ) infer confident potential use of the novel bipolar membranes in emerging sustainable technologies. Bipolar membranes integrated water dissociation and acid-base generations have great potential in emerging sustainable technologies but remains inefficient. Here, the authors circumvent this inefficiency and instability of the membranes by developing polyaniline shielded catalytic bipolar membranes.

The autocatalytic redox interaction between aqueous Fe(II) and Fe(III)-(oxyhydr)oxide minerals such as goethite and hematite leads to rapid recrystallization marked, in principle, by an atom exchange (AE) front, according to bulk iron isotopic tracer studies. However, direct evidence for this AE front has been elusive given the analytical challenges of mass-resolved imaging at the nanoscale on individual crystallites. We report successful isolation and characterization of the AE front in goethite microrods by 3D atom probe tomography (APT). The microrods were reacted with Fe(II) enriched in tracer 57Fe at conditions consistent with prior bulk studies. APT analyses and 3D reconstructions on cross-sections of the microrods reveal an AE front that is spatially heterogeneous, at times penetrating several nanometers into the lattice, in a manner consistent with defect-accelerated exchange. Evidence for exchange along microstructural domain boundaries was also found, suggesting another important link between exchange extent and initial defect content. The findings provide an unprecedented view into the spatial and temporal characteristics of Fe(II)-catalyzed recrystallization at the atomic scale, and substantiate speculation regarding the role of defects controlling the dynamics of electron transfer and AE interaction at this important redox interface.

Most plants living in tropical acid soils depend on the arbuscular mycorrhizal (AM) symbiosis for mobilizing low-accessible phosphorus (P), due to its strong bonding by iron (Fe) oxides. The roots release low-molecular-weight organic acids (LMWOAs) as a mechanism to increase soil P availability by ligand exchange or dissolution. However, little is known on the LMWOA production by AM fungi (AMF), since most studies conducted on AM plants do not discriminate on the LMWOA origin. This study aimed to determine whether AMF release significant amounts of LMWOAs to liberate P bound to Fe oxides, which is otherwise unavailable for the plant. Solanum lycopersicum L. plants mycorrhized with Rhizophagus irregularis were placed in a bicompartmental mesocosm, with P sources only accessible by AMF. Fingerprinting of LMWOAs in compartments containing free and goethite-bound orthophosphate (OP or GOE-OP) and phytic acid (PA or GOE-PA) was done. To assess P mobilization via AM symbiosis, P content, photosynthesis, and the degree of mycorrhization were determined in the plant; whereas, AM hyphae abundance was determined using lipid biomarkers. The results showing a higher shoot P content, along with a lower N:P ratio and a higher photosynthetic capacity, may be indicative of a higher photosynthetic P-use efficiency, when AM plants mobilized P from less-accessible sources. The presence of mono-, di-, and tricarboxylic LMWOAs in compartments containing OP or GOE-OP and phytic acid (PA or GOE-PA) points toward the occurrence of reductive dissolution and ligand exchange/dissolution reactions. Furthermore, hyphae grown in goethite loaded with OP and PA exhibited an increased content of unsaturated lipids, pointing to an increased membrane fluidity in order to maintain optimal hyphal functionality and facilitate the incorporation of P. Our results underpin the centrality of AM symbiosis in soil biogeochemical processes, by highlighting the ability of the AMF and accompanying microbiota in releasing significant amounts of LMWOAs to mobilize P bound to Fe oxides.

The large uncertainty in the mineral dust direct radiative effect (DRE) hinders projections of future climate change due to anthropogenic activity. Resolving modeled dust mineral speciation allows for spatially and temporally varying refractive indices consistent with dust aerosol composition. Here, for the first time, we quantify the range in dust DRE at the top of the atmosphere (TOA) due to current uncertainties in the surface soil mineralogical content using a dust mineral-resolving climate model. We propagate observed uncertainties in soil mineral abundances from two soil mineralogy atlases along with the optical properties of each mineral into the DRE and compare the resultant range with other sources of uncertainty across six climate models. The shortwave DRE responds region-specifically to the dust burden depending on the mineral speciation and underlying shortwave surface albedo: positively when the regionally averaged annual surface albedo is larger than 0.28 and negatively otherwise. Among all minerals examined, the shortwave TOA DRE and single scattering albedo at the 0.44–0.63 µm band are most sensitive to the fractional contribution of iron oxides to the total dust composition. The global net (shortwave plus longwave) TOA DRE is estimated to be within −0.23 to +0.35 W/sq. m. Approximately 97 % of this range relates to uncertainty in the soil abundance of iron oxides. Representing iron oxide with solely hematite optical properties leads to an overestimation of shortwave DRE by +0.10 W/sq. m at the TOA, as goethite is not as absorbing as hematite in the shortwave spectrum range. Our study highlights the importance of iron oxides to the shortwave DRE: they have a disproportionally large impact on climate considering their small atmospheric mineral mass fractional burden (∼2 %). An improved description of iron oxides, such as those planned in the Earth Surface Mineral Dust Source Investigation (EMIT), is thus essential for more accurate estimates of the dust DRE.