American Mineralogist

Li, Ke Jin; Kurniawan, Alfin; Christidis, Georgios E.; He, Jia Yong; Zhou, Chun Hui

doi: 10.2138/am-2022-8834pmid: N/A

AbstractMontmorillonite (Mt) is a ubiquitous swelling clay mineral and major component of soft rocks, sediments, and soils with an inherent capability to sorb metal cations. This unique feature renders Mt important for the enrichment and mobilization of environmentally important metal cations, retardation of heavy metals and radionuclide ions, the evolution of clay mineral itself, soils and sediments, and other geological processes. Understanding the interfacial interactions of Mt with metal cations at the molecular level is of fundamental importance in all these processes, but still remains elusive, due to the chemical and structural complexity of Mt surfaces and the diverse chemistries of metal cations. In this Review, we aim to provide the reader with a comprehensive overview of the adsorption modes of metal cations on basal and edge surfaces of Mt, local chemical environments of the cation binding sites, the driving forces for metal sorption, and factors influencing the dynamics of cation uptake onto Mt surfaces. Various surface complexation models [i.e., nonelectrostatic model (NEM), constant capacitance model (CCM), diffuse layer model (DLM), and triple-layer model (TLM)], advanced spectroscopic techniques (i.e., NEM, CCM, DLM, and TLM), and atomistic simulation methods (i.e., MD, DFT, and FPMD) have been used in conjunction with macroscopic adsorption experiments to gain detailed insights into the interfacial interactions of metal cations on Mt. Mt adsorbs metal cations via three independent pathways: (1) cation exchange; (2) surface complexation; and (3) nucleation and surface precipitation. The principal driving force for cation exchange is electrostatic interaction, while chemical bonding governs the two other mechanisms that depend on the basal and edge surface properties of Mt. The siloxane cavities on the tetrahedral basal plane exhibit the strongest adsorption sites for cation exchange and are greatly affected by the the degree of Al3+/Si4+ tetrahedral substitutions. At the amphoteric edge surfaces bearing hydroxyl groups, metal cations could form mono/multidentate surface complexes on Mt [010] and [110] edges. Ionic strength, pH, the presence of competing cations, temperature, and layer charge have been shown to affect the adsorption mechanisms and quantity of adsorbed cations. The updated information on the interfacial interactions of metal cations with Mt basal and edge surfaces presented in this review provides an improved understanding of the enrichment of metals, formation of metal ores, and natural biogeochemical cycles, as well as may promote technological and engineering applications of this important clay mineral in environmental remediation, geological repository, petroleum exploration and extraction, and extraterrestrial research.

Xi, Jiaxin; Yang, Yiping; He, Hongping; Xian, Harvang; Tan, Wei; Li, Rui; Zhu, Jianxi; Xu, Huifang

doi: 10.2138/am-2023-8984pmid: N/A

AbstractThe composition and microstructure of phyllosilicates are prone to transformation due to their great sensitivity to surrounding physicochemical changes. Berthierine [(R2+,R3+,□)6(Si,Al)4O10(OH)8] (□ represents octahedral vacancy) is a typical ferromagnesian phyllosilicate that commonly occurs in ferruginous rocks of shallow-marine habitats and has been used as an indicator of local depositional and/or hydrothermal activity in marine environments. However, little is known about the formation and mineralogy of non-marine berthierine, particularly in volcanic systems. Using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), we have identified a berthierine twin structure within weakly altered biotite in a rhyolite from Long Valley, California, U.S.A. The presence of nanoscale Fe-rich layers in the host biotite is revealed by energy-dispersive spectroscopy and electron energy loss spectroscopy (EELS). The HAADF-STEM pictures with atomic resolution demonstrate that the Fe-rich layers are composed of twinning berthierine layers rather than a single chlorite layer. The transformation of biotite to berthierine requires the dissolution of a tetrahedral (T) layer and the introduction of a new TO (O represents octahedral sheet) structure into the biotite stacking sequence, resulting in substituting one biotite layer (i.e., TOT) with two twinning berthierine layers (i.e., TO-OT). Observations based on morphology indicate that the transformation began at biotite defect locations (such as screw dislocation, edge dislocation, and microcleavage fracture), concurrent with the rearrangement of metal cations. During the fluid alteration of biotite, berthierine was produced via an interface-coupled dissolution-reprecipitation process. The EELS analyses further demonstrate that the Fe-rich biotite promotes the production of berthierine as the principal alteration product in low-temperature environments. Additionally, this study suggests that the combination of HAADF-STEM and EELS is effective for identifying nanominerals and elucidating their formation and alteration mechanisms.

Zhao, Yun; Xue, Chunji; Liu, Sheng-Ao; Mathur, Ryan; Zhao, Xiaobo; Seltmann, Reimar; Jiao, Jiangang; Huang, Yongsen; Wang, Xuefeng

doi: 10.2138/am-2022-8888pmid: N/A

AbstractElucidating metal transport agents is the key to understanding the genesis of deposits and tracking the locations of concealed orebodies. Here, we integrate H-O-S-Cu isotopic data from the shear-zone-hosted Lingyun Cu deposit, China, as a means to fingerprint metal transport agents. Sulfide mineralization can be divided into early and late stages, which consist of chalcopyrite + bornite + quartz veins and chalcopyrite + bornite + ankerite veinlets, respectively. Both δ18Ofluid and δD values of fluid inclusions hosted by quartz (δ18Ofluid: 0.5‰ to 9.9‰, δD: –103.9‰ to –60.1‰) and δ65Cu values of sulfides (–1.85‰ to +0.39‰) from the early stage progressively decrease from the southeastern to northwestern portions of the Lingyun deposit, whereas sulfide δ34S simultaneously shifts toward heavier values (–14.4‰ to 5.0‰). The δ34S and δ65Cu values of sulfides from the late stage have restricted ranges from –11.2‰ to –9.3‰ and –0.30‰ to 0.05‰, respectively. The possibilities of meteoric water addition, water-rock interaction, inter-mineral Cu partitioning, diffusion, and oxidation could be ruled out as reasons for having caused systematic H-O-S-Cu isotope variations. Vapor-liquid separation resulted in preferential incorporation of light Cu, H, and O isotopes into the vapor phase. The decrease in oxygen fugacity in the fluids resulted in a shift toward heavier δ34S values as fluid flowed outward. Vapor-phases are the dominant transport agents for Cu in the Lingyun deposit, which may be widely applicable to shear-zone-hosted deposits. The direction of progressively increasing δ65Cu, δD, and δ18O values and decreasing δ34S values allows identification of potential locations of concealed orebodies.

Foerder, Andrew B.; Englert, Peter A.J.; Bishop, Janice L.; Koeberl, Christian; Burton, Zachary F.M.; Patel, Shital; Gibson, Everett K.

doi: 10.2138/am-2022-8779pmid: N/A

AbstractThe McMurdo Dry Valleys of Antarctica provide a testbed for alteration processes on Mars due to the cold, arid, and windy conditions. Analysis of three sediment cores collected from Don Juan Basin, Wright Valley, Antarctica, reveals that surface sediment formation is primarily dominated by physical alteration. Chemical alteration occurs sporadically in this region and is frequently indicated by the accumulation of sulfates and Cl-bearing salts. We investigated the effects of physical and chemical alteration in Don Juan Basin by considering major and trace element abundances in the sediments based on depth and location. Our results indicate inversely related chemical- and physical-alteration gradients with proximity to Don Juan Pond where the current center of the pond represents a more chemically altering environment and the perimeter a more physically altering one. Comparing calculated sulfate abundances for Don Juan Basin cores to rock and soil samples taken by the rover Curiosity at Gale crater, we observed that the core from within Don Juan Pond best matches Curiosity soil sulfate abundances.A new Chemical Index of Alteration equation that adjusts for salt dilution was also applied to the Antarctic cores and Curiosity rocks and soils. Our analysis indicates a significantly higher degree of chemical alteration than originally reported for most Antarctic and martian samples. Our investigation provides evidence for aqueous-based chemical alteration under cold, hyperarid conditions in Don Juan Basin, Antarctica. Our work also demonstrates the analogous nature of terrestrial microenvironments to similar, local-scale sample sites on Mars, thereby supporting past or present chemical alteration on Mars.

Martirosyan, Naira S.; Efthimiopoulos, Ilias; Jahn, Sandro; Lobanov, Sergey S.; Wirth, Richard; Reichmann, Hans-Josef; Koch-Müller, Monika

doi: 10.2138/am-2022-8737pmid: N/A

AbstractIn this study, we investigated four different ferroan dolomite samples using in situ Raman spectroscopy and powder X-ray diffraction (XRD) at pressures up to 48 GPa and room temperature. Our results show that the transition from Dolomite-I (Dol-I) to Dolomite-II (Dol-II) occurs above 13–16 GPa, and the transition pressure depends on the composition of the solid solution. Compression above 32–35 GPa results in the appearance of Dolomite-IIIc (Dol-IIIc) or Dolomite-IIIb (Dol-IIIb). In the high-pressure XRD study, we found that the XRD patterns of Ca0.97(Mg0.77Fe0.23Mn0.03)(CO3)2 (xFe = 0.23, Ank23) can be indexed as Dol-IIIc at 44 GPa, while the rhombohedral Dol-IIIb structure matches better with the XRD patterns of the xFe = 0.40 (Ank40) and 0.64 (Ank64) solid solutions. Additionally, in the Raman spectra of the Fe-richest sample (Ank64), we observed an abrupt frequency downshift of the CO3-stretching vibrations between 40–42 GPa, which may reflect a pressure-induced Fe2+ spin transition.We further investigated two samples with xFe = 0.19 (Ank19) and 0.23 (Ank23) at high pressure and high temperatures, up to at least 2600 K. The experiments revealed that the unquenchable Dol-IIIc structure could be a stable high-pressure/high-temperature polymorph in ferroan dolomite up to at least 2600 K.

Xie, Yuan-Hui; Schwartz, Joshua J.; Li, Xiao-Wei; Cai, Keda; Thomas, Bader; Li, Huan; Wang, Fang-Yue; Zhang, Xiao-Bing; Mo, Xuan-Xue; Dong, Guo-Chen

doi: 10.2138/am-2022-8873pmid: N/A

AbstractHigh-Sr/Y granitoids in continental settings are sometimes erroneously regarded as the products derived from partial melting of thickened/delaminated mafic lower curst under relatively higher pressures (>1.5 GPa) in a collisional orogenic setting. In fact, multiple magmatic processes in the trans-crustal magma system, such as recycling of antecrysts, crustal assimilation, and fractional crystallization, can create or modify the primary “adakitic” signature. As a result, the generation of adakitic magmas in continental settings remains controversial from a bulk-rock perspective. Here, we address the origin of adakitic plutonic rocks through geochemical and textural characterization of rock-forming minerals in the pyroxene-bearing Zhuyuan granodiorite, West Qinling, China. The Zhuyuan granodiorite formed in a post-collisional setting and primarily consists of resorbed orthopyroxene, three types of clinopyroxene, amphibole, two types of plagioclases, K-feldspar, biotite, and quartz. Type-1 Cpx has high XMg (70.0–81.7). Type-2 Cpx displays normal zoning and decreasing XMg (80.9 to 71.5) from the core to rim. Type-3 Cpx is reversely zoned, where the rims have higher XMg (75.5–86.9), Ni, Cr, suggesting a recharge event. Orthopyroxene has high-Ni and -Cr contents, as well as high XMg (80.9–82.8), indicative of antecrysts that grew in mafic magma reservoirs. The injection of magmas from different sources is supported by sieve-textured plagioclase and crystal size distributions of non-poikilitic amphibole. Finally, non-sieve textured plagioclase, biotite, K-feldspar, and quartz are late-crystallized phases, indicative of an orthocrystic origin. The melts in equilibrium with these orthocrysts display significantly higher Sr/Y values than the magma batches that crystallized other mafic phases (i.e., amphibole, clinopyroxene, and orthopyroxene). Thus, we propose that the system involved an initial high-Sr/Y melts in equilibrium with the orthocryst assemblage was generated by water-fluxed melting of intermediate to felsic sources. The addition of low Sr/Y non-orthocrysts (e.g., amphibole and pyroxene) and associated melt diluted the original “adakitic signal” in the magma reservoir and drove the bulk composition to more mafic values. Consequently, the Zhuyuan pyroxene-bearing granodiorite represents a mixture of crystals with diverse origins and distinct magma batches of various compositions (from felsic to mafic compositions). Our study emphasizes that the origin of adakitic granitoids cannot be clearly deciphered without geochemical analysis of the constituent minerals. We also suggest that Sr/Y values in plutons should be cautiously used in paleo-crustal thickness estimates in collisional settings because of possible open system scenarios as described here.

Xu, Jingui; Fan, Dawei; Zhang, Dongzhou; Li, Bo; Zhou, Wenge; Dera, Przemyslaw

doi: 10.2138/am-2022-8879pmid: N/A

AbstractOrthopyroxene is an abundant mineral in subducting slabs. Studying its phase transitions at high pressure is important to the understanding of mineralogy of subducting slabs in the deep Earth. Synchrotron-based single-crystal X-ray diffraction experiments were conducted on a synthetic Ni-bearing ferrosilite (Ni-En31Fs65) at pressures up to 33.8 GPa. Three phase transitions were observed at 12.1(6), 15.6(6), and 31.3(25) GPa. The first two phase transitions in Ni-En31Fs65 resemble the previously described phase transitions in Ni-free Fe-rich orthopyroxenes, i.e., the initial α-opx (Pbca) transforms to β-opx (P21/c ), then the latter transforms to γ-opx (Pbca). This indicates that the incorporation of a few mol% NiSiO3 does not influence the phase transition path of Fe-rich orthopyroxene. After the third phase transition, the structure (P21 ca) of Ni-En31Fs65 resembles the previously reported β-popx observed in En90 at high pressure, although the onset pressure of the phase transition in Ni-En31Fs65 is ~7 GPa lower than that in En90. β-popx has a post-pyroxene structure that contains fivefold- and sixfold-coordinated Si cations. Our results indicate that the post-pyroxene structure is β-popx (P21 ca) for either Fe-poor or Fe-rich orthopyroxenes, although the phase transition path before the pyroxene → post-pyroxene is compositionally dependent. Additionally, unlike the second and third transitions, whose onset pressures are monotonously decreased by increasing Fe content, the Fe effect on shifting the first transition is much more significant for orthopyroxenes within En <50 mol% than that within En >50 mol%.

Münchhalfen, Marie; Schreuer, Jürgen

doi: 10.2138/am-2023-8986pmid: N/A

AbstractThe thermoelastic properties and thermal expansion of natural single-crystal zircon without detectable radiation damage were determined in the temperature range between 100 and 1650 K on five samples from Cambodia, Sri Lanka, and Tanzania. Up to about 1500 K, the results are in excellent agreement and fully reversible. The average adiabatic elastic stiffness coefficients at room temperature in GPa are c11 = 426.8(6), c12 = 68.1(4), c13 = 152.0(4), c33 = 490.8(9), c44 = 113.1(2), and c66 = 49.0(1). Polycrystalline averaging for the aggregate bulk and shear modulus (Voigt-Reuss-Hill average) yields K = 229.3(4) GPa and G = 109.3(1) GPa. From 293 to 1573 K, the elastic stiffnesses soften almost linearly with the temperature coefficients in MPa/K: dc11/dT = –45.36(7), dc12/dT = –2.03(7), dc13/dT= –9.59(7), dc33/dT = –42.85(12), dc44/dT = –9.60(3), and dc66/dT = –2.19(1). Below room temperature, the behavior of the cij is nonlinear, with decreasing absolute values of the temperature coefficients. Above about 1500 K, a temperature- and time-dependent irreversible elastic stiffening accompanied by an increasing ultrasound dissipation was observed in all samples. These anomalies are interpreted to be the consequence of increased dislocation densities.

Ji, YunHao; Xie, GuiQing; Romer, Rolf L.; Li, Wei; Zhu, QiaoQiao; Fu, Bin

doi: 10.2138/am-2022-8917pmid: N/A

AbstractScheelite (CaWO4) is an economically important W mineral in skarns that form when magmatic fluids exsolved from a granitic intrusion react with carbonate wall rocks. In the Fujiashan W skarn deposit, scheelite formed during four stages of the hydrothermal skarn development. We present cathodoluminescence (CL) images and in situ trace element and Sr-O isotope data of scheelite from these four stages, i.e., scheelite in prograde and retrograde skarn, quartz-sulfide veins, and late calcite replacements. Scheelite from prograde skarn and quartz sulfide veins are homogeneous and show oscillatory zoning textures in CL images, whereas scheelite from retrograde skarn and late carbonate stages display dissolution-reprecipitation and patchy textures. The brightness of CL textures decreases with a higher substitution of Mo. Molybdenum-rich scheelite (up to 2.1 wt%) is characterized by relatively high contents of Nb and Ta (up to 156 and 0.9 ppm, respectively), positive Eu anomalies, high-δ18O values (5.2 to 5.9‰), and relatively low-87Sr/86Sr values (0.70661 to 0.70727), and has grown in a system with a continuous supply of magmatic fluid. Molybdenum-poor scheelite (0.2 wt%) has low contents of Nb and Ta, negative Eu anomalies, low-δ18O values (4.2 to 4.3‰), and relatively high-87Sr/86Sr ratios (0.70748 to 0.70804). This type of scheelite formed in a system with a restricted flow of magmatic fluid during scheelite precipitation became increasingly depleted in elements that substitute into scheelite. The continued reaction of the magmatic fluid with the wall rocks and the precipitation of minerals from the fluid resulted in a systematic change of the δ18O and 87Sr/86Sr ratios. Chemical and isotopic variations in scheelite may reflect the pulsed flow of a magmatic fluid and do not require the involvement of different fluids or contrasting redox conditions.

Yan, Hao; Xu, Lingang; Mao, Jingwen; Tang, Dongjie; Yang, Xiuqing; Bai, Yinzeng; Li, Chao; Konhauser, Kurt O.; Robbins, Leslie J.

doi: 10.2138/am-2022-8919pmid: N/A

AbstractAncient manganese (Mn) deposits are primarily characterized by the presence of Mn(II) carbonates that likely formed by the diagenetic reduction of precursor Mn(IV) oxides. As such, Precambrian sedimentary Mn deposits have been used as a line of evidence for the evolution of oxygen in Earth’s surface environments. However, recent studies have shown that these Mn(II)-carbonates have the ability to directly accumulate within anoxic water columns, where free oxygen does not play a role in their formation. This alternative pathway casts uncertainty on the robustness of using ancient Mn deposits to constrain the redox fabric of the past marine water columns. Here, we investigate the Wafangzi Mn and Fe ore deposit from the 1.45 billion-year-old Tieling Formation, North China. The deposit contains Mn(II,III) mineral phases (hausmannite, braunite) as inclusions, or unreacted residues, trapped within Mn(II) carbonate (Ca-rhodochrosite). Some nodules and oolites of Mn(II) and Fe(II)-carbonate phases are also present and display a banded structure with concentric rings. Mn(III) oxide (manganite) is present in a paragenetic assemblage along with hematite and replacement textures with braunite. The negative carbon isotope composition (δ13C, –7‰ to –4‰) from Mn(II) carbonate samples in the Wafangzi Mn deposit which are distinct from that of contemporaneous seawater (~0‰), along with petrographic and speciation analyses, collectively suggest that the Mn(II,III)- and Fe(II)-bearing mineral phases formed through the diagenetic reduction of primary Mn(IV)/Fe(III) minerals coupled to the oxidation of organic matter. Therefore, the Wafangzi Mn deposit suggests the presence of sufficiently oxygenated marine waters, overlying anoxic ferruginous deeper waters with a transitional manganous water layer that could have driven the redox cycling of Mn, Fe, and C. Given the contemporaneous economic Mn deposits in the 1.45 Ga Ullawarra Formation in Western Australia, our findings imply the existence of a transient, and perhaps widespread, pulsed oxygenation event in the mid-Proterozoic oceans.