Showing papers by "Jianxi Zhu published in 2022"

Photoreductive Dissolution of Iron (Hydr)oxides and Its Geochemical Significance

Abstract: Iron (hydr)oxides are the most abundant metal oxides, which are widespread on Earth’s surface in the major form of micro/nanoparticles. Dissolution of iron (hydr)oxides significantly controls their compositions on Earth’s surface and is a critical step for the global Fe cycling. Photoreductive dissolution of iron (hydr)oxides is recognized as one of the most important process for generating Fe2+ in surface water and is also a common pathway for transforming solar energy into chemical energy. This review article dissects the main characteristics of photoreductive dissolution of iron (hydr)oxides and discusses its geochemical and environmental significance. We categorize the mechanisms for photoreduction of iron (hydr)oxides into three types: reduction by intrinsic photogenerated electrons, reduction by ligand to metal electron transfer (LMCT), and reduction by direct injection of exogenous photoelectrons. The efficiency of photoreductive dissolution is constrained by both the structure of iron (hydr)oxides (e.g., crystal structure and particle size) and environmental conditions (e.g., light, pH, and concurrent chemicals). Therefore, different iron (hydr)oxides may exhibit quite distinctive photoreductive dissolution characteristics because of their unique crystal structures and physicochemical properties. Iron (hydr)oxides with low crystallinity (e.g., ferrihydrite, lepidocrocite) are subject to direct photoreductive dissolution, while those with high crystallinity (e.g., goethite, hematite) generally need ligands to proceed with photoreductive dissolution. The photoreductive dissolution of iron (hydr)oxides is involved in many important geochemical and environmental processes, such as the Fe availability to primary producers, the generation of reactive oxygen species, the transportation and fate of contaminants, and the phase transformation of iron (hydr)oxides. Given the ubiquitous occurrence of photoreductive dissolution of iron (hydr)oxides, this review will advance our understanding of the role of this process in Earth’s surface environments.

Hyperenrichment of gold in pyrite induced by solid-state transportation

Abstract: Abstract The hyperenrichment of gold is critical for the formation of high-grade gold deposits in orogenic systems, where gold enrichment can reach several percent. However, many details on the nature of the hyperenrichment mechanism remain unclear. Here we show a “self-purification” model that could explain the hyperenrichment of gold from nanoparticles to veinlets in deformed pyrite. The three-dimensional spatial relationship and coexistence of gold nanoparticles and veinlets indicate a direct transformation from the former to the latter in solid-state. Theoretical evaluation reveals that this transformation involves a thermodynamically favorable self-purification process. We thus propose that deformation/thermo drives the transport of gold nanoparticles towards veinlets in pyrite through atomic diffusion. This deformation/thermo-driven model is applicable to any deformed nano-gold-bearing pyrite and explains how solid-state transport can effectively concentrate gold to a very high grade. Similar mechanisms may have broad implications in both ore-forming and beneficiation processes.

Microorganisms Accelerate REE Mineralization in Supergene Environments

Abstract: Understanding the role of microorganisms in the formation of regolith-hosted rare earth element (REE) deposits is beneficial for improving the metallogenic theory and deposit exploitation, given that such deposits absolutely exist in subtropical regions with strong microbial activities. Little is known of the microbial community composition and its contribution to REE mineralization in this kind of deposit. ABSTRACT Exogenic deposits are an important source of rare earth elements (REEs), especially heavy REEs (HREEs). It is generally accepted that microorganisms are able to dissolve minerals and mobilize elements in supergene environments. However, little is known about the roles of microorganisms in the formation of exogenic deposits such as regolith-hosted REE deposits that are of HREE enrichment and provide over 90% of global HREE demand. In this study, we characterized the microbial community composition and diversity along a complete weathering profile drilled from a regolith-hosted REE deposit in Southeastern China and report the striking contributions of microorganisms to the enrichment of REEs and fractionation between HREEs and light REEs (LREEs). Our results provide evidence that the variations in REE contents are correlated with microbial community along the profile. Both fungi and bacteria contributed to the accumulation of REEs, whereas bacteria played a key role in the fractionation between HREEs and LREEs. Taking advantage of bacteria strains isolated from the profile, Gram-positive bacteria affiliated with Bacillus and Micrococcus preferentially adsorbed HREEs, and teichoic acids in the cell wall served as the main sites for HREE adsorption, leading to an enrichment of HREEs in the deposit. The present study provides the first database of microbial community in regolith-hosted REE deposits. These findings not only elucidate the crucial contribution of fungi and bacteria in the supergene REE mineralization but also provide insights into efficient utilization of mineral resources via a biological pathway. IMPORTANCE Understanding the role of microorganisms in the formation of regolith-hosted rare earth element (REE) deposits is beneficial for improving the metallogenic theory and deposit exploitation, given that such deposits absolutely exist in subtropical regions with strong microbial activities. Little is known of the microbial community composition and its contribution to REE mineralization in this kind of deposit. Using a combination of high-throughput sequencing, batch adsorption experiments, and spectroscopic characterization, the functional microorganisms contributing to REE enrichment and fractionation are disclosed. For bacteria, the surface carboxyl and phosphate groups are active sites for REE adsorption, while teichoic acids in the cell walls of G+ bacteria lead to REE fractionation. The above-mentioned findings not only unravel the importance of microorganisms in the formation of supergene REE deposits but also provide experimental evidence for the bioutilization of REE resources.

Relationship among Electrical Signals, Chlorophyll Fluorescence, and Root Vitality of Strawberry Seedlings under Drought Stress

Abstract: Drought area expansion has a great impact on the growth and development of plants. To contribute to the water management of strawberry, this work aims to study the chronological relationship between the electrical signals and representative physiological parameters of strawberry seedlings under drought stress. This study analyzed the characteristic variables of the electrical signals; physiological parameters under drought; and control treatments. Moreover, we compared the chronological sequence of the appearance of significant differences between drought and control treatment in terms of their physiological parameters and electrical signals. The results showed that with the increase of drought treatment, the time domain parameters (peak-to-peak value, standard deviation) and frequency domain parameters (spectral of central gravity, power spectrum entropy) of the drought-treated electrical signals showed significant differences from the control on Day 2 and Day 6, respectively (p < 0.05). The root vitality of the drought treatment was significantly different from the control on Day 4 (p < 0.05); the Fv/Fm and the SPAD were significantly different (p < 0.05) on Day 7. Electrical signals first start to show a significant difference between drought and control treatment, followed by physiological parameters. Therefore, the electrical signal can be used as an early indicator of drought stress conditions. This will provide a scientific basis for the actual water management of strawberry seedlings. It also provides a methodological and theoretical basis for other studies analyzing the relationship between plant physiological parameters and electrical signals under other stress conditions.

Heterogeneous and retarded phase transformation of ferrihydrite on montmorillonite surface: The important role of surface interactions

Abstract: Abstract The formation of heteroaggregates is critical to controlling the stabilization and transformation of nanominerals and mineral nanoparticles (NMMNs) in nature, but the underlying mechanisms remain to be deciphered. In this work, we study the effect of surface interactions between ferrihydrite (Fh) and montmorillonite (Mnt) within their heteroaggregates on the transformation behaviors of Fh. A series of heteroaggregates composed of Fh and Mnt were synthesized by modulating their mass ratios and synthesis methods, i.e., directly complexing Fh with Mnt (Fh-Mnt) or in situ growing Fh on Mnt (Fh/Mnt). Structural characterization using XRD, TG-DSC, TEM, and FTIR indicated that Fh particles coated more evenly on the Mnt surface within the heteroaggregates synthesized by in situ growing Fh on Mnt and with lower Fh to Mnt ratio, and accordingly these heteroaggregates showed stronger surface interactions between Fh and Mnt. The phase transformation of Fh to hematite (Hem) on the heteroaggregates can be significantly affected during the heating treatment. Compared with that of pure Fh, the transformation of Fh on all of the heteroaggregates was retarded (e.g., slower transformation rate and smaller produced Hem particles), particularly for the samples with stronger surface interactions (e.g., Fh/Mnt with lower Fh to Mnt ratio). Noticeably, the heated heteroaggregates may simultaneously contain pristine Fh, intermediate maghemite, and transformed Hem, showing a heterogeneous transformation behavior of Fh. The strong interactions between Fh and Mnt will enhance the dispersion of Fh and restrict the structural rearrangement of Fh (particularly those at the interface) during the phase transformation process, resulting in retarded and heterogenous transformation of Fh on these heteroaggregates. These findings not only enrich our knowledge of the phase transformation characteristics of Fh but also advance our understanding of the important role of mineral surface interactions in stabilizing NMMNs in nature.

How clay delamination supports aseismic slip

Abstract: Abstract Aseismic slip is a stable fault slip, which allows strain to be relieved smoothly. Aseismic slip prevents the earthquake propagation, but it could nucleate an earthquake elsewhere. Understanding the mechanism of aseismic slip is promising in revealing the seismic cycle. Experimental evidence showed clay-rich fault gouge bears a low-friction strength, and the friction is strengthened with slip velocity (velocity-strengthening), which was thought to support aseismic slip. Clay minerals are comprised of platy crystalline layers with water intercalated between them, which may act as a lubricant. Sliding between clay layers was suspected to support aseismic slip but lacked a clarified mechanistic insight. We use non-equilibrium molecular dynamics simulations to show that shear-induced interlayer sliding is frictionally weak and velocity-strengthening, which evidences the role of clay minerals in aseismic slip. We find that interlayer water is a viscous fluid at most times, which explains the shear response of interlayer sliding. Depending on temperature and pressure conditions, intercalated water can be monolayer or bilayer, fluidic or ice like. Shear induces ice-like water to transform into fluidic water, which happens as a stick-slip phenomenon reflecting a first-order transition. Increased pore fluid pressure leads to the transformation from monolayer to bilayer intercalated water, resulting in a lower friction strength and enhanced velocity-strengthening behavior. Our work suggests that disclosing the hydration state of a clay mineral is preliminary when studying fault mechanics.

Revision 1 2 Heterogeneous and retarded phase transformation of 3 ferrihydrite on montmorillonite surface: the important role of 4 surface interactions

Abstract: 19 The formation of heteroaggregates is critical to dictating the stabilization and 20 transformation of nanominerals and mineral nanoparticles (NMMNs) in the nature, but 21 the underlying mechanisms remain to be deciphered. In this work, we study the effect 22 of surface interactions between ferrihydrite (Fh) and montmorillonite (Mnt) within their 23 heteroaggregates on the transformation behaviors of Fh. A series of heteroaggregates 24 composing of Fh and Mnt were synthesized by modulating their mass ratios and 25 synthesis methods, i.e., directly complexing Fh with Mnt (Fh-Mnt) or in-situ growing 26 Fh on Mnt (Fh/Mnt). The structural characterization results from XRD, TG-DSC, TEM, 27 and FTIR indicated that Fh particles coated more evenly on the Mnt surface within the 28 heteroaggregates synthesized by in-situ growing Fh on Mnt and with lower Fh to Mnt 29 ratio, and accordingly these heteroaggregates showed stronger surface interactions 30 between Fh and Mnt. The phase transformation of Fh to hematite (Hem) on the 31 heteroaggregates can be significantly affected during the heating treatment. Compared 32 with that of pure Fh, the transformation of Fh on all of the heteroaggregates was 33 retarded (e.g., slower transformation rate and smaller produced Hem particles), 34 particularly for the samples with stronger surface interactions (e.g., Fh/Mnt with lower 35 Fh to Mnt ratio). Noticeably, the heated heteroaggregates may simultaneously contain 36 pristine Fh, intermediate maghemite, and transformed Hem, showing a heterogeneous 37 transformation behavior of Fh. The strong interactions between Fh and Mnt will benefit 38 the dispersion of Fh and restrict the structural rearrangement of Fh (particularly those 39 at the interface) during the phase transformation process, resulting in retarded and 40 heterogenous transformation of Fh on these heteroaggregates. The findings of this work 41 not only enrich our knowledge of the advance our understanding of the important role of mineral surface interactions on 43 stabilizing NMMNs in the nature. This study aims to unveil the influence of surface interactions between clay minerals and Fh on the transformation of Fh during heat treatment. Two different types of heteroaggregates composing of Fh and montmorillonite (Mnt) are synthesized, i.e., directly complexing Fh with Mnt (Fh-Mnt) and in-situ growing of Fh on Mnt (Fh/Mnt). We expect these heteroaggregates will have different surface interaction behaviors and thus provide proper samples for the study. Heating treatment (300-600°C) will be applied to accelerate the transformation process, and simulate the temperature conditions for wildfire. We are concerned with how Mnt can affect the transformation rate and pathway of Fh, and the mineral phases and morphology of the samples before and after heating will be studied in detail.

Evaluating the physicochemical conditions for gold occurrences in pyrite

Abstract: Abstract While noble metals often occur as minor components in host minerals in various ore deposits, little theoretical assessment exists to predict the occurrence of these metals. Here, we probe the fundamental controls responsible for the occurrence of trace elements in host minerals through first-principles calculations. We apply the theoretical model to understanding the debated issues concerning the occurrence of gold (Au) in pyrite, in which the valence of Au is ascribed to either positive or negative values. Our results indicate that (1) both positive and negative valent Au may occur in pyrite and (2) higher sulfur fugacity and lower temperature lead to more Au+ occupying Fe sites in pyrite. These findings suggest that chemical states and speciation of the Au in host pyrite are ultimately controlled by temperature and sulfur fugacity, providing insight into the formation conditions of ore deposits and facilitating strategy design for beneficiation.