One year in situ incubation of pyrite at the deep seafloor and its microbiological and biogeochemical characterizations

2021 ◽  
Author(s):  
S. Mitsunobu ◽  
Y. Ohashi ◽  
H. Makita ◽  
Y. Suzuki ◽  
T. Nozaki ◽  
...  
Keyword(s):  
Oxidation Rate ◽  
Microbial Community Analysis ◽  
Pyrite Surface ◽  
Ambient Seawater ◽  
Mineralogical Characterization ◽  
Edge Structure ◽  
X Ray ◽  
Hydrothermal Environments ◽  
X Ray Absorption

In this study, we performed a year-long in situ incubation experiment of a common ferrous sulfide (Fe-S) mineral, pyrite, at the oxidative deep seafloor in the hydrothermal vent field in the Izu-Bonin arc, Japan, and characterized its microbiological and biogeochemical properties to understand the microbial alteration processes of the pyrite, focusing on the Fe(II) oxidation. The microbial community analysis of the incubated pyrite showed that the domain Bacteria heavily dominated over Archaea compared with that of the ambient seawater, and Alphaproteobacteria and Gammaproteobacteria distinctively co-dominated at the class level. The mineralogical characterization by surface-sensitive Fe X-ray absorption near-edge structure (XANES) analysis revealed that specific Fe(III) hydroxides (schwertmannite and ferrihydrite) were locally formed at the pyrite surface as the pyrite alteration products. Based on the Fe(III) hydroxide species and proportion, we thermodynamically calculated the pH value at the pyrite surface to be pH 4.9-5.7, indicating that the acidic condition derived from pyrite alteration was locally formed at the surface against neutral ambient seawater. This acidic microenvironment at the pyrite surface might explain the distinct microbial communities found in our pyrite samples. Also, the acidity at the pyrite surface indicates that abiotic Fe(II) oxidation rate was much limited at the pyrite surface kinetically, 3.9 × 10 3 −1.6 × 10 5 -fold lower than that in the ambient seawater. Moreover, the nanoscale characterization of microbial biomolecules using carbon near-edge X-ray absorption fine structure (NEXAFS) analysis showed that the sessile cells attached to pyrite excreted the acidic polysaccharide-rich extracellular polymeric substances at the pyrite surface, which can lead to the promotion of biogenic Fe(II) oxidation and pyrite alteration. Importance Pyrite is one of the most common Fe-S minerals found in submarine hydrothermal environments. Previous studies demonstrated that the Fe-S mineral can be a suitable host for Fe(II)-oxidizing microbes in hydrothermal environments; however, the details of microbial Fe(II) oxidation processes with Fe-S mineral alteration are not well known. The spectroscopic and thermodynamic examination in the present study suggests that moderately acidic pH condition was locally formed at the pyrite surface during pyrite alteration at the seafloor due to proton releases with Fe(II) and sulfidic S oxidations. Following previous studies, the abiotic Fe(II) oxidation rate significantly decreases with a decrease in pH, but the biotic (microbial) Fe(II) oxidation rate is not sensitive to the pH decrease. Thus, our findings clearly suggest the pyrite surface is a unique microenvironment where abiotic Fe(II) oxidation is limited and biotic Fe(II) oxidation is more prominent than that in neutral ambient seawater.

scholarly journals High-energy resolution X-ray absorption and emission spectroscopy reveals insight into unique selectivity of La-based nanoparticles for CO2

2015 ◽  
Vol 112 (52) ◽  
pp. 15803-15808 ◽  
Author(s):  
Ofer Hirsch ◽  
Kristina O. Kvashnina ◽  
Li Luo ◽  
Martin J. Süess ◽  
Pieter Glatzel ◽  
...  
Keyword(s):  
Energy Resolution ◽  
Emission Spectroscopy ◽  
High Energy ◽  
Unit Cell ◽  
High Energy Resolution ◽  
Electron Configuration ◽  
Edge Structure ◽  
X Ray ◽  
X Ray Absorption

The lanthanum-based materials, due to their layered structure and f-electron configuration, are relevant for electrochemical application. Particularly, La2O2CO3 shows a prominent chemoresistive response to CO2. However, surprisingly less is known about its atomic and electronic structure and electrochemically significant sites and therefore, its structure–functions relationships have yet to be established. Here we determine the position of the different constituents within the unit cell of monoclinic La2O2CO3 and use this information to interpret in situ high-energy resolution fluorescence-detected (HERFD) X-ray absorption near-edge structure (XANES) and valence-to-core X-ray emission spectroscopy (vtc XES). Compared with La(OH)3 or previously known hexagonal La2O2CO3 structures, La in the monoclinic unit cell has a much lower number of neighboring oxygen atoms, which is manifested in the whiteline broadening in XANES spectra. Such a superior sensitivity to subtle changes is given by HERFD method, which is essential for in situ studying of the interaction with CO2. Here, we study La2O2CO3-based sensors in real operando conditions at 250 °C in the presence of oxygen and water vapors. We identify that the distribution of unoccupied La d-states and occupied O p- and La d-states changes during CO2 chemoresistive sensing of La2O2CO3. The correlation between these spectroscopic findings with electrical resistance measurements leads to a more comprehensive understanding of the selective adsorption at La site and may enable the design of new materials for CO2 electrochemical applications.

Fluorescence Extended X-Ray Absorption Fine Structure Study on Local Structures of Rare-Earth-Doped InGaGdN

2016 ◽  
Vol 1133 ◽  
pp. 429-433
Author(s):  
Siti Nooraya Mohd Tawil ◽  
Shuichi Emura ◽  
Daivasigamani Krishnamurthy ◽  
Hajime Asahi
Keyword(s):  
Fine Structure ◽  
Rare Earth ◽  
Nearest Neighbor ◽  
Structure Study ◽  
Edge Structure ◽  
X Ray ◽  
Local Structures ◽  
Absorption Fine ◽  
X Ray Absorption

Local structures around gadolinium atoms in rare-earth (RE)-doped InGaGdN thin films were studied by means of fluorescence extended X-ray absorption fine structure (EXAFS) measured at the Gd LIII-edges. The samples were doped with Gd in-situ during growth by plasma-assisted molecular beam epitaxy (PAMBE). Gd LIII-edge EXAFS signal from the GaGdN, GdN and Gd foil were also measured as reference. The X-ray absorption near edge structure (XANES) spectra around Gd LIII absorption edge of InGaGdN samples observed at room temperature indicated the enhancement of intensities with the increase of Gd composition. Further EXAFS analysis inferred that the Gd atoms in InGaN were surrounded by similar atomic shells as in the case of GaGdN with the evidence indicating majority of Gd atoms substituted into Ga sites of InGaGdN. A slight elongation of bond length for the 2nd nearest-neighbor (Gd–Ga) of sample with higher Gd concentration was also observed.

In situ XANES Study of Co2+ Ion Adsorption on Fe3O4 Nanoparticles in Supercritical Aqueous Fluids

2012 ◽  
Vol 1383 ◽  
Author(s):  
Hao Yan ◽  
Robert A. Mayanovic ◽  
Joseph Demster ◽  
Alan J. Anderson
Keyword(s):  
Angular Momentum ◽  
Density Of States ◽  
Fe3o4 Nanoparticles ◽  
Ion Adsorption ◽  
Edge Structure ◽  
X Ray ◽  
Peak Fitting ◽  
X Ray Absorption ◽  
In Situ Xanes

ABSTRACTIn situ x-ray absorption spectroscopy (XAS) measurements were made on Fe3O4 nanoparticles in supercritical aqueous fluids to 500 °C in order to study their reactivity with Co2+ aqua ions and to investigate the structural properties of the reacted nanoparticles. The analyses of the x-ray absorption near edge structure (XANES) of XAS indicate that reactivity of Fe3O4 nanoparticles with Co2+ ions is minimal to 200 °C but becomes significant in the 250–500 °C temperature range. XANES and angular momentum projected density of states (l-DOS) calculations were carried out using the FEFF8.2 code and analyses were made using multi-peak fitting to determine the origin of the features exhibited in the spectra.

scholarly journals In situ X-Ray Absorption Near-Edge Structure Spectroscopy Reveals Arsenic Ligation in Rice

2020 ◽  
Author(s):  
Benjamin Bostick ◽  
Yating Shen ◽  
Elizabeth Wiita ◽  
Athena Nghiem ◽  
Jingyu Liu ◽  
...  
Keyword(s):  
Edge Structure ◽  
X Ray ◽  
X Ray Absorption

scholarly journals In situ X-ray absorption spectroscopic studies of TiO2 photocatalytic active sites for degradation of trace CHCl3 in drinking water

2021 ◽  
Vol 28 (6) ◽  
Author(s):  
T.-L. Hsiung ◽  
L.-W. Wei ◽  
H.-L. Huang ◽  
H. Paul Wang
Keyword(s):  
Drinking Water ◽  
Photocatalytic Degradation ◽  
Active Sites ◽  
Spectroscopic Studies ◽  
Band Gap Energy ◽  
Disinfection Byproducts ◽  
Edge Structure ◽  
X Ray ◽  
X Ray Absorption

Toxic disinfection byproducts such as trihalomethanes (e.g. CHCl3) are often found after chlorination of drinking water. It has been found that photocatalytic degradation of trace CHCl3 in drinking water generally lacks an expected relationship with the crystalline phase, band-gap energy or the particle sizes of the TiO2-based photocatalysts used such as nano TiO2 on SBA-15 (Santa Barbara amorphous-15), TiO2 clusters (TiO2–SiO2) and atomic dispersed Ti [Ti-MCM-41 (Mobil Composition of Matter)]. To engineer capable TiO2 photocatalysts, a better understanding of their photoactive sites is of great importance and interest. Using in situ X-ray absorption near-edge structure (XANES) spectroscopy, the A1 (4969 eV), A2 (4971 eV) and A3 (4972 eV) sites in TiO2 can be distinguished as four-, five- and six- coordinated Ti species, respectively. Notably, the A2 Ti sites that are the main photocatalytic species of TiO2 are shown to be accountable for about 95% of the photocatalytic degradation of trace CHCl3 in drinking water (7.2 p.p.m. CHCl3 gTiO2 −1 h−1). This work reveals that the A2 Ti species of a TiO2-based photocatalyst are mainly responsible for the photocatalytic reactivity, especially in photocatalytic degradation of CHCl3 in drinking water.

scholarly journals A compact furnace for in situ X-ray absorption spectroscopy: design, fabrication and study of cationic oxidation states in Pr6O11 and NiO

2021 ◽  
Vol 28 (2) ◽  
pp. 455-460
Author(s):  
Suchinda Sattayaporn ◽  
Somboonsup Rodporn ◽  
Pinit Kidkhunthod ◽  
Narong Chanlek ◽  
Chutarat Yonchai ◽  
...  
Keyword(s):  
Oxidation State ◽  
Absorption Spectroscopy ◽  
Heating Temperature ◽  
Reduction Process ◽  
Oxidation States ◽  
Quartz Tube ◽  
Edge Structure ◽  
X Ray ◽  
X Ray Absorption

A well designed compact furnace has been designed for in situ X-ray absorption spectroscopy (XAS). It enables various heat ramps from 300 K to 1473 K. The furnace consists of heaters, a quartz tube, a circulated refrigerator and a power controller. It can generate ohmic heating via an induction process with tantalum filaments. The maximum heating rate exceeds 20 K min−1. A quartz tube with gas feedthroughs allows the mixing of gases and adjustment of the flow rate. The use of this compact furnace allows in situ XAS investigations to be carried out in transmission or fluorescence modes under controlled temperature and atmosphere. Moreover, the furnace is compact, light and well compatible to XAS. The furnace was used to study cationic oxidation states in Pr6O11 and NiO compounds under elevated temperature and reduced atmosphere using the in situ X-ray absorption near-edge structure (XANES) technique at beamline 5.2 SUT-NANOTEC-SLRI of the Synchrotron Light Research Institute, Thailand. At room temperature, Pr6O11 contains a mixture of Pr3+ and Pr4+ cations, resulting in an average oxidation state of +3.67. In situ XANES spectra of Pr (L 3-edge) show that the oxidation state of Pr4+ cations was totally reduced to +3.00 at 1273 K under H2 atmosphere. Considering NiO, Ni2+ species were present under ambient conditions. At 573 K, the reduction process of Ni2+ occurred. The Ni0/Ni2+ ratio increased linearly with respect to the heating temperature. Finally, the reduction process of Ni2+ was completely finished at 770 K.

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