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Keywords = carbonyl sulphide

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13 pages, 7362 KiB  
Article
Density Functional Theory Study on the Adsorption Mechanism of Sulphide Gas Molecules on α-Fe2O3(001) Surface
by Li Zhou, Huadong Zhu and Wen Zeng
Inorganics 2021, 9(11), 80; https://doi.org/10.3390/inorganics9110080 - 4 Nov 2021
Cited by 16 | Viewed by 3983
Abstract
Sulphide gas is an impurity that affects the quality of natural gas, which needs reasonable storage and transportation. In this work, we investigated the adsorption structure and electronic behavior of hydrogen sulfide (H2S), carbonyl sulfur (COS), and methyl mercaptan (CH3 [...] Read more.
Sulphide gas is an impurity that affects the quality of natural gas, which needs reasonable storage and transportation. In this work, we investigated the adsorption structure and electronic behavior of hydrogen sulfide (H2S), carbonyl sulfur (COS), and methyl mercaptan (CH3SH) on sulphide gas molecules on pure and vacant α-Fe2O3(001) surfaces by density functional theory with geometrical relaxations. The results show that H2S and CH3SH are mainly adsorbed in the form of molecules on the pure Fe2O3(001) surface. On the vacant α-Fe2O3(001) surface, they can be adsorbed on Fe atoms in molecular form and by dissociation. The absolute value of the adsorption energy of H2S and CH3SH on the vacancy defect α-Fe2O3 surface is larger, and the density of states show that the electron orbital hybridization is more significant, and the adsorption is stronger. The charge differential density and Mulliken charge population analysis show that the charge is rearranged and chemical bonds are formed. The affinity of H2S to the vacancy α-Fe2O3(001) surface is slightly higher than that of CH3SH, while COS molecules basically do not adsorb on the α-Fe2O3(001) surface, which may be related to the stable chemical properties of the molecules themselves. Full article
(This article belongs to the Section Inorganic Solid-State Chemistry)
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Figure 1

Figure 1
<p>(<b>a</b>) The crystal structure and spin arrangement of α-Fe<sub>2</sub>O<sub>3</sub>; (<b>b</b>) the band structure of α-Fe<sub>2</sub>O<sub>3</sub>; and (<b>c</b>) the DOS and PDOS analysis of α-Fe<sub>2</sub>O<sub>3</sub>.</p>
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<p>(<b>a</b>) The geometrically optimized slab model of α-Fe<sub>2</sub>O<sub>3</sub>(001) surface; (<b>b</b>) the adsorption site on pure α-Fe<sub>2</sub>O<sub>3</sub>(001) surface; and (<b>c</b>) the adsorption site of oxygen vacancy α-Fe<sub>2</sub>O<sub>3</sub>(001) surface.</p>
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<p>The geometrically optimized (<b>a</b>) H<sub>2</sub>S, (<b>b</b>) COS, and (<b>c</b>) CH<sub>3</sub>SH molecules, and their HOMO (Highest Energy Occupied Orbital) and LUMO (Lowest Energy Empty Orbital).</p>
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<p>The stable adsorption configuration of H<sub>2</sub>S molecules on pure α-Fe<sub>2</sub>O<sub>3</sub>(001) surface (<b>A1</b>, <b>A2</b>); and the stable adsorption configuration of H<sub>2</sub>S molecules on vacancy α-Fe<sub>2</sub>O<sub>3</sub>(001) surface (<b>A3</b>, <b>A4</b>). The unit of number is Å.</p>
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<p>The PDOS of S atom in free H<sub>2</sub>S molecule.</p>
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<p>(<b>a</b>) The PDOS of Fe atoms on the pure and vacant α-Fe<sub>2</sub>O<sub>3</sub>(001) surface before adsorption; (<b>b</b>) the PDOS of pure α-Fe<sub>2</sub>O<sub>3</sub>(001) surface of Fe atom and S atom of H<sub>2</sub>S after adsorption; and (<b>c</b>) the PDOS of Fe atom and S atom of H<sub>2</sub>S on the surface of the adsorbed vacancy α-Fe<sub>2</sub>O<sub>3</sub>(001).</p>
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<p>The Mulliken charge population analysis of H<sub>2</sub>S adsorption on the α-Fe<sub>2</sub>O<sub>3</sub>(001) surface. (<b>a</b>) Three dimensional drawing of the Mulliken charge population for A2 configuration; (<b>b</b>) Two dimensional drawing of the Mulliken charge population for A2 configuration; (<b>c</b>) Three dimensional drawing of the Mulliken charge population for A4 configuration; (<b>d</b>) Two dimensional drawing of the Mulliken charge population for A4 configuration.</p>
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<p>The stable adsorption configurations (<b>B1</b>,<b>B2</b>) of COS molecules on a pure α-Fe<sub>2</sub>O<sub>3</sub>(001) surface; the stable adsorption configurations (<b>B3</b>,<b>B4</b>) of COS molecules on the vacancy α-Fe<sub>2</sub>O<sub>3</sub>(001) surface (the unit of number is Å).</p>
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<p>The stable adsorption configuration C1 of CH<sub>3</sub>SH molecules on the pure α-Fe<sub>2</sub>O<sub>3</sub>(001) surface; the stable adsorption configuration C2 of SH molecule on the vacancy α-Fe<sub>2</sub>O<sub>3</sub>(001) surface (the unit of number is Å).</p>
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<p>(<b>a</b>) The PDOS of the S atom in a free CH<sub>3</sub>SH molecule; (<b>b</b>) the PDOS of pure α-Fe<sub>2</sub>O<sub>3</sub>(001) surface Fe atom and S atom of CH<sub>3</sub>SH after adsorption; (<b>c</b>) the PDOS of the Fe atom and the S atom of CH<sub>3</sub>SH atom on the surface of the vacancy α-Fe<sub>2</sub>O<sub>3</sub>(001) after adsorption; (<b>d</b>,<b>e</b>) the charge difference density of CH<sub>3</sub>SH molecules adsorbed on the pure α-Fe<sub>2</sub>O<sub>3</sub>(001) surface; and (<b>f</b>,<b>g</b>) the charge difference density of CH<sub>3</sub>SH molecules adsorbed on the vacancy α-Fe<sub>2</sub>O<sub>3</sub>(001) surface.</p>
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18 pages, 1206 KiB  
Article
Nitrogen Fertilization Reduces the Capacity of Soils to Take up Atmospheric Carbonyl Sulphide
by Aurore Kaisermann, Sam P. Jones, Steven Wohl, Jérôme Ogée and Lisa Wingate
Soil Syst. 2018, 2(4), 62; https://doi.org/10.3390/soilsystems2040062 - 15 Nov 2018
Cited by 8 | Viewed by 3832
Abstract
Soils are an important carbonyl sulphide (COS) sink. However, they can also act as sources of COS to the atmosphere. Here we demonstrate that variability in the soil COS sink and source strength is strongly linked to the available soil inorganic nitrogen (N) [...] Read more.
Soils are an important carbonyl sulphide (COS) sink. However, they can also act as sources of COS to the atmosphere. Here we demonstrate that variability in the soil COS sink and source strength is strongly linked to the available soil inorganic nitrogen (N) content across a diverse range of biomes in Europe. We revealed in controlled laboratory experiments that a one-off addition of ammonium nitrate systematically decreased the COS uptake rate whilst simultaneously increasing the COS production rate of soils from boreal and temperate sites in Europe. Furthermore, we found strong links between variations in the two gross COS fluxes, microbial biomass, and nitrate and ammonium contents, providing new insights into the mechanisms involved. Our findings provide evidence for how the soil–atmosphere exchange of COS is likely to vary spatially and temporally, a necessary step for constraining the role of soils and land use in the COS mass budget. Full article
(This article belongs to the Special Issue Formation and Fluxes of Soil Trace Gases)
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Figure 1
<p>Variations in the (<b>a</b>) net carbonyl sulphide (COS) flux, (<b>b</b>) the COS production rate (<span class="html-italic">P</span>), and (<b>c</b>) COS hydrolysis rate (<span class="html-italic">k</span>) with soil inorganic N content (NO<sub>3</sub><sup>−</sup> and NH<sub>4</sub><sup>+</sup> contents, expressed in log) across the 27 soils in Europe. Each point represents the mean flux ± standard deviation for each soil (n = 3). Best statistical models were found comparing the adjusted R<sup>2</sup> and the Akaike’s Information Criterion (AIC) of each models with the easynls package [<a href="#B47-soilsystems-02-00062" class="html-bibr">47</a>].</p>
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<p>Variations in the (<b>a</b>) net COS flux, (<b>b</b>) the COS production rate (<span class="html-italic">P</span>), and (<b>c</b>) the COS hydrolysis rate (<span class="html-italic">k</span>) with soil nitrate (NO<sub>3</sub><sup>−</sup>) and ammonium (NH<sub>4</sub><sup>+</sup>) contents across 27 soils in Europe. The two levels of NO<sub>3</sub><sup>−</sup> and NH<sub>4</sub><sup>+</sup> content are below and above 10 μg g<sup>−1</sup> of N–NO<sub>3</sub><sup>−</sup> and N–NH<sub>4</sub><sup>+</sup> respectively. Each black point represents the replicate means (n = 3) for one soil. Letters represents results of TukeyHSD test when analysis of variance (ANOVA) was significant.</p>
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<p>Plots of the best model explaining (<b>a</b>) the COS production (<span class="html-italic">P</span>) and (<b>b</b>) the COS hydrolysis rate constant (<span class="html-italic">k</span>) measured at 23 °C on 27 European soils. Each point represents the mean ± standard deviation for each soil (n = 3). Dark-green circles represent the two alkaline soils with low nitrate content. MBC represents the microbial biomass C, and NO3 is the soil N–NO<sub>3</sub><sup>−</sup> content (in log). The grey areas indicate the 85% confidence intervals for the exponential (<b>a</b>) and linear (<b>b</b>) models. Low (respectively High) NO<sub>3</sub><sup>−</sup> contents correspond to concentrations below (respectively above) 10 μg g<sup>−1</sup> of N–NO<sub>3</sub><sup>−</sup>. Acidic (respectively alkaline) pH corresponds to pH below (respectively above) 7. Linear model coefficients and statistical analysis are presented in <a href="#app1-soilsystems-02-00062" class="html-app">Table S3</a>.</p>
Full article ">Figure 4
<p>Effect of N fertilization (ANOVA <span class="html-italic">p</span>-value &lt; 0.05) at two field sites (Laqueuille and Rosinedal, n = 3) and in the lab study across nine soils (addition of ammono-nitrate, n = 27) in the (<b>a</b>,<b>d</b>) net COS flux (<span class="html-italic">F</span>); (<b>b</b>,<b>e</b>) the COS production rate (<span class="html-italic">P</span>) and (<b>c</b>,<b>f</b>) COS hydrolysis rate (<span class="html-italic">k</span>).</p>
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<p>Relationships between the percentage change in (<b>a</b>) COS production <span class="html-italic">P</span> and (<b>b</b>) COS hydrolysis rate <span class="html-italic">k</span> and the percentage change in microbial biomass C following ammono-nitrate addition. Each point represents the mean ± standard deviation for each soil type (n = 3). The colour represents the total N inorganic content (N<sub>inorganic</sub>, in μg g<sup>−1</sup>) before N addition (i.e., in the control soils), that is the sum of the nitrate (NO<sub>3</sub><sup>−</sup>) and ammonium (NH<sub>4</sub><sup>+</sup>) contents (see inset subplot in (<b>a</b>)).</p>
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17 pages, 7573 KiB  
Article
Recovery of Residual Silver-Bearing Minerals from Low-Grade Tailings by Froth Flotation: The Case of Zgounder Mine, Morocco
by Boujemaa Drif, Yassine Taha, Rachid Hakkou and Mostafa Benzaazoua
Minerals 2018, 8(7), 273; https://doi.org/10.3390/min8070273 - 27 Jun 2018
Cited by 15 | Viewed by 6886
Abstract
The need to explore more complex and low-grade silver ores and to develop novel and cost-effective processes to recover silver from waste is becoming an important challenge. This paper aims to characterize old, low-grade, silver tailings generated by the former Zgounder silver mine, [...] Read more.
The need to explore more complex and low-grade silver ores and to develop novel and cost-effective processes to recover silver from waste is becoming an important challenge. This paper aims to characterize old, low-grade, silver tailings generated by the former Zgounder silver mine, located in Morocco. Understanding the mineralogical composition, particularly the silver deportment, was critical to allow the recovery of silver from these tailings. More than 88 samples of low grade tailings were sampled and characterized using chemical and mineralogical techniques. Froth flotation was used to recover silver bearing minerals using a combination of different collectors (dithiophosphate, dialkyl dithiophosphinates, Aero 7518, Aero 7640, alkyl dithiophosphates and potassium butyl-xanthate). The main goal was to optimize the flotation process at a laboratory scale through the testing of different parameters, such as collectors and frother types and dosage, activators and sulphidizing agents, and pH conditions. The characterization results showed that silver content varied between 30 and 440 ppm with an overall average content of 148 ppm. Silver occurs mainly in the form of native silver as well as in association with sulphides, such as acanthite and pyrite. Minor amounts of sphalerite, chalcopyrite, arsenopyrite, and hematite were identified. The flotation results showed the following optimum conditions: particle size of 63 µm, conditioning pH of 8.5, a combination of butyl-xanthate and dithiophosphate as collectors at a dosage of 80 g/t each, a concentration of 200 g/t of the activating agent (CuSO4), 30 g/t of methyl isobutyl carbonyl (MIBC) frother and a duration time of 8 min with slow kinetics. With these optimal conditions, it was possible to achieve a maximum silver recovery yield of 84% with 1745 ppm Ag grade to be cyanided. Moreover, the environmental behavior of the final clean tailings was demonstrated to be inert using Toxicity characteristic leaching procedure (TCLP) leaching tests. Full article
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<p>Location of the Zgounder mine tailings storage facilities and the used sampling procedure.</p>
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<p>The methodology scheme used in this study.</p>
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<p>Zgounder mine tailing (ZMT) preparation and flotation test scheme.</p>
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<p>Variation of silver grade in the different samples taken from Zgounder mine tailings (TSF).</p>
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<p>Combined BSE SEM and X-mapping images of some minerals in the ZMT composite sample.</p>
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<p>Distributions and grades of silver in different grain size fractions.</p>
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<p>Flotation kinetics of mineral silver at two grain sizes: (<b>a</b>) silver recovery and (<b>b</b>) mass recovery as a function of flotation residence time.</p>
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<p>Grade and recovery of silver for different collector combinations and under different pH conditions.</p>
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<p>Grade and recovery of silver for different types of frothers and under different pH levels.</p>
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<p>The evolution of silver grade and recovery as a function of the dosage of collector combinations given; BX = butyl-xanthate and A = Dithiophosphate (Aerofloat-242).</p>
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<p>Evolution of silver grade and recovery as a function of: (<b>a</b>) pH; (<b>b</b>) grain size fraction (D90); (<b>c</b>) CuSO<sub>4</sub> dosage (g/t) and (<b>d</b>) Na<sub>2</sub>S dosage (g/t).</p>
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<p>Silver recovery and grade under the optimized conditions.</p>
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<p>Combined BSE SEM and X-mapping images of the main silver bearing minerals.</p>
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2522 KiB  
Article
Application of Cavity Enhanced Absorption Spectroscopy to the Detection of Nitric Oxide, Carbonyl Sulphide, and Ethane—Breath Biomarkers of Serious Diseases
by Jacek Wojtas
Sensors 2015, 15(6), 14356-14369; https://doi.org/10.3390/s150614356 - 17 Jun 2015
Cited by 36 | Viewed by 7532
Abstract
The paper presents one of the laser absorption spectroscopy techniques as an effective tool for sensitive analysis of trace gas species in human breath. Characterization of nitric oxide, carbonyl sulphide and ethane, and the selection of their absorption lines are described. Experiments with [...] Read more.
The paper presents one of the laser absorption spectroscopy techniques as an effective tool for sensitive analysis of trace gas species in human breath. Characterization of nitric oxide, carbonyl sulphide and ethane, and the selection of their absorption lines are described. Experiments with some biomarkers showed that detection of pathogenic changes at the molecular level is possible using this technique. Thanks to cavity enhanced spectroscopy application, detection limits at the ppb-level and short measurements time (<3 s) were achieved. Absorption lines of reference samples of the selected volatile biomarkers were probed using a distributed feedback quantum cascade laser and a tunable laser system consisting of an optical parametric oscillator and difference frequency generator. Setup using the first source provided a detection limit of 30 ppb for nitric oxide and 250 ppb for carbonyl sulphide. During experiments employing a second laser, detection limits of 0.9 ppb and 0.3 ppb were obtained for carbonyl sulphide and ethane, respectively. The conducted experiments show that this type of diagnosis would significantly increase chances for effective therapy of some diseases. Additionally, it offers non-invasive and real time measurements, high sensitivity and selectivity as well as minimizing discomfort for patients. For that reason, such sensors can be used in screening for early detection of serious diseases. Full article
(This article belongs to the Special Issue Chemical Sensors based on In Situ Spectroscopy)
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<p>(<b>a</b>) The absorption of NO at pressures of 1 atm (<b>b</b>) and of 0.1 atm for concentrations occurring in human breath: NO—35 ppb, CO<sub>2</sub>—5%, H<sub>2</sub>O after the drying procedure—279 ppm.</p>
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<p>(<b>a</b>) The absorption of the OCS at pressures of 1 atm (<b>b</b>) and of 0.1 atm for concentrations occurring in human breath: OCS—10 ppb, CO—10 ppm, CO<sub>2</sub>—5%, H<sub>2</sub>O after the drying procedure—279 ppm.</p>
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<p>(<b>a</b>) The absorption of C<sub>2</sub>H<sub>6</sub> at pressures of 1 atm (<b>b</b>) and of 0.1 atm for concentrations occurring in human breath: C<sub>2</sub>H<sub>6</sub>—10 ppb, NH<sub>3</sub>—2 ppm, CH<sub>4</sub>—1.7 ppm, H<sub>2</sub>O after the drying procedure—279 ppm.</p>
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<p>(<b>a</b>) Comparison of lasers linewidths and the nitric oxide absorption spectrum; (<b>b</b>) and block diagram of the experimental setup.</p>
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<p>Example of the NO concentration measurements in human breath at atmospheric pressure.</p>
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<p>(<b>a</b>) The decay time changes of radiation in the optical cavity filled with reference concentration of NO (<b>b</b>) and OCS registered in the CEAS setup equipped with the tested QCL.</p>
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<p>(<b>a</b>) Example of measurements results for ethane reference samples (<b>b</b>) and for OCS reference samples registered in the CEAS setup equipped with the PG711-DFG-SH system.</p>
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