FeS2 Research Articles

Reaction mechanisms and diagnostic mineralogy of intertidal steel corrosion: An X-ray photoelectron spectroscopy study

The products of intertidal and super tidal (splash zone) corrosion on steel piles have been characterised at 3 UK sites with contrasting environmental conditions in order to determine corrosion reaction mechanism and if a common mechanism for accelerated low water corrosion occurs across sites. Intertidal corrosion samples at Shoreham and Newhaven ports show an internal composition of iron mono- and bi-sulphide, with intermediate sulphur oxidation state compounds, and an outer surface dominated by iron oxides and oxyhydroxides with a component of iron sulphates. The FTIR spectra are characteristic of sulphate green rust. In contrast, samples from Southend have all sulphur species below detection levels and are dominated by iron oxides and oxyhydroxides. Carbon binding energy spectra are consistent with the development of biofilms at all sites except for a splash zone sample at Southend. The results demonstrate a common mechanism for ALWC at Newhaven and Shoreham, involving the action of sulphate-reducing bacteria generating iron sulphides on the steel surface. These are subsequently oxidised to produce sulphate green rust, which may in turn oxidise to produce lepidocrocite. At Southend differences in environment are inferred to restrict the activity of sulphate reducing bacteria, resulting in direct oxidation of steel to generate iron oxyhydroxide gels, which subsequently recrystallise, dehydrate and oxidise to goethite, magnetite and ultimately hematite in both splash zone and intertidal samples. The multi-technique approach used here characterises the full range of corrosion products.

Inorganic Fe-O and Fe-S oxidoreductases: paradigms for prebiotic chemistry and the evolution of enzymatic activity in biology.

Oxidoreductases play crucial roles in electron transfer during biological redox reactions. These reactions are not exclusive to protein-based biocatalysts; nano-size (<100nm), fine-grained inorganic colloids, such as iron oxides and sulfides, also participate. These nanocolloids exhibit intrinsic redox activity and possess direct electron transfer capacities comparable to their biological counterparts. The unique metal ion architecture of these nanocolloids, including electron configurations, coordination environment, electron conductivity, and the ability to promote spontaneous electron hopping, contributes to their transfer capabilities. Nano-size inorganic colloids are believed to be among the earliest 'oxidoreductases' to have 'evolved' on early Earth, playing critical roles in biological systems. Representing a distinct type of biocatalysts alongside metalloproteins, these nanoparticles offer an early alternative to protein-based oxidoreductase activity. While the roles of inorganic nano-sized catalysts in current Earth ecosystems are intuitively significant, they remain poorly understood and underestimated. Their contribution to chemical reactions and biogeochemical cycles likely helped shape and maintain the balance of our planet's ecosystems. However, their potential applications in biomedical, agricultural, and environmental protection sectors have not been fully explored or exploited. This review examines the structure, properties, and mechanisms of such catalysts from a material's evolutionary standpoint, aiming to raise awareness of their potential to provide innovative solutions to some of Earth's sustainability challenges.

Iron decoration in binary graphene oxide and copper iron sulfide nanocomposites boosting catalytic antibacterial activity in acidic microenvironment against antimicrobial resistance

The strong antimicrobial resistance (AMR) of multidrug-resistant (MDR) bacteria and biofilm, especially the biofilm with extracellular polymeric substance (EPS) protection and persister cells, not only renders antibiotics ineffective but also causes chronic infections and makes the infectious tissue difficult to repair. Considering the acidic properties of bacterial infection microenvironment and biofilm, herein, a binary graphene oxide and copper iron sulfide nanocomposite (GO/CuFeSx NC) is synthesized by a surfactant free strategy and utilized as an alternative smart nanozyme to fight against the MDR bacteria and biofilm. For the GO/CuFeSx NC, the iron decoration facilitates the well distribution of bimetallic CuFeSx NPs on the GO surfaces compared to monometallic CuS NPs, providing synergistically enhanced peroxidase (POD)-like activity in acidic medium (pH 4 ∼ 5) and intrinsic strong near infrared (NIR) light responsive photothermal activity, while the ultrathin and sharp structure of 2D GO nanosheet allows the GO/CuFeSx NC to strongly interact with the bacteria and biofilm, facilitating the catalytic and photothermal attacks on the bacterial surfaces. In addition, the GO in GO/CuFeSx NC exhibits a “Pseudo-Photo-Fenton” effect to promote the ROS generation. Therefore, the GO/CuFeSx NC can effectively kill bacteria and biofilm both in vitro and in vivo, finally eliminating the infections and accelerating the tissue repair when treating the biofilm-infected wound. This work paves a new way to the design of novel nanozyme for smart antibacterial therapy against antimicrobial resistance.

In-situ reactivation and reuse of micronsized sulfidated zero-valent iron using SRB-enriched culture: A sustainable PRB technology

Sulfidated zero-valent iron (S-ZVI) is an attractive material of permeable reactive barriers (PRBs) for the remediation of contaminated groundwater. However, S-ZVI is prone to be passivated due to the oxidation of reactive and conductive iron sulfide (FeSx) shell and the formation of inactive and non-conductive ferric (hydr)oxides, which serve as electron transfer barriers to hinder the electron flow from Fe° core to contaminants. This study thus proposed a novel approach for in-situ reactivation and reuse of micronsized S-ZVI (S-mZVI) in PRB using sulfate-reducing bacteria (SRB) enriched culture to realize long-lasting remediation of Cr(VI)-contaminated groundwater. S-mZVI were passivated after reactions with Cr(VI) due to the formation of electron transfer barriers (mainly inactive and non-conductive Fe(III) (hyd)oxides, which increased the polarization resistance from 16.38 to 27.38 kΩ cm2 and hindered the electron transfer from the Fe° core. Interestingly, the passivated S-mZVI was efficiently reactivated by providing the SRB-enriched culture and organic carbon within 12 h, and the Cr(VI) removal capacity of S-mZVI in the three use cycles increased to 37.4 mg Cr/g, which was 2.1 times higher than that of the virgin S-mZVI. After biological reactivation, the Rp of reactivated S-mZVI decreased to 12.30 kΩ cm2. SRB-mediated reactivation removed the electron transfer barriers via biotic and abiotic reduction of Fe(III) (hyd)oxides. Especially, the microbial Fe(III) reduction mediated by FmnA-dmkA-fmnB-pplA-ndh2-eetAB-dmkB protein family enhanced the Fe2+ release from the surface and the subsequent re-formation of reactive and conductive FeSx shell. A long-term PRB column test further demonstrated the feasibility of in-situ biological reactivation and reuse of S-mZVI for enhanced Cr(VI)-contaminated groundwater remediation. Within 64 days, the Cr(VI) removal capacity of S-mZVI in the four use cycles increased by 3.2 times, compared to the virgin one. The bio-reactivation using the SRB-enriched culture and sulfate locally-available in groundwater will reduce the chemical and maintenance costs associated with the frequent replacement of reactive ZVI-based materials. The PRB technology based on the bio-renewable S-mZVI can be a sustainable alternative to the conventional PRBs for the long-lasting and low-cost remediation of groundwater contaminated by oxidative pollutants.

Remagnetization of the Upper Permian–Lower Triassic limestones in the western Lhasa Terrane and its tectonic implications

SUMMARY The drift history of the Lhasa terrane plays an essential role in understanding the tectonic evolution of the Bangong-Nujiang Tethyan Ocean and the Neo-Tethyan Ocean, as well as the evolutionary history of the Tibetan Plateau. Here, a combined rock magnetic, petrographic, and palaeomagnetic study is performed on the Upper Permian–Lower Triassic limestones (∼259–251 Ma) in the western Lhasa terrane. The site-mean direction for the 28 sites is Dg = 32.1°, Ig = 50.3°, kg = 47.9 and α95 = 4.0° in situ and Ds = 342.9°, Is = 32.7°, ks = 43.2 and α95 = 4.2° after tilt-correction, yielding a palaeopole at 68.9°N, 314.4°E with A95 = 4.3°, corresponding to a palaeolatitude of 18.0° ± 4.3°N. The fold tests are not significant because the sampling section shows monoclinic features with minor variations in their bedding attitudes. The palaeopoles for the directions before and after tilt-correction are compared with reliable Late Permian–Palaeogene palaeopoles obtained from the Lhasa terrane. Based on these comparisons, the studied limestones were remagnetized prior to tilting and this remagnetization most likely occurred during the Early Cretaceous. The depositional environment of the limestones may have changed from anoxic to suboxic and oxic during the Early Cretaceous, leading to the oxidation of iron sulphide to authigenic magnetite. Meanwhile, the Late Jurassic–Early Cretaceous convergence between the western Lhasa and Qiangtang terranes may have resulted in tectonic fluid migration and the formation of calcite veins and stylolites in the limestones. This is supported by the presence of small calcite veins and stylolites in some samples, as well as the fact that the framboidal oxides were formerly sulphides (mostly pyrite), implying that the majority of the iron oxides observed in the limestones were authigenic. These processes indicate that chemical remanent magnetization caused by the growth of magnetic minerals related to tectonic fluid migration was most likely the mechanism for the limestone remagnetization.

Analysis of Early Iron Sulfide, Carbonate, and Phosphate Mineral Analogues Produced by Flow-Driven Precipitation in a Microchannel.

Most of the chemical and physical interactions of interest to the astrobiology community are influenced by the mineralogy of the systems under consideration. Often, this mineralogy occurs in sediment or sediment-like aqueous microenvironments in which the early minerals differ dramatically from the mature version that results from a long diagenesis, which are tied to complex interactions of pH, redox state, concentration, and temperature. This interconnectedness is difficult to reproduce in a laboratory setting yet is essential to understanding how the physical and chemical demands of living systems alter and are altered by their geological context. We present a facile means for producing precipitated mineral analogues within a microchannel and demonstrate its analytical efficacy through instrumental and modeling techniques. We show that amorphous, early-stage analogues of iron sulfide, iron carbonate, and iron phosphate can be formed at the boundary between flowing solutions, modeled on the microscale, and analyzed by standard instrumental techniques such as scanning electron microscopy/energy-dispersive spectroscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy.

Persulfate activation via iron sulfide nanoparticles for enhanced trichloroethylene degradation and its applications in groundwater remediation

Trichloroethylene (TCE) is known for its carcinogenic properties and limited environmental degradation. Therefore, TCE degradation was carried out using a catalyzed system, i.e., an advanced oxidation process (AOP) for an aqueous solution. This study focuses on activating sodium persulfate (PS) by laboratory-synthesized iron sulfide nanoparticles (FeS-NPs) with a particle size of 115.17 nm for enhanced TCE degradation. Field emission scanning electron microscope (FESEM), transmission electron microscopy (TEM), X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR), and Brunauer-Emmett-Teller (BET) analyses were employed to investigate physio-chemical properties and surface morphologies of synthesized FeS-NPs catalyst. PS/FeS-NPs exhibited outstanding performance, achieving a remarkable degradation (99.07 %) of TCE in 60 min of reaction time, surpassing the degradation demonstrated by commercially available PS/FeS (25 %). The dominant involvement of Fe transformation and SO4•ˉ, OH•, and 1O2 radicals in TCE degradation was validated through scavenging and electron paramagnetic resonance (EPR) investigation. Moreover, the PS/FeS-NPs system was found efficient (97⁓99 %) in both acidic and basic solutions, although it is noteworthy that highly basic (pH 11) mediums may impact the degradation efficiency (13.8 %). Recycling and stability experiments revealed significant efficiency of the PS/FeS-NPs system during the second run (90.02 %) and third run (68.25 %). These core revelations validate the efficiency of FeS-NPs in TCE degradation in an aqueous solution. Conclusively, the PS/FeS-NPs system encouraged TCE degradation outcomes, depicting strong potential for prolonged benefits in the remediation of TCE-polluted water.

Synthesis of Iron Sulfide Nanocrystals Encapsulated in Highly Porous Carbon‐Coated CNT Microsphere as Anode Materials for Sodium‐Ion Batteries (Small 7/2024)

Synthesis of Iron Sulfide Nanocrystals Encapsulated in Highly Porous Carbon‐Coated CNT Microsphere as Anode Materials for Sodium‐Ion Batteries (Small 7/2024)

A novel iron sulfide phase with remarkable hydroxyl radical generation capability for contaminants degradation

The hydroxyl radical (·OH) stands as one of the most potent oxidizing agents, capable of engaging in non-selective and instantaneous reactions with contaminants in water. Herein, we present a novel iron sulfide phase (S-FeS) characterized by an unprecedented structure, accompanied by its remarkable hydroxyl radical generation capability and contaminant degradation efficiency surpassing that of the conventional metastable iron sulfide phase, namely, the Mackinawite (FeS). In comparison to FeS, S-FeS exhibits enhanced degradation kinetics and higher efficacy in the removal of methylene blue, ciprofloxacin, and trivalent arsenic. Utilizing density functional theory (DFT) calculations, we postulate the mechanism for the exceptional contaminant degradation performance of S-FeS to be attributed to the increased exposure of the highly reactive (110) crystal facets. This research uncovers a new metastable phase that expands the polymorphisms within the iron sulfide family and showcases its capability for driving the oxygen reduction reaction.

Intervention of HCHO on the FeSx structure transition during sulfidation of zero-valent iron

Iron sulfides (FeSx) enhancing the properties of sulfidated zero-valent iron (SZVI) to contaminants removal has been extensively studied, however, it is difficult to further regulate the FeSx species to control the SZVI properties. Based on the transformation of formaldehyde (HCHO) on FeSx, this work introduced HCHO into SZVI preparation process to regulate the FeSx structure. Results show that the HCHO-intervened SZVI (SZVIHCHO) has better Cr(VI) removal performance, which is due to the batter electrochemical properties. The FeSx structure of SZVIHCHO is evidently changed by HCHO, that is flaky FeSx transforms into granular FeSx and locally aggregated on SZVIHCHO surface. The composition of FeSx species shows that HCHO can weaken the conversion of FeS to FeS2, but directionally induce the conversion of FeS to Fe3S4. The electrostatic attraction of Fe atom in FeSx to the –CHO and the electron-withdrawing property of –CHO are the causes of electron loss from Fe atom and thus increase the Fe valence state. This study provides the inspirations for the future regulation of SZVI by inserting organics with specific structure and functions during SZVI preparation.

Enhancement of immobilized biochar/FeS on nitrogen removal in constructed wetland at low temperature

Constructed wetland (CW) is an eco-friendly and economically treatment for the deep nitrogen removal. Microbial denitrification, a key process in CW, is temperature-sensitive, with decreased nitrogen removal efficiency at low temperature. To enhance the nitrogen removal efficiency at low temperature, this study explored the use of functional substrates, focusing on iron sulfide (FeS) nanoparticles and biochar (BC). The results showed that immobilized BC/FeS significantly improved nitrate (NO3-N) and total nitrogen (TN) removal in CW at low temperature (8–13 °C), which reached 93.59 ± 2.07 and 80.06 ± 3.00 %, respectively, with 30 % immobilized BC/FeS. Increasing the dosage of immobilized BC/FeS accelerated denitrification rate and reduced nitrite (NO2-N) accumulation. Autotrophic denitrification was the primary pathway, with the contribution of autotrophic denitrification increasing from 64.06 % (10 % immobilized BC/FeS) to 83.25 % (30 % immobilized BC/FeS). Sulfurimonas was the dominant denitrifying bacteria identified as a cold-tolerant denitrifying bacteria. The study underlines the potential of composite electron donor substrates to enhance nitrogen removal in CW, providing a sustainable solution to nitrogen pollution in cold climates.

The fate of primary iron sulfides in the CM1 carbonaceous chondrites: Effects of advanced aqueous alteration on primary components

AbstractWe have carried out a SEM‐EPMA‐TEM study to determine the textures and compositions of relict primary iron sulfides and their alteration products in a suite of moderately to heavily altered CM1 carbonaceous chondrites. We observed four textural groups of altered primary iron sulfides: (1) pentlandite+phyllosilicate (2P) grains, characterized by pentlandite with submicron lenses of phyllosilicates; (2) pyrrhotite+pentlandite+magnetite (PPM) grains, characterized by pyrrhotite–pentlandite exsolution textures with magnetite veining and secondary pentlandite; (3) pentlandite+serpentine (PS) grains, characterized by relict pentlandite exsolution, serpentine, and secondary pentlandite; and (4) pyrrhotite+pentlandite+magnetite+serpentine (PPMS) grains, characterized by features of both the PPM and PS grains. We have determined that all four groups were initially primary iron sulfides, which formed from crystallization of immiscible sulfide melts within silicate chondrules in the solar nebula. The fact that such different alteration products could result from the same precursor sulfides within even the same meteorite sample further underscores the complexity of the aqueous alteration environment for the CM chondrites. The different alteration reactions for each textural group place constraints on the mechanisms and conditions of alteration with evidence for acidic environments, oxidizing environments, and changing fluid compositions (Ni‐bearing and Si‐Mg‐bearing).

Investigation of pharmacokinetics and immunogenicity of magnetosomes

Magnetosomes are iron oxide or iron sulphide nano-sized particles surrounded by a lipid bilayer synthesised by a group of bacteria known as magnetotactic bacteria (MTB). Magnetosomes have become a promising candidate for biomedical applications and could be potentially used as a drug-carrier. However, pharmacokinetics and immunogenicity of the magnetosomes have not been understood yet which preclude its clinical applications. Herein, we investigated the pharmacokinetics of magnetosomes including Absorption, Distribution, Metabolism, and Elimination (ADME) along with its immunogenicity in vitro and in vivo. The magnetosomes were conjugated with fluorescein isothiocyanate (Mag-FITC) and their conjugation was confirmed through fluorescence microscopy and its absorption in HeLa cell lines was evaluated using flow cytometry analysis. The results revealed a maximum cell uptake of 97% at 200 µg/mL concentration. Further, the biodistribution of Mag-FITC was investigated in vivo by a bioimaging system using BALB/c mice as a subject at different time intervals. The Mag-FITC neither induced death nor physical distress and the same was eliminated post 36 h of injection with meagre intensities left behind. The metabolism and elimination analysis were assessed to detect the iron overload which revealed that magnetosomes were entirely metabolised within 48-h interval. Furthermore, the histopathology and serum analysis reveal no histological damage with the absence of any abnormal biochemical parameters. The results support our study that magnetosomes were completely removed from the blood circulation within 48-h time interval. Moreover, the immunogenicity analysis has shown that magnetosomes do not induce any inflammation as indicated by reduced peaks of immune markers such as IL 1β, IL 2, IL 6, IL8, IFN γ, and TNF α estimated through Indirect ELISA. The normal behaviour of animals with the absence of acute or chronic toxicities in any organs declares that magnetosomes are safe to be injected. This shows that magnetosomes are benign for biological systems enrouting towards beneficial biomedical applications. Therefore, this study will advance the understanding and application of magnetosomes for clinical purposes.

High-energy-density fiber-shaped aqueous Ni//Fe battery enabled by metal-organic framework derived spindle-like carbon incorporated iron disulfide

Metal dichalcogenides are regarded as encouraging electrode materials for aqueous rechargeable batteries on account of their excellent conductivity and theoretical capacity. Nevertheless, the structure's instability and low conductivity have restricted their development. Herein, MIL-101-Fe-derived spindle-like carbon incorporated FeS2 are successfully prepared exactly grown on carbon nanotube fibers (S–FeS2/CNTFs) with significantly enhanced conductivity and structure's stability due to the introducing of sulfur. Furthermore, we successfully constructed an outstanding-capacity fiber-shaped aqueous rechargeable (FAR) Ni//Fe batteries using the S–FeS2/CNTFs as advanced anodes. Density functional theory reveals that the S-doping significantly increase the conductivity and accomplish the structural reconstruction of the MIL-101-Fe. The S–FeS2/CNTF electrode exhibits a distinguished capacity of 0.55 mAh cm−2 at a current density of 6 mA cm−2, and maintains a capacity of 0.42 mAh cm−2 at a high current density of 200 mA cm−2, signifying outstanding rate performance. Notably, the as-assembled FAR Ni//Fe batteries achieve a phenomenal energy density of 137.5 mW h cm−3 at power density of 2200 mW cm−3. This approach affords an innovative opinion for developing outstanding-performance flexible aqueous energy-storage devices.

Decoding the divalent cation effect on sulfidation of zero-valent iron: Phase evolution and FeSx assembly

The decontamination ability of sulfidated zero-valent iron (S-ZVI) can be enhanced by the effective assembly of iron sulfides (FeSx) on neglected heterogeneous surfaces by liquid-phase precipitation. However, S-ZVI preparation with the usual pickling is detrimental to orderly interfacial assembly and leads to an imbalance between electron transfer optimization and electron storage. In this work, S-ZVI was prepared in solutions containing trace divalent cation, and it removed Cr(VI) up to 323.25 times higher than ZVI. This result is achieved by surface sites protonation of divalent cations regulating the phase evolution on the ZVI surface and inducing FeSx chemical assembly. Regulation of divalent cation and S(-II) content further promotes FeSx targeted assembly and reduces electron storage consumption as much as possible. The barrier for FeSx assembly is found to lie at the ZVI interface rather than in the deposition between FeSx. Chemical assembly at heterogeneous interfaces is a prerequisite for the ordered assembly of FeSx. In addition, S-ZVI prepared in simulated groundwater showed extensive preparation pH and universality for remediation scenarios. These findings provide new insights into the development of in-situ sulfidation mechanisms with particular implications for S-ZVI applied to soil and groundwater remediation by the regulation of heterogeneous interfacial assembly.

A Mott-Schottky Heterojunction with Strong Chemisorption and Fast Conversion Effects for Room-Temperature Na-S Batteries.

The practical application of the room-temperature sodium-sulfur (RT Na-S) batteries is currently limited by low reversible capacity and serious capacity decay due to the sluggish reaction kinetics and shuttle effect. It is necessary to design a suitable sulfur host integrated with electrocatalysts to realize effective chemisorption and catalysis of sodium polysulfides (NaPSs). Herein, under the guidance of theoretical calculation, the Mott-Schottky heterojunction with a built-in electric field composed of iron (Fe) and iron disulfide (FeS2) components anchored on a porous carbon matrix (Fe/FeS2-PC) is designed and prepared. The enhanced chemisorption effect of Fe, the fast electrocatalytic effect of FeS2, and the fast transfer effect of the built-in electric field within the Fe/FeS2 heterojunction in the cathode of RT Na-S batteries work together to effectively improve the electrochemical performance. As a result, the Fe/FeS2-PC@S cathode exhibits high reversible capacity (815 mAh g-1 after 150 cycles at 0.2 A g-1) and excellent stability (516 mAh g-1 after 600 cycles at 5 A g-1, with only 0.07% decay per cycle). The design of the Fe/FeS2 heterojunction electrocatalyst provides a new strategy for the development of highly stable RT Na-S batteries.

S-vacancy-rich NiFe-S nanosheets based on a fully electrochemical strategy for large-scale and quasi-industrial OER catalysts

The oxygen evolution reaction (OER) is regarded as a critical component in the water splitting system. Creating vacancies, increasing active surface area, and optimizing electronic structure would improve electrocatalytic performance. Herein, a facile electrochemical reduction method is used to generate sulfur vacancies in nickel iron sulfide (NiFe-S) with a large geometry area of 15 × 16 cm2, which is synthesized using an electrodeposition process assisted with the ion exchange (IOE) method. The X-ray absorption spectroscopies (XAS) are applied for atomic-level structural analysis, verifying that electrochemical desulfurization generates abundant S vacancies. The NiFe-S with abundant sulfur vacancies (NiFe-S-Vs) exhibits a low overpotential (252 mV at 100 mA cm−2), and long stability for 260 h at 500 mA cm−2. More importantly, the NiFe-S-Vs catalyst also delivers a small overpotential (235 mV at 1000 mA cm−2) and high alkaline tolerance (140 h at 500 mA cm−2) in 6 M KOH at 60 °C), implying a potentially significant industrial application prospect. Finally, theory calculation further illustrates the high performance of as-prepared vacancies-rich catalyst.

CHEMICAL REMOVAL OF IRON SULFIDE DEPOSIT IN PIPES FROM OIL AND SOUR GAS PRODUCTION

Hydrogen sulfide (H2S) and carbon dioxide (CO2) present in oil and natural gas cause mild steel corrosion, potentially resulting in formation of corrosion product layers on the internal surfaces of tubulars. In field experiences relating to the research reported herein, this has led to restrictions on the flow of water produced from a three-phase horizontal separator. This paper demonstrates a specific case of chemical removal of relatively hard, dark, and adherent heterogeneous deposits on the internal surface of the pipe. The phases involved in this process are iron sulfide, iron oxides and calcium carbonate existing as scales/corrosion products. To evaluate their dissolution, laboratory tests were conducted using hydrochloric acid (HCl) with additions of chlorine in the form of calcium hypochlorite [Ca(ClO)2]. Appropriate safety measures were taken employed, considering hazards associated with chlorine and toxicity of hydrogen sulfide. The treatment regime had 87 % effectiveness for scale removal in combination with propargyl alcohol (2-propyn-1-ol) as a corrosion inhibitor.

Analysis of the Formation Mechanism of Hydrogen Sulfide in the 13# Coal Seam of Shaping Coal Mine.

In order to accurately predict the law of occurrence and migration of hydrogen sulfide (H2S) in the underground and effectively solve the problem of excessive concentration of H2S gas, laboratory experiments on the content of various forms of sulfur in coal, sulfur isotopes, thermal evolution history, and coal seam water samples were carried out by applying the theories of coal mine geology, microbiology, and analytical chemistry, and based on the experimental results, the cause of H2S gas was explored. Through the analysis of the geological conditions of the coal seam mined, it can be seen that the coal mine experienced the alternation of marine and continental phases in the process of coal formation and that there was no magma intrusion. The experimental results showed that iron sulfide in coal accounts for 73.25% of the total sulfur, indicating that the coal seam was rich in pyrite. The results of the isotope test showed that the sulfur isotopes in coal samples were all negative, indicating that the sulfur isotope fractionation in coal was large, the loss was serious, and the coal seam was greatly affected by seawater. According to the experimental results of vitrinite reflectance, it can be concluded that the highest temperature during the thermal evolution of the coal seam is 108.12 °C, which has not reached the temperature condition of sulfate thermochemical reduction. Comparing the concentration of acid ions in coal seam water and tap water, it was found that the concentration of SO42- in coal seam water is low, while the concentration of HCO3- is high. According to the experimental results and theoretical analysis, the H2S gas in the high-sulfur coal mine was caused by microbial sulfate reduction. Finally, the transformation path of sulfur in the coal seam was deduced and analyzed. The results showed that sulfur in coal is positively correlated with H2S gas concentration.

Origin of the Filizchay ore field (the southern slope of the Greater Caucasus)

&#x0D; &#x0D; &#x0D; he article deals with the origin of the Filizchay ore field, which is a valuable object for the extraction of zinc, lead, copper, silver as well as for the extraction of the associated com- ponents. The data and types (VMS, SEDEX, VMT) of the pyrite deposits in the world have been briefly presented. Their comparative analysis has been carried out and it has been revealed that the Filizchay ore field is very different from the VMS-type pyrite deposits and it belongs to the SEDEX type. A direct relationship with vol- canism has not been observed in this deposit. Unlike the containing rocks related to volcanism in the Filizchay field , there are fine-rhyth- mic flyschoids with packages of sandstones, clay shales and silt-clay shales . The ratio of the natural ore types composed of the different mineral associations, with stages of the folded and disjunctive dislocations, allows us to divide the process of the deposit formation into the following three stages of the ore formation: 1. deposits of the massive hydrothermal-sedimentary essentially pyrite ores; 2. formation of the hydrothermal-metasomatic ores of the pyrite-copper-polymetallic composition; 3. deposition of the hydrothermal-meta- morphogenic ores of the copper-pyrrhotite composition. The available data indicate a favorable environment for sedimentary pyrite ore formation subject to a significant role of Corg. and sulfate-reducing bacteria. Moreover, the hydrothermal-sedimentary processes played the main role in the accumulation of the main volume of the sulfide masses. On the basis of the sulfur isotopic composition (according to Zairi, 1992) of the main minerals (pyrite, galena, sphalerite, pyrrhotite, chalcopyrite) from various types of the Filizchay ore field ores it was concluded that the deposit formation occurred from several portions of the entered hydrothermal solutions. It was found that by the period of accumulation of sediments of the ore-bearing horizon in the northern block – there occurred outpouring of the spilites and basalts in the narrow trough-like depression. The iron sulfides supplying the more southern basin with stagnant waters can be associated with their post-volcanic exhalations (as primary sources). The Filizchay ore field being connected with basaltic volcanism is combined according to formation method. It has been formed due to components which have been carried out by hydrothermal flows and due to basalts, which are associated with underwater alteration. The temperatures of the primary pyrite-polymetallic ores formation are relatively low (200-100 0С).&#x0D; &#x0D; &#x0D;