Formation Of Iron Sulfides Research Articles

Sulfide mediated zero valent iron for enhanced nickel removal under neutral condition: Reaction kinetic, mechanism, and stability

The application of sodium sulfide (Na2S) as sulfidation reagent of zero valent iron (ZVI) has been well studied, however, the effect of Na2S existence on ZVI reactivity remains obscure. In this study, Ni(II) removal performance, mechanism, and stability by ZVI with Na2S were investigated at neutral condition. The results showed that Ni(II) removal sharply increased from < 5–100% by ZVI within 60 min with the increase of Na2S concentration, but the subsequent Ni(II) release occurred. In addition to the slight Ni(II) removal by Na2S in aqueous phase, Ni(II) was mainly removed by the adsorption and reduction by Na2S mediated ZVI system. Characterization analysis indicated that Na2S could lead to the severe Fe0 corrosion and the main corrosion product on ZVI was lepidocrocite, which played the dominant role for Ni(II) immobilization. Meanwhile, the formation of iron sulfides on ZVI surface would enhance Ni(II) reduction and partially transform the adsorbed Ni(II) to NiS. Moreover, the higher ionic strength could further enhance the initial Ni(II) removal rate but the stability became poor. Regardless of the additive methods, the Ni(II) removal significantly enhanced in the system of ZVI and Na2S combination. Overall, this work reveals the sulfide mediated Fe0 corrosion and provides a potential method for enhancing the reactivity of ZVI in the treatment of Ni(II) pollution.

Influence of hydrogen sulphide on the corrosion and hydrogenation of 07Cr16Ni6 steel

The effect of hydrogen sulphide concentration on the corrosion behaviour of 07Cr16Ni6 austenitic-martensitic stainless steel in a 5% NaCl + 0.5% CH3COOH solution was studied to determine the role of H2S in the corrosion product formation and corrosion mechanism. Unstable passivation of steel is detected in a solution containing &lt;100 mg/dm3 H2S. Steel corrodes in an electrochemically active state at &gt;100 mg/dm3 H2S. When the pitting potential is reached, pitting damage occurs at the grain boundaries. The corrosion rate decreases by ∼five times after exposition for 720 h due to the formation of nickel and iron sulphides on the surface. Corrosion is accompanied by the absorption of 4.2–17.5 ppm hydrogen, 62…70% of which is diffusible and can cause hydrogen embrittlement. The scheme of steel corrosion under the influence of different concentrations of hydrogen sulphide is proposed.

Late Pleistocene and Holocene Sedimentation in the glacial Lake Sosednee, Magadan region

Lake Sosednee is located in the Yagodninsky district of the Magadan region. It was formed in the Late Pleistocene around 22,500 cal. years ago. The rock magnetic, geochemical, palynological, and mineralogical characteristics of the sediments of four cores, as well as moraine, and various grain size fractions of the hillslope sediments were studied. It has been established that the geochemical and rock magnetic properties of sediments from lake Sosednee reflect different sedimentation conditions, changing from the cold climate of the Late Pleistocene to the warm climate of the Holocene. In the lower part of the core, authigenic (hemogenic) formation of iron sulfides, including magnetic ones, was revealed. According to the rock magnetic and geochemical data, the Younger Dryas was identified, the end of which corresponds to the Pleistocene–Holocene boundary.

ASSESSMENT OF CORROSION DAMAGE TO OIL-WELL TUBING IN MINERAL ENVIRONMENTS

At present, the issue of improving the stability of production equipment due to high water cut of well products and the impact of mineral salt deposits contained in it at local oil fields Kumkol and others has not lost its relevance. The article discusses the mechanism of corrosion destruction of metal tubing pipes and well pumps in the oil and gas industry, i.e. it contains information about the initial development of corrosion during operation. One of the main problems encountered in oil fields is studied with regard to the effect of the chemical composition in layered water on tubing and hence corrosion. Experimental studies are performed here with respect to iron sulphide formation in downhole underground equipment. According to the nature of performance of underground production equipment, the value of corrosion rate of steel materials is determined. Graphical treatments of the average surface fluid result at the depth of the borehole of the required size are carried out. In this regard, based on the control of technological processes, the purpose of introducing a system for measuring and diagnosing the development of corrosion on downhole equipment, as well as the effective implementation of a set of anti-corrosion measures on oilfield equipment and pipelines is determined.

Cuprous ions influence on the biocorrosion of a carbon steel in the presence of sulphate reducing bacteria marine biofilm

The influence of marine sulphate reducing bacteria (SRB) biofilm on naval carbon steel corrosion in seawater was studied in the presence or not of cuprous ions as polluting agent. The optical density measurement showed that a concentration of 15 mg L−1 in cuprous ions can cause a significant slowdown in the proliferation of planktonic bacteria. However, electrochemical impedance results indicated that there was still bacterial activity on the metal substrate. Indeed, biofilm was grown on the surface of material in seawater containing SRB. Initially, an increase in the charge transfer resistance values due to the iron sulphide layer formed by the bacteria precipitation reactions was recorded during growth phase. This film acts as a barrier, preventing further oxidation of the underlying metal; then, the localized breakdown of iron sulphide layer generates an acceleration of corrosion. Similar behaviour occurs in the presence of sulphate reducing bacteria flora with 15 mg L−1 cuprous ions. In order to protect themselves when the seawater media containing toxic metals, sulphate reducing bacteria embed into clusters and increase the production of extracellular polymeric substances on materials. Sulphur was present on specimens in both cases and EDS spectra revealed the formation of iron sulphide. After the removal of biofilm, carbon steel surfaces exhibited a plenty of micropits scattered on the entire surface compared to the surface immersed in the seawater without bacteria.

Impact of redox fluctuations on microbe-mediated elemental sulfur disproportionation and coupled redox cycling of iron

Elemental sulfur (S0) plays a vital role in the coupled cycling of sulfur and iron, which in turn affects the transformation of carbon and various pollutants. These processes have been well characterized under static anoxic or oxic conditions, however, how the natural redox fluctuations affect the bio-mediated sulfur cycling and coupled iron cycling remain enigmatic. The present work examined S0 disproportionation as driven by natural microbial communities under fluctuating redox conditions and the contribution of S0 disproportionation to ferrihydrite transformation. Samples were incubated at either neutral or alkaline pH values, applying sequential anaerobic, aerobic and anaerobic conditions over 60 days. Under anaerobic conditions, S0 was found to undergo disproportionation to sulfate and sulfide, which subsequently reduced ferrihydrite at both pH 7.4 and 9.5. Ferrihydrite promoted S0 disproportionation by scavenging biogenic sulfide and maintaining a suitable degree of sulfate formation. After an oxic period, during the subsequent anoxic incubation, bioreduction of sulfate occurred and the biogenic sulfide reduced iron (hydr)oxides at a rate approximately 25 % lower than that observed during the former anoxic period. A 16S rDNA-based microbial community analysis revealed changes in the microbial community in response to the redox fluctuations, implying an intimate association with the coupled cycling of sulfur and iron. Microscopic and spectroscopic analyses confirmed the S0-mediated transformation of ferrihydrite to crystalline iron (hydr)oxide minerals such as lepidocrocite and magnetite and the formation of iron sulfides precipitated under fluctuating redox conditions. Finally, a reaction mechanism based on mass balance was proposed, demonstrating that bio-mediated sulfur transformation maintained a sustainable redox reaction with iron (hydr)oxides under fluctuating anaerobic-aerobic-anaerobic conditions tested in this study. Altogether, the finding of our study is critical for obtaining a more complete understanding of the dynamics of iron redox reactions and pollutant transformation in sulfur-rich aquatic environments.

Sulfidation Impacts on the Hydrophobicity of Stepped Iron Surfaces

Nanoscale zero‐valent iron (nZVI) has demonstrated high potential for the remediation of contaminated groundwater. Its lifetime is directly related to the hydrophobicity of nZVI. A promising approach to enhance the lifetime of nZVI is through sulfidation. Herein, the density functional theory (DFT) is applied to understand the impact of sulfidation on the hydrophobicity of stepped Fe surfaces. Adsorption properties of sulfur (S) at different coverages on the flat Fe(110) and stepped Fe(210) and Fe(211) surfaces are investigated. Sulfur has the stronger adsorption at a low surface coverage due to limited S–S repulsion. At the highest coverage (⊖ = 1 ML) on Fe(210) and Fe(211), the atoms at the step edges catalyze the formation of iron sulfides. The DFT results show surface hydrophobicity is mainly determined by the S coverage. At the low S coverage, the surface may become more hydrophilic due to the enhanced adsorption strength of water on the surface. However, an increase in the S coverage can efficiently block water adsorption, which is further evidenced by ab initio molecular dynamics (AIMD) results. The findings show that controlling S coverages is essential to engineer the hydrophobicity of nZVI surfaces for practical water remediation applications.

Controls on sulfide accumulation in coastal soils during simulated sea level rise

A likely consequence of sea level rise during the next century will be progressive inundation of seawater through the current unsaturated zone in coastal-margin soils. It is unclear how this will change the biogeochemical cycling of iron, sulfur and carbon over different time scales and soil types. A long-term (540 day) laboratory experiment, slowly inundating intact coastal soil cores with seawater from the ‘bottom up’, was conducted to observe how coupled iron and sulfur dynamics change in different soil types. Pore water was extracted from the 60 cm cores at 10 cm depth intervals every 90 days and analysed for pH, electrical conductivity (EC), Fe2+, HS− and dissolved metals (Fe, Mn, As, Cd, Cu, Ni, Pb, Co, Zn) as well as stable sulfur (34S/32S) and radiogenic strontium (87Sr/86Sr) isotopes. Destructive solid phase analyses (for reactive Fe, acid volatile and chromium reducible sulfur (AVS and CRS) and total organic carbon (TOC)) were made at the start and end of the experiment. Iron and sulfate reduction was induced in soils with readily available TOC as anoxic conditions established, evidenced by statistically significant increases (P < 0.001) in dissolved Fe2+ and sulfide concentrations in porewaters, as well as simultaneous and progressive increase in the sulfur isotope (34S/32S) ratios. An increase in AVS indicated formation of metastable iron sulfide (FeS) minerals resulting from Fe2+ and sulfide in porewaters post inundation. This was supported by PHREEQC modelling of local mineral saturation states/indices in the system. Overall, the Fe2+ concentration increased to a peak at between 270 and 360 days, and then began decreasing at some depths, indicating slowing iron reduction, presumably because reactive iron (oxyhydro)oxides became progressively consumed by microbially driven reductive processes. However, microbially mediated sulfate reduction continued as abundant sulfate was still available from seawater. In the absence of free Fe2+, sulfide accumulated in the porewater, but only in those soils inundated the longest (>360 days), and with greater than 5% TOC. The combined use of sulfur (34S/32S) and strontium (87Sr/86Sr) isotopes supported the observed results, and represents a new and robust technique to quantify progressive sulfate reduction and seawater mixing phenomena in coastal soils. This study gives new insights into the biogeochemical cycling of sulfur and iron in soils experiencing seawater inundation from sea level rise over longer timescales. It is likely that sulfidisation (due to in-situ sulfate reduction) will begin to affect coastal wetland soils, especially in areas where TOC is high and where reactive iron depletes over time. This has potential consequences for sulfide toxicity in coastal soils and environments globally.

Magnetic properties of gas hydrate-bearing sediments and their association with iron geochemistry in the Sea of Marmara, Turkey

The anaerobic oxidation of methane, a key geochemical process that is involved in the cycling of sulfate and iron (oxyhydr)oxides in marine sediments, results in the formation of iron sulfides. Although ferrimagnetic iron sulfides have been identified in seepage systems, the link between iron migration and sediment magnetic properties remains poorly understood. Here, we investigate two cores from the Sea of Marmara to evaluate biogeochemical iron cycling and iron sulfide mineralogy in gas hydrate-bearing sediments. Magnetic analyses indicate the presence of greigite and pyrrhotite in a core from a hydrate-rich site with a high hydrocarbon flux, which contrasts with a lack of these minerals in a core characterized by only mild seepage. This is supported by the results of rock magnetic and scanning electron microscope analyses of the sediments. The presence of authigenic greigite is critical for assessing local redox records and together with the occurrence of monoclinic pyrrhotite may suggest specific diagenetic processes in gas hydrate environments. Our analysis demonstrates the usefulness of these ferrimagnetic minerals, with a high saturation isothermal remanent magnetization to magnetic susceptibility ratio (SIRM/χ > 15 kAm−1) and a high index of hysteresis parameters (DJH > 0.2) indicative of magnetic mineralogy changes, for evaluating variability in the intensity of seepage fluxes and for estimating gas hydrate distributions.

The Tailings of Cold War U.S. Foreign Policy

Start with manganese (Mn). With an atomic number of twenty-five, Mn sits next to chromium and iron in the middle of an industrially indispensable row of what are called “transition metals” on the periodic table. The element is named for the Greek region of Magnesia—confusingly also the origin of the chemically very different magnesium, itself not to be confused with the magnetic lodestone also associated with the region—and in its most common form as manganese oxide it has been used for pigmentation and in glassmaking since antiquity. It is also essential to good steelmaking. At high temperatures, manganese forms a high-melting sulfide, preventing the formation of liquid iron sulfide and making high temperature steel more workable. Steel alloys of between eight percent and twelve percent manganese achieve significantly higher tensile strength, and as a deoxidizer manganese helps prevent corrosion and wear, especially in low-cost stainless steel. Aluminum, vanadium, and a number of other transition metals have similar properties to manganese, but as the authors of a 1952 report to U.S. President Harry Truman’s administration on the United States’ long-term material supply needs noted, in the early 1950s—as today—there was really no practical way to produce steel at an industrial scale without manganese. And in the 1950s, with steel a vital commodity at the heart of the U.S. civilian and military economies, the United States did not produce very much manganese.1

Inorganic sulfur cycles in sediments of the Pearl River Estuary: Processes, mechanisms, and isotopic indicators

The burial of inorganic sulfur is one of the important components in the global sulfur cycle. In this study, the cycling of inorganic sulfide species and the underlying control mechanisms were examined in sediments found in distinct sub-regions of the Pearl River Estuary (PRE). Specifically, the content and isotopic composition of SO42−, acid-volatile sulfides (AVS), and pyrite were determined, along with sedimentary sulfate reduction rates (SRR). The results show that the formation of iron sulfides (such as AVS and pyrite) was mainly controlled by the content of available reactive iron in the sediments of the PRE, and therefore formed mainly in the shallow sediments, with little variation in the deeper parts of the sediments. The δ34S values of AVS and SO42− increased synchronously with depth in the middle and lower part of the sediment, indicating a closed diagenetic environment. In contrast, the δ34S value of pyrite only increased slowly with depth in the case of a small portion of AVS converted to pyrite, which was controlled by the burial time. There are obvious differences in the formation and burial of pyrite in sediments of different sub-regions of the PRE. The surface layer of stations QA and HQ in the upper estuary and brackish coast was an open environment due to sedimentary reworking, and the contents of AVS and pyrite in the sediment was extremely low due to re-oxidation, while the oxidation of 32S-rich H2S also resulted in lower δ34S values of sulfate in the sediment pore water than in the overlying seawater. Station GS in the estuarine mouth had a much higher percentage of AVS converted to pyrite in the sediments than that at stations QA and HQ due to the relatively long burial time. In addition, near the sulfate methane transition zone (SMT), only the estuarine mouth (station GS) produced iron sulfides (AVS) synchronously with the anaerobic oxidation of methane (AOM), and then converted to pyrite gradually; in contrast, the effect of AOM on the formation of iron sulfides in the sediments of the upper estuary and the brackish coast was almost negligible. The results show that the contribution of AOM processes to the final burial of inorganic sulfur is generally small in PRE.

Effect of Sulfate-Reducing Bacteria on the Production of Iron Sulfides

Using Fourier transform infrared spectroscopy (FTIR) to identify the sulfate-reducing bacteria (SRB) in Daqing Oilfield sewage. The growth curve of SRB and the adsorption ability of extracellular polymeric substances (EPS) to the Fe2+ were combined to explore iron sulfide generation. X-ray diffraction (XRD) results showed that different species of SRB produce iron sulfides, mainly composed of mackinawite. The growth characteristics of SRB affected the formation of iron sulfides and had a negative charge. Various SRB growth trends were different. The growth of the bacterium in an exponential phase or log phase can be described by the greater concentration of inoculation. And smooth growth trends were contributed to the formation of FeS. At the same time, sulfur-rich, like FeS2, was easily formed when S2− (or S2 2−) played a major role compared with the protein and polysaccharide functional groups in the negatively charged EPS at the process of Fe2+ adsorption.

Thermodynamic stability reversal of iron sulfides at the nanoscale: Insights into the iron sulfide formation in low-temperature aqueous solution

Understanding the formation of iron sulfides at low temperatures is essential for interpretation of geochemical signatures recorded in sedimentary sulfide minerals related to the evolution of the Earth’s surface environment. Observed variations in the precipitation of nanoparticulate metastable phases prior to the formation of the stable-phase pyrite have been discussed from a kinetic perspective only. Here, using the ab-initio thermodynamic scheme to integrate surface thermodynamics with solid–aqueous equilibria, we demonstrate that stability relations among iron sulfides are dependent on particle size. The lower surface energies of metastable mackinawite and greigite than pyrite can drive reversals in relative thermodynamic stability at the nanoparticle scale and also lead to faster nucleation rates of the metastable phases, which are dependent on aqueous Eh-pH and Fe(II)/H2S conditions. This study emphasizes the role of surface energy in the formation pathways of iron sulfides and their particle-size dependent redox equilibria in anoxic aqueous solutions.

In-situ X-ray diffraction and radiography of iron–silicate–water–sulfur system simulating behaviors of light elements during early Earth’s core–mantle segregation

ABSTRACT The Earth’s iron-rich core contains light elements. Studying the interaction of multiple light elements with iron and silicates during core–mantle segregation process in early Earth evolution has become important. In-situ X-ray diffraction and imaging observations of the iron–silicate–water–sulfur system at 5–10 GPa, up to approximately 1900°C, were used to elucidate sequential reactions: phase transformation and hydrogenation of iron, and formation of iron sulfide and silicates. The newly constructed X-ray imaging system achieved spatial resolution of approx. 10 μm for this study to show iron blob formation and motion. Sulfur distorted the iron blob shape and affected blob growth during heating by reducing the interfacial energy between molten iron and silicates. Light elements in the molten iron and the remaining silicate grains affected core–mantle segregation in the primitive Earth as temperatures increased. Carbon and silicon were incorporated into liquid Fe during later processes at higher temperatures.

Wear of Mechanochemically Treated High-Speed Steel Cutting Tools

Abstract This paper presents a study of the wear of high-speed steel cutting tools modified mechanochemically by shot peening their rake faces with a mixture of Al2O3 and Cu2S particles. This treatment has been recently proved to reduce cutting forces significantly, but little is known about the wear resistance of the modified tools. To pave the way for practical implementation of this technology, here we bridge this gap. Orthogonal cutting tests performed under base oil lubrication demonstrate at least a twofold increase in the tool life compared to the untreated references. This is attributed to the formation of iron sulfide and its ability to retain oil at the cutting interface, which results in lower stresses and temperature. This environmentally friendly technique shows good potential to lower manufacturing costs, reduce energy consumption, and improve machining quality.

Biogeochemistry and element speciation in sapropel from freshwater Lake Dukhovoe (East Baikal region, Russia)

This paper presents results of biogeochemical investigation of the Holocene organic-rich sapropelic sediments of Lake Dukhovoe situated not far from the Baikal. The main source of organic matter in Lake Dukhovoe is phytoplankton, which serves as a biogeochemical barrier where elements are accumulated from water and then buried in the bottom sediments. Microorganisms (e.g., bacteria, micromycete and actinomycetes) play significant role in decomposition of organic matter and formation of organic-mineral complexes in four distinguished types of sapropels: organic, organic-mineral, mineral-organic and mineral. Diagenetic transformations of the Lake Dukhovoe sapropels under influence of mechanical, biochemical, microbiological and physicochemical processes lead to transformation of element speciation. A boundary between oxidizing and reducing diagenesis conditions is at the depth of 167 cm in the sapropel core. Change of the conditions forms geochemical barrier in bottom sediments and control the formation of secondary phases (organic-mineral complexes, diatomite, framboidal pyrite, vivianite, carbonates, etc.) as well as processes of accumulation and leaching of chemical elements. Additionally, high contents of Fe, Mn, Cu, Zn, Pb, Cd, and Mo in the upper 10 cm of the sapropel might have been caused by forest fires and anthropogenic factors. The fact of marcasite formation in the stomatocysts of Chrysophyte algae (golden algae) is new and was established for the first time. Based on the results and geochemical equilibrium modelling, the stomatocysts of Chrysophyte algae can be considered as a microreactor for iron sulfide formation.

The low-temperature heat capacity and thermodynamic properties of greigite (Fe3S4)

Heat capacity measurements provide important insights into the energetic, thermodynamic, and magnetic properties of materials. Herein we report the heat capacity of greigite (Fe3S4) from 1.8 to 300 K. Greigite is a magnetic spinel mineral and through a ferromagnetic magnon term, Cfsw = BfswT3/2, ferrimagnetic ordering is observed in the low-temperature heat capacity. Using a set of theoretical fits of the experimental data, we calculate the thermodynamic functions, including the standard entropy (Δ0TSm°). Greigite is important in iron sulfide formation and reaction pathways in environmental, ore-forming, and technological settings and previous work has measured enthalpies (ΔHr°) of formation and decomposition to neighboring phases. In this work, the stability of greigite relative to the elements is demonstrated with a negative Gibbs energy (ΔGr°) of formation and the stability relative to decomposition products of pyrrhotite (FeS1.092) and pyrite (FeS2) is demonstrated with a positive Gibbs energy (ΔGr°) of decomposition. Values of the standard thermodynamic functions Cp,m°, Δ0TSm°, Δ0THm°, andΦm° are tabulated.

Diagenetic dissolution, maghemitization and sulphidization of magnetic minerals in rapidly deposited gas hydrate bearing sediments from the Bay of Bengal

We conducted a comprehensive rock magnetic investigation complemented by a scanning electron microscopy analyses on a 148.8 m sediment core (NGHP-01-20A) from the methane-hydrate bearing site in the Bay of Bengal to systematically evaluate how magnetic minerals selectively respond to a range of diagenetic processes in the sulfidic and methanic sediments. For diagenetic analysis, we defined five distinct sediment magnetic zones (I–V) based on the sediment magnetic signatures. Rock magnetic property is mainly carried by complex magnetic mineral assemblages of detrital (titanomagnetite, silicate hosted magnetic inclusions), altered (titanomaghemite, titanohematite) and fine-grained diagenetic (pyrite) and authigenic (greigite) iron sulfide minerals. Three distinct bands of enhanced magnetic susceptibility in Z-II, Z-III and Z-V mainly comprised of detrital magnetite-rich minerals delivered by the peninsular river systems as a result of higher sedimentation events in the Krishna-Godavari (K-G) basin. Progressive diagenetic dissolution of primary iron oxide and consequent formation of iron sulfide in the uppermost sulfidic zone (Z-I) is clearly mirrored in the magnetic susceptibility (χlf) profile. Presence of moderately altered coarse-grained detrital Fe–Ti particles in the deeper methanic and magnetically enhanced zones (Z-II, Z-III, Z-V) suggest that sediment diagenesis at this site was significantly constrained by the multiple events of rapid sedimentation which might have restricted the complete dissolution of the primary minerals. Decline in magnetic grain size diagnostic proxy (ARM/IRM2.5T) in the uppermost sulfidic zones (Z-I, Z-II) can be attributed to the preferential dissolution of fine-grained magnetite. Further, downcore increases could be linked with the authigenic formation of fine-grained magnetite in methanic zones (Z-III to Z-V). Ferrimagnetic iron sulfide (greigite) indicative (SIRM/χlf) parameter showed sudden rise in Z-II and remain fairly constant throughout, suggesting the presence of authigenic greigite. Scanning electron microscopy in-line with energy dispersive X-ray spectroscopy analyses of magnetic particles from different sediment magnetic zones revealed a range of ferrimagnetic (titanomagnetite, titanomaghemite), antiferromagnetic (titanohematite) iron oxides and iron sulfide (pyrite). Detrital titanomagnetite with angular, irregular, spherical and well-defined octahedral with micron and submicron sized particles mainly derived from Deccan Volcanic Province (DVP) dominates the rock magnetic signal of bulk sediments in the studied core. We noticed several evidence of diagenetic dissolution, sulphidization and maghemitization of magnetic particles in the studied sediment core. Few nanometre-sized detrital magnetic particles occur as inclusions within the silicate minerals and remains protected against the sulfidic dissolution fronts through geologic times. Optical microscopy revealed the dominance of diagenetic pyrite occurring as overgrowth on the ferrimagnetic particles. We demonstrate that the rockmagnetic methods in combination with focussed electron microscope analyses provide valuable insights into the mineralogy, genesis and state of preservation of magnetic particles in sulfidic and methanic environments and thereby enhances the interpretative value of rock magnetic proxies.

Isotopic reconstruction of iron oxidation-reduction process based on an Archean Ocean analogue

The chemical composition and redox conditions of the Precambrian ocean are key factors for reconstructing the temporal evolution of atmospheric oxygen through time. In particular, the isotopic composition of iron are useful proxies for reconstructing paleo-ocean environments. Yet, respective processes and related signatures are poorly constrained, hindering the reconstruction of iron redox mechanisms in the Archean ocean. This study centers on Sihailongwan Lake, a stratified water body with a euxinic lower water column considered as an Archean ocean analogue. Results show that the anaerobic oxidation layer is so different from other similar lakes in which dissolved Fe oxidation is present in redoxcline layer. And the fractionation factor between ferrous Fe and iron hydroxide observed in nature water body of Sihailongwan Lake reaches to 2.6‰, which would benefit the production of the oxidations of BIF in sediment. By the spatial distribution of Fe isotope, the benthic water in autumn and the hypolimnetic anoxic water in spring has been identified as iron sulfide zone, where iron isotopic fractionation factor during iron sulfide formation is 1.16‰, accounting for partial scavenging of dissolved Fe(II) with an associated isotopic fractionation. However, pyrite in the sediment records the iron isotopic signal from the redoxcline but not in the iron sulfide or oxide zones of the water column. Above findings indicate that neither the iron isotope fractionation during partial transfer of ferrous iron to iron sulfide nor the partial oxidation of ferrous iron are recorded as pyrite in sedimentary rock. Importantly, the signal of Fe isotopic fractionation in water was archived in the suspended particulate matter and transferred into the sediment, rather than via ferrous iron directly deposited in the sediment. This study reveals that Fe isotopes from modern natural environments are useful proxies for reconstructing iron oxidation-reduction process during Earth's early history.

Iron sulphide formation and interaction with corrosion inhibitor in H2S-containing environments

Corrosion of carbon steel in H2S-containing environments poses serious challenges to operations in oilfield and geothermal applications. Carbon steels exposed to H2S-containing environments are often susceptible to pitting and uniform corrosion, and linked to the properties of iron sulphide (FeS) layers that forms at the corroding interface. This paper investigates the corrosion characteristics of carbon steel in H2S-containing environments focussing on the early stage kinetics of FeS formation and its interaction with corrosion inhibitors (CI). Experiments were conducted in 3.5 and 5.8 wt% NaCl solution at 80 °C in 10% H2S-90% CO2-containing environments. In-situ electrochemical responses were measured using the linear polarisation resistance (LPR) technique. This was combined with post-experiment surface analysis; scanning electron microscopy (SEM) and X-ray diffraction (XRD) to investigate the nature and morphology of formed FeS. 3D surface profilometry was used to investigate the pitting corrosion characteristics of carbon steel caused by FeS interaction with CI. The results show a fast kinetics of FeS formation by direct reduction of H2S(aq) with a distinct and easily identifiable morphology, and evidence of minimum level of ferrite dissolution. The early stages of FeS formation and its interaction with CI have a strong influence on the overall corrosion characteristics of carbon steel. A dose of 30 ppm of a commercial corrosion inhibitor (CI); salts of nitrogenous molecules with a fatty acid group, at the corrosion interface induced a competition for surface absorption between CI and emerging FeS. Over the 48 h duration of this test, the FeS formation process was delayed and the mechanisms of its formation quickly became the main driver of pitting corrosion. The amount of CI dosed in this study was not able to prevent FeS-induced pitting corrosion attack on the surface.