Metastable Sulfide Research Articles

Sulfidation of Ni-bearing goethites to pyrite: The effects of Ni and implications for its migration between iron phases

Goethite and pyrite are common iron minerals in oxic or anoxic environments, respectively, both minerals being major reservoirs for Nickel, a bio-essential element. Mineral transformation between goethite and pyrite is frequent owing to the alternation of oxic and anoxic conditions in sulfate-rich environments. This mineral transformation has been amply studied, but the effect of Ni on this transformation and its fate along it remain poorly understood. Sulfidation of Ni-free and Ni-containing (through adsorption or isomorphic substitution) goethites was thus studied experimentally by reacting goethite with dissolved S(-II) (molar Fe:S≈1:1). X-ray diffraction and associated Rietveld refinement, thermogravimetric analysis, scanning/transmission electron microscopy, X-ray absorption spectroscopy, and wet chemistry were used to monitor mineralogical evolutions and unravel Ni association with reaction products. After 44 days of sulfidation, about half of initial goethite converted to iron sulfides: thermodynamically stable pyrite (67%–93%) with minor contents of mackinawite (2%–15%) and greigite (5%–25%). Although the overall content of iron sulfides formed was essentially independent of Ni presence, Ni hampered the conversion from metastable iron sulfides (i.e., mackinawite and greigite) to pyrite (67%–78% vs. 93%, in the presence and absence of Ni, respectively). Pyrite formation from metastable sulfide precursors yielded a uniform Ni distribution in newly formed pyrite, regardless of the initial Ni association with goethite. Although no Ni was released to solution during pyrite formation, Ni incorporation to pyrite results in an increased risk of release to the environment as iron sulfides will be oxidized when exposed to air and water in supergene environments, leading to highly acidic conditions favoring Ni solubility and mobility.

Reverse Conversion Treatment of Gaseous Sulfur Trioxide Using Metastable Sulfides from Sulfur-Rich Flue Gas.

Sulfur trioxide (SO3) is an unstable pollutant, and its removal from the gas phase of industrial flue gas remains a significant challenge. Herein, we propose a reverse conversion treatment (RCT) strategy to reduce S(VI) in SO3 to S(IV) by combining bench-scale experiments and theoretical studies. We first demonstrated that metastable sulfides can break the S-O bond in SO3, leading to the re-formation of sulfur dioxide (SO2). The RCT performance varied between mono- and binary-metal sulfides, and metastable CuS had a high SO3 conversion efficiency in the temperature range of 200-300 °C. Accordingly, the introduction of selenium (Se) lowered the electronegativity of the CuS host and enhanced its reducibility to SO3. Among the CuSe1-xSx composites, CuSe0.3S0.7 was the optimal RCT material and reached a SO2 yield of 6.25 mmol/g in 120 min. The low-valence state of selenium (Se2-/Se1-) exhibited a higher reduction activity for SO3 than did S2-/S1-; however, excessive Se doping degraded the SO3 conversion owing to the re-oxidation of SO2 by the generated SeO32-. The density functional theory calculations verified the stronger SO3 adsorption performance (Eads = -2.76 eV) and lower S-O bond breaking energy (Ea = 1.34 eV) over CuSe0.3S0.7 compared to those over CuS and CuSe. Thus, CuSe1-xSx can serve as a model material and the RCT strategy can make use of field temperature conditions in nonferrous smelters for SO3 emission control.

A simplified distillation-based sulfur speciation method for sulfidic soil materials

Speciation of inorganic sulfur species, mainly pyrite and metastable iron sulfides by operationally defined methods, is widely used for risk assessment of acid sulfate soils by quantifying the acidity producing elements, as well as for general characterisation of marine sediments and subaqueous soils. “Traditional” sulfur speciation methods commonly use highly specialised glassware which can be cumbersome for the operator, or, require long reaction times which limit the usability of the method. We present a simplified method which has a sufficiently low limit of detection (0.002%) and quantitation (0.006%) required for the analysis of sulfidic sulfur in acid sulfate soil materials. Commercially available sulfide reagents were used for determining reproducibility and the method was assessed on natural sulfidic soil materials, including fine to coarse grained soil materials as well as sulfide bearing peat, with a large variation of metastable sulfide and pyrite content.

Characteristics of sulfide bearing soil materials in peat extraction areas in N-Finland

Concern has been raised about the potential formation of acid sulfate soils and associated environmental problems related to peat extraction and, thus, peat, sediment and till characteristics of 15 well drained peat extraction fields were investigated in northern and northwestern Finland. The aim was to identify and characterize the occurrence/abundance of potential acid (hypersulfidic) and actual acid sulfate soil materials as well as metals with regards to their depositional environment (marine/non-marine), black schists and soil material properties. Sulfide-bearing marine sediments were commonly found; the highest contents and thickness of sulfide sediments were found in areas <50 m above the current sea level (a.c.s.l.), while the sulfide contents were relatively low in the mineral soil materials (mainly till) in the non-marine areas (>100 m a.c.s.l.). The highest content of sulfides in sediments was typically found just below the peat layer. The sulfides existed mostly as pyrite (up to 3.5 wt% S) but were occasionally also mixed with more reactive metastable sulfide (Fe:S ratio in the order of 1:1), which coincide with high Fe concentrations, indicating that an abundance of Fe2+ can diminish the rate of pyrite formation. Sediments contained very high amounts of potential acidity, but in-field oxidation of the sediments was very limited. Although the sulfur contents were much lower (max 0.3% S), several of the till samples still became acidic (pH < 4) upon oxidation, and contained, thus, some amounts of potential acidity due to a pore buffering capacity. Consequently, during peat extraction most of the acidity is still retained in sediments limiting environmental consequences and, thus, focus should be on appropriate management to prevent oxidation and leaching after peat extraction has been finished. Locally high Mn and Zn concentrations were found in the sediments in black schist areas, indicating that Zn and Mn have migrated with the ground water from the schists to the sediment layers. In several black schist areas, the peat layer contained high amounts of sulfides with a corresponding high potential acidity as well as elevated As, Pb and Zn. This indicates an upward transport of sulfur and some metals (As, Pb and Zn) through capillary rise and/or plant uptake and/or through lateral water transport from surrounding black schist affected soil material. Air pollution, i.e. atmospheric distribution, was most likely a source for high concentrations of Cd, Hg and Sr concentrations in the peat.

Sulfate reduction and alterability of sulfur species in sediments of an estuary with irregular hydrological regime

The irregular hydrological regime in Patos Lagoon estuary has been suggested as having a distinctive influence on sulfur speciation in sediments. We performed an investigation for different prolonged hydrological conditions focusing on the distribution of sulfides (acid volatile sulfide (AVS), chromium reducible sulfide (CRS), and Free-S2-) in sediment cores from salt marsh and non-vegetated shallow zone. Significant differences in sulfides content and distribution between the different hydrological periods were found. The predominance of more reducing conditions was observed during the freshwater period. It reflects a higher total reducible inorganic sulfur (TRIS) content in this period, with a great accumulation of AVS in sediments (> 100 mg kg-1). In the maximum salinity period, more oxidizing conditions prevailed, which significantly decreased the concentrations of metastable sulfides. The intense bioirrigation process exerts control over sulfide formation and distribution, which is as important as that exerted by the variations of the hydrological regime.

Ionization of Aromatic Sulfides in Nonpolar Media: Free vs Reaction-Controlled Electron Transfer

The primary products of the bimolecular free electron transfer (FET) from aromatic sulfides (PhSCH2Ph, PhSCHPh2, PhSCPh3) to n-butyl chloride radical cations are two radical cation conformers: a dissociative and a metastable one. In analogy with formerly studied donor systems, this result seems to reflect femtosecond oscillations in the ground state of the sulfides such as torsion motions around the Ar-S bond. This motion is accompanied by a marked electron fluctuation within the HOMO (or the n) orbitals. The FET products observed in the nanosecond time scale such as the metastable sulfide radical cations (Ar-S-CR3*+), the dissociation products R3C+; and R3C*, and their (experimentally) nondetectable counterparts Ar-S* as well as Ar-S+ can be understood with the simplified assumption of two extreme conformations, namely a planar and a twisted donor molecule. Using mediator radical cations (benzene, butylbenzene, biphenyl), the stepwise reduction of the free energy of the electron transfer from -DeltaH = 2.5 to <or=0.5 eV changes the dissociation pattern of the sulfide radical cations toward a uniform product such as the metastable sulfide radical cation. From that, we tentatively interpret the mechanism of the studied electron transfer as diffusion-controlled (collision-determined FET) at higher -DeltaH values and as reaction-controlled at -DeltaH below 0.5 eV.

High-temperature corrosion in mixed gas environments

Scaling reactions between pure metals and multiple oxidant gases are reviewed briefly. It is recognized that elemental oxidant activities are usually so low that the actual reactant species are heteronuclear molecules such as SO2, CO2, etc. The formation of duplex, sulfide-oxide scales on iron and manganese, even when sulfide is unstable with respect to oxide, is attributed to direct reaction with SO2. The persistence of the metastable sulfide is due to its preservation by the rapidly growing scale. The reaction of pure chromium with a number of mixed gases is also discussed. The continued formation of carbides and nitrides beneath an external Cr2O3 scale layer indicates that the latter material is permeable to gas species. Interaction among different gas species is observed, and is attributed to selective adsorption on internal surfaces within the chromium oxide. New work on the reaction of alloys with mixed gases is reported. Several austenitic heat-resistant alloys were exposed at 1000°C to gases containing one, two or all of the oxidants carbon, sulfur and oxygen. Gases containing two or more oxidants produced multiple zones of internal precipitation. The precipitates were chromium-rich oxides, sulfides and carbides arranged in order of thermodynamic stability: oxides beneath the external scale, carbides deepest within the alloys and sulfides in an intermediate zone overlapping the oxide zone. Each precipitate zone widened according to parabolic kinetics. This finding confirms the as yet untested prediction made by J. L. Meijering in 1971. However, the rate at which a particular zone grows changes according to presence of other oxidants. Interactions between the oxidants can be large and reaction rates are currently not predictable.

Kinetics and mechanisms of the oxidation of chromium in H2-H2O-H2S gas mixtures

The oxidation of pure chromium in H2-H2O-H2S gas mixtures was studied as a function of gas composition at 900°C. Oxidation kinetics were measured using a thermogravimetric apparatus, and the oxidation products were characterized using scanning electron microscopy (SEM) and scanning transmission electron microscopy (STEM). Chromia scales formed when the H2O/H2S ratio was about 10 or greater. Scales that comprised a mixture of Cr2O3 and chromium sulfides formed when the H2O/H2S ratio was about 3, even though Cr2O3 was the thermodynamically stable phase under these conditions; i.e., a kinetic boundary exists for pure chromium in H2-H2O-H2S gas mixtures. The transition from chromia scale formation to the formation of scales containing both oxide and sulfide with a change in gas composition (decrease in the H2O/H2S ratio) is associated with an inhibition of the overgrowth of growing, metastable sulfide nuclei by the thermodynamically stable Cr2O2 phase. Presulfidation experiments confirmed that metastable chromium sulfide can continue to grow after H2O is added to the gas phase when the H2O/H2S ratio in the gas phase is less than a critical value at the temperature of interest.

Oxidation-Sulfidation of an Fe-25Cr-10Al alloy in H 2-H 2O-H 2S gas mixtures

The “kinetic boundary” for the oxidation of an Fe-25Cr-10Al alloy (where the composition is in approximate weight per cent) in H 2-H 2O-H 2S gas mixtures at 900°C has been measured. The kinetic boundary occurs at much lower P H2O/ P H2S ratios in the gas phase than for an Fe-25Cr binary alloy ( P H2O/ P H2S reduced from about 50 to about 7). The shift in the boundary is attributed to an enrichment of sulfide nuclei, formed in the early stages of reaction, with aluminum, at the expense of iron. This enhances the overgrowth of metastable sulfide nuclei with oxide at a given P H2O/ P H2S ratio.

Factors controlling the proportionality of vanadium to nickel in crude oils

The proportionality of V to Ni in crude oils is determined by the environmental conditions in which their source rocks were deposited. Thermal maturation, migration, and reservoir alterations may change the concentrations of these two metals by addition or subtraction of more labile portions of a crude oil, but their tenacious bonding with high-MW organics suggests that their proportionality to one another should remain unchanged. Eh-pH diagrams offer an explanation of the factors controlling their proportionality and its relationship with S contents. Three Eh-pH regimes are proposed for the natural system. Regime I represents conditions under which Ni +2 is available for bonding and vanadium is unavailable because of its quinquivalent state. Crude oils expelled from source rocks deposited within this regime are expected to have V (Ni + V) less than 0.10 and low S (<1 weight percent). Regime II represents conditions under which Ni +2-Nickelous cations and vanadyl cations are available with vanadyl cations being hindered in part by the formation of hydroxides and nickelous cations being hindered in part of metastable sulfide ions. Source rocks deposited within this regime expel crude oils with low S contents and V-Ni fractions that range from 0.10 to 0.90. Regime III represents conditions under which vanadyl and trivalent vanadium cations are available for bonding but Ni +2 may be partially hindered by sulfide complexing. Source rocks deposited within this regime expel crude oils that have high S contents and V-Ni fractions greater than 0.50.