Synchrotron scanning photoemission microscopy of homogeneous and heterogeneous metal sulfide minerals

Scanning photoemission microscopy (SPEM) has been applied to the investigation of homogeneous and heterogeneous metal sulfide mineral surfaces. Three mineral samples were investigated: homogeneous chalcopyrite, heterogeneous chalcopyrite with bornite, and heterogeneous chalcopyrite with pyrite. Sulfur, copper and iron SPEM images, i.e. surface‐selective elemental maps with high spatial resolution acquired using the signal from the S 2p and Cu and Fe 3p photoemission peaks, were obtained for the surfaces after exposure to different oxidation conditions (either exposed to air or oxidized in pH 9 solution), in addition to high‐resolution photoemission spectra from individual pixel areas of the images. Investigation of the homogeneous chalcopyrite sample allowed for the identification of step edges using the topography SPEM image, and high‐resolution S 2p spectra acquired from the different parts of the sample image revealed a similar rate of surface oxidation from solution exposure for both step edge and a nearby terrace site. SPEM was able to successfully distinguish between chalcopyrite and bornite on the heterogeneous sample containing both minerals, based upon sulfur imaging. The high‐resolution S 2p spectra acquired from the two regions highlighted the faster air oxidation of the bornite relative to the chalcopyrite. Differentiation between chalcopyrite and pyrite based upon contrast in SPEM images was not successful, owing to either the poor photoionization cross section of the Cu and Fe 3p electrons or issues with rough fracture of the composite surface. In spite of this, high‐resolution S 2p spectra from each mineral phase were successfully obtained using a step‐scan approach.     

Stable Sulfur Isotope Effects Related to Local Intense Sulfate Reduction in a Tidal Sandflat (Southern North Sea): Results from Loading Experiments

Abstract

Anoxic sediment surfaces coloured black by iron monosulfides (“black spots”) evolve in tidal sandflats of the Wadden Sea (southern North Sea) as a result of the degradation of buried organic matter. To follow the short- and long-term effects of organic matter burial on pore water and sediment isotopic biogeochemistry, formation of artificial black spots was initiated on the Groninger Plate (site RP63) in the backbarrier tidal flats of Spiekeroog island. Changes in concentrations (DOC, TA, TOC, sulfate, sulfide, TRS, Fe) and isotopic compositions (sulfate, sulfide, TRS, pyrite, TOC) were followed for up to 12 months and compared to reference areas. 13°C ratios of TOC clearly mirror the early diagenetic degradation of organic matter. At least temporarily closed system sulfate reduction is inferred for the artificial black spot from the variation of sulfate concentrations and stable sulfur isotope partitioning, In the interstitial waters of the black spot, 34S/32S values of coexisting dissolved sulfate and sulfide yield fractionation degrees between ?5 and ?25%. On the reference area, 34S/32S are fractionated by ?32 to ?42% as calculated from the isotope composition of solid phase reduced sulfur and pore water sulfate. Sulfur isotope fractionation seems to increase with decreasing sulfate reduction rate. Limiting factor seems to be the availability of DOC. Between the pyrite pool and the dissolved sulfide in the black spot, no significant isotope exchange is observed within 12 months.     

Iron speciation in fault gouge from the Ushikubi fault zone central Japan

Chemical species of iron and sulfur were measured using ⁵⁷Fe Mössbauer spectroscopy and X-ray near edge structure, respectively, for the fault gouge samples collected from two sites along the ENE-WSW trending Ushikubi fault zone in central Japan. These gouge samples have distinguishable variations in their physical properties such as surface color and structure and these features are also reflected by the chemical speciation of iron and sulfur. Newly formed minerals, including calcite, dolomite, siderite, iron sulfide and pyrite, have close relation to the colors of fault gouge and respective to the geochemical environment within the fault zone. In addition, the variations in iron and sulfur species may have significance to evaluate the redox conditions in the fractures and furthermore to estimate the history and activity of the faults. Generally there is observacious enrichment of reducing species of iron and sulfur as well as chlorite in the relatively younger fracture, indicating favorable connection pathway with deep position and the fault zone is active. On the other hand, the stable fracture with a longer history is relatively enriched in ferric iron species and almost no sulfur in the gouge. These results from iron and sulfur speciation have a good agreement with evidence indicated by ¹⁴C dating from this fault zone.     

Surficial phase-identification and structural profiles from weathered natural pyrites: A grazing-incidence X-ray diffraction study

Five pyrites with original crystal face (1 0 0) with different tarnish colours were selected from one pyrite-bearing ore sample from Tongling multi-metal deposit, Anhui, China. They are henna mottled with dark violet, yellow mottled with red, yellow, blue mottled with violet and reddish brown in surface colour. Grazing-incidence X-ray diffractometry (GIXRD) was used to study the phases formed or precipitated on the surface of pyrite (1 0 0) face during chemical weathering. By changing the incident angle, GIXRD can provide information on the changes in the mineral phases from the surface as a function of depth. Products formed or precipitated on the surface of pyrite (1 0 0) face are one or several sulfur or iron-bearing hydrated oxides and include gypsum, jalpaite, goethite, goldichite. The sulfur-bearing minerals present on the surface imply the oxidation of sulfur to sulfate, or the reduction of sulfur to sulfide. By analyzing a series of GIXRD patterns obtained at different angles of incidence for a single pyrite, the mineral assemblage differs from the surface into the body of the crystal. Taking the reddish brown sample as an example, four diffraction profiles at 2.575, 2.2105, 1.9118 and 1.613 Å are present in the pattern of a 2° incident angle experiment whereas they cannot be found at a GIXRD angle smaller than 0.6°.     

Influence of ferric iron on the electrochemical behavior of pyrite

The electrochemical behavior of a pyrite electrode in a sulfuric acid solution with different concentrations of ferric iron (Fe³⁺) was investigated using electrochemical techniques including measurements of open circuit potential, cyclic voltammetry, Tafel polarization curves and electrochemical impedance spectroscopy (EIS). The results show that the pyrite oxidation process takes place via a two-step reaction at the interface of the pyrite electrode and the electrolyte, and that a passivation film composed of elemental sulfur, polysulfides, and metal-deficient sulfide is formed during the process of the first-step reaction. Ferric iron plays an important role in the dissolution of pyrite by enhancing the direct oxidation. The Tafel polarization curves indicate that the polarization current of the pyrite electrode increases with an increase in Fe³⁺ concentration. It has also been shown that the higher concentration of Fe³⁺, the more easily the pyrite can be transformed into the passivation region. Moreover, the EIS response is found to be sensitive to changes in Fe³⁺ concentration.     

The effect of surface sulfur on the oxidation of zirconium

In order to examine the effect of surface sulfur on the oxidation of zirconium, we have tried to make a quantitative analysis of sulfur segregation on Zr and made a study of the oxidation of sulfur segregated Zr. Depth profiles of the S-segregated Zr surface determined after high temperature annealing in vacuum show that the saturated surface concentration of sulfur has an S/Zr atomic ratio of about 1 and the total amount of segregated S is about 1 monolayer. These values do not depend on the annealing time. The S-segregated surface is exposed to an oxygen atmosphere in a pressure range of 10⁻⁶−10⁻⁵ Pa up to a total exposure of 9000 L at RT. Changes of the surface concentration of S, O and Zr are monitored by in situ AES analysis. Depth profiling of O, S and Zr for the oxidized specimen is also carried out. Surface oxidation is clearly delayed by segregated sulfur. This effect, however, is not so significant as for the S---Fe system, and three oxidation stages are clearly distinguished in the same manner as in the oxidation of clean Zr surfaces. This is because S is simultaneously oxidized and removed in the form of a volatile oxide such as SO or SO₂.     

Iron oxide nanoparticle synthesis in aqueous and membrane systems for oxidative degradation of trichloroethylene from water

The potential for using hydroxyl radical (OH^?) reactions catalyzed by iron oxide nanoparticles (NPs) to remediate toxic organic compounds was investigated. Iron oxide NPs were synthesized by controlled oxidation of iron NPs prior to their use for contaminant oxidation (by H₂O₂ addition) at near-neutral pH values. Cross-linked polyacrylic acid (PAA) functionalized polyvinylidene fluoride (PVDF) microfiltration membranes were prepared by in situ polymerization of acrylic acid inside the membrane pores. Iron and iron oxide NPs (80–100 nm) were directly synthesized in the polymer matrix of PAA/PVDF membranes, which prevented the agglomeration of particles and controlled the particle size. The conversion of iron to iron oxide in aqueous solution with air oxidation was studied based on X-ray diffraction, Mössbauer spectroscopy and BET surface area test methods. Trichloroethylene (TCE) was selected as the model contaminant because of its environmental importance. Degradations of TCE and H₂O₂ by NP surface generated OH^? were investigated. Depending on the ratio of iron and H₂O₂, TCE conversions as high as 100 % (with about 91 % dechlorination) were obtained. TCE dechlorination was also achieved in real groundwater samples with the reactive membranes.     

Cu adsorption on pyrite (1 0 0): Ab initio and spectroscopic studies

Surface optimised S 2p photoelectron spectra show that both surface S²⁻ monomers and (S-S)²⁻ dimers are present at pyrite (1 0 0) fracture surfaces. In order to determine which sulfur species are involved in Cu adsorption, fresh pyrite surfaces were exposed to Cu²⁺ in solution. The S 2p spectra suggest that both types of S surface species are involved in the mechanism of Cu adsorption (activation). Ab initio density functional theory was used to model Cu adsorbed onto pyrite (1 0 0) to support the interpretation of the spectroscopy. Mulliken population analysis confirms the charge distribution suggested by the core line shifts as observed in the photoelectron spectra. The ab initio calculations were consistent with a two-coordinate bond between Cu(I), a surface S monomer and a surface S dimer.     

Surface processing techniques using controlled environments and atomically-clean surfaces: Nitrogen-stabilized iron

Purposeful exposure of an atomically clean surface to controlled environments is explored as a technique for obtaining surfaces with desired properties. The incorporation of nitrogen into atomically clean iron at room temperature is discussed as an example of clean surface modification, resulting in significant enhancement of resistance to corrosion at room temperature in dry and moist air, relative to intially air-exposed samples. Treated and untreated sides of samples — subsequently exposed to air and moist air environments — have been characterized by optical and scanning electron microscopy, grazing-incidence electron diffraction, and depth-profiling Auger spectroscopy. Nitrogen treatment was found to inhibit iron from forming crystalline oxides.     

Mössbauer spectroscopic study on chemical changes of iron compounds with the aid of sulfate-reducing bacteria

⁵⁷Fe Mössbauer spectra were measured of reaction products formed during an incubation experiment with sulfate-reducing bacteria, which were isolated from estuarine sediments of the Tama River in Tokyo. The spectrum of the product incubated for several days showed some overlapping sextets. This product had a different chemical form from amorphous iron monosulfide produced by inorganic reaction between ferrous and sulfide ions. It was estimated that the structure of nearest neighbor of iron in this product was similar to that of pyrrhotite (Fe_1?x S). After several months of incubation, other singlet and doublet appeared successively on the spectrum, corresponding to mackinawite (FeS_1?x ) and new sulfide, respectively. Both values of isomer shift and quadrupole splitting of new sulfide increased with increasing incubation time and approached those of pyrite (FeS₂). Extended X-ray absorption fine structure (EXAFS) showed that iron atoms were coordinated by sulfur in the incubation product.     

Interaction of H2S with α-Fe2O3(0 0 0 1) surface

The atomic-scale structural changes in an α-Fe₂O₃ (hematite) (0 0 0 1) surface induced by sulfidation and subsequent oxidation processes were studied by X-ray photoemission spectroscopy, LEED, and X-ray standing wave (XSW) measurements. Annealing the α-Fe₂O₃(0 0 0 1) with a H₂S partial pressure of 1 × 10⁻⁷ Torr produced iron sulfides on the surface as the sulfur atoms reacted with the substrate Fe ions. The oxidation state of the substrate Fe changed from 3+ to 2+ as a result of the sulfidation. The XSW measured distance of the sulfur atomic-layer from the unrelaxed substrate oxygen layer was 3.16 Å. The sulfide phase consisted of three surface domains identified by LEED. Formation of the two-dimensional FeS₂ phase with structural parameters consistent with an outermost layer of (1 1 1) pyrite has been proposed. Atomic oxygen exposure oxidized the surface sulfide to a sulfate () and regenerated the α-Fe₂O₃(0 0 0 1) substrate, which was indicated by a (1 × 1) LEED pattern and the re-oxidization of Fe to 3+.     

Sulfur and oxygen isotope geochemistry of acid mine drainage--the polymetallic sulfide deposit "himmelfahrt fundgrube" in Freiberg (Germany)

We investigated physical, chemical and isotope (S, O) parameters of sulfate from acid mine drainage from the polymetallic sulfide ore deposit Freiberg (Gennany), which was mined for more than eight hundred years. Two main groups of water were distinguished: 1. Flowing mine water with sulfate concentrations of less than 9,000 mg/l and pH values higher than 3.2, 2. Pore water in weathered low grade ores and pools with sulfate concentrations higher than 9000mg/l and pH values below 3.2. The sulfur and oxygen isotope composition of sulfate from flowing mine waters reflects mixing of sulfate from two sulfur sources: a) atmospheric sulfur from precipitation and b) sulfate formed as a result of sulfide oxidation processes. Sulfur isotope values of mine water sulfate were used to estimate the contribution of sulfate derived through oxidation of sulfides. The sulfur isotope composition of pore water sulfate and precipitated sulfate (jarosite) from weathered low grade ore samples is identical to the sulfur isotope composition of primary sulfides. The oxygen isotope composition of pore water sulfate from low grade ore samples indicates that the oxidation process proceeds relatively slowly in 02-depleted waters, probably without significant microbial catalysis.     

Surface composition modification of high-carbon low-alloy steels oxidized at high temperature in air

Segregating alloys across a metal/oxide interface, which occurs when an iron alloy is heated at high temperature in air, was studied on five high-carbon low-alloy steels. The metallographic analyses showed differences between the oxidation kinetics, the decarburisation rates of the surfaces and the number of surface defects. The results of the AES analyses enabled the characterization of the concentration profiles of the alloy elements and to explain the differences observed between the oxidation kinetics, the decarburisation rates and the number of surface defects. All the concentration profiles are discussed and possible mechanisms are proposed in order to understand the profiles obtained.     

Evolution of steel surface composition with heating in vacuum and in air

X-ray photoelectron spectroscopy (XPS) has been used to investigate the changes in surface composition of three steels as they have undergone heating. The steels were mild steel, and two austenitic stainless steels, commonly designated 304 and 316 stainless steels. XPS measurements were made on the untreated samples, and then following heating for 30 min in vacuo and in a 1 × 10⁻⁶ Torr partial pressure of air, at temperatures between 100 °C and 600 °C.Mild steel behaves differently to the two stainless steels under the heating conditions. In mild steel the iron content of the surface increased, with oxygen and carbon decreasing, as a function of increasing temperature. The chemical state of the iron also changed from oxide at low temperatures, to metallic at temperatures above 450 °C.In both stainless steels the amount of iron present in the surface decreased with increasing temperature. The decrease in iron at the surface was accompanied by an increase in the amount of chromium at the steel surface. At temperatures above 450 °C the iron in both 304 and 316 stainless steels showed significant contributions from metallic iron, whilst the chromium present was in an oxide state. In 316 stainless steel heated to 600 °C there was some metallic chromium present in the surface layer.The surfaces heated in air showed the least variation in composition, with the major change being the loss of carbon from the surfaces following heating above 300 °C. There was also a minor increase in the concentration of chromium present on both the stainless steels heated under these conditions. There was also little change in the oxidation state of the iron and chromium present on the surface of these steels. There was some evidence of the thickening of the surface oxides as seen by the loss of the lower binding energy signal in the iron or chromium core level scans.The surfaces heated in vacuum showed a similar trend in the concentration of carbon on the surfaces, however the overall concentration of oxygen decreased throughout the heating of these steels. There were also significant changes in the oxidation state of the iron and chromium on these surfaces with significant amounts or iron and chromium present in the metallic form following heating up to 600 °C.It appears that the carbon contamination on the surfaces plays an important role in the fate of the surface oxide layer for all of the steels heated in a vacuum environment.     

Chemical and electronic properties of sulfur-passivated InAs surfaces

Treatment with ammonium sulfide ((NH₄)₂S_x) solutions is used to produce model passivated InAs(0 0 1) surfaces with well-defined chemical and electronic properties. The passivation effectively removes oxides and contaminants, with minimal surface etching, and creates a covalently bonded sulfur layer with good short-term stability in ambient air and a variety of aqueous solutions, as characterized by X-ray photoelectron spectroscopy, atomic force microscopy, and Hall measurements. The sulfur passivation also preserves the surface charge accumulation layer, increasing the associated downward band bending.     

利用黄铁矿去除地下水中Se(Ⅳ)污染的XPS分析

硒是生物生长所需的微量元素,但是过度摄入对人体是有害的。主要利用X射线光电子能谱仪(X-ray photoelectron spectroscopy, XPS)分析了湿法制备的黄铁矿去除水中Se(Ⅳ)的产物形态。利用X射线衍射仪(X-ray diffraction, XRD)和扫描电子显微镜(scanning electron microscope, SEM)对湿法球磨制备的黄铁矿进行了表征。XRD图谱表明该法制备的黄铁矿纯度较高,图谱中除了FeS₂特征衍射峰外基本没有杂峰;SEM观测发现处理后的黄铁矿颗粒形状接近球形,尺寸在80～180 nm范围内。上述相关表征结果表明,湿法球磨制备的黄铁矿具有颗粒粒径更小、比表面积更大、反应活性更高等优点。实验结果表明, 在12 h反应时间内, 该法制备的黄铁矿颗粒对初始浓度为20 mg·L-1的Se(Ⅳ)去除效率达到95%。对该组实验数据进行动力学拟合,其结果满足准一级动力学方程, 表观反应速率常数k_obs为0.26 h-1。XPS分析得到如下结论：(1)反应后黄铁矿中铁和硫的结合能均有所降低,即黄铁矿表面出现了新价态的铁元素和硫元素;(2)在反应后的黄铁矿表面有新形态的硒—Se(0)形成,同时也检测到了Se(Ⅳ)形态,但Se(0)的含量占主导优势。由此推测,黄铁矿去除水体中的Se(Ⅳ)以氧化还原为主, 同时伴随着吸附反应。该结果对于利用黄铁矿去除水体中具有高毒性的Se(Ⅳ)具有重要的理论意义和实际应用价值。     

Sulfur and Oxygen Isotope Geochemistry of Acid Mine Drainage—The Polymetallic Sulfide Deposit “Himmelfahrt Fundgrube” in Freiberg (Germany)

Abstract

We investigated physical, chemical and isotope (S, O) parameters of sulfate from acid mine drainage from the polymetallic sulfide ore deposit Freiberg (Germany), which was mined for more than eight hundred years. Two main groups of water were distinguished:

1. Flowing mine water with sulfate concentrations of less than 9000 mg/1 and pH values higher than 3.2

2. Pore water in weathered low grade ores and pools with sulfate concentrations higher than 9000 mg/1 and pH values below 3.2.

The sulfur and oxygen isotope composition of sulfate from flowing mine waters reflects mixing of sulfate from two sulfur sources: a) atmospheric sulfur from precipitation and b) sulfate formed as a result of sulfide oxidation processes. Sulfur isotope values of mine water sulfate were used to estimate the contribution of sulfate derived through oxidation of sulfides. The sulfur isotope composition of pore water sulfate and precipitated sulfate (jarosite) from weathered low grade ore samples is identical to the sulfur isotope composition of primary sulfides. The oxygen isotope composition of pore water sulfate from low grade ore samples indicates that the oxidation process proceeds relatively slowly in O₂-depleted waters, probably without significant microbial catalysis.     

The adsorption of adenine on mineral surfaces: Iron pyrite and silicon dioxide

The adsorption of the nucleobase adenine on surfaces of the minerals iron pyrite and silica has been studied by photoemission and soft X-ray photoabsorption spectroscopy. Pyrite samples were prepared by fracture under nitrogen followed by transfer to ultrahigh vacuum, or by cleavage in vacuum. By comparing data with multilayer spectra, adenine was found to chemisorb on pyrite, with small changes in the valence band spectrum, and stronger changes in the NEXAFS spectrum. The molecules were bonded with the molecular plane at a steep angle to the surface plane. On silica the molecule was found to adsorb at a reduced angle to the surface. The C and N 1s photoemission spectra on this surface suggest chemisorption, although the nitrogen NEXAFS spectra are similar to multilayer spectra.     

Investigation of the initial stages of oxidation of microcrystalline silicon by means of X-ray photoelectron spectroscopy

XPS Si2p spectra of microcrystalline silicon (μc-Si), prepared by plasma chemical transport are reported and the initial stages of oxidation are studied: In comparison with single crystal Si(111) surfaces, μc-Si samples are remarkable resistant to surface oxidation. A short exposure to air results in negligible oxygen adsorption (intensity ratio of 01s to Si2p peaks is less than 0.018 after more than3 × 10¹¹ Langmuirs exposure to air). Intensive oxidation treatment is required to produce an oxide layer and evidence supporting a preferential grain boundary oxidation mechanism is presented. The surface plasmon structure observed in the Si2p spectrum provides complementary information on the remarkably low oxidation rate of the crystallite surfaces as compared to the grain boundaries.     

XPS investigation of chemical states in monolayers: Recent progress in adsorbate redox chemistry on sulphides

The paper presents new results on the adsorption of 2-mercaptobenzothiazole (MBT) and 2-mercaptobenzoxazole (MBO) on galena (PbS) and pyrite (FeS₂). Adsorption of MBT and MBO on galena and pyrite surfaces from 10⁻⁵ M aqueous solution results in monolayers of chemisorbed deprotonated molecules bound to the surface via the thiolate group. A secondary interaction between the lone pair of the nitrogen and the sulphide surface may be possible. From the unequal intensity of the two S2p emissions in MBT an upright orientation of the molecule can be assumed. Adsorption of MBT from 10⁻⁴ M aqueous solution leads to the formation of 2,2′-dithiobis(benzothiazole) as an oxidation product of MBT. Oxidation of MBO is not observed which may be the result of its 100 mV higher redox potential.

Optical activation of the MBT oxidation on CdS and FeS₂ in contrast to PbS is suggested from the increase of the S2p signals attributed to the bridging –S–S– group of BBTD during illumination. We conclude that a surface photovoltage reducing the band bending may be responsible for the higher oxidation rate at the pyrite/electrolyte interface during illumination with respect to the dark.

Oxidation of sulphide surfaces by UV light in air produces lead(II) sulphate soluble in aqueous solution. Dissolved Pb²⁺ ions lead to the formation and precipitation of a Pb(mbt)₂ complex in alkaline MBT solution.