塔里木盆地奥陶系碳酸盐岩中黄铁矿的成因

塔里木盆地下古生界(特别是奥陶系)碳酸盐岩地层中常见大量自生黄铁矿存在于碳酸盐岩、裂缝和溶蚀孔洞以及岩溶角砾和岩溶孔洞充填砂泥碎屑物质中。根据产状和硫同位素值,黄铁矿可分为两组,一组的δ34S值范围为-25.7‰～-4.7‰,平均为-17.6‰,为细菌硫酸盐还原作用(BSR)成因,发生在碳酸盐岩被抬升至地表接受岩溶改造的时期;另一组的δ34S值范围为+11.2‰～+31.3‰,平均为21.8‰,是受岩浆作用的影响,在热化学硫酸盐还原作用(TSR)下形成的。通过分析认为塔里木盆地下古生界地层天然气中较高含量的H2S主要是TSR作用的产物。     

The role of carbonate ions in pyrite oxidation in aqueous systems

The mechanism of pyrite oxidation in carbonate-containing alkaline solutions at 80 °C was investigated with the help of rate experiments, thermodynamic modeling and diffuse reflectance infrared spectroscopy (DRIFTS). Pyrite oxidation rate increased with pH and was enhanced by addition of bicarbonate/carbonate ions. The carbonate effect was found to be limited to moderately alkaline conditions (pH 8-11). Metastable Eh-pH diagrams, at 25 °C, indicate that soluble iron-carbonate complexes (FeHCO₃⁻, FeCO₃⁰, Fe(CO₃)(OH)⁻ and FeCO₃²⁻) may coexist with pyrite in the pH range of 6-12.5. Above pH 11 and 13, the Fe(II) and Fe(III) hydroxocomplexes, respectively, become stable, even in the presence of carbonate/bicarbonate ions. Surface-bound carbonate complexes on iron were also identified with DRIFTS as products of pyrite oxidation in addition to iron oxyhydroxides and soluble sulfate species. The conditions under which thermodynamic and DRIFTS analyses indicate the presence of carbonate compounds also correspond to those in which the fastest rate of pyrite oxidation in carbonate solutions was observed. Following the Singer-Stumm model for pyrite oxidation in acidic solutions, it is assumed that Fe(III) is the preferred pyrite oxidant under alkaline conditions. We propose that carbonate ions facilitate the electron transfer from soluble iron(II)-carbonate to O₂, increase the iron solubility, and provide buffered, favorable alkaline conditions at the reaction front, which in turn favors the overall kinetics of pyrite oxidation. Therefore, the electron transfer from sulfur atoms to O₂ is facilitated by the formation of the cycle of Fe(II)-pyrite/Fe(III)-carbonate redox couple at the pyrite surface.     

鄂尔多斯盆地东南部奥陶系马家沟组碳酸盐岩中黄铁矿成因

鄂尔多斯盆地东南部广泛发育黄铁矿,通过对黄铁矿的矿物学特征、元素组成、硫同位素等的分析,讨论和揭示了该黄铁矿的成因。岩石矿物学研究结果显示黄铁矿具有多种赋存形式,呈零星或集合体充填于膏溶孔和溶蚀孔洞中,或与层状硬石膏相伴生;硫同位素地球化学分析结果显示,黄铁矿的δ34S值介于10. 50‰～24. 00‰之间,平均值为17. 33‰。盆地东南部具备薄层硬石膏、高温驱动和充足的烃类气体等热化学硫酸盐还原作用发生的条件,结合其产状证据认为黄铁矿形成于热化学硫酸盐还原作用。黄铁矿出现的地层中Fe含量较高,介于3 387. 50×10~(-6)～23 112. 50×10~(-6)之间,平均值为13 233. 33×10~(-6),为黄铁矿的形成提供了物质来源。盆地东南部多产低含H2S天然气,研究认为黄铁矿的形成是造成该地区H2S含量较低的主要原因。     

Framboidal pyrite associated with lead-zinc mineralisation in mid-Wales

Framboidal pyrite occurs in the breccia fragments of country rock found in lead-zinc veins, while it is generally absent from unmineralised rocks. It is thought to be cogenetic with the main mineralisation, representing an early stage of deposition.     

Evaluating the S-isotope fractionation associated with Phanerozoic pyrite burial

This study examines the sulfur isotope record of seawater sulfate proxies using δ³⁴S and Δ³³S to place constraints on the average global fractionation (Δ³⁴S_py) associated with pyrite formation and burial and the exponent λ that relates variations of the ³⁴S/³²S to variations of the ³³S/³²S. The results presented here use an analysis of the sulfur isotope record from seawater sulfate proxies and sedimentary sulfide to extract this quantity as the arithmetic difference between δ³⁴S of seawater sulfate and contemporaneous sulfide. It also uses an independent method that draws on inferences about the Δ³³S evolution of seawater sulfate to evaluate this further. These two methods yield similar results suggesting that Δ³⁴S_py and λ changed over the course of the Phanerozoic from slightly lower values of Δ³⁴S_py (lower values of λ) in the early Phanerozoic (Cambrian-Permian) to higher values of Δ³⁴S_py (higher values of λ) starting in the Triassic. This change of Δ³⁴S_py and the exponent λ is interpreted to reflect a change in the proportion of sulfide that was reoxidized and processed by bacterial disproportionation on a global scale. The revised record of Δ³⁴S_py also yields model pyrite burial curves making them more closely resemble model evolution curves for other element systems and global sea level curves. It is suggested that possible links to sea level may occur via changes in the area of submerged continental shelves which would provide additional loci for pyrite burial.The slightly different constraints used by the two approaches to calculate this fractionation may allow for additional information to be obtained about the sulfur cycle with future studies. For instance, the correspondence of these results suggests that the inferred variation of ³⁴S/³²S of pyrite is real, and that there is no significant missing sink of fractionated sulfur at the resolution of the present study (such as might be associated with organic sulfur). Burial of organic sulfur may, however, have been important at some times in the Phanerozoic and shorter timescale deviations between results provided by these methods may be observed with higher resolution sampling. If observed, this would suggest either that the record for pyrite (or less likely sulfate) is biased, or that another sink (possibly as organic sulfur) was important during these times in the Phanerozoic.     

Environmental and diagenetic variations in carbonate associated sulfate: An investigation of CAS in the Lower Triassic of the western USA

An integrated stable isotope, elemental and petrographic analysis of Early Triassic (Spathian) carbonates and evaporites along a proximal to deep environmental transect reveals significant variations in δ³⁴S composition of carbonate associated sulfate (CAS). The variations in the δ³⁴S of CAS are strongly correlated with the Ca/Mg composition of carbonates, suggesting that the variations are driven by the degree of dolomitization. The δ³⁴S of dolostones and evaporites are similar to one another and exhibit lower δ³⁴S values than limestones from all localities.Three hypotheses may explain the differences in δ³⁴S between proximal dolostones/evaporites and inner/middle shelf limestones: (1) limestones experienced anaerobic sulfate reduction and subsequent incorporation of ³⁴S-enriched sulfate into CAS during diagenesis, while dolostones did not—this is unlikely because of the lack of correlation between δ³⁴S_CAS and TOC, as well as other indicators of diagenesis, (2) dolomitization controlled the δ³⁴S_CAS in proximal paleoenvironments, where the source of the ³⁴S depleted fluids was either continentally-derived or the result of Rayleigh distillation during evaporite formation, and (3) a δ³⁴S depth gradient existed during the Early Triassic such that limestones formed in distal waters are more enriched in ³⁴S versus evaporites and dolostones formed in proximal settings—we do not favor this hypothesis because the strong correlation between Ca/Mg and δ³⁴S_CAS implies that dolomitization controls the δ³⁴S_CAS in these samples. Results from subtidal, well-preserved (non-dolomitized) limestones suggest that the δ³⁴S of Spathian seawater sulfate may have been heavier than previously suggested from analyses of evaporite deposits alone.     

Oxygen and sulfur isotope systematics of sulfate produced by bacterial and abiotic oxidation of pyrite

To better understand reaction pathways of pyrite oxidation and biogeochemical controls on δ¹⁸O and δ³⁴S values of the generated sulfate in acid mine drainage (AMD) and other natural environments, we conducted a series of pyrite oxidation experiments in the laboratory. Our biological and abiotic experiments were conducted under aerobic conditions by using O₂ as an oxidizing agent and under anaerobic conditions by using dissolved Fe(III)_aq as an oxidant with varying δ¹⁸O_H2O values in the presence and absence of Acidithiobacillus ferrooxidans. In addition, aerobic biological experiments were designed as short- and long-term experiments where the final pH was controlled at ∼2.7 and 2.2, respectively. Due to the slower kinetics of abiotic sulfide oxidation, the aerobic abiotic experiments were only conducted as long term with a final pH of ∼2.7. The δ³⁴S_SO4 values from both the biological and abiotic anaerobic experiments indicated a small but significant sulfur isotope fractionation (∼−0.7‰) in contrast to no significant fractionation observed from any of the aerobic experiments. Relative percentages of the incorporation of water-derived oxygen and dissolved oxygen (O₂) to sulfate were estimated, in addition to the oxygen isotope fractionation between sulfate and water, and dissolved oxygen. As expected, during the biological and abiotic anaerobic experiments all of the sulfate oxygen was derived from water. The percentage incorporation of water-derived oxygen into sulfate during the oxidation experiments by O₂ varied with longer incubation and lower pH, but not due to the presence or absence of bacteria. These percentages were estimated as 85%, 92% and 87% from the short-term biological, long-term biological and abiotic control experiments, respectively. An oxygen isotope fractionation effect between sulfate and water (ε¹⁸O_SO4-H2O) of ∼3.5‰ was determined for the anaerobic (biological and abiotic) experiments. This measured value was then used to estimate the oxygen isotope fractionation effects between sulfate and dissolved oxygen in the aerobic experiments which were −10.0‰, −10.8‰, and −9.8‰ for the short-term biological, long-term biological and abiotic control experiments, respectively. Based on the similarity between δ¹⁸O_SO4 values in the biological and abiotic experiments, it is suggested that δ¹⁸O_SO4 values cannot be used to distinguish biological and abiotic mechanisms of pyrite oxidation. The results presented here suggest that Fe(III)_aq is the primary oxidant for pyrite at pH < 3, even in the presence of dissolved oxygen, and that the main oxygen source of sulfate is water-oxygen under both aerobic and anaerobic conditions.     

Oxidation of pyrite in low temperature acidic solutions: Rate laws and surface textures

Rate laws have been determined for the aqueous oxidation of pyrite by ferric ion, dissolved oxygen and hydrogen peroxide at 30°C in dilute, acidic chloride solutions. Fresh, smooth pyrite grain surfaces were prepared by cleaning prior to experiments. Initial specific surface areas were measured by the multipoint BET technique. Surface textures before and after oxidation were examined by SEM. The initial rate method was used to derive rate laws.The specific initial rates of oxidation (moles pyrite cm⁻² min⁻¹) are given by the following rate laws (concentrations in molar units): r_sp,Fe³⁺ = −10^−9.74M^0.5_Fe³+M^−0.5_H+ (pH 1–2)r_sp,_o2 = −10^−6.77M^0.5_O2 (pH 2–4)r_sp,_h2o2 = −10^−1.43M_H2O2 (pH 2−4)An activation energy of 56.9 ± 7.5 kJ mole⁻¹ was determined for the oxidation of pyrite by dissolved oxygen from 20–40°C. HPLC analyses indicated that only minor amounts of polythionates are detectable as products of oxidation by oxygen below pH 4; the major sulfur product is sulfate. Ferric ion and sulfate are the only detectable products of pyrite oxidation by hydrogen peroxide. Hydrogen peroxide is consumed by catalytic decomposition nearly as fast as it is by pyrite oxidation.SEM photomicrographs of cleaned pyrite surfaces indicate that prior to oxidation, substantial intergranular variations in surface texture exist. Reactive surface area is substantially different than total surface area. Oxidation is centered on reactive sites of high excess surface energy such as grain edges and corners, defects, solid and fluid inclusion pits, cleavages and fractures. These reactive sites are both inherited from mineral growth history and applied by grain preparation techniques. The geometry and variation of reactive sites suggests that the common assumption of a first-order, reproducible dependence of oxidation rates on surface area needs to be tested.     

Stratabound lead-zinc pyrite ore deposits in upper precambrian carbonate rocks,Rodna Mountains,Romania

The Blazna-Guset mining area is located in the Rodna Mountains, Eastern Carpathians, North Romania. It is mostly covered by the metamorphic rocks of the Rebra Series (Upper Precambrian; K/Ar dating gave 800 m.y.). The middle part of this series — called the Carbonate Formation — contains lead-zinc pyrite ores hosted by prevailingly carbonate rocks. The ores form flat and thin lenses occurring together with fine intercalations of silicate-, graphite- and quartz-bearing rocks within the calcite-dominated limestones. Pyrite, ironpoor sphalerite and galena are the main ore minerals. Chalcopyrite, pyrrhotite and magnetite also occur in small amounts. Within the highly deformed and partly recrystallized parts of the ore bodies bournonite, arsenopyrite and pearceitepolybasite were locally encountered. Ba, Ti and Mn are the most significant ore-accompanying elements.     

Triple-oxygen-isotope determination of molecular oxygen incorporation in sulfate produced during abiotic pyrite oxidation (pH = 2-11)

Aqueous oxidation of sulfide minerals to sulfate is an integral part of the global sulfur and oxygen cycles. The current model for pyrite oxidation emphasizes the role of Fe²⁺-Fe³⁺ electron shuttling and repeated nucleophilic attack by water molecules on sulfur. Previous δ¹⁸O-labeled experiments show that a variable fraction (0-60%) of the oxygen in product sulfate is derived from dissolved O₂, the other potential oxidant. This indicates that nucleophilic attack cannot continue all the way to sulfate and that a sulfoxyanion of intermediate oxidation state is released into solution. The observed variability in O₂% may be due to the presence of competing oxidation pathways, variable experimental conditions (e.g. abiotic, biotic, or changing pH value), or uncertainties related to the multiple experiments needed to effectively use the δ¹⁸O label to differentiate sulfate-oxygen sources. To examine the role of O₂ and Fe³⁺ in determining the final incorporation of O₂ oxygen in sulfate produced during pyrite oxidation, we designed a set of aerated, abiotic, pH-buffered (pH = 2, 7, 9, 10, and 11), and triple-oxygen-isotope labeled solutions with and without Fe³⁺ addition. While abiotic and pH-buffered conditions help to eliminate variables, triple oxygen isotope labeling and Fe³⁺ addition help to determine the oxygen sources in sulfate and examine the role of Fe²⁺-Fe³⁺ electron shuttling during sulfide oxidation, respectively.Our results show that sulfate concentration increased linearly with time and the maximum concentration was achieved at pH 11. At pH 2, 7, and 9, sulfate production was slow but increased by 4× with the addition of Fe³⁺. Significant amounts of sulfite and thiosulfate were detected in pH ? 9 reactors, while concentrations were low or undetectable at pH 2 and 7. The triple oxygen isotope data show that at pH ? 9, product sulfate contained 21-24% air O₂ signal, similar to pH 2 with Fe³⁺ addition. Sulfate from the pH 2 reactor without Fe³⁺ addition and the pH 7 reactors all showed 28-29% O₂ signal. While the O₂% in final sulfate apparently clusters around 25%, the measurable deviations (>experimental error) from the 25% in many reaction conditions suggest that (1) O₂ does get incorporated into intermediate sulfoxyanions (thiosulfate and sulfite) and a fraction survives sulfite-water exchange (e.g. the pH 2 with no Fe³⁺ addition and both pH 7 reactors); and (2) direct O₂ oxidation dominates while Fe³⁺ shuttling is still competitive in the sulfite-sulfate step (e.g. the pH 9, 10, and 11 and the pH 2 reactor with Fe³⁺ addition). Overall, the final sulfate-oxygen source ratio is determined by (1) rate competitions between direct O₂ incorporation and Fe³⁺ shuttling during both the formation of sulfite from pyrite and from sulfite to final sulfate, and (2) rate competitions between sulfite and water oxygen exchange and the oxidation of sulfite to sulfate. Our results indicate that thiosulfate or sulfite is the intermediate species released into solution at all investigated pH and point to a set of dynamic and competing fractionation factors and rates, which control the oxygen isotope composition of sulfate derived from pyrite oxidation.     

Constraining atmospheric oxygen and seawater sulfate concentrations during Paleoproterozoic glaciation: In situ sulfur three-isotope microanalysis of pyrite from the Turee Creek Group, Western Australia

Previous efforts to constrain the timing of Paleoproterozoic atmospheric oxygenation have documented the disappearance of large, mass-independent sulfur isotope fractionation and an increase in mass-dependent sulfur isotope fractionation associated with multiple glaciations. At least one of these glacial events is preserved in diamictites of the ∼2.4 Ga Meteorite Bore Member of the Kungarra Formation, Turee Creek Group, Western Australia. Outcrop exposures of this unit show the transition from the Boolgeeda Iron Formation of the upper Hamersley Group into clastic, glaciomarine sedimentary rocks of the Turee Creek Group. Here we report in situ multiple sulfur isotope and elemental abundance measurements of sedimentary pyrite at high spatial resolution, as well as the occurrence of detrital pyrite in the Meteorite Bore Member. The 15.3‰ range of Δ³³S in one sample containing detrital pyrite (−3.6‰ to 11.7‰) is larger than previously reported worldwide, and there is evidence for mass-independent sulfur isotope fractionation in authigenic pyrite throughout the section (Δ³³S from −0.8‰ to 1.0‰). The 90‰ range in δ³⁴S observed (−45.5‰ to 46.4‰) strongly suggests microbial sulfate reduction under non-sulfate limiting conditions, indicating significant oxidative weathering of sulfides on the continents. Multiple generations of pyrite are preserved, typically represented by primary cores with low δ³⁴S (<−20‰) overgrown by euhedral rims with higher δ³⁴S (4-7‰) and enrichments in As, Ni, and Co. The preservation of extremely sharp sulfur isotope gradients (30‰/<4 μm) implies limited sulfur diffusion and provides time and temperature constraints on the metamorphic history of the Meteorite Bore Member. Together, these results suggest that the Meteorite Bore Member was deposited during the final stages of the “Great Oxidation Event,” when pO₂ first became sufficiently high to permit pervasive oxidative weathering of continental sulfides, yet remained low enough to permit the production and preservation of mass-independent sulfur isotope fractionation.     

二叠纪末期海洋缺氧:来自黄铁矿形态的证据

晚二叠世是古生代环境和生物演化的重要时期,也是重要的"冰室气候"时期,但其中仍然含有大量的富有机质沉积,并发育成为我国南方扬子板块重要的烃源岩层位.为恢复这一时期古海洋氧化还原状态,我们对湖北恩施赵家坝剖面大隆组硅质岩和四川广元上寺长江沟剖面大隆组碳酸盐岩中草莓状黄铁矿的粒径大小和分布进行了测量、统计和研究.统计结果显...     

二叠纪末期海洋缺氧：来自黄铁矿形态的证据

晚二叠世是古生代环境和生物演化的重要时期,也是重要的“冰室气候”时期,但其中仍然含有大量的富有机质沉积,并发育成为我国南方扬子板块重要的烃源岩层位。为恢复这一时期古海洋氧化还原状态,我们对湖北恩施赵家坝剖面大隆组硅质岩和四川广元上寺长江沟剖面大隆组碳酸盐岩中草莓状黄铁矿的粒径大小和分布进行了测量、统计和研究。统计结果显示,这些硅质岩和灰岩样品中的草莓状黄铁矿基本为原生,少见自行晶和后期充填,具有如下特点：单体粒径普遍偏小,变化范围相当狭窄,大多数草莓状黄铁矿粒径小于5 μm, 80％以上的粒径小于77 μm。这些粒径特征和分布特点表明,我国南方记录的晚二叠世大隆组烃源岩沉积于台内盆地极度缺氧（甚至硫化）的海洋环境,有利于有机质的保存。另外,该时期的极度缺氧为晚二叠世—早三叠世之交的大规模生物灭绝拉开了序幕。     

Fractionation of sulfur isotopes during laboratory synthesis of pyrite at low temperatures

The reaction products and the accompanying sulfur isotope fractionations during the reaction of H₂S with goethite in aqueous media at 22–24°C for periods from 0.5 hr to 65 days were studied. Fine-grained pyrite formed within two days and was isotopically 0.8‰ lighter than the H₂S source. After 65 days reaction time the pyrite had nearly the same isotopic value as the H₂S. Aqueous precipitation of pyrite from H₂S and goethite at room temperature involved three major steps, namely: (1) the rapid oxidation of H₂S and reduction of Fe³⁺ during which elemental S is formed; (2) the formation of acid-volatile sulfides and the disappearance of elemental S; and (3) the formation of pyrite at the expense of acid-volatile sulfides.     

Oxidation states and speciation of secondary products on pyrite and arsenopyrite reacted with mine waste waters and air

Summary Three morphologically distinct generations of Fe-oxyhydroxides were identified on pyrite surfaces reacted with unsaturated zone waters of a waste rock pile from the CON Mine (Northwest Territories, Canada). The paragenetic sequence includes an early mottled coating and a late massive (featureless) coating, separated by a generation of Fe(III)-oxyhydroxide of crystalline habit. Gypsum and halite precipitation were the last paragenetic events, and indicate intense wetting and drying in the unsaturated zone of the waste rock pile prior to collection.Fe 2p X-ray photoelectron spectra (XPS) of tarnished pyrite surfaces indicate at least two distinct secondary Fe(III)-oxyhydroxide phases, and combined with O 1s spectra, indicate ferrihydrite, goethite, hematite or maghemite. Minor As(IV) and As(III) are incorporated into these coatings.Fresh arsenopyrite surfaces reacted with air for 14 days, 16 months and 25 years develop exceptionally thin oxidized secondary coatings no more than about 50 A thick. XPS Fe 2p, O 1s and As 3d spectra indicate that the overlayer is composed of Fe(III)-hydroxides, arsenate (AsO[OH]3 or FeAsO₄), and reduced arsenic species, including arsenite (As[OH]3 or FeAsO₃). The abundance of reduced arsenic species is explained by diffusion of reduced As (e.g. As) from the unoxidized interior of the mineral to the near-surface where it reacts with oxidants. Continuous supply of reduced As from the bulk, and progressive oxidation of arsenic in the near-surface, result in an effective passivating layer. Whereas these oxidized coatings passivate the surface against airoxidation, aqueous solutions cause extensive leaching of arsenopyrite surfaces beneath the oxidized coatings. Apparently, the coatings offer little protection against leaching by oxidizing aqueous solutions, perhaps because the oxidized overlayer is compromised by dissolution of acidic and ferric arsenite and arsenate salts.

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Oxidationszustand und Spezifikation sekundärer Produkte auf Pyrit und Arsenkies nach Reaktion mit Grubenwässern und Luft

Zusammenfassung Drei morphologisch definierte Generationen von Eisen-Oxyhydroxyden wurden auf den Oberflächen von Pyrit nachgewiesen, der mit Wässern der ungesättigten Zone einer Abraumhalde der CON Mine (Nordwest-Territorium, Kanada) reagiert hat. Die paragenetische Abfolge umfaßt einen frühen fleckigen und einen späten massiven Überzug der durch eine Generation von Fe(III)-Oxyhydroxyden von kristallinem Habitus getrennt werden. Gips und Steinsalz Ausfällung waren die letzten paragenetischen Stadien und weisen auf intensive Befeuchtung und Trocknung in der ungesättigen Zone der Abraumhalden vor der Probennahme hin. Fe2p Röntgenfotoelektronspektren (XPS) von angelaufenen Pyritoberflächen weisen auf zumindest zwei unterscheidbare sekundäre Fe(III)-Oxyhydroxydphasen hin; in Kombination mit O is Spektren zeigen sie auch, daß Ferrihydrit, Goethit, Hämatit oder Maghemit vorliegen. Geringere Mengen von As(IV) und As(111) liegen in diesen Überzügen vor.Frische Arsenkiesoberflächen, die mit Luft für 14 Tage, 16 Monate und 25 Jahre reagiert haben, entwickeln außerordentlich dünne sekundäre Oxydationsfilme, die nicht mehr als 50 A dick sind. XPS, Fe 2p, O l s und As 3d Spektren zeigen, daß diese aus Fe(III)-Hydroxyden, Arsenat (AsO[OH]₃ oder FeAsO₄), und reduzierten Arsenphasen, die Arsenit (As[OH[]₃ oder FeAsO₃) umfassen, bestehen. Die weite Verbreitung von reduzierten Arsenphasen wird durch die Diffusion von reduziertem As (e.g. As°) aus dem nichtoxidierten Teil des Minerals in den Oberflächenbereichen erklärt, dort reagiert es mit Oxidanzien. Kontinuierliche Zufuhr von reduziertem As aus dem Haldenmaterial und progressive Oxidation des Arsens nahe der Oberläche führt zur Bildung einer effektiv passivierenden Schicht. Während diese oxidierten Schichten die Oberfläche gegen Luftoxidation passivieren, verursachen wäßrige Lösungen umfangreiches Leaching von Arsenkiesoberflächen unter den oxidierten Schichten. Offensichtlich bieten diese Schichten geringen Schutz gegen Leaching durch oxidierende wäßrige Lösungen, wahrscheinlich weil die oxidierte Überschicht durch Auflösung von sauren sowie Ferritischen Arsenit- und Arsenatsalzen beschädigt ist.

     

Oxygen isotope evidence for sorption of molecular oxygen to pyrite surface sites and incorporation into sulfate in oxidation experiments

Experiments were conducted to investigate (i) the rate of O-isotope exchange between SO₄ and water molecules at low pH and surface temperatures typical for conditions of acid mine drainage (AMD) and (ii) the O- and S-isotope composition of sulfates produced by pyrite oxidation under closed and open conditions (limited and free access of atmospheric O₂) to identify the O source/s in sulfide oxidation (water or atmospheric molecular O₂) and to better understand the pyrite oxidation pathway. An O-isotope exchange between SO₄ and water was observed over a pH range of 0–2 only at 50 °C, whereas no exchange occurred at lower temperatures over a period of 8 a. The calculated half-time of the exchange rate for 50 °C (pH = 0 and 1) is in good agreement with former experimental data for higher and lower temperatures and excludes the possibility of isotope exchange for typical AMD conditions (T  25 °C, pH  3) for decades.Pyrite oxidation experiments revealed two dependencies of the O-isotope composition of dissolved sulfates: O-isotope values decreased with longer duration of experiments and increasing grain size of pyrite. Both changes are interpreted as evidence for chemisorption of molecular O₂ to pyrite surface sites. The sorption of molecular O₂ is important at initial oxidation stages and more abundant in finer grained pyrite fractions and leads to its incorporation in the produced SO₄. The calculated bulk contribution of atmospheric O₂ in the dissolved SO₄ reached up to 50% during initial oxidation stages (first 5 days, pH 2, fine-grained pyrite fraction) and decreased to less than 20% after about 100 days. Based on the direct incorporation of molecular O₂ in the early-formed sulfates, chemisorption and electron transfer of molecular O₂ on S sites of the pyrite surface are proposed, in addition to chemisorption on Fe sites. After about 10 days, the O of all newly-formed sulfates originates only from water, indicating direct interaction of hydroxyls from water with S at the anodic S pyrite surface site. Then, the role of molecular O₂ is as proposed in previous studies: acting as electron acceptor only at the cathodic Fe pyrite surface site for oxidation of Fe(II) to Fe(III).     

Element fractionation by sequential extraction in a soil with high carbonate content

The influence of carbonate and other buffering substances in soils on the results of a 3-step sequential extraction procedure (BCR) used for metal fractionation was investigated. Deviating from the original extraction scheme, where the extracts are analysed only for a limited number of metals, almost all elements in the soils were quantified by X-ray fluorescence spectroscopy, in the initial samples as well as in the residues of all extraction steps. Additionally, the mineral contents were determined by X-ray diffractometry. Using this methodology, it was possible to correlate changes in soil composition caused by the extraction procedure with the release of elements. Furthermore, the pH values of all extracts were monitored, and certain extraction steps were repeated until no significant pH-rise occurred. A soil with high dolomite content (27%) and a carbonate free soil were extracted. Applying the original BCR-sequence to the calcareous soil, carbonate was found in the residues of the first two steps and extract pH-values rose by around two units in the first and second step, caused mainly by carbonate dissolution. This led to wrong assignment of the carbonate elements Ca, Mg, Sr, Ba, and also to decreased desorption and increased re-adsorption of ions in those steps. After repetition of the acetic acid step until extract pH remained low, the carbonate was completely destroyed and the distributions of the elements Ca, Mg, Sr, Ba as well as those of Co, Ni, Cu, Zn and Pb were found to be quite different to those determined in the original extraction. Furthermore, it could be shown that the effectiveness of the reduction process in step two was reduced by increasing pH: Fe oxides were not significantly attacked by the repeated acetic acid treatments, but a 10-fold amount of Fe was mobilized by hydroxylamine hydrochloride after complete carbonate destruction. On the other hand, only small amounts of Fe were released anyway. Even repeated reduction steps did not destroy the amorphous Fe oxides completely, showing that 0.1 mol L⁻¹ hydroxylamine hydrochloride was not strong enough to attack these oxides effectively.The extraction sequences were carried out not only on the soil samples, but also on their coarse and fine fractions (> or <2 μm). The fine fraction of the calcareous soil contained only 10% dolomite, but was enriched in organic matter and clay minerals, which also resulted in increased extract pH-values during the sequential extraction. Hence, the effects on ion release in the fine fraction were similar to those of the whole soil. Since the destruction of the organic matter was incomplete after regular oxidation, the H₂O₂-treatment of the fine fraction had to be repeated. The addition of the extractable amounts of the two fractions showed good agreement to the results obtained for extraction of the whole soils. Likewise the pH-values of the carbonate-free soil extracts did not increase significantly, therefore it was concluded that repetitions of extraction steps for this soil were not necessary.Extract-pHs should always be controlled so that extraction conditions are comparable; to be able to use the BCR extraction scheme or similar ones for carbonate- and organic-rich samples this is mandatory. Single extraction steps should be repeated if pH rises too much; additionally the oxidizing step should be performed more than twice for samples rich in organic substances, depending upon the violence of the reaction with H₂O₂. If these precautions are neglected the validity of the extraction data is likely to be questionable.     

Constraining pathways of microbial mediation for carbonate concretions of the Miocene Monterey Formation using carbonate-associated sulfate

Carbonate concretions can form as a result of organic matter degradation within sediments. However, the ability to determine specific processes and timing relationships to particular concretions has remained elusive. Previously employed proxies (e.g., carbon and oxygen isotopes) cannot uniquely distinguish among diagenetic alkalinity sources generated by microbial oxidation of organic matter using oxygen, nitrate, metal oxides, and sulfate as electron acceptors, in addition to degradation by thermal decarboxylation. Here, we employ concentrations of carbonate-associated sulfate (CAS) and δ³⁴S_CAS (along with more traditional approaches) to determine the specific nature of concretion authigenesis within the Miocene Monterey Formation.Integrated geochemical analyses reveal that at least three specific organo-diagenetic reaction pathways can be tied to concretion formation and that these reactions are largely sample-site specific. One calcitic concretion from the Phosphatic Shale Member at Naples Beach yields δ³⁴S_CAS values near Miocene seawater sulfate (～+22‰ VCDT), abundant CAS (ca. 1000 ppm), depleted δ¹³C_carb (～?11‰ VPDB), and very low concentrations of Fe (ca. 700 ppm) and Mn (ca. 15 ppm)—characteristics most consistent with shallow formation in association with organic matter degradation by nitrate, iron-oxides and/or minor sulfate reduction. Cemented concretionary layers of the Phosphatic Shale Member at Shell Beach display elevated δ³⁴S_CAS (up to ～+37‰), CAS concentrations of ～600 ppm, mildly depleted δ¹³C_carb (～?6‰), moderate amounts of Mn (ca. 250 ppm), and relatively low Fe (ca. 1700 ppm), indicative of formation in sediments dominated by sulfate reduction. Finally, concretions within a siliceous host at Montaña de Oro and Naples Beach show minimal CAS concentrations, positive δ¹³C values, and the highest concentrations of Fe (ca. 11,300 ppm) and Mn (ca. 440 ppm), consistent with formation in sediments experiencing methanogenesis in a highly reducing environment. This study highlights the promise in combining CAS analysis with more traditional techniques to differentiate among diagenetic reactions as preserved in the geologic record and shows potential for unraveling subsurface biospheric processes in ancient samples with a high degree of specificity.     

Oxygen isotope fractionation during the dolomitization of calcium carbonate

The oxygen isotope fractionation accompanying the hydrothermal dolomitization of CaCO₃ between 252 and 295°C has been investigated. Dolomitization (which occurs via the crystallization of one or more intermediate magnesian calcite phases) is characterised by a progressive lowering in δ⁸O, which smoothly correlates with the change in the Mg/(Mg + Ca) and the $\text{Sr}\text{(Mg + Ca)}$ ratios and with the sequential phase formation. The data support the proposals of Katz and Matthews (1977) that (a) all reaction occurs by solution and reprecipitation, (b) intermediate phases and dolomite form sequentially and (c) the intermediate phases form within limited solution zones surrounding the dissolving precursor. Calculated volumes of the solution zone for the aragonite → low magnesian calcite transformation are within the range 3.7–6.7 × 10^?5 liters (out of 5 × 10^?3 liters, the volume of the bulk solution used in the present study), and agree well with those calculated from strontium and magnesium partitioning data. Dolomite precipitates in apparent isotopic equilibrium with the bulk solution. The temperature dependence of the fractionation is defined by the equation 1000 Inα_D-H2O = 3.06 × 10⁶T^?2 ? 3.24 Dolomite-water fractionations from this equation are significantly lower than those obtained by extrapolation of the Northrop And Clayton (1966) calibration. The reaction zone model can be applied to explain near zero dolomite-calcite oxygen isotope fractionations reported by Epsteinet al. (1964).     

Kinetic fractionation of carbon-13 during calcium carbonate precipitation

Kinetic isotope fractionation of ¹³C during precipitation of CaCO₃ under open system conditions has been investigated. The isotope enrichment factor ?_HCO3^?-CaCO₃ varies between ?0.35 ± 0.23 and ?3.37 ± 0.36%. at 25°C depending on the rate of precipitation and mineralogy, the enrichment of ¹³C in the solid carbonate phase decreasing with increasing precipitation rate. An estimate of equilibrium ?_HCO3-Calcite of between ?1.83 ± 0.32 and ?2.26 ± 0.31%. is calculated from slow precipitation runs. A surface diffusion crystal growth model is used to describe the combination of kinetic isotope effects on thermodynamic isotope fractionation during rapid diffusion controlled crystal growth. Under slow precipitation conditions ?_{Calcite-Aragonite} was estimated as ?1.4%.; however, during rapid precipitation this fractionation appears to diminish and aragonite becomes less enriched in ¹³C.