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1.
When pyrite oxidizes at near neutral pH in the presence of sufficient alkalinity, Fe oxyhydroxide coatings develop on the surface. As these coatings grow thicker and denser they block oxidant transport from the solution to the pyrite surface and reduce the rate of pyrite oxidation. The authors’ measurements of pyrite oxidation rates in a NaHCO3 solution show that the coating grows in two stages. In the first stage Fe oxyhydroxide colloids form and then attach to the pyrite surface to produce a slight reduction in oxidant transport. In the second stage interstitial precipitation of Fe oxyhydroxide material between the colloidal particles reduces the oxidant’s diffusion coefficient by more than five orders of magnitude. This causes the pyrite oxidation rate to decline as the square root of time. The kinetic predominance diagram, which compares the rates of Fe transformation reactions, shows that when pyrite oxidation releases Fe quickly enough for the total Fe concentration to rise to about 10−8 m, ferrihydrite forms but lower rates of Fe release will not produce coatings. Extrapolation of the results to longer times predicts that pyrite-bearing materials need to be treated with an extra source of alkalinity for several decades to produce coatings that are thick enough to be sustained by alkalinity levels typical of groundwater. However, once the coatings develop no additional treatment is needed and further pyrite oxidation simply causes the coating to grow thicker and denser until the entire pyrite grain is pseudomorphically replaced by goethite.  相似文献   

2.
Pyrite oxidation: a state-of-the-art assessment of the reaction mechanism   总被引：1，自引：0，他引：1  
The oxidation of pyrite to release ferrous iron and sulfate ions to solution involves the transfer of seven electrons from each sulfur atom in the mineral to an aqueous oxidant. Because only one or, at most, two electrons can be transferred at a time, the overall oxidation process is quite complex. Furthermore, pyrite is a semiconductor, so the electrons are transferred from sulfur atoms at an anodic site, where oxygen atoms from water molecules attach to the sulfur atoms to form sulfoxy species, through the crystal to cathodic Fe(II) sites, where they are acquired by the oxidant species. The reaction at the cathodic sites is the rate-determining step for the overall process. This paper maps out the most important steps in this overall process.  相似文献   

3.
The effect of carbon or graphite coating on the adsorption of gold cyanide on pyrite was investigated with pure pyrite and a pyrite concentrate. In the carbon or graphite contaminated pyrite systems carbon and graphite not only acted as gold sorbents, but also enhanced gold adsorption on pyrite. The carbon coating enhanced gold adsorption on pyrite to a larger extent, in comparison with the graphite coating. The carbon or graphite coating on pyrite reduced the negativity of the pyrite surfaces, and hence improved the physical adsorption of gold cyanide on pyrite. In addition, the highly conductive coating of carbon or graphite on pyrite could enhance electron transfer in the electrochemical reactions occurring in the chemical adsorption of gold and gold reduction on pyrite. The preg-robbing by pyrite or the graphite-coated pyrite was reduced and further eliminated at higher cyanide concentrations. However, gold adsorption on the carbon-coated pyrite could not be prevented even at higher cyanide concentrations due to gold adsorption on the carbon coating. In comparison with pure pyrite, the pyrite concentrate had a higher capacity adsorbing gold, due to the presence of carbonaceous matter in the pyrite concentrate. Fine grinding intensified the smearing of carbon or graphite on the mineral particles, resulting in a larger extent of enhancement in the preg-robbing of the concentrate by the carbon or graphite coating.A diagnostic elution of the preg-robbing pyrite samples indicated that the reduction of gold at the pyrite surfaces was the dominant mechanism for gold adsorption on pyrite, followed by physical and chemical adsorption. Surface topological studies by SEM/EDX showed that gold adsorbed at defect sites on pyrite surfaces. For the pyrite with a 5% carbon coating, gold was observed to adsorb not only at the defect sites, but also at the smooth surfaces with carbon present. For the pyrite with a 5% graphite coating, carbon was also found at the pyrite surfaces, but gold was only detected at the defect sites. XPS studies revealed that part of the gold physically and chemically adsorbed on pyrite or pyrite coated with carbon or graphite. Some gold cyanide was reduced at the pyrite surfaces, with the sulphide ions of pyrite being oxidised to elemental sulphur.  相似文献   

4.
The effect of carbon or graphite coating on the adsorption of gold cyanide on pyrite was investigated with pure pyrite and a pyrite concentrate. In the carbon or graphite-contaminated pyrite systems carbon and graphite not only acted as gold sorbents, but also enhanced gold adsorption on pyrite. The carbon coating enhanced gold adsorption on pyrite to a larger extent, in comparison with the graphite coating. The carbon or graphite coating on pyrite reduced the negativity of the pyrite surfaces, and hence improved the physical adsorption of gold cyanide on pyrite. In addition, the highly conductive coating of carbon or graphite on pyrite could enhance electron transfer in the electrochemical reactions occurring in the chemical adsorption of gold and gold reduction on pyrite. The preg-robbing by pyrite or the graphite-coated pyrite was reduced and further eliminated at higher cyanide concentrations. However, gold adsorption on the carbon-coated pyrite could not be prevented even at higher cyanide concentrations due to gold adsorption on the carbon coating. In comparison with pure pyrite, the pyrite concentrate had a higher capacity adsorbing gold, due to the presence of carbonaceous matter in the pyrite concentrate. Fine grinding intensified the smearing of carbon or graphite on the mineral particles, resulting in a larger extent of enhancement in the preg-robbing of the concentrate by the carbon or graphite coating.A diagnostic elution of the preg-robbing pyrite samples indicated that the reduction of gold at the pyrite surfaces was the dominant mechanism for gold adsorption on pyrite, followed by physical and chemical adsorption. Surface topological studies by SEM/EDX showed that gold adsorbed at defect sites on pyrite surfaces. For the pyrite with a 5% carbon coating, gold was observed to adsorb not only at the defect sites, but also at the smooth surfaces with carbon present. For the pyrite with a 5% graphite coating, carbon was also found at the pyrite surfaces, but gold was only detected at the defect sites. XPS studies revealed that part of the gold physically and chemically adsorbed on pyrite or pyrite coated with carbon or graphite. Some gold cyanide was reduced at the pyrite surfaces, with the sulphide ions of pyrite being oxidised to elemental sulphur.  相似文献   

5.
Synthetic pyrite crystals doped with As, Co, or Ni, undoped pyrite, and natural arsenian pyrite from Leadville, Colorado were investigated with electrochemical techniques and solid-state measurements of semiconducting properties to determine the effect of impurity content on pyrite’s oxidation behavior. Potential step experiments, cyclic voltammetry, and AC voltammetry were performed in a standard three-electrode electrochemical cell setup. A pH 1.78 sulfuric acid solution containing 1 mM ferric iron, open to atmospheric oxygen, was chosen to approximate water affected by acid drainage. Van der Pauw/Hall effect measurements determined resistivity, carrier concentration and carrier mobility.The anodic dissolution of pyrite and the reduction of ferric iron half-reactions are taken as proxies for natural pyrite oxidation. Pyrite containing no impurities is least reactive. Pyrite with As is more reactive than pyrite with either Ni or Co despite lower dopant concentration. As, Co, and Ni impurities introduce bulk defect states at different energy levels within the band gap. Higher reactivity of impure pyrite suggests that introduced defect levels lead to higher density of occupied surface states at the solid-solution interface and increased metallic behavior. The current density generated from potential step experiments increased with increasing As concentration. The higher reactivity of As-doped pyrite may be related to p-type conductivity and corrosion by holes. The results of this study suggest that considering the impurity content of pyrite in mining waste may lead to more accurate risk assessment of acid producing potential.  相似文献   

6.
In this work, the electrochemical oxidation of succinic acid on boron-doped diamond (BDD) anodes was investigated. Voltammetric study had shown that no peaks appeared in the region of electrolyte stability which indicates that succinic acid oxidation can take place at a potential close to the potential region of electrolyte oxidation. Galvanostatic electrolyses achieved total chemical oxygen demand (COD) removals and high mineralization yields under different operating conditions (initial COD, current density and nature of supporting electrolyte). Oxalic, glycolic and formic acids were the main intermediates detected during anodic oxidation of succinic acid on BDD electrode and carbon dioxide as the final product. The mean oxidation state of carbon reached the value of 4 at the end of electrolysis which is indicative of mineralization of almost all organics present in aqueous solution. The exponential profile of COD versus specific electrical charge has shown that mass transfer is the limiting factor for the kinetics of electrochemical process. A simple mechanism was proposed for the mineralization of succinic acid. First, hydroxyl radicals attack of succinic acid leading to formation of glycolic, glyoxylic, fumaric and maleic acids. Then, theses acids undergo rapid and non-selective oxidation by hydroxyl radicals to be transformed into oxalic and formic acids which leads to further oxidation steps to mineralize these acids into carbon dioxide and water.  相似文献   

7.
Data on abundance and isotopic composition of porewater and sedimentary sulfur species are reported for relatively uncontaminated and highly contaminated fine-grained anoxic sediments of St. Andrew Bay, Florida. A strong contrast in amount and composition of sedimentary organic matter at the two sites allows a comparative study of the historical effects of increased organic loading on sulfur cycling and sulfur isotopic fractionation. In the contaminated sediments, an increase in organic loading caused increased sedimentary carbon/sulfur ratios and resulted in higher rates of bacterial sulfate reduction, but a lower efficiency of sulfide oxidation. These differences are well reflected in the isotopic composition of dissolved sulfate, sulfide, and sedimentary pyrite. Concentration and isotopic profiles of dissolved sulfate, organic carbon, and total sulfur suggest that the anaerobic decomposition of organic matter is most active in the upper 8cm but proceeds at very slow rates below this depth. The rapid formation of more than 90% of pyrite in the uppermost 2 cm which corresponds to about 3 years of sediment deposition allows the use of pyrite isotopic composition for tracing changing diagenetic conditions. Sediment profiles of the sulfur isotopic composition of pyrite reflect present-day higher rates of bacterial sulfate reduction and lower rates of sulfide oxidation, and record a profound change in the diagenetic cycling of sulfur in the contaminated sediments coincident with urban and industrial development of the St. Andrew Bay area.  相似文献   

8.
The oxidation of ethyl xanthate on pyrite electrodes, and the influence of the flotation depressants hydroxide, cyanide, and sulphide, have been investigated using cyclic voltammetry. A layer of a hydrated iron oxide has been identified on pyrite surfaces. Xanthate does not interact with this layer but is oxidized to dixanthogen at positive potentials. An increase in pH results in an increase in the background current due to oxidation of the mineral, and at pH=11 this reaction becomes faster than xanthate oxidation. Cyanide interacts with the electrode to form a surface species which inhibits xanthate oxidation. Sulphide gives rise to an anodic wave preceding the wave due to xanthate oxidation. The flotation and depression of pyrite are interpreted in terms of mixed-potential mechanisms.  相似文献   

9.
《Applied Geochemistry》2001,16(7-8):803-819
Sulfide mineral oxidation, primarily pyrite and pyrrhotite, generates acid mine drainage during weathering. Successful management of acid generating wastes entails the suppression of the initiation of oxidation reactions. The reactivity of pyrite depends on ore mineralogy, including the effects of associated sulfide impurities. The electrochemical surface characterization study using cyclic voltammetry with carbon paste electrodes containing minerals particles (CPE-Mineral) is an effective tool for demonstrating how the various mineral characteristics work together to influence the overall reactivity of the mineral. This study was supported by chemical, mineralogical and leachate chemistry data. The results show that the presence of other sulfides in contact with pyrite at the beginning of the weathering process is the most important parameter affecting pyrite reactivity, which is likely to be oxidized and passivated. In more advanced stages of leaching, mineral coatings which passivate the pyrite surfaces tend to play the most important role in defining the reactivity of pyrite. The electrochemical response of pyritic samples in conjunction with the evolution of the chemical quality of the leach solution in the simple experimental device here used, could then provide valuable information on acid mine drainage generation.  相似文献   

10.
Kinetics of arsenopyrite oxidative dissolution by oxygen   总被引：1，自引：0，他引：1  
We used a mixed flow reactor system to determine the rate and infer a mechanism for arsenopyrite (FeAsS) oxidation by dissolved oxygen (DO) at 25 °C and circumneutral pH. Results indicate that under circumneutral pH (6.3-6.7), the rate of arsenopyrite oxidation, 10−10.14±0.03 mol m−2 s−1, is essentially independent of DO over the geologically significant range of 0.3-17 mg L−1. Arsenic and sulfur are released from arsenopyrite in an approximate 1:1 molar ratio, suggesting that oxidative dissolution by oxygen under circumneutral pH is congruent. Slower rates of iron release from the reactor indicate that some of the iron is lost from the effluent by oxidation to Fe(III) which subsequently hydrolyzes and precipitates. Using the electrochemical cell model for understanding sulfide oxidation, our results suggest that the rate-determining step in arsenopyrite oxidation is the reduction of water at the anodic site rather than the transfer of electrons from the cathodic site to oxygen as has been suggested for other sulfide minerals such as pyrite.  相似文献   

11.
柱子淋洗模拟研究磷酸铁膜抑制黄铁矿氧化效果   总被引：1，自引：0，他引：1  
自然室温条件下用柱子淋洗模拟研究了接氧化亚铁硫杆菌（Ｔｈｉｏｂａｃｉｌｌｕｓ ｆｅｒｒｏｏｘｉｄａｎｓ,简称Ｔ．Ｆ菌）时磷酸铁膜抑制黄铁矿氧化的效果。试验结果首次指出：用ＫＨ２ＰＯ４与Ｈ２Ｏ２淋洗黄铁矿,在其表面形成的磷酸铁膜不能抑制黄铁矿的生物氧化,反而在一定程度上加速其氧化进程。经包膜后的黄铁矿矿石柱子间歇循环淋洗一年后的收集液中ＳＯ４＾２－累积量高达３３７５６．１ｍｇ;为对照组的１．６倍,是  相似文献   

12.
When galvanic interactions between pyrite and chalcopyrite occur in solution, pyrite, with the higher rest potential, acts as a cathode and is protected whereas chalcopyrite, with the lower rest potential, acts as an anode and its oxidation is increased. In this work a three-electrode system was used to investigate the corrosion current density and mixed potential of a galvanic cell comprising a pyrite cathode and a chalcopyrite anode in a flowing system. The results showed that with increasing concentration of ferric ion in the solution, with increasing acidity, and with increasing flow rate of the solution, the corrosion current density increased and the mixed potential of the galvanic cell became more positive. These experimental results are of direct significance to the control of environmental pollution in mining activity. By using the galvanic model, mixed potential theory, and the Butler–Volmer equation, the experimental results were explained theoretically.  相似文献   

13.
We used ‘Voltammetry of MicroParticles’ to investigate electrochemically samples from the Boda Albitic Claystone, a potential site for deep underground disposal of nuclear waste in Hungary. The samples were collected near the surface and at a depth of 1050 m. The electrochemical characterization in acidic media allowed the identification of Fe2+ and Fe3+ ions associated with clays, hematite and pyrite. The cathodic detection of pyrite does not raise special difficulties, but the anodic one is complex and depends on the time of the samples exposure to the atmosphere. This work completes a previous Mössbauer spectroscopy study by clarifying the presence, or absence, of extremely small amounts of pyrite in some samples.  相似文献   

14.
Acid mine drainage (AMD) is a widespread environmental problem associated with working and abandoned mining operations. It results from the microbial oxidation of pyrite in the presence of water and air, affording an acidic solution that contains toxic metal ions. Pyrite microencapsulation, utilizing silica coating, is a novel approach for controlling AMD that has been shown to be very effective in controlling pyrite oxidation. The roles of the solution pH and silica concentration in the formation mechanism for the AMD-preventing coating were investigated. A silica coating can be formed from silica solution at pH 7, at which the amount of Fe eluted from pyrite into the solution is small. No coating was formed at other pH values, and the amounts of eluted Fe were larger than at pH 7, especially at pH 11. The silica coating forms from 2,500 to 5,000 mg/L silica solutions, but not from 0 or 1,000 mg/L silica solutions. The coating formation rate was slower in the 2,500 mg/L silica solution than in the 5,000 mg/L silica solution. The formation of silica coating on pyrite surfaces depends on three main steps: formation of Fe(OH)3 on the surface of pyrite, reaction between Fe(OH)3 and silicate in the solution on the pyrite surface, and growth of the silica layer on the first layer of silica. The best pH condition to enable these steps was around 7, and the silica coating formation rate can be controlled by the concentration of silica.  相似文献   

15.
《Geochimica et cosmochimica acta》1999,63(19-20):3171-3182
The oxidation rate of pyrite at pH 7, 25°C and at constant partial pressure of oxygen (0.21 and 0.177 atm) was measured in the presence of the Fe(III)-chelators NTA, oxalate, leucine, EDTA, citrate, IDA and the Fe(III)-reductant ascorbic acid. With the exception of leucine and EDTA, non-reducing Fe(III)-chelators increased the oxidation rate relative to the reference state of formation of the Fe(OH)2+ complex at pH 7. The rate increase was proportional to the logarithm of the conditional stability constant of the ligands for the complexation of Fe3+. No effect on the oxidation rate was observed in the presence of EDTA, which shifted the redox potential of the redox couple Fe2+/Fe3+ to a value below that in the absence of any ligand at pH 7. Ascorbic acid decreased the pyrite oxidation rate by a factor of 5 at ascorbic acid concentrations between 10−4 and 10−2 mol L−1. Comparison of the rate constants for the oxidation of ascorbic acid by surface bound Fe(III) in the absence and presence of pyrite shows that the pyrite surface accelerates this reaction by a factor of 10. The oxidation of both pyrite and ascorbic acid is of fractional order with respect to ascorbic acid (HAsc): rpy=0.55 c(HAsc)−0.35 rHAsc=3.6 c(HAsc)0.59. Both the results from experiments with Fe(III)-chelating ligands and the Fe(III)-reductant, suggest a very efficient interference in the electron cycling between Fe(II) and Fe(III) at the pyrite surface. The interference seems to be mainly related to the reductive side of the iron cycling. It is therefore concluded that the electron transfer between ferric iron and pyritic sulfur limits the pyrite oxidation rate at pH 7.  相似文献   

16.
Hydrogen peroxide and hydroxyl radical are readily formed during the oxidation of pyrite with molecular oxygen over a wide range of pH conditions. However, pretreatment of the pyrite surface influences how much of the intermediates are formed and their fate. Acid-washed pyrite produces significant amounts of hydrogen peroxide and hydroxyl radical when suspended in air-saturated water. However, the hydrogen peroxide concentration shows an exponential decrease with time. Suspensions made with partially oxidized pyrite yield significantly lower amounts of hydrogen peroxide product. The presence of Fe(III)-oxide or Fe(III)-hydroxide patches facilitates the conversion of hydrogen peroxide to oxygen and water. Hence, the degree to which a pyrite surface is covered with patches of Fe(III)-oxide or Fe(III)-hydroxide patches is an important control on the concentration of hydrogen peroxide in solution.Hydrogen peroxide appears to be an important intermediate in the four-electron transfer from pyrite to molecular oxygen. Addition of catalase, an enzyme that decomposes hydrogen peroxide to water and molecular oxygen, to a pyrite suspension reduces the oxidation rate by 40%. By contrast, hydroxyl radical does not appear to play a significant role in the oxidation mechanism. It is estimated on the basis of a molecular oxygen and sulfate mass balance that 5-6% of the molecular oxygen is consumed without forming sulfate.  相似文献   

17.
《Chemical Geology》2006,225(1-2):16-29
Pyrite oxidation rates were examined at various concentrations of dissolved oxygen (DO) in the presence of the sulfur and iron oxidizer Acidithiobacillus ferrooxidans. Five different batch experiments were performed at room temperature for 75 days under various DO levels (273, 129, 64.8, 13.2, and ≤ 0.006 μM), containing pyrite grains (particle size 63–250 μm) and a modified 9K nutrient medium at pH 3. The reactors were inoculated with A. ferrooxidans. In all experiments, pH decreased with time and sulfur and iron were released to the solution, indicating pyrite oxidation at all DO levels. Pyrite oxidation rates (ca. 5 × 10− 10 mol m− 2 s− 1 at 273 μM DO) from all experiments showed positive correlation with DO, Fe(III), and bacterial concentration. These rates were significantly slower than rates presented in other published studies, but this is probably due to the significantly greater Fe(III) concentration at lower pH in these previous studies. The results obtained in this study suggest that ferric iron reduction at the pyrite surface is the primarily mechanism for microbial pyrite oxidation in the presence of DO. The results from our study support the indirect mechanism of sulfide oxidation, where A. ferrooxidans oxidizes ferrous iron in the presence of DO, which then oxidizes pyrite.  相似文献   

18.
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).  相似文献   

19.
The formation and subsequent reactions of magnesiancalcite overgrowths on calcite were investigated bymeans of closed system seeded precipitationexperiments. These experiments demonstrated that(1) thin overgrowths of magnesian calcite are precipitatedon calcite seeds suspended in seawater;(2) the solubilities of the coatings increase outward from theseed crystals as a linear function of the log ofrelative coating thickness;(3) during the period ofthese experiments (up to 5.5 months), the magnesiancalcite coatings continued to increase in thickness,but became less soluble in composition. Thestabilization reaction, referred to asrecrystallization, can be described by the followingequation:Cax Mg(1-x) CO3 + [z + y(x + z)]Ca2++ 2yHCO3- ]= (1 + y)Ca(x + z)Mg(1 - x -z)CO3 + [z + y(x + z - 1)]Mg2++ y CO2 + yH20;]4) recrystallization rate is dependent on solutionsaturation state, with a reaction order of 3.2 forartificial seawater and 4.0 for natural seawater; and(5) by the cessation of the closed system experiments,overgrowth compositions approached that of the stablecalcite (a few mol % MgCO3).Armoring of suspended carbonate particles in thesurface oceans with magnesian calcite overgrowthswould provide an effective barrier to release of theoceanic supersaturation with respect to calcite. Thicknesses of such coatings would be limited by therecrystallization rate of the magnesian calcite. Estimates based on the recrystallization ratesdetermined in this work indicate coatings on the orderof 0.02 µm in thickness could form on particles asthey sink through the mixed layer. According to thesecalculations, the total amount of carbon precipitatedannually in magnesian calcite overgrowths iscomparable to the riverine flux of dissolved carbon tothe oceans. Field observations of severalinvestigators indicate the likely presence ofmagnesian calcite coatings on planktonic particles,and provide evidence for possible recrystallization ofbiogenic magnesian particles in the marineenvironment.  相似文献   

20.
A multicomponent diagenetic model was developed and applied to reconstruct the conditions under which the most recent sapropel, S1, was deposited in the eastern Mediterranean Sea. Simulations demonstrate that bottom waters must have been anoxic and sulphidic during the formation of S1 and that organic matter deposition was approximately three times higher than at present. Nevertheless, most present day sediment and pore water profiles — with the exception of pyrite, iron oxyhydroxides, iron-bound phosphorus and phosphate — can be reproduced under a wide range of redox conditions during formation of S1 by varying the depositional flux of organic carbon. As a result, paleoredox indicators (e.g., Corg:S ratio, Corg:Porg ratio, trace metals) are needed when assessing the contribution of oxygen-depletion and enhanced primary production to the formation of organic-rich layers in the geological record. Furthermore, simulations show that the organic carbon concentration in sediments is a direct proxy for export production under anoxic bottom waters.The model is also used to examine the post-depositional alteration of the organic-rich layer focussing on nitrogen, phosphorus, and organic carbon dynamics. After sapropel formation, remineralisation is dominated by aerobic respiration at a rate that is inversely proportional to the time since bottom waters became oxic once again. A sensitivity analysis was undertaken to identify the most pertinent parameters in regulating the oxidation of sapropels, demonstrating that variations in sedimentation rate, depositional flux of organic carbon during sapropel formation, bottom water oxygen concentration, and porosity have the largest impact. Simulations reveal that sedimentary nutrient cycling was markedly different during the formation of S1, as well as after reoxygenation of bottom waters. Accumulation of organic nitrogen in sediments doubled during sapropel deposition, representing a significant nitrogen sink. Following reventilation of deep waters, N2 production by denitrification was almost 12 times greater than present day values. Phosphorus cycling also exhibits a strong redox sensitivity. The benthic efflux of phosphate was up to 3.5 times higher during the formation of S1 than at present due to elevated depositional fluxes of organic matter coupled with enhanced remineralisation of organic phosphorus. Reoxygenation of bottom waters leads to a large phosphate pulse to the water column that declines rapidly with time due to rapid oxidation of organic material. The oxidation of pyrite at the redox front forms iron oxyhydroxides that bind phosphorus and, thus, attenuate the benthic phosphate efflux. These results underscore the contrasting effects of oxygen-depletion on sedimentary nitrogen and phosphorus cycling. The simulations also confirm that the current conceptual paradigm of sapropel formation and oxidation is valid and quantitatively coherent.  相似文献   

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