Reduction of iron(III) minerals by natural organic matter in groundwater

Construction of the entrance tunnel to the Äspö Hard Rock Laboratory, a prototype repository in Sweden for research into the geological disposal of spent nuclear fuel, has resulted in increased transport of organic carbon from the surface into the groundwater. This increased input of organic matter has induced accelerated oxidation of organic carbon associated with reduction of iron(III) minerals as the terminal electron acceptor in microbial respiration. Hydrochemical modeling of major solute ions at the site indicates an apparent first-order decay constant for organic carbon of 3.7 ± 2.6/yr. This rapid turnover is not accompanied by an equivalent mobilization of ferrous iron. Thermodynamic calculation of iron mineral solubility suggests that ferrous clay minerals may form in hydraulically transmissive fractures. The conditional potentials for the oxidation–reduction of such phases coincide with measured redox potentials at the site. The calculated potential is sufficiently low so that such phases would provide reducing capacity against future intrusion of O₂ into the groundwater, thus buffering a repository against oxic corrosion of the engineered barriers.     

Reaction-based modeling of quinone-mediated bacterial iron(III) reduction

This paper presents and validates a new paradigm for modeling complex biogeochemical systems using a diagonalized reaction-based approach. The bioreduction kinetics of hematite (α-Fe₂O₃) by the dissimilatory metal-reducing bacterium (DMRB) Shewanella putrefaciens strain CN32 in the presence of the soluble electron shuttling compound anthraquinone-2,6-disulfonate (AQDS) is used for presentation/validation purposes. Experiments were conducted under nongrowth conditions with H₂ as the electron donor. In the presence of AQDS, both direct biological reduction and indirect chemical reduction of hematite by bioreduced anthrahydroquinone-2,6-disulfonate (AH₂DS) can produce Fe(II). Separate experiments were performed to describe the bioreduction of hematite, bioreduction of AQDS, chemical reduction of hematite by AH₂DS, Fe(II) sorption to hematite, and Fe(II) biosorption to DMRB. The independently determined rate parameters and equilibrium constants were then used to simulate the parallel kinetic reactions of Fe(II) production in the hematite-with-AQDS experiments. Previously determined rate formulations/parameters for the bioreduction of hematite and Fe(II) sorption to hematite were systematically tested by conducting experiments with different initial conditions. As a result, the rate formulation/parameter for hematite bioreduction was not modified, but the rate parameters for Fe(II) sorption to hematite were modified slightly. The hematite bioreduction rate formulation was first-order with respect to hematite ”free“ surface sites and zero-order with respect to DMRB based on experiments conducted with variable concentrations of hematite and DMRB. The AQDS bioreduction rate formulation was first-order with respect to AQDS and first-order with respect to DMRB based on experiments conducted with variable concentrations of AQDS and DMRB. The chemical reduction of hematite by AH₂DS was fast and considered to be an equilibrium reaction. The simulations of hematite-with-AQDS experiments were very sensitive to the equilibrium constant for the hematite-AH₂DS reaction. The model simulated the hematite-with-AQDS experiments well if it was assumed that the ferric oxide “surface” phase was more disordered than pure hematite. This is the first reported study where a diagonalized reaction-based model was used to simulate parallel kinetic reactions based on rate formulations/parameters independently obtained from segregated experiments.     

Microbial reduction of iron(III)-rich nontronite and uranium(VI)

To assess the dynamics of microbially mediated U-clay redox reactions, we examined the reduction of iron(III)-rich nontronite NAu-2 and uranium(VI) by Shewanella oneidensis MR-1. Bioreduction experiments were conducted with combinations and varied concentrations of MR-1, nontronite, U(VI) and the electron shuttle anthraquinone-2,6-disulfonate (AQDS). Abiotic experiments were conducted to quantify U(VI) sorption to NAu-2, the reduction of U(VI) by chemically-reduced nontronite-Fe(II), and the oxidation of uraninite, U^(IV)O_2(s), by nontronite-Fe(III). When we incubated S. oneidensis MR-1 at lower concentration (0.5 × 10⁸ cell mL⁻¹) with nontronite (5.0 g L⁻¹) and U(VI) (1.0 mM), little U(VI) reduction occurred compared to nontronite-free incubations, despite the production of abundant Fe(II). The addition of AQDS to U(VI)- and nontronite-containing incubations enhanced both U(VI) and nontronite-Fe(III) reduction. While U(VI) was completely reduced by S. oneidensis MR-1 at higher concentration (1.0 × 10⁸ cell mL⁻¹) in the presence of nontronite, increasing concentrations of nontronite led to progressively slower rates of U(VI) reduction. U(VI) enhanced nontronite-Fe(III) reduction and uraninite was oxidized by nontronite-Fe(III), demonstrating that U served as an effective electron shuttle from S. oneidensis MR-1 to nontronite-Fe(III). The electron-shuttling activity of U can explain the lack or delay of U(VI) reduction observed in the bulk solution. Little U(VI) reduction was observed in incubations that contained chemically-reduced nontronite-Fe(II), suggesting that biologic U(VI) reduction drove U valence cycling in these systems. Under the conditions used in these experiments, we demonstrate that iron-rich smectite may inhibit or delay U(VI) bioreduction.     

The anaerobic degradation of organic matter in Danish coastal sediments: iron reduction, manganese reduction, and sulfate reduction

We used a combination of porewater and solid phase analysis, as well as a series of sediment incubations, to quantify organic carbon oxidation by dissimilatory Fe reduction, Mn reduction, and sulfate reduction, in sediments from the Skagerrak (located off the northeast coast of Jutland, Denmark). In the deep portion of the basin, surface Mn enrichments reached 3.5 wt%, and Mn reduction was the only important anaerobic carbon oxidation process in the upper 10 cm of the sediment. In the less Mn-rich sediments from intermediate depths in the basin, Fe reduction ranged from somewhat less, to far more important than sulfate reduction. Most of the Mn reduction in these sediments may have been coupled to the oxidation of acid volatile sulfides (AVS), rather than to dissimilatory reduction. High rates of metal oxide reduction at all sites were driven by active recycling of both Fe and Mn, encouraged by bioturbation. Recycling was so rapid that the residence time of Fe and Mn oxides, with respect to reduction, ranged from 70-250 days. These results require that, on average, an atom of Fe or Mn is oxidized and reduced between 100-300 times before ultimate burial into the sediment. We observed that dissolved Mn2+ was completely removed onto fully oxidized Mn oxides until the oxidation level of the oxides was reduced to about 3.8, presumably reflecting the saturation by Mn2+ of highly reactive surface adsorption sites. Fully oxidized Mn oxides in sediments, then, may act as a cap preventing Mn2+ escape. We speculate that in shallow sediments of the Skagerrak, surface Mn oxides are present in a somewhat reduced oxidation level (< 3.8) allowing Mn2+ to escape, and perhaps providing the Mn2+ which enriches sediments of the deep basin.     

Microbial contributions to N-immobilization and organic matter preservation in decaying plant detritus

Microbial contributions to the detritus of two vascular plant tissues, smooth cordgrass (Spartina alterniflora) and black mangrove leaves (Avicennia germinans), were estimated over a 4-year decomposition period under subaqueous marine conditions. During this period, 93-97% of the initial plant tissues was decomposed. Bulk elemental and isotopic compositions of the detritus were measured along with hydrolyzable amino sugars (AS) and amino acids (AA), including the bacterial biomarkers muramic acid and the d-enantiomers of AA. A major enrichment in N relative to C occurred during decomposition. Net increases of AS, AA, and bacterial biomarkers in decaying detritus were observed. Three independent approaches indicated that on average 60-75% of the N and 20-40% of the C in highly decomposed detritus were not from the original plant tissues but were mostly from heterotrophic bacteria. During decomposition hydrolyzable AS + AA yields (∼54% of total N) were strongly correlated with total N in both types of detritus. The uncharacterized N appeared to have the same origin and dynamics as AA, suggesting the contribution of other bacterial biomolecules not measured here. There was little indication of humification or abiotic processes. Instead, N-immobilization appeared primarily bacterially mediated. Although varying dynamics were observed among individual molecules, bacterial detritus exhibited an average reactivity similar to plant detritus. Only a minor fraction of the bacterial detritus escaped rapid biodegradation and the relationship between bacterial activity and N-immobilization is consistent with an enzymatically mediated preservation mechanism. Bacteria and their remains are ubiquitous in all ecosystems and thus could comprise a major fraction of the preserved and uncharacterized organic matter in the environment.     

Enhanced microbial reduction of Cr(VI) and U(VI) by different natural organic matter fractions

Although direct microbial reduction of Cr(VI) and U(VI) is known, few studies have examined the kinetics and the underlying mechanisms of the reduction of these contaminants by different natural organic matter (NOM) fractions in the presence or absence of microorganisms. In this study, NOM was found to chemically reduce Cr(VI) at pH 3, but the reduction rates were negligible at pH ∼7. The abiotic reduction of U(VI) by NOM was not observed, possibly because of the presence of small amounts of nitrate in the reactant solution. However, all NOM fractions, particularly the soil humic acid (HA), enhanced the bioreduction of Cr(VI) or U(VI) in the presence of Shewanella putrefaciens CN32. The reduction rates varied greatly among NOM fractions with different chemical and structural properties: the polyphenolic-rich NOM-PP fraction appeared to be the most reactive in abiotically reducing Cr(VI) at a low pH, but soil HA was more effective in mediating the microbial reduction of Cr(VI) and U(VI) under anaerobic, circumneutral pH conditions. These observations are attributed to an increased solubility and conformational changes of the soil HA with pH and, more importantly, its relatively high contents of polycondensed and conjugated aromatic organic moieties. An important implication of this study is that, depending on chemical and structural properties, different NOM components may play different roles in enhancing the bioreduction of Cr(VI) and U(VI) by microorganisms. Polycondensed aromatic humic materials may be particularly useful in mediating the bioreduction and rapid immobilization of these contaminant metals in soil.     

Sulfate reduction and the nature of organic matter in estuarine sediments

The reduction of sulfate by sulfate reducing bacteria in the anoxic zone is an extremely important process during early diagenesis of marine sediments. Our data from Great Bay, NH reinforce the proposal that the rate of sulfate reduction is directly proportional to the reactivity of the organic matter or the amount of readily metabolizable organic matter present in the sediment and, hence, the source of the organic material in the anoxic zone. It appears that organic matter rich in marine organic remains is more easily degraded in the anoxic zone and that sulfate reduction rates can vary considerably in an estuarine system where many types of organic material may be deposited.     

Superoxide-mediated reduction of organically complexed iron(III): Impact of pH and competing cations (Ca)

The mechanism and kinetics of superoxide-mediated reduction of a variety of organic iron(III) complexes has been investigated over the pH range 7-9. Our experimental results show that the rate of iron(II) formation is a function of pH, ligand type and ligand concentration with the measured rate varying between 0.44 ± 0.07 and 39.25 ± 1.77 pM s⁻¹ in the systems investigated. Additionally, our results show that the presence of competing cations such as Ca²⁺ have a significant impact on iron(II) formation if the organic ligand is strongly complexed by Ca²⁺. Formation of iron(II) occurs by either (or, in some instances, both) reaction of superoxide with inorganic iron(III) after its dissociation from the complex (dissociative reduction) or by direct reaction of superoxide with the complex (non-dissociative reduction). In the presence of weak ligands, dissociative reduction (DR) dominates; however non-dissociative reduction (NDR) becomes important in the presence of either strongly binding ligands or high concentrations of weakly binding ligands. The major factors contributing to the pH dependence of the iron(II) formation rate are the complexation kinetics of inorganic iron(III) (which controls the DR contribution) and the reduction kinetics of the iron(III) complex (which controls the NDR contribution). The relative NDR contribution increases with increasing superoxide and ligand concentration and decreasing pH for all ligands examined. Since iron(II) formation occurring via NDR results in a significantly larger increase in the proportion of iron in free aquated form than does DR, this non-dissociative pathway of superoxide-mediated iron(III) reduction is particularly effective in increasing the lability of iron in aquatic systems.     

夏季丰水期河流输入对太湖有色可溶性有机物的贡献

结合2008年夏季丰水期对太湖上游直湖港、大浦河、长兜港3条河流有色可溶性有机物(CDOM)吸收和三维荧光的测定分析,探讨了夏季丰水期时河流输入对太湖中CDOM的贡献.3条河流中直湖港CDOM浓度最高,大浦河次之,长兜港最低,反映了太湖北部外源河流污染物输入大于西南部.3条河流内CDOM吸收α(355)的均值为(4.7...     

The effect of silica and natural organic matter on the Fe(II)-catalysed transformation and reactivity of Fe(III) minerals

The Fe(II)-catalysed transformation of synthetic schwertmannite, ferrihydrite, jarosite and lepidocrocite to more stable, crystalline Fe(III) oxyhydroxides is prevented by high, natural concentrations of Si and natural organic matter (NOM). Adsorption isotherms demonstrate that Si adsorbs to the iron minerals investigated and that increasing amounts of adsorbed Si results in a decrease in isotope exchange between aqueous Fe(II) and the Fe(III) mineral. This suggests that the adsorption of Si inhibits the direct adsorption of Fe(II) onto the mineral surface, providing an explanation for the inhibitory effect of Si on the Fe(II)-catalysed transformation of Fe(III) minerals. During the synthesis of lepidocrocite and ferrihydrite, the presence of equimolar concentrations of Si and Fe resulted in the formation of 2-line ferrihydrite containing co-precipitated Si in both cases. Isotope exchange experiments conducted with this freeze-dried Si co-precipitated ferrihydrite species (Si-ferrihydrite) demonstrated that the rate and extent of isotope exchange between aqueous Fe(II) and solid ⁵⁵Fe(III) was very similar to that of 2-line ferrihydrite formed in the absence of Si and which had not been allowed to dry. In contrast to un-dried ferrihydrite formed in the absence of Si, Si-ferrihydrite did not transform into a more crystalline Fe(III) mineral phase over the 7-day period of investigation. Reductive dissolution studies using ascorbic acid demonstrated that both dried Si-ferrihydrite and un-dried 2-line ferrihydrite were very reactive, suggesting these species may be major contributors to the rapid release of dissolved iron following flooding and the onset of conditions conducive to reductive dissolution in acid sulphate soil environments.     

Solubility and dissimilatory reduction kinetics of iron(III) oxyhydroxides: A linear free energy relationship

Rates of reduction of Fe(III) oxyhydroxides by the bacterium Shewanella putrefaciens were measured as a function of the bacterial density and the Fe(III) substrate concentration. The results show that an earlier reported positive correlation between the solubility products (^*K_so) and the maximum cell-specific reduction rates (v_max) of predominantly poorly crystalline Fe(III) oxyhydroxides also applies to insoluble and crystalline Fe(III) oxyhydroxides. The mineral solubilities were measured by a dialysis bag technique under acidic conditions (pH 1 up to 2.5) at 25 °C. Initial iron reduction rates by S. putrefaciens were determined in the presence of excess lactate as electron donor. In all cases, the microbial reduction rate exhibited saturation behavior with respect to the Fe(III) oxyhydroxide concentration. On a double logarithmic scale, the maximum rates v_max and the solubility products defined a single linear free energy relationship (LFER) for all the Fe(III) oxyhydroxides considered. The solubility provided a better predictor of v_max than the specific surface area of the mineral phase. A rate limitation by the electron transfer between an iron reductase and a Fe(III) center, or by the subsequent desorption of Fe²⁺ from the iron oxide mineral surface, are both consistent with the observed LFER.     

Spectroscopic evidence of microbial organic matter in secondary mineral deposits at Naica Underground System (NUS) and the biological role in its mineralization

The Naica Underground System (NUS) hosts the largest gypsum crystals (>10 m in length and >1 m in width) ever found in natural caves; these are growing from conspicuous Fe-oxyhydroxide deposits that presumably were formed in processes controlled by microorganisms. In contrast to other studies where microbial participation is elucidated only from morphological textural characterization and total DNA sequencing, here, we report a comprehensive FTIR characterization of the conspicuous secondary mineral deposits in the NUS that provides physicochemical evidence suggesting that the NUS microbial communities contributed to the mineralization of the Fe-oxyhydroxides and gypsum at the NUS.FTIR analyses of gypsum and Fe-oxyhydroxides, as well as the mineral fraction dissolved in aqueous samples collected from different sites at NUS, reveal that such minerals are intimately associated with organic material, such as polysaccharides, phospholipids, proteins, and, to a minor extent, nucleic acids; suggesting that the formation of gypsum and Fe-oxyhydroxides at NUS was microbially mediated. Our results also provide compelling evidence that FTIR is a valuable tool for the characterization of biomineralization processes and should be used as a complement to morphological and massive DNA analyses.     

Densification of iron(III) sludge in neutralization

Acid mine drainage (AMD), of which iron is a substantial component, is a potential by-product in the mining industry. Conventional neutralization is a common approach to treat AMD, although it creates a major disposal problem due to the generation of voluminous sludge. Sludge recirculation improves solid density by slowing down the rate of neutralization and allowing the growth of precipitates, while existing solids act as seed particles by providing necessary surface area for precipitation. The mechanisms of iron sludge densification are not fully understood, mainly because of the complex nature of iron chemistry, and the variety of amorphous, polymeric oxides that could be formed. In this work, the effects of alkaline reagents, flocculant addition, and dosing sequence, on the precipitation of iron (III) hydroxide and densification of the recycled sludge were investigated. Slowly dissolving lime (Ca(OH)₂) was found to be more effective than caustic (NaOH) in producing sludge with higher solid contents. Polymers addition created stronger aggregates that could withstand shearing without significant size reduction, but the overall sludge density was lower than those produced without flocculant. Conditioning the sludge at pH between 3.5 and 4.5 by adding fresh lime in a specific dosing manner appeared to be conducive to the growth of large agglomerates. The final sludge solid content of ∼15 wt.% was considerably higher than others produced under different conditions. The plate-like structures of precipitates generated with more recycles in this instance, possibly helped ease the release of entrapped water between solids during shearing, thus producing sludge with higher solid density.     

新疆巴什布拉克地区有机地球化学特征及其对铀成矿的控制

巴什布拉克铀矿床是新疆典型的与地沥青有关的砂岩型铀矿床。研究该矿床油气有机质来源、演化程度及后期降解过程,有助于深入解读原生红层在油气二次还原条件下的铀富集机理。本文针对该区铀矿化与油气密切相关的特点,采集了钻孔中具明显油浸的铀矿化砂岩和砾岩进行提取物分析。通过对提取物氯仿沥青“A”及其族组成和饱和烃气相色谱分析可见,有机质正构烷烃主峰碳为C17、C18、C20、C24和C25;(C21+C22)/(C28+C29)为0.58～12.17;Pr/Ph为0.40～1.47;Ts/Tm为1.3～16.1,高含量的系列重排藿烷化合物和“V”型甾烷分布,显示该区油气有机质主要来源于中下侏罗统湖相沉积。OEP为1.04～1.14,深部样品的OEP＜1.0;C-21/C+22为0.18～2.11,指示局部烃源岩可能受到热改造提前进入生油门限,导致矿区深部浸入的油气有机质演化程度较高。早期浸入的油气有机质饱和烃气相色谱基线呈上飘“鼓包”状突出,Pr/nC17为0.6～0.9,Ph/nC18为0.8～11.98,表明受到氧化和微生物降解作用,在此过程中铀发生沉淀和富集。铀矿化主要受油气氧化和降解产物地沥青分布范围控制。     

Influence of water-extractable organic matter from Opalinus Clay on the sorption and speciation of Ni(II), Eu(III) and Th(IV)

The influence of water-extractable organic matter from 6 Opalinus Clay (OPA) samples from Mont Terri and Benken (Switzerland) on the sorption of Ni(II), Eu(III) and Th(IV) has been measured using an ion exchange technique. OPA is considered to be one of the potential host rocks for the deep geological disposal of high-level and long-lived intermediate-level radioactive waste in Switzerland. Within the range of estimated uncertainties, no significant differences in sorption were observed in most cases as compared with suitable synthetic waters devoid of organic C. Only in certain individual cases were slight reductions in sorption (less than a factor of 5) for Eu(III) and Ni(II) found. The results of accompanying laser fluorescence spectroscopy experiments did not show any influence of the extracts on Cm(III) speciation. This would suggest that the reduction of sorption occasionally observed in the ion exchange experiments is probably not caused by the formation of complexes between the radionuclides and the organic matter in the extracts, but is rather due to an underestimation of systematic uncertainties. From these findings, and from UV–VIS spectroscopic characterisation of the organic matter in the extracts, it can be concluded that only a negligible fraction of the organic matter present may be in the form of humic or fulvic acids. It is consequently justified to put aside overly conservative assumptions with respect to the complexing behaviour of the organic matter used towards the metal ions investigated and their chemical analogues. In view of the site-specific character of the present study, these conclusions may not be arbitrarily applied to other geological formations considered as possible host rocks for the disposal of radioactive waste.     

Nitrogen and phosphorus mineralization in sediments of Taihu Lake after the removal of light fraction organic matter

Mineralization of organic matter (OM) in sediment is crucial for biogeochemical cycle of nitrogen (N) and phosphorus (P) in lake ecosystem. Light fraction OM (LFOM) is a reactive pool in sediment and is considered as labile fraction contributing to N and P cycling. In our study, the effect of LFOM on the process and characteristics of N and P mineralization in sediments of Taihu Lake were investigated with 77-day waterlogged incubation plus intermittent leaching at 27°C. Sediments from Yuantouzhu (Y) and Gonghu (G) were used, which were removed the LF. Results indicated that the organic nitrogen mineralized ranged from 14.3 to 19.5% of total nitrogen (193.49–378.93 mg kg⁻¹ sediment) and the organic phosphorus mineralized ranged from 5.7 to 7.9% of total phosphorus (19.86–60.65 mg kg⁻¹ sediment). The heavily polluted sediment had a higher mineralization rate and net mineral-N and mineral-P than slightly polluted sediment. LF stimulated the initial amounts of inorganic N and P and also can be the potential source for mineralization. After the LFOM removal, the net mineral-N of Y and G decreased 116.47 mg kg⁻¹ sediment and 48.03 mg kg⁻¹sediment, respectively, and the net mineral-P decreased 2.67 mg kg⁻¹sediment for Y and 4.82 mg kg⁻¹sediment for G. Two models were used to fit the observed mineral-N data vs. incubation days using a non-linear regression procedure: one is the effective cumulated temperature model, a thermodynamic model which assumes that N mineralization is affected by temperature; the other is the single first-order exponential model, which is a dynamic model. Based on root mean square error values for the two models, the effective cumulated temperature model made a better prediction of N mineralization than the other model for all the four treatments. The single first-order exponential model underestimated N mineralization during the first 14 days and the last 21 days, and overestimated it in the other days during the 77-day incubation. This indicated that temperature was the primary factor influencing N mineralization and the amount of mineral-N were correlated significantly with the effective cumulated temperature (T ≥ 15°C) and incubation time when waterlogged incubation plus intermittent leaching was used.     

陕西马元铅锌矿有机质与成矿作用的关系研究

陕西马元铅锌矿石的显著特征之一是富含有机质。除了肉眼和显微镜下能够识别的沥青外,还有丰富的呈分散状的有机质,要通过有机化学分析来确定其成分。笔者试图通过岩矿石光薄片显微鉴定、有机质含量、有机质碳同位素、饱和烃气相色谱等的测试分析,了解有机质在岩矿石中的赋存状态、有机质组成,认为沥青成因类型属于同生-成岩沥青、后生(改造)沥青及表生沥青;并根据正构烷烃、姥鲛烷、植烷等生物标志物,判别有机质母源,分析成矿环境,认为有机质与铅锌成矿有一定的关系。     

Role of Iron(III) and Aluminum Hydroxides in Concentration/reduction of Au(III) Complexes

Abstract: The adsorption of gold on iron(III) and aluminum hydroxides from solutions containing Au(III) complexes has been studied as a function of pH and chloride concentration at 30C. Iron(III) hydroxide was more effective in adsorbing gold from solution than aluminum hydroxide. However, both hydroxides controlled the behavior of Au(III) complex with very similar manner. The most effective gold adsorption occurred in aqueous solution with near neutral pH and low Cl concentration. In this solution condition, Au(III) complexes were mainly dissolved as AuCl₂(OH)₂^- and AuCl(OH)₃^-, and the surface charge for both hydroxides was positive. In addition, the adsorbed Au(III) complexes were spontaneously reduced to elemental gold in spite of the absence of a specific reducing agent.
The results of this study suggest that adsorption and spontaneous reduction of gold complexes on the surface of hydrous metal oxides with positive charge play an important role in gold precipitation in subsurface environment.     

Revisiting amorphous organic matter in Kimmeridgian laminites: what is the role of the vulcanization process in the amorphization of organic matter?

Kimmeridgian bituminous laminites from Orbagnoux (France) contain abundant amorphous organic matter (AOM). Previous studies have shown that the vulcanization pathway was the dominant preservation mechanism of AOM in these laminites, and led to its structureless aspect (a process called amorphization) at the nanoscale. In contrast, new observations in scanning electron microscopy and transmission electron microscopy demonstrate that this AOM exhibits typical cyanobacterial structures (exopolymeric substances, filamentous and coccoid bacteria) and ultralaminae. This identification is supported by a comparison with a recent cyanobacterial biofilm considered as an analogue. Moreover, this comparison demonstrates that ultralaminae in the Orbagnoux environment cannot solely be attributed to microalgal cell walls, but also to constituents of cyanobacteria. The microscopic identification of a ubiquitous cyanobacterial imprint demonstrates that the selective preservation pathway has been largely underestimated in Orbagnoux AOM and/or that the vulcanization process does not lead to the amorphization of organic matter automatically.     

Relative contributions of abiotic and biological factors in Fe(II) oxidation in mine drainage

The oxidation of Fe(II) is apparently the rate-limiting step in passive treatment of coal mine drainage. Little work has been done to determine the kinetics of oxidation in such field systems, and no models of passive treatment systems explicitly consider iron oxidation kinetics. A Stella II^™ model using Fe(II)_init concentration, pH, temperature, Thiobacillus ferrooxidans and O₂ concentration, flow rate, and pond volume is used to predict Fe(II) oxidation rates and concentrations in seventeen ponds under a wide range of conditions (pH 2.8 to 6.8 with Fe(II) concentrations of less than 240 mg L⁻¹) from 6 passive treatment facilities. The oxidation rate is modeled based on the combination of published abiotic and biological laboratory rate laws. Although many other variables have been observed to influence Fe(II) oxidation rates, the 7 variables above allow field systems to be modeled reasonably accurately for conditions in this study.Measured T. ferrooxidans concentrations were approximately 10⁷ times lower than concentrations required in the model to accurately predict field Fe(II) concentrations. This result suggests that either 1) the most probable number enumeration method underestimated the bacterial concentrations, or 2) the biological rate law employed underestimated the influence of bacteria, or both. Due to this discrepancy, bacterial concentrations used in the model for pH values of less than 5 are treated as fit parameters rather than empirically measured values.Predicted Fe(II) concentrations in ponds agree well with measured Fe(II) concentrations, and predicted oxidation rates also agree well with field-measured rates. From pH 2.8 to approximately pH 5, Fe(II) oxidation rates are negatively correlated with pH and catalyzed by T. ferrooxidans. From pH 5 to 6.4, Fe(II) oxidation appears to be primarily abiotic and is positively correlated with pH. Above pH 6.4, oxidation appears to be independent of pH. Above pH 5, treatment efficiency is affected most by changing design parameters in the following order: pH>temperature≈influent Fe(II)>pond volume≈O₂. Little to no increase in Fe(II) oxidation rate occurs due to pH increases above pH 6.4. Failure to consider Fe(II) oxidation rates in treatment system design may result in insufficient Fe removal.