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1.
Cathodoluminescence observations give information on the presence of europium in several minerals including apatite, fluorite, strontianite, and scheelite. Information on the oxidation state of the crystallization environment and on the partitioning of europium between coexisting mineral pairs may be obtained.The apatite in carbonatites and genetically related igneous rocks almost always contains europium in the divalent state. Occasionally both divalent and trivalent europium are observed.Europium is preferentially incorporated into strontianite when it crystallizes together with apatite in these same rocks. Similar results are found for fiuorite. 相似文献
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八卦庙大型金矿床稀土元素地球化学研究 总被引：22，自引：2，他引：22
八卦庙大型金矿床是秦岭造山带中的一种与碳酸盐岩有关的中温热液矿床。本系统总结了该矿床的稀土元素地球化学特征，对矿石、围岩、含金石英脉、酸性岩脉、铁的硫化物中的稀土元素组成、关系及成因进行了分析研究，论证了这个金矿床的形成与围岩、酸性岩脉、地壳深部金的矿源层有关。在此基础上应用简化了的Ｇｒｅｓｅｎｓ方程－Ｇｒａｎｔ方法讨论了热液蚀变过程中稀土元素地球化学行为，并分析了样品中出现Ｃｅ和Ｅｕ异常的原因， 相似文献
4.
在1/5万袁家房子等四幅区域矿产地质填图的基础上,对乌兰巴山复式岩体的野外地质特征、岩石学、矿物学、地球化学和同位素年代学等方面进行了初步研究.同位素锆石U-Pb分析结果表明,206 Pb/238 U表面年龄为225.4±1.6 Ma岩体,侵位时代为早三叠纪.该岩体总体展布受区域北东向构造控制明显.岩石化学、地球化学表明该复式岩体属钙碱性岩;东壕欠闪长岩可能为地幔成因,并有地壳物质的加入,乌兰巴山等花岗岩、二长花岗岩可能为壳源成因.稀土元素配分曲线显示出向右倾的平坦曲线型,轻稀土富集,重稀土明显亏损,无明显的铕异常 相似文献
5.
电感耦合等离子体质谱（ICP-MS） 测定地质样品中稀土元素的过程中,尤其对于高Ba基体的地质样品,由Ba形成
的氧化物和氢氧化物离子对Eu元素会产生质谱峰的重叠干扰,严重影响Eu测定结果的准确度和精确度。通过标准溶液的
条件实验,测定Ba干扰项相对Ba总量的比例（干扰率） 并进行相应的Eu扣除,是一种解决干扰导致Eu测定结果偏高的思
路。然而该干扰率在不同基质溶液中是否一致,且随着Ba含量变化是否稳定目前尚不明确。本文通过对不同基体溶液中Ba
对Eu干扰率的测定（低分辨模式测定）,发现随着溶液中Ba浓度的变化,同一基体溶液中该干扰率较为恒定,而不同基体
溶液中干扰率有明显的差别。这说明在对Eu测定结果进行干扰扣除时,需要利用匹配的基体溶液来获取准确的Ba干扰
率。应用这种方法扣除得到的Eu结果与质谱的高分辨模式（R=10000） 下的测定结果较为一致,数据的重现性也较为理
想。因此,利用基体匹配的方式来进行Ba对Eu的数学扣除是一种可行的方法。 相似文献
6.
The data on photoluminescence (PL) that precisely detects Eu2+ centers and X-ray luminescence (XL) were compared for plagioclases and potassium feldspars in 21 samples from muscovite pegmatites of the Mama region. The Eu contents determined in 10 samples vary from 10?4 to 10?6 wt %. Europium occurs mainly as bivalent species that replaces Sr2+, Ca2+, and Ba2+. Eu is gained in the products of early crystallization, and its relative amounts decrease by an order of magnitude in the course of pegmatite formation down to complete disappearance in late generations of feldspars. It is shown that Eu2+ can be detected in XL spectra, and the Eu2+ content can be determined in qualitative terms, for instance, by the intensity of radiation band 400–420 nm in plagioclase. 相似文献
7.
Z. Luo Ph.D. A. Wadhawan M. Sc. E. J. Bouwer Ph.D. 《International Journal of Environmental Science and Technology》2010,7(1):1-10
Sorption data were obtained with a Matawan soil and the following chromium (III) organic complexes: chromium (III) ascorbate, chromium (III) glutamate, chromium (III) histidine, chromium (III) mandelate, chromium (III) citrate, chromium (III) cysteine, chromium (III) serine, chromium (III) pyruvate and chromium (III) oxalate. The influence of pH (2–12), ionic strength (0.005–1 M) and concentration of sorbate (1–10 mg/L) on the extent of sorption was evaluated. The pH value did not influence the percent sorption at environmentally relevant pH 7. Ionic strength between 0.005 and 0.01 M KNO3 did not influence the sorption. Sorption and desorption data obtained at pH 7, 0.01 M KNO3 and 1–10 mg/L for each chromium (III) organic complex were analyzed using Freundlich and Langmuir models. The Freundlich model provided good fits for all of the chromium (III) organic complexes. Sorption data for chromium (III) glutamate, chromium (III) pyruvate, chromium (III) oxalate, chromium (III) cysteine, chromium (III) ascorbate and chromium (III) citrate were described well by the Langmuir model. Estimates for the saturated sorption capacities were 141, 70.9, 36.5, 35.5, 28.6 and 4.4 μg/g, respectively. It was not possible to desorb significant amounts of the previously sorbed chromium (III) organic complexes. At the same pH, ionic strength and solid:liquid ratio, the order of the observed sorption to the Matawan soil from highest to lowest was chromium (III) mandelate, chromium (III) glutamate, chromium (III) histidine, chromium (III) cysteine, chromium (III) serine, chromium (III) pyruvate, chromium (III) oxalate, chromium (III) ascorbate and chromium (III) citrate. 相似文献
8.
Michael M. Kimberley 《Chemical Geology》1979,25(3):185-212
Classification of iron formations according to the sedimentary-volcanic environments in which they formed reveals that chemical compositions of major iron-formation types are largely independent of deposit age. No evidence is found in iron formations for atmospheric-hydrospheric compositional evolution. However, chronological variation in relative abundance among major environmental types may indicate an Archean to Phanerozoic tectonic-magmatic evolution from abundant shallow-volcanic platforms through predominantly non-volcanic shallow platforms or flat continental shelves to abundant inland seas. Shallow-volcanic-platform iron formations typically display large positive europium anomalies and vary widely in silica, phosphorus and alkali content, even within individual iron formations. Various minor-element abundances may be substantial, particularly where phosphatic or near sulfide ore bodies. Iron formations which formed on extensive, chemical-sediment-rich continental shelves or non-volcanic oceanic platforms are generally silica-rich, phosphorus-poor, alkali-poor and minor-element-poor. Europium anomalies are normally small and mostly negative. Oolitic-inland-sea iron formations are poor in silica, except where gradational to sandstone, and are typically enriched in phosphorus and several ferrides. 相似文献
9.
内蒙古东北部阿龙山地区早白垩世A型花岗岩特征及其意义 总被引：1，自引：0，他引：1
内蒙古东北部阿龙山地区的早白垩世花岗岩岩体就位于火山喷发形成的塌陷破火山口中央或火山断裂中,岩石类型有石英二长（斑）岩、晶洞正长花岗岩、文象碱长石英正长岩等。岩石普遍具文象结构、晶洞构造,但未见碱性暗色矿物;岩石化学上具高硅、富碱和富铝、低钛镁等特征,且岩石中富集高场强元素（HFSE）,在微量元素蛛网图中出现Sr、Ba相对亏损,稀土配分曲线呈轻稀土富集的不对称右倾“海鸥”型,δEu亏损中等,岩石具较低的εNd（t）值（-3．00）和低的86Sr／87Sr初始值（0．708734）。以上岩体的岩石学、主微量元素及同位素特征表明,岩体具有铝质A1型花岗岩的特征,其成因与陆内巨量火山喷发造成的伸展、崩塌机制有关,反映了非造山板内拉张的构造环境。 相似文献
10.
Oxidation of As(III) by natural manganese (hydr)oxides is an important geochemical reaction mediating the transformation of highly concentrated As(III) in the acidic environment such as acid mine drainage (AMD) and industrial As-contaminated wastewater, however, little is known regarding the presence of dissolved Fe(II) on the oxidation process. In this study, oxidation of As(III) in the absence and presence of Fe(II) by MnO2 under acidic conditions was investigated. Kinetic results showed that the presence of Fe(II) significantly inhibited the removal of As(III) (including oxidation and sorption) by MnO2 in As(III)-Fe(II) simultaneous oxidation system even at the molar ratio of Fe(II):As(III) = 1/64:1, and the inhibitory effects increased with the increasing ratios of Fe(II):As(III). Such an inhibition could be attributed to the formation of Fe(III) compounds covering the surface of MnO2 and thus preventing the oxidizing sites available to As(III). On the other hand, the produced Fe(III) compounds adsorbed more As(III) and the oxidized As(V) on the MnO2 surface with an increasing ratio of Fe(II):As(III) as demonstrated in kinetic and XPS results. TEM and EDX results confirmed the formation of Fe compounds around MnO2 particles or separated in solution in Fe(II) individual oxidation system, Fe(II) pre-treated and simultaneous oxidation processes, and schwertmannite was detected in Fe(II) individual and Fe pre-treated oxidation processes, while a new kind of mineral, probably amorphous FeOHAs or FeAsO4 particles were detected in Fe(II)-As(III) simultaneous oxidation process. This suggests that the mechanisms are different in Fe pre-treated and simultaneous oxidation processes. In the Fe pre-treated and MnO2-mediated oxidation pathway, As(III) diffused through a schwertmannite coating formed around MnO2 particles to be oxidized. The newly formed As(V) was adsorbed onto the schwertmannite coating until its sorption capacity was exceeded. Arsenic(V) then diffused out of the coating and was released into the bulk solution. The diffusion into the schwertmannite coating and the oxidation of As(III) and sorption of both As(V) and As(III) onto the coating contributed to the removal of total As from the solution phase. In the simultaneous oxidation pathway, the competitive oxidation of Fe(II) and As(III) on MnO2 occurred first, followed by the formation of FeOHAs or FeAsO4 around MnO2 particles, and these poorly crystalline particles of FeOHAs and FeAsO4 remained suspended in the bulk solution to adsorb As(III) and As(V). The present study reveals that the formation of Fe(III) compounds on mineral surfaces play an important role in the sorption and oxidation of As(III) by MnO2 under acidic conditions in natural environments, and the mechanisms involved in the oxidation of As(III) depend upon how Fe(II) is introduced into the As(III)-MnO2 system. 相似文献
11.
Experimental batch and miscible-flow cultures were studied in order to determine the mechanistic pathways of microbial Fe(III)
respiration in ferruginous smectite clay, NAu-1. The primary purpose was to resolve if alteration of smectite and release
of Fe precedes microbial respiration. Alteration of NAu-1, represented by the morphological and mineralogical changes, occurred
regardless of the extent of microbial Fe(III) reduction in all of our experimental systems, including those that contained
heat-killed bacteria and those in which O2, rather than Fe(III), was the primary terminal electron acceptor. The solid alteration products observed under transmission
electron microscopy included poorly crystalline smectite with diffuse electron diffraction signals, discrete grains of Fe-free
amorphous aluminosilicate with increased Al/Si ratio, Fe-rich grains, and amorphous Si globules in the immediate vicinity
of bacterial cells and extracellular polymeric substances. In reducing systems, Fe was also found as siderite. The small amount
of Fe partitioned to the aqueous phase was primarily in the form of dissolved Fe(III) species even in the systems in which
Fe(III) was the primary terminal electron acceptor for microbial respiration. From these observations, we conclude that microbial
respiration of Fe(III) in our laboratory systems proceeded through the following: (1) alteration of NAu-1 and concurrent release
of Fe(III) from the octahedral sheets of NAu-1; and (2) subsequent microbial respiration of Fe(III). 相似文献
12.
Particulate matter plays an important role in the removal of metal ions from water in natural aquifers. Some of the most important of these materials consist of associations of inorganic particles (clay minerals, oxides) with humic substances, associations that can form readily in such an environment due to the strong affinity between inorganic particles and humic substances. These associations are referred to in this paper as organic-inorganic hybrids. However, it is not clear whether the sorbed species of metal ions in such organic-inorganic hybrids are organic or inorganic species because of the complexity of such hybrids and the lack of appropriate methods for characterizing the trace metal ions incorporated in them. In this study, laser-induced fluorescence spectroscopy (LIF) was used successfully to characterize the Cm(III) species on an FA(fulvic acid)-montmorillonite hybrid, an example of such organic-inorganic hybrids. The LIF clearly showed that Cm(III) can be sorbed as Cm(III)-fulvate complex in the FA-montmorillonite hybrid. These results were consistent with those of experiments of solid-water partitioning of Cm(III) (or Eu(III) used as an analogue) and speciation calculations based on the stability constants of Cm(III)-fulvate complexes determined in this study. The results of LIF and the partitioning experiments showed that the solid-water distribution of humic substances governed that of Cm(III) under our experimental conditions. The Cm(III) preference for forming Cm(III)-fulvate complexes was also evident under a condition that would be found in a natural aquifer with a fairly low concentration of organic matter in freshwater (dissolved organic carbon: 2 mg/dm3), as determined by our speciation calculations. These findings on the importance of humic substances in the migration of Cm(III) indicate that the clarification of the environmental behavior of humic substances is necessary to understand fully the behavior of Cm(III), or actinide(III) and lanthanide(III) ions, in natural aquifers. 相似文献
13.
Arsenic and Sb are common mine-water pollutants and their toxicity and fate are strongly influenced by redox processes. In this study, simultaneous Fe(II), As(III) and Sb(III) oxidation experiments were conducted to obtain rates under laboratory conditions similar to those found in the field for mine waters of both low and circumneutral pH. Additional experiments were performed under abiotic sterile conditions to determine the biotic and abiotic contributions to the oxidation processes. The results showed that under abiotic conditions in aerated Fe(III)–H2SO4 solutions, Sb(III) oxidizes slightly faster than As(III). The oxidation rates of both elements were accelerated by increasing As(III), Sb(III), Fe(III), and Cl− concentrations in the presence of light. For unfiltered circumneutral water from the Giant Mine (Yellowknife, NWT, Canada), As(III) oxidized at 15–78 μmol/L/h whereas Sb(III) oxidized at 0.03–0.05 μmol/L/h during microbial exponential growth. In contrast, As(III) and Sb(III) oxidation rates of 0.01–0.03 and 0.01–0.02 μmol/L/h, respectively, were obtained in experiments performed with acid unfiltered mine waters from the Iberian Pyritic Belt (SW Spain). These results suggest that the Fe(III) formed from microbial oxidation abiotically oxidized As(III) and Sb(III). After sterile filtration of both mine water samples, neither As(III), Sb(III), nor Fe(II) oxidation was observed. Hence, under the experimental conditions, bacteria were catalyzing As and Sb oxidation in the Giant Mine waters and Fe oxidation in the acid waters of the Iberian Pyrite Belt. 相似文献
14.
In the present study, we investigated As behavior in a high-As hot spring (Sambe hot spring, Shimane, Japan) by coupling direct chemical speciation by synchrotron-based XAFS and HPLC–ICP-MS with microbial As-redox transformation gene analysis. The concentration of soluble As in the spring streamwater decreased immediately along the flow in correlation with Fe behavior, indicating that As in the streamwater was naturally attenuated in the streamwater. Iron XAFS analysis suggested deposition of Fe(III) oxyhydroxides along the flow. Thus, considering the strong affinity of As to Fe oxyhydroxides, the observed attenuation in As was possibly caused by sorption (or incorporation) of As on Fe(III) oxyhydroxides. Both dissolved As(III) and As(V) were present in the aqueous phase, and As(III) was rapidly oxidized to As(V) (<30 s) along the flow. The oxidation kinetics indicated the occurrence of biotic As(III) oxidation, because obtained As(III) oxidation rate (6.7–7.8 μM min−1) was much faster than the reported abiotic oxidation rates. Furthermore, the bacterial arsenite oxidase gene (aioA) was detected in DNA extracted from all samples (average of 2.0 × 105 copies dry g−1), which also supported potential attributes of biological As(III) oxidation in situ. In solid phase samples from sampling points analyzed by XAFS, most of the As existed as oxidized pentavalent form, As(V). This result indicated that this form was preferentially partitioned to the solid phase because of the much higher affinity of As(V) than of As(III) to Fe(III) oxyhydroxides. Considering the kinetic and microbiological findings, it is indicated that biotic process was predominantly responsible for As(III) oxidation at the present site, and this biotic As(III) oxidation to As(V) controlled the observed attenuation of As, because oxidized As(V) was removed from the aqueous phase by Fe(III) oxyhydroxides more efficiently. 相似文献
15.
Samantha L. Shumlas Soujanya Singireddy Akila C. Thenuwara Nuwan H. Attanayake Richard J. Reeder Daniel R. Strongin 《Geochemical transactions》2016,17(1):5
The effect of simulated solar radiation on the oxidation of arsenite [As(III)] to arsenate [As(V)] on the layered manganese oxide, birnessite, was investigated. Experiments were conducted where birnessite suspensions, under both anoxic and oxic conditions, were irradiated with simulated solar radiation in the presence of As(III) at pH 5, 7, and 9. X-ray absorption spectroscopy (XAS) was used to determine the nature of the adsorbed product on the surface of the birnessite. The oxidation of As(III) in the presence of birnessite under simulated solar light irradiation occurred at a rate that was faster than in the absence of light at pH 5. At pH 7 and 9, As(V) production was significantly less than at pH 5 and the amount of As(V) production for a given reaction time was the same under dark and light conditions. The first order rate constant (kobs) for As(III) oxidation in the presence of light and in the dark at pH 5 were determined to be 0.07 and 0.04 h?1, respectively. The As(V) product was released into solution along with Mn(II), with the latter product resulting from the reduction of Mn(IV) and/or Mn(III) during the As(III) oxidation process. Post-reaction XAS analysis of As(III) exposed birnessite showed that arsenic was present on the surface as As(V). Experimental results also showed no evidence that reactive oxygen species played a role in the As(III) oxidation process. 相似文献
16.
John M. Zachara Ravi K. Kukkadapu Alice Dohnalkova Todd Anderson 《Geochimica et cosmochimica acta》2004,68(8):1791-1805
The Bemidji aquifer in Minnesota, USA is a well-studied site of subsurface petroleum contamination. The site contains an anoxic groundwater plume where soluble petroleum constituents serve as an energy source for a region of methanogenesis near the source and bacterial Fe(III) reduction further down gradient. Methanogenesis apparently begins when bioavailable Fe(III) is exhausted within the sediment. Past studies indicate that Geobacter species and Geothrix fermentens-like organisms are the primary dissimilatory Fe-reducing bacteria at this site. The Fe mineralogy of the pristine aquifer sediments and samples from the methanogenic (source) and Fe(III) reducing zones were characterized in this study to identify microbiologic changes to Fe valence and mineral distribution, and to identify whether new biogenic mineral phases had formed. Methods applied included X-ray diffraction; X-ray fluorescence (XRF); and chemical extraction; optical, transmission, and scanning electron microscopy; and Mössbauer spectroscopy.All of the sediments were low in total Fe content (≈ 1%) and exhibited complex Fe-mineralogy. The bulk pristine sediment and its sand, silt, and clay-sized fractions were studied in detail. The pristine sediments contained Fe(II) and Fe(III) mineral phases. Ferrous iron represented approximately 50% of FeTOT. The relative Fe(II) concentration increased in the sand fraction, and its primary mineralogic residence was clinochlore with minor concentrations found as a ferroan calcite grain cement in carbonate lithic fragments. Fe(III) existed in silicates (epidote, clinochlore, muscovite) and Fe(III) oxides of detrital and authigenic origin. The detrital Fe(III) oxides included hematite and goethite in the form of mm-sized nodular concretions and smaller-sized dispersed crystallites, and euhedral magnetite grains. Authigenic Fe(III) oxides increased in concentration with decreasing particle size through the silt and clay fraction. Chemical extraction and Mössbauer analysis indicated that this was a ferrihydrite like-phase. Quantitative mineralogic and Fe(II/III) ratio comparisons between the pristine and contaminated sediments were not possible because of textural differences. However, comparisons between the texturally-similar source (where bioavailable Fe(III) had been exhausted) and Fe(III) reducing zone sediments (where bioavailable Fe(III) remained) indicated that dispersed detrital, crystalline Fe(III) oxides and a portion of the authigenic, poorly crystalline Fe(III) oxide fraction had been depleted from the source zone sediment by microbiologic activity. Little or no effect of microbiologic activity was observed on silicate Fe(III). The presence of residual “ferrihydrite” in the most bioreduced, anoxic plume sediment (source) implied that a portion of the authigenic Fe(III) oxides were biologically inaccessible in weathered, lithic fragment interiors. Little evidence was found for the modern biogenesis of authigenic ferrous-containing mineral phases, perhaps with the exception of thin siderite or ferroan calcite surface precipitates on carbonate lithic fragments within source zone sediments. 相似文献
17.
Fe(III) complexed by organic ligands (Fe(III)L) is the primary form of dissolved Fe in marine and coastal environments. Superoxide, typically produced in biological and photochemical processes, is one of the reducing agents that contributes to transformation of Fe(III)L to bioavailable, free dissolved Fe(II) (Fe(II)′). In this work, the kinetics of superoxide-mediated Fe(II)′ formation from Fe(III)L in a simulated coastal water system were investigated and a comprehensive kinetic model was developed using citrate and fulvic acid as exemplar Fe-binding ligands. To simulate a coastal environment in laboratory experiments, Fe(III)L samples with various ligand/Fe ratios were incubated for 5 min to 1 week in seawater medium. At each ratio and incubation time, the rate of superoxide-mediated Fe(II)′ formation was determined in the presence of the strong Fe(II) binding ligand ferrozine by spectrophotometrically measuring the ferrous-ferrozine complex generated at a constant concentration of superoxide. The Fe(II)′ formation rate generally decreased with incubation time, as Fe(III)L gradually dissociated to form less reactive Fe(III) oxyhydroxide. However, when the ligand/Fe ratio was sufficiently high, the dissociation of Fe(III)L (and subsequent Fe precipitation) was suppressed and Fe(II)′ was formed at a higher rate. The rate of Fe(II)′ produced during the experiment was explained by the kinetic model. The model confirmed that both the ligand/Fe ratio and incubation time have a significant effect on the pathway via which Fe(II)′ is formed from Fe(III)-fulvic acid complexes. 相似文献
18.
19.
Microbial reduction of Fe(III) in clay minerals is an important process that affects properties of clay-rich materials and iron biogeochemical cycling in natural environments. Microbial reduction often ceases before all Fe(III) in clay minerals is exhausted. The factors causing the cessation are, however, not well understood. The objective of this study was to assess the role of biogenic Fe(II) in microbial reduction of Fe(III) in clay minerals nontronite, illite, and chlorite. Bioreduction experiments were performed in batch systems, where lactate was used as the sole electron donor, Fe(III) in clay minerals as the sole electron acceptor, and Shewanella putrefaciens CN32 as the mediator with and without an electron shuttle (AQDS). Our results showed that bioreduction activity ceased within two weeks with variable extents of bioreduction of structural Fe(III) in clay minerals. When fresh CN32 cells were added to old cultures (6 months), bioreduction resumed, and extents increased. Thus, cessation of Fe(III) bioreduction was not necessarily due to exhaustion of bioavailable Fe(III) in the mineral structure, but changes in cell physiology or solution chemistry, such as Fe(II) production during microbial reduction, may have inhibited the extent of bioreduction. To investigate the effect of Fe(II) inhibition on CN 32 reduction activity, a typical bioreduction process (consisting of lactate, clay, cells, and AQDS in a single tube) was separated into two steps: (1) AQDS was reduced by cells in the absence of clay; (2) Fe(III) in clays was reduced by biogenic AH2DS in the absence of cells. With this method, the extent of Fe(III) reduction increased by 45-233%, depending on the clay mineral involved. Transmission electron microscopy observation revealed a thick halo surrounding cell surfaces that most likely resulted from Fe(II) sorption/precipitation. Similarly, the inhibitory effect of Fe(II) sorbed onto clay surfaces was assessed by presorbing a certain amount of Fe(II) onto clay surfaces followed by AH2DS reduction of Fe(III). The reduction extent consistently decreased with an increasing amount of presorbed Fe(II). The relative reduction extent [i.e., the reduction extent normalized to that when the amount of presorbed Fe(II) was zero] was similar for all clay minerals studied and showed a systematic decrease with an increasing clay-presorbed Fe(II) concentration. These results suggest a similar inhibitory effect of clay-sorbed Fe(II) for different clay minerals. An equilibrium thermodynamic model was constructed with independently estimated parameters to evaluate whether the observed cessation of Fe(III) reduction by AH2DS was due to exhaustion of reaction free energy. Model-calculated reduction extents were, however, over 50% higher than experimentally measured, indicating that other factors, such as blockage of the electron transfer chain and mineralogy, restricted the reduction extent. Another important result of this study was the relative reducibility of Fe(III) in different clays: nontronite > chlorite > illite. This order was qualitatively consistent with the differences in the crystal structure and layer charge of these minerals. 相似文献
20.
A quantitative study was performed to understand how Fe(III) site occupancy controls Fe(III) bioreduction in nontronite by Shewanella putrefaciens CN32. NAu-1 and NAu-2 were nontronites and contained Fe(III) in different structural sites with 16 and 23% total iron (w/w), respectively, with almost all iron as Fe(III). Mössbauer spectroscopy showed that Fe(III) was present in the octahedral site in NAu-1 (with a small amount of goethite), but in both the tetrahedral and the octahedral sites in NAu-2. Mössbauer data further showed that the octahedral Fe(III) in NAu-2 existed in at least two environments- trans (M1) and cis (M2) sites. The microbial Fe(III) reduction in NAu-1 and NAu-2 was studied in batch cultures at a nontronite concentration of 5 mg/mL in bicarbonate buffer with lactate as the electron donor. The unreduced and bioreduced nontronites were characterized by X-ray diffraction (XRD), Mössbauer spectroscopy, and transmission electron microscopy (TEM). In the presence of an electron shuttle, anthraquinone-2,6-disulfonate (AQDS), the extent of bioreduction was 11%-16% for NAu-1 but 28%-32% for NAu-2. The extent of reduction in the absence of AQDS was only 5%-7% for NAu-1 but 14%-18% for NAu-2. The control experiments with heat killed cells and without cells did not show any appreciable reduction (<2%). The extent of reduction in experiments performed with a dialysis membrane to separate cells from clays (without AQDS) was 2%-3% for NAu-1 but 5%-7% for NAu-2, suggesting that cells probably released an electron shuttling compound and/or Fe(III) chelator. The reduction rate was also faster in NAu-2 than that in NAu-1. Mössbauer data of the bioreduced nontronite materials indicated that the Fe(III) reduction in NAu-1 was mostly from the presence of goethite, whereas the reduction in NAu-2 was due to the presence of the tetrahedral and trans-octahedral Fe(III) in the structure. The measured aqueous Fe(II) was negligible. As a result of bioreduction, the average nontronite particle thickness remained nearly the same (from 2.1 to 2.5 nm) for NAu-1, but decreased significantly from 6 to 3.5 nm for NAu-2 with a concomitant change in crystal size distribution. The decrease in crystal size suggests reductive dissolution of nontronite NAu-2, which was supported by aqueous solution chemistry (i.e., aqueous Si). These data suggest that the more extensive Fe(III) bioreduction in NAu-2 was due to the presence of the tetrahedral and the trans-octahedral Fe(III), which was presumed to be more reducible. The biogenic Fe(II) was not associated with biogenic solids or in the aqueous solution. We infer that it may be either adsorbed onto surfaces of nontronite particles/bacteria or in the structure of nontronite. Furthermore, we have demonstrated that natural nontronite clays were capable of supporting cell growth even in medium without added nutrients, possibly due to presence of naturally existing nutrients in the nontronite clays. These results suggest that crystal chemical environment of Fe(III) is an important determinant in controlling the rate and extent of microbial reduction of Fe(III) in nontronite. 相似文献