Simultaneously Quantifying Ferrihydrite and Goethite in Natural Sediments Using the Method of Standard Additions with X-ray Absorption Spectroscopy.
ABSTRACT: The presence of ferrihydrite in sediments/soils is critical to the cycling of iron (Fe) and many other elements but difficult to quantify. Extended X-ray absorption fine structure (EXAFS) spectroscopy has been used to speciate Fe in the solid phase, but this method is thought to have difficulties in distinguishing ferrihydrite from goethite and other minerals. In this study, both conventional EXAFS linear combination fitting (LCF) and the method of standard-additions are applied to the same samples in attempt to quantify ferrihydrite and goethite more rigorously. Natural aquifer sediments from Bangladesh and the United States were spiked with known quantities of ferrihydrite, goethite and magnetite, and analyzed by EXAFS. Known mineral mixtures were also analyzed. Evaluations of EXAFS spectra of mineral references and EXAFS-LCF fits on various samples indicate that ferrihydrite and microcrystalline goethite can be distinguished and quantified by EXAFS-LCF but that the choice of mineral references is critical to yield consistent results. Conventional EXAFS-LCF and the method of standard-additions both identified appreciable amount of ferrihydrite in Bangladesh sediments that were obtained from a low-arsenic Pleistocene aquifer. Ferrihydrite was also independently detected by sequential extraction and 57Fe M?ssbauer spectroscopy. These observations confirm the accuracy of conventional EXAFS-LCF and demonstrate that combining EXAFS with additions of reference materials provides a more robust means of quantifying short-range-ordered minerals in complex samples.
Project description:In situ precipitation of magnetite and other minerals potentially sequesters dissolved arsenic (As) in contaminated aquifers. This study examines As retention and transport in aquifer sediments using a multistage column experiment in which magnetite and other minerals formed from added nitrate and ferrous iron (Fe). Sediments were collected from the Dover Municipal Landfill Superfund site. Prior to nitrate-Fe(II) addition, As was not effectively retained within the sediments in the column. The combination of nitrate (10 mM) and Fe(II) (4 mM), resulted in mineral precipitation and rapidly decreased effluent As concentrations to <10 ?g L(-1). Mineralogical analyses of sectioned replicate columns using sequential extractions, magnetic susceptibility and X-ray absorption spectroscopy indicate that magnetite and ferrihydrite formed in the column following nitrate-Fe(II) addition. This magnetite persisted in the column even as conditions became reducing, whereas ferrihydrite was transformed to more stable Fe oxides. This magnetite incorporated As into its structure during precipitation and subsequently adsorbed As. Adsorption to the minerals kept effluent As concentrations <10 ?g L(-1) for more than 100 pore volumes despite considerable Fe reduction. The results indicate that it should be feasible to produce an in situ reactive filter by nitrate-Fe(II) injection.
Project description:Serpentine soils and ultramafic laterites develop over ultramafic bedrock and are important geological materials from environmental, geochemical, and industrial standpoints. They have naturally elevated concentrations of trace metals, such as Ni, Cr, and Co, and also high levels of Fe and Mg. Minerals host these trace metals and influence metal mobility. Ni in particular is an important trace metal in these soils, and the objective of this research was to use microscale (µ) techniques to identify naturally occurring minerals that contain Ni and Ni correlations with other trace metals, such as Fe, Mn, and Cr. Synchrotron based µ-XRF, µ-XRD, and µ-XAS were used. Ni was often located in the octahedral layer of serpentine minerals, such as lizardite, and in other layered phyllosilicate minerals with similar octahedral structure, such as chlorite group minerals including clinochlore and chamosite. Ni was also present in goethite, hematite, magnetite, and ferrihydrite. Goethite was present with lizardite and antigorite on the micrometer scale. Lizardite integrated both Ni and Mn simultaneously in its octahedral layer. Enstatite, pargasite, chamosite, phlogopite, and forsterite incorporated various amounts of Ni and Fe over the micrometer spatial scale. Ni content increased six to seven times within the same 500 µm µ-XRD transect on chamosite and phlogopite. Data are shown down to an 8 µm spatial scale. Ni was not associated with chromite or zincochromite particles. Ni often correlated with Fe and Mn, and generally did not correlate with Cr, Zn, Ca, or K in µ-XRF maps. A split shoulder feature in the µ-XAS data at 8400 eV (3.7 Å<sup>-1</sup> in k-space) is highly correlated (94% of averaged LCF results) to Ni located in the octahedral sheet of layered phyllosilicate minerals, such as serpentine and chlorite-group minerals. A comparison of bulk-XAS LCF to averaged µ-XAS LCF results showed good representation of the bulk soil via the µ-XAS technique for two of the three soils. In the locations analyzed by µ-XAS, average Ni speciation was dominated by layered phyllosilicate and serpentine minerals (76%), iron oxides (18%), and manganese oxides (9%). In the locations analyzed by µ-XRD, average Ni speciation was dominated by layered phyllosilicate, serpentine, and ultramafic-related minerals (71%) and iron oxides (17%), illustrating the complementary nature of these two methods.
Project description:Fe(III) (oxyhydr)oxides are electron acceptors for some hyperthermophilic archaea in mildly reducing geothermal environments. However, the kinds of iron oxides that can be used, growth rates, extent of iron reduction, and the morphological changes that occur to minerals are poorly understood. The hyperthermophilic iron-reducing crenarchaea Pyrodictium delaneyi and Pyrobaculum islandicum were grown separately on six different synthetic nanophase Fe(III) (oxyhydr)oxides. For both organisms, growth on ferrihydrite produced the highest growth rates and the largest amounts of Fe(II), although P. delaneyi produced four times more Fe(II) (25 mM) than P. islandicum (6 mM). Both organisms grew on lepidocrocite and akaganéite and produced 2 and 3 mM Fe(II). Modest growth occurred for both organisms on goethite, hematite, and maghemite where ?1 mM Fe(II) was produced. The diameters of the spherical mineral end-products following P. delaneyi growth increased by 30 nm for ferrihydrite and 50-150 nm for lepidocrocite relative to heated abiotic controls. For akaganéite, spherical particle sizes were the same for P. delaneyi-reacted samples and heated abiotic controls, but the spherical particles were more numerous in the P. delaneyi samples. For P. islandicum, there was no increase in grain size for the mineral end-products following growth on ferrihydrite, lepidocrocite, or akaganéite relative to the heated abiotic controls. High-resolution transmission electron microscopy of lattice fringes and selected-area electron diffraction of the minerals produced by both organisms when grown on ferrihydrite showed that magnetite and/or possibly maghemite were the end-products while the heated abiotic controls only contained ferrihydrite. These results expand the current view of bioavailable Fe(III) (oxyhydr)oxides for reduction by hyperthermophilic archaea when presented as synthetic nanophase minerals. They show that growth and reduction rates are inversely correlated with the iron (oxyhydr)oxide crystallinity and that iron (oxyhydr)oxide mineral transformation takes different forms for these two organisms.
Project description:Mineral elements in soil solutions are thought to be the precursor of the formation of reactive minerals, which play an important role in global carbon (C) cycling. However, information regarding the regulation of mineral elements release in soil is scarce. Here, we examined the long-term (i.e., 23 yrs) effects of fertilisation practices on Fe minerals in a red soil in Southern China. The results from chemical analysis and Fourier-transform infrared spectroscopy showed that long-term swine manure (M) treatment released greater amounts of minerals into soil solutions than chemical fertilisers (NPK) treatment, and Fe played a dominant role in the preservation of dissolved organic C. Furthermore, Fe K-edge X-ray absorption near-edge fine structure spectroscopy demonstrated that reactive Fe minerals were mainly composed of less crystalline ferrihydrite in the M-treated soil and more crystalline goethite in the NPK-treated soil. In conclusion, this study reported spectroscopic evidence of the improvement of reactive Femineral content in the M-treated soil colloids when compared to NPK-treated soil colloids.
Project description:Microbial iron reduction is considered to be a significant subsurface process. The rate-limiting bioavailability of the insoluble iron oxyhydroxides, however, is a topic for debate. Surface area and mineral structure are recognized as crucial parameters for microbial reduction rates of bulk, macroaggregate iron minerals. However, a significant fraction of iron oxide minerals in the subsurface is supposed to be present as nanosized colloids. We therefore studied the role of colloidal iron oxides in microbial iron reduction. In batch growth experiments with Geobacter sulfurreducens, colloids of ferrihydrite (hydrodynamic diameter, 336 nm), hematite (123 nm), goethite (157 nm), and akaganeite (64 nm) were added as electron acceptors. The colloidal iron oxides were reduced up to 2 orders of magnitude more rapidly (up to 1,255 pmol h(-1) cell(-1)) than bulk macroaggregates of the same iron phases (6 to 70 pmol h(-1) cell(-1)). The increased reactivity was not only due to the large surface areas of the colloidal aggregates but also was due to a higher reactivity per unit surface. We hypothesize that this can be attributed to the high bioavailability of the nanosized aggregates and their colloidal suspension. Furthermore, a strong enhancement of reduction rates of bulk ferrihydrite was observed when nanosized ferrihydrite aggregates were added.
Project description:Reactive Fe(III) minerals can influence methane (CH<sub>4</sub> ) emissions by inhibiting microbial methanogenesis or by stimulating anaerobic CH<sub>4</sub> oxidation. The balance between Fe(III) reduction, methanogenesis, and CH<sub>4</sub> oxidation in ferruginous Archean and Paleoproterozoic oceans would have controlled CH<sub>4</sub> fluxes to the atmosphere, thereby regulating the capacity for CH<sub>4</sub> to warm the early Earth under the Faint Young Sun. We studied CH<sub>4</sub> and Fe cycling in anoxic incubations of ferruginous sediment from the ancient ocean analogue Lake Matano, Indonesia, over three successive transfers (500 days in total). Iron reduction, methanogenesis, CH<sub>4</sub> oxidation, and microbial taxonomy were monitored in treatments amended with ferrihydrite or goethite. After three dilutions, Fe(III) reduction persisted only in bottles with ferrihydrite. Enhanced CH<sub>4</sub> production was observed in the presence of goethite, highlighting the potential for reactive Fe(III) oxides to inhibit methanogenesis. Supplementing the media with hydrogen, nickel and selenium did not stimulate methanogenesis. There was limited evidence for Fe(III)-dependent CH<sub>4</sub> oxidation, although some incubations displayed CH<sub>4</sub> -stimulated Fe(III) reduction. 16S rRNA profiles continuously changed over the course of enrichment, with ultimate dominance of unclassified members of the order Desulfuromonadales in all treatments. Microbial diversity decreased markedly over the course of incubation, with subtle differences between ferrihydrite and goethite amendments. These results suggest that Fe(III) oxide mineralogy and availability of electron donors could have led to spatial separation of Fe(III)-reducing and methanogenic microbial communities in ferruginous marine sediments, potentially explaining the persistence of CH<sub>4</sub> as a greenhouse gas throughout the first half of Earth history.
Project description:Long-term exposure to trace levels of arsenic (As) in shallow groundwater used for drinking and irrigation puts millions of people at risk of chronic disease. Although microbial processes are implicated in mobilizing arsenic from aquifer sediments into groundwater, the precise mechanism remains ambiguous. The goal of this work was to target, for the first time, a comprehensive suite of state-of-the-art molecular techniques in order to better constrain the relationship between indigenous microbial communities and the iron and arsenic mineral phases present in sediments at two well-characterized arsenic-impacted aquifers in Bangladesh. At both sites, arsenate [As(V)] was the major species of As present in sediments at depths with low aqueous As concentrations, while most sediment As was arsenite [As(III)] at depths with elevated aqueous As concentrations. This is consistent with a role for the microbial As(V) reduction in mobilizing arsenic. 16S rRNA gene analysis indicates that the arsenic-rich sediments were colonized by diverse bacterial communities implicated in both dissimilatory Fe(III) and As(V) reduction, while the correlation analyses involved phylogenetic groups not normally associated with As mobilization. Findings suggest that direct As redox transformations are central to arsenic fate and transport and that there is a residual reactive pool of both As(V) and Fe(III) in deeper sediments that could be released by microbial respiration in response to hydrologic perturbation, such as increased groundwater pumping that introduces reactive organic carbon to depth.IMPORTANCE The consumption of arsenic in waters collected from tube wells threatens the lives of millions worldwide and is particularly acute in the floodplains and deltas of southern Asia. The cause of arsenic mobilization from natural sediments within these aquifers to groundwater is complex, with recent studies suggesting that sediment-dwelling microorganisms may be the cause. In the absence of oxygen at depth, specialist bacteria are thought able to use metals within the sediments to support their metabolism. Via these processes, arsenic-contaminated iron minerals are transformed, resulting in the release of arsenic into the aquifer waters. Focusing on a field site in Bangladesh, a comprehensive, multidisciplinary study using state-of-the-art geological and microbiological techniques has helped better understand the microbes that are present naturally in a high-arsenic aquifer and how they may transform the chemistry of the sediment to potentially lethal effect.
Project description:Trace-element concentrations in acid mine drainage (AMD) are primarily controlled by the mineralogy at the sediment-water interface. Results are presented for a combined geochemical and mineralogical survey of Dabaoshan Mine, South China. Developed sequential extraction experiments with the analysis of the main mineralogical phases by semi-quantitative XRD, differential X-ray diffraction (DXRD) and scanning electron microscopy (SEM) were conducted to identify the quantitative relationship between iron minerals and heavy metals. Results showed that schwertmannite, jarosite, goethite and ferrihydrite were the dominant Fe-oxyhydroxide minerals which were detected alternately in the surface sediment with the increasing pH from 2.50 to 6.93 along the Hengshi River. Decreasing contents of schwertmannite ranging from 35 wt % to 6.5 wt % were detected along the Hengshi River, which was corresponding to the decreasing metal contents. The easily reducible fractions exert higher affinity of metals while compared with reducible and relatively stable minerals. A qualitative analysis of heavy metals extracted from the sediments indicated that the retention ability varied: Pb > Mn > Zn > As ? Cu > Cr > Cd ? Ni. Results in this study are avail for understanding the fate and transport of heavy metals associated with iron minerals and establishing the remediation strategies of AMD systems.
Project description:Recent laboratory studies have demonstrated that coinjection of nitrate and Fe(II) (as ferrous sulfate) to As-bearing sediments can produce an Fe mineral assemblage containing magnetite capable of immobilizing advected As under a relatively wide range of aquifer conditions. This study combined laboratory findings with process-based numerical modeling approaches, to quantify the observed Fe mineral (trans)formation and concomitant As partitioning dynamics and to assess potential nitrate-Fe(II) remediation strategies for field implementation. The model development was guided by detailed solution and sediment data from our well-controlled column experiment. The modeling results demonstrated that the fate of As during the experiment was primarily driven by ferrihydrite formation and reductive transformation and that different site densities were identified for natural and neoformed ferrihydrite to explain the observations both before and after nitrate-Fe(II) injection. Our results also highlighted that when ferrihydrite was nearing depletion, As immobilization ultimately relied on the presence of magnetite. On the basis of the column model, field-scale predictive simulations were conducted to illustrate the feasibility of the nitrate-Fe(II) strategy for intercepting advected As from a plume. The predictive simulations, which suggested that long-term As immobilization was feasible, favored a scenario that maintains high dissolved Fe(II) concentration during injection periods and thereby converts ferrihydrite to magnetite.
Project description:Bacterial adhesion onto mineral surfaces and subsequent biofilm formation play key roles in aggregate stability, mineral weathering, and the fate of contaminants in soils. However, the mechanisms of bacteria-mineral interactions are not fully understood. Atomic force microscopy (AFM) was used to determine the adhesion forces between bacteria and goethite in water and to gain insight into the nanoscale surface morphology of the bacteria-mineral aggregates and biofilms formed on clay-sized minerals. This study yields direct evidence of a range of different association mechanisms between bacteria and minerals. All strains studied adhered predominantly to the edge surfaces of kaolinite rather than to the basal surfaces. Bacteria rarely formed aggregates with montmorillonite, but were more tightly adsorbed onto goethite surfaces. This study reports the first measured interaction force between bacteria and a clay surface, and the approach curves exhibited jump-in events with attractive forces of 97?±?34?pN between E. coli and goethite. Bond strengthening between them occurred within 4?s to the maximum adhesion forces and energies of -3.0?±?0.4 nN and -330?±?43 aJ (10(-18)?J), respectively. Under the conditions studied, bacteria tended to form more extensive biofilms on minerals under low rather than high nutrient conditions.