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Colloidal-facilitated transport of inorganic contaminants in ground water: part 1, sampling considerations

Investigations at Pinal Creek, Arizona, evaluated routine sampling procedures for determination of aqueous inorganic geochemistry and assessment of contaminant transport by colloidal mobility. Sampling variables included pump type and flow rate, collection under air or nitrogen, and filter pore diameter. During well purging and sample collection, suspended particle size and number as well as dissolved oxygen, temperature, specific conductance, pH, and redox potential were monitored. Laboratory analyses of both unfiltered samples and the filtrates were performed by inductively coupled argon plasma, atomic absorption with graphite furnace, and ion chromatography. Scanning electron microscopy with Energy Dispersive X-ray was also used for analysis of filter particulates. Suspended particle counts consistently required approximately twice as long as the other field-monitored indicators to stabilize. High-flow-rate pumps entrained normally nonmobile particles. Difference in elemental concentrations using different filter-pore sizes were generally not large with only two wells having differences greater than 10 percent in most wells. Similar differences (>10%) were observed for some wells when samples were collected under nitrogen rather than in air. Fe 2+ /Fe 3+ ratios for air-collected samples were smaller than for samples collected under a nitrogen atmosphere, reflecting sampling-induced oxidation.

Arizona

Evidence for deposition of 10 million tonnes of impact spherules across four continents 12,800 y ago

Airbursts/impacts by a fragmented comet or asteroid have been proposed at the Younger Dryas onset (12.80 ± 0.15 ka) based on identification of an assemblage of impact-related proxies, including microspherules, nanodiamonds, and iridium. Distributed across four continents at the Younger Dryas boundary (YDB), spherule peaks have been independently confirmed in eight studies, but unconfirmed in two others, resulting in continued dispute about their occurrence, distribution, and origin. To further address this dispute and better identify YDB spherules, we present results from one of the largest spherule investigations ever undertaken regarding spherule geochemistry, morphologies, origins, and processes of formation. We investigated 18 sites across North America, Europe, and the Middle East, performing nearly 700 analyses on spherules using energy dispersive X-ray spectroscopy for geochemical analyses and scanning electron microscopy for surface microstructural characterization. Twelve locations rank among the world’s premier end-Pleistocene archaeological sites, where the YDB marks a hiatus in human occupation or major changes in site use. Our results are consistent with melting of sediments to temperatures >2,200 °C by the thermal radiation and air shocks produced by passage of an extraterrestrial object through the atmosphere; they are inconsistent with volcanic, cosmic, anthropogenic, lightning, or authigenic sources. We also produced spherules from wood in the laboratory at >1,730 °C, indicating that impact-related incineration of biomass may have contributed to spherule production. At 12.8 ka, an estimated 10 million tonnes of spherules were distributed across ∼50 million square kilometers, similar to well-known impact strewnfields and consistent with a major cosmic impact event.

Proceedings of the National Academy of Sciences of

The importance of particulate texture to the flow strength of ice + dust

Preliminary experimental surveys of the flow of dilute mixtures of ice plus hard particulates under planetary conditions indicate a strengthening effect with respect to pure ice, but with dependencies on environmental conditions (temperature, stress, grain size) that vary widely from study to study [1-4]. With the expectation that the textural character of the particulate fraction (size, shape, spatial distribution of particulates; relationship of particulates to ice grain boundaries, etc.) also influences rheological behavior, we have begun a more systematic investigation of the effect of particulates on strength. We rely extensively on cryogenic scanning electron microscopy (CSEM) and to maximize planetary relevance we focus on behavior at low stress and small grain size.

Conference Paper

Tonsteins and clay-rich layers in coal-bearing intervals of the Eocene Manning formation, east-central Texas

Six samples from clay-rich intervals in the coal-bearing upper part of the Eocene Manning Formation were analyzed by scanning-electron microscopy and energy-dispersive X-ray fluorescence to determine the origin of minerals in the samples. Two samples were from surface-mine exposures of the 3500 coal bed near Bryan, Texas, and the remaining samples were from an exposure of a correlative interval at the Lake Somerville spillway about 60 km (37 mi) southwest of Bryan. Preliminary data suggest that both a 2-cm-thick (0.75-in) claystone from the upper part of the 3500 bed and the upper part of an 11-cm-thick (4.25-in) mudstone from the floor of the lower coal bed at the spillway were derived from volcanic ash falls. Both clay layers identified as possible tonsteins are composed of kaolinite and accessory quartz, euhedral to subhedral zircon, feldspars, and Ca-Al phosphates (crandallite?). Both alkali and plagioclase feldspars are observed in the two samples, but K-feldspar predominates in the upper clay layer of the 3500 bed, and plagioclase, with accessory Ti-bearing biotite, predominates in the sample from the floor of the spillway. These compositional differences suggest two separate volcanic ash falls. The other sampled clay layers contain rounded to subrounded zircons and feldspars in a mixed-layer clay groundmass, which suggests detrital rather than ash-fall origins.

Texas

Analytical electron microscopy in mineralogy; exsolved phases in pyroxenes

Analytical scanning transmission electron microscopy has been successfully used to characterize the structure and composition of lamellar exsolution products in pyroxenes. At operating voltages of 100 and 200 keV, microanalytical techniques of x-ray energy analysis, convergent-beam electron diffraction, and lattice imaging have been used to chemically and structurally characterize exsolution lamellae only a few unit cells wide. Quantitative X-ray energy analysis using ratios of peak intensities has been adopted for the U.S. Geological Survey AEM in order to study the compositions of exsolved phases and changes in compositional profiles as a function of time and temperature. The quantitative analysis procedure involves 1) removal of instrument-induced background, 2) reduction of contamination, and 3) measurement of correction factors obtained from a wide range of standard compositions. The peak-ratio technique requires that the specimen thickness at the point of analysis be thin enough to make absorption corrections unnecessary (i.e., to satisfy the “thin-foil criteria”). In pyroxenes, the calculated “maximum thicknesses” range from 130 to 1400 nm for the ratios Mg/Si, Fe/Si, and Ca/Si; these “maximum thicknesses” have been contoured in pyroxene composition space as a guide during analysis. Analytical spatial resolutions of 50–100 nm have been achieved in AEM at 200 keV from the composition-profile studies, and analytical reproducibility in AEM from homogeneous pyroxene standards is ± 1.5 mol% endmember.

Ultramicroscopy

Evaluating aromatization of solid bitumen generated in the presence and absence of water: Implications for solid bitumen reflectance as a thermal proxy

Geological models for petroleum generation suggest thermal conversion of oil-prone sedimentary organic matter in the presence of water promotes increased liquid saturate yield, whereas absence of water causes formation of an aromatic, cross-linked solid bitumen residue. To test the influence of hydrogen from water, organic-rich (22 wt% total organic carbon , TOC) mudrock samples from the Eocene lacustrine Green River Formation Mahogany zone oil shale were pyrolyzed under hydrous and anhydrous conditions in closed system batch reactors at temperatures between 300 and 370 °C for 72 h. Pre- and post-pyrolysis samples were characterized using petrographic approaches including optical microscopy , reflectance, Raman spectroscopy , and scanning electron and transmission electron microscopy to quantify differences in relative appearance, abundance, and composition of solid bitumen newly generated during the pyrolysis experiments. Petrographic analyses were supplemented by geochemical screening measurements (TOC content and programmed temperature pyrolysis). Results show post-hydrous pyrolysis residues contain lower TOC, are comprised of solid bitumen with greater aromaticity , and have textures indicative of lower viscosities, relative to anhydrous residues from the same temperature pyrolysis conditions. These observations suggest solid bitumen forming from thermal conversion of oil-prone sedimentary organic matter under anhydrous conditions may be less aromatic, although more cross-linked, than solid bitumen forming under hydrous conditions at the same time-temperature combination. To explain these results, we suggest that a radical disproportionation mechanism is favored in the presence of hydrogen donated from water, and that this disproportionation promotes aromatization in the solid residue with concomitant expulsion of saturated hydrocarbons.

International Journal of Coal Geology

Effect of calcium on the bioavailability of dissolved uranium(VI) in plant roots under circumneutral pH

We integrated field measurements, hydroponic experiments, microscopy, and spectroscopy to investigate the effect of Ca(II) on dissolved U(VI) uptake by plants in 1 mM HCO 3 – solutions at circumneutral pH. The accumulation of U in plants (3.1–21.3 mg kg –1 ) from the stream bank of the Rio Paguate, Jackpile Mine, New Mexico served as a motivation for this study. Brassica juncea was the model plant used for the laboratory experiments conducted over a range of U (30–700 μg L –1 ) and Ca (0–240 mg L –1 ) concentrations. The initial U uptake followed pseudo-second-order kinetics. The initial U uptake rate ( V 0 ) ranged from 4.4 to 62 μg g –1 h –1 in experiments with no added Ca and from 0.73 to 2.07 μg g –1 h –1 in experiments with 12 mg L –1 Ca. No measurable U uptake over time was detected for experiments with 240 mg L –1 Ca. Ternary Ca–U–CO 3 complexes may affect the decrease in U bioavailability observed in this study. Elemental X-ray mapping using scanning transmission electron microscopy–energy-dispersive spectrometry detected U–P-bearing precipitates within root cell walls in water free of Ca. These results suggest that root interactions with Ca and carbonate in solution affect the bioavailability of U in plants. This study contributes relevant information to applications related to U transport and remediation of contaminated sites.

Environmental Science & Technology

Mercury speciation in the Mt. Amiata mining district (Italy): interplay between urban activities and mercury contamination

A fundamental step to evaluate the biogeochemical and eco-toxicological significance of Hg dispersion in the environment is to determine speciation of Hg in solid matrices. In this study, several analytical techniques such as scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), sequential chemical extractions (SCEs), and X-ray absorption spectroscopy (XANES) were used to identify Hg compounds and Hg speciation in samples collected from the Mt. Amiata Hg mining district, southern Tuscany, Italy. Different geological materials, such as mine waste calcine (retorted ore), soil, stream sediment, and stream water suspended particulate matter were analyzed. Results show that the samples were generally composed of highly insoluble Hg compounds such as sulphides (HgS, cinnabar and metacinnabar), and more soluble Hg halides such as those associated with the mosesite group. Other moderately soluble Hg compounds, HgCl 2 , HgO and Hg 0 , were also identified in stream sediments draining the mining area. The presence of these minerals suggests active and continuous runoff of soluble Hg compounds from calcines, where such Hg compounds form during retorting, or later in secondary processes. Specifically, we suggest that, due to the proximity of Hg mines to the urban center of Abbadia San Salvatore, the influence of other anthropogenic activities was a key factor for Hg speciation, resulting in the formation of unusual Hg-minerals such as mosesite.

Tuscany

Dating fault damage along the eastern Denali fault zone with hematite (U-Th)/He thermochronometry

Unraveling complex slip histories in fault damage zones to understand relations among deformation, hydrothermal alteration, and surface uplift remains a challenge. The dextral eastern Denali fault zone (EDFZ; southwest Yukon, Canada) bounds the Kluane Ranges and hosts a variety of fault-related rocks, including hematite fault surfaces, which have been exhumed through the brittle regime over a protracted period of geologic time. Scanning electron microscopy-based microtextural observations and hematite (U-Th)/He (hematite He) thermochronometry from these surfaces indicate multiple generations of foliated, high-aspect ratio hematite plates. Single-aliquot hematite He dates ( n = 38 "> n=38 ) from 11 samples range from 11.5 ± 3.2 Ma (2 σ ) to 3.4 ± 2.1 Ma and exhibit moderate inter- and intrasample dispersion. A subset of dates is 15-20 Myr younger than previously published apatite (U-Th)/He dates from collocated host rocks, despite similar closure temperatures, precluding a simple ambient cooling interpretation for our hematite He data. Mixture modeling defines hematite He date populations at ∼8 Ma, ∼6 Ma, and ∼4 Ma, and when combined with microtextural observations, supports episodes of hydrothermal alteration and fault reactivation at aseismic to subseismic slip rates. There is no evidence that hematite experienced deformation- or hydrothermal fluid-related He loss. Hematite He dates overlap previously documented Kluane Ranges surface uplift and shifting dynamics of the Yakutat microplate, pinpointing fault networks and deformation processes that accommodate regional deformation in response to far-field plate boundary processes.

Alaska

Authigenic mineral texture in submarine 1979 basalt drill core, Surtsey volcano, Iceland

Micrometer-scale maps of authigenic microstructures in submarine basaltic tuff specimens from a 1979 Surtsey volcano, Iceland, drill core acquired 15 years after eruptions terminated provide fresh perspectives for deciphering the initial alteration of oceanic basalt in a low temperature hydrothermal system. A novel investigative approach integrates synchrotron source X-ray microdiffraction (µXRD), X-ray microfluoresence (µXRF), micro-computed tomography (µCT), and scanning transmission electron microscopy (S/TEM) coupled with Raman spectroscopy to create finely resolved spatial frameworks that record a continuum of alteration in glass and olivine. Micro-analytical maps of vesicular and fractured lapilli in specimens from 157.1, 137.9, and 102.6 m depth, and borehole temperatures of 83, 93.9 and 141.3 °C measured in 1980, respectively, record the production of nanocrystalline clay mineral, zeolites, and Al-tobermorite in diverse microenvironments. Nanocrystalline clay mineral (nontronite) and zeolite (amicite) texture in linear microstructures have concentrically-oriented crystallographic preferred orientation. Raman spectra indicating degraded organic carbonaceous matter are associated with nanocrystalline clay mineral in 10–25 nm, sub-circular nanoscale cavities in altered glass at 137.9 m depth and in a concentrically-layered, crystallographically-oriented linear microstructure in altered olivine at 102.6 m. These features have little resemblance to previously described alteration features in basalt. Irregular alteration fronts between fresh and altered glass at 157.1 depth, however, show a resemblance to microchannels in older basalts. The integrated analyses describe the complex organization of previously unrecognized mineral textures in very young basalt and provide a foundational mineralogical reference for longitudinal, time-lapse characterizations of palagonitized basalt in oceanic environments.

Geochemistry, Geophysics, Geosystems

Phosphates in some Missouri refractory clays

This paper describes in detail phosphate minerals occurring in refractory clays of Missouri and their effect on the refractory degree of the clays. The minerals identified include carbonate-fluorapatite (francolite), crandallite, goyazite, wavellite, variscite and strengite. It is emphasized that these phosphates occur only in local isolated concentrations, and not generally in Missouri refractory clays. The Missouri fireclay region comprises 2 districts, northern and southern, separated by the Missouri River. In this region, clay constitutes a major part of the Lower Pennsylvanian Cheltenham Formation. The original Cheltenham mud was an argillic residue derived from leaching and dissolution of pre-Pennsylvanian carbonates. The mud accumulated on a karstic erosion surface truncating the pre-Cheltenham rocks. Fireclays of the northern district consist mainly of poorly ordered kaolinite, with variable but minor amounts of illite, chlorite and fine-grained detrital quartz. Clays of the southern district were subjected to extreme leaching that produced well-ordered kaolinite flint clays. Local desilication formed pockets of diaspore, or more commonly, kaolinite, with oolite-like nubs or burls of diaspore (“burley”" clay). The phosphate-bearing materials have been studied by X-ray diffraction (XRD), scanning electron microscopy-energy dispersive spectral analysis (SEM-EDS) and chemical analysis. Calcian goyazite was identified in a sample of diaspore, and francolite in a sample of flint clay. A veinlet of wavellite occurs in flint clay at one locality, and a veinlet of variscite-strengite at another locality. The Missouri flint-clay-hosted francolite could not have formed in the same manner as marine francolite. The evidence suggests that the Cheltenham francolite precipitated from ion complexes in pore water, nearly simultaneously with crystallization of kaolinite flint clay from an alumina-silica gel. Calcian goyazite is an early diagenetic addition to its diaspore host. The wavellite and variscite-strengite veinlets are secondary, precipitated from ion complexes in ground water percolating along cracks in the flint clay. The flint clay host of the variscite-strengite veinlet contains strontian crandallite. All of the phosphates contain significant amounts of strontium. The source of P, Ca and Sr was the marine carbonates. Dissolution of these carbonates produced the argillic residue that became the primordial Cheltenham paludal mud, which ultimately altered to fireclay. Preliminary firing tests show that the presence of phosphates lowers fusion temperature. However, it is not clear whether poor refractoriness is due to the presence of phosphates, per se, or to Ca, Sr and other alkaline elements present in the phosphates.

Clays and Clay Minerals

MICROCHARACTERIZATION OF ARSENIC- AND SELENIUM-BEARING PYRITE IN UPPER FREEPORT COAL, INDIANA COUNTY, PENNSYLVANIA.

Optical and scanning electron microscope as well as electron and proton microprobe techniques have been used in a detailed investigation of the modes of occurrence of arsenic and selenium in pyrite in Upper Freeport coal from the Homer City area, Indiana County, Pennsylvania. Polished blocks were prepared from columnar samples of the coal bed to represent particular zones continuously from top to bottom. Initial selection of zones to be studied was based on chemical analysis of bench-channel samples. Microprobe data indicate that the highest concentrations of arsenic (as great as 1. 5 wt. %) are apparently in solid solution in pyrite within a limited stratigraphic interval of the coal bed. Smaller amounts of arsenic and selenium (concentrations up to approximately 0. 1 and 0. 2 wt. % respectively) were detected at isolated points within pyrite grains in various strata of the coal bed.

Scanning Electron Microscopy

Dominance of 'Gallionella capsiferriformans' and heavy metal association with Gallionella -like stalks in metal-rich pH 6 mine water discharge

Heavy metal-contaminated, pH 6 mine water discharge created new streams and iron-rich terraces at a creek bank in a former uranium-mining area near Ronneburg, Germany. The transition from microoxic groundwater with ~5 m m Fe(II) to oxic surface water may provide a suitable habitat for microaerobic iron-oxidizing bacteria (FeOB). In this study, we investigated the potential contribution of these FeOB to iron oxidation and metal retention in this high-metal environment. We (i) identified and quantified FeOB in water and sediment at the outflow, terraces, and creek, (ii) studied the composition of biogenic iron oxides ( Gallionella -like twisted stalks) with scanning and transmission electron microscopy (SEM, TEM) as well as confocal laser scanning microscopy (CLSM), and (iii) examined the metal distribution in sediments. Using quantitative PCR, a very high abundance of FeOB was demonstrated at all sites over a 6-month study period. Gallionella spp. clearly dominated the communities, accounting for up to 88% of Bacteria , with a minor contribution of other FeOB such as Sideroxydans spp. and ‘ Ferrovum myxofaciens ’. Classical 16S rRNA gene cloning showed that 96% of the Gallionella -related sequences had ≥97% identity to the putatively metal-tolerant ‘ Gallionella capsiferriformans ES-2’, in addition to known stalk formers such as Gallionella ferruginea and Gallionellaceae strain R-1. Twisted stalks from glass slides incubated in water and sediment were composed of the Fe(III) oxyhydroxide ferrihydrite, as well as polysaccharides. SEM and scanning TEM-energy-dispersive X-ray spectroscopy revealed that stalk material contained Cu and Sn, demonstrating the association of heavy metals with biogenic iron oxides and the potential for metal retention by these stalks. Sequential extraction of sediments suggested that Cu (52–61% of total sediment Cu) and other heavy metals were primarily bound to the iron oxide fractions. These results show the importance of ‘ G. capsiferriformans ’ and biogenic iron oxides in slightly acidic but highly metal-contaminated freshwater environments.

Geobiology

Recommended procedures and techniques for the petrographic description of bituminous coals

Modern coal petrology requires rapid and precise description of great numbers of coal core or bench samples in order to acquire the information required to understand and predict vertical and lateral variation of coal quality for correlation with coal-bed thickness, depositional environment, suitability for technological uses, etc. Procedures for coal description vary in accordance with the objectives of the description. To achieve our aim of acquiring the maximum amount of quantitative information within the shortest period of time, we have adopted a combined megascopic-microscopic procedure. Megascopic analysis is used to identify the distinctive lithologies present, and microscopic analysis is required only to describe representative examples of the mixed lithologies observed. This procedure greatly decreases the number of microscopic analyses needed for adequate description of a sample. For quantitative megascopic description of coal microlithotypes, microlithotype assemblages, and lithotypes, we use (V) for vitrite or vitrain, (E) for liptite, (I) for inertite or fusain, (M) for mineral layers or lenses other than iron sulfide, (S) for iron sulfide, and (X 1 ), (X 2 ), etc. for mixed lithologies. Microscopic description is expressed in terms of V representing the vitrinite maceral group, E the exinite group, I the inertinite group, and M mineral components. volume percentages are expressed as subscripts. Thus (V) 20 (V 80 E 10 I 5 M 5 ) 80 indicates a lithotype or assemblage of microlithotypes consisting of 20 vol. % vitrite and 80% of a mixed lithology having a modal maceral composition V 80 E 10 I 5 M 5 . This bulk composition can alternatively be recalculated and described as V 84 E 8 I 4 M 4 . To generate these quantitative data rapidly and accurately, we utilize an automated image analysis system (AIAS). Plots of VEIM data on easily constructed ternary diagrams provide readily comprehended illustrations of the range of modal composition of the lithologic units making up a given coal bed. The use of bulk-specific-gravity determinations is alo recommended for identification and characterization of the distinctive lithologic units. The availability of an AIAS also enhances the capability to acquire textural information. Ranges of size of maceral and mineral grains can be quickly and precisely determined by use of an AIAS. We assume that shape characteristics of coal particles can also be readily evaluated by automated image analysis, although this evaluation has not yet been attempted in our laboratory. Definitive data on the particulate mineral content of coal constitute another important segment of petrographic description. Characterization of mineral content may be accomplished by optical identification, electron microprobe analysis, X-ray diffraction, and scanning and transmission electron microscopy. Individual mineral grains in place in polished blocks or polished this sections, or separated from the coal matrix by sink-float methods are studied by analytical techniques appropriate to the conditions of sampling.

International Journal of Coal Geology

Microbial reduction of structural iron in interstratified illite-smectite minerals by a sulfate-reducing bacterium

Clay minerals are ubiquitous in soils, sediments, and sedimentary rocks and could coexist with sulfate‐reducing bacteria (SRB) in anoxic environments, however, the interactions of clay minerals and SRB are not well understood. The objective of this study was to understand the reduction rate and capacity of structural Fe(III) in dioctahedral clay minerals by a mesophilic SRB, Desulfovibrio vulgaris and the potential role in catalyzing smectite illitization. Bioreduction experiments were performed in batch systems, where four different clay minerals (nontronite NAu‐2, mixed‐layer illite‐smectite RAr‐1 and ISCz‐1, and illite IMt‐1) were exposed to D. vulgaris in a non‐growth medium with and without anthraquinone‐2,6‐disulfonate (AQDS) and sulfate. Our results demonstrated that D. vulgaris was able to reduce structural Fe(III) in these clay minerals, and AQDS enhanced the reduction rate and extent. In the presence of AQDS, sulfate had little effect on Fe(III) bioreduction. In the absence of AQDS, sulfate increased the reduction rate and capacity, suggesting that sulfide produced during sulfate reduction reacted with the phyllosilicate Fe(III). The extent of bioreduction of structural Fe(III) in the clay minerals was positively correlated with the percentage of smectite and mineral surface area of these minerals. X‐ray diffraction, and scanning and transmission electron microscopy results confirmed formation of illite after bioreduction. These data collectively showed that D. vulgaris could promote smectite illitization through reduction of structural Fe(III) in clay minerals.

Geobiology

The role of clay minerals in the preservation of organic matter in sediments of Qinghai Lake, NW China

The role of saline lake sediments in preserving organic matter has long been recognized. In order to further understand the preservation mechanisms, the role of clay minerals was studied. Three sediment cores, 25, 57, and 500 cm long, were collected from Qinghai Lake, NW China, and dissected into multiple subsamples. Multiple techniques were employed, including density fractionation, X-ray diffraction, scanning and transmission electron microscopy (SEM and TEM), total organic carbon (TOC) and carbon compound analyses, and surface area determination. The sediments were oxic near the water-sediment interface, but became anoxic at depth. The clay mineral content was as much as 36.8%, consisting mostly of illite, chlorite, and halloysite. The TEM observations revealed that organic matter occurred primarily as organic matter-clay mineral aggregates. The TOC and clay mineral abundances are greatest in the mid-density fraction, with a positive correlation between the TOC and mineral surface area. The TOC of the bulk sediments ranges from 1 to 3% with the non-hydrocarbon fraction being predominant, followed by bitumen, saturated hydrocarbon, aromatic hydrocarbons, and chloroform-soluble bitumen. The bimodal distribution of carbon compounds of the saturated hydrocarbon fraction suggests that organic matter in the sediments was derived from two sources: terrestrial plants and microorganisms/algae. Depthrelated systematic changes in the distribution patterns of the carbon compounds suggest that the oxidizing conditions and microbial abundance near the water-sediment interface promote degradation of labile organic matter, probably in adsorbed form. The reducing conditions and small microbial biomass deeper in the sediments favor preservation of organic matter, because of the less labile nature of organic matter, probably occurring within clay mineral-organic matter aggregates that are inaccessible to microorganisms. These results have important implications for our understanding of mechanisms of organic matter preservation in saline lake sediments.

Qinghai Lake

Microbial reduction of structural Fe3+ in nontronite by a thermophilic bacterium and its role in promoting the smectite to illite reaction

The illitization process of Fe-rich smectite (nontronite NAu-2) promoted by microbial reduction of structural Fe3+ was investigated by using a thermophilic metal-reducing bacterium, Thermoanaerobacter ethanolicus, isolated from the deep subsurface. T. ethanolicus was incubated with lactate as the sole electron donor and structural Fe3+ in nontronite as the sole electron acceptor, and anthraquinone-2, 6-disulfonate (AQDS) as an electron shuttle in a growth medium (pH 6.2 and 9.2, 65 ??C) with or without an external supply of Al and K sources. With an external supply of Al and K, the extent of reduction of Fe3+ in NAu-2 was 43.7 and 40.4% at pH 6.2 and 9.2, respectively. X-ray diffraction and scanning and transmission electron microscopy revealed formation of discrete illite at pH 9.2 with external Al and K sources, while mixed layers of illite/smectite or highly charged smectite were detected under other conditions. The morphology of biogenic illite evolved from lath and flake to pseudo-hexagonal shape. An external supply of Al and K under alkaline conditions enhances the smectite-illite reaction during microbial Fe3+ reduction of smectite. Biogenic SiO2 was observed as a result of bioreduction under all conditions. The microbially promoted smectite-illite reaction proceeds via dissolution of smectite and precipitation of illite. Thermophilic iron reducing bacteria have a significant role in promoting the smectite to illite reaction under conditions common in sedimentary basins.

American Mineralogist