Control of Fe(III) site occupancy on the rate and extent of microbial reduction of Fe(III) in nontronite

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.     

Correlation of the Hakkoda–Kokumoto Tephra, a widespread Middle Pleistocene tephra erupted from the Hakkoda Caldera, northeast Japan

Abstract A Middle Pleistocene widespread tephra referred to here as Hakkoda–Kokumoto Tephra (Hkd–Ku) has been newly recognized. Hkd–Ku, derived from the Hakkoda Caldera located in northernmost Honshu Is. of northeast Japan, covers much of Honshu Is. At the type locality in the proximal area, Hkd–Ku comprises Plinian pumice deposits and an immediately overlying ignimbrite. The fine vitric ash nature of the distal ash‐fall deposits of Hkd–Ku suggests that they are coignimbrite ash‐fall deposits. Hkd–Ku was identified using a combination of refractive indices and chemical compositions of major, trace and rare earth elements of glass shards, heavy mineral content, refractive indices of orthopyroxene and paleomagnetic polarity. On the basis of these properties, Hkd–Ku was identified in Oga and Boso Peninsulas and Osaka Plain, 830 km southwest of the source. Stratigraphic positions in Boso Peninsula and Osaka Plain within marine sediments that have a reliable chronology based on oxygen‐isotope, and litho‐, bio‐, magneto‐ and tephrostratigraphy indicate that the age of Hkd–Ku is ca 760 ka, positioned in the transition between marine oxygen‐isotope stages 19.1 and 18.4. The widespread occurrence of Hkd–Ku providing a tie line between many different Pleistocene sections over a distance of 800 km is a key marker horizon in the early part of the Middle Pleistocene. This tephra gives a time control point of ca 760 ka to marine sediments in the Oga Peninsula – where no datum plane exists between the Brunhes–Matuyama chron boundary and oxygen‐isotope stage 12 – and to the volcanostratigraphy of the Hakkoda Caldera. The distribution of Hkd–Ku showing emplacement of coignimbrite ash‐fall deposits in the area 830 km southwest of the source emphasizes the upwind transport direction, relative to the prevailing westerly winds, typical of other coignimbrite ash‐fall deposits in the Japanese islands.     

Turbulence in an almond orchard: Vertical variations in turbulent statistics

Three-dimensional wind velocity components were measured above and within a uniform almond orchard. Turbulent statistics associated with the turbulent flow inside the canopy are examined in detail. Turbulence in an almond orchard is characterized by relatively high turbulent intensities and large skewness and kurtosis values. These results indicate that the frequency distribution of wind velocity components is non-Gaussian. Conditional sampling of the turbulent measurements show that large, infrequent sweeps provide the predominant mechanism for tangential momentum stress in the canopy crown. Deep inside the canopy, a secondary wind maximum and small, but positive, tangential momentum stresses are observed.     

Silica diffusion at Ascutney Mountain,Vermont

A suite of pelitic schists from the contact metamorphic aureole around the syenite stock at Ascutney Mountain, Vermont, shows a decrease in the amounts of cordierite, quartz, and andalusite and an increase in pleonaste and corundum as the contact is approached. Whole rock chemical analyses show a distinct SiO₂ concentration gradient from the wall rocks toward the intrusion; however, the syenite has a higher weight percent SiO₂ than the adjacent schists. It is suggested that silica diffused down an SiO₂ activity gradient into the intrusive; other major oxide components were apparently immobile. The diffusion of silica was probably through intergranular fluids, and the amount of silica available for diffusion was governed by the solubilities of cordierite, andalusite, and quartz in the interstitial fluid.     

Comparison of oil shales and kerogen concentrates by C nuclear magnetic resonance

Six oil shales and their kerogen concentrates have been studied using ¹³C CP/MAS NMR techniques to study the distribution of organic carbon species. It is found that if the aromatic and aliphatic regions are divided at about 80 or 100 ppm, the apparent aromaticities of a raw shale and its kerogen concentrate are in good agreement. The presence of oxygen-substituted carbons in the raw shales and their depletion in the kerogen concentrates are observed and discussed.     

Fractionation of carbon and hydrogen isotopes by methane-oxidizing bacteria

Carbon isotopic analysis of methane has become a popular technique in the exploration for oil and gas because it can be used to differentiate between thermogenic and microbial gas and can sometimes be used for gas-source rock correlations. Methane-oxidizing bacteria, however, can significantly change the carbon isotopic composition of methane; the origin of gas that has been partially oxidized by these bacteria could therefore be misinterpreted.We cultured methane-oxidizing bacteria at two different temperatures and monitored the carbon and hydrogen isotopic compositions of the residual methane. The residual methane was enriched in both ¹³C and D. For both isotopic species, the enrichment at equivalent levels of conversion was greater at 26°C than at 11.5°C. The change in δD relative to the change in δ¹³C was independent of temperature within the range studied. One culture exhibited a change in the fractionation pattern for carbon (but not for hydrogen) midway through the experiment, suggesting that bacterial oxidation of methane may occur via more than one pathway.The change in the δD value for the residual methane was from 8 to 14 times greater than the change in the δ¹³C value, indicating that combined carbon and hydrogen isotopic analysis may be an effective way of identifying methane which has been subjected to partial oxidation by bacteria.     

Geochemistry and petrogenesis of the Laramie anorthosite complex,Wyoming

A geochemical investigation of the Laramie anorthosite complex determined that monsonite associated with the complex are characterized by positive Eu anomalies and display a regular variation in composition with distance from the monzonite/county rock contact. Anorthositic rocks have major and trace element abundance typical of similar complexes. The internal variations in the monzonite were produced by in situ fractionation and contamination. The data indicate that anorthosite and monzonite cannot be comagmatic. It is proposed that the anorthosite and monzonite of the complex evolved from two distinct magmas, and that two stages of anatectic melting contributed to the evolution of the monzonite. An initial stage of partial melting was induced by intrusion of a gabbroic anorthosite magma into the lower crust; a second partial melting event occurred after emplacement where heat from the intrusions melted country rocks resulting in extensive contamination ofthe monzonite.     

An investigation of GNSS atomic clock behavior at short time intervals

A technique for obtaining clock measurements from individual GNSS satellites at short time intervals is presented. The methodology developed in this study allows for accurate satellite clock stability analysis without an ultra-stable clock at the ground receiver. Variations in the carrier phase caused by the satellite clock are isolated using a combination of common GNSS carrier-phase processing techniques. Furthermore, the white phase variations caused by the thermal noise of the collection and processing equipment are statistically modeled and removed, allowing for analysis of clock performance at subsecond intervals. Allan deviation analyses of signals collected from GPS and GLONASS satellites reveal distinct intervals of clock noise for timescales less than 100 s. The clock data collected from GPS Block IIA, IIR, IIR-M, and GLONASS satellites reveal similar stability performance at time periods greater than 20 s. The GLONASS clock stability in the 0.6–10 s range, however, is significantly worse than GPS. Applications that rely on ultra-stable clock behavior from the GLONASS satellites at these timescales may therefore require high-rate corrections to estimate and remove oscillator-based errors in the carrier phase.     

Global river discharge and water temperature under climate change

Climate change will affect hydrologic and thermal regimes of rivers, having a direct impact on freshwater ecosystems and human water use. Here we assess the impact of climate change on global river flows and river water temperatures, and identify regions that might become more critical for freshwater ecosystems and water use sectors. We used a global physically based hydrological-water temperature modelling framework forced with an ensemble of bias-corrected general circulation model (GCM) output for both the SRES A2 and B1 emissions scenario. This resulted in global projections of daily river discharge and water temperature under future climate. Our results show an increase in the seasonality of river discharge (both increase in high flow and decrease in low flow) for about one-third of the global land surface area for 2071–2100 relative to 1971–2000. Global mean and high (95th percentile) river water temperatures are projected to increase on average by 0.8–1.6 (1.0–2.2) °C for the SRES B1–A2 scenario for 2071–2100 relative to 1971–2000. The largest water temperature increases are projected for the United States, Europe, eastern China, and parts of southern Africa and Australia. In these regions, the sensitivities are exacerbated by projected decreases in low flows (resulting in a reduced thermal capacity). For strongly seasonal rivers with highest water temperatures during the low flow period, up to 26% of the increases in high (95th percentile) water temperature can be attributed indirectly to low flow changes, and the largest fraction is attributable directly to increased atmospheric energy input. A combination of large increases in river temperature and decreases in low flows are projected for the southeastern United States, Europe, eastern China, southern Africa and southern Australia. These regions could potentially be affected by increased deterioration of water quality and freshwater habitats, and reduced water available for human uses such as thermoelectric power and drinking water production.     

Linking Hydrogeomorphology and Food Webs in Intertidal Creeks

Intertidal creeks are shallow, photic ecosystems that potentially serve as sources of prey for many predators within estuaries. In a previous study, the link between nekton community structure and hydrogeomorphological variables for eight intertidal creeks was assessed for North Inlet estuary, South Carolina. Herein, we advance their findings through ecological network analysis of foodweb structure within two creeks and infer nekton trophic relationships to geomorphology and potential influences of hydrological condition and change. A summer network of a shallow, wide creek demonstrated greater carbon recycling, trophic efficiency and flow through consumers than that of a deep, narrow creek representing the same period. We infer greater export of nekton carbon from the former creek. These results were supported by analyses of nekton effective trophic levels and guilds across the eight creeks. Shallow, wide intertidal creeks appear to provide both physical and foodweb attributes that promote good nekton habitat relative to deeper and narrower creeks. Human alterations to flow regimes and sea-level rise have the ability to affect geomorphology of individual creeks and the landscape as a whole. These changes in turn have the potential to alter food webs of intertidal creeks and their ability to serve as sources of food for the larger estuary.